TW200900449A - Compositions and methods for polymer composites - Google Patents

Abstract

This invention relates to organic salt compositions useful in the preparation of organoclay compositions, polymer-organoclay composite compositions, and methods for the preparation of polymer nanocomposites. In one embodiment, the present invention provides a method of making a polymer-organoclay composite composition, said method comprising melt mixing a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polyetherimide composition; said melt mixing being carried out at a temperature in a range between about 300DEG C and about 450DEG C to provide a polymer-organoclay composite composition, said polymer-organoclay composite composition being characterized by a percent exfoliation of at least 10 percent.

Description

200900449 IX. INSTRUCTIONS: RELATED APPLICATIONS AND PRIORITY STATEMENT This application claims the US non-provisional application number 11/766,843, which was filed on June 22, 2007, and the serial number filed on June 26, 2006. The priority of U.S. Provisional Application Serial No. 60/945, filed on Jun. [Technical field to which the invention pertains]

The present invention relates to an organic salt composition which can be used in the preparation of an organic clay composition 'polymer-organic clay composite composition, & a method of preparing a composite nanocomposite. [Prior Art] The organic clay is used in the preparation of a polymer composition having enhanced physical properties. The additive is used with respect to the unfilled polymeric material and the polymer composite composition relative to the :3 inorganic clay. Organic clays are typically made by replacing the inorganic cations present in a typical inorganic chelate salt layer with organic cations. The organic clay composition-----[====================================================================================== There is no (four) acid salt layer: there is a degree of =. Exist in organic soil expansion, meaning that relative to the phase Hi, the d-... in the organic viscose clay, the d-spacing in the clay will increase and there will be reinforcement = and fall and accept in the polymer matrix The tendency of organic clay to peel off when shearing. In some cases, the spalling system is such that 123170 200900449, so that the polymer composition containing the extremely highly dispersed money salt layer of this organic clay-containing polymer composition is called the same: although in the past ten years in this field Impressive progress, mutual intercourse: the organic clay composition of the positive is actively sought, and when found - pay attention to it. The disadvantage of many organic clays is the thermal instability that makes them unsuitable for applications where the polymer _ ί'' must be treated at elevated temperatures, for example, in containment, "Polymer-containing polymer composition of polymers such as polyetherimine: that is the case. Another disadvantage of many known organic clay compositions is that when the organic clay composition is dispersed in a polymer matrix The organoclay = compound can adversely interact with the polymer based oxime and can result in the marginal properties of the organic clay containing polymer composition. For example, when the organic cation is the primary ammonium cation and the polymer matrix is sensitive to the amine group , the decline of the polymer matrix

The composition, the compound, occurs intact. The solution can be caused, for example, during the melt mixing of the polymer matrix with the organic binder. Thus, there is a (4) interest in the development of organic Thai soil compositions which have thermal stability and which will advantageously interact with the polymer matrix in organic clay polymer compositions. The present invention seeks to address these and other techniques. sgb 戮0 [Invention] In various embodiments, the present invention provides novel quaternary organic scale salts and novel quaternary pyridinium salts useful in the preparation of organic clay compositions. . Accordingly, in one embodiment, the present invention provides a novel organic clay composition made using the novel organic salt provided by the present invention 123170 200900449. In still another aspect, the invention provides a novel poly-organoclay composite composition comprising the organoclay composition disclosed herein. In still another aspect, the present invention is a novel process for preparing a polymer_organic clay composite composition. These and other aspects of the invention are disclosed in detail herein. DETAILED DESCRIPTION OF THE INVENTION In the following patent specification and subsequent claims, reference is made to a number of terms, which are defined as having the following meanings. The singular forms "a", "an", "," and "the" are meant to include the plural referents, unless the context clearly dictates otherwise. "option" or "as appropriate" means the event or The condition may or may not occur, and the description includes the circumstances in which the event will occur and the circumstances in which it does not occur. The term "solvent" as used herein may refer to a single solvent or a mixture of solvents. In the context of use, the approximating language may be applied throughout the specification and claims to modify any quantitative statement that can be changed as appropriate without causing a change in its basic functionality. Terms such as the values modified by "about" are not limited to the specified numerical values. In some cases, the approximate language may correspond to the precision of the instrument used to measure the value. The term "aromatic group" as used herein refers to an array of atoms having at least one valence bond comprising at least one aromatic group. The array comprising at least one aromatic group having at least one valence bond An atom, which may contain a hetero atom, is sin. 123170 200900449 such as nitrogen, sulfur, selenium, tellurium and oxygen, or may consist entirely of carbon and hydrogen. The "aromatic group" as used herein includes but is not limited to benzene. Base, pyridyl, furyl, porphinyl, fluorenyl, phenylene and biphenyl. As indicated, the group of the group contains at least a group of groups. The aromatic group is invariably a ring structure with 411 + 2 de-localized "electrons, where "η" is equal to i or more ^, an integer, such as by phenyl (n=1) ), p-mercapto (n = 1), biting base (η = ι tea base (n = 2), t-base (n = 2), E & (n = 3), etc. The group may also contain a non-aromatic component. For example, the benzyl group is an aromatic group containing a benzene ring (aromatic group) and a fluorenylene group (non-aromatic component). Similarly, the tetrahydronaphthyl group is fused. To the aromatic group of the aromatic group (C6h3) of the non-aromatic component (αΐ2)4_. For convenience, the term "aromatic group" is defined herein to cover a wide range of functional groups. , for example, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a aryl group, a cofluorenyl group, an alcohol group, a fluorenyl group, an aryl group, a keto group, a carboxylic acid group, a fluorenyl group (for example, a carboxylic acid derivative) For example, esters and amides, amines, nitro groups, etc. For example, 4-methylphenyl is a heart-containing aromatic group containing a fluorenyl group, and a fluorenyl group is an S-energy group, which is an alkyl group. Similarly, the 2-nitrophenyl group is a heart-containing aromatic group containing a nitro group, and the nitro group is a functional group. The group includes a dentate aromatic group such as 4-trifluoromethylphenyl or hexafluoroisopropylidene bis(4-benzoindole-yloxy) (ie, -〇PhC(CF3)2PhO- ), 4-chloromercaptophenyl-1-yl, 3-trifluorovinyl-2-pyromenyl, 3-dichloromethylbenzene_ι-yl (ie 3-CCl3 Ph-), 4- (3-Bromopropan-1-yl) phenyl-yl (i.e., 'BrC^Ci^a^Ph-), etc. Further examples of the aromatic group include 4-allyloxybenzene_ι_oxy , 4-aminophenyl-1-yl (ie, 4_H2NPh-), 3-aminosulfenyl-1-yl (ie, M^COPli-), 4-benzylidenebenzene small group, dicyano group Methylene bis(4-phenyl-1-yloxy) (ie, 〇PhC(CN)2PhO-), 3-mercaptobenzene 123170 200900449, methylene bis(4-phenyl-1-yloxy) () _ 〇 phCH2ph 〇 _), 2-ethyl phenyl small group, phenyl vinyl, 3-methylcarbonyl 2 - pyrenyl, 2-hexyl · 5 - fluorenyl, hexamethylene - 1,6-bis(4-phenyl-1-yloxy) (ie _〇ph(CH2)6ph〇_), 4-methylphenyl-1-yl (ie 4-H〇CH2Ph-), 4-mercaptomethylphenyl-1-yl (ie 4-HSCH2 Ph-), 4-decyl sulfenyl small group (ie 4_CH3 sph_), 3-methoxybenzene +

, 2-methoxycarbonylphenyl-1-yloxy (eg, fluorenyl), 2-nitromethylphenyl-1-yl (ie, 2-N〇2CH2Ph), 3-trimethyldecyl Benzene small group, 4_third-butyl dimethyl fluorenyl phenyl-1-yl group, 4-vinyl benzene-μ group, vinylidene bis(phenyl), and the like. "C3_C1() aromatic group, the term includes an aromatic group containing at least three but no more than 10 slave atoms. The aromatic group 1-imidazolyl (c3 H2N2-) represents a C3 aromatic group. Benzyl represents a c7 aromatic group. The term "cycloaliphatic group" as used herein refers to a group having at least one valence bond and comprising an array of atoms which are cyclic, but which are not aromatic. As defined herein, "cycloaliphatic group" does not contain an aromatic group. "cycloaliphatic group, 'may contain - or a variety of acyclic components. For example, hexylmethyl group (C^HnCH2·) is a cycloaliphatic group containing a cyclohexyl ring (an atomic group which is cyclic but not aromatic) and a methylene group (acyclic component). The cycloaliphatic group may contain a hetero atom such as nitrogen, sulfur, selenium, tellurium and oxygen or may consist entirely of carbon and hydrogen. For convenience, the term "cycloaliphatic group" is defined herein to encompass a wide range of functional groups, #domain group, dilute group, block group, haloalkyl group, conjugated dienyl group, alcohol a group, an ether group, an aldehyde group, a ketone group, a carboxylic acid group, a decyl group (for example, a carboxylic acid derivative such as an ester and a guanamine), an amine group, a nitro group, etc. For example, 4-methylcyclopentyl group a Q cycloaliphatic group containing a methyl group, the methyl group being a functional group 'is an alkyl group. Similarly, the ' 2 -cyanocyclobutane · group is a 123170 200900449 Q cycloaliphatic group containing a nitro group, The stone base is a functional group. The cycloaliphatic group may contain one or more halogen atoms, which may be the same or different. South atoms include, for example, gas, gas, brook, and moth. The cycloaliphatic group containing one or more halogen atoms includes 2_trimethylmethylcyclohexanyl, 4-glycolyldimethylcyclooctyl+yl, 2—a gas dimethylaminocyclohexyl, Hexafluoroisopropylidene-2,2_bis(cyclohexyl) (ie, 2_chloroindenylcyclohexyl, 3_di-methylenecyclohexan-i-yl, 4-tri Chloromethylcyclohexyloxy, 4_enyl dimethyl ring = f, -1-ylthio, transylethylcyclopentanyl, (tetra)propylcyclohexyloxy (eg CHsCHBrO^ Further examples of the cycloaliphatic group of QH^O-) and the like include 4-dipropoxycyclohexyl group, 4-aminocyclohexanyl group (ie, h2NC6d, 4-aminocarbonylcyclopentyl group ( That is, Ν^αχ^ϊ^), 4_acetoxycyclohexyl, 2,2-dicyanoisopropylidene bis(cyclohexyl-4-yloxy) (meaning -(Χ^) Η〗 oCXCNhC6!^ 0〇-), 3-fluorenylcyclohexyl, methylenebis(cyclohexyl-4-yloxy) (meaning -OQHmCH^HuO·), 1·ethylcyclobutanyl, cyclopropyl Vinyl, 3-methylindol-2-indolehydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy) (meaning -〇) C6 H! 0 (CH2 )6 C6 % 〇Ο), 4-hydroxyindole Hex-1-yl (ie, 4_H〇CH2C6Hi〇_) ' 4_mercaptoalkylcyclohexan-1-yl (ie 4-HSCH2C6H10-), 4-methylthiocyclohexyl (ie 4 -CH3SC6H10-), 4-methoxycyclohex_1-yl, 2-methoxycarbonylcyclohexyl-yloxy (2-CH3OCOC6H10O-), 4-nitromethylcyclohexyl-yl-yl ( That is, N〇2CH2C6H10-), 3-tridecylfluorenylcyclohexanyl, 2-tris-butyldidecylfluorenylcyclopentan-1-yl, 4-trimethoxyoxydecylethyl Cyclohexyl group (for example, (CH30)3 SiCi^CHzC^Hi 〇-), 4·vinylcyclohexen-1-yl, vinylidene bis(%·hexyl), etc. C3 -C1 〇 〇 〇 The term "family group" includes a cycloaliphatic group bromo group containing at least three 123170 •11·200900449. cycloaliphatic group 2_tetrahydrofurocyclohexylmethyl but not more than 10 carbon atoms (C4H7〇- ) represents a c4 cycloaliphatic group. Represents a C7 cycloaliphatic group.

The term "aliphatic group" as used herein refers to an organic group having a valence bond of at least - consisting of an array of linear or branched atoms that are not cyclic. An aliphatic group is defined to contain at least one carbon atom. The array of atoms comprising aliphatic groups may comprise heteroatoms such as nitrogen, sulfur u and oxygen: or may consist entirely of carbon and ruthenium. For convenience, the term "aliphatic group" is defined herein to encompass a wide range of functional groups as part of a "linear or branched atomic array that is not circular". Functional groups such as alkyl, olefin alkynyl-alkyl, co-dienyl, alcohol, ether, acid, keto, carboxylic acid, sulfhydryl (eg, carboxylic acid derivatives, such as esters and oximes) Amine-based amino group, schlossyl group, etc. For example, a 4-methylpenta group is a C6 aliphatic group containing a methyl group, and a methyl group is a functional group, which is a burnt group. Similarly, 4_stone The C4 aliphatic group containing a nitro group is a functional group. The aliphatic group may be a tooth alkyl group containing one or more halogen atoms which may be the same or different. The tooth atom includes, for example, fluorine, chlorine, and bromine. And iodine. The aliphatic group containing one or more halogen atoms includes an alkyl group, a triyl group, a dimethyldifluoromethane group, a gas dimethyl group, a hexafluoroisopropylidene group, and a chloromethyl group. , difluorovinylidene, trichloromethyl, bromodimethylmethyl, bromoethyl, 2-bromotriindolyl (eg -CI^CHBrCH2-), etc. Further implementation of aliphatic groups Examples include allyl, aminocarbonyl (ie, -CONH2), carbonyl, 2,2-dicyanoisopropylidene (meaning -cH2C(cn)2CH2.), methyl (ie, even), sub Methyl (ie _Ch2_), ethyl, sec-ethyl, decyl (ie _CH 〇), hexyl, hexamethylene, hydroxymethyl 123170 -12- 200900449 (meaning -CH2 OH),巯 曱 ( (meaning _Ch2 8η), methylthio (meaning -SCH3), methylthiomethyl (ie -CH2 SCH3), methoxy, methoxycarbonyl (meaning CH3 OCO-), nitrate Methyl group (ie, -CH2 N〇2), thiol group, tridecyl group (meaning (CH3)3 Si-), tert-butyldimethyl sulphide, trimethoxy A sulfopropyl group (ie (CH3〇)3SiCH2CH2CH2-), a vinyl group, a vinylidene group, etc. As a further example, the aliphatic group contains at least one but no more than 10 carbon atoms. CH3_) is an example of a Cl aliphatic group. The fluorenyl group (ie, CH3(CH:2)9-) is an example of a C! oxime group. In one embodiment, the invention provides a structure τ Organic

Feng Wei 2 < 5 〇 aromatic group; Ar4 is a bond or mesh 1 to about 200; V' is the number 〇 to 3; ri , where Ar1, Ar2 and Ar3 are independently c2_c5〇 ^^ halogen atom, (Vc20 An aliphatic group, a C5_c2 fluorene group; R2 is a halogen atom, a Cl_C2G aliphatic C2 0 group or a polymer chain; and X·

Cj C2-C5 〇 aromatic group; "a" is a number from 1 to about 2 〇〇; in each presence, is independently a halogen atom, a Ci cycloaliphatic group or a C2_C2 〇 aromatic group; 2 is ^ group, kernel 5_ (: 2 〇 cycloaliphatic group, C2_c5 〇 aromatic is a charge balance counterion.

The structure shown in Table I General Structure I and Table Login Line iadj Login Line la represents the species covered by General Structure I, 123170 • 13- 200900449, where each of Ar1 - Ar3 is phenyl (C6H5) -), Ar4 is a meta-phenyl group, the variable "c" is zero, the variable "a" is 2, X_ is iodide, and the group R2 is a divalent C15 aromatic group -0C6H4C3H6C6H40-. Salt f - ί._

123170 -14- 200900449

Ar1 - Ar3 is a phenyl group; Ar4 is a meta-phenyl group, V' = 1, "c" is 0, R2 is a C4 aliphatic group C4F90-, and X. is a chloride ion. 123170 -15- 200900449 The log line lg of Table I describes the organic scale salt, wherein A^-Ar3 is phenyl; Ar4 is p-phenyl, "a" = l, V, is 〇, r2 is Q aromatic The group C6H5〇_(phenoxy), and X- is a bromide ion. The log line lh of Table I is an organic scale salt in which Arl_Ar3 is a phenyl group; Ar4 is a p-phenoxy group, "a" = l, V, is (^^ is an aromatic group 〇6115_(benzene) Base), and X· is a tetrafluorocyanate ion, BF4 -. The log line of Table I is an organic scale salt in which Arl_Ar3 is a phenyl group; A〆Γ is a p-phenoxy group, "a" = 2, V, is 〇, R2 is a polyether fluorene imine chain represented by a parenthesis structure, which is equal to 50 by the subscript "η,, modification" for the purpose of the organic salt salt. The meta-phenylene moiety is located between the right parenthesis and the group Q. In other specific embodiments, "η" is from 1 to about 500. The counterion X· is sulfate (so4= In the specific embodiment, the group represented by W in structure 1 is a polyether quinone imine polymer chain (see, for example, the registration scheme of Table I). In another specific embodiment, The group represented by R2 in the structure is a poly(tetra) polymer U bond. In still another embodiment, the group represented by β in the structure I is a polyether fluorene polymer chain. In the embodiment, wherein r2 is a polymer bond, the polymer bond may have a molecular weight of 7 or a low molecular weight. When the polystyrene amount is measured by colloidal osmotic chromatography using a polystyrene amount, the number of high molecular weight polymer chains is Umbrella Dip 8 ^ ~ ^ 2: The amount (Mn) is greater than 8,000 grams. When measured by the gel permeation chromatography amount standard, the 'low molecular weight polymer chain is a number average molecular weight (Mn) of 8,000 grams or more In a specific embodiment, the present invention provides an organic scale salt having the structure I, 123170 • 16- 200900449, wherein R2 is a polymer ruthenium, and when measured by the gel permeation layer, each mole is The number average molecular weight Mn is in the range of about 1 Torr to about (9) gram. In the ~, the body A example, R2 is a polymer chain, and when measured by gel permeation chromatography, the number per mole is The average molecular weight Mn is in the range of from about 10,000 to about 10,000 gram. In yet another embodiment, the polymer chain, when determined by gel permeation chromatography, has an average molecular number Mn per mole. Within the range of about ι〇0〇 to about 5, 〇〇〇克. Choi a particular embodiment, the invention provides an organic phosphonium salt having the structure of the π

Where X is a charge balance counterion. In another specific embodiment, the invention provides a structure having

Where X' is a charge balance counterion. In yet another embodiment, the present invention provides a structure having an organic scale salt 123170 • 17- 200900449

Ar5 •, IV where X is the charge balance counterion, the number of T m horses in the range of from about 1 约 to about 1 ’ and Ar5 is c2_c5. An aromatic group or a polymer chain. In a specific embodiment, the present invention provides an organic scale salt having structure IV wherein the group Ar5 has a structure 乂

v where X is the charge balance counterion. In Structure 1 and elsewhere in the disclosure, the group X- represents a charge balance counterion as is well known to those skilled in the art, and a wide variety of charge balance counterions can be employed. Typically, 'X- denotes a charge balancing counterion, which is a monovalent, divalent or trivalent anionic species. For example, in one embodiment, 'χ· is selected from the group consisting of fluoride, chloride, Li, Egan, sulfate, sulfite, carbonate, bicarbonate, acetate, oxalate, and:: . Inorganic anions such as fluoride, chloride, morgan, iodide and bicarbonate are examples of early-valent anions. The inorganic anionic carbonate and sulfate, and the organic anionic oxalate are examples of dianion. The three anion ions of Kemp's triacid are examples of trivalent anions. The novel organic scale salts provided by the present invention can be prepared by a variety of methods. The experimental paragraphs of the present disclosure provide various specific methods and conditions for preparing organic scale salts having the structure. In one embodiment, the organic 123170 -18- 200900449 scale salt can be prepared by reacting an aryl group with a triaryl phosphine, optionally in the presence of a catalyst such as palladium acetate (II). In an alternate embodiment, the amine substituted scale salt is reacted with an anhydride to provide a chitosan product comprising a scale salt moiety. In a specific embodiment, the present invention provides a method of producing an organic scale salt comprising (4) an amine substituted scale salt having a structure VI.

Ar3

Ar2—P——Αγ4-ΝΗ2 Ar1

Χθ VI ,...,A# ′ heart and Ar system are independently _C:5 ο aromatic group, and are charge balance counter ions; contact with anhydride compound having crucible structure 11

VII

V' is a number from 1 to about 2 GG; v is a number from G to 3; R is independently _屌 early r ρ π 在, ", Cl-C2 〇 aliphatic group, C5-C20 cycloaliphatic group or a C2-C20 group; 2^ 圃 is (4). a thiol group, a c5-c2 cycloaliphatic diol group or a polymer chain; and (6) an isolated product organic squama salt. := In the example, 'Compound VI is the same as the amine-purchased base: the base: the aniline, and the charge balance counterion _2) is the para-position, the compound ^ is The counter-ion ion with a pair of amines is "the aniline of the present I moiety" and wherein the charge is flat 123170 -19- 200900449. In one embodiment, the anhydride compound VII is selected from the group consisting of biguanide A dianhydride (BPADA). 4,4'-biphenyl dianhydride and 4,4 oxydiphthalic acid liver (4,4, _DPA). In one embodiment, the anhydride compound VII is a double A liver. In another specific embodiment, the anhydride compound VII is a polymeric two-needle comprising an anhydride end group, the polymeric second is a polyether quinone imine derived from BPADA and m-phenylenediamine, the polymeric dianhydride having The number of moles of the average molecular weight % is about 1 〇, gram. Typically, the reaction ("contact" between an amine substituted scale salt having the structure VI and the compound having the structure VII is carried out in a solvent at a temperature exceeding 100 t, and removed in the condensation reaction. The product forms water. In one embodiment, the reaction is carried out in an organic solvent at a temperature ranging from about 12 〇〇c to about 16 ° C. In another embodiment, the reaction system This is carried out in a lysate. In some cases, it may be advantageous to carry out the reaction in the presence of a catalyst, such as a user in a ruthenium imidization reaction, such as sodium phenylphosphinate (spp). Including ODCB (o-dichlorobenzene), terpene, diphenyl, chlorobenzene, nonylphenyl ether, verazone and combinations thereof.

In a specific embodiment, the present invention provides a method of preparing an organic scale salt, which comprises (a) an amine substituted scale salt having the structure IX 123170

IX -20- 200900449 where x- is the charge balance counterion and has a release

Anhydride compound contact

The system is independently a tooth atom, a C] aliphatic group, and a C5_c2 anthracycline aliphatic group t C: -C2. An aromatic group; and R2 is a tooth? , Ci _C2. An aliphatic group, c A [a lunar steroid group, a c 2 -c 5 0 aromatic group or a polymer chain; and (b) an isolated product organic squama salt. In two specific embodiments, the liver compound having the structure W is selected from the group consisting of 4,4,-oxydiphthalic anhydride, 3,4,-oxydiphthalate, m-oxybenzoquinone Anhydride, bisphenol A dianhydride, 6F-dianhydride, 3, biphenyl dianhydride, 4, 4, _ biphenyl dianhydride, and combinations thereof. In yet another embodiment, the invention provides a method of preparing an organic scale salt, which comprises (4) contacting an aromatic amine with a hydrazine-substituted anhydride to provide a halogen-substituted quinone imine; (b) The imine substituted imide is reacted with a triarylphosphine to achieve nucleophilic substitution of the triarylphosphine; and (4) the isolated organic salt. In a specific embodiment, the halogen-substituted anhydride is selected from the group consisting of 3-gas phthalic anhydride (3_C1PA), 4-chlorophthalic anhydride (4-C1PA), and fluoro-phthalic acid. Anhydride and 4-fluorophthalic anhydride. In another specific embodiment, the anhydride substituted with _ 素 includes 4-chloro phthalic anhydride. In another embodiment of the invention, the halogen-substituted anhydride comprises a mixture of 3-chloro phthalate 123170 -21 - 200900449 acid liver and 4-chlorophthalic anhydride. The aromatic amine can be a monoamine or a polyamine. In a particular embodiment, the aromatic amine is a polymer comprising an amine group. The monoamines are described by aniline, amphoteric tea, gas aniline, 4-air aniline, 2,4-dichloroaniline, 4-chloro-aminobiphenyl, and the like. Suitable diarylphosphines include triphenylphosphine, tolylphosphine, tris(dimethylphenyl)phosphine, ginseng (4-tris-butoxyphenyl) scales and the like. The field reaction conditions for the preparation of the functionally substituted quinone imine and its subsequent reaction with the triarylphosphine are provided in the experimental paragraphs of the present disclosure. In a specific embodiment, the present invention provides novel pyridinium salts having the structure XV

, Ar9 - Ί:

XV

/, Central Ar, Ar and Ar are independent of C2_c5〇 aromatic group;" is the number 〇 to 2; "dM is the number 〇 to 4; R3 disk r4, force master ^ ^,, R in the presence of the mother, Is independently a tooth atom, Q-c2. Aliphatic group, C5_C2 anthracycline aliphatic group or c2々. Aromatic group; Z is a bond, a divalent Cl_c2G aliphatic group, a divalent %. a group, a divalent C2-C2J group, an oxygen linking group, a sulfur linking group, a hydrazine group or a Se linking group; Ar9 is a Ci〇_C2. an aromatic group, "containing at least - a polymer chain of an aromatic group; Μ- is a charge-balance counterion. As is stated in the text, the read salt covered by the structure χν can be used to prepare an organic clay composition in combination with a polymer organic clay composite. Object. Borrow 123170 -22· 200900449

Representative pyridinium salts encompassed by the general structure XV are shown in Table II. Table II exemplified pyridinium salt XV

It will be apparent to those skilled in the art that the pyridinium salt of the table π-registered row 2a represents a pyridinium salt having the structure XV, wherein each of Ar6, Ar7 and Ar8 is a phenyl group;" b" is 0; "d" is 2; R4 is a fluorenyl group; Z is an oxygen linking group; Ar9 is a C! 2 aromatic group; and X· is a chloride ion. Similarly, the pyridinium salt of Table II in line 2b represents a pyridinium salt having a structure XV of 123170 -23 - 200900449, wherein Ar6, Ar7 and Ar8 are phenyl groups; "b" is 〇; ,, d, is 0; Z is an oxygen linking group; ^ is (^2 aromatic group; and χ- is an acetate ion. In a specific embodiment, the present invention provides a ton salt having a structure χν, wherein Ar9 is Poly-trans-imine polymer chain. In another embodiment, the invention provides a pyridinium salt having the structure XV, wherein Ar9 is a polyfluorenone polymer chain. In one embodiment, Ar9 is The polymer chain has a number average Mn of 〆 per mole of Mn in the range of from about 1000 to about 50. In another embodiment, Ar9 is a polymer chain having an average number per mole. The molecular weight Mn is in the range of from about 1000 to about 20,000 grams. In yet another embodiment, 'Ar9 is a polymer chain having a number average molecular weight Mn per mole in the range of from about 1 Torr to about 5,000 grams. In another embodiment, Ar9 is a polyetherimine polymer chain having a number per mole The average molecular weight Mn is in the range of from about 1000 to about 20,000 grams. In a particular embodiment, Ar9 is a polyetherimine polymer chain, {) having a number average molecular weight Mn of about 1 Torr per mole. Up to about 50,000 grams. In a specific embodiment, the present invention provides a pyridinium salt encompassed by a general structure XV having the structure XVJ 123170 -24· 200900449

Ph XVI / where x_, in each presence, is independently a charge-balanced counterion. In a particular embodiment, χ- is bf4_. In a specific embodiment, the invention provides a pyridinium salt having the structure XVII

In a particular embodiment, X- is acetate. In yet another specific embodiment, the invention provides a pyridyl salt having the structure XVIII

XVIII wherein X_ is a charge balancing counterion; "e" is a number in the range of from about 10 to about 1000; and Ar1G is a C2-C5〇 aromatic group or polymer chain. In a particular embodiment X· is a tetrafluoroborate (BF4_) anion, the variable V′ is about 123170 •25· 200900449 ί j i. 100, and the Ar^c25-aromatic group tetrafluoro-acid 2,4,6-triphenyl It is understood by those skilled in the art that the aromatic group may comprise an associated counterion, here BV, and still fall within the definition of the term aromatic group as defined herein. Similarly, fat The group of groups and the cycloaliphatic group may also comprise an associated counterion. The group of helium-loaded counterions may be included in the group after the group contains multiple charges requiring the presence of a charge balance counterion. Generally known to those skilled in the art (4), the fractional portion of the charge balance counterion can also be included in the group. For example, in which a single positive charge is balanced by a divalent anion such as sulfate (S〇4 = ). In a composition, a single sulfate anion can be associated with two separate molecules or groups. Mao an aromatic group denier embodiments thereof, V is containing 1/2 (= s〇4) of. In one specific embodiment 'Arl〇 having structure XIX of aromatic groups

Ph

Χθ

XIX where X- is the charge balance counterion. In a particular embodiment, X is a fractional portion of a valence ion selected from the group consisting of sulfate, carbonate, and oxalate. In the specific embodiment, _ is 1/2_", which is a fractional part of the carbonate anion. The charge-balanced counter ion which may be present in the bismuth salt structure is included in the structure I disclosed herein. In a specific embodiment, the charge balance counterion is selected from the group consisting of a gas radical, a chloride root, a sulfate, a sulfite, a sulphate, a bicarbonate, an acetate, an oxalate, and combinations thereof. In a specific embodiment, the present invention provides a method for preparing a lysine having a structure χν, which comprises (4) an aromatic amine having a structure of bis-123170 -26- 200900449

Wherein "d" is the number 〇 to 4; only 4, the family - R is in the presence of the parent, independently of a halogen atom, a Ci-C2 steroid group, a cc 5 aliphatic group or a CVQo aromatic group; Is a bond, divalent C (3·) ^ ϋ 1*1 a 1 20 曰 曰 group, divalent C5-C20 cycloaliphatic group, ii j C2 - C; 20 0 aromatic group, Oxygen έ 其 其 其 平 平 % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % An aromatic group, or a polymer chain comprising to an aromatic group; Η. is a charge balance counterion;

Wherein Ar, Ar7 and Ar8 are independently C2_c5〇 aromatic groups; "b" is the number 〇 to 2; each of R3'f is present as a functional atom, Cl_C2 〇 aliphatic group, C5-C20 a % aliphatic group or a c2_C2 〇 aromatic group; and a χ_ ion; and (9) a product read salt having a structure XV. The reaction produced by contacting the aromatic amine XX with pyridinium salt XX is typically It is contemplated to contact such reactants at temperatures ranging from about -2 G ° C to about 15 G ° C. Although a solvent is typically employed, the reaction can also be carried out in a melt. In one embodiment, the invention The invention provides a method for preparing a pyridinium salt and a preparation thereof. The polymerized pyridinium salt can be prepared in the following manner, (4) reacting (contacting) a polymeric aromatic diamine with a pyridinium salt having the structure XXI, and (9) separating the product 123170. 27· 200900449 Polymerized cerium ingot salt. In one embodiment, the polymeric aromatic diamine system comprises structural units derived from at least one non-polymeric aromatic diamine and at least one dianhydride. For example, molar excess Diamines such as 4,4'-diphenylamine (4,4,-ODA) can be combined with 4 4ι-oxydiphenyl Acid field (4,4,_〇DpA) 'in o-dioxene benzene (〇dcb), reacted under reflux to provide amine-terminated polyether oximine. Amine-terminated polyether oximine The reaction of the pyridinium salt of structure XXI 'is obtained as a product-polymerized pyridinium salt' which can be isolated by, for example, anti-solvent precipitation. In one embodiment, the #polymerized aromatic diamine is m-phenylenediamine. In one embodiment, the non-polymeric aromatic diamine is meta-phenylenediamine and the dianhydride is BPADA. In one embodiment, the dianhydride used is Face A and 4, 4'- Mixture of ODPA. In one embodiment, the present invention provides a polymeric pyridinium salt Ph having a structure

Ph XXII wherein "Γ is a number from 1 () to about 1000, and X- is a charge balance counterion uramine. Thus, in one embodiment, the invention provides a method comprising (a) having a structure ΧΧΠΙ Polymeric aromatic 123170 -28- 200900449

Wherein the number 变 is from 1〇 to about 10〇〇〇; in contact with P having a structure XXIV

Ph

/ wherein X is a charge-balanced counterion; and (b) is a product of a polymeric pyridinium salt having a structural enthalpy. As discussed herein, polymeric diamines, for example, can be prepared by reacting an excess of an aromatic diamine with a di-hepatic ' under polycondensation conditions (e.g., by refluxing oDCB). It will be apparent to those skilled in the art that diamines can be prepared by reacting excess meta-phenylenediamine with 4,4,-ODPA under polycondensation conditions. Pyridoxium salt I, such as XXIV, is commercially available or can be prepared by methods known in the art. In one embodiment, the invention provides a polymeric P-bond having the structure XXn; the salt' wherein the number 变 is from 1 〇 to about 1 〇〇. In addition to providing a novel organic scale salt J and a pyridinium salt xv, the present invention provides for obtaining other organic salts of a polymer/organic clay composite composition useful for preparing an organic mold soil composition and derived from the organic clay composition. . Thus, in one embodiment, the invention provides for the acquisition of a pyridinium salt comprising a cation of XXV 123170 -29· 200900449

丫 >

Know 6 XXV where ΑΛ Ar7 and Ar8 are independent of %. An aromatic base ring; "b" is a number of 〇 to Μ, in each presence, independently 歯 atom, M. aliphatic group, c5-c20 ring (tetra) group or c2_C2. aromatic group; a group, or a polymer bond comprising at least one aromatic group. A read salt containing a cation XXV is shown in Table W. The cation bond salt comprising a cationic coffee can be injurious using the methods disclosed herein and Into the organic composition and the polymer-organic clay composite composition. For example, the preparation and use of a structure with a strong reading salt can be applied to the preparation and use of a pyridinium salt containing cation XXV. Illustrative XX of XXV

Login line

Ar6 Ar7 Ar8 Ar1] Ph Ph Ph Ph — Ph ----- H Ph 4-ClPh Ph ------ Ph Ph 4-CF3 Ph Ph Ph Ph — --------- 2-p Than bite

123170 30· 200900449 The composition of the composition contains a stupid base_organic salt. Accordingly, in one embodiment, the present invention provides for the acquisition of a phenyl ketone salt comprising a quaternary cation having a structure

Ar wherein ArKAr14 and Arl5 are independently a c2-c5() aromatic group; and &16 is C2-C2Q. An aromatic group, or a polymer bond comprising at least one aromatic group. The phenyl ketone salt containing a quaternary cation having a structure of XXXIII is shown in Table IV. A phenyl ketone salt comprising a quaternary quaternary cation of Guta; prepared as disclosed herein. A phenyl ketone salt comprising a quaternary cation cation of π can be incorporated into the organic clay composition and the polymer-organic clay composite composition using the methods disclosed herein, and can be tailored to be suitable for organic scales. I and read salt XV. For example, a method in which a cationic component of a salt preparation is incorporated into an organic clay composition can be applied to a phenyl group-containing salt containing a quaternary cation XXXIII, and a salt is used for the preparation of an organic clay composition. Illustrative phenyl ketone test

123170 -31 - 200900449 4d 3,4-Dioxa 3,4-dimethyl 3,4-dipyrene ratio σ定-2,6-——·---- ---------- Benzene Phenylphenyldiyl Ph cf3 S03 - In a particular embodiment, the invention provides for the acquisition of a phenyl ketone salt comprising a quaternary cation XXXIII, wherein Αι.16 is a polyether-polymer chain. Such a salt composition can be prepared, for example, by reacting a polyetherketone comprising one or more terminal chlorobenzonitriles with a triarylphosphine such as triphenylphosphine in a solvent, optionally in the presence of a catalyst. to make. In one embodiment, the invention provides a phenylketone-containing salt comprising a quaternary squamous ionic ion XXXIII, wherein Ari 6 is a polymer chain having a number average molecular weight Mn of about 1 Torr per mole. 〇 to the range of about 50,000 grams. In another embodiment, the present invention provides a phenylketone-containing salt comprising a quaternary quaternary cation XXXIII, wherein the polymer chain has a number average molecular weight Mn per mole of from about 1000 to about 20,000 grams. Inside. In yet another embodiment, the present invention provides a phenylketone-containing salt comprising a quaternary quaternary cation XXXIII having a central oxime 6 of a polymer chain having a number average molecular weight Mn of about 1000 per mole. About 5, within the range of the gram. (In one embodiment, the present invention provides for obtaining a phenyl-containing salt comprising a quaternary town cation XXXIII, wherein the towel Arl6 is a polyether quinone imine polymer chain having a number average molecular weight 母η of about 1〇〇〇 to about 5〇, 〇(8) grams of fe. In another specific embodiment, the present invention provides for obtaining a phenyl-containing salt comprising a quaternary cation XXXH! The poly-chain 'has a number average % of molecular weight per mole in the range of from about 1 Torr to about 20,000 grams. The present invention provides a phenyl ketone salt containing a quaternary scale cation XXXIV. As is well known to those skilled in the art, the cationic system 123170-32·200900449 falls within the scope of the species defined by structure XXXIII. Thus, structure XXXIV represents that Ar1 5 of structure XXXIII is an ortho-phenyloxy group, And

The case where Ar1 6 is 4-(2-triphenylpyridinyloxy)phenyl. 0

Ph-P-Ph Ph

Ph-P-ph

I

Ph XXXIV f In another specific embodiment, the invention provides for the acquisition of a phenyl ketone salt comprising a quaternary cation XXXV. Ο

Ph

XXXV In a specific embodiment, the present invention provides a polymeric phenyl ketone salt comprising a polymer quaternary cation having a structure XXXVII.

\

XXXVII wherein "g" and "h" are independently 0 to 4; W is a bond, a divalent q-C20 aliphatic group, a divalent c5-c20 cycloaliphatic group, a divalent c2-c20 aromatic group a group, an oxygen linking group, a sulfur linking group, a S02 linking group or a Se linking group; R5 and R6, in each presence, are independently a halogen atom, a q-C20 aliphatic group, 123170-33 · 200900449

The number of Cs-Cu% aliphatic groups or c2_C2 〇 aromatic groups; and Ar17 is a c10-c2 00 aromatic group, a polymer chain of the group. "i" is from about 10 to about 1000 or contains at least one aromatic group. The polymeric ketone salt having the structure χχχνπ is shown in the following table ν. Polymerization of quaternary cations

Table V

123170 •34- 200900449

The xxxvm polymerized phenyl ketone containing salt, such as those shown in Table ν, can be prepared by reacting a triarylphosphine as described herein with its corresponding element. ^Halogen-substituted polyether ketones can be obtained by methods known to those skilled in the art, and can be, for example, made from a disodium salt of bisphenol (e.g., a disodium salt of bisphenolphthalein) and a molar excess (e.g., 5). a molar excess of the molar benzophenone (eg, 4,4·. difluorobiphenyl (4), in an inert solvent (eg, o-dichlorobenzene), at elevated temperatures (eg, 130-fu), The invention is prepared by reacting a phase transfer catalyst (for example, gasified hexaethyl sulfonium salt). In one specific embodiment, the present invention is a composite of an organic clay containing a fourth-order organic cation. The double 'machine % ion can be a quaternary cation, a quaternary cation, and a combination of four. The quaternary organic cation is the various quaternary organic cations of the quaternary organic cations disclosed herein. , organic scale salt I is a fourth-order organic salt containing a fourth-order organic cation

u y 'work call, ~ two bond i is the number 1 to about 200; V, the number 〇 to 3; r1

X C2-C50 aromatic group 123170 200900449 f Each place is independently * atom, cvc2. An aliphatic group, a C5_C2〇% aliphatic group or a cc aromatic group 20-squared scheme, and R2 is a halogen atom, c丨-c20 aliphatic earth group, c5-c2. A cycloaliphatic group, μ. Aromatic group $ polymer chain. Similarly, the salt of the bond is a four-grade organic salt containing a four-stage organic cation XXVI.

Wherein Ar, Ar7 and Ar8 are independently Γ Γ — #拍马C2_C5〇方族团;,, b" is the number 〇 to 2;, “d" is the number W4; _R4, in each _ existence, the system is independent Dentate q-c2. aliphatic group, c5_C2q cycloaliphatic group or μ. aromatic group; =mCl.C2. aliphatic group, divalent C5; cycloaliphatic group,

a 4 Å (3⁄4 -C2 0 aromatic group, oxygen far A A A 虱,, ° ° group, sulfur linking group, so2 linkage or inclusion to ? V. group or se linkage group; and Α γ9 A polymer chain with one aromatic group for the Ci〇C2〇〇 aromatic group. Paper (R3) Plant

In this same vein, P sleeps more than the ingot 2:: Guangguang and Xin # is independent. An aromatic group;, ~' is a number 0 to ί, Γ is in the presence of a parent, is independently a halogen atom, an aliphatic group, C5'C2〇m"^ffl5tC^^^-^c2-c200,« 123170 • 36 - 200900449 = polymer bond of at least one aromatic group; and - is a charge flat map counter ion (R3) b 1

Is a four-level organic sleep containing four organic cations XXV

Ar7,

^ < XXV r , medium Ar 'Ar and Ar8 are independent. .... The aromatic group 丨 Π ′ is a polymer chain which is independent of the halo... 2 2 ^ 5匕^ to an aromatic group of sand.

Similarly, phenyl ketone-containing organic scale salt XXXVI

Ar14

0

XXXVI, middle ArI2, Ari3, Ar "and Ar" 5 series independently of the aromatic group ni6 is a C2_C2 °〇, a group, or a polymer chain containing at least one aromatic group; ^Electrical equilibrium counterion; It is a quaternary organic salt containing a quaternary organic cation having the following structure'·

Ar13-p 112

^ ^ ^ Μ XXXIII wherein Ar 3 , and Ar are independently 匸2-(:50 aromatic groups; and 々16 is C2 C2Q. Read group' or a polymer bond containing at least one aromatic group. 123170-37-200900449 As discussed above and as will be apparent to those skilled in the art, the structural features present in the various quaternary organic salts disclosed herein are reproduced in their corresponding quaternary organic cations. For example, The aromatic group Ar1 as defined in the organic scale salt j has the same meaning as the one core square group Ar1 in the organic scale cation X. Therefore, if Ar1 is the cage A in the organic scale salt I. The base, which is also a phenyl group in the organic scale cation X. rv The organic clay composition of the present invention comprises an alternating inorganic layer of an organic layer. The inorganic citrate layer can be derived from any suitable source, for example Natural clay. In one embodiment, the inorganic silicate layer is derived from synthetic clay. Suitable clays include kaolin, double kaolin, pearl clay: halloysite, serpentine, chrysotile, pyrophyllite, De-soil, Bede stone, smectite, Stone, Shi Xi Na Ci Ming Shi, Shi Xi Zhen Shi, Shui Hui Shi, Si Shi Xi Sour Acid Mica, Nalu Stone, Muscovite, Pearl Mica, Talc, Insect Stone, Phlogopite, Green Crisp Mica, Asian Gas The more the acid is combined with the Japanese brothers and their combinations. In a particular embodiment, the 'inorganic tantalate layer is derived from montmorillonite. The organic clay composition provided by the present invention is characterized The intermediate layer between the layers of the inorganic sulphuric acid wind is 5 to about 1 angstrom. In a specific embodiment, the organic clay composition provided by the present invention is characterized by an intermediate layer between the layers The distance is from 10 to about angstroms, and in the other two embodiments, from about 20 to about 1 angstrom. In one specific implementation, the organic clay group provided by the present invention is in the following manner Manufactured in the first reaction mixture, in the presence of a solvent, and (b) isolated from the product, a right-handed clay composition. The occupant is in a specific embodiment, a quaternary organic salt. Is an organic scale salt with 123170 -38· 200900449 structure i. In the embodiment, the quaternary organic salt is a pyridinium salt having the structure XV. In still another specific embodiment, the quaternary organic salt is a P ratio ingot salt having the structure XXXI. Yet another specific embodiment The quaternary organic salt is a phenyl ketone-containing organic squama salt having the structure XXXVI. As indicated, the organic clay composition provided by the present invention can be present in a solvent via a quaternary organic salt and a layered silicate. Made in the next contact. In one embodiment, the layered tantalate is a natural clay. In another embodiment, the layered tantalate is a synthetic clay. In one embodiment, the layer The bismuth citrate system includes inorganic clay, and is selected from the group consisting of kaolin, double kaolin, pearl clay, kaolin kaolin, montmorillonite, beide, bismuth; κbed stone, smectite, soapstone. , serpentine, chrysotile, saponite, strontium galaxite, strontite, hectorite, tetramethane methane, sodium nickel feldspar, muscovite,: phlogopite, talc, vermiculite, phlogopite, green Crisp mica, chlorite and combinations. In another embodiment, the layered citrate system comprises montmorillonite

123170 -39- 200900449 In the experimental part. In a specific embodiment, the present invention provides an organic clay composition comprising alternating inorganic bismuth (IV) and an organic layer. The organic layer comprises a structure.

-R2 where ΑΛ β and β are independently %. An aromatic group; Ar4 is a bond or a four-level squamous

X C2_C50 aromatic group; "a" for number! Up to about 2 〇〇; v, the number 〇 to 3^, in each of the existences, the system is independently a halogen atom, Γ 〇^... 1<:20 aliphatic group, C5-C20 steroid group or C2_C2 An aromatic group; and only 2 # ^ is a _ atom, a CVC20 aliphatic group, a c5-c20 cycloaliphatic group, a cc 20 曰 . ^ ^ 芳 芳 或 或 或 或The organic squamous cation X is illustrated by the succinct components in Table 1. h "The cation of the organic scale salt A A in a specific example, the quaternary cation has a structure XI.

The quaternary cation has a structure XII in another embodiment,

123170

XII -40- 200900449 In an embodiment, the organic clay composition of Yin ion is provided by the invention.

XIV I. In a specific embodiment, the present invention provides an organic clay composition comprising an alternating salt layer and an organic layer, the (four) layer of acid XXV pyridinium cation, structured

Ar8 N, © ''Ar"

Ar XXV where Ar6, Ar7 and Ar8 are independent pt inverted as C2_C5 〇 aromatic group '·, v straight 2; R3, at each existence, the number of horses is 0 to ~ free, independent _ atom, Ci_c Q a Qo cycloaliphatic group or a cc 9 group, an octa 2 2 120 group; and the core 11 is a 2 to C 2 〇〇 aromatic 123170 -41 · 200900449 group, or comprises at least one aromatic group Polymer chain. The pyridinium cation having structure XXV is illustrated by the cationic component of the pyridinium salt disclosed in the Tables herein. In a specific embodiment, the present invention provides an organic clay composition comprising an alternating inorganic bismuth salt layer and an organic layer comprising a pyridinium cation having structure XXVI

(R3)b wherein Ar6, Ar7 and Ar8 are independently c2_c5( 2; "d" is the number 〇 to 4; R3 and R4 are in each sub, <^-(:20 aliphatic group, c5- C20 cyclolipid; j Z is a bond, a monovalent Ci -C 2 〇 aliphatic group, a monovalent C 2 -C 2 〇 基 group, an oxygen linkage to a n 丨 5 〇 aromatic group; "b" is the number 〇 to /, R, in each presence, is independently a halogen C5_C20 cycloaliphatic group or a C2-C20 aromatic group; > aliphatic group, divalent C5_c2 anthracycline aliphatic group, oxygen a linking group, a group or a Se linking group; and Ar9 is a polymer chain having one aromatic group of CiC_C2〇〇, a sulfur linking group, an 802 linking 2 fluorene group, or The pyridinium cations having structure XXVI as shown in Table II herein are illustrated by the cationic component of the pyridinium salt.

The present invention provides an organic clay composition comprising a '» specific bond: a cation provided by the present invention having a structure XXVII in a specific embodiment. 123170 -42- 200900449

XXVII In another embodiment, the invention provides an organic clay composition comprising a pyridinium cation having structure XXVIII.

The system comprises a polymeric quaternary organic cation which is a polymeric pyridinium cation. In a specific embodiment, the polymeric pyridinium cation comprises structure XXIX

Wherein the variable "e" is a number from about 10 to about 1000; and Ar1G is a C2-C5 〇 aromatic group or a polymer chain. In a specific embodiment, Ar1 G is a C23 aromatic group having the structure XXX. 123170 -43- 200900449 ——N7 \-Ph ®\=/

Ph XXX In another embodiment, the invention provides an organic clay composition comprising a polymeric ingot cation having structure XXXII

XXX11 where 'f' is a number from about 1 〇 to about 1000. In a particular embodiment, the corpse has a value of about 10. In another particular embodiment, "f" has a value of about 30. In one embodiment, the present invention provides an organic clay composition comprising an alternating inorganic oxalic acid salt layer and an organic layer comprising a quaternary cation having a structure XXXIII

Ar14

XXXIII

Ar13- ©

Ar12 wherein Ar12, Ari3, Ari4 and A# are independently a C2_c5〇 aromatic group; and ArU is a Q-C^o aromatic group, or a polymer chain comprising at least one aromatic group. A quaternary cation having a structure of XXXIII, sometimes referred to herein as " an organic scale cation containing a phenyl ketone." A quaternary lock cation having a cation of an organic squama salt as disclosed in Table IV herein. Sexual Component Theory 123170-44-200900449. In one embodiment, the present invention provides an organic clay composition comprising a quaternary cation having a structure of XXXIV.

Ph-®P--Ph

Ph

XXXIV In another specific embodiment, the present invention provides an organic clay composition comprising a quaternary cation having a structure of XXXV.

Ph Ο

I μ ^ xxxv In yet another embodiment, the present invention provides an organic clay composition comprising a polymeric quaternary quaternary cation having structure XXXVII

0, 0. -Ar17

XXXVII where "g" and "quot" are independent of the number 〇 to 4; W is a bond, a divalent q-CM aliphatic group, a divalent C5-C20 cycloaliphatic group, a divalent C2-C20 aryl a family group, an oxygen linking group, a sulfur linking group, a S02 linking group or a Se linking group; R5 123170 -45 - 200900449 and R6, in each presence, independently a halogen atom, a qc^o aliphatic group a group, a cVQo cycloaliphatic group or a C2_C2 fluorene aromatic group; 〒 is a number from about 1 〇 to about ι〇〇〇, and 八 1*7 is a 匚1〇_€2〇() aromatic group Or a polymer chain comprising at least one aromatic group. In one particular embodiment, Arl? is an aromatic group having the structure XXXVIII.

Ph

XXXVIII The polymeric quaternary quaternary cation having structure XXXVII is illustrated by the cationic component of the polymeric organic squama salt disclosed in Table V herein. In a specific embodiment, the present invention provides a polymer_organic clay composite composition comprising (4) a polymeric resin and (b) an organic clay composition comprising an alternating inorganic silicate layer and an organic layer, wherein the organic The layer system contains four organic cations. In one embodiment, the polymeric resin comprises an amorphous thermoplastic polymer. In another embodiment, the polymeric resin comprises a crystalline thermoplastic polymer. In another embodiment, the polymeric resin comprises a non-ruthenium thermoplastic polymer and a crystalline thermoplastic polymer. Amorphous thermoplastic poly& systems are made of PPSU (polyphenyl hydrazine), pEI (polyether sulfimine), pES (polyether sulfone), PC (polycarbonate), PP0 (polyphenylene ether), pMMA ( Polymethyl methacrylate), ABS (acrylonitrile butadiene styrene) and ruthenium (polystyrene) are said to be a crystalline thermoplastic resin by the following description, PFA (perfluoroalkoxy 123170 • 46- 200900449 burned) ), MFA (copolymer of tetrafluoroethylene and perfluorinated vinyl ether), FEp (fluorinated ethylene propylene polymer), PPS (polyphenylene sulfide), PEK (polyether ketone), pEEK (polyether-ether ketone) ), ECTFE (ethylene gas trifluoroethylene), PVDF (polydifluoroethylene), PTFE (polytetrafluoroethylene), pet (polyethylene terephthalate), p〇M (polyacetal), PA (polyamide), UHMW-ΡΕ (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene), LDpE (low density polyethylene), and advanced engineering resins , such as PBI (polybenzimidazole) and PAI (polyamine-imine), polyphenyls, polybenzoxazoles, polybenzothiazoles, and blends and copolymers thereofIn a specific embodiment, the polymeric resin is selected from the group consisting of polyether oximines, polyamines, polyesters, polyaryl thioethers, polyarylene ethers, polyether oximes, poly An ether ketone, a polyetheretherketone, a polyphenylene, a polycarbonate, and a combination comprising at least one of the foregoing polymers. In a particular embodiment, the polymeric resin comprises a polyetherimide resin, for example, available from GE Plastics. In another specific embodiment, the polymeric resin comprises a polyphenylene resin, such as PRIM(R) SPIRE, available from s〇lvay. In yet another specific embodiment, the polymeric resin comprises a polyether oxime, such as RADEL A, available from Solvay Corporation. In yet another specific embodiment, the polymeric resin comprises a polyether ketone. The organic clay composition present in the polymer-organic clay composite composition is preferably highly exfoliating, meaning that the distance between the inorganic tellurite layers is relative to the corresponding tantalate layer in the same organic clay composition. The distance is large before it is incorporated into the polymer matrix of the polymer_organic clay composite composition. The organic clay composition provided by the present invention is designed to pass the 123170-47·200900449 design to promote the relatively easy separation of the layer of the silicate layer when the organic clay composition is subjected to shearing force in the presence of a polymeric resin or a solvent. . Therefore, in a specific embodiment, the polymer/organic clay composite composition provided by the present invention comprises a right 嫉μ 禋 organic clay composition comprising a bismuth oxide layer and an organic layer, wherein The alternating inorganic silicate layer is highly dispersed relative to the organic clay composition from which the polymer layer composition of the polymer-synthesis clay composition is derived. r. v In a specific embodiment, the polymer-organic clay composite composition of the present invention comprises a layer of inorganic silicate which is derived from inorganic clay, and the inorganic clay is selected from the group consisting of inorganic clay. Including kaolin, double kaolin, pearl clay, :: soil, leaf serpentine, chrysotile, ochre, montmorillonite, beide, smectite, vermiculite, shixi zinc, stone, stone shizhen stone , Sprite, Si Shi Xi = Mica, Na-Shishi, Muscovite, Pearl Yunjin Mica, Green Crisp Mica, 砟 醢 _ a 廿 example of melon and 彳, combination. In one embodiment + conversion to an organic clay composition, the strontium organic clay composition is then used to prepare a concentrate right M + % & composition. In the preparation of the polymer-organic clay M^ organic clay composition, which is characterized by a large amount of organic clay combination used in the preparation of the polymer-organic clay M^ organic clay composition. The compound: organic clay composite composition is highly exfoliated, at least... the organic clay combination used is in the range of about 100 angstroms. The inter-layer distance is at 5 to a specific embodiment, and the present invention comprises the present invention, which comprises a polymer organic clay composite composition. In a case of 123170 -48 - 200900449 body month, the object is a film. In a particular embodiment, the article is a dust film. In another specific embodiment, the article is a mixture casting phase. (d) Films Solvent cast films of the G 3 polymer-organic clay composite compositions can be prepared using the techniques described herein, and can be prepared by methods recognized in the art.

In a specific implementation, the present invention provides a solvent-transformed film which comprises poly-imine having a m and diamine component and a glass transition temperature (Tg) of between about 45 Gt, and wherein The film has a CTE of less than 70 ppmrC; a thickness between about 1 and 25 microns and c) a residual solvent of less than 5% by weight. In one embodiment, the present invention provides a polymer-organic clay composite composition comprising a polymeric resin which is a polyether quinone imine having a dianhydride component and a diamine component. This means that the polyether oximine comprises structural units derived from at least one dianhydride and at least one diamine. A polyether quinone having a dianhydride component and a diamine component and a desired Tg can be prepared by reacting one or more diamines with one or more dianhydrides under polycondensation conditions (for example, ortho-benzene) Reflux in the installed reaction vessel to remove the water of reaction in the presence of sodium phenylphosphinate (SPP). Suitable dianhydrides include: 2,2-bis[4-(3,4-dioxaphenoxy)phenyl]propane dianhydride; bis(3,4-dicarboxyphenoxy)diphenyl ether Dihydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylthio dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)dibenzofluorone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride; 123170 •49- 200900449 2,2-bis[4·(2,3-dicarboxyphenoxy)phenyl Propane dianhydride; 4.4-bis(2,3-mercaptophenoxy)diphenyl myrrh; 4,4·-bis(2,3-dicarboxyphenoxy)diphenyl sulphate; 4,4'-bis(2,3-dicarboxyphenoxy)diphenylfluorenone dianhydride; 4.4-bis(2,3-disulfophenoxy)diphenylphosphoric dianhydride; 4-(2 ,3-di-reoxyphenoxy)_4ι_(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)_4,_ (3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-indenyl basic oxy)_4'-(3,4-di-repentylphenoxy)diphenyl sulphide Anhydride; 4-(2,3-one rebellious base)·4'_(3,4-dioxaphenoxy)benzophenone dianhydride; 4-(2,3-mercaptophenoxy Base)-4'-(3,4-dicarboxyl Phenyloxy)diphenyl thiacetate; 1,3-bis(2,3-dicarboxyphenoxy)phthalic anhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene Anhydride; 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride; 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride; cyclobutane tetracarboxylic dianhydride; Cyclopentane tetrasodium dianhydride; cyclohexan-1,2,5,6-four rebellious liver; 2.3.5-trisylcyclopentyl acetic acid di-hepatic; 5-(2,5-di-yltetrahydrofuran Aldehyde)_3_methyl_3·cyclohexene_u_dicarboxylic dianhydride; l,3,3a,5-diketo-3-furanyl[nc]·biting _u_dione; 3,5,6·二致基正伯院-2-Acetate di-hepatic; 2.3.4.5- Tetrahydrofurfury succinic anhydride; 3,3',4,4, diphenyltetradonia; 123170 50- 200900449 3,3',4,4丨-benzophenone tetracarboxylic dianhydride; acetal dianhydride, such as (2,3,6,7-formaldehyde dianhydride, etc.); 3,3 ,, 4,4'-biphenylsulfonic acid tetracarboxylic dianhydride; 3,3丨,4,4'-biphenyl ether tetracarboxylic dianhydride; 3,3',4,-dimethyldiphenyl Decane tetracarboxylic dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulphate; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl fluorene 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride; 3,3',4,4'-perfluoroleaf I: succinic dianhydride; 3',4,4'-biphenyltetracarboxylic dianhydride; bis(phthalic acid) phenylsulfinium oxide dianhydride; p-phenylene-bis(triphenylphthalic acid) dianhydride; m-Phenyl-bis(triphenylphthalic acid) dianhydride; bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride; bis(triphenylphthalic acid)- 4,4·-diphenylmethane dianhydride; 2,2'-bis-(3,4-dicarboxyphenyl)hexafluoro-propane dianhydride; 4,4'-oxydiphthalic anhydride; 2,4,5-benzoic acid dianhydride; 3,3',4,4'-diphenyl maple tetracarboxylic dianhydride; 4',4'-bisphenol A dianhydride; hydroquinone diphenyl dimethyl hydride Anhydride; ethylene glycol trimellitic anhydride; 6,6,-bis(3,4-dicarboxyphenoxy)-2,2|,3,3,-tetrahydro-3,3,3|,3 '-Tetramethyl-1,1'-spiro[lh-茚] dianhydride; 123170 -51 - 200900449 7,7'-bis(3,4-dicarboxyphenoxy)-3,3',4, 4'-tetrahydro-4,4,4',4'-tetradecyl-2,2'-spiro[2h-l-benzopyran]dianhydride; 1,1'-bis[1-(3 ,4-dicarboxyphenoxy)-2-indolyl-4-phenyl]cyclohexane Anhydride; 3_3',4,4丨-diphenylsulfone tetracarboxylic dianhydride; 3.3',4,4'-diphenylthiotetracarboxylic dianhydride; 3.3',4,4,-diphenylarylenetetracarboxylic acid Dihydride; 3, oxydiphthalic anhydride; 3,3'-oxydiphthalic anhydride; 3,3,-benzophenone tetracarboxylic dianhydride; 4,4'-diaminodiphenyl Formic anhydride; 3.3',4,4'-diphenylmethanetetracarboxylic dianhydride; 2.2-bis(4-(3,3-dicarboxyphenyl)propane dianhydride; 2.2-bis(4-(3,3- Dicarboxyphenyl)hexafluoropropane dianhydride; (3,3',4,4'-diphenyl)phenylphosphine tetracarboxylic dianhydride; (3,3,4,4'-diphenyl)phenyl Phosphine oxide tetracarboxylic dianhydride; 2,2'-dichloro-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-dimercapto-3,3',4,4 '-biphenyltetracarboxylic dianhydride; 2,2'-dicyano-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-dibromo-3,3' , 4,4'-biphenyltetracarboxylic dianhydride; 2,2'-diiodo-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-di(trifluoro Methyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis-mercapto-4-phenyl)-3,3',4,4'-biphenyl Tetracarboxylic dianhydride; 2,2'-bis(1-trifluoromethyl-2-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis(1-trifluoromethyl-3-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride; 123170 •52- 200900449 2,2·-double ( 1-trifluoromethyl-4-phenyl)-3,3,,4,4'-linked streptoic tetra dianhydride; 2,bis(1-phenyl-4-phenyl)-3,3' , 4,4'-biphenyl tetrasodium; 4,4,-bisphenol phthalic anhydride; 5,5'-[1,4-phenylene bis(oxy)] bis[I,3· Isobenzofuranedione]; 3,3',4,4'-diphenylarylenetetracarboxylic dianhydride; 4,4'-carbonyldiphthalic anhydride; 3,3',4,4·- Diphenylmethanetetracarboxylic dianhydride; 2,2-bis(1,3-disorganomethyl-4-phenyl)-3,3|,4,4'-biphenyltetrasulphonic acid; Things; and combinations thereof. Suitable diamines include: ethylenediamine; propylenediamine; trimethylenediamine; diethylenetriamine; triethylenetetramine; hexamethylenediamine; heptanediamine; octanediamine; stilbene diamine; 1,12-dodeced diamine; 1,18-octadecaned diamine; 3-mercaptoheptanediamine; 4,4-dimercaptoheptanediamine; 4-methylindolediamine; 5_曱Base diamine; 2,5-didecylhexylamine, 2,5-dimethylheptanediamine; 2,2-dimercaptopropanediamine; N_mercapto_bis(3-aminopropyl Alkylamine; 3-methoxyhexamethylenediamine; 1,2-bis(3-aminopropoxy) phenylene, bis(3-aminopropyl)comb; 1,4_cyclohexyl Amine; bis-(4-aminocyclohexyl)methane; m-phenylenediamine; p-phenylenediamine; 2,4-diphenylaniline; 2,6-monoaniline; m-phenyldidecyldiamine ; p-Benzyldiamine; 2_mercapto_4,6-diethyl-1,3-phenylene-diamine; 5-methyl·4,6-diethyl-l,3- Phenylene-diamine'-benzidine; 3,3'-dimethylbenzidine, ·3,3,-dimethoxybenzidine; 1,5-diaminopurine; bis(4-aminobenzene) Methane; bis(2-chloro-4-amino-3,5-diethylphenyl)methane; bis(4-aminophenyl)propane ; 2,4-bis(b-amino-tri-butyl) toluene; bis(p-b-amino-tri-butylphenyl) shout; bis (p-methyl-ortho-amino group) Phenyl)benzene, bis(p-b-methyl-o-aminopentyl)benzene, i,3-diamine-based ice isopropyl 123170-53- 200900449 base benzene, bis(4-aminophenyl) Sulfide, bis(aminophenyl) hydrazine, bis(4-aminophenyl)ether and 1,3-bis(3-aminopropyl)tetramethyldioxane; 4,4,-di Aminobiphenylpropane, 4,4'-diaminodiphenyl decane (4,4,·methylenediphenylamine); 4,4,-diaminobiphenyl sulfide; 4,4'-di Aminobiphenyl hydrazine; 3,3,-diaminobiphenyl hydrazine; 4,4,·diaminobiphenyl sulfide; 3,3,-diaminobiphenyl sulfide; 4,4, _ Aminobiphenyl ether (4,4'-oxydiphenylamine); 1,5-diaminoguanidine; 3,3,-dimethylbenzidine; & methyl heptamine, 4,4- Mercaptoheptyldiamine; 2,11-dodecene diamine; octanediamine; bis(3-aminopropyl)tetramethyldioxane; bis(4-aminobutyl)tetramethyl Oxane; bis(p-amino-tri-butylphenyl) shout; bis(p-methyl-o-aminophenyl) Benzene; bis(p-fluorenyl-o-aminopentyl) stupid; 2,2,,3,3,_tetrahydro-3,3,3,3,4-tetramethyl-U'-spiro lH-tH-6,6,-diamine; 3,3',4,4,_tetrahydrogen, 4, 4,_tetramethyl [2H-1-benzophenone. South]_7,7'-diamine; u,, [L-amino-2-methyl-4_phenyl] cyclohexane, its isomer; and its combination β by the polymer provided by the invention The organic clay composite composition comprises an organic clay composition. In the specific embodiment, the organic

The clay composition is an organic clay composition provided by the present invention. Accordingly, in the specific embodiment, the 'polymer-organic clay composite composition comprises at least one type of organic clay composition comprising a quaternary organic cation selected from the group consisting of organic scaly cations having a structure χ, having a structure XXV The yttrium cation of the yttrium yttrium having the structure XXVI has a structural sk-containing organic cation cation. In this particular embodiment, the present invention provides a polymeric organic clay composite composition, (4) a polymeric resin; an organic clay composition comprising a fine layer of a salt layer, the organic layer comprising 2 123170 • 54 - 200900449 Structure x of the quaternary cations. In another specific embodiment, the present invention provides a polymer-organic clay composite composition, (4) a polymeric resin; and (9) an alternating inorganic salt layer and an organic layer t organic clay composition. It has four grades of cations along the structure. In still another specific embodiment, the present invention provides a polymer_organic clay composite composition '(8) a polymeric resin; and (8) an organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic The layer comprises a quaternary structure having a structure χπ#, a cation %, in a specific embodiment, the invention provides an article comprising a polymer-organic clay composite composition, the composition comprising (4) a polymeric resin; and (9) comprising An organic clay composition of an alternating inorganic silicate layer and an organic layer comprising a quaternary cation having a structure X. In another embodiment, the present invention provides a method of preparing a polymer_organic clay composite composition comprising subjecting a polymeric resin to an alternating inorganic silicate layer and an organic layer under conditions of melt mixing In the case where the organic layer comprises a quaternary cation of the quaternary structure having the structure Χ in a specific embodiment, the present invention provides a polymer _ organic clay composite composition, (4) a polymeric resin; (b) An organic clay composition comprising an alternating inorganic silicate layer and an organic layer comprising a pyridinium cation having the structure XXV. In another embodiment, the present invention provides a polymer-organic clay composite composition, (4) a polymeric resin; and (9) an organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising P having a structure XXVI than an ingot cation. In another embodiment, the present invention provides a polymer_organic clay composite composition, (4) a polymeric resin, and (b) an alternating inorganic mineral layer and an organic layer. A layer of an organic clay composition comprising a read cation having a structure. In still another embodiment, the present invention provides a polymer-organic clay composite composition, (4) a polymeric resin; and (9) an organic clay composition comprising an alternating protonic acid layer and an organic layer, The organic layer comprises a P specific ingot cation having structure XXVIII.

In a specific embodiment, the present invention provides an article comprising a polymer-organic clay composite composition comprising: (4) a polymeric resin; and (9) an organic clay composition comprising an alternating layer of (4) acid salt and an organic layer The organic layer comprises (10) having a structure XXV in another embodiment, and the present invention provides an article comprising a polymer rhyme clay composite composition comprising: (4) a polymeric resin; and (b) An organic clay composition comprising an alternating inorganic silicate layer and an organic layer comprising a ruthenium cation having structure xxvi. In another embodiment, the present invention provides a method of preparing a polymer organic clay composite red, which comprises polymerizing a resin and comprising an alternating inorganic lithitic acid layer under a blending condition. Contact with an organic clay composition of an organic layer comprising a double bond cation having the structure χχν. In another embodiment, the present invention provides a method of preparing a polymer-organic clay composite composition comprising: reacting a polymeric resin with an alternating inorganic silicate layer under melt mixing conditions The organic layer is contacted with an organic clay composition comprising a pyridinium cation having a structured toilet. 123170 -56- 200900449 Thus, in the specific embodiment, the invention provides a polymer _ organic clay composite composition, (4) a polymeric resin; and (9) an organic clay comprising an alternating inorganic silicate layer and an organic layer A composition comprising the quaternary cation of a quaternary structure of xxxm. In another specific embodiment, the present invention is a polymer-organic clay composite composition, (4) a polymeric tree, and (b) an organic clay comprising an alternating inorganic layer and an organic layer. combination

The organic layer contains a squaring cation having a structure ν. In another embodiment, the present invention provides a polymer_organic clay mouthwash composition, (4) a polymeric resin; and (9) an organic clay composition comprising an alternating inorganic silicate layer and an organic layer, The organic layer comprises a quaternary cation having a structure of prison V. In a specific embodiment, the present invention provides an article comprising a polymer·organic clay composite composition comprising: (a) a polymeric resin; and (9) comprising an alternating inorganic lithitic acid layer and an organic layer Organic clay composition 'The organic layer contains a quaternary scale cation having a structure. In another embodiment, the present invention provides a method of preparing a polymer_organic clay composite composition, which method comprises the steps of: subjecting a polymeric resin to comprising an alternating inorganic mineral acid salt under smelting mixing conditions. The layer is contacted with an organic clay composition of an organic layer comprising a quaternary cation having a structure of quaternary. Melt mixing route of a poly-[beta]-organic clay composite composition - In a specific embodiment, the invention provides a method of preparing a polymer-machine clay composite composition, which comprises comprising an alternating inorganic stone salt a quaternary organic # soil composition of a layer and an organic layer, the organic layer comprising four organic cations of 123130-57-200900449, melt-mixed with a polymeric resin at a temperature ranging between about t and about , to provide polymerization An organic clay composite composition characterized by a percentage exfoliation of at least 1%. The quaternary organic clay composition is an organic clay composition comprising a quaternary organic cation, such as an organic scale cation having a structural meaning.

It must be sufficiently stable during the mixing step of the four-stage organic cation used. There can be a significant degree in the polymer matrix, without particular limitation, but it is dissolved so that the organic clay composition is peeled off there. A quaternary organic cation is considered to be stable if more than about 90 percent of the quaternary organic cation is still present after a melt mixing step sufficient to achieve a percentage flaking of at least U). In the specific embodiment, the fourth-order organic cation has the structure R9 R8 — i—Rl〇 I®

R7 XXXIX where Q is nitrogen or phosphorus; and Han 7, r8, R4Rl. It is independently an aliphatic group, a C5-C20 cycloaliphatic group, a C2_C2 fluorene aromatic group or a polymer chain. Yu Yi

In a particular embodiment, the quaternary organic cation having structure XXXIX is a sulfonium cation, such as tetraphenyl squara cation tpp. In the other specific example, the fourth-order organic cation having the structure χχχ1χ is a scaly cation having a structure 乂. In yet another embodiment, the quaternary organic cation having structure XXX is a quaternary cation having a structure ΧΧΧΠΙ. In a specific embodiment, the fourth-order organic cation having structure XXXIX is a tetra-order cation, such as tetraphenylammonium cation. 123170 - 58 - 200900449 π In one embodiment, a four-stage cerium ingot cation. In another specific embodiment, the fourth-level ancient drag is _yang#+ with structure xxvi. In a specific embodiment, the inorganic sulphuric acid soil is selected from the group consisting of kaolin, - Α ★ from the inorganic adhesive door territory - heavy territory, pearl clay, earth, leaf serpentine, wenshiwa Shuihuilingshi, Shishi, Shixi Nalu, montmorillonite, Bede's sulphate meteorite, strontite, hectorite, tetradecanoic acid mica, nano, muscovite, pearl mica, talc, insect To the stone crisp mica chlorite and its combination mother, green implementation of wealth, organic sticky! Things. It is made in some cases when the organic clay is smashed and σ is in the presence of a polymeric resin. Suitable: There are: the clay composition includes the organic clay combination disclosed herein. In the embodiment, the organic viscosity is used as the intermediate layer distance of about 5 to about & + mouth initial product polymer - Organic sticky...:. In this case, at least the ΙΟΟ^^Φ n m refill composition is also characterized by about 5 to about

The distance between the middle layers of V JUU. In a specific embodiment, the polymer-organic clay composite is prepared by accommodating or mixing a ja-grade organic clay composition with a group of four people including a four-stage organic cation. For example, polyphenylene sulfide (four). In another soil composition and a polymeric tree, the quaternary organic viscous enthalpy of the organic cation, θ is about 3 〇〇 C and about 45 (the range between the TC and the temperature is 0 0 5 - The organic clay composite composition, the system 3..., includes, for example, a copolymer derived from a chelate of bisphenol A and bis(4-chlorophenyl)sulfone, in the form of a structure of 123170-59-200900449. In the example, a polymer-organic clay composite prepared by melt-mixing a four-stage organic clay composition containing a four-stage organic cation with a polymeric resin at a temperature in a range between about 300 C and a force of 450 C The composition comprises a polyether ketone, for example, a copolymer comprising structural units derived from succinyl A and 4,4- benzophenone. Melt mixing can be carried out using any melt mixing technique, which combines organic clay And the polymeric resin is at a temperature of about 3 Torr. 〇 and about 45 〇. The temperature in the range of 〇 is added with m ' and under sufficient shear force to achieve at least a percentage of the organic clay composition in the polymeric resin. 1% capacity. Typically, the extruder can be used up to Melt mixing. In one embodiment, the machine is a vented twin screw reciprocating machine. In another specific embodiment, the extruder is a vented single screw reciprocating extruder. The melt mixing is carried out in a kneader. In one embodiment, the melt mixing has sufficient duration and strength to achieve a percentage peeling of the organic clay composition in the polymeric resin of at least 20 percent. In a specific embodiment, the melt blend has sufficient duration and strength to achieve a percentage exfoliation of the organic clay composition in the polymeric resin of at least 3%. In one embodiment, the present invention provides an article a polymer-organic clay composite composition prepared in the following manner, comprising (4) a fourth-order organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising a quaternary organic cation; and (9) The polymeric resin, at a temperature in the range of between about 3 (10) ° C and about 450 t, is sufficient to achieve a percentage of the organic clay composition in the polymeric resin The flaking is at least 1% of the shear force 123170-60·200900449 under melt mixing. In a specific embodiment, the present invention provides a method of making a polymer_organic clay composite composition comprising alternating a quaternary organic clay composition of a balance layer and an organic layer, the organic layer comprising a quaternary organic cation mixed with a polymeric resin comprising at least one polymer selected from the group consisting of polyfluorene Amines, polyesters, polyaryl sulfides, polyaryl ethers, polyether oximes, polyether ketones, polyether ethers, r

Polyphenylenes and polycarbonates' The polymeric resin is substantially free of polyetherimines; the melt mixing is carried out at a temperature in the range between about ≤t and about 45 (r) to provide a polymer _ an organic clay composite composition characterized by a ratio of 100 & peeling at least (7) hundred. When the polymeric resin contains 5 weight percent of the poly-longimine, the system Substantially free of poly(tetra)imine, based on the total weight of the polymeric resin. Polymeric resins containing hydrazine by weight of polyether quinone imine are also stated to be substantially free of polyether quinone imine. In an embodiment, the present invention provides an article comprising a polymer-organic clay composite composition, the polymer-organic clay composite combination, and a chemical organic clay layer and an organic layer. Clay, and σ, the organic layer comprising a quaternary organic cation; and (b) a polymeric resin comprising a poly-sigma complex selected from the group consisting of polyamines, hydrazine

曰, 'polyaryl thioethers, polyaryl ethers, polyether oximes, poly-bond oximes, fcik 3L & shouting _ class, poly benzenes and polycarbonates; the polymeric resin is essential JL >C ytv w- 3 polythenimine; wherein the polymer-organic clay composite is characterized by a percentage exfoliation of at least 1%. In one embodiment 123170 - 61 - 200900449, the article is a film. In another specific embodiment, the article is a solvent cast film comprising a polymylonimine having a composition of two components and a diamine component and a glass transition temperature (Tg) of between about 18 〇1 M 5 〇t, and wherein The thin system has: a) a CTE of less than 70 ppmrc; b) a thickness of between about 1 micrometer and 250 micrometers; and a magical content of less than 5% by weight residual solvent. In one embodiment, the present invention provides a method of making a soil composite composition comprising: an extruder comprising: an intermediate inorganic clay having an alternating inorganic silicate layer and an organic layer; a composition, the layer comprising a quaternary organic cation, blended with a polyether stone-containing polymeric resin, the polymeric resin being substantially free of polyetherimine; the melt mixing is at about 30 (TC and Performing at a temperature in the range of about 45 (between rc) to provide a polymer-organic clay composite composition characterized by a percentage spalling of at least 10 percent. In one embodiment, the quaternary organic cation has structural enthalpy. In another embodiment, the quaternary organic cation has structure XXV. In another embodiment, the quaternary organic cation has structure XXVI. In yet another embodiment, the quaternary organic cation has a structure. In a specific embodiment, the present invention provides a method of making a polymer _1 clay composition comprising a quaternary organic clay composition comprising an alternating inorganic ruthenium salt layer and an organic layer, the organic layer comprising a tetra-, and an organic cation, melt-mixed with the polyether quinone imine composition. The second system is at about 30 (rC and about 45 (at a temperature within the range of rc to provide a compound-organic clay composite composition characterized by a percentage peeling of at least 1 mouthpiece to a specific 123170 -62- 200900449 In the examples, the quaternary organic cation has structure x. In another embodiment, the quaternary organic cation has structure XXV. In another embodiment, the quaternary organic cation has Structure XXVJ. In yet another embodiment, the quaternary organic cation has a structure. In one embodiment, the polyether quinone imide composition further comprises at least one polymer selected from the group consisting of polyvinyl chloride. , polyolefin, polyester, polyamide, polyfluorene, polyether oxime, polyphenylene sulfide, polyether ketone, polyetheretherketone, ABS, polystyrene, polybutadiene, poly(acrylate), poly( Alkyl acrylate), Acrylonitrile, polyacetal, polycarbonate, polyphenylene ether, ethylene-vinyl acetate copolymer, polyvinyl acetate, liquid crystal polymer, aromatic polyester, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride, Polydifluoroethylene, polydivinylidene, polytetrafluoroethylene, and a combination comprising at least one of the foregoing polymers. In one embodiment, the polyether quinone composition comprises a polyether oxime. In another embodiment, the polyether quinone imide composition comprises a polyether ketone. In a specific embodiment, the present invention provides an article comprising a poly delta organic point clay composite composition, (4) a quaternary organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising a quaternary organic cation, and (8) a polyether quinone composition, wherein the polymer-organic clay composite composition Characterized by a percentage exfoliation of at least 10 percent beta suitable polyether quinone imine compositions include ultem polyether quinone imine available from GE plastics. In a specific embodiment, the present invention provides a method of making a polymer_organic clay composite composition comprising: alternating three layers of an inorganic inorganic layer and an organic layer of a package 3 in an extruder The organic clay composition, the 123170 • 63· 200900449 organic layer contains a quaternary organic cation, and contains at least one species of polylysine with at least one other desirable. The polyether oxime imine composition is melt-mixed, and the other polymers are selected from white, π, ι including polyamines, polyesters, polyaryl sulfides, polyaryl ethers, poly M & ', wind, ketones, polyether ketones, polyphenyls, and poly(4); the rubber-melt mixture is provided under the range of the range between the assignment and the assignment, to provide A polymer-organic clay composite composition characterized by a percentage exfoliation as a fraction. In a specific embodiment, a quaternary organic cation is used. In a specific embodiment, the quaternary organic cation has a structure XXV. In another and/or embodiment, the quaternary organic cation system has a "sigma structure XXVI. In addition, the ion system has a structure xxxm. Shouting organic cation polymer · organic clay composite composition On-site polymerization route soil: human two:: In the example, the present invention provides an operation method for preparing a polymer_organic clay composite composition, and a polymer resin is produced in the presence of a clay composition. The knowing method of Park Ge Tzan proposes the advantages of 'in particular the close contact of the organic clay composition. Gray ash tree, such as the 'in the aspect', the invention provides a kind of polymer-organic bonding, combination Method of the method comprising: (4) using a monomer, a second monomer, a solvent, and an organic clay composition under polycondensation conditions, the organic clay composition comprising an alternating inorganic citrate layer = for the first polymerization a reaction mixture in which the first species is =, one of the extracts is a diamine, and the other is a dimer; (b) in the second single polymerization mixture 123170 -64 - 200900449 mouth = upper cut stoichiometry (4) Steps; (4) Add as appropriate Other reactants are added to the first polymerization mixture to provide a second polymerization mixture, and (4) the self-selective polymerization mixture or the second polymerization mixture is removed to provide a polymer component and The first-polymer-organic clay composite composition of the earthy component, in which the organic clay component is exfoliated for at least 10%. In „jg i 丨点丨士, in the concrete case, the polymer component is agglomerated The more the imine. The polymerization is carried out in the presence of a sodium phenylphosphinate (SPP). In a specific embodiment, the first monomer is a di-hepatic and the second monomer is an m-amine and a bi-series including those disclosed herein, such as BPADA and m-phenylenediamine. Suitable solvents include aromatic solvents such as o-dichlorobenzene, toluene, diphenylbenzene, chlorobenzene and combinations of the foregoing solvents. The organic clay composition can be any of the organic clay compositions disclosed herein. The stoichiometry step can be carried out using any analytical technique suitable for accurately determining the ratio of the first monomer to the second monomer in the first reaction mixture. For example, the ratio of the first monomer to the second monomer in the first reaction mixture can be determined by infrared analysis of a film which is prepared from a sample of the first reaction mixture. As described in the experimental paragraphs of the present disclosure. Alternatively, the ratio of the first monomer to the second monomer in the first reaction mixture can be determined by techniques recognized by techniques such as two-performance liquid chromatography (j^PLC), nuclear magnetic resonance, and end 123170. -65 - 200900449 Base titration. The stoichiometric proving step is important to the careful control of the stoichiometry, so that the composition of the composition of the composition of the composition - organic clay complex / (four) sign. In a specific embodiment, the chemistification step includes determining the ratio of amine to liver. If the trap is detected in the monomer after the stoichiometric step, other monomers may be added. Alternatively, the stoichiometric step can = = add another reagent such as a chain terminator. When other anti f

~ 樘 "When in the reaction mixture" is considered to constitute a mixture of a kind of polymerization reaction, which can be reacted by, for example, heating. After the completion of the polymerization reaction, the solvent is removed to provide a composition containing the poly The first-polymer of organic clay ingredients - organic clay complex composition - where the organic clay ingredients are exfoliated for at least the secret. Solvent removal can be achieved by techniques recognized by the art, such as steaming, filtration, and anti-solvent precipitation. The effect is followed by hydrazine, etc. In a specific embodiment, the solvent is removed from the first polymerization mixture or the second polymerization mixture using a devolatilizing extruder, a wipe film evaporator, or a combination thereof. In one embodiment, the first polymer-organic clay composite composition is further subjected to a melt mixing step at a temperature in the range of between about 300 ° C and about 45 Torr. In a particular embodiment, such melt mixing further enhances the degree of exfoliation of the organic clay component of the polymer-organic clay composite composition. In one embodiment, Contacting under polycondensation conditions includes heating at temperatures greater than 100 C. In an alternate embodiment, contacting under polycondensation conditions includes heating at temperatures below 10 (rc. in another specific 123170 • 66) · 200900449 Implementation of the shot, contact under polycondensation conditions, #, including (4) agent and catalyst in the presence of temperature, the temperature is greater than the bribe. In the alternative embodiment, the contact under polycondensation conditions is included in the solvent and touch In the presence of the medium, the temperature is heated at a temperature lower than 100 ° C. The anhydride is used in the case of the item, and the first fresh body has the structure red

Is independently a halogen atom, c r ^ m, a ClC2 〇 曰 group, a c5_C2 〇 ring aliphatic group or

XL group; and is rated as a bond, a bivalent Ci_c2 〇 aliphatic group, a divalent 5 20 衣月日 & group, a price c2_c2. An aromatic group, an oxygen linking group, a sulfur linking group, an S〇2 linking group or a Se linking group. :- specific embodiment of the order, Erxuan red is selected from the group consisting of double-prepared A two-needle nail gold A), 4,4'-oxydipicdicarboxylic anhydride (4,4,-〇DPA), 3,4 ,-oxydiphthalic anhydride (3,4,-ODPA), 33,_枭---rolling a dicarboxylic anhydride (3,3,_〇DpA), 4 4,_biphenyl Anhydride, 3,4,-biphenylmei- hemp' which base-anhydride, a combination thereof. In another embodiment, one of the dianhydrides used is any dianhydride as disclosed herein. In any of the diamines disclosed in one embodiment, the second monomer is an aromatic diamine selected from the group consisting of stupid, and the second monomer is a diamine, selected from the group, for example, · Phenylenediamine. In a specific implementation of the family diamine. In one embodiment, the aryl-amine, p-diphenylamine, 4,4,-diaminobiphenyl 123170-67-200900449 is reduced to μ'-diphenylamine. In a beta embodiment, the organic clay composition comprises a quaternary organic % ion. In the case of specific implementation, the fourth-order organic cation has a knot

XXXIX R8—__Rio R7 χχχιχ wherein Q is a nitrogen material' and 117, R8, R9 and R1G are independently a Cl_c2G aliphatic group, a C5-C2G cycloaliphatic group, and C2_C2. An aromatic group or a polymer chain. Organic clay compositions comprising a grade of organic cationic cerium, in some cases are commercially available. Alternatively, an organic clay composition comprising a four-stage organic cation XXXIX can be prepared for use in the techniques disclosed herein. In a specific embodiment, the fourth-order organic cation is selected from the group consisting of fluorenyl thiol cations, decyltrimethylammonium cations, tetradecyltrimethyl cations, and xenon butyl groups. Dimethylammonium cation, octadecyltrimethylammonium cation, and combinations thereof. In an embodiment, the 'organic clay composition comprises a non-quaternary organic cation' such as a protonated aromatic amine. As indicated by the Φ 4^, the organic clay composition used consists of alternating inorganic acid AS. » , S Xing organic layer. The inorganic citrate layer, as set forth herein, can be derived from an inorganic clay material. In a specific embodiment, the inorganic bismuth layer is derived from inorganic clay, which is selected from the group consisting of kaolin, sorghum, earth, pearl terracotta, eucalyptus, serpentine, chrysotile, pyrophyllite. , Mengde, Deshibao stone, soap stone, Shi Xi Na zinc Mingshi;; Yuxi ore, Shuihui 123170 -68- 200900449 Shisi Shixi acid soda mica, Nashi stone, muscovite, pearl Mica, talc, vermiculite, phlogopite, green fragile mica, sulphite and combinations thereof. In one embodiment, the invention provides a method of making a polymer_organic clay composite composition comprising (4) dianhydride and a diamine in a solvent, at about i0. (: contact with an organic clay composition at a temperature in the range of about 25 (TC), the organic clay composition comprising an alternating inorganic layer and an organic | to provide a first polymerization reaction a mixture; (6) measuring the ratio of amine to anhydride in the first polymerization mixture; (6) optionally adding an additional dianhydride or diamine to the first polymerization mixture to provide a first polymerization mixture; and (4) using a devolatilizing extruder for removing a solvent from the first polymerization mixture or the second polymerization mixture to provide a first polymer comprising a polymer component and an organic clay component. The organic clay composite composition, wherein The organic clay component is at least 1% exfoliated. In a specific embodiment, the method further comprises (iv) mixing the first polymer at a temperature within a range between about 眞. The steps of the composition. In a specific embodiment, the present invention provides a method for producing a squamous organic clay composite composition, which comprises (4) making a double-anticipated A (BPADA) The amine is in o-dichlorobenzene and is about 125. in contact with the organic clay composition at a temperature in the range of about 25 Torr, the organic clay composition comprising alternating inorganic silicate layers and an organic layer. To provide a first polymerization mixture to determine the ratio of amine to anhydride in the first polymerization mixture, (e) optionally adding an additional dianhydride or diamine to the first polymerization mixture to provide a second polymerization mixture ; and (4) make: 123170 •69- 200900449 devolatilizing extruder, from the first sputum, the scorpion from the first polymerization mixture or the second polymerization mixture to remove the Zheng - preparation ^ ° clay into the evening Chu, - ', to provide a polymer component and an organic" first polymer-organic clay composite composition, wherein the organic clay component is at least 1 〇 () / ', in a specific embodiment, organic The clay composition has structural flaws.

In a specific embodiment, the present invention provides a method for producing a polymyachinium:organic clay composite composition comprising (4) a 4,4,-oxydiyl group, a formic anhydride (4,4' 〇DPA) is contacted with a diamine in o-dichlorobenzene at a temperature between about 耽 and about 250 C in the presence of an organic clay composition comprising alternating inorganic salt layers and organic a layer to improve the first polymerization mixture; (b) to determine the ratio of amine to anhydride in the first polymerization mixture; (c) optionally add another dianhydride or diamine to the first polymerization mixture To provide a second polymerization mixture; and (4) using a devolatilizing extruder to remove the o-diphenylbenzene from the first polymerization mixture or the second polymerization mixture to provide a polymer component and an organic clay. The first polymer of ingredients _ organic clay composite composition, wherein the organic clay ingredients are exfoliated for at least 1%. EXAMPLES The following examples are merely intended to illustrate the methods and specific examples in accordance with the present invention, and therefore should not be construed as being limited to the claims. Bisphenol A dianhydride (BPADA, CAS No. 38103-06-9) (97.7% purity) was obtained from GE Plastics. 4,4'-Oxydic phthalic anhydride (ODPA, CAS No. 1823-59-2) (99% purity) was obtained from Chriskev Corporation, Lenexa, Kansas, USA. 123170 •70- 200900449 Tetrafluoroboric acid 2,4,6-triphenyl-pyridinium, aniline, 4-phenoxyaniline, 4-cumylphenol, potassium carbonate, 1-fluoro-4-nitro - Benzene, palladium/carbon and ammonium formate derived from Aldrich ° organic clay composition (organically modified clay) made of Kunipia F montmorillonite unless otherwise indicated. See, for example, an organic clay composition made from Nanocor PGN. Kunipia F montmorillonite is purchased from Kunimine Industries. The manufacturer reported a cation exchange capacity (CEC) of 115 meq/100 g. The un-dried Kunipia F contains 8% by weight of water at room temperature, while the un-dried Kunipia F sample has a nano-analysis of 23,850 (500 ppm), which is shown for un-dried tests. As such, the CEC is 103.7 meq/100 g. For the purposes of this disclosure, a cation exchange capacity value of 100 meq/100 grams is used for all calculations and material preparation. KunipiaF montmorillonite has an aspect ratio of 320 (average), 80 (lowest), and 1120 (highest). Quite a smectite is available from Nanocor. The products PGV and PGN have individual aspect ratios of 150-200 and 300-500 nm. The cation exchange capacity of PGV and PGN clay is 145 (± 10%) and 120 (± 10%) milliequivalent/100 g, respectively. The acoustic vibration of the organically modified montmorillonite in a solvent is carried out using a 450 W model of a Branson vibrator 450 having a 0.5" diameter solid state probe. About large-scale sound vibration (> 1 gram clay The 1500 W model from the Autotune series of high-strength Ultrasonic processors from Sonics & Materials was used. The TGA measurement was performed on a Perkin Elmer TGA 7 using Pyris software. At a rate of 20 ° C / min, spanning The temperature rise of 25 to 900 ° C is used for all climbed samples. The isothermal operation is carried out at 400 ° C to test the thermal stability at the standard 123170 • 71 - 200900449 = processing / extrusion temperature The thermal stability is reported as the starting temperature of the mass deduction, and for isothermal operation, it is reported for 3 minutes. The thermal mechanical analysis (TMA) is used to measure the film sample (10). It is cut in a custom fixture by 2 thorn blades with a spacing of 4 mm. The minute is performed on the TMA Q4 Thermal Mechanical Analyzer No. 0400-0007, which can be obtained from the TA instrument. The experimental parameters are set. In the power of 〇〇5〇N, 5 〇〇〇克静The weight is 50.0 ml / min of nitrogen gas, and 〇 5 seconds / point injection interval. cte calibration m standard, at rc / min climb rate, under nitrogen gas, from 0 to 200 C. The temperature calibration was performed with an indium standard at a hole/min ramp rate at a nitrogen scrub τ. After calibration, the CTE calibration was confirmed to be within 1 ppm/t, and the temperature calibration was confirmed to be at the desired value. 〇.5 ° C. Transmission electron microscopy (TEM) measurements were carried out on film samples embedded in epoxy resin (-epoxy matrix), and then at room temperature using Reichert Utoacut E microscopy A microtome was microsectioned to a thickness of ~ ι 〇〇 nm. Microsectioned sections were collected on a copper grid' followed by phi^ CM100- (100 KV) transmission electron microscopy. X-ray winding The shot (XRD) (low-angle XRD) metric is performed on the 81^ over-infrared diffractometer using 'Θ-Θ geometry. Μ _ 遽 遽 CuKa radiation system and M-Bmun PSD-50m position sensitivity detector It is used together with a 6 mm entrance slit. The scan range is 1.4-25 degrees 2 0. Sodium content analysis system It was carried out by plasma atomization inductive coupling plasma spectroscopy (ICP-AES 'VarianLiberty II). Combustion analysis (C_H analysis) on organic clay composition (Clay modified by 123170-72-200900449) is in LEC The company is located at www.leco.com. A small-scale refining mixing experiment of polymer and modified clay was performed on a Haake Rheomix 600 instrument. The percentage peeling is defined as follows. The inorganic filler has a volumetric metering effect on the coefficient of thermal expansion (CTE). There is a corresponding % reduction in CTE for each volume %' of the filler incorporated into the polymer matrix. Thus, when the organic clay composition is added to the polymeric resin, any reduction in the CTE above the volumetric metering is directly related to the spalling of the organic clay composition in the polymer matrix. Percent flaking can be calculated by normalizing the CTE (CTE due to volume filling) versus the ratio of experimentally measured CTE. To calculate the normalized CTE, the density of the tantalate (2_86 g/cm3 according to the supplier's technical data) and the density of the standard polyetherimine (1.27 g/cm3 according to the supplier's technical data) were used. The converted weight percent citrate is converted to volume %. Thus, each wt% citrate can be converted to volume 〇/0 by multiplying by 0.00444. Therefore, normalized CTE = unfilled CTE _ (〇〇〇444 * unfilled CTE * wt% citrate), while percentage stripping is % flaking = filled CTE (experimental metric) / Normalized CTE representation. Preparation of quaternary scale salt Example 1 Preparation of moth (3-aminophenyl) triphenyl scale 1 123170 •73· 200900449

Add about 329 33 g (125 mol) triphenylphosphine (pph3), acetate) 2 (2.82 g) to a 3 mL 3-neck round bottom flask equipped with a condenser, mechanical stirrer and gas inlet tube. , 0.0126 mol) and brain ml degassed xylene. The mixture was stirred under argon until pph3 was dissolved. Add m-mothylamine (about 275.00 g; U5 mol) and reflux the yellow orange solution for about 80 minutes. The product scaly compound (iodinated (3-aminophenyl)triphenyl scale) was isolated from the solution as a yellow-orange solid. Avoid excessive reflux to prevent discoloration of the product scaly compound. The progress of the reaction was monitored by thin layer chromatography (TLC) using a 5 〇/5 己 hexane/ethyl acetate effluent. After refluxing, the product was filtered. The product 1 was reconstituted as a liquid solution with hot benzene and stirred for 15 minutes to wash the solution, and rinsed with additional toluene/xylene. After drying in a 15 rc vacuum oven, 585.01 g of an off-white product was obtained in 96% yield. The melting point and the data were consistent with the structure of product 1. Melting point: 316 〇 <t. lH W D6-DMSO): 8-6.6 (m, 19H, aromatic compound), 5 88 (s, 2H)

In a 3 liter flask, 4-cumylphenol (17 〇 9 g, 〇 8 〇 Mo), * decyl phthalonitrile (150 g, ο·87 mol), potassium carbonate (155) were added. 8 g, ιΐ3 123170 -74- 200900449 Moer) and dimercaptomethylamine (1.4 liters). The solution was heated under nitrogen and stirred to about 90 ° C for about 1 minute. The progress of the reaction was monitored by thin layer chromatography. The dark brown reaction mixture was cooled, and a 2M HCl solution (6 liters) was added and stirred. The organic layer was extracted with an air-mesh (3 X 300 ml) to separate the gas layer and washed with water (3 X 1 mL) and dehydrated (MgS 4). The mixture was filtered and the solvent was evaporated on a hot oil bath to afford crude <RTI ID=0.0># </ RTI> </ RTI> </ RTI> </ RTI> as a viscous green oil (278 g, 84% yield). 1 Η NMR ( ^, D6-DMSO) : 8.09 (d, 1H), 7.78 (d, 1H), 7.40-7.15 (m, 8H), 7.10 (d, 2H), 1.66 (s, 6H, Me). Example 3 Preparation of 4-(4-isopropylphenyl)phenoxy-phthalic anhydride 3

A 3-liter 3-neck round bottom flask was fitted with a condenser, a mechanical stirrer, and a liquid addition funnel. To the flask was added 4-(4-isopropylphenyloxy)-phthalonitrile (278 g '0.82 mol) and acetic acid (1·6 liter). The addition funnel was filled with 7% sulfuric acid (67 mL). The solution was heated to 12 CTC, and then sulfuric acid was added dropwise to the reaction mixture over 2 hours. The resulting mixture was refluxed overnight (12 hours). The reaction mixture was allowed to cool to room temperature and poured into a mixture of ice water (~jg). The product was extracted with ethyl acetate (3×300 mL). The ethyl acetate layer was isolated and dried under anhydrous MgS 4 . The solution was filtered to remove MgS〇4 and the solvent was removed on a rotary evaporator. The resulting brown liquid was dried in a vacuum oven at 160 ° C overnight. This produces the desired anhydride as a viscous brown oil (276 g '94% yield). iH-NMR (5, D6-DMSO): 7.96 123170 -75- 200900449 (d, 1H), 7.50-7.20 (m, 9H), 7.03 (d, 2H), 1.76 (s, 6H, Me). Synthesis of cumene PA-mATPP-I 4

In a 5 (8) ml glass reaction vessel equipped with a mechanical stirrer, a nitrogen inlet tube and a gas outlet tube, 66.27 g (0.1848 mol) of 4-(4-isopropylphenyl)phenoxy phthalic anhydride 3 was added. With 88_97 g (0.1848 mol) iodized 3-aminophenyl) triphenylsulfonium (mATPP iodide) 1. The container is then placed in the heating mantle closure and heated to about 3 Torr (TC to produce a molten reaction mixture. After stirring for about three minutes, vacuum is applied to remove water formed as by-products. After a total reaction time of 15 minutes, the reaction mixture was poured into a Teflon tray and cooled to provide compound 4 (145-19 g '95.6%) as a smooth brown glass material. 1 H NMR (5, D6- DMSO) : 8_07-7·08 (31H, aromatic), 1.68 (s, 6Η). Alternate synthesis of isopropyl phenyl-PAATPP-I. Iodine iodide-amino tetraphenyl scale 22.14 g (0.046 Mox) was weighed out with 8-[0]- phthalic anhydride 8-40 g (0.046) and added to a 250 mL round bottom flask equipped with a Dean_stark condenser and dissolved in 150 mL of o-dibenzene. The contents were heated to reflux and the water was removed by azeotropic distillation with nitrogen. After 4 hours under reflux, &lt;RTI ID=0.0&gt;&gt; And heating for another 4 hours. After cooling to room temperature, the solution was poured into 400 liters of diethyl ether, and the solid formed by vacuum filtration was collected. The solid was redissolved in 1 mL of chloroform and the resulting solution was poured into 123170-76-200900449 300 ml of diethyl ether. The solid formed was collected by vacuum filtration and dried overnight under vacuum. 13 C- NMR was consistent with the structure. Total yield: about 60%. Example 5 Synthesis of BPADAPA-mATPP-I 5

About 58.0 g (0.1114 mol) of bisphenol a dianhydride (BPADA) was shaken with 107.27 g (0.2229 mol) of deuterated 3·aminophenyl)triphenylphosphonium (mATPP-I) 1 . Then, the anhydrous mixture was added to the glass reaction flask using a long paper funnel to prevent the reagent from adhering to the upper inner side of the flask. The reaction flask was evacuated and counter-filled twice with nitrogen. Start the external heater and set it to about 3〇〇〇c. When the reagent melts, a brown solution forms. After the reagent has been melted for 3-5 minutes, the reaction flask is evacuated to remove water. First set the pressure to 6 mbar (mb) and continuously decrease to 10 mb. When the reaction was completed, the pressure was dialed back to 1000 mb' and the stirrer was turned off to cool the product diterpene imine 5 to yield 158.48 g (98_28%) of brown glass material. Ijj nmr ( 3, "D6-DMSO" : υ-7] (m, 52H, aromatic compound), i 73 (s, 6H) Example 6 AMS dimer diamine bis (chlorophthalic phthalic acid) Synthesis of imine) 6 HC ru

123170 -77- 200900449 o-Dichlorobenzene. The mixture was heated to 19 〇 2 Torr (rc for 4 hours under nitrogen flow, and water was removed. The reaction mixture was allowed to cool to ambient temperature and the product bis (glycol phthalimide) 6 was borrowed. Precipitated by the addition of methanol (15 mL). The product was filtered and dried in an oven at 1 〇 0. Dry under reduced pressure to constant weight. Yield 40 g (91%). Example 7 Bis (isophthalate) Synthesis of amine)

2 g (0.05 mol) of bis(oxyphenylene phthalimide) 6 in a 3-necked flask equipped with a stirrer, a nitrogen inlet tube and a condenser, 245 g (〇〇9 mol) Triphenylphosphine and 6.05 g of anhydrous nickel dichloride. Then, the mixture was heated to 30 (TC for 4 hours) under a nitrogen flow. During this period, all of the reactants turned into a green-blue liquid form. The reaction mass was cooled to ambient temperature and solidified into a glassy green. A blue solid substance to which was added dichloromethane (250 ml). The mixture was heated to dissolve a large portion of solid, and water (200 ml) was added. The organic layer was separated and washed repeatedly (2 ml 乂4) Sub-washing) until the water layer remained colorless. The solvent was removed under reduced pressure to give the product as a double salt as an oil. Toluene (1 mL) was added to afford a solid. Toluene. Toluene addition and removal were repeated 4 times to ensure water removal. Finally, the last portion of toluene (1 mL) was added to produce a slurry of double scale salt 7. The solids were passed and In an oven, dry to constant weight at the contact c. The yield was 30.3 g (60%). Example 8: Synthesis of bis (scale dimethyl quinone imine 123170 -78- 200900449

13.54 g (0.11 mol) of 4_gas-aniline and 3 were added to the ruthenium (tetra) molybdenum bromide anhydride in a reaction flask equipped with a stirrer, a nitrogen inlet tube and a Dean_Stark apparatus equipped with a condenser. 〇〇ml o-dichlorobenzene. The mixture was heated to 19 Torr to 2 ° C under a nitrogen flow for 4 hours and water was removed. The sigma was allowed to cool to ambient temperature and the product was precipitated from 15 (8) mL of methanol. The product was filtered, and dried in an oven at 10 (rc) to a constant weight yield of 35 g (89%). 15 g of a flask equipped with a stirrer, a nitrogen inlet tube and a condenser above. 4 moles of the product quinone imine, adding 2 〇·5 g (〇〇8 mol) triphenylphosphine and 5 g of anhydrous nickel dichloride. The mixture was heated to 220 C under nitrogen flow for 4 hours' A green-blue liquid was obtained. The reaction mixture was allowed to cool to ambient temperature to give a solid material. The product was sedated and purified to afford a double-salt salt. The yield was 30.5 g (75%). -10

Synthesis of amine substituted scale salts 9 and 10

Adding a diamine (4,4'-diaminobiphenyl hydrazine (DDS) or α-methylstyrene dimer 123170 •79- 200900449 diamine (AMSDDA) (0.3 mol)) to the stirring In a round bottom flask with a nitrogen inlet tube, a Dean-Stark unit and a condenser. About 1 mole (18 26 grams) of 4-acha phthalic anhydride was added to the diamine along with about 3 liters of o-diphenylbenzene. The round bottom flask was heated to about 19 Torr 2 Torr &lt;t under nitrogen for 4 hours and water was removed. Then, the reaction mixture was cooled to room temperature, and added to about 1500 ml of hexane, and stirred. The product monochloro phthalic acid quinone imine was collected and placed in an oven at 1 Torr. Dry under the armpits. Monogas ruthenium imine (0.1 mole) was added to a flask equipped with a stirrer, a nitrogen inlet tube and a condenser. Triphenylphosphine (τρρ) (262 g, 〇1 mol) and nickel (II) chloride 0.05 mol (6.5 g) were added, and the mixture was heated to the desired temperature under nitrogen for 6 hours. Then, the reaction mixture was cooled to room temperature and stirred in about 1 ml of dichloromethane and water (1 ml). The liquid layer is separated and the organic layer is washed until it does not contain the color of the nickel dicarbide. The solvent was removed under vacuum, and toluene was added to the adhesive residue, and then toluene was removed under reduced pressure. The benzene is added and removed until the solid product is obtained. The final product is then dried under vacuum. The structures of the products 9 and 1 were confirmed by iH-NMR. Example 11 Synthesis of bis(squamium imine) 11 Ο 〇

Adding Erxuan (oxydiphenyl phthalic anhydride (0.1 mol)), 3 chloro phenylamine (26 77 g '0.21 mol) and o-dichloro stupid (3 (8) ml) to the stirrer, Gas 123170 200900449 Gas inlet tube, Dean-Stark unit and condenser in a reaction flask. The reaction mixture was heated to about 19 〇 2 〇〇 ° C under nitrogen for 4 hours and water was removed. The reaction mixture was then allowed to cool to room temperature and added to about 15 mL of methanol. Next, the intermediate bis(chloroquinoneimine) was filtered and dried in an oven at l ° C until constant weight. The bis(gas-quinone imine) was converted to bis(sinoinimide) 11 according to Examples 9 and 1 Torr. Example 12 Synthesis of bis-imine and single scale salt 12

Add one amine (bicycloundecyldiamine (0.3 mol)), phthalic acid liver (〇1 mol) and o-diphenylbenzene (300 ml) to a stirrer, nitrogen inlet tube, Dean - Stark and condenser in the reaction flask. The mixture was heated to about 190-200 ° C under nitrogen for 4 hours and water was removed. Then, the reaction mixture was allowed to cool to room temperature, and stirred in about 1500 ml of hexane/increol to obtain a mixture of the intermediates (monomethylene phthalimide) as an isomer at 1 (10). Dry to constant weight under c. Add monophthalimide (0J mole), 4_aerophthalic anhydride (〇丄mole) and o-dichlorobenzene (300 ml) to the above Installed flask _. Heat the mixture to about 19 〇 -2 Torr under nitrogen. (:, after 4 hours, remove water. Then 'cool the reaction mixture to room temperature and at about 15 〇〇 Stir in the sulphur/sterol to obtain the intermediate mono-o-xylyleneimine·mono-glycine phthalimide as a mixture of isomers, which is dried to constant weight at 1 〇 (rc) 123170 -81 - 200900449 The reaction of mono-o-phenylenediamine-monochlorophthalimide intermediate with triphenylphosphine in the presence of vaporized nickel (11) was carried out as described in Example 8. The product bisindoleimide-single scale salt 12 is a mixture of isomers. Preparation Example 13 of an organic clay composition containing a quaternary phosphonium cation comprises a scaly cation 13 organic clay composition

In a 1 liter beaker, cesium salt 1 (example i, 17 36 g, 〇 36 mol) and methanol (900 ml) were added and heated to 64 t:. In a separate flask, sodium montmorillonite (Na-MMT/Kimipia F clay, 3 〇.00 g, 〇 3 〇 molar equivalent) was mixed with about 2.1 liters of deionized water. When the clay is dispersed, the slurry is heated to about C and added to the large preheat blender. The salt solution in methanol was slowly added to the clay slurry in the blender while stirring vigorously. A thick foam is first formed which is then dispersed. The mixture was vigorously blended for 1 minute and then slowly for another 20 minutes. The temperature is about 65 ι. After mixing for 3 minutes, the mixture was filtered using a large fine fritted funnel. The solid clay was reconstituted in hot water (80 ° C), mixed for 15 minutes, and transitioned. Next, the solid clay is slurried in hot methanol (64. (:), then filtered. The purified clay is dried under vacuum and at room temperature until it can be ground into a powder. Under vacuum, make the moisture The powder was dried at 150 for about 12 hours and again ground to obtain about 30 grams of dry organic clay composition clay in 76% yield. Example 14 Organic clay composition comprising scale cation 14 123170 -82 - 200900449

PPh3, in a 5000 ml round bottom flask, filled with 2000 ml of deionized (DI) water and stirred using a mechanical stirrer. Then, slowly add about 25.00 grams (0.025 equivalents) of Kunipia F clay and stir until the clay is completely dispersed. Next, the dispersed clay solution is heated to about 80 °C. Separately, 20.80 g (0.01437 mol, 15% excess) of BPADA-mATPP iodide 5 was dissolved in 410 ml of acetonitrile and heated to about 80 °C. Then, a BPADA-mATPP iodide salt solution was added to the clay dispersion, at which time the combined mixture was stirred at about 80 ° C for one hour. The clay was then filtered, slurried in 2500 ml of deionized water, and stirred at 8 (TC for 15 minutes. After filtering the clay, it was also washed with acetonitrile, followed by final filtration. The modified clay was at 25 °C. Drying under vacuum for 24 hours until it can be blended with the synthetic powder. The modified clay is further blended under vacuum at 150 ° C for 12 hours to obtain an organic clay composition containing the cation 14 Fine powder, about 84% yield. Examples 15-16 Organic clay compositions containing scaly cations 15 or 16.

Further, an organic clay composition comprising an organic scale cation 15 (Example 15, cumene-MMT) or 16 (Example 16) was prepared as in Example 14. 123170 -83- 200900449 Information on organic bituminous compositions containing organic squamous cations is provided in i. &quot;CE-Γ refers to the comparative example! , &quot;CE_2,, refers to the comparison example 2 and so on. ΈΧ-14&quot; refers to &quot;examples 14&quot;,&quot;Εχ_15" means &quot;example 15&quot; etc. As for organic squamous organic iodine composition examples cationic modifier d-spacing (A) at 400° Weight loss after 30 minutes under c and N2 (%) CE-1 Tetraphenyl scale 17.8 3.1 CE-2 13 19 Ί 2.3 EX-14 14 29 7.0 EX-15 15 25.5 13.0 EX-16 16 25.5 8.0 Example Π 26 The general procedure for the preparation of organic clay compositions is to use inorganic clay (sodium montmorillonite &quot;Na_MMT, available from s〇uthem clay company) in 75 volumes of deionized water relative to the weight of clay. Slurry and stir at room temperature (22_25aC) for hrs, then at 9 〇·95 c for 1 hour. Then add the solution of organic squama salt in methanol or acetonitrile to the slurry of inorganic clay. The reaction mass is stirred at 65-95 for 18-20 hours under cooling. Upon cooling, the crude organic clay composition is filtered and washed until the washing liquid contains no halide, and then dried to constant weight at 125_15 (rc). Organic clay composition of bismuth imine organic scaly cation, accompanied The water gap data measured by X-ray diffraction (XRD) are collected in Table 2. 123170 -84- 200900449 Table 2: Examples of organic clay compositions containing singular bis-imineimine cations Qualitative d-spacing (A) EX-17 〇-N^〇xoXX^N^ Ph3P' 0 0 17 17.5 EX-18 0 18 19.57 EX-19 ο 19 0 15.05 EX-20 ph f 0^0 Ph7 X= =/ 20 18.3 An organic clay composition containing diquaternium imine organic scaly cations, accompanied by d-spacing data measured by X-ray diffraction (XRD), is collected in Table 3. Table 3 : an organic clay composition comprising a bis-biquinone imine cation

123170 -85- 200900449 ί

An organic clay composition comprising an amine-scale monoimine organic cation is accompanied by d-spacing data as measured by X-ray diffraction (XRD). -fee-scale singular imine cation organic clay composition

Preparation of a polymer-organic clay composite composition comprising a quaternary cation cation Example 27 comprises a polymer of cation 14 - an organic clay composite composition in a 1 liter 3-neck round bottom flask containing (9) ml of anhydrous ortho-benzene , Add 123170 -86 - 200900449 Example 7·% g (4.77 g citrate) BPADA-mATPP-MMT. The nanoclay-o-dichlorobenzene dispersion was sonicated at a 20% output for one hour with a 400 W Branson Sonificator 450 with a 1/2" diameter solid state probe. After the sonication, 16.17 g (0.150 m) was added. p-Phenylenediamine (pPD) with 50 ml of o-diphenylbenzene and stir on heat until pPD is dissolved. Then, add 75.31 (0.145 mol) BPADA, 1.43 g (0.0096 mol) phthalate Anhydride and an additional 225 ml of o-dichlorobenzene. The mixture was allowed to warm to reflux, at which time 225 mL of o-dichlorobenzene and water were removed over time. The solution was then cooled and stirred with 300 mL of heptane. The solid polymer formed was dried in a 15 (TC vacuum oven for 15 hours to yield a 89.17 g (93.4% yield) polymer-organic clay composite composition. The polymerized resin had a degree of polymerization of 30. Formulated weight percent citrate was 3%. Example 28 Polymer-organic clay composite composition containing cation 15 was added to a 3 liter 3-neck round bottom flask containing 850 ml of anhydrous cucurbitone, and 210.0 g (0.395 mol) was added. ) BPADA with 40.1 g (23.6 g of citrate) Example 15 Prepared cumene PA-mATPP-MMT. The mixture was sonicated for three hours at 40% output with a 400 W Branson Sonificator 450 with a 1/2" diameter solid state probe. After sonication, add 100.7.克(0.406 mol) 4,4'-diaminobiphenyl hydrazine (DDS), 2.0 g (0.013 mol) phthalic anhydride (PA) and 350 ml of cucurbit ether. The mixture is heated to reflux and 200 ml of the gourd-water mixture was removed over a period of 12 hours. Then, another 400 ml of verazone was distilled from the reaction vessel over a period of 3 hours. Then, the reaction mixture was cooled to 80 ° C and poured. Into a high speed blender containing 2 liters of sterol. The solid polymer formed was filtered and dried in a vacuum oven at 250 ° C for 15 hours. The product polymer was obtained in a yield of 123170 - 87 - 200900449 75%. - an organic clay composite composition (253 g). The formulated degree of polymerization was 35. The formulated weight percent decanoate was 7%. Example 29 Polymer comprising a cation 14 - an organic clay composite composition containing 150 Add 7.51 g of 2 ml 3-neck round bottom flask in ML anhydrous oDCB (4 51 g of citrate) BPADA-mATPP-MMT prepared as in Example 14. The nanoclay-oDCB dispersion was sonicated at a 20% output with a 400 W Branson Sonificator 450 with a 1/2&quot; diameter solid probe. One hour. After the sound vibration, add 34.90 g (0.174 mol) 4,4'-diphenylamine (4,4'-ODA), 52.00 (0.168 mol) 4,4'-oxydiphenyl Anhydride (ODPA), 1.987 g (0.0134 mol) phthalic anhydride, 20 ml xylene and 300 ml oDCB. The mixture was allowed to warm to reflux, at which time 225 mL solvent-water was removed over time. Then, the solution was cooled and stirred with 300 ml of heptane. The solid polymer formed was filtered and dried in a vacuum oven at 150 ° C for 15 hours to obtain 88.52 g of a polymer-organic clay composite composition containing a cation 14, 98.22% yield. The degree of polymerization is adjusted to 25. The formulated weight percent citrate is 5%. Example 30-37 Polymer-Organic Clay Composite Composition, Melt Preparation In Examples 30-37, the following general procedure was employed. Ultem® 1010 polyetherimine (58.2 g) was weighed and divided into two equal portions. Add 1.8 g of the organic clay composition (modified Na-MMT) to a portion and mix well. Next, two portions of the polyether oximine are simultaneously added to the Haake mixer maintained at 350 ° C in about 9 minutes, then mixed at 350 ° C for about 30 minutes, and periodically sampling. The product was then removed from the Haake mixer. The polymer-organic clay composite composition is collected by gel permeation chromatography (GPC) 123170-88-200900449 2 regarding the number and molecular weight data of various polymer/organic clay composite compositions. In Table 5. The product polymer _ having a clay composite composition is also prepared by a cardiac injection Μ ^ ^ ^ 啄% shot (_), a transmissive electron display, and a scent. In addition, the coefficient of thermal expansion (CTE) was measured. For reference to the inorganic clay (Na-MMt ' So her em clay) used to prepare the organic clay composition used, the purchased line shows a pitch of 97 angstroms. The polyether phthalimide used has each of the straight 虿 冥The initial weight average molecular weight (Mw) is

44' 965 g' and the initial number per mole average molecular weight was 19,200 g and showed a CTE of about 62.1 (ppm). Compound

In the organic clay composite composition, no or very little polyether quinone imide matrix was degraded. Furthermore, when detected, the d_spacing found is significantly greater than the d-spacing found in their respective organic clay compositions. Examples 38-51 comprise a polymer-organic clay composite composition prepared by field polymerization comprising a polymeric resin derived from a structural unit derived from DDS and BPADA or ODPA 123170-89-200900449 Polymer-organic clay composite composition 38-43 and 46-51 were prepared as described in the following examples (Example 43). 9.05 g of organic clay composition (BPADA-mATPP-MMT) containing cation 14 and 59.85 g of oxydiphthalic anhydride (ODPA) were added to 219 ml of o-dichlorobenzene (oDCB) and 146 ml of cucurbit ether. The mixture was mixed with a mechanical stirrer for 2 hours to dissolve the ODPA. Then, the container was immersed in a bath squeal and sonicated until a fine dispersion of clay was obtained. Next, the flask was equipped with an overhead stirrer and a Dean-Stark gas cylinder, and 46.33 g of 4,4'-diaminobiphenyl hydrazine (DDS) and 0.08913 g of aniline were added. Use 60 ml of oDCB with 40 ml of verazone to rinse the DDS into the container. The mixture was stirred and slowly heated to reflux for three hours and the water was removed by azeotropic distillation. After heating under reflux for 18 hours, a dispersion of fine powder was obtained. The dispersion was added to a larger volume of methanol, filtered, and dried under vacuum at 180 °C. Then, the formed dry powder was transferred to a Haake melt mixer and mixed at 390 ° C and 50 rpm for 60 minutes. The samples were removed at 5 minute intervals. A 15 minute sample was pressed into a film between two sheets of Teflon lining foil at 760 °F. Then, the film samples were subjected to analysis by thermomechanical analysis and CTE, and were measured in the range of 30 to 200 °C. The polymer-organic clay composite composition 44-45 was made as follows. Use a SILVERSON mixer (laboratory line mixer assembly L4R-PA, square hole high shear filter, pumped at ~600 ml/min) to mix organic clay with solvent. 450 ml of o-dichlorobenzene (oDCB) was pumped through a SILVERSON mixer. 13.1 g of the organic clay composition (BPADA-mATPP-MMT) containing the cation 14 was slowly added to the recycled oDCB. The mixture was passed through a SILVERSON high shear mixer in recirculation mode for 45 minutes at 6000 rpm. The mixture was then transferred to a 1 liter three-necked flask. Next, the flask was fitted with an overhead stirrer and a Dean-Stark gas cylinder. 74.2 g of bisphenol A dianhydride (BPADA) was added, and the flask was heated to 100 ° C to dissolve the dianhydride. Then, 33.90 g of 4,4'-diaminobiphenyl hydrazine (DDS) was added, and 20 ml of oDCB was used to rinse the DDS into the vessel. The mixture was stirred and slowly heated to reflux and the water by-product was removed by azeotropic distillation. After heating at reflux for 3.5 hours, the heat was removed and the reaction mixture was cooled to room temperature. The resulting viscous mixture was transferred to a Haake melt mixer and mixed for 60 minutes at 390 ° C and 50 rpm. The samples were removed at 5 minute intervals. A 15 minute sample was pressed into a film between two sheets of Teflon lining foil at 760 °F. Next, the film samples were subjected to measurement by thermomechanical analysis and CTE, and were measured in the range of 30 to 200 °C. The results for the polymer-organic clay composite compositions of Examples 38-51 are shown in Table 6. Table 6: CTE results from DDS and ODPA and BPADA compression molded samples obtained from on-site polymerization. Example of dianhydride solvent cation modifier 1 clay loading method t CTE %Εχι 38 BPADA o-diphenyl benzene no 0% ΝΑ 58 0.0% 39 BPADA ortho-benzene DP DP 7% sound vibration 37 34.2% 40 BPADA oDCB cumene 7% sound vibration 34 39.5% 41 BPADA v* TPP 3.80% sound vibration 48 15.8% 42 BPADA NMP TPP 3.80% sound vibration 47 17.5% 43 BPADA o/v** DP 3.8 Sound Vibration 44 22.8% 44 BPADA o/v** DP 7.60% Sound Vibration 36 35.7% 123170 -91 - 200900449 45 BPADA oDCB DP 7% Silverson 50 11.0% 46 BPADA oDCB Cumene 7% Silverson 38 32.4% 47 BPADA v* Cumene 3.8 Sound Vibration 45 21.0% 48 ODPA oDCB No 0% ΝΑ 49 0.0% 49 ODPA o/v** DP 3.80% Sound Vibration 34 29.5% 50 ODPA v* TPP 5% sound vibration 39 18.6% 51 ODPA o/v** cumene 3.8 sound vibration 36 25.3% 1 "DP" = cation 14, π cumene "= cation 15, ΤΡΡ = tetraphenyl Base, 1· In Examples 45-40, the mixing step was performed using a SILVERSON high shear mixer. 1 &quot;%Ex" organic clay ingredients in polymer-organic clay composites The percentage of the composition is exfoliated. v'V" = cucurbit ether. **&quot;〇/V**&quot; = mixture of oDCB and veratrol. Examples 52-53 and control polymer prepared by solution blending followed by melt extrusion - Organic Clay Composite Composition The following procedure is generally applicable to the preparation of a film sample comprising the polymer_organic clay composite composition of the present invention. Example 52 An organic clay composition comprising a cation 15 in a veratramine The medium-acoustic vibration. The sound-accepting mixture contains about 2.7% organic clay composition in 500 ml of cucurbit ether. The sound vibration system is used in a 1 〇〇〇 ml round bottom flask immersed in a water bath. A 1/2" sonic probe, Branson 450W vibrator at ~40% power output, is carried out for ~16 hours. A total of five substantially identical organic clay compositions - solvent batches were sonicated and then combined. To the combined batch of the sonicated organic clay composition, a 20 weight percent solution of BPADA-DDS polyetherimine in the gourd was added and the mixture was thoroughly mixed. This mixture was then added to a blender containing sterol. The solid powder formed was filtered and dried at 220 ° C under vacuum, and then blended with a sufficient amount of a second polyether quinone imine ODPA-DDS polyether phthalimide to obtain 69:31 to 123170-92. - 200900449 Example of BPADA-DDS polyether quinone imine and ODPA-DDS polyether quinone imine. The resulting mixture was extruded through a 3&quot;film die into a film. The resulting film had a nano-manganate loading of 7%, a mechanical direction CTE of 33.0 ppm/°C, and a Tg of 255 °C (see Figure 1 for TEM images). The control group contained the same ratio of BPADA-DDS polyether quinone imine to ODPA-DDS polyether quinone without a control film of clay, showing a mechanical orientation CTE of 48.5 ppm/°C and a Tg of 262 °C. Example 53 A film was also prepared using BPADA-DDS polyether quinone imine for ODPA-DDS polyether oxime imine at 60:40 and a nano citrate loading of 7%. The film had a mechanical direction CTE of 28.7 ppm/°C and a Tg of 266 °C. Preparation of a quaternary pyridinium salt Example 54 Preparation of 1,2,4,6-tetraphenylpyridinium tetrafluoroborate 27

In a 500 ml round bottom flask equipped with a condenser, filled with 2,4,6-triphenyl-pyridinium tetrafluoroborate (22.4 g, 0.056 mol), aniline (5.8 g, 0.060 mol) and ethanol ( 200 ml). The resulting solution was magnetically stirred and refluxed for 6 hours under a nitrogen atmosphere. The solution was allowed to cool to room temperature and product 27 was precipitated as a green-yellow crystalline solid. The product was collected by filtration and dried in a vacuum oven (3 g, 87% yield). Melting point = 253 ° C Example 55 Preparation of 1-(4-phenoxyphenyl)-2,4,6-triphenylpyridinium 28 tetrafluoroborate 123170 -93 - 200900449

In a 1 liter round bottom flask equipped with a condenser, 'shock-filled acid 2,4,6-triphenyl-p ratio ingot (50.0 g, 0. Π6 mol), 4-phenoxyaniline ( 25 J g, 0.138 mol) and ethanol (400 ml). The resulting solution was magnetically stirred and refluxed for 6 hours under a nitrogen atmosphere. The solution was allowed to cool to room temperature, and the condensation product was precipitated by milky yellow crystals. The crystals were collected by filtration and dried in a vacuum oven to give the desired product (68 g, 95% yield). Melting point = 201.7 ° C Example 56 Preparation of 4-(4-(indolyl-1-phenyl-ethyl)-phenoxy)aniline 29 in a Dean Stark gas cylinder, condenser and mechanical stirring In a 5 liter round bottom flask filled with 1-fluoro-4-nitro-benzene (159 g, 1.128 mol), 4-cumylphenol (239 g, 1.128 mol), anhydrous potassium carbonate (1 〇 3 g, οι Mo), Ν, Ν-dimethylformamide (1.5 liters) and benzene (150 ml). The resulting mixture was stirred and refluxed for 2 hours under a nitrogen atmosphere (solution temperature ~ 160 ° C). During this time, water is collected at the trap. The reaction mixture was allowed to cool to room temperature. Palladium on carbon (1% by weight pd, 25 grams '0.025 moles) was added to the reaction mixture followed by ammonium formate (35 gram ' 5.463 moles). During the reaction, cold water was used to keep the internal temperature of the reaction mixture solution below 55 eC. After 2 hours, the reaction was filtered and a clear solution of the filtrate was collected. Add 123170 •94- 200900449 water (2 liters) to the filtrate, ice, α &quot; and the desired product is milky yellow white powder from / preparation; &lt;益讲,, see fine filtration to collect the precipitated powder, and in a vacuum oven '100. Dry under the armpits] 2 d spit 'Bugan New 12 hours, and get the desired product (303 grams, 88% yield). = Example 57 Synthesis of tetrafluoro-decanoic acid i-(1_fluorenylphenyl-ethyl)-phenoxy)-phenyl&gt;2,4,6-triphenylpyridinium 3〇

ί

In a 5 liter round bottom flask equipped with a condenser and a mechanical stirrer, filled with 2,4,6-triphenyl-indole in tetrafluoroboric acid (2〇6 g, 〇.5丨9 mol), 4_ [(丨_Methyl·μ phenyl-ethyl)-phenoxy]-aniline (174 g, 0 574 mol) and ethanol (2 L). The resulting solution was stirred and refluxed for 3 hours under a nitrogen atmosphere. The solution was allowed to cool to room temperature, and the condensation product was precipitated as green-yellow crystals. The crystals were collected by filtration and dried in a vacuum oven (10 ° C) to give the desired product (333 g &apos; 94% yield). Melting point = 283.7C Example 58: Synthesis BAPP-TPPy-BF4 31

ΒΑΡΡ (4,4'·(4,4'-isopropylidenediphenyl-1,nonyl-diyldioxy)diphenylamine) (220.0 g, 0.049 mol), triphenyltetrafluoroborate Pyridine (40_5 g, 0.102 mol) and ethyl yeast (400 ml) were mixed together and refluxed for 5 hours. The reaction mixture was allowed to cool to room temperature and filtered to afford product dipyridinium salt &lt;RTI ID=0.0&gt;&gt;&gt; Yield 54 g (95%). Melting point = 354 ° c. Table 7 provides data on the yield and characterization of the pyridinium salts 27, 28, 30 and 31. Table 7: Yield characteristics of pyridinium salts Identification of pyridinium salts (abbreviations) Starting amine yield (%) Melting point CC) TGA 5 wt% Loss temperature (°C) 27 (TPPy-BF4) Aniline.X 87 253 420 ~ 28 (phenoxy-TPPy-BF4;) 4-phenoxyaniline Η2Ν^Ό 95 202 420 30 (isopropylphenyloxy-TPPy-BF4) cumylphenoxyaniline 94 284 420 31 (BAPP-TPPy-BF4) ΒΑΡΡ 95 354 "400 The data in Table 7 shows that the bismuth salt has a very high and surprising degree of thermal stability/thermogravimetric analysis (TGA) as a benchmark. The temperature loss of 5% by weight found by the salt is higher than that of C. In contrast, the starting bismuth salt 'four said (four) 2,4'6-triphenyl-money, under the test plan used, Not far from the lower stability, and showing a 5% by weight loss under the boot. Preparation of an organic clay composition containing a four-stage pyridinium cation 59 General method for the preparation of organic clay compositions is generally Explain how to prepare an organic clay composition containing a key cation. Therefore, give cumene phenoxy group here to chat 123170 -96 - 200900449 Synthetic. Packed in a 5 liter round bottom flask equipped with a mechanical stirrer, filled with sodium montmorillonite (40 g of 'mole equivalent) and deionized water (3 liters). The solution was sprayed and heated to 85 C. The montmorillonite was well dispersed. The solution of cumene phenoxy-TPPy-BF4 3G (31.4 g of _6 mol) in acetonitrile (625 ml) was added to the suspension of sodium montmorillonite. In the liquid, it was taken for 1 minute. After adding the salt solution, the reaction mixture was further given for 3 hours at 85 ° C. The modified montmorillonite was collected by hydrazine and hot water (2 liters, 赃) The strip was washed to remove the inorganic salt by-product NaBF4^ to further purify the modified clay (organic clay composition) by arbitrarily dissolving it in acetonitrile (2 liters) at 6 Torr. To remove any excess pyridinium salt. The purified clay was dried under vacuum at 15 G ° C for 24 hours' and ground to obtain a fine powder (50.3 g, 80% yield). Example 60 modified Large-scale de-soil synthesis in Pfaudler's 50-gallon stainless steel container (container 1} at room temperature, 47 G of montmorillonite (10) De) Clay, added to the deionized water of the ascending and falling. When dispersing the clay, heat the mixture to 8 〇t. Prepare a solution of the organic modifier in a Brightonl O gallon stainless steel container (container 2). 'The way is to stir 352 grams of cumene phenoxy _Tppy_BF4 3 ❶ modifier into 7 liters of acetonitrile' and heat to 8 〇. 'Until all organic salts are dissolved. The salt solution was added over a period of about 1 minute and in the main reactor Yin, the montmorillonite was constantly stirred at 80 C. When the two liquids were equilibrated to the starting temperature C. The reaction mixture was stirred at 8 Torr for 6 minutes. Mixing is effective and no part of the reaction mixture is excluded. After mixing, the modified clay mixture is gravity transferred to a filtered centrifuge equipped with a micron filter bag. 123170 • 97· 200900449 The machine is operated at low and high speeds, and the hardened cake is made of modified clay. By placing the clay back in the container 1, the modified clay was washed with 47 liters of water and allowed to mix for 15 minutes at 8 Torr. Once again, the modified clay mixture was tampered. Then, the modified clay was re-washed with 15 liters of acetonitrile by placing the clay back in the vessel 1, and under the _ (four) for 15 minutes. The clay is again k; the X is removed from the unexchanged organic modifier. The soil in the centrifuge basket was briefly rinsed with methanol to help dry the uniformity. Make the modified clay without fines in low temperature vacuum, pull, T+&gt; with two nine phases (100 C) or in a centrifuge

Gas, dry overnight, plaque + A ^ Grind the clay in a PCT mixer to obtain a blister to further dry in a 150 C vacuum oven, followed by further push to obtain a low at about 70% yield (&lt; 2%) Very fine powder of moisture content. . About the characteristics of the series of organic clay compositions, Yunding data is available at k. The title &quot;C's experiment tongue county 0 / 丨丨 master - each "continued re-reading table is measured in the experimental group of organic clay group π 八 L,, τ carbon weight percentage". The title, the experimental weight of Ή indicates that it exists in the experiment of the organic clay composition towel (4) score ratio &quot;etc. Similarly, the 'title' &quot;calculated weight % c&quot; means that it is present in: a calculated weight percent carbon in a clay composition, and the like. Experiment of machine c Weight % Test of Weight % Experimental weight % Na Calculated weight % C Calculated weight % Η

Prime analysis nanoclay ^ t ^ a sodium montmorillonite

TPPy-MMT

phenoxy-TPPy-MMT 123170 -98- 200900449 The further characteristic of the organic clay composition is that the "burning percentage of inorganic ions by organic ions" is taken from the viewpoint of "quoting the ratio of inorganic ions to "exchange percentage" of organic ions, using carbon combustion analysis data, hydrogen combustion Analyze data and sodium ion concentration data. The data is presented in Table 9, and although the degree of exchange shows a slight change depending on the analytical method used for the calculation, all three methods show extensive exchange of sodium ions by the pyridinium cation. Table 9: Percentage exchange of D-spacing organic clay composition with organic clay composition and percent ion exchange (%) Based on C analysis, based on Η analysis, based on Na analysis, d spacing by XRD (A) sodium montmorillonite Soil... --- ... 11 TPPy-MMT 76 108 91 19 phenoxy-TPPy-MMT 80 106 94 19 cumene phenoxy-TPPY-MMT 72 94 91 23 BAPP-TPPy-MMT 75 100 94 19 Contains Preparation of a polymer of a quaternary phosphonium cation-organic clay composite composition Example 61 A melt mixing experiment using an ODPA-DDS polyether oxime imine polymer to test a polyether quinone imine comprising a structural unit derived from ODPA and DDS The chain-growth behavior in the presence of an organic clay composition containing a ruthenium-arylpyridinium cation was performed on a Haake Rheomix instrument. A low molecular weight polymer consisting essentially of structural units derived from ODPA and DDS was melt blended with TPPy-MMT at a 5% by weight decanoate content at 390 ° C and 40 rpm. Monitor changes in torque over a 60 minute period. The same experiment was carried out with the same low molecular weight polymer, no additional organic clay, and the use of cumene PA-mATPP-MMT, an organic clay composition containing cations. In each of the three experiments, samples were taken at different time intervals from 123170 to 99 to 200900449 and the molecular weight was measured. From the molecular weight and torque data, it is determined that the low molecular weight polymer is present in the presence of an organic clay composition comprising a pyridinium cation and in the absence of organic clay, the molecular weight is increased. In contrast, the conversion of the polymer to a higher molecular weight polymer in the presence of a scale nanoclay (organophenyl PA-mATPP-MMT) comprising an organic scale cation 15 relative to a composition comprising an indole cation The behavior with compositions that do not contain organic clay is slow. Example 62 BPADA-DDS-aniline polyether quinone imine with 7 wt% layered decanoate TPPy-MMT - 0 0 〇 BPADA-DDS-aniline polyether oximine in a 3 liter round bottom flask filled with DDS (54.28 g, 〇_2186 mol), cumene phenoxy-TPPy-MMT (43.8 g) and veratrol (7 g). The resulting mixture was shaken for 3 hours at a 40% output setting using a 450W model of a Brans〇n vibrator 450 having a 固态.5&quot; diameter solid state probe. After the sound vibration, the mixture became extremely thick and difficult to stir. At this time, DDS (6112 g, 0.2461 mol), BPADA (25 g, Kirin Mo), aniline (1 g, _ _ Mo) and cucurbit ether (700 g) were added. The reaction mixture was mechanically stirred and heated to 200. (:, after a period of two hours, and held at this temperature for another 3 hours, and collected in a Dean-Stark gas cylinder for azeotropic removal of water. When the theoretical amount of water has been removed, about 5 The cucurbit ether was removed and the resulting mixture was allowed to cool to room temperature and poured into 0 liters of methanol in a high speed blender. The product polymer·organic clay composite composition was filtered, 123170-100-200900449 and the filter cake was rinsed with 500 ml of decyl alcohol, and dried in a vacuum oven at 150 ° C for 24 hours, then at 200 Another 24 hours (350 g, 88% yield) at °C. Example 63 Preparation of ODPA-DDS-aniline with 7 wt% layered decanoate TPPy-MMT ODPA-DDS-aniline polyether quinone imine: Typical procedure for ODPA-DDS polyether oxime synthesis is as follows. ODPA (15.18 kg) was added to a stirred glass-lined reactor having 123.65 kg (kg) of oDCB and 0.35 kg of aniline. Using oil heating, the reactor was heated to 180 ° C and 8 kg of oDCB was removed. The reactor was cooled to about 120 ° C and 11.215 kg of DDS was added and stirred. The oil temperature was raised to 155 ° C for 210 minutes and the slurry temperature reached about 146 ° C. Water begins to release; a nitrogen sweep is used to help remove water from the reactor. The oil temperature was raised to 171 ° C and in this case held for 115 minutes. When water is released, the reaction temperature is increased to about 166 °C. The slurry is still easy to stir. The oil temperature was raised to 186 ° C and the reaction temperature was increased to about 177 ° C for the next 25 minutes. DDS incorporation was judged to be sufficient to further increase the oil temperature to 195 ° C to obtain a reaction slurry temperature of 179 ° C. In the next hour, 45 kg of condensate was removed. The heat was reduced and the reaction was cooled to 50 °C. No stickiness of the polymer was found. The precipitated polyether oximine was removed from the solution by centrifugation at about 12 ° C using a 5 micron centrifuge bag. The polymer was dried in a double cone dryer at 15 °C. The resulting powder was passed through a 2 mm screen. In a 3 liter round bottom flask, DDS (41.14 g, 0.1657 mol), isopropylphenylphenoxy-TPPy-MMT (19.9 g) and veratrol (350 g) were added. The resulting mixture was modeled using a 450 W model of a Branson vibrator 450 having a 0.5" diameter solid state probe, and sonicated for 3 hours at a 40% output setting. After the sound vibration, the mixture 123170 101 - 200900449 became extremely concentrated and It was difficult to stir. At this time, DDS (3171 g, 〇1277 mol), ODPA (95 g, 0.303 mol), aniline (〇 714 g, 〇〇〇77 mol) and cucurbit ether (300 g) were added. The reaction mixture was mechanically stirred and heated to 200 ° C for a period of two hours and maintained at this temperature for an additional 3 hours, and the water removed in azeotropic manner was collected in a Dean-Stark gas cylinder. When the theoretical amount of water has been removed, about 250 ml of the cucurbit ether is removed and the resulting polymer mixture is allowed to cool to room temperature overnight. Then, decyl alcohol (3 liters) is added and stirred. The formed polymer_organic clay composite composition powder was separated by filtration, rinsed with 500 ml of methanol, and dried in a vacuum oven at 150 C for 24 hours, followed by 2 at 24 ° C. Hour (158 g, 88% yield). Example 64 contains N-aryl Film of the pyridinium cation polymer/organic clay composite composition The film of 3 inches wide and 4 mils thick was extruded from the resin composition containing 31% by weight of the polymer produced in Example 63. - an organic clay composite composition (DpA_DDS polyether quinone containing 7 wt% of layered decanoate τρρρΜΜτ) and 69% by weight of the polymer prepared in Example 62_organic clay composite composition (containing 7 Weight percent layered bismuth citrate xppy-MMT BPADA-DDS polyether quinone imine. A 16 mm PRISM extruder equipped with a vent/finish screw and a 3 inch film die was used. Feed at a rate of about 0.5 min. The screw speed is set at 2 〇〇 φ 1 η, the electric cylinder temperature is 370 ° C, and the film die temperature is 380 ° C. During the film extrusion, the die pressure is Approximately 1500 psi. For the purpose of comparing the effect of organic clay on the pressure of the die, a similar composition but lacking the organic clay. Thin film 123170 -102- 200900449 The film is dusted on the same extruder system, and the die is measured. And found only about _ 泗. GPC analysis of the film showed that the polymer established the amount of the knife in the film extrusion process. Although the film was formed by wrinkles, the TEM image of the film showed relatively poor dispersion of TpPy_MMT organic clay in the polyimide matrix. The relatively poor dispersion of organic clay is reflected in

In the -, σ fruit, relative to the unfilled control sample, only 18% CTE was found to decrease. This is due to the fact that the relative moderateness of the c TE salt per weight % is lower. GPC spot r.TF of pressure_film analysis sample melting point* (kg/mole) Mw (kg/mole) Μη (kg/mole) CTE 0-200°C (ppm/°C) Starting material 28.8 36.9 15.6 NA extruded film Jfe ff 1,1, Λτ ^ .. 50.5 52.2 20.7 50 peak molecular weight&quot; The data collected in Table 10 confirms that the molecular weight of the polymer organic clay composition can be significantly increased by extrusion It is added as a film. Examples 65-72 contained 31% by weight of BPADA-DDS polyetherimine with 69 weight percent. ODPA-DDS polyether phthalimide resin blend polymer·organic clay composite composition and film made therefrom prepared a series of polyether sulfimine (ODPA-DDS polyether ruthenium or BPADA) A polymer-organic clay composite composition of -DDS polyetherimine) and an organic clay composition (cumenylphenoxy-TPPy-MMT), and is shown in Table 11 below. In each of Examples 65-68, the diamine was DDS and the blocking agent was aniline. The amount of blocking agent in each of Examples 65-68 was adjusted according to the "target" molecular weight. Two molecular weight standards were prepared for each resin, 25 kg/mole (&quot;Lo&quot;) and 3 〇 public 123170 -103 ~ 200900449 kg/mole γ·). Table 11: Polyimine composition containing cumene phenoxy-TPPy-MMT Example of polymer anhydride Mw Μ η (kg / mol) Anhydride / amine ratio wt % citrate Mw (kg / mo Ear) Μη (kg/mole) 65 ODPA-DDS Polyether quinone imine-Hi ODPA 30 15.6 1.02 7 30.6 14.8 66 ODPA-DDS Polyether quinone imine-Lo ODPA 25 13.1 1.02 7 26.0 13.0 67 BPADA-DDS Ether quinone imine-Hi BPADA 30 22.0 1.00 7 78.9 30.4 68 BPADA-DDS polyether quinone imine-Lo BPADA 25 18.3 1.00 7 58.0 24.6 Next, 31% by weight of BPADA-DDS polyether quinone and 69% by weight ODPA- A blend of DDS polyether oxime polyimides was prepared from the individual resins of Examples 65-68 and four films of different molecular weight combinations were extruded (Table 11). These combinations were used to study the effect of molecular weight on film ductility at 7 wt% citrate loading. A 16 mm Prism extruder with a 3 inch film die with a vent/finish screw was used. These combinations are silvered at a rate of 0.5 pounds per hour. The screw system was set at 200 RPM, the electric cylinder temperature was 380 ° C, and the film die temperature was 390 ° C. The die pressure is approximately 1200 psi. The data on the extruded film is collected in Table 12. 123170 -104- 200900449 Table 12: Combination of polyether quinones as a polymerized resin component of a polymer-organic clay composite composition. Example of an extruded film Polyimine blend composition Resin extruded film Mw (kg/mole) Μη (kg/mole) Mw (kg/mole) Μη (kg/mole) ctemi^i secondary heating, 0-200. . (ppm/°C) 69 31% by weight ODPA-DDS Polyether sulfimine-Lo 69% by weight BPADA-DDS Polyether quinone imine-Lo 46.9 18.9 49.5 20.2 nd* 70 31% by weight ODPA-DDS Polyether 醯Amine-Hi 69% by weight BPADA-DDS Polyether quinone imine-Lo 65.9 22.8 56.9 21.9 nd 71 31% by weight ODPA-DDS Polyether quinone imine-Lo 69% by weight BPADA-DDS Polyether phthalimide-Hi 46.3 19.1 51.8 21.2 nd 72 31% by weight ODPA-DDS Polyether sulfimine-Hi 69% by weight BPADA-DDS Polyether quinone imine-Hi 57.8 20.8 61.0 23.6 44 Control group 31% by weight PDFS48 ODPA-DDS Polyether quinone imine 69 Weight % Combination BPADA-DDS Polyether sulfimide 40.1 15.3 50.5 21.7 61 \ *nd =&quot;Untested&quot; The data of the extruded film shows that the molecular weight of the ODPA-DDS polyether sulfimide resin is improved. It is represented in a polymer-organic clay composite composition comprising an organic clay composition of cumene phenoxy-TPPy-MMT. Thus, in Example 69, a film of a polymer-organic clay composite composition of a low molecular weight ODPA-DDS polyether fluorene imine resin and a low molecular weight BPADA-DDS polyether oxime resin was prepared, after extrusion. Molecular weight, equivalent to a control blend that does not contain organic clay. However, although the control group was a film sample having an extension of 123170 - 105 - 200900449, Example 69 was brittle. In the four film samples of Table 12 containing the polymer·organic clay composite composition, only the film of Example 72 (&quot;ft"'Hi&quot;) was found to be a wrinkle film which was reliable and often The ductility index used. This result indicates that a higher molecular weight polymeric resin is necessary to compensate for the decrease in ductility due to the relatively large amount (7 weight percent) of the phthalate present in the film. TEM image of the film of -TPPy-MMT, showing that the organic clay system is well dispersed in the polymer matrix. The TEM analysis is consistent with the CTE metric. Compared to the unfilled control group, the overall CTE is found to be 28%. This is equivalent to a 4% reduction in CTE per percentage of strontium loading. A film comprising a polymer_organic clay composite composition, as shown in Example 69_72, is sometimes referred to as &quot ; nanocomposite film&quot;, which is due to the extremely high level of exfoliation of the organic clay composition contained in the polymer-organic clay composite composition used to prepare the film. Salt Preparation Example 73 Preparation of 4-iodo-phenoxy-benzophenone A 1000 ml 3-neck round bottom flask equipped with a Dean-Stark gas cylinder, a condenser, a stir bar and a nitrogen adapter was charged with 4-iodine. Phenol (19_〇克, 0.086 mol), 4-fluorobenzophenone (15.72 g, 0. 〇79 mol), potassium carbonate (7.16 g, 0.0518 mol), DMF (157 ml) and hydrazine Benzene (16 ml). The resulting mixture was stirred and refluxed for 2 hours under nitrogen atmosphere (solution temperature ~16 (TC). During this time, the water system was collected at the gas cylinder. After 2 hours, The reaction was cooled to room temperature and water (400 mL) was added to the reaction mixture, and the desired product was precipitated from the solution as a creamy white solid. The product was allowed to recrystallize by 123170 • 106· 200900449. Further purification from isopropanol (400 ml) gave the desired product as a white crystalline solid (25 g, 87% yield). Example 74 4-(4-phenylmethyl-phenoxy) iodide Synthesis of _phenyltriphenyl scale 32

Pi η in a 250 ml 3-neck round bottom flask equipped with a condenser and a nitrogen inlet tube, 4-iodo-phenoxy-benzophenone (25 gram, 〇〇624 mole), triphenyl Phosphine (% (16.38 g '0.0624 mol), acetic acid (0.14 g, 0.624 mmol) and degassed diphenylbenzene (125 ml). Argon was bubbled through the solution for 1 hour to remove oxygen. The mixture was refluxed for 2 hours at which time a dark orange solution was formed. The reaction mixture was allowed to cool to room temperature, and the salt was separated from the dimethyl ester to afford a dark orange solid phase. Methane/methanol developing solution, using TLC ^ Μ], the product was subjected to flash chromatography, and the product was purified by using a mixture of 6 〇 (500 g) and a solvent of 5% methanol. Impurity, followed by the desired squamous salt 32 (4 g, 82% yield), which was isolated from the ν solvent and separated by a milky yellow powder. Two gasified double _4_(triphenyl squamous) diphenyl Preparation of ketone. Pack 20 ml capped test tube with nitrogen scrubbing and add

The mixture was separated by 2 liters of diethyl ether and collected by vacuum filtration. By GC_MS sub-123170 107. 200900449, two absorption peaks were observed, _ corresponding to the single-scale product and the second to the second-scale product. The final single yield is L1 grams. Preparation Example 75 of a polymer organic clay composite composition containing a quaternary cation containing phenyl fluorene derived from 4-(4-benzoyl-phenoxy)-phenyl-triphenyl iodide Synthesis of sodium montmorillonite PhEK-MMT organic clay composition in a 5 liter round bottom flask equipped with a mechanical stirrer, filled with sodium montmorillonite (3 gram gram .03 mol) and deionized water (2.5 liters) ). The solution was stirred and heated at 85 ° C until the montmorillonite was well dispersed. The solution of the scaly salt 32 (22 8 g, 0.034 mol) in acetonitrile ((iv)(d)) was warmed to about thief and then added to a suspension of sodium montmorillonite for 1 minute. After the addition of the salt solution, the reaction mixture was stirred at 85 ° C for about 3 hours. Hunting filter collects organic clay compositions (sometimes referred to as modified montmorillonite or simply modified clay) and washes with hot water (2 liters, 8 〇. 〇) to remove In addition to inorganic salt impurities and exchange reaction sodium iodide by-product. The modified clay was further purified by redispersing under thief in acetonitrile (2 liters), followed by filtration to remove any excess cerium salt. The purified clay was dried under vacuum at 150 C for 24 hours and ground, and it was taken as a fine powder (40 g, 72% yield). Synthesis of bis-4-(triphenylscale)benzophenone_MMT in a 500 ml beaker, filled with 2 ml of water and 〇7183 g of bis-4-(triphenylphosphonium) diphenyl ketone. The mixture was heated to reflux over 2 hours. After cooling to room temperature, the organic clay was centrifuged, washed with two 2 ml portions of deionized water, and collected by centrifugation. 123170 -108- 200900449 Preparation of a polymer organic clay composite composition containing a quaternary cation containing a phenyl fluorene Example 76-78 comprising a polymer on the PEEK side _ an organic clay composite composition will be a PEEK 450G tree Low temperature grinding, #3 mm mesh. The resulting material has a mixture of fine powder and larger particles. The ground material was passed through a 1 mm screen&apos; and fine powder particles were collected. This grinding is necessary to pass through the small straight 16 mm extruder and to ensure good mixing of the ground clay. /' 1 \ The ground resin was blended with the powdered ancestor-form (Ref. Example 75 for preparation) in an amount corresponding to the inorganic ceric acid loading amount of %. Two other organically modified clays (Examples 77 and 78) were also prepared for the comparison of the chemical structure of organic cations for the polymer_organic clay composite composition! Therefore, the blend of the ground PEEK45〇G resin was also made into an isopropenyl-MMt with an organic clay composition (Example 77) and π&gt;Ρ_ΜΜΤ (Example 78), an organic scale-containing cation ^ The organic clay composition, the preparation thereof is shown in the examples of the present disclosure. The tearing is an organic: soil composition containing the salt layer of the material of the quaternary tetracycline (tetra) and can be used herein. The method disclosed in the method is shown in the table. The amount of the organic clay red compound and the polymer resin used in the example is shown in the table. The formulas are mixed by placing the two components in a plastic bag' Vibration for a few minutes. 123170 200900449 Table 13 Example control group 76 77 78 Polymer resin PEEK 450G PEEK 450G PEEK 450G PEEK 450G Tellurate loading 0% 5% 5% 5% Organic clay composition without PhEK-MMT cumene -MMT* TPP-MMT** Weight % in clay Cyanate 0% 65% 58% 75% Weight of organic clay composition gram grams 16.92 grams 18.97 grams 14.67 grams PEEK 450G weight 220.00 grams 203.08 grams 201.3 grams 205.33 grams The total weight of the formula is 220.00 g 220.00克220.00克220.00克*Organic clay composition The preparation of cumene-MMT is shown in Example 15. **TPP-MMT is an organic clay composition derived from sodium montmorillonite and tetraphenylphosphonium halide. After shaking, a mixture of the organic clay composition and the polymeric resin was extruded at 0.5 lbs per hour on a 16 mm twin screw extruder (L/D = 25) having co-rotating and intermeshing screws. The extrudate was granulated. The granules collected for each material were compression molded into a thin disc at a low throughput (0.5 lb/hr) using a hot press. The disc was subjected to TEM analysis to determine The degree of dispersion. The results are collected in Table 14. Table 14: TEM analysis results Example Organic clay composition Polymer resin TEM evaluation 76 PhEK-MMT PEEK 450G Good dispersion 77 cumene·ΜΜΤ PEEK 450G Poor dispersion 78 ΤΡΡ-ΜΜΤ PEEK 450G poorly dispersed transmission electron microscopy (TEM) analysis of the extruded polymer-organic clay composite composition (Example 76) of PeEK-MMT modified clay in PEEK, showing good organic clay composition Dispersed in polymerization In the matrix, the dispersion obtained was superior to those found in Examples 77 and 78. No 123170-110-200900449 and large talc-like clays were seen, and most of the clays showed a small stack of salt layers. The height of the organic clay composition is shown to the polymer base. The enhanced dispersion found with respect to the polymer-organic clay composite composition of Example 76 is due to the structural similarity between the polymeric resin used and the organoclay composition used. The ancestor resin and the organic clay composition _ clear system contains a 4-phenyloxy substituted benzophenone moiety. None of the organic clay compositions employed in Examples 77 and 78 contained a 4 aryloxy substituted benzophenone moiety. Transmittance electron microscopy (ΤΕΜ) analysis of the extruded polymer rhyme-clay composite composition of Example 78 (c-phenylene-hydrazine-modified clay in the soil) showed relatively poor dispersion. A large class of organic clay compositions, talc, can be seen in the transmission electron micrographs taken and show that at least a portion of the organic clay composition does not completely flaking into the pro-polymeric matrix. The results of the ΤΡΡ-ΜΜΤ modified clay (Example 78) in PEEK also show a relatively poor dispersion of the organic clay composition in the polymeric resin. A large class of clay talc can be seen in the transmission electron micrographs taken, and it is shown that at least a portion of the organic binder composition is not completely exfoliated into the PEEK polymer matrix. Preparation of Polymer-Organic Clay Composite Compositions Using Melt Mixing Technique in Compositions Substantially Free of Polyetherimine Compositions Examples 79-81 The following examples illustrate the use of the procedures provided by the present invention to prepare polymers. An organic clay composite composition which is substantially free of polyether oxime 123170-111 - 200900449 amine and which has a peeling degree of at least ίο% of the compositional organic clay composition. Therefore, 70 g of a polymer resin (see Table 15 below) was combined with 4.98 g of the organic clay composition BAPP-TPPy-MMT. The powder was blended by shaking in a closed container for 2 minutes. The resulting mixture was heated in a HAAKE mixing drum at 50 rpm. The mixture was maintained at the temperature according to Table 15. The molten mixture in the HAAKE mixing drum was sampled every five minutes. A 15 minute sample was pressed into a film between two sheets of Teflon liner foil at 760 °F. Next, the film samples were subjected to analysis by thermomechanical analysis and CTE, and were measured in the range of 30 to 200 °C. The pressed film had the CTE values listed in Table 15. Table 15: Polymer-organic clay composite composition prepared by melt mixing

Examples Polymeric Resin Organic Clay Composition Mixing Temperature Film CTE (30-230 〇C) 79 PEEK 150P BAPP-TPPy-MMT 380 〇C 67 ppm/. . 80 PPSU* BAPP-TPPy-MMT 340〇C 61 ppm/°C 81 PES**(ULTRASON E2010) BAPP-TPPy-MMT 330〇C 54 ppm/°C *PPSU = RADEL R,** PES =Polyether 飒The data in Table 15 demonstrates that the polymer-organic clay composite composition substantially free of polyether sulfimine can be subjected to a method according to the present invention by passing a quaternary organic clay composition with a polymeric resin at about 300 ° C. It is prepared by melt-mixing at a temperature in the range of about 450 ° C. The data indicates that in order to achieve a high degree of spalling (&gt; 10% spalling), the polymeric resin and organic clay composition should be melted at a greater shear force than would normally be provided in a low shear mixer such as a Haake mixer. mixing. The composition of Xianxin 79-81, after melt mixing has been carried out in a high shear environment, has achieved a peeling of more than 10%, such as 123170 - 112 - 200900449 between about 300 C and about 450 C A twin-screw extruder operating at temperatures within the range. Preparation of a polymer-organic clay composite composition in a composition comprising a polymylinimide using a melt mixing technique Example 82 Preparation of a polymer-organic clay composite composition comprising a polyether sulfimine/' 0.20 g of clogosite clay (Southern Clay Company, 0.000926 cationic equivalent per gram) was dispersed in 200 ml of water with vigorous stirring. 0.692 g of methylene blue was added to the dispersion, and the mixture was heated under reflux for 60 minutes. Then, the mixture was cooled to room temperature, and the product organic clay composition (modified clay) was separated by centrifugation. The moist clay was washed twice by redispersing in 200 ml of DI water and by centrifugation and separation. The washed moist clay was dried at 12 °t for 2 hours, followed by grinding to give a fine blue-gray solid. 5.19 g of the above-prepared organic clay composition (methylene blue, modified clay) (4% by weight vermiculite) and 59 85 g of oxydiphthalic anhydride were added to 365 ml of oDCB, and the container was immersed In a bath vibrator, and heated until a fine clay dispersion resistant to settling is obtained. Then, the flask was fitted with an overhead stirrer and a Dean_Stark gas cylinder, and 牝% g DDS and 0.08978 g aniline were added. The mixture was stirred, and the dispersion of the water powder was removed by distillation. Then. Use 100 ml of oDCB to rinse the DDS to a suitable temperature and slowly heat to reflux for three hours. After heating under reflux for 18 hours, fines were obtained. The dispersion was transferred to a Haake melt mixer, and the solvent was removed by devolatilization at 390 C and 50 rpm for 60 minutes from 123170-113 to 200900449. Samples were taken at 5 minute intervals during devolatilization. Under the bribe, a 15-minute sample was pressed into a film between two Teflon liner boxes. Next, the film samples were subjected to analysis by spectroscopic CTE by thermomechanical analysis at 30 to. Measure within C range. The film had a cTEM ppm/C with a 14.8% peeling. Examples 83-93 First, a series of polymeric (tetra) organic clay composite compositions comprising poly-bonded imines were prepared using one of the melt mixing, field polymerization or solvent mixing techniques contemplated herein (see, for example, Example 27-29). Spot polymerization technology). The material is obtained from this polymerization process in a large solid block of dry cake. The cake was broken into a number of 4 pieces, and the pieces were ground into a fine powder using a fine grinder and a 3 mm mesh screen. Then, the fine powdery polymer-organic clay composite composition is extruded alone or mixed with another powdery polymer-organic clay composite composition and extruded. The extruder used is a 16 mm twin screw extruder (L/D = 25) with co-rotating and intermeshing screws configured to allow the polymer-organic clay composite composition to be directly removed. Filming, or first granulating, and then forming a film in a second bunking step. The snail design provides melting, mixing, devolatilization, and transport of the ruthenium polymer/organic clay composite composition from the feed inlet of the extruder to the exit of the film die. A 3" (3 inch) or 6 (6 inch) mold is used routinely to convert a polymer-organic clay composite composition containing a polyetherimine in a molten state into a film. In Example 83.85, the powdered polymer-(4) soil composite system was first granulated using a 123170-114·200900449 16 mm Pnsm extruder with a venting/finishing screw and a 3 mm granulation die. Organic clay composition - The polymer resin mixture (Polymer #End Blend) is at a rate of &quot;Hunger&quot;. The screw speed is set at 25 (), the electric cylinder temperature is under the air, and the head pulse is at 385. (: The pellets from the facing M are in a vacuum supply box, dried overnight under the boots, and used a single screw extrusion with a 6, wide film die and a barrier 31 screw Welex ΐ·ι/4” The machine presses out the film. The extruder screw system f \ at a rate of 4 lb / h &quot; starvation feed &quot;, and the screw speed is 25 RPM. The die gap is about 8 mils, and the thin tether is extruded. With a film take-up unit, pull down at various speeds to obtain a film of many different thicknesses. - Generally speaking, when flowing out of the die with a slit, the molten resin is pulled and the roll is pulled, and the roll speed can be adjusted. In order to pull down the film at a faster rate than the molten polymer-, machine-clay composite composition leaving the die, the film is thinned and stretched. The circulating oil passing through the inside of the roll allows the maintenance of the characteristic μ degree. The film is extruded using a cooling cast film process in which the system is configured in an "S-cladding" configuration in which the film is wound around the middle and bottom rotating rods to allow sufficient time to cool the heat transfer. A group of pro (swing) pull film On the film, keep the film in close contact with the front. Then 'film is passed through the roll' and collected on the take-up I. Other conventional film processing equipment can also be used. Preparation of polymer containing polyacrylamide - organic clay An example film of the composite composition, and the degree of thermal expansion (CTE) of the selected diterpene sample in the mechanical and transverse directions. The test results are collected in Table 16. 123170 115· 200900449 Table 16 CTE and glass transition temperature (Tg) of extruded film of polymer-organic clay composite composition as polymer component A 100% BPADA-DDS polymer Example % Citrate modifier process CTE1 CTE2 % Falling MD /TD Tg°C Extrusion control group 0 — 58.2 — ... 2x 83 5 TPP Melt mixing * 48.4 ... 15% / 2x 84 5 14 Melt mixing 45.0 ... 20.9% / 2x 85 10 14 Melt mixing 39.9 ... 28.2% / 2x 86 5 15 Solvent mixing** 48.7 50.9 14.5%/ 10.5% 233 87 10 15 Solvent mixing 38.4 41.8 30.9%/ 24.9% 226 88 5 14 Field polymerization t 39.6 42.0 30.5% / 26.3% 240 89 10 14 Spot polymerization 33.7 34.2 39.3 %/ 38.5% 236 9 0 5 15 Field polymerization 39.9 44.6 29.9%/ 21.6% 241 91 10 15 Spot polymerization 31.6 33.5 43.1% / 39.7% 233 92 5 15 Spot polymerization 39.2 44.9 31.2% / 21.1% 239 93 5 15 Spot polymerization 43.6 45.2 23.3% / 20.6 % 238 * A polymer-organic clay composite composition was prepared using a melt mixing technique (see Examples 76-78). ** Solvent mixing techniques (see Examples 52-53) were used to prepare polymer-organic clay composite compositions. The on-site polymerization technique (see Examples 27-29 and 38-51) was used to prepare a polymer-organic clay composite composition. Polymer-organic clay composite composition 123170-116-200900449 was prepared via on-site polymerization and in combination with proof stoichiometry. Example 94 comprises an organic clay composition of 1,2-dimethyl.3_hexadecylphosphonium cation. Prepared in a 2-liter three-necked round bottom flask equipped with an overhead mechanical stirrer, adding chlorohexadecane (260 g, U 〇m), u dimethylimidazole (9) gram, 〇95 莫And 03⁄4 CN (500 ml), and the two-phase reaction mixture was stirred in an oil bath at 80 C. After 72 hours, the reaction mixture was cooled to room temperature and the product was crystallised overnight. The solid which had been crystallized was filtered, washed thoroughly with cold, and dried under vacuum at 7 (TC for 3 days to give i, 2, dimethyl hexyl hexyl imino) as a slightly off-white solid 220 g, 62% yield In a 2 liter, three-necked round bottom flask equipped with an overhead stirrer, add dracisite (dg iSite) (30 g, Southern Clay, USA) with deionized water (1 liter) and clay Stir mechanically for 2 hours at room temperature. In this clay dispersion, add cesium chloride, 2·didecyl·3_hexadecyl hydrazine solution (16 g, in 200 ml) via a pipette. Medium), and the reaction mixture was briefly heated to 8 (rc, over 2 hours, and stirred at room temperature overnight. The precipitate was filtered, washed with cold water, and finally washed thoroughly with CH^OH, and vacuum at 7 (TC) Drying for 3 days gave the product organic clay composition as an off-white solid (33g, 94% yield). Example 95 was polymerized on site and combined with stoichiometric proof to obtain a polyether phthalimide containing BPADA-DDS and modified with hydrazine Clay (7% citrate loading) polymer-organic clay composite composition in SILVERSON high shear mixer Add the mash-modified clay (14 grams) and oDCB (450 ml) and heat the mixture to 12 °c for 2 hours while maintaining intense mixing. Hybrid system with SILVERSON high shear mixer The tank is equipped with a heating belt and a temperature controller. The contents of the 123170 • 117- 200900449 tank are introduced into the bottom of the SILVERSON mixer. The recirculation line is further connected to the SILVERSON mixer to return to the tank. After cooling to room temperature, the reaction mixture was transferred to a 2-liter three-necked round bottom flask equipped with an overhead mechanical stirrer, a Dean-Stark gas cylinder and a condenser. BPADA (74. 2 g) was added to the flask, and The mixture was stirred at 150 ° C. After 2 hours, DDS (29.4 g) was added, and the oil bath temperature was gradually increased to 210 ° C, and the reaction was allowed to continue for another 3 hours. During the polymerization, the reaction mixture was tested at least Once, and if necessary, add a diamine or dianhydride to achieve the desired pre-selected stoichiometry. The polymerization is then continued. After the polymerization, the reaction mixture is cooled and precipitated into CH3OH. Filtration and vacuum drying gave the product polymer-organic clay composite composition as a brown solid which showed a CTE of about 37 ppm / ° C. Example 96 BPADA-DDS polyether phthalimide at 7 wt% cumene In the presence of phenoxy-Tppy-MMT layered citrate, the on-site polymerization and stoichiometry proved that the degree of polymerization was 30. Using aniline as the end capping agent, DDS (280 g, 1.128) was added to a 12 liter round bottom flask. Mohr), cumene phenoxy-TPPy-MMT (280 g) and veratrol (5.5 kg). The mixture was homogenized for 45 minutes using a Fisher Scientific PowerGen rotor-fixer homogenizer (manufactured by Omni International) equipped with a 32 mm mineral tooth tip at 9000 RPM. The resulting mixture was sonicated for 2 hours at a 70% setting using a 1500W model of the Autotune series of high-strength Ultrasonic processors equipped with a 1-inch pair of diameter solid-state probes. After the sound vibration, the mixture became extremely thick and difficult to stir. In a 10 gallon reactor, fill the dispersed clay mixture DDS (458.8 g, 1.848 mol), BPADA (1600 g, 3.004 mol), aniline (11.68 g, 123170 _ 118· 200900449 0.125 mol) and gourd Ether (4 kg). The reaction mixture was mechanically stirred and heated to 200. (:, over a period of two hours, and held at this temperature for an additional 2 hours, and the water distilled from the reaction mixture was collected. A 1 gram sample of the reaction mixture was taken, and the solvent was removed under nitrogen and 35 〇〇c. The residual polymer sample was pressed into a film, and the infrared (IR) spectrum of the film was measured, and the ratio of the amine end group to the anhydride end group was determined. From the IR spectrum, the polymer sample was found to contain 〇·4 mol% excess amine. Using this information, the reaction stoichiometry was adjusted by adding BPADA (6_4 g) to correct the excess amine content. Then, the reaction mixture was allowed to stand at 2 Torr for another hour. When no further release of water was found When the '3 liters of verazone was steamed from the reactor' and the resulting mixture was allowed to cool to room temperature overnight. The reaction mixture was poured into methanol (5 liters) at ambient temperature in a high speed blender. The formed powder was transferred to a filter centrifuge equipped with a micron filter bag. The product polymer-organic clay composite composition was rinsed with an additional 1 liter of sterol. The powder was collected and placed in a vacuum oven at 15 〇°c The polymer-organic clay composite composition (2175 g, 86% yield) was purified by drying for 24 hours and then at 200 ° C for 24 hours. Example 97 BPADA-DDS polyether oxime On-site polymerization and stoichiometry in the presence of 30B stratified lithospermite using the SILVERSON mixer (laboratory online mixer assembly L4R_pA type 'square hole high shear filter, at ~6〇 Pump in ML/min, install according to Example 95) to mix the organic clay with the solvent. Heat 27 ml of o-dichlorobenzene (〇DCB) with 180 ml of cucurbit ether to 80 ° C and pass the SILVERSON mixer Send. Add the organic sulphide group of closexite (cl〇isite) 3〇B (13 56g) and bisphenol A dianhydride 123170 -119- 200900449 (BPADA) (74.51g) to the σ Circulating solution

In the agent. The mixture was passed through a recycle pole 1. W. The placket is passed through a SILVERSON high-shear mixer at 6,000 rpm for 45 laps. Φ Γ (four) 45 knives. The solution temperature was from 56. (: Increase to 79 ° C. The resulting solution is transparent, and the surface is peeled off from the organic clay mixture. The mixture is transferred to a 1 liter three-necked scorpion and a beryllium bottle. Then, the flask is mounted on an overhead stirrer. Collect the gas bottle with Dean-Stark and place it on the right side. The double crucible is heated to 1 °°〇 in oil cooling. Add 33.88 g of 4,4′-diamine to run it! 7 Base sulfone (DDS). The mixture was stirred and heated to reflux. Water was removed by co-storage distillation. Phthalic anhydride (0.86 g) was added and allowed to react for 2 hours. 〇克*式' and remove the solvent under nitrogen and 35G ° C. The residual polymer sample is pressed into a film 'and the infrared (10) spectrum of the film is measured, and the ratio of the guanamine end group to the anhydride end group is determined. The spectrum was found to contain a 〇5 mol % excess needle. This information was used to adjust the reaction stoichiometry by adding DDs 2 gram to correct the excess needle content. Then, the reaction mixture was kept at ° C for an additional hour. A second 1 G gram sample or reaction mixture was treated as described above. The polymer sample was found to contain α5 mol% excess anhydride from IR (d). An additional 0.189 g of DDS was added to the reaction mixture and allowed to react for an hour. At this point, heat is removed&apos; and the reactants are allowed to cool to the chamber. The resulting viscous mixture was transferred to a Haake melt mixer and mixed at 39 Torr (with 5 〇 1 : {3111) for 6 knives. At 5 minute intervals, the sample was removed. At 760T, A 15 minute sample was pressed into a film between two sheets of Teflon lining foil. Next, the film samples were subjected to analysis by thermomechanical analysis and CTE, and were measured in the range of 3 Torr to 200 °C. 123170 200900449 Example 98 Field-on-site polymerization and stoichiometry of BPADA-DDS polyetherimine in the presence of cliosite 15A layered phthalate. Use SILVERSON mixer (laboratory line mixer assembly L4R-PA type) , square hole high shear filter, pumped at ~600 ml / min) to mix organic clay and solvent. Heat 270 ml of o-dichlorobenzene (oDCB) and 180 ml of verazone to 60 ° C, and Pumped by a SILVERSON mixer. Organic clay composition containing cliosite 15A (13.51 g), 4,4'-diaminobiphenyl hydrazine (DDS) (33.90 g) and 1 ml of acetic acid , slowly added to the recycled solvent. The mixture is passed through the SILVERSON high shear in a recirculating mode. The mixer was operated at 6000 rpm for 45 minutes. The solution temperature was increased from 60 ° C to 86 ° C. The resulting solution was viscous and showed peeling of the organic clay. The mixture was transferred to a 1 liter three-necked flask using 50 The ml was transferred to the oDCB to complete the transfer. Then, the flask was mounted on an overhead stirrer and a Dean-Stark gas cylinder, and placed in an oil bath, which was heated to 140 ° C. 70.02 g of bisphenol A was added in two portions. Anhydride (BPADA) over 15 minutes. The mixture was stirred and heated to reflux for 2 hours. Water was removed by azeotropic distillation. phthalic anhydride (0.86 g) was added and allowed to react for 3 hours. 10 g of the reaction mixture was sampled, and the solvent was removed under nitrogen at 350 ° C. The residual polymer sample was pressed into a film, and the infrared (IR) spectrum of the film was measured, and the amine terminal group was determined to the terminal group of the anhydride. Proportion. The polymer sample was found to contain 4.7 mol% excess anhydride from the IR spectrum. Using this information, the reaction stoichiometry was adjusted by adding DDS (1.55 g) to correct the excess anhydride content. Then, the reaction mixture was allowed to be at 200°. Keep 3 small under C An additional 0.6 g of DDS was added and allowed to react for 1 hour. A second 10 g sample or reaction mixture was treated as above. From IR light 123170 • 121 - 200900449 β Lu found that the polymer sample contained 〇·8 mol % excess liver. An additional 31 grams of DDS was added to the reaction mixture and allowed to react for 1 hour. At this point, heat was removed and the reaction allowed to cool to room temperature. The resulting viscous mixture was transferred to a Haake melt mixer and mixed for 6 minutes at 39 ° C with 50 rpm. At 5 minute intervals, the sample was removed. At 76 ,, a 15-minute sample was pressed into a film between two Teflon-lined pigs. Next, the film sample was subjected to analysis by thermomechanical analysis and CTE at 3 Torr to 2 Torr. (: In-range metric. Obtain 40.1 ppm/C (28.6% spalling). The examples are only illustrative and are only used to illustrate some of the features of the present invention. The accompanying claims are intended to claim the present invention. As it has been constructed in a wide variety, and the examples presented herein are illustrative examples of selected specific embodiments from a wide variety of possible embodiments. The intention of the applicant is attached. The claims are not limited to the choices used to illustrate the examples of the features of the present invention. When used in a claim, the words "package" &quot;Fengan-, 丄Ζ, grammar variants, logically include and include Changes and differences, such as, but not limited to, basically consist of, and "when necessary, the scope has been provided, and such ranges are inclusive of all sub-ranges. Day L _ expects that the variation in these dry circumferences will be the result of a general skill in the art, and in the case of undisclosed

In the case of such changes, I.κ', where possible, should be interpreted as being covered by the accompanying request.介:w The development of science and technology is expected to make the equivalent of things equivalent. It is obvious that the language is not tight and is not covered. But in the case of such variations. It should also be interpreted as being covered by the request attached to the text. 123170 • 122· 200900449 [Simplified description of the drawings] Fig. 1 shows the formed film of the invention having a nano silicate loading of 7%, a mechanical direction CTE of 33.0 ppm/°C, and a Tg of 255 °C. 123170 -123 -

Claims (1)

200900449 X. Patent Application Range: L. A method for producing a polymer-organic clay composite composition, the method comprising: comprising a fourth-order organic clay composition comprising an alternating inorganic silicate layer and an organic layer, the organic layer comprising four The organic cation is melt-mixed with the polyether quinone composition; &quot;Heil melt mixing is about 300. (: enthalpy at a temperature in the range between about 45 (rc) to provide a polymer-organic clay composite composition characterized by a percentage of at least a percentage of ι. The method of claim 1, wherein the fourth-order organic cation has the structure R9 R8·Q-Rl〇ιφ R7 XXXIX 123170 200900449 C2-C50 aromatic group; to the number of about; ν is the number of c-head cRr in the mother-existence is independent of the halogen atom, ci-c2. An aliphatic group, a c^o nucleoside group or an aromatic group; R2 is a dentate aliphatic group, a c5-c20 cycloaliphatic group, a c2_c aryl 1 chain; and X- is a charge balance counterbalance ion. 5 gather "object 5. The method of claim 3, which is a four-level town. Cation has structure xxxm , , xxxm where Ar1 2, Ar13, δ»·]4 η A 1 5 &quot; _ 6 Γ is independently a C2 _C5 〇 aromatic group; and r is. Hey. A fluorene aromatic group or a polymeric bond comprising at least one aromatic group. 6. The method of claim i, wherein the fourth organic cation is a quaternary cation. 7. The method of claim 6, wherein the quaternary ammonium cation is a pyridinium cation having a structure XXV ^ , ^ XXV ', , &amp; 7 and ^8 are independently &&lt;5〇 aromatic groups; V, is 〇 to 2, 目r; R3 is independently a halogen atom in each presence (4). The aliphatic group, 匕5-720 cycloaliphatic group Γ^β is called a C2 〇 group; and Ar&quot; is a C2-C2 〇〇 aromatic or a polymer bond containing at least one aromatic group. 8. As in the case of claim 6, the quaternary ammonium cation is a structure _1 123170 200900449 pyridinium cation 4 丄Λ ▽ XXVI wherein Ar, Ar7 and Ar8 are independently % 〇 aromatic groups · "b, 〇 to 2 = sub 2 is 0 to 4; R, R4 are independent in each - existence For the soil mass ' Ζ is a bond, two 僧 ρ» ρ its _ _ 1-20 month 曰 group, divalent c5-c20 cycloaliphatic so-link:: C2-C2 ° aromatic group, oxygen linkage a group, followed by 2 people connected to a knot group or Se linking group; and ~ (10) package 3 at least - a polymer chain of an aromatic group. 9 · As in the method of claim 1, the inorganic citrate is poor The layer is derived from inorganic clay 'selected from the group consisting of kaolin, - tongue ancient &amp; 1 person 丄 - heavy π Ling soil, pearl clay, watery kaolin fruit % stone, chrysotile, 辇 pullite stone, fish r wax Stone, earthworm de-soil 'Bed stone, smectite stone, strontium zinc Zn-alumina, strontium magnesium steel record stone, white four stone Xiyuan acid mica, ^ &gt; pearl mica, talc, vermiculite, phlogopite , green crisp mica, chlorite and combinations thereof. "Mother, 4 10. If the claim 1 soil, method, wherein the inorganic silicate layer is derived from inorganic clay including synthetic clay. 11. The distance between the intervening layers of the request item 1 $ f, , + is characterized by a mid-gate spacing 、 , and the polymer_organic clay composite composition is from about 5 to about 100 angstroms. 12. The method of claim i wherein the poly-imide composition is incorporated into the polymer, selected from the group consisting of polyethanes, polysaturated hydrocarbons, polyacetates, polyfluorene 123170 200900449 amines, polylithic winds, Polyether oxime, polyphenyl sulphide, polyether ketone, ψ J 1 蜒 ether _, abs, polystyrene, polybutadiene, poly(acrylate), flat a; ash (alkyl acrylate), polyacrylonitrile, Polyacetal, polycarbonate, polystyrene, g-vinyl acetate copolymer, polyvinyl acetate, liquid crystal polymer, aromatic polyester, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride, poly Fluorine, polydivinylidene, polytetrafluoroethylene&apos; and a combination comprising at least one of the foregoing polymers. 13. The method of claimant wherein the polylysine composition comprises agglomeration. As in the method of the request, wherein the polylysine composition contains a poly shout. 15. The method of claim 1, wherein the melt mixing is carried out in an extruder. 16_ as requested! The method in which the melt mixing is carried out in a kneader. 17. The method of claim wherein the polymer/organic clay composite composition is characterized by a percentage of at least 20 percent exfoliation. The 18' species, the crucible comprises a polymer_organic clay composite composition, the polymer-organic clay composite composition comprising: (4) a four-stage organic clay composition comprising an alternating inorganic tellurite layer and an organic layer, The organic layer comprises a quaternary organic cation; and (b) a polyether quinone composition; the s-organic-organic clay composite composition is characterized by at least a percentage of flaking. 19. The article of claim 18 which is a film. 20. The article of claim 18, which is a solvent cast film comprising a polyether having a composition of two components and a diamine component and having a Tg between about 850 ° C and about 45 ° C. a) a CTE of less than 7〇ppm^c; b) a thickness of between about oi micrometers/250 micrometers; and a residual solubility of less than $wt% of 123170 200900449 21, a polymer/organic clay composite A method of the composition, comprising: 'in a press machine, 'a fourth-order organic clay composition comprising an alternating inorganic lithitic acid layer and an organic layer, the organic layer comprising a quaternary organic cation' and comprising at least one polyether The polyether quinone imine composition of the quinone imine and at least one other polymer is melt-mixed. The other polymer is selected from the group consisting of polyamines, polyesters, polyaryl sulfides, polyaryl ethers, Polyethersulfones, polyether ketones, polyetheretherketones, polyphenyls, and polycarbonates; the molten mixture is carried out at a temperature of about 30 (rc and about 45 (in the range between rc) to provide Polymer-organic clay composite composition, the polymer _ organic clay composite The characteristics of the composition as a percentage of exfoliation at least 1〇 percentages. 2 'as item 21 ^ kiss seeking method, wherein the organic quaternary cation having the structure χ 123170 200900449 Ar. The method of claim 21, wherein the quaternary organic cation has the structure χχν XXV wherein Ar6, Ar7 and Ar8 are independent main p ^ ^ . are C2-C50 aromatic groups; &quot;b" is 0 to The number of 2; R3 in each of the places where you are independent of the tooth atom, Cl_c2 〇 aliphatic group, c5-c20 cycloaliphatic group or (: Γ, 广' 2. 2 〇 heart group; Ar&quot; is C2_C2. An aromatic group or a polymer chain containing at least one aromatic group. 123170 200900449 VII. Designated representative figure: (1) The representative representative of the case is: (1). A brief description of the symbol of the representative figure: (No description of the symbol of the component) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 123170