HK1172360A

HK1172360A - Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers

Info

Publication number: HK1172360A
Application number: HK12112996.5A
Authority: HK
Inventors: ．加恩 J
Original assignee: 陶氏环球技术有限责任公司
Priority date: 2004-05-28
Filing date: 2012-12-17
Publication date: 2013-04-19

Description

Phosphorus-containing compounds useful for making halogen-free ignition resistant polymers

this application is a divisional application of the chinese patent application having the title "phosphorous-containing compound useful for making halogen-free ignition-resistant polymers" filed on 5/20/2005 under the application number 200580017144.7.

Technical Field

The present invention relates to phosphorus-containing compounds; their use as flame retardants for polymers, especially for epoxy resins, polyurethane resins, thermosetting resins and thermoplastic polymers; and the use of these flame retardant-containing polymers for the manufacture of protective coating formulations and ignition resistant articles such as electrical laminates, polyurethane foams, and various molded and/or foamed thermoplastic products.

Background

Ignition resistant polymers typically employ halogen-containing compounds to provide ignition resistance. However, there is an increasing demand for halogen-free compositions in the ignition resistant polymer market. It has been proposed to use phosphorus-based flame retardants in thermosetting epoxy resin formulations instead of halogenated flame retardants, as described in EP A0384939, EP A0384940, EP A0408990, DE A4308184, DE A4308185, DE A4308187, WO A96/07685 and WO A96/07686.

However, there is still a need for further improvement of flame retardancy. There is also a need to improve the manufacture and performance of ignition resistant polymer compositions.

Thus, there remains a need to provide halogen-free polymer compositions having good ignition and heat resistance; which overcomes the disadvantages of prior art compositions that exhibit low properties such as low moisture resistance and low Tg.

Disclosure of Invention

One aspect of the present invention relates to a method for producing a phosphorus-containing compound, comprising reacting (a) with (B):

(A) at least one organophosphorus compound containing a group selected from H-P ═ O, P-H and P-OH; and

(B) at least one compound having the following formula (I):

formula (I) [ R' (Y)_m’]_m(X-O-R”)_n

Wherein

R' is an organic group;

y is a functional group capable of reacting with an epoxy, ethoxy or propoxy group, said Y being selected from the group consisting of hydroxyl, carboxylic acid, carboxylic ester, anhydride, amine, -SH, -SO₃H、-CONH₂-NHCOOR, phosphite and phosphonite groups;

x is an alkylene group;

r "is hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms;

r is an alkyl or aryl group having 1 to 12 carbon atoms; and is

m', m and n are independently a number equal to or greater than 1.

Another aspect of the present invention relates to a phosphorus-containing compound (referred to herein as "Compound (I)") obtainable according to the above process, particularly a phosphorus-containing compound comprising the reaction product of:

(B) at least one compound having the following formula (I):

formula (I) [ R' (Y)_m’]_m(X-O-R”)_n

Wherein

R' is an organic group;

y is selected from the group consisting of hydroxy, carboxylic acid, carboxylic ester, anhydride, amine, -SH, -SO₃H、-CONH₂Functional groups of-NHCOOR, phosphonite, and phosphate groups;

x is an alkylene group;

r "is hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms, R is an alkyl or aryl group having 1 to 12 carbon atoms;

m', m and n are independently a number equal to or greater than 1.

More particularly, the phosphorus-containing compound is a phosphorus-containing compound containing at least two phenol aromatic rings preferably connected by an alkylene or alkylene ether group and having a phosphorus content of at least 4 wt.%.

Other aspects of the invention include, for example, compounds, compositions and/or formulations that can be made by reacting, blending or mixing compound (I) with other components (e.g., a thermosetting resin or a thermoplastic or a mixture of a thermosetting resin and a thermoplastic) to form various ignition resistant compounds, compositions or formulations that can be used in applications such as prepregs, laminates, coatings, molded articles and composite articles.

For example, one aspect of the present invention relates to a phosphorus-containing epoxy compound which can be obtained by reacting at least one of the above-mentioned phosphorus-containing compounds (compound (I)) with at least one compound containing one epoxy group per molecule (e.g., epichlorohydrin, glycidyl ethers of polyphenols (e.g., bisphenol a, bisphenol F, phenol novolac resins, cresol novolac resins), glycidyl ethers of methacrylates, glycidyl ethers of acrylates, and other similar compounds). Such phosphorus-containing epoxy compounds may also be mixed with at least one curing agent, and optionally at least one crosslinkable epoxy resin in addition to the phosphorus-containing epoxy compound, to give a curable ignition-resistant epoxy resin composition. Such epoxy resin compounds and phosphorus-containing epoxy compounds are useful in the manufacture of prepregs, which are useful in the manufacture of laminates and circuit boards useful in the electronics industry. The epoxy compound can also be used to coat metal foils such as copper foil to make resin coated copper foil for use in the so-called build up (built up) technology.

Another aspect of the present invention relates to a phosphorous epoxy resin curable formulation comprising (I) a compound (I), (ii) an epoxy resin or a mixture of epoxy resins, (iii) optionally, a co-crosslinking agent, (iv) optionally, a catalyst and (v) optionally, a Lewis acid.

Yet another aspect of the present invention relates to a benzoxazinyl-containing compound, which can be prepared by reacting: (i) at least one of the above-mentioned phosphorus-containing compounds having a phenol function or an amine function (compound (I)) is reacted with (ii) a primary amine and formaldehyde or with (iii) a hydroxyl-containing compound and formaldehyde to form a phosphorus-containing benzoxazine compound. Also useful in the present invention are benzoxazine compounds that generate polybenzoxazines upon heating.

Yet another aspect of the present invention relates to a curable flame retardant epoxy resin composition comprising (i) the above-described phosphorus-containing, benzoxazine-containing compound, (ii) a crosslinkable epoxy resin, or a mixture of two or more epoxy resins containing more than one epoxy group per molecule, (iii) optionally a curing agent and (ii) optionally a curing catalyst to give a curable flame retardant epoxy resin composition. Such curable flame retardant epoxy resin compositions are useful in the manufacture of prepregs, which are useful in the manufacture of laminates and circuit boards useful in the electronics industry. The epoxy compound can also be used to coat metal foils such as copper foil to make resin coated copper foil for so-called assembly technology.

Another aspect of the invention relates to a phosphorus-containing compound containing thermolabile groups, which can be prepared by reacting: (i) at least one of the above-mentioned phosphorus-containing compounds having a phenolic function, compound (I), and (ii) a thermolabile group-containing compound, such as a tert-butoxycarbonyl-containing compound, are reacted to form a modified phosphorus-containing compound. The modified phosphorus-containing compound is stable at room temperature, and its thermolabile group decomposes at high temperature to generate a gas. These modified phosphorus-containing compounds can be mixed with different thermosetting systems to generate bubbles, thereby enclosing the gas in a cross-linked system or lighter weight product with lower dielectric constant and loss factor, while adequately controlling the processing temperature.

Yet another aspect of the present invention relates to a polyol, which can be prepared by reacting: (i) at least one of the above-mentioned phosphorus-containing compounds, compound (I), and (ii) an ethoxy group and/or a propoxy group. Such polyols are useful intermediates for making ignition resistant polyurethane resins.

The phosphorus-containing compound of the present invention, compound (I) and derivatives thereof, may also be mixed with at least one thermoplastic resin to produce an ignition-resistant thermoplastic composition.

The phosphorus-containing compounds of the present invention, compound (I) and derivatives thereof, may also be mixed with at least one thermoplastic resin and a thermosetting system (epoxy and curing agent) to make a thermosetting composition containing ignition resistant thermoplastic material.

Other aspects of the invention will become apparent from the following detailed description and claims.

Definition of

The terms "organic" and "organic" as used herein refer to compounds or moieties containing carbon and hydrogen atoms and optionally heteroatoms (i.e., atoms other than carbon or hydrogen) primarily covalently bonded to each other. Preferred optional heteroatoms include oxygen and nitrogen atoms. The number of heteroatoms in the organic compounds and moieties is less than the number of carbon atoms, preferably less than half the number of carbon atoms.

The terms "hydrocarbyl" and "hydrocarbylene" refer to chemical structures or moieties that contain carbon and hydrogen atoms covalently bonded to each other. Such structures or moieties may contain atoms other than carbon and hydrogen (referred to herein as "hetero" atoms) so long as the hetero atoms do not add significant reactive functionality to the moieties. An example of such an acceptable heteroatom is an ether oxygen atom. These moieties preferably do not contain any heteroatoms.

The expression "substantially free", as used herein when used with respect to a particular substance, means that the starting material or product typically contains less than 10 wt%, preferably less than 5 wt%, more preferably less than 1 wt%, more preferably 0 wt% of the particular substance.

The expression "wt%" means "weight percent".

Phosphorus-containing Compound, Compound (I)

The phosphorus-containing compound of the present invention, referred to herein as compound (I), can be produced by a reaction between an organophosphorus compound, referred to herein as component (A), and a compound of formula (I), referred to herein as component (B). One of the advantages of the compound (I) is that it contains phosphorus in its chemical structure, making it useful as a raw material for preparing flame retardant materials. Another advantage of compound (I) is that it contains active hydrogen groups, making it useful as a reactive starting material for reactions with other polymers. For example, the compound (I) may contain an active hydrogen group such as a hydroxyl group, which makes it reactive with an epoxy resin. In this embodiment, compound (I) may be considered as a cross-linking agent, curing agent or hardener for epoxy resins.

The compounds (I) generally have a phosphorus content of at least 4% by weight, preferably at least 6% by weight, which makes them useful as flame-retardant materials. The compound (I) is preferably substantially free of bromine atom, more preferably substantially free of halogen atom. The compounds (I) can also be used as non-reactive additives, for example when used with thermoplastic or other thermosetting systems. For example, compound (I) may be used as a charring agent to provide a carbon insulation layer for thermoplastic and thermoset formulations at high temperatures.

A compound conforming to formula (I), component (B)

Compounds falling within the scope of formula (I) above are also referred to herein as component (B).

In formula (I), each (-X-O-R ') group may be bonded to the same or different atom in "R'. Preferably, each (-X-O-R ") group is bonded to a different atom in" R' ".

"X" preferably has 1 to 8, more preferably 1 to 4 carbon atoms. In a preferred embodiment, "X" is an alkylene group having 1 to 8, preferably 1 to 4, more preferably 1 or 2 carbon atoms, such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene. Methylene is the most preferred "X" group.

"R" "may be a hydrogen atom or a hydrocarbyl group having 1, preferably at least 2, more preferably at least 3 carbon atoms and preferably up to 20, more preferably up to 12, up to 6 and more preferably up to 5 carbon atoms. The hydrocarbon group is preferably an alkylene group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, and octyl. The R "groups are most preferably methyl, butyl and isobutyl.

"R'" preferably contains at least one arylene group and optionally at least one alkylene or alkylene ether group. "R'" more preferably contains at least two aromatic groups connected to one another by alkylene or alkylene ether groups. The aromatic group is preferably a phenyl group, the alkylene group is preferably "X" as defined above, most preferably a methylene group, and the alkylene ether group is preferably a methyleneoxy group.

"Y" is a functional group capable of reacting with an epoxy, ethoxy, or propoxy group. The "Y" functional group is preferably selected from hydroxyl (-OH), carboxylic acid (-C (O) OH), carboxylic acid ester (-C (O) OR' "), carboxylic acid anhydride, primary OR secondary amine (-NH)₂-NHR "" or ═ NH, where "═" means covalent double bonds bonded to the same or different atoms of "R'"), -SH₅、-SO₅H、-CONH₂NHCOOR, and phosphonite (HO-P [ R ] "]₂O), OR phosphites (H-P [ OR "]₂＝O)。

"R" "can be an alkali metal, such as Na⁺Or K⁺Or contain up to 8Hydrocarbon groups of one, preferably up to 4 and more preferably up to 2 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl.

"R" "is hydrogen or a hydrocarbyl group, such as aryl, alkyl or alkaryl, preferably having up to 20, more preferably up to 12, more preferably up to 4 carbon atoms.

The carboxylic acid anhydride is preferably selected from substituted or unsubstituted succinic, maleic and phthalic anhydrides. When present, each substituent is one or more hydrogen atoms or a hydrocarbyl group, for example an alkyl group preferably having up to 12, more preferably up to 4 carbon atoms.

For the R "" group, hydroxyl, carboxylic acid and carboxylic acid anhydride functionalities are preferred, with hydroxyl functionalities being most preferred.

Preferred compounds of the formula (I) are those corresponding to the formula (I), [ R' (Y)_m’]_m(X-O-R”)_nAnd at least one (X-O-R') group is in the center of the backbone of the chemical structure. For example, preferred compounds include those in which at least one of the same R' (Y)_m'those compounds which contain at least two (X-O-R') groups in the group. In addition, compounds useful in the present invention include, for example, those that meet the following criteria:

(a) n is preferably greater than m; or

(b) When n is equal to 1, m must be greater than 3 and at least one (X-O-R') group is in the middle of the main chain of the chemical structure; or

(c) When m is equal to 1, n must be greater than 1; or

(d) When n is equal to 2, at least one (X-O-R') group must be in the center of the backbone of the chemical structure.

In formula (I), m' is preferably less than 10, m is preferably less than 100, and n is preferably less than 200.

Preferred compounds of formula (I) may be represented by the following formula (II):

formula (II)

[Ar(Y)_m’-X’]_a[Ar(Y)_m’-X]_b(X-O-R”)_n

Wherein each "Ar" is independently an aryl group, preferably a phenyl group, optionally substituted with one or more groups having 1 to 4 carbon atoms (e.g., methyl, methoxy, carbinol, ethyl, ethoxy, ethanolyl, propyl, propoxy, propanolyl, isopropyl, isopropanolyl, butyl, butoxy, butanoyl), preferably selected from alkyl, alkoxy and alkanol, e.g., tolyl and/or xylyl; at least one (X-O-R') group on at least one Ar group; "n", "m", "X", "Y" and "R" have the same meaning as in formula (I); "X'" are each independently X, X-O-X, or X-O-X-O-X; "a" and "b" each independently represent a number equal to or greater than 0, but not both 0.

In formula (II), "a" is preferably at most 100, "b" is at most 100, and "n" is preferably at most 200.

More preferred compounds of formula (I) may be represented by the following formula (III):

formula (III)

(R”-O-X)_c[Ar(Y)_m’-X-O-X]_a[Ar(Y)_m’-X]_b[Ar(Y)_m’]_b’(X-O-R”)_d

In formula (III), "Ar", "m'", "a", "b", "X", "Y" and "R" have the same meaning as in formula (II); subscripts "b", "c", and "d" each independently represent a number equal to or greater than 0. In formula (III), "c" is preferably at most 200 and "d" is preferably at most 200.

The "Y" group is preferably bonded directly to the Ar group. Examples of preferred "Ar (Y)" include phenol, cresol and xylenol, and their corresponding divalent counterparts.

The (X-O-R') group in each unit with subscripts "c" and "d" greater than 0 is directly bonded to a member of the "Ar" group of another unit of formula (III) having the same or different unit formula.

The units bearing subscripts "a", "b'" and "b" may be present in any order, in random or block configuration. Each of the subscripts "a", "b'", "c", and "d" independently is preferably at least 1. Each of subscripts "a", "b'", "c", and "d" independently is preferably 0, more preferably at least 1, and even more preferably at least 5; more preferably at least 10 and preferably not more than 1000, more preferably not more than 100. In one embodiment, subscripts "a", "b'", "c", and "d" are independently preferably no greater than 50, more preferably no greater than 30, and even more preferably no greater than 10.

Preferred compounds of formula (I) may be further represented by the following formula (IV):

formula (IV)

Wherein "e" is an integer from 0 to 4; "f" is 1 or greater, and preferably less than 50; m', R ", Ar, Y, X," a "," b "," c "and" d "are as defined above for formula (III).

Preferred compounds of formula (III) may be represented by the following formulae, formula (V) and formula (VI):

formula (V)

Formula (VI)

Wherein each "R1" is independently hydrogen or an alkyl group having 1 to 10 carbon atoms;

"p" each independently represents a number of 0 to 4;

"a" and "b" each independently represent a number equal to or greater than 0;

"X", "Y" and "R" have the same meaning as in formula (III).

In a preferred embodiment, the compound of formula (III), component (B), may be prepared as follows: phenol, cresol, xylenol, bisphenol a and/or other alkylphenols (a) are first reacted with formaldehyde (b) to form monomeric, dimeric or higher condensation products. Subsequently, the condensation product resulting from the reaction of (a) with (b) is modified by etherification (partial or complete etherification) with at least one monomeric alcohol. The monomeric alcohol is ROH, wherein R is as defined above for formula (I). Examples of the resulting etherification products that can be used as component (B) are etherified resole resins as described, for example, in U.S. patent 4,157,324 and U.S. patent 5,157,080.

The component (B) produced by the reaction of the above-mentioned (a) and (B) preferably contains a small amount of a starting material (e.g., phenol, cresol, etc.) in the reaction product (i.e., the component (B))Bisphenol AAnd formaldehyde) as residual monomers, for example less than 3 wt.%, preferably less than 2 wt.% and more preferably less than 1 wt.%.

It is preferred in the present invention to use an etherified resol resin as component (B) rather than a non-etherified resol resin because etherified resols can be stored more stably at room temperature (about 25 ℃), whereas non-etherified resols are susceptible to self-condensation; also at elevated temperatures, generally above 25 ℃, preferably above 100 ℃ and more preferably above 150 ℃ and more preferably above 170 ℃ and generally below 250 ℃ and preferably below 220 ℃, resol resins tend to undergo self-condensation rather than reaction with the phosphorus compound of component (a). For the purposes of the present invention, it is therefore advantageous to select etherified resoles as component (B), which are less prone to self-condensation and tend to contribute to the main condensation reaction with component (a), for example via alkyl groups R ".

Preferred examples of condensation products prepared by the reaction of (a) and (b) as described above are described according to the following general chemical formula:

wherein "p" is independently an integer from 1 to 4; "R1" is independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

The above reaction provides a mixture of different isomeric condensation products having methylene or dimethylene ether linkages, e.g. (1) having two CH groups₂OH (one on each phenyl ring); or (2) having a CH on a benzene ring₂And (4) OH groups.

CH in the above condensation product described in the above chemical formula₂The OH groups are partially or completely etherified with an alcohol to provide component (B) useful in the present invention. In this embodiment, a mixture of different isomers of the condensation product may be formed.

The number average molecular weight of the compounds of formulae (I) to (IV) is preferably at least 50, more preferably at least 200, more preferably at least 500; and preferably no greater than 10,000, more preferably no greater than 8,000, and more preferably no greater than 5000. The weight average molecular weight is preferably at least 100, more preferably at least 400, more preferably at least 1000; and preferably not more than 15,000, more preferably not more than 3,000, and more preferably not more than 1,500.

Component (B) is preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

Examples of component (B) are shown in the following formula (VII):

formula (VII)

Wherein "R2" are each independently hydrogen, alkyl having 1 to 10 carbon atoms, CH₂OH or CH₂OR”；

Each "R1" is independently hydrogen or an alkyl group having 1 to 10 carbon atoms;

"R" "is hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms; and is

"b" represents a number equal to or greater than 0.

Some other examples of component (B) are shown in the following formulas, formula (VIII) and formula (VIIIa):

formula (VIII)

Formula (VIIIa)

"R" "is hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms; and is

"a" represents a number equal to or greater than 0.

Still other examples of component (B) are set forth in the following formulas, formula (IX) and formula (IXa):

formula (IX)

Formula (IXa)

Wherein "R" "is hydrogen or a hydrocarbyl group having 1 to 8 carbon atoms; "b" represents a number equal to or greater than 0; and is

"p" represents a number equal to or greater than 0.

Examples of commercially available products suitable for use as component (B) include SANTOLINK^TMEP560 (which is a butyl etherified phenol formaldehyde condensation product) and PhenodUR^TMVPR 1785/50 (which is a butoxymethylated phenolic resin described by the manufacturer as a highly butyl etherified resol based on a cresol mixture, having a weight average molecular weight of 4000 to 6000 and a polydispersity of 2 to 3). These products are available from the UCB Group (a company, headquartered in Brussels, Belgium) and its branch-UCB GmbH&Kg (a company built in germany). Other resole compounds available from UCB include, for example, PHENODURPR401, PHENODURPR411, PHENODURPR 515, PHENODURPR711, phenodurr PR 612, phenodurr PR 722, phenodurr PR 733, PHENODURPR 565, and phenodurr VPR 1775.

Other resole compounds available from Bakelite include, for example, Bakelite PF 0751LA, Bakelite PF 9075DF, Bakelite 9900LB, Bakelite 9435LA, Bakelite0746 LA, Bakelite 0747 LA, Bakelite 9858 LG, Bakelite 9640 LG, Bakelite 9098LB, Bakelite 9241LG, Bakelite 9989LB, Bakelite 0715LG, Bakelite 7616LB, and Bakelite 7576 LB.

Organic phosphorus-containing compound, component (A)

The organophosphorus-containing compound, component (a), may be selected from compounds containing groups selected from H-P ═ O, P-H and P-OH, each mono "-" or each "-" of the groups being a bond between the phosphorus atom "P" and the organic moiety. The phosphorus atom may be bonded to two separate organic moieties, or may be bonded to one organic moiety. When bonded to an organic moiety, the bond may be to the same atom of the organic moiety to form a double bond, or preferably may be a single bond linking the phosphorus atom to a different atom of the same organic moiety.

The aforementioned organophosphorus-containing compounds preferably conform to the following formulae (X) to (XXH):

formula (X) formula (XI)

Formula (XH) formula (XIII)

Formula (XIV) R^APH₂

Formula (XV) (R)^AO)₂P(O)H

R of formula (XVI)^AP(O)(OH)H

Formula (XVII) R^AP(O)(OH)₂

Formula (XVIII) R^AR^BP(O)OH

Formula (XIX) (R' O)₂P(O)H

Formula (XX) (R')₂P(O)H

R' P (O) (OH) H of the formula (XXI)

Formula (XXII) R' P (O) (OH)₂

Wherein "R^A"and" R^B"same or different, and is selected from substituted or unsubstituted aryl or aryloxy and hydroxy, provided that R^AAnd R^BNo more than one of which is hydroxy; "R^C"and" R^D"the same or different" is selected from the group consisting of alkylene and hydrocarbenylene. R^CAnd R^DPreferably each independently, more preferably each arylene.

Phenylphosphine is an example of formula (XIV), diphenyl or diethyl phosphite or dimethyl phosphite is an example of formula (XV), phenylphosphinic acid (C)₆H₅) P (O) (OH) H is an example of formula (XVI), benzenephosphonic acid (C)₆H₅)P(O)(OH)₂Is an example of the formula (XVII), dimethylphosphinic acid (CH)₃)₂P (O) OH is an example of formula (XVIII).

In a preferred embodiment, the organophosphorus-containing compound, component (A), corresponds to one of the following formulae (XXIII) to (XXVIII):

formula (XXIII) formula (XXIV)

Formula (XXV) formula (XXVI)

Formula (XXVII) formula (XXVIII)

Wherein R is¹To R⁸Each independently being a hydrogen atom or a hydrocarbyl group optionally containing one or more heteroatoms (e.g. O, N, S, P or Si), with the proviso that R¹To R⁴Not more than 3 of which are hydrogen atoms, and R¹To R⁸Two or more of which may be linked to each other to form one or more cyclic groups. R¹To R⁸The total number of carbon atoms is preferably 6 to 100.

In a more preferred embodiment, the organophosphorus-containing compound, component (A), corresponds to the following formula (XXIX):

formula (XXIX)

Wherein R is⁹Represents H, each R¹⁰Independently represent a hydrogen atom or a hydrocarbyl group optionally containing one or more heteroatoms (e.g. O, N, S, P or Si). Two or more R10 may be linked to each other to form one or more cyclic groups.

Preferred embodiments of the above-mentioned organophosphorus-containing compounds are described in more detail in EP-A-806429.

The organophosphorus-containing compound, component (A), is preferably 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (also referred to as "DOP"), for example "Sanko-HCA" (available from Sanko of Japan), or "Struktol polydis^TMPD3710 "(which is available from Schill of Germany)&Seilacher); dimethyl phosphite, diphenyl phosphite, ethylphosphonic acid, diethylphosphinic acid, methylethylphosphinic acid, phenylphosphonic acid, phenylphosphinic acid, dimethylphosphinic acid, phenylphosphine, vinylphosphoric acid; or mixtures thereof.

The above-mentioned organic phosphorus-containing compound, component (A), is preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

Component (A) and component (B)(B) To give compound (I)

To prepare compound (I), component (a) and component (B) are first blended or mixed together to form a reactive composition. The reactive compositions of components (a) and (B) are then subjected to a temperature sufficient to initiate a reaction between the two components, thereby producing compound (I).

Component (a) is mixed with component (B) in a reaction vessel and the mixture is heated at an elevated temperature preferably below the decomposition temperature of the starting materials. Generally, the reaction temperature is above 25 ℃, preferably above 150 ℃, more preferably above 170 ℃. The reaction is preferably carried out for a period of time sufficient to allow the H-P ═ O, P-H OR P-OH moiety of component (a) to react with the OR "moiety of component (B). The reaction time is usually 30 minutes to 20 hours, preferably 1 hour to 10 hours, more preferably 2 hours to 6 hours.

Since water readily reacts with component (a), the reaction of the present invention is preferably carried out in the absence of water (typically water is present in an amount of less than 5 wt%, more preferably less than 3 wt% and most preferably less than 1 wt%). Removal of alcohols and other volatile byproducts (e.g., other solvents generated as byproducts of the present reaction) often helps drive the reaction to completion. The pressure in the reaction vessel is therefore preferably reduced to a pressure below atmospheric pressure, for example 0.1 bar or less, to assist in the removal of alcohol or by-products at temperatures below the minimum decomposition temperature mentioned above. The reaction vessel is optionally purged with a gas or volatile organic liquid to further assist in the removal of by-products. The gas or volatile organic liquid is preferably inert to the contents of the reaction vessel.

Component (B) is often dissolved in organic solvents well known to those skilled in The art, such as butanol, xylene or Dowanol PM (trademark of The Dow Chemical Company); a portion of the solvent may be removed by heating the solution or applying a vacuum prior to adding component (a). The order of addition of component (A) and component (B) to the reaction mixture is not critical.

Components (A) and (B) are preferably mixed in a weight ratio of from 10: 1 to 1: 10, preferably from 5: 1 to 1: 5, more preferably from 2: 1 to 1: 2, most preferably from 1.1: 1 to 1: 11, based on the total solids content of the composition.

If desired, other materials such as catalysts or solvents may be added to the reaction mixture of components (A) and (B).

The phosphorus-containing product of the present invention, which is obtained from the reaction between component (A) and component (B), has a phosphorus content of preferably at least 4 wt.%, more preferably at least 6 wt.%. The phosphorus content of the compound (I) is generally from 4 to 12%, preferably from 5 to 9, more preferably from 6 to 8% by weight. Component (I) is preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

The Mettler softening point of compound (I) is generally higher than 100 ℃ and preferably higher than 120 ℃; and preferably below 250 c, more preferably below 200 c. For better storage, shipping and handling, the product is preferably a solid at room temperature (about 25 ℃).

In general, the compound (I) obtained by the reaction of component (A) with component (B) may be a mixture of one or more different oligomers.

Ignition resistant epoxy resin composition

In one embodiment of the present invention, the phosphorus-containing compound obtainable by reacting component (A) with component (B), compound (I), as described above, may be used as one component of a curable (crosslinkable) phosphorus-containing flame-retardant epoxy resin composition. In this embodiment, The curable phosphorus-containing flame retardant epoxy resin composition contains (I) a phosphorus-containing compound of The present invention, compound (I), (ii) at least one epoxy resin, such as selected from halogen-free epoxy resins, phosphorus-free epoxy resins, brominated epoxy resins, and phosphorus-containing epoxy resins and mixtures thereof, including but not limited to DEN 438, DER 330(DEN and DER are trademarks of The Dow Chemical Company), epoxy functionalized polyoxazolidone-containing compounds, cycloaliphatic epoxy resins, GMA/styrene copolymers, reaction products of Liquid Epoxy Resins (LER) with tetrabromobisphenol a (tbba) resins, DER 539, and reaction products of DEN 438 with DOP resins; and optionally (iii) at least one curing agent. The curable flame retardant epoxy resin composition optionally contains at least one additional crosslinkable epoxy resin or a mixture of two or more epoxy resins other than the above-mentioned component (ii). The curable flame retardant epoxy resin composition may also optionally contain at least one curing catalyst and at least one inhibitor. All of the above ingredients may be blended or mixed together in any order to form the curable phosphorus-containing flame retardant epoxy resin composition.

In another embodiment, compound (I) is first reacted with an epoxy compound to form a phosphorus-containing epoxy compound (referred to herein as "epoxy compound (I)"), and then the epoxy compound (I) is mixed with at least one curing agent to form a curable flame retardant epoxy resin composition. The curable flame-retardant epoxy resin composition of this embodiment optionally contains at least one additional crosslinkable epoxy resin or a mixture of two or more epoxy resins other than the above-mentioned epoxidized compound (I). The curable flame retardant epoxy resin composition described above may also optionally contain at least one curing catalyst and at least one inhibitor. This embodiment of the invention, which involves first forming the epoxidized compound (I), has the advantage of forming a low molecular weight epoxy compound which can be further formed into a larger molecular weight epoxide or mixed with other epoxy resins in a subsequent step. The epoxidized compound (I) can be obtained by reacting the above-mentioned (I) phosphorus-containing compound, compound (I) and (ii) at least one epoxy compound having at least one epoxy group per molecule. For example, the epoxy resin containing one epoxy group per molecule that can be used in the present invention may be epichlorohydrin. Using epichlorohydrin, it is possible to obtain epoxidized compounds (I) of lower molecular weight, for example resins having a molecular weight of less than 700. In another embodiment, higher molecular weight epoxy resins, such as those having a molecular weight above 700, can be prepared by reacting (I) the above-described phosphorus-containing compound, compound (I), and (ii) at least one epoxy compound containing at least one, preferably two or more epoxy groups per molecule.

For example, a crosslinkable phosphorus-containing epoxy compound, an epoxidized compound (I), can be obtained by reacting the above-mentioned phosphorus-containing compound, compound (I) with at least one epoxy compound having more than 1, preferably at least 1.8, more preferably at least 2 epoxy groups per molecule, wherein the epoxy group is a 1, 2-epoxy group. Typically, such polyepoxides are saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compounds containing more than one 1, 2-epoxy group. The polyepoxide may be substituted with one or more substituents such as lower alkyl. Such polyepoxides are well known in the art. Exemplary polyepoxides that can be used in the practice of the present invention are described in Handbook of Epoxy Resins, published by McGraw-Hill, New York, H.E Lee and K.Neville, 1967, and in U.S. Pat. No. 4,066,628.

The phosphorus element-containing epoxidized compound (I) can be used to form a curable epoxy composition with the addition of a crosslinking agent and optionally a catalyst to make a curable flame retardant epoxy resin composition.

The curable flame-retardant epoxy resin composition prepared according to the present invention, whether prepared by reacting a mixture of compound (I), an epoxy resin and a curing agent or by reacting an epoxidized compound (I) with a curing agent, can be used to make prepregs, which in turn can be used to make laminates and circuit boards useful in the electronics industry. The above curable composition can also be used for coating a metal foil such as a copper foil to manufacture a resin-coated copper foil for use in a so-called mounting technique.

Any epoxy resin that may be used in the above compositions in the practice of the present invention includes polyepoxides having the following general formula (XXX):

formula (XXX)

Wherein "R3" is a substituted or unsubstituted aromatic, aliphatic, alicyclic or heterocyclic group having the valence "q", which preferably has an average value of 1 to less than about 8. Examples of polyepoxides useful in the present invention include the diglycidyl ethers of the following compounds: resorcinol, catechol, hydroquinone, bisphenol a, bisphenol AP (1, 1-bis (4-hydroxyphenyl) -1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol a, phenol-formaldehyde phenol resin, alkyl substituted phenol-formaldehyde resin, phenol-hydroxybenzaldehyde resin, toluene-hydroxybenzaldehyde resin, dicyclopentadiene-phenol resin, dicyclopentadiene-substituted phenol resin, tetramethyl biphenol, tetramethyl-tetrabromobiphenol, tetramethyl tribromobiphenol, tetrachlorobisphenol a, and any mixtures thereof.

Examples of specific polyepoxides useful in The present invention include The diglycidyl ethers of bisphenol A sold by The Dow Chemical Company under The trademark D.E.R.330 with an Epoxy Equivalent Weight (EEW) of 177 to 189; halogen-free epoxy-terminated polyoxazolidone resins disclosed in U.S. Pat. No. 5,112,932, phosphorus-containing compounds disclosed in U.S. Pat. No. 6,645,631; a cycloaliphatic epoxide; and copolymers of glycidyl methacrylate ether and styrene.

Preferred polyepoxides include epoxy novolac resins such as d.e.n.438 or d.e.n.439 (trade marks of the dow Chemical Company); cresole epoxy novolac resins such as QUATREX 3310, 3410 and 3710 available from ciba geigy; tri-epoxy compounds such as TACTIX 742 (trade mark of Ciba Geigy Corporation of Switzerland, Basel); epoxidized bisphenol a novolac, dicyclopentadiene phenol epoxy novolac; glycidyl ethers of tetraphenylethane; diglycidyl ether of bisphenol a; diglycidyl ether of bisphenol F; and diglycidyl ethers of hydroquinone.

In one embodiment, the most preferred epoxy compound is an epoxy novolac resin (sometimes referred to as an epoxidized novolac resin, which term is intended to encompass both epoxy phenol novolac resins and epoxy cresol novolac resins). Such epoxy novolac resin compounds have the general chemical structure shown in formula (XXXI) below:

formula (XXXI)

Wherein "R4" is hydrogen or C₁-C₃Alkyl groups such as methyl; "r" is 0 or an integer from 1 to 10; "n" preferably has an average value of 0 to 5. A preferred epoxy novolac resin is one in which "R4" in formula (XXXI) above is preferably a hydrogen atom.

Epoxy novolac resins, including epoxy cresol novolac resins, are readily available, for example under The trade name d.e.n. (a trademark of The Dow Chemical Company) and QUATREX and tacix 742 (a trademark of Ciba Geigy). Commercially available materials typically comprise mixtures of various species of formula (XXXI) above, and a convenient method of characterizing such mixtures is by reference to the average value of the r values, r', for the various species. Preferred epoxy novolac resins for use according to the present invention are those having r' of from 0 to 10, more preferably from 1 to 5.

Further examples of epoxy-containing compounds which can be used in the present invention are the reaction products of epoxy compounds containing at least two epoxy groups with chain extenders as described in WO 99/00451. The preferred reaction product described in WO99/00451 which can be used in the present invention is an epoxy-polyisocyanate adduct or an epoxy-terminated polyoxazolidone as described in U.S. patent No. 5,112,932. The isocyanate compound as the chain extender includes, for example, diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), and isomers thereof.

The polyepoxides useful in the present invention are preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

Examples of polyepoxides which can be used in the present invention and are substantially free of halogen atoms are the phosphorous containing epoxy resins described in U.S. Pat. No. 6,645,631. Polyepoxides disclosed in U.S. Pat. No. 6,645,631 are reaction products of epoxy compounds containing at least two epoxy groups with reactive phosphorus-containing compounds, such as 3, 4,5, 6-dibenzo-1, 2-oxaphosphine (oxaphoshane) -2-oxide (DOP) or 10- (2 ', 5' -dihydroxyphenyl) -9, 10-dihydro-9-oxo-10-oxaphosphaphenanthrene-10-oxide (DOP-HQ).

As described above, a curable flame retardant epoxy resin composition may be formed by mixing (I) a phosphorus-containing product obtainable by reacting component (A) with (B), compound (I), (ii) at least one crosslinkable phosphorus-containing epoxy compound prepared according to U.S. Pat. No. 6,645,631, and optionally (iii) at least one curing agent; or a curable flame retardant epoxy resin composition may be formed by mixing (I) an epoxidized compound (I), at least one crosslinkable phosphorous-containing epoxy compound prepared according to U.S. Pat. No. 6,645,631, and (iii) at least one curing agent. The above curable epoxy resin composition may optionally contain at least one crosslinkable epoxy resin other than the crosslinkable phosphorus-containing epoxy compound in the above (ii).

Although the polyepoxides useful in the present invention are preferably substantially free of bromine atoms, and more preferably substantially free of halogen atoms, in some applications, halogen-containing epoxy resin compositions may be desirable. In these cases, The polyepoxide used in The present invention may be, for example, a brominated epoxy compound such as a brominated epoxy resin sold by The Dow chemical Company under The trademark DER 530 having an EEW of 400 to 450.

Any number of crosslinking or co-crosslinking agents may be used with any of the compositions described above in which the epoxy resin is present. Suitable co-crosslinking agents optionally present in admixture with the phosphorus-containing Epoxy compounds of the present invention include, for example, the polyfunctional co-crosslinking agents described in many documents, such as, for example, Vol.6 Encyclopedia of Poly.Sci. & Eng., "Epoxy Resins" at 348-56(J.Wiley & Sons 1986).

Other preferred co-crosslinkers are described in WO 98/31750. These co-crosslinking agents include, for example, molecular weight (M)_w) Is 1500 to 50,000 andcopolymers of styrene and maleic anhydride with an anhydride content of more than 15%. Commercially available examples of these materials include SMA 1000, SMA 2000, SMA 3000, and SMA 4000, available from Elf Atochem S.A., having styrene-maleic anhydride ratios of 1: 12: 13: 1 and 4: 1, respectively, and molecular weights of 6,000 to 15,000.

Other preferred co-crosslinking agents useful in the present invention include hydroxyl-containing compounds such as those of the formula (XXXII):

formula (XXXII)

Wherein "R5" is hydrogen or an alkyl group having 1 to 20, preferably 1 to 10, more preferably 2 to 5 carbon atoms and "t" is an integer of 0 to 20, preferably 1 to 10, more preferably 2 to 5.

Commercial products having the above formula (XXXII) include, for example, PERSTORP 85.36.28, which is a phenolic resin made from phenol and formaldehyde, having an average Mettler softening point of 103 ℃, a melt viscosity equal to 1.2Pa.s at 150 ℃ and a functionality of 6 to 7. Other examples include DURITE SD 1731 from Borden Chemical of USA.

Other phenolic functional materials include compounds that generate a phenolic crosslinker having a functionality of at least 2 upon heating. Examples of such compounds are benzoxazinyl-containing compounds. Examples of compounds that generate phenolic crosslinkers upon heating include phenols obtained by heating benzoxazine, for example as shown in the following chemical equation:

benzoxazine polybenzoxazines

Wherein "u" is greater than 1, preferablyA maximum of 100,000; wherein "R6" and "R7" are each independently (the same or different) hydrogen, C₁-C₁₀Alkyl (e.g. methyl), C₆-C₂₀Aryl radicals (e.g. phenyl) or C₄-C₂₀Alicyclic groups (e.g., cyclohexane).

Examples of the above compounds also include benzoxazines of phenolphthalein, benzoxazines of bisphenol a, benzoxazines of bisphenol F, benzoxazines of phenol resin, and mixtures thereof. Other compounds useful in the present invention are described in WO 00/27921 and U.S. patent 6,545,631. Mixtures of these compounds and of formula (XXXII) may also be used in the present invention.

The amount of polyfunctional phenolic crosslinker in the epoxy resin composition is preferably from 50% to 150% of the stoichiometric amount required to cure the epoxy resin, more preferably from 75% to 125% of the stoichiometric amount required to cure the epoxy resin, and even more preferably from 85% to 110% of the stoichiometric amount required to cure the epoxy resin.

When a co-crosslinking agent is used in the present invention, the co-crosslinking agent is present in an amount that is less than 40% of the stoichiometric amount required to cure the epoxy resin.

Any of the above curable compositions of the present invention may contain a catalyst. Examples of suitable catalyst materials that can be used in the present invention include compounds containing amine, phosphine, ammonium, phosphonium, arsonium, or sulfonium moieties, or mixtures thereof. Particularly preferred catalysts are heterocyclic nitrogen-containing compounds.

The catalyst (other than the co-crosslinker) preferably contains an average of no more than about 1 active hydrogen moiety per molecule. The active hydrogen moiety includes a hydrogen atom bonded to an amine group, a phenolic hydroxyl group, or a carboxylic acid group. For example, the amine and phosphine moieties in the catalyst are preferably tertiary amine or phosphine moieties; ammonium and phosphonium moieties are preferably quaternary ammonium and phosphonium moieties.

Preferred among the tertiary amines useful as catalysts are those mono-or polyamines having an open chain or cyclic structure, all of the amine hydrogens of which are substituted with suitable substituents (e.g., hydrocarbyl, preferably aliphatic, alicyclic, or aromatic groups).

Examples of such amines include 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU), methyldiethanolamine, triethylamine, tributylamine, dimethylbenzylamine, triphenylamine, tricyclohexylamine, pyridine, and quinoline. Preferred amines are trialkyl, tricycloalkyl and triarylamines (e.g. triethylamine, triphenylamine, tris- (2, 3-dimethylcyclohexyl) amine), alkyl dialkanolamines (e.g. methyldiethanolamine), and trialkanolamines (e.g. triethanolamine). Particularly preferred are weak tertiary amines, for example amines having a pH of less than 10 in aqueous solution at a concentration of 1M. Particularly preferred tertiary amine catalysts are benzyldimethylamine and tris- (dimethylaminomethyl) phenol.

Examples of suitable heterocyclic nitrogen-containing catalysts include those described in U.S. Pat. No. 4,925,901. Preferred heterocyclic secondary and tertiary amines or nitrogen-containing catalysts which may be used herein include, for example, imidazole, benzimidazole, imidazolidine, imidazoline, oxazole, pyrrole, thiazole, pyridine, pyrazine, morpholine, pyridazine, pyrimidine, pyrrolidine, pyrazole, quinoxaline, quinazoline, phthalazine, quinoline, purine, indazole, indole, indolazine, phenazine, phenothiazine, pyrroline, indoline, piperidine, piperazine, and mixtures thereof. Especially preferred are alkyl substituted imidazoles; 2, 5-dichloro-4-ethylimidazole; and phenyl substituted imidazoles, and mixtures thereof. More preferred is N-methylimidazole; 2-methylimidazole; 2-ethyl-4-methylimidazole; 1, 2-dimethylimidazole; and 2-methylimidazole and mixtures thereof. Especially preferred is 2-phenylimidazole.

Preferably, a Lewis acid is also used in any of the above curable epoxy resin compositions of the present invention, especially when the catalyst is a heterocyclic nitrogen-containing compound.

Examples of heterocyclic nitrogen-containing catalysts which are preferably used in combination with Lewis acids are those described in EP A526488, EP A0458502 and GB A9421405.3.

Lewis acids useful in the present invention include, for example, one or a mixture of two or more of halides, oxides, hydroxides, and alkoxides of zinc, tin, titanium, cobalt, manganese, iron, silicon, aluminum, and boron, such as boron lewis acids and boron lewis acid anhydrides, such as boric acid, metaboric acid, optionally substituted boroxine (boroxine) (e.g., trimethoxyboroxine), optionally substituted boron oxides, alkyl borates, boron halides, zinc halides (e.g., zinc chloride), and other lewis acids that tend to have relatively weak conjugate bases. Preferably, the lewis acid is a lewis acid of boron, or an anhydride of a lewis acid of boron, such as boric acid, metaboric acid, an optionally substituted boroxine (e.g., trimethoxyboroxine, trimethylboroxine, or triethylboroxine), an optionally substituted oxide of boron, or an alkyl borate. The most preferred lewis acid is boric acid. When combined with the heterocyclic nitrogen-containing compounds described above, these lewis acids are very effective in curing epoxy resins.

The lewis acid and amine may be combined prior to incorporation into the formulation, or by mixing with the catalyst in situ to make a curing catalyst combination (combination).

The amount of lewis acid used is preferably at least 0.1 moles lewis acid per mole heterocyclic nitrogen-containing compound, more preferably at least 0.3 moles lewis acid per mole heterocyclic nitrogen-containing compound.

The curable compositions of the present invention may optionally contain boric acid and/or maleic acid as curing inhibitors as described in US 5,308,895 and US 5,314,720. In this case, the curing agent is preferably a polyamine or polyamide as described in U.S. Pat. No. 4,925,901.

The curable compositions of the present invention may also optionally contain one or more additional flame retardant additives, including red phosphorus, encapsulated red phosphorus, or liquid or solid phosphorus-containing compounds, such as "EXOLIT OP 930", EXOLIT OP 910 from Clariant GmbH, and ammonium polyphosphates (such as "EXOLIT 700" from Clariant GmbH), phosphites, or phosphazenes; nitrogen-containing flame retardants and/or synergists, e.g. melamine, melem, cyanuric acid, isocyanuric acid and theseDerivatives of nitrogen-containing compounds; halogenated flame retardants and halogenated epoxy resins (especially brominated epoxy resins); synergistic phosphorus-halogen containing chemicals or compounds containing organic acid salts; inorganic metal hydrates, e.g. Sb₂O₃、Sb₃O₅Aluminum hydroxide and magnesium hydroxide, such as "ZEROGEN 30" from Martinswerke GmbH, Germany, more preferably aluminum hydroxide, such as "MARTINAL TS-610" from Martinswerke GmbH, Germany; a boron-containing compound; an antimony-containing compound; silica and mixtures thereof. Examples of suitable additional Flame Retardant additives are given in the listed articles "Flame retardants-101Basic dynamics-Panel effect future opportunities", Fire Retardant Chemicals Association, Baltimore MarriotInner Harbour Hotel, Baltimore Maryland, March 24-27, 1996.

When additional halogen-containing flame retardants are used in the compositions of the present invention, the halogen-containing flame retardants are present in an amount such that the total halogen content of the epoxy resin composition is less than 10 weight percent, preferably less than 5 weight percent, and more preferably less than 1 weight percent.

When an additional flame retardant containing phosphorus is present in the composition of the present invention, the phosphorus-containing flame retardant is preferably present in an amount such that the total phosphorus content in the epoxy resin composition is from 0.2 wt% to 5 wt%.

The curable composition of the invention optionally also contains other additives of the usual conventional type, including for example stabilizers, other organic or inorganic additives, pigments, wetting agents, flow modifiers, UV blockers, and fluorescent additives. These additives may be present in an amount of 0 to 5 wt%, and preferably in an amount of less than 3 wt%. Examples of suitable additives are described in US 5,066,735 and c.a. epsoy Resins-Second ed.d. page 506-512 (Mercel Dekker, inc. 1988).

The curable composition of the present invention can be made by mixing all the components together in any order. The composition of the present invention can also be made by preparing a first composition containing an epoxy resin and a second composition containing a curing agent. The first epoxy resin composition may contain the compound (I) and an epoxy resin; or may simply be the epoxidized compound (I). All other optional or desired components, such as a cure catalyst or inhibitor, may be present in the same composition, or some may be present in the first composition and some in the second composition. The first composition is then mixed with a second composition and cured to produce a flame retardant epoxy resin.

As defined above with respect to the manner "substantially free" described above, the flame retardant epoxy resin is preferably substantially free of bromine atoms, and more preferably substantially free of halogen atoms.

The compositions of the present invention may be used to make composites by techniques well known in the industry, such as by pultrusion, molding, encapsulation or coating. The invention is particularly useful for making B-stage prepregs, laminates, bonding sheets, and resin coated copper foils by techniques well known in the industry, as described in the background of the invention section of EP- ｃA-787161 and US 5,314,720.

Benzoxazine ring-containing compound

In another embodiment of the present invention, the compound (I) can be used for producing a benzoxazine ring-containing compound, a phosphorus-containing product obtainable by reacting the component (a) with the component (B).

In this embodiment, the benzoxazine compound may be prepared by reacting (I) the above-described phosphorus-containing compound having a phenol function, compound (I), with (ii) a primary amine and (iii) formaldehyde. These phosphorus-containing benzoxazine ring-containing compounds may:

(a) using itself and self-crosslinking at elevated temperatures, for example 100 ℃ to 250 ℃, to form a highly crosslinkable network with flame retardant properties; or

(b) Mixed with an epoxy resin or other thermosetting composition and cured at the elevated temperatures described above to form a flame retardant hybrid cross-linked network; or

(c) Mixing with a thermoplastic system (e.g., polystyrene, polyethylene, polypropylene, polyphenylene oxide (PPO)) to form a flame retardant hybrid cross-linked network; or

(d) With a thermoplastic resin (e.g., PPO) and a thermosetting resin (e.g., an epoxy and a curing agent) to form a mixed system.

As an illustration of the above embodiments, benzoxazines may be produced according to the following general chemical reaction:

phenolic compound amine formaldehyde benzoxazine

In the similar reaction as above, the phenol-containing compound (I) of the present invention is reacted with an amine and formaldehyde to produce a benzoxazine ring-containing compound.

In another embodiment, if compound (I) has an amine functional group, a known phenol compound can then be reacted with the amine-containing compound (I) and formaldehyde to form the benzoxazine ring-containing compound.

The molar ratio of these three components used in the present invention is usually 1 mole of phenolic OH groups, 1 mole of amine groups and 2 moles of formaldehyde groups as shown in the above reaction formula. Other ratios between the above components may be used. Mixtures of different amine compounds may be used.

Amines useful in the present invention include, for example, aniline, n-butylamine, 1, 4-aminophenol, other primary amines, and mixtures thereof.

Phenols that may be used in the present invention include, for example, bisphenol a, 2-allylphenol, 4' -methylenebisphenol, other monophenols, and polyphenols, and mixtures thereof.

Compounds containing thermolabile groups

In another embodiment of the present invention, the compound (I) can be used for the production of a compound containing a thermolabile group, a phosphorus-containing product obtainable by reacting component (A) with component (B).

In this embodiment, the thermolabile group-containing phosphorus-containing compound can be produced by reacting (I) the above-mentioned phosphorus-containing compound having a phenol or amine functional group, compound (I), and (ii) a thermolabile group-containing compound, for example, a compound having a tert-butoxycarbonyl group. These modified phosphorus compounds are stable at room temperature and their thermolabile groups decompose at high temperatures, for example from 100 to 250 ℃, to form gases. When the processing temperature is sufficiently controlled, these modified phosphorus compounds can be mixed into different thermosetting systems to generate bubbles, thereby enclosing the gas in a cross-linked system having a lower dielectric constant (e.g., 10% lower than the starting value without the modified phosphorus compound) and having a 10% reduced loss factor or a product having a lower weight by 10% lower, as described in U.S. patent application 10/456,127 entitled "nanoporosius amines", filed 6 months 2003.

Thermolabile group-containing compounds useful in the present invention include, for example, heavy carbonates and derivatives thereof, carbazates and derivatives thereof, and other compounds containing t-butyl carbonate. Examples of compounds containing thermolabile groups are, but are not limited to, di-tert-butyl dicarbonate, di-tert-amyl dicarbonate, diallyl dicarbonate, diethyl pyrocarbonate, dimethyl dicarbonate, dibenzyl dicarbonate, tert-butyl carbazate, and mixtures thereof. The tert-butyl carbonate thermolabile group is advantageously stable to many nucleophiles and does not hydrolyze under basic conditions, but it can be easily cleaved under moderately acidic conditions or by pyrolysis.

The molar ratio of the two components used in the present invention is typically 1 mole of active hydrogen groups to 1 mole of thermolabile groups to form the phosphorus-containing, thermolabile group-containing compound of the present invention.

Flame-retardant polyurethane

In another embodiment of the invention, compound (I) produces a phosphorus-containing polyol using a phosphorus-containing product obtainable by reacting component (a) with component (B), which in turn can be used to produce flame-retardant polyurethanes.

The phosphorus-comprising polyol of the invention is preferably prepared by reacting (I) an alkylene oxide, for example ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with (ii) the phosphorus-comprising compound of the invention, compound (I). The resulting phosphorus-containing polyol product of the present invention preferably contains from 1 to 8, more preferably from 2 to 6, active hydrogen atoms.

A catalyst may be used in the above reaction to produce the phosphorus-containing polyol. The catalyst used in the above reaction may be anionic or cationic. Suitable catalysts include KOH, CsOH, boron trifluoride, double cyanide complex (DMC) catalysts (e.g., zinc hexacyanocobaltate), and catalysts described in U.S. patent No. US6,201,101.

The phosphorus-containing polyols of the present invention may be used alone or in combination with one or more other known polyols to form a base polyol composition that can be reacted with a polyisocyanate to form a polyurethane. The properties of the final polyurethane product will depend on the nature of the various polyols used in the polyol composition.

The phosphorus-containing polyol or mixture thereof used to make the polyurethane resin depends on the end use of the polyurethane product to be produced. The molecular weight or hydroxyl number of the base polyol can thus be selected so that when the polyol made from the base polyol is converted into a polyurethane product by reaction with an isocyanate, a flexible, semi-flexible, self-skinning or rigid foam, elastomer or coating can be produced, and depending on the end product of the blowing agent present. The number of hydroxyl groups and the molecular weight of the polyols used can therefore be varied within wide limits. Generally, the polyols used have a hydroxyl number of from 20 to 800.

In the production of the flexible polyurethane foam, the polyol is preferably a polyether polyol and/or a polyester polyol. The polyols generally have an average functionality of from 2 to 5, preferably from 2 to 4, and an average hydroxyl number of from 20 to 100mg KOH/g, preferably from 20 to 70mg KOH/g. As a further improvement, the particular foam application will also influence the choice of base polyol. For example, for molded foams, the base polyol has a hydroxyl number of about 20 to 60 and is capped with Ethylene Oxide (EO), while for sponge boards, the hydroxyl number is about 25 to 75 and is a mixed feed EO/PO (propylene oxide) or is only slightly capped with EO, or is 100% PO groups. For elastomeric applications, it is generally desirable to use base polyols of relatively high molecular weight (2,000 to 8,000) and having relatively low hydroxyl numbers (e.g., 20 to 50).

In general, polyols suitable for use in the preparation of rigid polyurethanes include polyols having an average molecular weight of from 100 to 10,000, preferably from 200 to 7,000. Such polyols also advantageously have a functionality of at least 2, preferably 3, and contain up to 8, preferably up to 6, active hydrogen atoms per molecule. Polyols for rigid foams typically have hydroxyl numbers of 200 to 1,200, more preferably 300 to 800.

For the production of semi-rigid foams, preference is given to using trifunctional polyols having a hydroxyl number of from 30 to 80.

Flame-retardant polyurethane resins can be obtained by reacting (i) at least one phosphorus-containing polyol according to the invention, alone or in combination with one or more polyols conventionally used for the production of polyurethanes, other than the phosphorus-containing polyol of the invention, with (ii) compounds containing more than one isocyanate group per molecule. Isocyanates that may be used with the polyols of the present invention include aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates and mixtures thereof. Aromatic isocyanates, especially aromatic polyisocyanates, are preferred.

Examples of suitable aromatic isocyanates include the 4,4 '-, 2, 4' -and 2, 2 '-isomers of diphenylmethane diisocyanate, mixtures and polymeric and monomeric MDI mixtures thereof, toluene-2, 4-and 2, 6-diisocyanate (TDI), m-and p-phenylene diisocyanate, chlorophenylene-2, 4-diisocyanate, diphenylene-4, 4' -diisocyanate, 4,4 '-diisocyanate-3, 3' -dimethyldiphenyl, 3-methyldiphenyl-methane-4, 4 '-diisocyanate and diphenyl ether diisocyanates with 2,4, 6-triisocyanatotoluene and 2,4, 4' -triisocyanatodiphenyl ether, and mixtures thereof. Hydrogenation products of these isocyanate compounds may also be used.

Mixtures of isocyanates may be used, for example the commercially available mixtures of the 2, 4-and 2,6 isomers of toluene diisocyanate. Crude polyisocyanates, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylenedianiline, may also be used in the practice of this invention. Mixtures of TDI/MDI may also be used. MDI or TDI based prepolymers made from different polyols may also be used. The isocyanate-terminated prepolymer may be prepared by reacting an excess of polyisocyanate with a polyol (including aminated polyols or imines/enamines thereof) or polyamine.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1, 4-diisocyanate, 4' -dicyclohexylmethane diisocyanate, saturated analogs of the above aromatic isocyanates, and mixtures thereof.

Preferred polyisocyanates for making rigid or semi-rigid foams are polymethylene polyphenylene isocyanate, the 2, 2 ', 2,4 ' and 4,4 ' isomers of diphenylmethylene diisocyanate and mixtures thereof. For the production of flexible foams, the preferred polyisocyanates are toluene-2, 4-and 2, 6-diisocyanate or MDI or mixtures of TDI/MDI or prepolymers produced therefrom.

Isocyanate-terminated (tipped) prepolymers based on the phosphorus-containing polyols of the present invention may also be used in polyurethane formulations. The use of such polyols in polyol isocyanate reaction mixtures is believed to reduce/eliminate the presence of unreacted isocyanate monomers. This is especially important for volatile isocyanates (e.g., TDI and/or aliphatic isocyanates) in coating and adhesive applications because it improves operating conditions and worker safety.

For rigid foams, the organic polyisocyanate and its isocyanate-reactive compounds are reacted in an amount such that the isocyanate index (defined as the number of NCO groups or equivalents divided by the total number of isocyanate-reactive hydrogen atom equivalents multiplied by 100) is from 80 to less than 500, preferably from 90 to 100 in the case of polyurethane foams, and from 100 to 300 in the case of polyurethane-polyisocyanate foam mixtures. For flexible foams, the isocyanate index is generally between 50 and 120, preferably between 75 and 110.

For elastomers, coatings and adhesives, the isocyanate index is generally between 80 and 125, preferably between 100 and 110.

In order to make polyurethane-based foams, blowing agents are generally required. In the production of flexible polyurethane foams, water is preferred as the blowing agent. The amount of water is preferably 0.5 to 10 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the polyol. Carboxylic acids or salts may also be used as blowing agents.

In the manufacture of rigid polyurethane foams, the blowing agent comprises water, a mixture of water with a hydrocarbon or carbon dioxide, or a wholly or partially hydrogenated aliphatic hydrocarbon. The amount of water is preferably 2 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyol. When an excessive amount of water is used, the curing rate becomes low, the blowing process range becomes narrow, the foam density becomes low, or the moldability becomes poor. The amount of the hydrocarbon, chlorofluorocarbon or hydrofluorocarbon to be mixed with water may be appropriately selected depending on the desired foam density, and is preferably not more than 40 parts by weight, more preferably not more than 30 parts by weight based on 100 parts by weight of the polyol. When water is present as an additional blowing agent, it is typically present in an amount of from 0.5 to 10, preferably from 0.8 to 6, more preferably from 1 to 4 and most preferably from 1 to 3 parts by weight based on the total weight of the polyol composition.

In addition to the above components, it is often desirable to use certain other ingredients in the preparation of polyurethane polymers. These additional ingredients include surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, stabilizers, and fillers.

In the manufacture of polyurethane foams, it is generally preferred to use an amount of surfactant to stabilize the foamed reaction mixture until it cures. Such surfactants advantageously contain liquid or solid organosilicone surfactants. Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acids, sulfate esters, alkyl sulfonic acids and alkyl aryl sulfonic acids. Such surfactants are used in amounts sufficient to stabilize the foamed reaction mixture to prevent collapse and the formation of large, non-uniform cells. Generally, for this purpose, 0.2 to 3 parts of surfactant per 100 parts by weight of total polyol (b) are sufficient.

One or more catalysts for the reaction of the polyol (and water, if present) may be used with the polyisocyanate. Any suitable urethane catalyst may be used, including tertiary amine compounds, amines with isocyanate reactive groups and organometallic compounds and mixtures thereof. Preferably, the reaction is carried out in the absence or presence of minor amounts of amine or organometallic catalysts as described above. Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis (dimethylaminoethyl) ether, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, dimethylethanolamine, N-cocomorpholine, N-dimethyl-N 'N' -dimethylisopropylpropylenediamine, N-diethyl-3-diethylamino-propylamine, and dimethylbenzylamine. Exemplary organometallic catalysts include organomercury, organolead, organoiron, and organotin catalysts, with organotin catalysts being preferred. Suitable tin catalysts include stannous chloride, tin carboxylates (e.g., dibutyltin dilaurate), and other organometallic compounds as disclosed in U.S. Pat. No. 2,846,408. Catalysts for the trimerization of polyisocyanates (to produce polyisocyanurates), such as alkali metal alkoxides, may optionally be used herein. The amount of amine catalyst in the formulation may vary between 0.02 to 5%, or the organometallic catalyst may be used in an amount of 0.001 to 1% in the formulation.

If desired, a crosslinking agent or a chain extender may be added. Crosslinking agents or chain extenders include low molecular weight polyols such as ethylene glycol, diethylene glycol, 1, 4-butanediol, and glycerol; low molecular amine polyols such as diethanolamine and triethanolamine; and polyamines, such as ethylenediamine, xylylenediamine, methylene-bis (o-chloroaniline); and mixtures thereof. The use of such crosslinking agents or chain extenders is known in the art, as described in U.S. Pat. nos. 4,863,979 and 4,963,399; and EP 549,120.

In particular, when the rigid foams are used in building materials, additional flame retardants may be included as additives. Any known liquid or solid flame retardant may be used with the polyols of the present invention. Typically, such flame retardants are halogen substituted phosphate esters and inorganic flame retardants. Common halogen-substituted phosphates are tricresyl phosphate, tris (1, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylene diphosphate. The inorganic flame retardant comprises red phosphorus, hydrated alumina, antimony trioxide, ammonium sulfate, expanded graphite, urea or melamine cyanurate or a mixture of at least two flame retardants. Inorganic flame retardants are preferred when it is desired to reduce the amount of halogen in the formulation.

The use of the polyurethane foams made by the present invention is known in the industry. For example, rigid foams are used in the building industry and for insulation of appliances and refrigerators. The flexible foams and elastomers are useful in applications such as furniture, shoe soles, car seats, sun visors, steering wheels, arm rests, door panels, sound insulation parts, and instrument panels.

Methods of making polyurethane products are well known in the art. In general, the components of the Polyurethane-forming reaction mixture are mixed together in any convenient manner, for example using any of the mixing equipment described in the prior art for this purpose, such as those described in Polyurethane Handbook, g.

Polyurethane products can be made continuously or discontinuously by injection molding, casting, spraying, casting (casting), calendering; these are carried out under free foaming (free rise) or molding conditions with or without the use of mold release agents, in-mold coating (in-mold coating) or any insert or skin (skin) placed in the mold. In the case of flexible foams, they may be of single or dual hardness (dual-hardness).

For the production of rigid foams, the known one-shot or semi-prepolymer technique can be used together with conventional mixing methods, including impingement mixing. Rigid foams may also be produced as slabstock foams, moldings, void-filled spray foams, frothed foams, or laminates with other materials such as paper, metal, plastic, or wood. Flexible foams are either free-blown or molded, while microcellular elastomers are typically molded.

As defined above in the manner "substantially free" described above, the flame retardant polyurethane resin of the present invention is preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

Ignition resistant thermoplastic resin

In another embodiment of the present invention, compound (I) produces a phosphorus-containing ignition resistant thermoplastic resin using a phosphorus-containing product that can be made by reacting component (a) with component (B).

The halogen-free ignition-resistant thermoplastic resin composition can be prepared by mixing (I) the phosphorus-containing compound according to the present invention, the compound (I) and (ii) at least one thermoplastic resin.

Typical thermoplastic polymers include, but are not limited to, polymers made from vinyl aromatic monomers and hydrogenated versions thereof (including diene and aromatic hydrogenated versions, including aromatic hydrogenated), such as styrene-butadiene block copolymers, polystyrene (including high impact polystyrene)Alkenes), acrylonitrile-butadiene-styrene (ABS) copolymers and styrene-acrylonitrile copolymers (SAN); polycarbonate (PC), ABS/PC compositions, polyethylene terephthalate, epoxy resins, hydroxy phenoxyether Polymers (PHE) as described in U.S. Pat. Nos. 5,275,853, 5,496,910, 3,305,528; ethylene vinyl alcohol copolymers, ethylene acrylic acid copolymers, polyolefin carbon monoxide copolymers, chlorinated polyethylene, polyolefins (e.g. ethylene polymers and propylene polymers such as polyethylene, polypropylene, and copolymers of ethylene and/or propylene with each other or with alpha-olefins having at least 4, more preferably at least 6, preferably up to 12, more preferably up to 8 carbon atoms), cyclic olefin copolymers (COC's), other olefin copolymers (especially ethylene with another olefin monomer such as C)₁-C₁₂Copolymers of alk-1-yl groups) and homopolymers (such as those made using conventional heterogeneous catalysts), polyphenylene oxide polymers (PPO), and any combinations or mixtures thereof.

Thermoplastic polymers and methods for their manufacture are well known to those skilled in the art.

In one embodiment, the thermoplastic polymer is a rubber modified monovinylidene aromatic polymer made by polymerizing a vinyl aromatic monomer in the presence of a dissolved elastomer or rubber. Vinyl aromatic monomers include, but are not limited to, U.S. Pat. nos. 4,666,987; 4,572,819 and 4,585,825. Preferably, the monomer of formula (XXXIII):

formula (XXXIII)

Wherein "R10" is hydrogen or methyl, "Ar¹"is an aromatic ring structure containing 1 to 3 aromatic rings with or without alkyl, halogen or haloalkyl substitution, wherein any alkyl group contains 1 to 6 carbon atoms, and haloalkyl refers to a halogen substituted alkyl group. Preferably, "Ar¹"is phenyl or alkylphenylWherein alkylphenyl refers to alkyl substituted phenyl, with phenyl being most preferred. Typical vinyl aromatic monomers that may be used include, for example, styrene, alpha-methylstyrene, all isomers of vinyl toluene, especially p-vinyl toluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, vinyl anthracene, and mixtures thereof. The vinylaromatic monomers can also be combined with other copolymerizable monomers. Examples of such monomers include, but are not limited to, acrylic monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid, and methyl acrylate; maleimide, phenylmaleimide, and maleic anhydride, and mixtures thereof.

The rubber used to make the rubber-modified monovinylidene aromatic polymer can be any rubber capable of enhancing the impact properties of the monovinylidene aromatic polymer, including any molecular architecture such as linear, branched, star-branched, and homo-and co-diene rubbers, block rubbers, functionalized rubbers, low cis, high cis rubbers, and mixtures thereof. The elastomers or rubbers preferably used are polymers and copolymers which exhibit a secondary transition temperature (as measured or estimated using conventional techniques, such as ASTM test method D52T) of not greater than 0 ℃, preferably not greater than 20 ℃, more preferably not greater than 40 ℃.

The rubber should generally be used in an amount such that the rubber-reinforced polymer product contains 3, preferably 4, more preferably 5, most preferably 6 to 20, preferably to 18, more preferably to 16, most preferably to 14 weight percent rubber, expressed as rubber or rubber equivalents, based on the total weight of the vinyl aromatic monomer and the rubber component. The term "rubber" or "rubber equivalent", as used herein, simply refers to the amount of rubber for a rubber homopolymer, such as polybutadiene, and the amount of copolymer made up of monomers that when homopolymerized form a rubber polymer, such as the butadiene-styrene block copolymer, the butadiene component of the block copolymer.

The rubber is present as discrete rubber particles in the monovinylidene aromatic polymer matrix and can be of any type, including monomodal, bimodal, or multimodal particle size distribution and particle size, and any morphology, including cellular, core-shell, onion skin, and any combination thereof.

The polymerization bar process and process conditions for the polymerization of vinyl aromatic monomers, the manufacture of rubber modified polymers thereof, and the conditions required to produce the desired average particle size are well known to those skilled in the art. Although any polymerization method can be used, typical methods are continuous bulk or solution polymerization as described in U.S. Pat. Nos. 2,727,884 and 3,639,372. The polymerization of vinyl aromatic monomers is carried out in the presence of a pre-dissolved elastomer to produce products containing impact modified or grafted rubbers, as described in U.S. Pat. nos. 3,123,655; 3,346,520; 3,639,522; and 4,409,369, which are incorporated herein by reference. The rubber is typically a butadiene or isoprene rubber, preferably polybutadiene. Preferably, the rubber modified vinyl aromatic polymer is High Impact Polystyrene (HIPS) or acrylonitrile-butadiene-styrene (ABS), with HIPS being most preferred.

At least 35 parts by weight, preferably at least 40 parts by weight, more preferably at least 45 parts by weight, and most preferably at least 50 parts by weight of a thermoplastic polymer or polymer blend is used in the halogen-free ignition resistant polymer composition of the present invention based on 100 parts by weight of the halogen-free ignition resistant polymer of the present invention. Generally, the thermoplastic polymer component is used in amounts of less than or equal to 99 parts by weight, preferably less than or equal to 95 parts by weight, more preferably less than or equal to about 90 parts by weight, and most preferably less than or equal to about 85 parts by weight, based on 100 parts by weight of the halogen-free ignition resistant polymer of the present invention.

In one embodiment, the halogen-free ignition resistant polymer composition of the present invention comprises compound (I) and a mixture of two thermoplastic polymers, wherein at least one thermoplastic polymer is, for example, polyphenylene ether. Polyphenylene ethers are manufactured from the corresponding phenol or reactive derivatives thereof by various well-known catalytic and non-catalytic processes. As examples, in U.S. Pat. nos. 3,306,874; 3,306,875, 3,257,357 and 3,257,358 disclose certain polyphenylene ethers which may be used in the present invention.

The polyphenylene ether resin is preferably of the type comprising the repeating structural formula (XXXIV):

formula (XXXIV)

Wherein the oxygen ether atom of one unit is attached to the benzene nucleus of the next adjacent unit, "v" is a positive integer and is at least 50 and preferably up to about 100,000, and each "Q" is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon groups containing no tertiary alpha-carbon atoms, halogenated hydrocarbon groups containing at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy containing at least two carbon atoms, and halogenated hydrocarbonoxy. The preferred polyphenylene ether resin is poly (2, 6-dimethyl-1, 4-phenylene) ether resin.

When used in combination with another thermoplastic polymer, the polyphenylene ether resin is preferably used in the halogen-free ignition resistant polymer composition of the invention in an amount of at least 5 parts by weight, preferably 10 parts by weight, more preferably at least 12 parts by weight, more preferably at least 15 parts by weight, most preferably at least 18 parts by weight, to 30 parts by weight, preferably to 28 parts by weight, more preferably to 25 parts by weight, based on 100 parts by weight of the halogen-free ignition resistant polymer of the invention. The thermoplastic polymer and polyphenylene ether polymer can be blended prior to incorporation into the composition of the present invention, or each polymer can be incorporated separately into the composition.

In an embodiment of the present invention, the ignition resistant thermoplastic polymer composition of the present invention may optionally comprise the epoxidized compound (I), the benzoxazine ring-containing compound or the thermolabile group-containing compound according to the present invention as described above.

In another embodiment of the present invention, the ignition resistant thermoplastic polymer composition of the present invention may be a mixture of (I) one or more thermoplastic resins and (ii) the epoxidized compound (I), the benzoxazine ring-containing compound or the thermolabile group-containing compound according to the present invention as described above.

The compositions of the present invention may include other additives, such as modifiers, including compounds containing functional groups capable of enhancing the properties of the composition and compatible with the thermoplastic resin. For thermoplastic resins such as monovinylidene aromatic compounds and conjugated dienes, these functional groups include, but are not limited to, butadiene, styrene-maleic anhydride, polybutadiene-maleic anhydride copolymers, carboxylic acid terminated butadiene, and carboxylic acid functionalized polystyrene. Any combination of modifiers may be used to modify the phosphorus element-containing epoxy compound.

The compound (I), epoxidized compound (I), benzoxazine ring-containing compound, or thermolabile group-containing compound used in the ignition resistant thermoplastic polymer composition of the present invention is generally at least 1 wt%, preferably at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, most preferably at least 20 wt%, and less than 50 wt%, preferably less than 45 wt%, more preferably less than 40 wt%, most preferably less than 35 wt%, based on the total weight of the ignition resistant polymer composition.

The preparation of the ignition resistant polymer composition of the present invention can be accomplished by any suitable mixing means known in the art, including dry blending the various components followed by mixing and melting, which can be done directly in the extruder used to make the final article or pre-mixed in another extruder. Dry blends of the compositions can also be directly injection molded without prior mixing and melting.

When softened or melted by the application of heat, the ignition resistant thermoplastic polymer compositions of the present invention can be formed or molded using conventional techniques, such as compression molding, injection molding, gas-assisted injection molding, calendering, vacuum forming, thermoforming, extrusion and/or blow molding, alone or in combination. The ignition resistant thermoplastic polymer composition can also be formed, spun, or drawn into films, fibers, multi-layer laminates or extruded sheets, or can be compounded with one or more organic or inorganic substances on any machine suitable for the purpose.

In one embodiment, the composition of the present invention may be used to prepare a foam. The ignition resistant polymer composition was extruded into a foam as follows: melt processing it with a blowing agent to form a foamable mixture, extruding the foamable mixture through an extrusion die to a zone of reduced pressure and allowing the foamable mixture to expand and cool. Conventional foam extrusion techniques such as screw extruders, twin screw extruders and accumulating extrusion devices may be used. In U.S. Pat. nos. 2,409,910; 2,515,250, respectively; 2,669,751, respectively; 2,848,428, respectively; 2,928,130, respectively; 3,121,130, respectively; 3,121,911, respectively; 3,770,688, respectively; 3,815,674, respectively; 3,960,792, respectively; 3,966,381, respectively; 4,085,073; 4,146,563, respectively; 4,229,396; 4,302,910, respectively; 4,421,866, respectively; 4,438,224, respectively; 4,454,086 and 4,486,550 describe processes suitable for making extruded foams from resin/blowing agent mixtures.

In another embodiment of the present invention, the halogen-free ignition resistant polymer composition of the present invention may further comprise other phosphorous containing compounds optionally in addition to compound (I). Optionally, the compositions of the present invention may also include other flame retardant additives, which may be phosphorus or non-phosphorus materials as described above.

The amount of optional phosphorus-containing compound and/or optional flame retardant additive other than compound (I) used in the composition of the present invention may be from 0 to 30 wt%. If an optional phosphorus-containing component other than compound (I) is present, the amount thereof is preferably at least 1% by weight to preferably at most 30% by weight of the total weight of the thermoplastic resin.

The amount of component compound (I) is preferably at least 5% by weight, preferably at most 20% by weight, based on the total weight of the thermoplastic resin.

As defined above in the above description of the manner "substantially free", the ignition-resistant thermoplastic resin is preferably substantially free of bromine atoms, more preferably substantially free of halogen atoms.

The halogen-free ignition resistant polymer compositions of the present invention can be used to make a variety of useful articles and parts. Some articles that are particularly suitable include television housings, computer monitors, and related printer housings, which are typically required to have excellent flammability ratings. Other uses include automotive and small electrical appliances.

Ignition resistant thermoset compositions

In another embodiment of the present invention, compound (I) produces a phosphorus-containing ignition resistant thermosetting composition using a phosphorus-containing product that can be made by reacting component (a) with component (B).

Halogen-free ignition-resistant thermosetting compositions can be prepared by mixing (I) the phosphorus-containing compound according to the invention, compound (I) and (ii) at least one thermosetting system. Examples of thermosetting systems are epoxides, polyurethanes, polyisocyanates, benzoxazine ring containing compounds, unsaturated resin systems containing double or triple bonds, polycyanates, bismaleimides, triazines, bismaleimides, and mixtures thereof.

In another embodiment of the present invention, the ignition resistant thermosetting polymer composition of the present invention may optionally comprise the epoxidized compound (I), the benzoxazine ring-containing compound or the thermolabile group-containing compound according to the present invention as described above.

In another embodiment of the present invention, the ignition resistant thermosetting polymer composition of the present invention may be a mixture of (I) one or more thermosetting systems and (ii) the epoxidized compound (I), the benzoxazine ring containing compound or the thermolabile group containing compound according to the present invention as described above.

Ignition resistant thermoplastic/thermoset hybrid system

In another embodiment of the invention, compound (I) produces a phosphorus-containing ignition resistant mixed resin system containing both a thermoplastic olefin and a thermoset system using a phosphorus-containing product that can be made by reacting component (a) with component (B).

The blended ignition resistant thermoplastic and thermoset compositions can be made by blending (I) the phosphorus-containing compound according to the present invention, compound (I), with (ii) the thermoplastic resin and (iii) the thermoset system. The thermoplastic resin is polyphenylene oxide (PPO), mixtures thereof, and other materials as described in the preceding paragraph. Thermosetting systems are epoxides, polyurethanes, polyisocyanates, benzoxazine ring containing compounds, double or triple bond containing unsaturated resin systems, polycyanates, bismaleimides, triazines, bismaleimides, and mixtures thereof.

In another embodiment of the present invention, the ignition resistant thermoplastic/thermosetting hybrid polymer composition of the present invention may optionally comprise the epoxidized compound (I), the benzoxazine ring-containing compound or the thermolabile group-containing compound according to the present invention as described above.

In another embodiment of the present invention, the ignition resistant thermoplastic/thermoset hybrid polymer composition of the present invention can be a mixture of (I) one or more thermoplastic resins, (ii) one or more thermoset systems and (iii) an epoxidized compound (I), a benzoxazine ring containing compound or a thermolabile group containing compound according to the present invention as described above.

The above compositions are useful in the manufacture of coating formulations, encapsulants, composites, adhesives, molded articles, bonding sheets, laminates. For example, the coating formulation may comprise (I) compound (I), (ii) a solid epoxy resin, and (iii) a hardener, such as an amine or phenolic hardener.

The following examples illustrate possible embodiments of the invention. Those skilled in the art can practice the full scope of the invention by procedures similar to those described below.

Detailed Description

Examples

The materials used in the examples are described below:

the test procedures used to measure the properties of the various materials in the examples are further described below:

the IPC test is an industry standard For electrical laminates developed by The Institute For Interconnection And Packaging Electronic Circuits, 3451 Church stress, Evanston, Illinois 60203.

The preparation of the phosphorus-containing compounds according to the invention is illustrated by the following examples

Example 1

Preparation A

24.69 grams (gm) of SANTOLINK EP560 was mixed with 30 grams of Struktol Polydis^TMPD3710 was mixed at 170 ℃ for 10 minutes and heated to 190 ℃ over 5 minutes and the mixture was held at 190 ℃ for 20 minutes. The resulting reaction product was left in a vacuum oven at 160 ℃ for another 30 minutes to complete the reaction by discharging butanol. The weight of the resulting final solid was about 45.6 grams.

The product obtained has a melt viscosity of 150 ℃ and a Tg equal to 78 ℃ of 16 Pa.s. The theoretical phosphorus content of the product was about 9.21 wt%.

Example 2

Preparation B

A1 liter glass reactor equipped with a mechanical stirrer and heating mantle and with a nitrogen inlet, condenser and solvent trap was charged with 480 g of solid Struktol Polydis^TMPD3710 and 640 g Phenodur VPR 1785 (50% solids in methoxypropanol). The mixture was heated to 120 ℃ under nitrogen atmosphere to obtain a homogeneous mixture. The homogeneous reaction mixture was heated from 120 ℃ to 205 ℃ at a rate of 1 ℃/min. Solvent (from VPR 1785) and butanol were collected stepwise as the temperature was increased. The reaction mixture was held at 205 ℃ for 30 minutes until no more volatiles were released from the reaction mixture. The resulting solid material was removed from the reactor. The total weight of the solid material was 757.8 grams, its Tg was 88 deg.C, and the theoretical phosphorus content was about 8.87 wt%.

Examples 3 to 5

The formulations in the table below were prepared using the product of preparation a described above in example 1.

Curable formulations based on preparation A

For formulations 1,2 and 3, the above components were combined and mixed for approximately 60 minutes at room temperature (-25 ℃) to form a varnish suitable for measuring gel time and glass transition temperature of the cured product, respectively.

Example 6

Formulation 1 described in example 3 above was dipped into a glass cloth reinforced substrate containing an aminosilane coating 731. The impregnated substrate was passed at a ramp rate of 1.4 meters/minute through a CARATSCH pilot processor (CARATSCH AG, bremsgarten, Switzerland construction) with an air temperature of about 177 ℃ with a 3 meter horizontal oven to form a prepreg. The resulting prepreg had a resin content of about 34.5 wt% and a residual gel time of 145 seconds at 171 ℃.

The prepreg formed as above was cut into 8 samples (30 cm × 30 cm samples), and then laminates were made from the prepreg samples as follows: the 8 layers of prepreg were pressed together with two layers of copper at 190 ℃ for 90 minutes to obtain a laminate having a TMA thickness of about 1.48 mm. The laminate has a TMATG of about 163 ℃, a CTE < Tg/> Tg of 40.2/241.9, and a T-288 of greater than 60 minutes. The copper peel strength of the laminate was about 14.3N/cm. The laminate passed the UL 94 flammability Vo rating.

Example 7

Preparation C

A1 liter glass reactor equipped with a mechanical stirrer and heating mantle and with a nitrogen inlet, condenser and solvent trap was charged with 440 g of solid Struktol Polydis^TMPD3710 and 720 grams Phenodur VPR 1785 (50% solids in methoxypropanol). The mixture was heated from 100 ℃ to 201 ℃ over 155 minutes. Solvent (from VPR 1785) and butanol were collected stepwise as the temperature was increased. The reaction mixture was held at 201 ℃ for 40 minutes until no more volatiles were released from the reaction mixture. The resulting solid material was removed from the reactor. Tg of 104 ℃ and melt viscosity at 200 ℃ of 2.34.

The resulting product of this example is considered to be a mixture of oligomers, one of which has the following structure:

example 8

Preparation D

1 liter glass equipped with a mechanical stirrer and heating jacket and equipped with a nitrogen inlet, condenser and solvent trapThe reactor was charged with 558.3 grams of solid Struktol Polydis^TMPD3710 and 391.6 g Phenodur PR411 (75% solids in butanol). The mixture was heated from 96 ℃ to 199 ℃ over 180 minutes. Butanol was collected gradually as the temperature increased. The reaction mixture was held at 200 ℃ for 20 minutes until no more volatiles were released from the reaction mixture. The resulting solid material was removed from the reactor. The Tg by DSC was about 108.5 ℃.

example 9

Preparation E

A1 liter glass reactor equipped with a mechanical stirrer and heating mantle and equipped with a nitrogen inlet, condenser and solvent trap was charged with 405.5 grams of solid Struktol Polydis^TMPD3710 and 391.6 g Phenodur PR411 (75% solids in butanol). The mixture was heated from 106 ℃ to 155 ℃ over 95 minutes. Butanol was collected gradually as the temperature increased. The reaction mixture was held at 155 ℃ for 300 minutes until no more volatiles were released from the reaction mixture. The resulting solid material was removed from the reactor. The Tg by DSC was about 138 ℃.

Claims

1. A composition, comprising:

2. an oligomer having the structure: