HK1192269B

HK1192269B - Multifunctional sulfur-containing polymers, compositions thereof and methods of use

Info

Publication number: HK1192269B
Application number: HK14105618.5A
Authority: HK
Inventors: S．J．霍布斯; G．J．麦克拉姆; J.蔡; M.伊藤; L.G.安德森; R.林
Original assignee: Prc-迪索托国际公司
Priority date: 2011-03-18
Filing date: 2012-03-16
Publication date: 2016-08-26

Description

Multifunctional sulfur-containing polymers, compositions and methods of use thereof

Cross reference to related applications

This application claims priority to U.S. provisional patent application serial No. 61/453,978, filed 3/18/2011.

Technical Field

The present disclosure relates to multifunctional sulfur-containing polymers, compositions comprising multifunctional sulfur-containing polymers, and methods of using multifunctional sulfur-containing polymers.

Background

It is known that thiol-terminated sulfur-containing polymers are well suited for use in different applications such as aerospace sealant compositions, primarily due to their fuel resistance. Other desirable properties of aerospace sealant compositions include low temperature flexibility, short cure times (time required to reach a predetermined strength), and high temperature resistance, among others. Sealant compositions that exhibit at least some of these properties and contain thiol-terminated sulfur-containing polymers are described, for example, in U.S. patent nos. 2466963, 4366307, 4609762, 5225472, 5912319, 59071, 6172179, 6232401, 6372849 and 6509418. Polythioethers are also used in aerospace sealant applications where they provide high tensile strength, high shear strength, high temperature heat resistance, and fuel resistance, as disclosed in U.S. Pat. No.7638162 and U.S. publication No. 2005/0245695.

Polythioethers, which are liquid at room temperature and pressure and which have excellent low temperature flexibility and fuel resistance, such as disclosed in U.S. patent No.6172179, may also be used in aerospace sealant applications. For example, difunctional polythioethers having terminal hydroxyl groups prepared by reacting a hydroxyl compound with an aldehyde are described in GB850178, U.S. Pat. Nos. 3,920,382, 3959227 and U.S. Pat. No. 3997614. Difunctional polythioethers terminated or capped with isocyanates are also known, as disclosed in GB850178 and U.S. Pat. Nos. 3290382, 3959227 and 3997614. Difunctional, i.e., linear polythioethers, however, often swell upon prolonged exposure to hydrocarbon fuels and other lubricants. On the other hand, sealants made using polyfunctional polythioethers can exhibit good fuel resistance, hardness, and flexibility, but often have compromised adhesion elongation.

It would be desirable to provide multifunctional polythioethers that can be used as fuel-and water-resistant sealants, and that have improved tensile strength and elongation, but without compromising adhesion.

Summary of The Invention

Multifunctional sulfur-containing polymers having improved properties suitable for aerospace sealant applications are provided.

In a first aspect of the present disclosure, there is provided a terminal-modified sulfur-containing polymer comprising the reaction product of reactants comprising: (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reactant selected from the group consisting of aldehydes, ketones, and combinations thereof.

In a second aspect of the present disclosure, there is provided a sulfur-containing polymer having the structure of formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mThe core of (1).

In a third aspect of the present disclosure, there is provided a terminal-modified sulfur-containing polymer comprising the reaction product of reactants comprising: (a) a sulfur-containing polymer of formula (I):

wherein each n is an integer selected from 1 to 50; m is a whole selected from 3 to 6Counting; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group, and an isocyanate group, and a group reactive with a hydroxyl group of the polymer of formula (I).

In a fourth aspect of the present disclosure, there is provided an amine-terminated sulfur-containing polymer comprising the reaction product of reactants (a) and (b) comprising: (a) a reaction product comprising reactants (i) and (ii) comprising: (i) a sulfur-containing polymer comprising formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) a first compound selected from the group consisting of diisocyanates, activated ethylenically unsaturated monoisocyanates, and tosylates; and (b) comprises a polymer containing an amine group and a functional group selected from the group consisting of a group reactive with isocyanate groups, a group reactive with ethylenically unsaturated groups, and a group reactive with toluene sulfonic acidEster reactive group of the second compound.

In a fifth aspect of the present disclosure, there is provided a thiol-terminated sulfur-containing polymer comprising the reaction product of reactants (a) and (b) comprising the reaction product of reactants (i) and (ii) comprising: (i) a sulfur-containing polymer comprising formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) comprises a first compound selected from the group consisting of diisocyanates, thioureas, ethylenically unsaturated monoisocyanates, and tosylates; and when (ii) comprises a diisocyanate, (b) comprises a mercaptoalkanol; when (ii) comprises thiourea, (b) comprises a metal hydrosulfide; when (ii) comprises an ethylenically unsaturated monoisocyanate, (b) comprises a dithiol; and when (ii) comprises tosylate, (b) comprises a metal hydrosulfide.

In a sixth aspect of the present disclosure, a terminal-modified sulfur-containing polymer is provided that includes a reaction product of reactants (a) and (b) comprising: (a) a reaction product comprising reactants (I) and (ii) comprising, wherein (I) comprises a sulfur-containing polymer of formula (I):

wherein n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) comprises a first compound selected from the group consisting of diisocyanates, ethylenically unsaturated monoisocyanates, and tosylates; and (b) a second compound comprising a terminal group selected from a vinyl group, a silyl group, and an epoxy group, and a group selected from a group reactive with an isocyanate group, a group reactive with an ethylenically unsaturated group, and a group reactive with a tosylate.

In a seventh aspect of the present disclosure, there is provided a terminal-modified sulfur-containing polymer of formula (II):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; each R⁵is-OR⁵', wherein R⁵' is independently selected from vinyl-terminated groups, silyl-terminated groups, amine-terminated groups, epoxy-terminated groups, thiol-terminated groupsA group, and an isocyanate-terminated group; and Z represents an m-valent parent polyol Z (OH)_mThe core of (1).

In an eighth aspect of the present disclosure, there is provided a composition comprising a terminal-modified sulfur-containing polymer provided by the present disclosure and a curing agent reacted with the terminal-modified sulfur-containing polymer.

In a ninth aspect of the present disclosure, an aperture sealed with a sealant is provided, the sealant comprising a composition comprising a terminal-modified sulfur-containing polymer provided by the present disclosure and a curing agent reacted with the terminal-modified sulfur-containing polymer.

The present disclosure also relates to methods of making sulfur-containing polymers and compositions thereof, such as sealant compositions, including aerospace sealant compositions, comprising the terminal-modified sulfur-containing polymers provided by the present disclosure.

Detailed Description

Definition of

A dash ("-") that is not between two letters or symbols is used to indicate a substituent or a point of bonding between two atoms. For example, -CONH₂Bonded to another moiety through a carbon atom.

"activated ethylenically unsaturated monoisocyanate" refers to a compound containing both ethylenically unsaturated groups and monoisocyanate groups in which the double bond is electron deficient such that it is activated towards a Michael addition, i.e., the double bond is a Michael acceptor.

"aldehyde" refers to a compound of the formula CH (O) R, wherein R is hydrogen or a hydrocarbon group such as alkyl, as defined herein. In certain embodiments, the aldehyde is C_1-10Aldehyde, C_1-6Aldehyde, C_1-4Aldehyde, C_1-3Aldehydes and in certain embodiments C_1-2An aldehyde. In certain embodiments, the aldehyde is formaldehyde. In certain embodiments of the aldehydes, R is selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl and substituted C_6-12And (4) an aryl group.

"Alkanediyl" refers to a diradical of a saturated, branched or straight chain acyclic hydrocarbon group having, for example, 1-18 carbon atoms (C)_1-18) 1 to 14 carbon atoms (C)_1-14) 1 to 6 carbon atoms (C)_1-6) 1 to 4 carbon atoms (C)_1-4) Or 1 to 3 hydrocarbon atoms (C)_1-3). In certain embodiments, the alkanediyl is C_2-14Alkanediyl, C_2-10Alkanediyl, C_2-8Alkanediyl, C_2-6Alkanediyl, C_2-4Alkanediyl, and in certain embodiments C_2-3An alkanediyl group. Examples of alkanediyl include methanealkanediyl (-CH)₂-, ethane-1, 2-diyl (-CH)₂CH₂-, propane-1, 3-diyl and isopropane-1, 2-diyl (e.g. -CH)₂CH₂CH₂-and-CH (CH)₃)CH₂-, butane-1, 4-diyl (-CH)₂CH₂CH₂CH₂-, pentane-1, 5-diyl (-CH)₂CH₂CH₂CH₂CH₂-, Hexane-1, 6-diyl (-CH)₂CH₂CH₂CH₂CH₂CH₂-), heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, dodecane-1, 12-diyl, and the like.

"alkanedithiol" refers to an alkane group in which two hydrogen atoms are replaced by a thiol group-SH. In certain embodiments, the alkanedithiol is C_2-12Alkanedithiol, C_2-10Alkanedithiol, C_2-8Alkanedithiol, C_2-6Alkanedithiols, and in certain embodiments C_2-3Alkanedithiol.

"alkylaromatic hydrocarbon" refers to a hydrocarbon having one or more aryl and/or arene diyl groupsAnd hydrocarbon groups of one or more alkyl and/or alkanediyl groups, wherein aryl, arenediyl, alkyl and alkanediyl are defined herein. In certain embodiments, each aryl and/or arene diyl group is C_6-12、C_6-10And in certain embodiments is phenyl or phenyl diyl. In certain embodiments, each alkyl and/or alkanediyl group is C_1-6、C_1-4、C_1-3And in certain embodiments, methyl, methanediyl, ethyl, or ethane-1, 2-diyl. In certain embodiments, the alkane aromatic group is C_4-18Alkane aromatic hydrocarbon, C_4-16Alkane aromatic hydrocarbon, C_4-12Alkane aromatic hydrocarbon, C_4-8Alkane aromatic hydrocarbon, C_6-12Alkane aromatic hydrocarbon, C_6-10Alkane aromatic hydrocarbons, and in certain embodiments C_6-9An alkane aromatic hydrocarbon. Examples of the alkane aromatic group include diphenylmethane.

An alkylaromatic diyl group "refers to a diradical of an alkylaromatic hydrocarbon group. In certain embodiments, the alkylaromatic diyl group is C_4-18Alkane-arene diyl, C_4-16Alkane-arene diyl, C_4-12Alkane-arene diyl, C_4-8Alkane-arene diyl, C_6-12Alkane-arene diyl, C_6-10An alkylaromatic diyl group, and in certain embodiments C_6-9An alkylaromatic diyl group. Examples of the alkylaromatic diyl group include diphenylmethane-4, 4' -diyl.

"Alkanoalkane" means a saturated hydrocarbon group having one or more cycloalkyl and/or cycloalkadiyl groups and one or more alkyl and/or alkanediyl groups, wherein cycloalkyl, cycloalkadiyl, alkyl and alkanediyl are defined herein. In certain embodiments, each cycloalkyl and/or cycloalkadiyl group is C_3-6、C_5-6And in embodiments is cyclohexyl or cyclohexanediyl. In certain embodiments, each alkyl and/or alkanediyl group is C_1-6、C_1-4、C_1-3And in certain embodiments, methyl, methanediyl, ethyl, or ethane-1, 2-diyl. In certain embodimentsThe alkane-cycloalkane group being C_4-18Alkane cycloalkane, C_4-16Alkane cycloalkane, C_4-12Alkane cycloalkane, C_4-8Alkane cycloalkane, C_6-12Alkane cycloalkane, C_6-10Alkane cycloalkanes, and in certain embodiments, are C_6-9Alkane cycloalkane. Examples of the alkane cycloalkane group include 1,1,3, 3-tetramethylcyclohexane and cyclohexylmethane.

"Alkanoalkandiyl" refers to a diradical of an alkanyl cycloalkane group. In certain embodiments, the alkanecycloalkanediyl group is C_4-18Alkanecycloalkanediyl, C_4-16Alkanecycloalkanediyl, C_4-12Alkanecycloalkanediyl, C_4-8Alkanecycloalkanediyl, C_6-12Alkanecycloalkanediyl, C_6-10Alkane cycloalkanediyl, and in certain embodiments, is C_6-9Alkane cycloalkanediyl group. Examples of the alkane cycloalkanediyl group include 1,1,3, 3-tetramethylcyclohexane-1, 5-diyl and cyclohexylmethane-4, 4' -diyl.

"alkoxy" refers to the group-OR, where R is alkyl as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. In certain embodiments, the alkoxy group is C_1-8Alkoxy radical, C_1-6Alkoxy radical, C_1-4Alkoxy, and in certain embodiments is C_1-3An alkoxy group.

"alkyl" refers to a saturated, branched, or straight chain, monocyclic hydrocarbon group having, for example, 1-20 carbon atoms, 1-10 carbon atoms, 1-6 carbon atoms, 1-4 carbon atoms, or 1-3 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, tetradecyl, and the like. In certain embodiments, the alkyl group is C_2-6Alkyl radical, C_2-4Alkyl and in certain embodiments C_2-3An alkyl group.

"aminoalkyl" is an alkyl group as defined herein, wherein one of the hydrogen atoms of the alkyl group is an amino groupgroup-NH₂Instead of that. In certain embodiments, the aminoalkyl group is C_1-10Aminoalkyl radical, C_1-6Aminoalkyl radical, C_1-4Aminoalkyl radical, C_1-3Aminoalkyl, and in certain embodiments, C_1-2An aminoalkyl group.

"Arsenediyl" refers to a diradical monocyclic or polycyclic aromatic group. Examples of arenediyl groups include benzenediyl and naphthalenediyl. In certain embodiments, the arene diyl group is C_6-12Aromatic diyl, C_6-10Aromatic diyl, C_6-9An arene diyl group, and in certain embodiments a phenyl diyl group.

"aryl" refers to a monovalent aromatic hydrocarbon group derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system. Aryl groups include 5-and 6-membered carbocyclic aromatic rings, such as benzene; bicyclic ring systems in which at least one ring is a carbocyclic ring and an aromatic hydrocarbon, such as naphthalene, indane and tetralin; and wherein at least one ring is a carbocyclic and an aromatic tricyclic ring system, such as fluorene. Aryl includes polycyclic ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic, cycloalkyl or heterocycloalkyl ring. For example, aryl includes 5-and 6-membered carbocyclic aromatic rings fused to a 5-to 7-membered heterocycloalkyl ring containing one or more heteroatoms selected from N, O and S. For such fused bicyclic ring systems where only one ring is a carbocyclic aromatic ring, the point of attachment may be on the carbocyclic aromatic ring or the heterocycloalkyl ring. Examples of aryl groups include, but are not limited to, groups derived from the cluster anthrylene, acenaphthene, acephenanthrene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexylene, hexene, asymmetric indacene, symmetric indacene, indane, indene, naphthalene, octacene, octaphene, octene, meta-dianthracene (ovalene), penta-2, 4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, dinaphthylene, pleiadene (pleiadene), pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene, and the like. In certain embodiments, the aryl group may have from 6 to 20 carbon atoms, and in certain embodiments from 6 to 12 carbon atoms. However, aryl does not include or overlap in any way with heteroaryl, which is otherwise defined herein. Thus, a polycyclic ring system in which one or more carbocyclic aromatic rings are fused to a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein. In certain embodiments, aryl is phenyl.

"arylalkyl" refers to an alkyl group in which one hydrogen atom is replaced with an aryl group. In certain embodiments of arylalkyl groups, a hydrogen atom on a terminal carbon atom of the alkyl group is replaced with an aryl group. In certain embodiments of arylalkyl, aryl is C_6-12Aryl, in certain embodiments C_6-10Aryl, and in certain embodiments phenyl or naphthyl. In certain embodiments, the alkane di-moiety of the arylalkyl group can be, for example, C_1-10Alkanediyl, C_1-6Alkanediyl, C_1-4Alkanediyl, C_1-3Alkanediyl, propane-1, 3-diyl, ethane-1, 2-diyl or methane-diyl. In certain embodiments, arylalkyl is C_7-18Arylalkyl radical, C_7-16Arylalkyl radical, C_7-12Arylalkyl radical, C_7-10Arylalkyl or C_7-9An arylalkyl group. E.g. C_7-9Arylalkyl groups may include C bonded to phenyl_1-3An alkyl group.

"Cycloalkanediyl" refers to a diradical saturated monocyclic or polycyclic hydrocarbon group. In certain embodiments, the cycloalkanediyl group is C_3-12Cycloalkanediyl group, C_3-8Cycloalkanediyl group, C_3-6A cycloalkanediyl group, and in certain embodiments is C_5-6A cycloalkanediyl group. Examples of the cycloalkanediyl group include cyclohexane-1, 4-diyl, cyclohexane-1, 3-diyl and cyclohexane-1, 2-diyl.

"cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon mono-radical group. In certain embodiments, the cycloalkyl group is C_3-12Cycloalkyl radical, C_3-8Cycloalkyl radical, C_3-6Cycloalkyl, and in certain embodiments is C_5-6A cycloalkyl group.

"CycloalkylalkanesRadical "refers to an alkyl radical in which one hydrogen atom is replaced by a cycloalkyl radical. In certain embodiments of cycloalkylalkyl groups, the hydrogen atom on the terminal carbon atom of the alkyl group is substituted with a cycloalkyl group. In certain embodiments of cycloalkylalkyl, the cycloalkyl is C_3-6Cycloalkyl, in certain embodiments is C_5-6Cycloalkyl, and in certain embodiments cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. In certain embodiments, the alkane di-moiety of the cycloalkylalkyl group can be, for example, C_1-10Alkanediyl, C_1-6Alkanediyl, C_1-4Alkanediyl, C_1-3Alkanediyl, propane-1, 3-diyl, ethane-1, 2-diyl or methane-diyl. In certain embodiments, the cycloalkylalkyl is C_4-16Cycloalkylalkyl radical, C_4-12Cycloalkylalkyl radical, C_4-10Cycloalkylalkyl radical, C_6-12Cycloalkylalkyl or C_6-9A cycloalkylalkyl group. E.g. C_6-9Cycloalkylalkyl includes C bonded to cyclopentyl or cyclohexyl_1-3An alkyl group.

"cycloalkylalkanediyl" refers to a diradical of a cycloalkylalkane group. In certain embodiments, the cycloalkylalkanediyl group is C_4-16Cycloalkyl alkanediyl, C_4-12Cycloalkyl alkanediyl, C_4-10Cycloalkyl alkanediyl, C_6-12Cycloalkylalkanediyl or C_6-9Cycloalkylalkanediyl. E.g. C_6-9Cycloalkylalkanediyl comprises a C bonded to a cyclopentyl or cyclohexyl group_1-3An alkyl group.

"cycloalkylalkane" group refers to a saturated, branched or straight-chain, acyclic hydrocarbon group in which one of the hydrogen atoms is replaced with a cycloalkane group. In certain embodiments of cycloalkylalkane groups, the hydrogen atom on the terminal carbon atom of the linear alkane group is replaced with a cycloalkyl group. In certain embodiments, the cycloalkyl group is C_3-6Cycloalkyl radicals, in certain embodiments C_5-6Cycloalkyl groups, and in certain embodiments cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl groups. The alkane moiety of the cycloalkylalkane group mayIs for example C_1-10Alkane, C_1-6Alkane, C_1-4Alkane, C_1-3Alkane, propane, ethane or methane. In certain embodiments, the cycloalkylalkane group is C_4-16Cycloalkyl alkane, C_4-12Cycloalkyl alkane, C_4-10Cycloalkyl alkane, C_6-12Cycloalkyl alkanes or C_6-9A cycloalkylalkane. E.g. C_6-9Cycloalkylalkanes comprising a C bonded to a cyclopentyl or cyclohexyl group_1-3An alkyl group.

"diisocyanate-derived group" refers to a linkage in which one or both of the terminal isocyanate groups of the parent diisocyanate form a carbamate (-O-C (O) -NR-), thiocarbamate (-S-C (O) -NR-) or urea linkage (-NR-C (O) -NR-). The diisocyanate-derived group includes an aliphatic diisocyanate-derived group and an aromatic diisocyanate-derived group. In certain embodiments, the diisocyanate-derived groups are aliphatic diisocyanate-derived groups, and in certain embodiments the diisocyanate-derived groups are aromatic diisocyanate-derived groups. For example, compounds derived from 2, 6-diisocyanatotoluene have the following structure:

wherein each R is a bond to an-O-, -S-, or-NR-group.

Examples of aliphatic diisocyanates include 1, 6-hexamethylene diisocyanate, 1, 5-diisocyanato-2-methylpentane, methyl 2, 6-diisocyanatohexanoate, bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, 2, 4-trimethylhexane 1, 6-diisocyanate, 2,4, 4-trimethylhexane 1, 6-diisocyanate, 2,5(6) -bis (isocyanatomethyl) cyclo [2.2.1 ].]Heptane, 1,3, 3-trimethyl-1- (isocyanatomethyl) -5-isocyanatocyclohexane, 1, 8-diisocyanato-2, 4-dimethyloctane, octahydro-4, 7-methylene-1H-indenemethyl diisocyanate and1, 1' -methylenebis (4-isocyanatocyclohexane), and 4, 4-methylenedicyclohexyldiisocyanate (H)₁₂MDI). Examples of the aromatic diisocyanate include 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 6-tolylene diisocyanate (2,6-TDI), 2, 4-tolylene diisocyanate (2,4-TDI), a blend of 2,4-TDI and 2,6-TDI, 1, 5-diisocyanatonaphthalene, diphenylether 4,4 '-diisocyanate, 4' -methylenediphenyl diisocyanate (4,4-MDI), 2,4 '-methylenediphenyl diisocyanate (2,4-MDI), 2' -diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate (MDI), 3 '-dimethyl-4, 4' -biphenylene isocyanate, 1, 6-tolylene diisocyanate, 2, 6-tolylene diisocyanate (2,6-TDI), 4 '-methylenediphenyl diisocyanate (4,4-MDI), 2' -diisocyanatodiphenylmethane (MDI), 3 '-dimethyl-4, 4' -biphenyl, 3,3 '-dimethoxy-4, 4' -diphenyldiisocyanate, 1- [ (2, 4-diisocyanatophenyl) methyl group]3-isocyanato-2-methylbenzene and 2,4, 6-triisopropyl-m-phenylene diisocyanate.

Examples of cycloaliphatic diisocyanates that may be optionally employed as diisocyanates include isophorone diisocyanate (IPDI), cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatocyclohexyl) -2, 2-propane, bis (isocyanatocyclohexyl) -1, 2-ethane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-5-isocyanato-heptane Esterylmethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane, and 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane.

Examples of aromatic diisocyanates in which the isocyanate group is not directly bonded to an aromatic ring include, but are not limited to, bis (isocyanato) benzene, α, α, α ', α' -tetramethylxylene diisocyanate, 1, 3-bis (1-isocyanato-1-methylethyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanato) phthalate, and 2, 5-bis (isocyanatomethyl) furan. Aromatic diisocyanates having an isocyanate group directly bonded to an aromatic ring include phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 4' -diphenylmethane diisocyanate, bis (3-methyl-4-isocyanatophenyl) methane, bis (isocyanatophenyl) ethylene, 3' -dimethoxy-biphenyl-4, 4' -diisocyanate, diphenyl ether diisocyanate, bis (isocyanatophenyl ether) ethylene glycol, bis (isocyanatophenyl ether) -1, 3-propylene glycol, benzophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 4' -diphenylmethane diisocyanate, p-phenylene diisocyanate, 2, 4-toluene diisocyanate, and 2, 6-toluene diisocyanate.

"group derived from an ethylenically unsaturated monoisocyanate" refers to a group in which the isocyanate groups of the parent ethylenically unsaturated monoisocyanate form a urethane, thiourethane or urea bond and the ethylenically unsaturated group is bonded to another moiety or it is not bonded to another moiety. In certain embodiments, a group derived from an ethylenically unsaturated isocyanate refers to a group in which the isocyanate groups of the parent ethylenically unsaturated monoisocyanate form a urethane, thiourethane or urea bond and the ethylenically unsaturated group is not bonded to another moiety. For example, the group derived from the ethylenically unsaturated monoisocyanate 2-isocyanatoethyl methacrylate can have the following structure:

wherein the carbonyl group is bonded to-O-, -S-, or-NR-to form a carbamate, thiocarbamate, or urea group, respectively. In certain embodiments, a group derived from an ethylenically unsaturated isocyanate refers to a group in which the isocyanate groups of the parent ethylenically unsaturated monoisocyanate form a urethane, thiocarbamate or urea linkage, and the ethylenically unsaturated group is bonded to another moiety. In such embodiments, the ethylenically unsaturated monoisocyanate, i.e., 2-isocyanatoethyl methacrylate, derived therefrom has the following structure:

wherein the carbonyl group is bonded to-O-, -S-, or-NR-to form a carbamate, thiocarbamate, or urea group, and the former vinyl group is bonded to another moiety.

"heteroalkanoarene" refers to an alkane arene radical in which one or more carbon atoms are replaced by a heteroatom such as N, O, S or P. In certain embodiments of the heteroalkane arene, the heteroatom is selected from N and O.

"Heteroalkylaromatic diyl" refers to an alkylaromatic diyl group in which one or more carbon atoms are replaced by a heteroatom such as N, O, S, or P. In certain embodiments of the heteroalkane arene, the heteroatom is selected from N and O.

"Heteroalkanecycloalkane" refers to an alkane-cycloalkane group in which one or more carbon atoms are replaced by a heteroatom such as N, O, S, or P. In certain embodiments of isoalkane cycloalkanes, the heteroatom is selected from N and O.

"Heteroalkanecycloalkanediyl" refers to an alkanecycloalkanediyl group wherein one or more carbon atoms have been replaced by a heteroatom such as N, O, S or P. In certain embodiments of the heteroalkane cycloalkanediyl group, the heteroatom is selected from N and O.

"Heteroalkanediyl" refers to alkanediyl groups in which one or more carbon atoms are replaced by a heteroatom such as N, O, S or P. In certain embodiments of the heteroalkyldiyl group, the heteroatom is selected from N and O.

"Heterocycloalkyldiyl" refers to a cycloalkyldiyl group in which one or more carbon atoms are replaced by a heteroatom such as N, O, S or P. In certain embodiments of heteroalkyldiyl, the heteroatom is selected from N and O.

"heteroalkyl" refers to an alkyl group in which one or more carbon atoms are replaced with a heteroatom such as N, O, S or P. In certain embodiments of heteroalkyl groups, the heteroatom is selected from N and O.

"Heteroarenediyl" refers to arenediyl groups in which one or more carbon atoms are replaced with a heteroatom such as N, O, S, or P. In certain embodiments of heteroarenediyl, the heteroatom is selected from N and O.

"heteroaryl" refers to a monovalent heteroaryl group derived by the removal of one hydrogen atom from a single atom of a parent heteroaromatic ring system. Heteroaryl includes polycyclic ring systems having at least one heteroaromatic ring fused to at least one other ring, which may be aromatic or non-aromatic. Heteroaryl includes 5-to 7-membered aromatic monocyclic rings containing one or more, e.g., 1-4, or in certain embodiments 1-3, heteroatoms selected from N, O, S and P, with the remaining ring atoms being carbon; and bicyclic heterocycloalkyl rings containing one or more, e.g., 1-4, or in certain embodiments 1-3, heteroatoms selected from N, O, S and P, the remaining ring atoms being carbon and wherein at least one heteroatom is present in the aromatic ring. For example, heteroaryl includes a 5-to 7-membered heteroaromatic ring fused to a 5-to 7-membered cycloalkyl ring. For such fused bicyclic heteroaryl ring systems, wherein only one ring contains one or more heteroatoms, the point of attachment may be at the heteroaryl or cycloalkyl ring. In certain embodiments, wherein the total number of N, O, S and P atoms in the heteroaryl group exceeds 1, the heteroatoms are not each otherAdjacent to each other. In certain embodiments, the total number of N, O, S and P atoms in the heteroaryl group is no greater than 2. In certain embodiments, the total number of N, O, S and P atoms in the aromatic heterocycle is no greater than 1. Heteroaryl does not include or overlap with aryl as defined herein. Examples of heteroaryl groups include those derived from: acridine, arsenoindole, carbazole, alpha-carboline, chroman, benzopyran, phthalazine, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isobenzopyran, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine (perimidine), phenanthridine, phenanthroline, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, quinazoline, quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and the like. In certain embodiments, the heteroaryl is C_5-20Heteroaryl group, C_5-12Heteroaryl group, C_5-10Heteroaryl, and in certain embodiments is C_5-6A heteroaryl group. In certain embodiments, heteroaryl is derived from: thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole or pyrazine.

"Ketone" refers to the formula CO (R)₂Wherein each R is a hydrocarbon group. In certain embodiments of the ketones, each R is independently selected from C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl and substituted C_6-12A cycloalkylalkyl group. In certain embodiments of the ketone, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, the ketone is selected from the group consisting of propan-2-one, butan-2-one, pentan-2-one, and heptan-3-one. In certain embodiments of the ketones, each R is independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl and substituted C_6-12And (4) an aryl group.

"phenylalkyl" refers to an alkyl group in which one hydrogen atom is replaced with a phenyl group. In certain embodiments of phenylalkyl groups, one hydrogen atom on a terminal carbon atom of the alkyl group is replaced with a phenyl group. In certain embodiments, the phenylalkyl group is C_7-12Phenylalkyl, C_7-10Phenylalkyl, C_7-9Phenylalkyl, and in certain embodiments benzyl.

"substituted" refers to groups in which one or more hydrogen atoms are each independently substituted with the same or different substituents. In certain embodiments, the substituent is selected from halogen, -S (O)₂OH、-S(O)₂-SH, -SR, wherein R is C_1-6Alkyl, -COOH, -NO₂、-NR₂Wherein each R is independently selected from hydrogen and C_1-3Alkyl, -CN, = O, C_1-6Alkyl radical, C_1-3Alkyl, -CF₃-OH, phenyl, C_2-6Heteroalkyl group, C_5-6Heteroaryl group, C_1-6Alkoxy and-COR, wherein R is C_1-6An alkyl group. In certain embodiments, the substituent is selected from the group consisting of-OH, -NH₂And C_1-3An alkyl group.

For the purposes of the following description, it is to be understood that the embodiments of the invention provided may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in the examples, or unless otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of about 1 and the recited maximum value of about 10, i.e., a minimum value equal to or greater than about 1 and a maximum value of equal to or less than about 10.

Reference is now made to the polymers, compositions, and methods of certain embodiments. The disclosed embodiments are not intended to limit the claims. On the contrary, the intent is to cover all alternatives, modifications and equivalents.

Multifunctional sulfur-containing polymers

As indicated, certain embodiments provided by the present disclosure relate to multifunctional sulfur-containing polymers. Sulfur-containing polymers include polythioethers, polydisulfides, and polymers containing both thioether and disulfide groups. Polythioethers generally refer to polymers containing at least two sulfide groups, such as 2-C-S-C-groups. Polydisulfides are polymers which contain at least two disulfide groups, for example 2-C-S-C-groups. In addition to at least two thioether and/or disulfide groups, the sulfur-containing polymers provided by the present disclosure further comprise at least two formaldehyde, acetal, and/or ketal groups, e.g., at least 2-O-CR₂-O-group, wherein each R is independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl and substituted C_6-12And (4) an aryl group. As used herein, "polymer" refers to oligomers, homopolymers, and co-polymers. Molecular weight unless otherwise stated, is polyThe number average molecular weight of the compound material, denoted by "Mn", is determined, for example, by gel permeation chromatography using polystyrene standards in a manner recognized in the art.

In certain embodiments, the sulfur-containing polymers provided by the present disclosure comprise the reaction product of reactants comprising: (a) a sulfur-containing diol; (b) a polyol containing at least three (3) hydroxyl groups per polyol molecule; and (c) a reactant selected from the group consisting of aldehydes, ketones, and combinations thereof. The reactants may include one or more types of sulfur-containing diols, one or more types of polyols, and/or one or more types of aldehydes and/or ketones.

In certain embodiments of the reaction, the sulfur-containing diol comprises the structure:

wherein p is selected from 1 and 2; and each R¹Is independently selected from C_2-6An alkanediyl group. In certain embodiments of the sulfur-containing diol, p is 1, and in certain embodiments p is 2. In certain embodiments of the sulfur-containing diol, each R¹Are the same, and in certain embodiments, each R is¹Is different. In certain embodiments, each R is¹Is selected from C_2-5Alkanediyl, C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments, R¹Is ethane-1, 2-diyl. In certain embodiments of this reaction, the sulfur-containing diol comprises a sulfur-containing diol selected from the group consisting of 2,2 ' -thiodiethanol, 3' -thiobis (propan-1-ol), 4' -thiobis (butan-1-ol), and combinations of any of the foregoing. In certain embodiments of this reaction, the sulfur-containing diol comprises 2, 2' -thiodiethanol.

In certain embodiments of this reaction, the sulfur-containing diols comprise a single type of sulfur-containing diol, and in certain embodiments, comprise a mixture of sulfur-containing diols. The mixture of sulfur-containing diols may constitute from 5mol% to 95mol% of the one or more thioethers (p is 1) and from 95mol% to 5mol% of the one or more disulfides (p is 2). In certain embodiments, the mixture of sulfur-containing diols comprises 50 mole% of the one or more sulfides and 50 mole% of the one or more disulfides. In certain embodiments, the mixture of sulfur-containing diols comprises 0mol% to 30mol% of the one or more disulfides and 100mol% to 70mol% of the one or more thioethers.

In certain embodiments, the polyol contains at least three hydroxyl groups per polyol molecule. For example, the polyol may contain from 3 to 10 hydroxyl groups per polyol molecule, from 3 to 8 hydroxyl groups per polyol molecule, from 3 to 6 hydroxyl groups per polyol molecule, and in certain embodiments, from 3 to 4 hydroxyl groups per polyol molecule. In certain embodiments, the polyol contains 4 hydroxyl groups per polyol molecule, and in certain embodiments, the polyol contains three hydroxyl groups per polyol molecule. The polyol can be a single type of polyol or a mixture of different polyols having the same or different number of hydroxyl groups per molecule.

In certain embodiments, the polyol comprises a triol of formula (1):

wherein each R²Independently is C_1-6An alkanediyl group; and in certain embodiments, the polyol comprises a triol of formula (2):

wherein each R²Independently is C_1-6An alkanediyl group. In certain embodiments of the polyols of formula (1) and formula (2), each R is²Can be independently selected from C_1-4Alkanediyl, in certain embodiments selected from C_1-3An alkanediyl group. In certain embodiments, each R is²May be the same, in certain embodiments, each R²May be different. In a certain of the polyols of formula (1) and formula (2)In some embodiments, each R is²Selected from methane diyl, ethane-1, 2-diyl, propane-1, 3-diyl, and, in certain embodiments, butane-1, 4-diyl.

In certain embodiments of this reaction, reactant (c) is an aldehyde. In certain embodiments wherein reactant (C) is an aldehyde, the aldehyde comprises C_1-6Aldehyde, C_1-4Aldehyde, C_1-3The aldehyde, in certain embodiments, is C_1-2An aldehyde. In certain embodiments, the aldehyde comprises an alkyl group and is selected from the group consisting of acetaldehyde, propionaldehyde, isobutyraldehyde, and butyraldehyde. In certain embodiments, the aldehyde is formaldehyde.

In certain embodiments of this reaction, reactant (c) is a ketone. In certain embodiments wherein reactant (c) is a ketone, the ketone has the formula C (O) R₂Wherein each R is independently selected from C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12And (4) an aryl group. In certain embodiments of the ketone, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, the ketone is selected from the group consisting of propan-2-one, butan-2-one, pentan-3-one, and 3-methylbutan-2-one.

In certain embodiments, the sulfur-containing polymer of formula (I) is the reaction product of reactants comprising: 2, 2' -thiodiethanol and formaldehyde, and in the present invention is preferred as thiodiglycol polythioether or thiodiglycol polyoxymethylene.

In embodiments where the one or more polyols used to form the sulfur-containing polymers provided by the present disclosure have the same number of hydroxyl groups, the sulfur-containing polymer has a hydroxyl functionality that is about equal to the polyol. For example, when a polyol having a hydroxyl functionality of three, or a mixture of polyols in which the hydroxyl functionality of each polyol in the mixture is three, is used to prepare a sulfur-containing polymer, the sulfur-containing polymer has a hydroxyl functionality of three. In certain embodiments, the sulfur-containing polymer may have an average hydroxyl functionality of 3, 4, 5, and in certain embodiments 6.

When polyols having different hydroxyl functionalities are used to prepare the multifunctional sulfur-containing polymer, the multifunctional sulfur-containing polymer can have a range of functionalities. For example, the polyfunctional sulfur-containing polymers provided by the present disclosure can have an average hydroxyl functionality of from 3 to 12, 3 to 9, 3 to 6, 3 to 4, and in certain embodiments, 3.1 to 3.5. In certain embodiments, a sulfur-containing polymer having an average hydroxyl functionality of 3 to 4 can be prepared by reacting one or more polyols having 3 hydroxyl functionalities with a combination of one or more polyols having 4 hydroxyl functionalities.

In certain embodiments, the sulfur-containing polymer of formula (I) has a hydroxyl number of from 10 to 100, from 20 to 80, from 20 to 60, from 20 to 50, and in certain embodiments, from 20 to 40. The hydroxyl number is the hydroxyl content of the sulfur-containing polymer and can be determined, for example, by ethylating the hydroxyl groups and titrating the resulting acid with potassium hydroxide. The hydroxyl number is the weight of potassium hydroxide in milligrams used to neutralize acid from 1 gram of sulfur-containing polymer.

In certain embodiments, the sulfur-containing polymers provided by the present disclosure have a number average molecular weight of 200-.

In certain embodiments, the sulfur-containing polymers provided by the present disclosure are the reaction product of reactants comprising: 2, 2' -thiodiethanol, formaldehyde, and a triol of formula (1). In certain embodiments, the sulfur-containing polymers provided by the present disclosure are the reaction product of reactants comprising: 2, 2' -thiodiethanol, formaldehyde, and a triol of formula (2).

The reaction for preparing the sulfur-containing polymer of formula (I) can occur in the presence of an acidic catalyst, such as sulfuric acid, sulfonic acid, or a combination thereof. In certain embodiments, sulfonic acids may be used. Examples of sulfonic acids include alkylsulfonic acidsSuch as methanesulfonic acid, ethanesulfonic acid, tert-butanesulfonic acid, 2-propanesulfonic acid and cyclohexylsulfonic acid; olefin sulfonic acids such as α -olefin sulfonic acid, dimerized α -olefin sulfonic acid, and 2-hexene sulfonic acid; aromatic sulfonic acids such as p-toluenesulfonic acid ester, benzenesulfonic acid and naphthalenesulfonic acid; and polymer supported sulfonic acids, such as AMBERLYST available from Dow Chemical^TMA sulfonic acid catalyst.

In certain embodiments, the multifunctional sulfur-containing polymer has the structure of formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mThe core of (1). Each R¹Which may be the same or different, each R²May be the same or may be different.

In certain embodiments of the sulfur-containing polymer of formula (I), each R¹Independently selected from C_2-6Alkanediyl, C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments ethane-1, 2-diyl. In certain embodiments of the compounds of formula (I), each R is¹Is ethane-1, 2-diyl.

In certain embodiments of the sulfur-containing polymer of formula (I), each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_1-4Alkyl radical, C_1-3Alkyl radical, C_1-2An alkyl group. In certain embodiments of the compounds of formula (I), each R is³Is methyl and, in certain embodiments, is ethyl. In certain embodiments of the compounds of formula (I), each R is³Is hydrogen, and in certain embodiments, each R is³Selected from hydrogen, methyl, and ethyl. In certain embodiments of the compounds of formula (I), each R is¹Is ethane-1, 2-diyl, each R³Is hydrogen.

In certain embodiments of the sulfur-containing polymer of formula (I), each R¹Are identical and are selected from C_2-3Alkanediyl such as ethane-1, 2-diyl and propane-1, 3-diyl; and each R³Is the same and is selected from hydrogen and C_1-3Alkyl groups such as methyl, ethyl, and propyl. In certain embodiments of the sulfur-containing polymer of formula (I), each R³Is hydrogen, and in certain embodiments, each R is³Is methyl. In certain embodiments of the sulfur-containing polymer of formula (I), each R¹Is ethane-1, 2-diyl and each R³Is hydrogen. In certain embodiments of the sulfur-containing polymer of formula (I), each R¹Identical and selected from ethane-1, 2-diyl and propane-1, 3-diyl; and each R³Independently selected from hydrogen, methyl, and ethyl.

In certain embodiments of the sulfur-containing polymers of formula (I), n is an integer selected from 1 to 50, an integer selected from 2 to 40, an integer selected from 4 to 30, and in certain embodiments, an integer selected from 7 to 30.

In certain embodiments of the sulfur-containing polymer of formula (I), each p is the same and is 1, and in certain embodiments, each p is the same and is 2.

In certain embodiments of the compounds of formula (I), m is 1, m is 2, m is 3, m is 4, m is 5, and in certain embodiments, m is 6.

In certain embodiments of compounds of formula (I), m is 3, and the parent polyol Z (OH)_mA triol of formula (1):

wherein each R²Independently is C_1-6Alkanediyl, and in certain embodiments, a triol of formula (2):

wherein each R²Independently is C_1-6An alkanediyl group. Therefore, Z has the following structure:

bond of internal group.

In certain embodiments, the sulfur-containing polymer of formula (I) has a hydroxyl number of from 10 to 100, from 20 to 80, from 20 to 60, from 20 to 50, and in certain embodiments, from 20 to 40.

In some embodiments, the sulfur-containing polymer of formula (I) has a number average molecular weight of 200-.

Terminal-modified sulfur-containing polymers

The hydroxy-terminated multifunctional sulfur-containing polymer of formula (I) can be derivatized such that the terminal hydroxyl groups are replaced with a group selected from the group consisting of vinyl-terminated groups, epoxy-terminated groups, amine-terminated groups, silyl-terminated groups, thiol-terminated groups, and isocyanate-terminated groups.

In certain embodiments, the terminal-modified sulfur-containing polymer comprises the reaction product of reactants comprising (a) a sulfur-containing polymer of formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group, and an isocyanate group, and a group reactive with the terminal hydroxyl group of the polymer of formula (I).

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, and an epoxy group, and a group reactive with the terminal hydroxyl group of the polymer of formula (I).

In certain embodiments of the terminal-modified sulfur-containing polymer, the terminal group is a vinyl group and the compound comprising a terminal vinyl group is selected from the group consisting of ethylenically unsaturated monoisocyanates and ethylenically unsaturated alcohols.

Ethylenically unsaturated monoisocyanates include ethylenically unsaturated aromatic monoisocyanates and ethylenically unsaturated aliphatic monoisocyanates. Examples of ethylenically unsaturated monoisocyanates include vinyl isocyanate, allyl isocyanate, 3-isocyanato-2-methyl-2-propene, methacryloyl isocyanate, isocyanatoethyl methacrylate, vinyl-benzyl isocyanate, 3-isocyanato-1-butene, 3-isocyanato-3-methyl-1-butene, 4-isocyanato-2-methyl-1-butene, 4-isocyanato-3, 3-dimethyl-1-butene, 4-isocyanato-4-methyl-1-pentene and 5-isocyanato-1-pentene, 2-isocyanatoethyl methacrylate and dimethyl-m-isopropenylbenzyl isocyanate.(TMI). In certain embodiments, the ethylenically unsaturated monoisocyanate is selected from the group consisting of vinyl isocyanate, allyl isocyanate, and methacryl isocyanate. In certain embodiments, the ethylenically unsaturated aliphatic monoisocyanates are selected from C_2-10Alkenyl isocyanates, C_2-8Alkenyl isocyanates, C_2-6Alkenyl isocyanates, and in certain embodiments, is C_2-3An alkenyl isocyanate.

Examples of the ethylenically unsaturated alcohols include, for example, allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, ethylene glycol monovinyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, glycerol monoallyl ether, trimethylolethane monoallyl ether, trimethylolpropane monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1-vinylcyclobutanol, 2-vinylcyclobutanol, 3-vinylcyclobutanol, vinylphenol, 2-allylphenol, 4-allyl-2-methoxyphenol, 4-allyl-2, 6-dimethoxyphenol, 4- (2-propenyl) -1, 2-benzenediol and 4- (2, 4-dihydroxyphenyl) -3-buten-2-one. In certain embodiments, the ethylenically unsaturated alcohol is selected from the group consisting of allyl alcohol, ethylene glycol monoallyl ether, 2-allylphenol, and 4-allylphenol.

In certain embodiments, the vinyl group-containing compound is an ethylenically unsaturated monoisocyanate and is selected from the group consisting of 3-isopropenyl- α, α -dimethylbenzyl isocyanate (CAS2094-99-7) and 2-isocyanatoethyl methacrylate.

In certain embodiments of the reaction to form the terminal-modified sulfur-containing polymer, the terminal group is a silyl group and the compound comprising the terminal silyl group is an isocyanatoalkylalkoxysilane. Examples of suitable isocyanatoalkylalkoxysilanes include, for example, isocyanatopropylmethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltriisopropoxysilane, isocyanatopropylmethyldiisopropoxysilane, isocyanatoneohexyltrimethoxysilane, isocyanatoneohexyldimethoxysilane, isocyanatoneohexyldiethoxysilane, isocyanatoneohexyltriethoxysilane, isocyanatoneohexyltriisopropoxysilane, isocyanatoneohexyldiisopropoxysilane, isocyanatoisoprenyltrimethoxysilane, isocyanatoisopentyldimethoxysilane, isocyanatoisopentylmethylsilane, isocyanatoisopentylmethyldiethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatopropyltriisopropoxysilane, isocyanatopropyltriisopropyltrimethoxysilane, isocyanatopropyldimethoxysilane, isocyanatoethyldimethoxysilane, isocyanatoethyl, Isocyanato isopentyl triethoxysilane, isocyanato isopentyl triisopropoxy silane, and isocyanato isopentyl methyl diisopropoxy silane. In certain embodiments, the isocyanatoalkyltrialkoxysilane is 3-isocyanatopropyltrimethoxysilane.

In certain embodiments of the reaction to form the terminal-modified sulfur-containing polymer, the terminal group is an epoxy group and comprises a member selected from the group consisting of C_1-6Epoxyalkanol, C_1-6Epoxy haloalkanes, and combinations thereof. Suitable C_1-6Examples of alkanol epoxides include oxirane2-ol, oxirane2-ylcarbinol, and 2- (oxirane2-yl) ethanol. Suitable C_1-6Examples of epoxy haloalkanes include, for example, 2- (chloromethyl) oxirane and 2- (2-chloroethyl) oxirane.

In certain embodiments, the terminal-modified sulfur-containing polymer comprises the reaction product of reactants comprising: (a) and (b), wherein (a) comprises a reaction product comprising reactants of (I) and (ii), wherein (I) comprises a sulfur-containing polymer of formula (I), each n is an integer selected from 1 to 50, and m is an integer selected from 3 to 6; each p is independently selected from 1-2; each R¹Is independently selected from C_2-6An alkanediyl group; and each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl and substituted C_6-12Aryl, Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) comprises a first compound selected from the group consisting of diisocyanates, ethylenically unsaturated monoisocyanates, and p-toluenesulfonates; and (b) comprises a second compound comprising a terminal group selected from the group consisting of a vinyl group, a silyl group, and an epoxy group, and a group selected from the group consisting of a group reactive with an isocyanate group, a group reactive with an ethylenically unsaturated group, and a group reactive with p-toluenesulfonate.

In certain embodiments, the amine-terminated sulfur-containing polymer comprises the reaction product of reactants comprising (a) and (b), wherein (a) comprises the reaction product of reactants comprising: (i) and (ii), wherein (I) comprises a sulfur-containing polymer of formula (I):

wherein each n is selected from an integer from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) comprises a first compound selected from the group consisting of diisocyanates, ethylenically unsaturated monoisocyanates, and tosylates; and (b) includes a second compound comprising an amine group and a group selected from the group consisting of an isocyanate group, an ethylenically unsaturated group, and a tosylate reactive group.

In certain embodiments, the first compound is a diisocyanate and is selected from, for example, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 6-toluene diisocyanate (2,6-TDI), 2, 4-toluene diisocyanate (2,4-TDI), a blend of 2,4-TDI and 2,6-TDI, 1, 5-diisocyanatonaphthalene, diphenyl ether 4,4 '-diisocyanate, 4' -methylenediphenyl diisocyanate (4,4-MDI), 2,4 '-methylenediphenyl diisocyanate (2,4-MDI), 2' -diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate (MDI), 3 '-dimethyl-4, 4' -diphenylisocyanate, 3 '-dimethoxy-4, 4' -diphenyldiisocyanate, 1- [ (2, 4-diisocyanatophenyl) methyl group]3-isocyanato-2-methylbenzene, 2,4, 6-triisopropyl-m-phenylene diisocyanate and 4, 4-methylenedicyclohexyl diisocyanate (H)₁₂MDI), and combinations of any of the foregoing.

In certain embodiments of this reaction to form the terminal-modified sulfur-containing polymer, the first compound is an ethylenically unsaturated monoisocyanate, such as 2-isocyanatoethyl methacrylate. Examples of other ethylenically unsaturated monoisocyanates are disclosed herein.

In certain embodiments, the first compound is a tosylate, such as a sulfonyl chloride, for example, p-toluenesulfonyl chloride.

In certain embodiments of the reaction to form the terminal-modified sulfur-containing polymer, the second compound comprising a terminal amine group is selected from the group consisting of aniline, aminoalkyl-substituted aniline, aminoalkyl and sulfur-containing diamine. In certain embodiments, the aminoalkyl-substituted aniline is selected from the group consisting of 4- (aminomethyl) aniline and 4- (aminoethyl) aniline. In certain embodiments, the aminoalkyl is selected from ethylamine, propan-1-amine, and butan-1-amine. Suitable sulfur-containing diamines include, for example

In certain embodiments of the reaction to form the terminal-modified sulfur-containing polymer, the second compound is an alkyl aminobenzoate. Examples of suitable alkyl aminobenzoates include, for example, methyl 4-aminobenzoate, ethyl 4-aminobenzoate, methyl 3-aminobenzoate, ethyl 3-aminobenzoate, methyl 2-aminobenzoate, and ethyl 3-aminobenzoate. In certain embodiments, the alkyl aminobenzoate is ethyl 4-aminobenzoate.

In certain embodiments, the thiol-terminated sulfur-containing polymer comprises the reaction product of reactants comprising: (a) and (b), wherein (a) comprises the reaction product of reactants comprising: (i) and (ii), wherein (I) comprises a sulfur-containing polymer of formula (I):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and Z represents an m-valent parent polyol Z (OH)_mA core of (a); and (ii) comprises a first compound selected from the group consisting of diisocyanates, thioureas, ethylenically unsaturated monoisocyanates, and tosylates; and (b) comprises a mercaptoalkanol when (ii) comprises a diisocyanate; when (ii) comprises thiourea, (b) comprises a metal hydrosulfide; when (ii) comprises an ethylenically unsaturated monoisocyanate, (b) comprises a dithiol; and (b) includes a metal hydrosulfide when (ii) includes a tosylate.

In certain embodiments, the first compound is a diisocyanate, including any of those disclosed herein.

In certain embodiments, the first compound is an ethylenically unsaturated monoisocyanate, including any of those disclosed herein.

In certain embodiments, the first compound is a tosylate, including any of those disclosed herein, such as p-toluenesulfonyl chloride.

In certain embodiments, the second compound is a mercaptoalkanol, e.g., C_2-6Mercaptoalkanols, for example 2-mercaptoethane-1-ol, 3-mercaptopropane-1-ol, 4-mercaptobutan-1-ol, 5-mercaptopentan-1-ol, and 6-mercaptohexan-1-ol. Examples of suitable dithiols include, for example, C_2-10Alkanedithiols, such as ethane-1, 2-dithiol, propane-1, 3-dithiol, butane-1, 4-dithiol, pentane-1, 5-dithiol, and hexane-1, 6-dithiol.

In certain embodiments, the second compound is a metal hydrosulfide, such as sodium hydrosulfide.

In certain embodiments of forming the terminal-modified sulfur-containing polymer, the compound comprising a terminal thiol group is selected from the group consisting of dithiols and alkyl (di) oxydialkanethiols. In certain embodiments, the second compound is a dithiol, including, for example, 1, 2-ethanedithiol, 1, 2-propanedithiol, 1, 3-butanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 3-pentanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 3-dimercapto-3-methylbutane, dipentenedithiol, ethylcyclohexyldithiol, dimercaptodiethylsulfide, methyl-substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, and 1, 5-dimercapto-3-oxapentane. The dithiols may have one or more side groups selected from C_1-4Alkyl radical, C_1-4Alkoxy, and hydroxy.

In certain embodiments, the dithiol is an alkyl (di) oxydialkanethiol. The alkyl (di) oxydialkylthiol may have the general formula HS-R-O-R-O-R-HS, wherein each R is an alkanediyl, e.g. C_2-6Alkanediyl, C_2-4Alkanediyl, or ethane-1, 2-diyl. Suitable dithiols include alkyl (bis) oxyalkanedithiols, such as 1, 8-dimercapto-3, 6-dioxaoctane (DMDO) or dimercapto diethyl sulfide (DMDS). In certain embodiments, the dithiols are selected from dimercaptosDiethylsulfide (DMDS), dimercaptodioxaoctane (DMDO), and 1, 5-dimercapto-3-oxapentane.

Further examples of suitable dithiols include compounds of the formula HS-R-SH, wherein R is C having one or more pendant groups_2-6Alkanediyl, which side group may be, for example, a hydroxyl group, C_1-6Alkyl groups such as methyl or ethyl groups; c_1-6Alkoxy radical, C_6-8Cycloalkanediyl group, C_6-10Alkanecycloalkanediyl- [ - (CH)₂)_s-X-]_q-(CH₂)_r-, or at least one of them-CH₂-substituted by a methyl group- [ - (CH)₂)_s-X-]_p-(CH₂)_rAnd wherein each s is an integer independently selected from 2 to 6, each q is an integer independently selected from 1 to 5, and each r is an integer independently selected from 2 to 10. The dithiols may include one or more heteroatom substituents in the carbon backbone, such as dithiols where X is a heteroatom such as O, S or other divalent heteroatom group, a secondary or tertiary amine group, such as-NR-, where R is hydrogen or methyl, or another substituted trivalent heteroatom. In certain embodiments, X is O or S, and in certain embodiments, p and r are equal, and in certain embodiments, both p and r are 2. In certain embodiments, X is a bond. Other examples of suitable dithiols are disclosed, for example, in U.S. Pat. No.6,172,179, the entire contents of which are incorporated herein by reference.

In certain embodiments of the above terminal-modified sulfur-containing polymers, the terminal-modified sulfur-containing polymer has a number average molecular weight of 200-.

Certain terminal-modified sulfur-containing polymers provided by the present disclosure have the structure of formula (II):

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; each R⁵is-OR⁵', wherein R⁵' is selected from the group consisting of vinyl-terminated groups, silyl-terminated groups, amine-terminated groups, epoxy-terminated groups, thiol-terminated groups, and isocyanate-terminated groups; and Z represents an m-valent parent polyol Z (OH)_mThe core of (1).

wherein each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; p is independently selected from 1 and 2; each R¹Independently selected from C_2-6An alkanediyl group; each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; each R⁵is-OR⁵' wherein R⁵' is selected from the group consisting of vinyl-terminated groups, silyl-terminated groups, amine-terminated groups, epoxy-terminated groups, and thiol-terminated groups; and Z represents an m-valent parent polyol Z (OH)_mThe core of (1).

In certain embodiments of the sulfur-containing polymer of formula (II), eachA R¹Is independently selected from C_2-6Alkanediyl, C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments, ethane-1, 2-diyl. In certain embodiments of the polymer of formula (II), each R¹Is ethane-1, 2-diyl.

In certain embodiments of the sulfur-containing polymer of formula (II), each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_1-4Alkyl radical, C_1-3Alkyl, and in certain embodiments, C_1-2An alkyl group. In certain embodiments of the sulfur-containing polymer of formula (II), each R³Is hydrogen, and in certain embodiments is methyl, and in certain embodiments is ethyl.

In certain embodiments of the sulfur-containing polymer of formula (II), each R¹Are identical and are selected from C_2-3Alkanediyl, such as ethane-1, 2-diyl and propane-1, 3-diyl; and each R²Are the same and are selected from hydrogen and C_1-3Alkyl groups such as methyl, ethyl and propyl. In certain embodiments of the sulfur-containing polymer of formula (II), each R¹Is ethane-1, 2-diyl. In certain embodiments of the sulfur-containing polymer of formula (II), each R³Is hydrogen. In certain embodiments of the sulfur-containing polymer of formula (II), each R¹Is ethane-1, 2-diyl, and each R³Is hydrogen.

In certain embodiments of the compounds of formula (II), m is 1, m is 2, m is 3, m is 4, m is 5, and in certain embodiments, m is 6.

In certain embodiments of the sulfur-containing polymer of formula (II), wherein m is 3, the parent polyol Z (OH)_mA triol of formula (1):

wherein each R²Independently is C_1-6Alkanediyl in someIn an embodiment, the triol is of formula (2):

wherein each R²Independently is C_1-6An alkanediyl group. Thus, in these embodiments, Z has the following structure:

wherein each R is²Independently is C_1-6An alkanediyl group.

In certain embodiments of the sulfur-containing polymer of formula (II), each n is an integer selected from 1 to 50, an integer selected from 2 to 40, an integer selected from 4 to 30, and in certain embodiments, n is an integer selected from 7 to 30.

In certain embodiments of the sulfur-containing polymer of formula (II), each p is the same and is 1, and in certain embodiments, each p is the same and is 2.

In certain embodiments, the sulfur-containing polymer of formula (II) has a number average molecular weight of 200-.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵The same is true.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵A vinyl-terminated group selected from formula (a), formula (b), formula (c), formula (d), and formula (e):

wherein each R⁶Is a moiety derived from an ethylenically unsaturated monoisocyanate; each R⁷Is selected from C_2-6Alkanediyl and C_2-6A heteroalkyldiyl group; each R⁸Selected from hydrogen, C_1-6Alkyl and phenyl; and each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarene diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_3-12Heterocycloalkanediyl, substituted C_3-12Heterocycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Heteroalkane arene diyl, C_4-18Alkanecycloalkanediyl and substituted C_4-18Alkanecycloalkanediyl.

In certain embodiments, each R is⁶Derived from ethylenically unsaturated aliphatic monoisocyanates, ethylenically unsaturated cycloaliphatic monoisocyanates, and, in certain embodiments, ethylenically unsaturated aromatic monoisocyanates.

In certain embodiments of formula (b) and formula (d), each R⁷Is selected from C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments is selected from ethane-1, 2-diyl, propane-1, 3-diyl, propane-1, 2-diyl, and propane-1, 1-diyl. In certain embodiments of formula (b) and formula (d) each R⁷Ethane-1, 2-diyl and propane-1, 3-diyl are selected.

In certain embodiments of formula (b), formula (c), formula (d), and formula (e), each R⁸Selected from the group consisting of hydrogen, methyl, ethyl, isopropyl and n-propyl.

In certain embodiments of formula (e), each R is⁹Is selected from C_2-6Alkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Alkane areneDiradicals, C_4-18Alkane cycloalkanediyl and substituted C_4-18Alkane cycloalkanediyl group. In certain embodiments of formula (e), each R is⁹Are identical and are selected from methanediyl, ethane-1, 2-diyl and propane-1, 2-diyl. In certain embodiments of formula (e), each R is⁹Is C_2-5Alkanediyl, C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments, ethane-1, 2-diyl.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵A silyl-terminated group selected from formula (f) and formula (g):

wherein each R is⁶Derived from an ethylenically unsaturated monoisocyanate; each R¹⁰Is independently selected from C_1-6Alkyl radical, C_1-6Alkoxy radical, C_5-6Cycloalkyl radical, C_6-12Cycloalkylalkyl, phenyl and C_7-12A phenylalkyl group; wherein at least one R¹⁰Is C_1-6An alkoxy group; and each R¹¹Is C_1-6An alkanediyl group.

In certain embodiments of formula (g), each R¹¹Selected from methane diyl, ethane-1, 2-diyl and propane-1, 2-diyl. In certain embodiments of formula (f) and formula (g), each R¹⁰Are the same and are selected from methoxy, ethoxy and propoxy. In certain embodiments of formula (f) and formula (g), the silyl end group is a trialkoxysilane, in certain embodiments a dialkoxysilane, and in certain embodiments a monoalkoxysilane.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵An amine-terminated group selected from formula (h), formula (i), formula (j), formula (k), formula (l), and formula (m):

wherein each R⁶Selected from the group consisting of diisocyanate-derived groups and ethylenically unsaturated monoisocyanates-derived groups; each R⁷Selected from the group consisting of a bond and C_2-6An alkanediyl group; each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarene diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_3-12Heterocycloalkanediyl, substituted C_3-12Heterocycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Heteroalkane arene diyl, C_4-18Alkane cycloalkanediyl and substituted C_4-18An alkane cycloalkanediyl group; and each R¹²Selected from hydrogen, C_1-6Alkyl radical, C_6-12Aryl, substituted C_6-12Aryl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_7-18Arylalkyl, substituted C_7-18Arylalkyl radical, C_4-18Alkylcycloalkyl and substituted C_4-18An alkylcycloalkyl group.

In certain embodiments of formula (h), each R⁶Are groups derived from diisocyanates and in certain embodiments the groups are derived fromW(H₁₂MDI) TDI and ISONATE^TM143L (polycarbodiimide-modified diphenylmethane diisocyanate),N3400(1, 3-diazetidine-2, 4-dione, 1, 3-bis (6-isocyanatohexyl) -),(I) (isophorone diisocyanate, IPDI).

In certain embodiments of formula (h), each R⁶Is a group derived from an ethylenically unsaturated monoisocyanate, and in certain embodiments is selected from 2-isocyanatoethyl methacrylate.

In certain embodiments of formula (j), formula (k), formula (l), and formula (m), each R⁷Is selected from C_2-4Alkanediyl, C_2-3Alkanediyl, and in certain embodiments is selected from ethane-1, 2-diyl, propane-1, 3-diyl, propane-1, 2-diyl, and propane-1, 1-diyl. In certain embodiments of formula (j), formula (k), formula (l), and formula (m), each R⁷Selected from ethane-1, 2-diyl and propane-1, 3-diyl.

In certain embodiments of formula (k) and formula (l), each R⁹Is selected from C_2-6Alkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Alkane-arene diyl, C_4-18Alkane cycloalkanediyl and substituted C_4-18Alkane cycloalkanediyl group.

In certain embodiments of formula (h), formula (i), formula (j), formula (k), formula (l), and formula (m), each R is¹²Is selected from C_1-6Alkyl, phenyl and amino substituted phenyl. In certain embodiments of formula (h), formula (i), formula (j), formula (k), formula (l), and formula (m), each R is¹²Selected from phenyl, methyl, ethyl, propyl, methyl-phenyl, ethyl-phenyl, propyl-phenyl, benzyl, phenethyl, - (CH)₂) -aniline and aminophenyl.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵An epoxy-terminated group selected from formula (n):

each of whichR¹¹Independently is C_1-6An alkanediyl group.

In certain embodiments of formula (n), each R¹¹Selected from methane diyl, ethane-1, 2-diyl and propane-1, 3-diyl. In certain embodiments, each R is¹¹Are identical and are selected from methanediyl, ethane-1, 2-diyl and propane-1, 3-diyl.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵A thiol-terminated group selected from formula (o), formula (p), formula (q), formula (r), formula(s), formula (t), formula (u), and formula (v):

wherein each R⁶Selected from the group consisting of diisocyanate-derived moieties and ethylenically unsaturated monoisocyanates-derived moieties; each R⁷Is selected from C_2-14Alkanediyl and C_2-14A heteroalkyldiyl group; and each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarene diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_3-12Heterocycloalkanediyl, substituted C_3-12Heterocycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Heteroalkane arene diyl, C_4-18Alkane cycloalkanediyl and substituted C_4-18Alkane cycloalkanediyl group.

In certain embodiments of formula (o), each R⁶Are groups derived from diisocyanates, and in certain embodiments the groups are derived from TDI, ISONATE^TM143L (polycarbodiimide-modified diphenylmethane diisocyanate),(1, 3-diazetidine-2, 4-)Diketone, 1, 3-bis (6-isocyanatohexyl) -),(isophorone diisocyanate, IPDI), or(H₁₂MDI)。

In certain embodiments of formula (o), each R⁶Are groups derived from ethylenically unsaturated monoisocyanates, and in certain embodiments are 2-isocyanatoethyl methacrylate.

In certain embodiments of formula (o), formula (p), formula (q), formula(s), formula (t), formula (u), and formula (v), each R is optionally substituted with one or more substituents selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl⁷Is selected from C_2-6An alkanediyl group. In certain embodiments of formula (o), formula (p), formula (q), formula(s), formula (t), formula (u), and formula (v), each R is optionally substituted with one or more substituents selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl⁷Is selected from-CH₂-S-(CH₂)₂-O-(CH₂)₂-O-(CH₂)₂-、-(CH₂)₂-O-(CH₂)₂-O-(CH₂)₂-and- (CH)₂)₂-S-(CH₂)₂-O-(CH₂)₂-O-(CH₂)₂-。

In certain embodiments of formula (t) and formula (u), each R⁹Is selected from C_2-6Alkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Alkane-arene diyl, C_4-18Alkane cycloalkanediyl and substituted C_4-18Alkane cycloalkanediyl group.

In certain embodiments of the sulfur-containing polymer of formula (II), each R⁵An isocyanate-terminated group selected from formula (w) and formula (x):

wherein each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarenediyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl, C_3-12Heterocyclane diyl, substituted C_3-12Heterocyclic alkanediyl, C_7-18Alkylaromatic diyl, substituted C_7-18Heteroalkanoarenediyl, C4-18 alkanecycloalkanediyl, and substituted C_4-18Alkanecycloalkanediyl; and each R¹²A group derived from a diisocyanate.

In certain embodiments of formula (w), each R⁹Is selected from C_2-6Alkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl, C_7-18Alkylaromatic diyl, substituted C_7-18Alkane-arene diyl, C_4-18Alkanecycloalkanediyl, and substituted C_4-18Alkanecycloalkanediyl.

In certain embodiments of formula (x), each R is¹²The groups derived from diisocyanates, in certain embodiments, from TDI, ISONATE^TM143L (polycarbodiimide-modified diphenylmethane diisocyanate),(1, 3-azetidine-2, 4-dione, 1, 3-bis (6-isocyanatohexyl) -),i (isophorone diisocyanate, IPDI), orW(H12MDI)。

Synthesis of sulfur-containing polymers

The multifunctional sulfur-containing polymers and precursors thereof provided by the present disclosure can be prepared by a number of methods known to those skilled in the art, including those described in the examples herein. For example, to obtain the multifunctional sulfur-containing polymer of formula (I), a sulfur-containing diol, a polyol having at least three hydroxyl groups per polyol molecule, and an aldehyde and/or ketone may be reacted in an organic solvent in a sulfonic acid catalyst such as AMBERLYST^TM15 to provide the corresponding multifunctional sulfur-containing polymer of formula (I).

Synthesis of terminal modified multifunctional sulfur-containing polymer derivatives

The terminal-modified multifunctional sulfur-containing polymers and precursors thereof provided by the present disclosure can be prepared by a number of methods well known to those skilled in the art, including those described in the examples herein. For example, to obtain the terminal-modified multifunctional sulfur-containing polymer of formula (II), the multifunctional sulfur-containing polymer of formula (I) can be reacted with a compound having suitable end groups and groups that react with the terminal hydroxyl groups of the polymer of formula (I).

For example, to obtain a vinyl-terminated sulfur-containing polymer of formula (II), the sulfur-containing polymer of formula (I) can be reacted with a compound containing a terminal vinyl group and an isocyanate group (e.g., an ethylenically unsaturated monoisocyanate such as TMI, 2-isocyanatoethyl methacrylate, or allyl isocyanate) in the presence of dibutyltin dilaurate and benzyl chloride at 76 ℃. As a further example, the sulfur-containing polymer of formula (I) can be reacted with an alkane alcohol such as 3-buten-1-ol and an aldehyde such as formaldehyde in an organic solvent such as toluene in a sulfonic acid (e.g., 4.7 meq/gH)⁺) Such as AMBERLYST^TM15 to provide a vinyl terminated sulfur containing polymer of formula (II).

The silyl-terminated sulfur-containing polymer of formula (II) may be prepared, for example, by reacting the sulfur-containing polymer of formula (I) with an isocyanatoalkyltrialkoxysilane, such as 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropylethoxysilane, in the presence of dibutyltin dilaurate at a temperature of 76 ℃ to provide the corresponding silyl-terminated sulfur-containing polymer of formula (II).

The epoxy-terminated sulfur-containing polymer of formula (II) can be prepared, for example, by reacting the sulfur-containing polymer of formula (I) in the presence of a monoepoxy compound, such as epichlorohydrin, to provide the corresponding epoxy-terminated sulfur-containing polymer of formula (II).

Can be prepared, for example, by reacting a vinyl-terminated sulfur-containing polymer of formula (II)) with an aniline, an amine-substituted aniline such as 4- (aminomethyl) aniline or an alkylamine such as n-butylamine, optionally in the presence of a catalyst such as 1, 8-diazabicyclo [5.4.0]Reacting undec-7-ene (DBU) in an organic solvent to provide the corresponding amine-terminated sulfur-containing polymer of formula (III) to produce the amine-terminated sulfur-containing polymer of formula (III). Alternatively, the corresponding amine-terminated sulfur-containing polymer of formula (III) can be provided by reacting the isocyanate-terminated sulfur-containing polymer of formula (II) with a diamine, such as 4- (aminomethyl) aniline, to obtain the amine-terminated sulfur-containing polymer of formula (III). It is also possible to prepare the sulfur-containing polymers of the formula (I) by reacting them with amino-substituted benzoic acids, for example ethyl-4-aminobenzoic acid, in Bu₂SnO or NaOMe at elevated temperature to provide the corresponding amine-terminated sulfur-containing polymer of formula (III), which may also be obtained. The amine-terminated sulfur-containing polymers of formula (III) can be prepared by reacting a tosylate ester of a sulfur-containing polymer of formula (III) with an amine-containing compound, such as aniline, in an organic solvent at elevated temperature to provide the corresponding amine-terminated sulfur-containing polymer of formula (III).

The thiol-terminated sulfur-containing polymer of formula (IV) can be prepared by reacting a vinyl-terminated sulfur-containing polymer of formula (IV), such as 2-isocyanatoethyl methacrylate adduct or an allyl isocyanate adduct as disclosed herein, with a dithiol, such as DMDO. By reacting tosyl esters of sulfur-containing polymers of formula (I) with NaSH in MeN (Bu)₃ ⁺Cl^-By reaction in water in the presence ofThe thiol-terminated sulfur-containing polymer of formula (IV) can be prepared by reacting the corresponding thiol-terminated sulfur-containing polymer of formula (IV). Alternatively, the tosyl ester of the sulfur-containing polymer of formula (I) can be reacted with thiourea in MeN (Bu)₃ ⁺Cl^-In water to provide the p-toluenesulfonate salt of the thiourea adduct, which can then be reacted at elevated temperature in the presence of a base to provide the corresponding thiol-terminated sulfur-containing polymer of formula (IV). Alternatively, to obtain the thiol-terminated sulfur-containing polymer of formula (IV), the sulfur-containing polymer of formula (I) can be first reacted with a diisocyanate, such as TDI, in the presence of dibutyltin dilaurate at 75 ℃ to 80 ℃ to provide the corresponding isocyanate-terminated sulfur-containing polymer of formula (IV). The isocyanate-terminated sulfur-containing polymer of formula (IV) can then be reacted with a mercaptoalkanol, such as 2-mercaptoethanol or 3-mercaptopropanol, to provide the corresponding thiol-terminated sulfur-containing polymer of formula (IV).

Can be prepared, for example, by reacting a sulfur-containing polymer of formula (I) with a diisocyanate such as TDI, ISONATE^TM143L (polycarbodiimide-modified diphenylmethane diisocyanate),(1, 3-diazetidine-2, 4-dione, 1, 3-bis (6-isocyanatohexyl) -),(isophorone diisocyanate, IPDI) or(H12MDI) optionally in the presence of a catalyst such as dibutyltin dilaurate at a temperature of 70 ℃ to 80 ℃ to prepare the isocyanate-terminated sulfur-containing polymer of formula (II). The isocyanate-terminated sulfur-containing polymers can be used as intermediates in the synthesis of other terminal-modified sulfur-containing polymers, such as certain amine-terminated and thiol-terminated sulfur-containing polymers provided by the present disclosure.

Properties of terminal-modified multifunctional Sulfur-containing polymers

In certain embodiments, the terminal-modified multifunctional sulfur-containing polymers provided by the present disclosure are liquid at room temperature. Moreover, in certain embodiments, the sulfur-containing polymer has a viscosity at 100% solids of no more than 500 poisson, e.g., 10-300 poisson or, in some cases, 100-200 poisson, at 25 ℃ and a pressure of 760mmHg as determined using a Brookfield CAP2000 viscometer, according to ASTM D-2849 § 79-90. In certain embodiments, T of the sulfur-containing polymers provided by the present disclosure_g(glass transition temperature) of not higher than-40 ℃ and, in certain embodiments, not higher than-50 ℃.

Use of

The multifunctional sulfur-containing polymers provided by the present disclosure may be used in compositions such as sealants, coatings, and/or electrical potting compositions comprising one or more sulfur-containing polymers provided by the present disclosure. Sealant compositions refer to compositions that are capable of producing films having the ability to withstand the operating conditions, such as moisture and temperature, and at least partially impede the permeation of substances such as water, fuel, and other liquids and gases. In certain embodiments, the sealant compositions provided by the present disclosure may be used, for example, as aerospace sealants and as liners for fuel tanks.

In certain embodiments, the composition comprises a hydroxyl terminated sulfur-containing polymer, or sulfur-containing polymer, of formula (I) prepared by the reaction of: (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reactant selected from the group consisting of aldehydes, ketones, and combinations thereof; a compound having a group reactive with a hydroxyl group; and a curing agent. In certain embodiments, the group reactive with a hydroxyl group is selected from isocyanates, alcohols, and thiols.

In certain embodiments, the composition comprises: a terminal-modified sulfur-containing polymer of formula (II), or a terminal-modified sulfur-containing polymer, which is a reaction product of any one of the reactions disclosed herein; and at least one curing agent reactive with the terminal-modified sulfur-containing polymer.

In certain embodiments, the present disclosure provides compositions comprising, in addition to the sulfur-containing polymer of formula (II), or the reaction product of the reaction disclosed herein, one or more additional sulfur-containing polymers. The sulfur-containing polymer can be any polymer having at least one sulfur atom in the repeating unit, including polymeric thiols, polythiols, thioethers, sulfur-containing polymers, polyoxymethylenes, and polythioethers. As used herein, "thiol" refers to a compound that contains a thiol or sulfhydryl group, i.e., -SH group, as the only functional group or in combination with other functional groups, such as hydroxyl groups, for example, thioglycerol. Polythiols refer to compounds having more than 1-SH group, such as dithiols or higher functionality polythiols. Such thiol groups are typically terminal and/or pendant such that they have a hydrogen that is reactive with other functional groups. The term "polythioether" as used herein refers to any compound comprising a sulfur-sulfur linkage (-S-S-). Polythiols can include terminal and/or pendant sulfur atoms (-SH) and non-reactive sulfur atoms (-S-or-S-S-). Thus, the term polythiol generally encompasses sulfur-containing polymers and polythioethers. Examples of other sulfur-containing polymers that can be used in the compositions provided by the present disclosure include, for example, those disclosed in U.S. Pat. nos. 6,172,179, 6,509,418, and 7,009,032.

In certain embodiments, the present disclosure provides compositions comprising a polythioether having the structure:

-R¹-[-S-(CH₂)₂-O-[-R²-O-]_t-(CH₂)₂-S-R¹-]_u-

wherein R is¹Is selected from C_2-6Alkanediyl, C_6-8Cycloalkanediyl, C_6-10Cycloalkyl alkane diyl (- [ (-CH)₂-)_s-X-]_q-(-CH₂-)_r-, and wherein at least one-CH₂- [ (-CH) with units substituted by methyl groups₂-)_s-X-]_q-(-CH₂-)_r-；R²Is selected from C_2-6Alkanediyl, C_6-8Cycloalkanediyl, C_6-10Cycloalkylalkanediyl, and- [ (-CH)₂-)_s-X-]_q-(-CH₂-)_r-; x is selected from O, S, and-NR-wherein R is selected from hydrogen and methyl; t is an integer selected from 0 to 10; u is an integer selected from 1 to 60; s is an integer selected from 2 to 6; q is an integer selected from 1 to 5, and r is an integer selected from 2 to 10. Such polythioethers are described in U.S. Pat. No.6,172,179, the entire contents of which are incorporated herein by reference. The one or more other sulfur-containing polymers may be difunctional or polyfunctional, e.g., having from 3 to 6 terminal groups, or mixtures thereof.

In certain embodiments, the compositions provided by the present disclosure comprise 10% to 90%, 20% to 80%, 30% to 70%, and in certain embodiments 40% to 60% by weight of the sulfur-containing polymer provided by the present disclosure, wherein weight% is based on the total weight (i.e., dry weight) of all non-volatile components of the composition. In certain embodiments, the compositions provided by the present disclosure comprise 10-90%, 20-90%, 30-90%, 40-90%, 50-90%, 60-90%, 70-90%, and in certain embodiments 80-90% by weight of the sulfur-containing polymer provided by the present disclosure, wherein weight% is based on the total weight (i.e., dry weight) of all non-volatile components of the composition.

Curing agents suitable for the compositions provided by the present disclosure include compounds reactive with the terminal groups of the sulfur-containing polymers provided by the reactions disclosed herein of formula (II), such as compounds reactive with hydroxyl groups, vinyl groups, epoxy groups, thiol groups, amine groups, or isocyanate groups.

Examples of suitable curing agents reactive with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are disclosed herein.

Examples of suitable curing agents reactive with vinyl groups include dithiols and polythiols, examples of which are disclosed herein.

The silyl-terminated sulfur-containing polymers provided by the present disclosure hydrolyze in the presence of water, causing self-polymerization by condensation. It will be appreciated that because the curing agent for the silyl terminated sulfur containing polymer may be atmospheric moisture, the composition comprising the silyl terminated sulfur containing polymer need not include a curing agent. Thus, the composition comprising the silyl terminated sulfur-containing polymer and the curing agent for the silyl groups refers to atmospheric moisture. The composition comprising the silyl-terminated sulfur-containing polymer may further comprise a catalyst. Other catalysts used with silyl-terminated sulfur-containing polymers include organotitanium compounds such as titanium tetraisopropoxide, titanium tetra-t-butoxide, titanium di (isopropoxy) bis (ethylacetoacetate) and titanium di (isopropoxy) bis (acetoacetoacetoacetate); organotin compounds, dibutyltin dilaurate, dibutyltin butyl tin diacetylacetate and tin octoate; metal dicarboxylates such as lead dioctoate; organozirconium compounds such as zirconium tetraacetylacetylacetonate; and organoaluminum compounds such as triacetyl-aluminum acetylacetonate. Specific examples include titanium diisopropoxybis (ethylacetopyruvate), titanium diisopropoxybis (acetoacetonate) and titanium dibutoxybis (methylacetoacetate).

Examples of suitable curing agents reactive with epoxy groups include amines such as Diethylenetriamine (DTA), triethylenetetramine (TTA), Tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), Diethylaminopropylamine (DEAPA), N-aminoethylpiperazine (N-AEP), Isophoronediamine (IPDA), m-xylylenediamine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS); aromatic amines, ketimines; a polyamine; a polyamide; a phenol resin; anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, glycerol trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride polythiols; a polythiol; ultraviolet curing agents such as diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate; and other curing agents known to those skilled in the art.

Examples of suitable curing agents reactive with thiol groups include diepoxides.

Examples of suitable curing agents reactive with amine groups include isocyanates, diisocyanates, polymeric polyisocyanates, non-limiting examples of which include polyisocyanates having backbone linkages selected from carbamate linkages (-NH-C (O) -O-), thiocarbamate linkages (-NH-C (O) -S-), thiocarbamate linkages (-NH-C (S) -O-), dithiocarbamate linkages (-NH-C (S) -S-), and any combination of the foregoing.

Examples of suitable curing agents reactive with isocyanate groups include diamines, polyamines, polythiols, and polyols, including those disclosed herein.

The compositions provided by the present disclosure may contain an amount of from 90% to 150%, from 95% to 125%, and in certain embodiments from 95% to 105% of the stoichiometric ratio, where the stoichiometric ratio is the ratio of the number of reactive isocyanate groups to the number of groups reactive with isocyanate groups. For example, a composition containing the same number of isocyanate groups and amine groups prior to reaction will have a stoichiometric amount of isocyanate groups and amine groups.

The compositions provided herein can include one or more different types of fillers. Suitable fillers include those generally known in the art, including inorganic fillers such as carbon black and calcium carbonate (CaCO)₃) And a lightweight filler. Suitable light weight fillers include, for example, those described in U.S. patent No. 6525168. In certain embodiments, the composition comprises from 5wt% to 60wt% of the filler or filler composition, from 10wt% to 50wt% and in certain embodiments from 20wt% to 40wt%, based on the total dry weight of the composition.

As can be appreciated, the selection of the sulfur-containing polymer, curing agent, and filler and any additives used in the composition can be made so as to be compatible with each other.

The compositions provided herein can include one or more colorants, thixotropic agents, accelerators, retarders, adhesion promoters, solvents, masking agents, or mixtures of any of the foregoing.

As used herein, the term "colorant" means any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant can be in any form such as discrete particles, dispersions, solutions, and/or flakes. A single colorant or a combination of two or more colorants can be used in the composition.

Examples of colorants include pigments, dyes and Color-imparting agents, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. The colorant may comprise, for example, a finely divided solid powder which is insoluble but wettable under the conditions of use. The colorant may be organic or inorganic, and may be aggregated or non-aggregated. The colorant may be incorporated into the composition by using a grinding media such as acrylic grinding media.

Examples of pigments and/or pigment compositions include carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (flake), benzimidazolone, isoindolinone, isoindoline, polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrene, perinone, triphenypyrene dione, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole red (DPPBO red), titanium dioxide, carbon black, and combinations of any of the foregoing.

Examples of dyes include, but are not limited to, solvent-and/or aqueous-based ones such as phthalocyanine green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, and quinacridone.

Examples of color-imparting agents include pigments such as AQUA-CHEM896 (commercially available from Degussa, Inc.), CHARISMA COLORANTS and maxiner input COLORANTS (commercially available from Accurate dispersions of Eastman Chemical, Inc.) dispersed in a water-based or water-miscible vehicle.

As noted above, the colorant can be in the form of a dispersion, including, for example, a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. The nanoparticle dispersion may include a colorant such as a pigment or dye having a particle size of less than 150nm, for example less than 70nm or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with milling media having a particle size of less than 0.5 mm. Examples of nanoparticle dispersions and methods for making them are disclosed in U.S. patent No. 6875800. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and/or chemical attrition (i.e., partial dissolution). To minimize re-aggregation of the nanoparticles in the coating, a dispersion of resin-coated nanoparticles may be used. As used herein, "dispersion of resin-coated nanoparticles" refers to a continuous phase in which are dispersed discrete "composite microparticles" comprising nanoparticles and a resin coating on the nanoparticles. Examples of dispersions containing resin-coated nanoparticles and methods for making them are disclosed in U.S. patent No. 7438972.

Examples of special effect compositions that can be used in the compositions provided herein include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or discoloration. Additional special effect compositions may provide other perceptible properties such as opacity or texture. In certain embodiments, special effect compositions can produce a color change such that the color of the composition changes when the coating is viewed from different perspectives. Examples of color effect compositions are disclosed in U.S. patent No. 6894086. Additional color effect compositions may include transparent coated mica and/or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and/or any composition wherein interference is caused by refractive index differences within the material and not by refractive index differences between the material and the air surface.

Generally, the colorant can comprise 1wt% to 65wt%, 2wt% to 50wt%, such as 3wt% to 40wt%, or 5wt% to 35wt% of the composition, with weight percentages based on the total dry weight of the composition.

Thixotropic agents such as silica may be used in amounts of 0.1wt% to 5wt%, based on the total dry weight of the composition.

Catalysts known in the art, such as amines, may be present in an amount of 0.1 to 5 weight percent based on the total weight of the composition. Examples of suitable catalysts include 1, 4-diaza-bicyclo [2.2.2]Octane (C)Available from Air Products, Chemical additives division) and(an accelerator composition comprising 2,4, 6-tris (dimethylaminomethyl) phenol).

Flame retardants, such as stearic acid, can be present in the composition in an amount of 0.1wt% to 5wt%, based on the total dry weight of the composition. The adhesion promoter may be present in an amount of 0.1wt% to 15wt% of the composition, based on the total dry weight of the composition. Examples of adhesion promoters include phenolic compounds, such as methyl ON phenolic resins available from Occidental Chemicals, and organosilanes such as epoxy, mercapto or amino-functionalized silanes, such as those available from MomentivePerformance MaterialsA-187 andand A-1100. Masking agentFor example, pine fragrance or other perfume (which can be used to mask any low level of malodor of the composition) may be present in an amount of from 0.1wt% to 1wt%, based on the total dry weight of the composition.

In certain embodiments, the compositions provided herein can include a plasticizer, which can facilitate the use of the glass transition temperature T_gSulfur-containing polymers above the glass transition temperature typically used in aerospace sealants. For example, the use of a plasticizer can be effective in reducing the T of the composition_gAnd thereby increasing the low temperature flexibility of the cured polymerizable composition beyond T based on the sulfur-containing polymer alone_gThe expected flexibility. Suitable plasticizers in certain embodiments of the composition include, for example, phthalates, chlorinated paraffins, and terphenyls. The plasticizer or plasticizer composition may comprise 1wt% to 40wt% of the composition or 1wt% to 10wt% of the composition. In certain embodiments, the composition may comprise one or more organic solvents, such as isopropanol, in an amount of, for example, 0wt% to 15wt%, 0wt% to 10wt%, or 0wt% to 5wt%, based on the non-dry weight of the composition.

In certain embodiments, the compositions provided herein are substantially free, or in some cases completely free, of any solvent, such as an organic solvent or an aqueous solvent, i.e., water. In certain embodiments, the different compositions provided herein are substantially 100% solids.

In certain embodiments, compositions, such as sealant compositions, can be provided as multi-pack compositions, such as two-pack compositions, wherein one pack comprises one or more prepolymers provided herein and a second pack comprises one or more curatives for one or more sulfur-containing polymers. Additives and/or other materials may be added to either package as desired or needed. The two packages may be combined and mixed prior to use. In certain embodiments, the shelf life of the mixed sulfur-containing polymer and curing agent is at least 30 minutes, at least 1 hour, at least 2 hours, and in certain embodiments greater than 2 hours, where shelf life refers to the time the mixed composition remains suitable for use as a sealant.

The compositions provided herein can be applied to any of a variety of substrates. Examples of substrates to which the composition may be applied include titanium, stainless steel and aluminum (which may be anodized, primed, organic coated or chromate coated); epoxy; a carbamate; graphite; a glass fiber composite;(ii) a Acrylic acid; and a polycarbonate.

The compositions provided herein can be applied directly onto the surface of the substrate or onto the underlying layer by any suitable coating method known to those skilled in the art.

In certain embodiments, the compositions provided herein are fuel-resistant. As used herein, the term "fuel-resistant" means that the composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that exhibits a percent volume swell of no greater than 40%, in some cases no greater than 25%, in some cases no greater than 20%, and in still other cases no greater than 10% according to a method similar to those described in ASTM D792 (american society for testing and materials) or AMS3269 (aerospace material specifications) immersed for one week at 140 ° f (60 ℃) and ambient pressure. As used to determine fuel resistance, jet reference Fluid JRF type I has the following composition (see AMS2629, published 7 months 1 days 1989, § 3.1.1, et al, available from SAE (society of automotive engineering)): toluene: 28 plus or minus 1 volume percent; cyclohexane (technical grade): 34 +/-1 volume percent; isooctane: 38 + -1 vol%; and tert-dibutyl disulfide: 1 + -0.005 vol%.

In certain embodiments, the compositions provide cured products, such AS sealants, that exhibit tensile strengths of at least 400psi and elongations of at least 100% when measured according to the procedures described in AMS3279, § 3.3.17.1, test procedures AS5127/1, § 7.7.

In certain embodiments, the composition provides a cured product, such AS a sealant, that exhibits a lap shear (lap shear) strength of greater than 200psi and in some cases at least 400psi when measured according to the procedure described in SAE AS5127/1, paragraph 7.8.

In certain embodiments, the cured sealant comprising the sulfur-containing polymer provided by the present invention meets or exceeds the requirements of aerospace sealants described in AMS 3277.

In addition, methods of sealing an aperture using the compositions provided herein are provided. These methods comprise, for example, applying the compositions provided herein to a surface to seal pores, and curing the composition. In certain embodiments, the composition may be cured under ambient conditions, wherein ambient conditions refer to a temperature of 20 ℃ to 25 ℃ and atmospheric humidity. In certain embodiments, the composition can be cured under conditions including a temperature of 0 ℃ to 100 ℃ and a humidity of 0% RH to 100% RH. In certain embodiments, the composition may be cured at elevated temperatures, such as at least 30 ℃, at least 40 ℃, and in certain embodiments at least 50 ℃. In certain embodiments, the composition may be cured at room temperature, e.g., 25 ℃. In certain embodiments, the composition may be cured by exposure to actinic radiation, such as ultraviolet radiation. It will also be appreciated that the method may be used to seal apertures on aerospace tools.

Examples

Embodiments provided herein are further illustrated with reference to the following examples, which describe the synthesis, performance, and use of certain sulfur-containing polymers. It will be apparent to those skilled in the art that many changes, both to materials and methods, may be practiced without departing from the scope of the invention.

Example 1

Synthesis of trifunctional Sulfur-containing polymers

Thiodiglycol (1,215.81g), p-formaldehyde (95% purity) (300.63g), AMBERLYST^TM15(212.80g, Dow Chemical Company), 1,3, 5-tris (2-hydroxyethyl) isocyanurate (13.14g, Aldrich), and toluene (500mL) were charged to a 3-liter, 4-neck round bottom flask. The flask was fitted with a heating mantle, thermocouple, temperature controller, and Dean-Stark trap fitted with a reflux condenser, dropping funnel, and positive pressure inlet for nitrogen. During this time, the collected water was periodically removed from the Dean-Stark separator. Stirring was started under nitrogen and the batch was heated to 120 ℃ and held at 120 ℃ for about 10 hours. The reaction mixture was then cooled to room temperature and filtered through a coarse fired Buchner funnel (600mL volume) with a 9.0cm diameter Whatman GF/a filter paper over the frit. The flask and filter cake were washed with 500mL of toluene. A filtrate was obtained. The filtrate was then taken up in a 2L round bottom flask (rotary evaporator, final vacuum of 5 torr, water bath at 90 ℃). A yellow viscous polymer (993.53g) was obtained. The resulting polyoxymethylene polymer had a hydroxyl number of 25.3 and a viscosity of 214 poisson.

Example 2

Synthesis of trifunctional Sulfur-containing polymers

Thiodiglycol (1.209.67g), p-formaldehyde (95% purity) (300.48g), AMBERLYST^TM15(26.18g, Dow Chemical Company), 1,3, 5-tris (2-hydroxyethyl) isocyanurate (20.9g, Aldrich), and toluene (500mL) were charged to a 3-liter, 4-neck round bottom flask. The flask was fitted with a heating mantle, thermocouple, temperature controller, and Dean-Stark trap fitted with a reflux condenser, dropping funnel, and positive pressure inlet for nitrogen. During this time, the collected water was periodically removed from the Dean-Stark separator. Stirring was started under nitrogen and the batch was heated to 120 ℃ and held at 120 ℃ for about 10 hours. The reaction mixture was then cooled to room temperature and filtered through a coarse fired Buchner funnel (600mL volume) with a 9.0cm diameter Whatman GF/a filter paper over the frit. The flask and filter cake were washed with 500mL of toluene. A filtrate was obtained. The filtrate was then used as a 2L circleBottom flask (rotary evaporator, final vacuum of 5 torr, water bath at 90 ℃). A yellow viscous polymer (953.33g) was obtained. The resulting polyoxymethylene polymer had a hydroxyl number of 22.8 and a viscosity of 377 poisson.

Example 3

Synthesis of trifunctional Sulfur-containing polymers

Thiodiglycol (1,197.45g), p-formaldehyde (95% purity) (300.83g), AMBERLYST^TM15(213.06g, Dow Chemical Company), 1,3, 5-tris (2-hydroxyethyl) isocyanurate (52.58g, Aldrich), and toluene (500mL) were charged to a 3-liter, 4-neck round bottom flask. The flask was fitted with a heating mantle, thermocouple, temperature controller, and Dean-Stark trap fitted with a reflux condenser, dropping funnel, and positive pressure inlet for nitrogen. During this time, the collected water was periodically removed from the Dean-Stark separator. Stirring was started under nitrogen and the batch was heated to 120 ℃ and held at 120 ℃ for about 10 hours. The reaction mixture was then cooled to room temperature and filtered through a coarse fired Buchner funnel (600mL volume) with a 9.0cm diameter Whatman GF/a filter paper over the frit. The flask and filter cake were washed with 500mL of toluene. A filtrate was obtained. The filtrate was then taken up in a 2L round bottom flask (rotary evaporator, final vacuum of 5 torr, water bath at 90 ℃). A yellow viscous polymer (1,039.64g) was obtained. The resulting polyoxymethylene polymer had a hydroxyl number of 23.2 and a viscosity of 942 poisson.

Example 4

Acrylate terminated sulfur-containing polymers

The sulfur-containing polymer of example 1 (222.40g) was charged to a 500-mL, 4-necked round bottom flask. The flask was equipped with a heating mantle, thermocouple, temperature controller, positive pressure inlet for nitrogen, and mechanical stirrer (PTFE paddle and bearings). The polyoxymethylene polyol was stirred and heated to 76.6 ℃ (170 ° f) at about 200rpm, followed by the addition of isocyanate ethyl methacrylate (15.68g) and a solution of 0.05% dibutyltin dilaurate dissolved in methyl ethyl ketone (2.51 g). The reaction mixture was kept at 76.6 ℃ for 5h and then cooled to room temperature. The resulting acrylate-terminated polymer (222.08g) had a viscosity of 299 poisson.

Example 5

Acrylate terminated sulfur-containing polymers

The sulfur-containing polymer of example 2 (247.26g) was charged to a 500-mL, 4-necked round bottom flask. The flask was equipped with a heating mantle, thermocouple, temperature controller, positive pressure inlet for nitrogen, and mechanical stirrer (PTFE paddle and bearings). The polyoxymethylene polyol was stirred and heated to 76.6 ℃ (170 ° f) at about 200rpm, followed by the addition of isocyanate ethyl methacrylate (15.61g) and a solution of 0.05% dibutyltin dilaurate dissolved in methyl ethyl ketone (2.66 g). The reaction mixture was kept at 76.6 ℃ for 5h and then cooled to room temperature. The viscosity of the resulting acrylate-terminated polymer (242.14g) was 439 poisson.

Example 6

Acrylate terminated sulfur-containing polymers

The sulfur-containing polymer of example 3 (243.71g) was charged to a 500-mL, 4-necked round bottom flask. The flask was equipped with a heating mantle, thermocouple, temperature controller, positive pressure inlet for nitrogen, and mechanical stirrer (PTFE paddle and bearings). The polyoxymethylene polyol was stirred and heated to 76.6 ℃ (170 ° f) at about 200rpm, followed by the addition of isocyanate ethyl methacrylate (15.58g) and a solution of 0.05% dibutyltin dilaurate dissolved in methyl ethyl ketone (2.74 g). The reaction mixture was kept at 76.6 ℃ for 5h and then cooled to room temperature. The resulting acrylate-terminated polymer (226.09g) had a viscosity of 1,026 Poisson.

Example 7

TMI-terminated sulfur-containing polymers

The sulfur-containing polymer from example 1 (222.6g) was charged to a 500-mL, 4-necked round bottom flask. The flask was equipped with a heating mantle, thermocouple, temperature controller, positive pressure inlet for nitrogen, and mechanical stirrer (PTFE paddle and bearings). The polyoxymethylene polyol was stirred and heated to 76.6 ℃ (170 ° f) at about 200rpm, followed by the addition of 3-isopropenyl- α, α -dimethylbenzyl isocyanate (TMI) (20.25g, Cytec Industries) and a solution of 0.05% dibutyltin dilaurate dissolved in methyl ethyl ketone (2.47 g). The reaction mixture was kept at 76.6 ℃ for 6 hours and then cooled to room temperature. The resulting TMI-terminated polymer (217.32) had a viscosity of 378 poisson.

Example 8

TMI-terminated sulfur-containing polymers

The sulfur-containing polymer from example 3 (243.70g) was charged to a 500-mL, 4-necked round bottom flask. The flask was equipped with a heating mantle, thermocouple, temperature controller, positive pressure inlet for nitrogen, and mechanical stirrer (PTFE paddle and bearings). The polyoxymethylene polyol was stirred and heated to 76.6 ℃ (170 ° f) at about 200rpm, followed by the addition of 3-isopropenyl- α, α -dimethylbenzyl isocyanate (20.18g, Cytec Industries) and a solution of 0.05% dibutyltin dilaurate dissolved in methyl ethyl ketone (2.62 g). The reaction mixture was kept at 76.6 ℃ for 6 hours and then cooled to room temperature. The resulting TMI-terminated polymer (230.42g) had a viscosity of 1.261 Poisson.

Example 9

Curing of acrylate terminated sulfur-containing polymers

The curing reaction was carried out in 100g plastic containers with lids. The acrylate-terminated sulfur-containing polymer of example 4 (40.8g) and2022(0.2g, 0.5wt%) was mixed manually in the vessel. The vessel was then placed in an accelerated mixer (DAC600FVZ) and mixed for 1 minute at 2,300 rpm. The polymer was poured onto a circular (5 inch diameter) metal cap (preheated with Valspar Mold Release 225) and placed under Ultraviolet (UV) radiation for 30 seconds before the polymer was fully cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300W H-bulb, which produced UV wavelengths in the range of 200nm to 450 nm. Total amount 3.103J/cm measured with a UV energy meter (EIT, Inc., Sterling, Va.)²UV energy is applied to the polymer composition. An 1/2 inch thick cured dish polymer was obtained. The hardness of the polymer was measured by a durometer and was 53 Shore A. Hardness was determined according to ASTM D2240.

Example 10

Curing of acrylate terminated sulfur-containing polymers

The curing reaction was carried out in 100g plastic containers with lids. The acrylate-terminated sulfur-containing polymer of example 5 (40.8g) and2022(0.2g, 0.5wt%) was mixed manually in the vessel. The vessel was then placed in an accelerated mixer (DAC600FVZ) and mixed for 1 minute at 2,300 rpm. The polymer was poured onto a circular (5 inch diameter) metal cap (preheated with Valspar Mold Release 225) and placed under Ultraviolet (UV) radiation for 30 seconds before the polymer was fully cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300W H-bulb, which produced UV wavelengths in the range of 200nm to 450 nm. Total amount 3.103J/cm measured with a UV energy meter (EIT, Inc., Sterling, Va.)²UV energy is applied to the polymer composition. 1/2 inches of cured polymer were obtained. The hardness of the polymer was measured by a durometer and was 51 Shore A. Hardness was determined according to ASTM D2240.

Example 11

Curing of acrylate terminated sulfur-containing polymers

The curing reaction was carried out in 100g plastic containers with lids. The acrylate-terminated sulfur-containing polymer of example 6 (40.8g) and2022(0.2g, 0.5wt%) was mixed manually in the vessel. The vessel was then placed in an accelerated mixer (DAC600FVZ) and mixed for 1 minute at 2,300 rpm. The polymer was poured onto a circular (5 inch diameter) metal cap (preheated with Valspar Mold Release 225) and placed under Ultraviolet (UV) radiation for 30 seconds before the polymer was fully cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300W H-bulb, which produced UV wavelengths in the range of 200nm to 450 nm. Total amount 3.103J/cm measured with a UV energy meter (EIT, Inc., Sterling, Va.)²UV energy is applied to the polymer composition. An 1/2 inch thick dish of cured polymer was obtained. The hardness of the polymer was measured by durometer and was 54 shore a. Hardness was determined according to ASTM D2240.

Example 12

Curing of TMI terminated sulfur-containing polymers

The curing reaction was carried out in 100g plastic containers with lids. TMI-terminated Sulfur-containing Polymer described in example 7 (40.8g) and2022(0.2g, 0.5wt%) was mixed manually in the vessel. The vessel was then placed in an accelerated mixer (DAC600FVZ) and mixed for 1 minute at 2,300 rpm. The polymer was poured onto a circular (5 inch diameter) metal cap (preheated with Valspar Mold Release 225) and placed under UV light for 60 seconds. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was fitted with a 300W H-bulb, which producedUV wavelength in the range of 200nm-450 nm. Total amount 3.103J/cm measured with a UV energy meter (EIT, Inc., Sterling, Va.)²UV energy is applied to the polymer composition. A1 mm-thick dish of cured polymer was obtained.

Example 13

Curing of TMI terminated sulfur-containing polymers

The curing reaction was carried out in 100g plastic containers with lids. TMI-terminated Sulfur-containing Polymer described in example 8 (40.8g) and2022(0.2g, 0.5wt%) was mixed manually in the vessel. The vessel was then placed in an accelerated mixer (DAC600FVZ) and mixed for 1 minute at 2,300 rpm. The polymer was poured onto a circular (5 inch diameter) metal cap (preheated with Valspar Mold Release 225) and placed under UV light for 60 seconds. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300W H-bulb, which produced UV wavelengths in the range of 200nm to 450 nm. Total amount 3.103J/cm measured with a UV energy meter (EIT, Inc., Sterling, Va.)²UV energy is applied to the polymer composition. A1 mm-thick dish of cured polymer was obtained.

Finally, it should be noted that there are alternative ways of implementing the embodiments disclosed herein. Accordingly, the present embodiments are to be considered as illustrative and not restrictive. Furthermore, the claims are not to be limited to the details given herein, and are to be accorded their full scope and equivalents.

Claims

1. A sulfur-containing polymer comprising the reaction product of reactants comprising:

(a) a sulfur-containing diol, wherein the sulfur-containing diol comprises the structure:

wherein:

p is selected from 1 and 2; and

each R¹Independently is C_2-6An alkanediyl group;

(b) a polyol having at least three hydroxyl groups per polyol molecule, wherein said polyol comprises a polyol having the structure Z (OH)_mOf a polyol of (a), wherein

m is an integer of 3 to 6; and

z represents the nucleus of the m-valent parent polyol; and

(c) a reactant selected from the group consisting of aldehydes, ketones, and combinations thereof, wherein

The aldehyde comprises a compound selected from C_1-6The aldehyde of (a); and

the ketone comprises a compound having the structure C (O) R₂Wherein each R is independently selected from C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12And (4) an aryl group.

2. The sulfur-containing polymer of claim 1, wherein said sulfur-containing diol comprises 2, 2' -thiodiethanol.

3. The sulfur-containing polymer of claim 1, wherein said polyol contains 3 hydroxyl groups per molecule and said polyol comprises a triol of formula (1) or a triol of formula (2):

wherein each R²Independently is C_1-6An alkanediyl group.

4. A sulfur-containing polymer having the structure of formula (I):

wherein:

each n is an integer selected from 1 to 50;

m is an integer selected from 3 to 6;

each p is independently selected from 1 and 2;

each R¹Independently is C_2-6An alkanediyl group;

each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group; and

z represents an m-valent parent polyol Z (OH)_mThe core of (1).

5. A terminal-modified sulfur-containing polymer comprising the reaction product of reactants comprising:

(a) a sulfur-containing polymer of formula (I);

wherein:

each n is an integer selected from 1 to 50;

m is an integer selected from 3 to 6;

each p is independently selected from 1 and 2;

each R¹Independently is C_2-6An alkanediyl group;

z represents an m-valent parent polyol Z (OH)_mA core of (a); and

(b) a compound selected from:

a compound comprising a vinyl group and a group reactive with a hydroxyl group of the polymer of formula (I);

a compound comprising a silyl group and a group reactive with a hydroxyl group of the polymer of formula (I);

a compound comprising an epoxy group and a group reactive with a hydroxyl group of the polymer of formula (I);

a compound comprising an isocyanate group and a group reactive with a hydroxyl group of the polymer of formula (I);

a compound comprising an amine group and a group selected from the group consisting of a group reactive with an isocyanate group, a group reactive with an ethylenically unsaturated group, and a group reactive with a tosylate; and

a compound selected from the group consisting of mercaptoalkanols, metal hydrosulfides, and dithiols.

6. The terminal-modified sulfur-containing polymer of claim 5, wherein:

(b) is a compound comprising an amine group and a group selected from the group consisting of a group reactive with an isocyanate group, a group reactive with an ethylenically unsaturated group, and a group reactive with a tosylate; and

the reactants further comprise (c) a compound selected from the group consisting of diisocyanates, activated ethylenically unsaturated monoisocyanates, and tosylates.

7. The terminal-modified sulfur-containing polymer of claim 5, wherein:

(b) selected from the group consisting of mercaptoalkanols, metal hydrosulfides, and dithiols; and

the reactants further comprise (c) a compound selected from the group consisting of diisocyanates, thioureas, ethylenically unsaturated monoisocyanates, and tosylates.

8. The terminal-modified sulfur-containing polymer of claim 5, wherein:

(b) a second compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group, and an isocyanate group; and a group selected from a group reactive with isocyanate groups, a group reactive with ethylenically unsaturated groups, and a group reactive with terminal groups of tosylate; and

the reactants further comprise (c) a compound selected from the group consisting of diisocyanates, ethylenically unsaturated monoisocyanates, and tosylates.

9. A terminal-modified sulfur-containing polymer of formula (I I):

wherein:

each n is an integer selected from 1 to 50;

m is an integer selected from 3 to 6;

each p is independently selected from 1 and 2;

each R¹Independently selected from C_2-6An alkanediyl group;

each R³Independently selected from hydrogen, C_1-6Alkyl radical, C_7-12Phenylalkyl, substituted C_7-12Phenylalkyl, C_6-12Cycloalkylalkyl, substituted C_6-12Cycloalkylalkyl radical, C_3-12Cycloalkyl, substituted C_3-12Cycloalkyl radical, C_6-12Aryl, and substituted C_6-12An aryl group;

each R⁵is-OR^5’Wherein R is^5’Independently selected from the group consisting of vinyl-terminated groups, silyl-terminated groups, amine-terminated groups, epoxy-terminated groups, thiol-terminated groups, and isocyanate-terminated groups; and

z represents an m-valent parent polyol Z (OH)_mThe core of (1).

10. The terminal-modified sulfur-containing polymer of claim 9, wherein each R is⁵A vinyl-terminated group selected from formula (a), formula (b), formula (c), formula (d), and formula (e):

wherein:

each R⁶Is a moiety derived from an ethylenically unsaturated monoisocyanate;

each R⁷Is selected from C_2-6Alkanediyl and C_2-6A heteroalkanediyl group;

each R⁸Selected from hydrogen, C_1-6Alkyl, and phenyl; and

each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarene diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_3-12Heterocyclane diyl, substituted C_3-12Heterocyclane diyl radical, C_7-18Alkane arene diyl, substituted C_7-18Heteroalkane arene diyl, C_4-18Alkanecycloalkanediyl, and substituted C_4-18Alkanecycloalkanediyl.

11. The terminal-modified sulfur-containing polymer of claim 9, wherein each R is⁵A silyl-terminated group selected from formula (f) and formula (g):

wherein:

each R⁶Derived from an ethylenically unsaturated monoisocyanate;

each R¹⁰Independently selected from C_1-6Alkyl radical, C_1-6Alkoxy radical, C_5-6Cycloalkyl radical, C_6-12Cycloalkylalkyl, phenyl, and C_7-12A phenylalkyl group; wherein at least one R¹⁰Is C_1-6An alkoxy group; and

each R¹¹Is C_1-6An alkanediyl group.

12. The terminal-modified sulfur-containing polymer of claim 9, whereinEach R⁵An amine-terminated group selected from formula (h), formula (i), formula (j), formula (k), formula (l), and formula (m):

wherein:

each R⁶Selected from the group consisting of diisocyanate-derived groups and ethylenically unsaturated monoisocyanates-derived groups;

each R⁷Selected from the group consisting of a bond and C_2-6An alkanediyl group;

each R⁹Is selected from C_2-6Alkanediyl, C_2-6Heteroalkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_6-12Heteroarenediyl, substituted C_6-12Heteroarene diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_3-12Heterocyclane diyl, substituted C_3-12Heterocyclane diyl radical, C_7-18Alkane arene diyl, substituted C_7-18Heteroalkane arene diyl, C_4-18Alkanecycloalkanediyl, and substituted C_4-18Alkanecycloalkanediyl; and

each R¹²Selected from hydrogen, C_1-6Alkanediyl, C_6-12Arenediyl, substituted C_6-12Aromatic diyl, C_3-12Cycloalkanediyl, substituted C_3-12Cycloalkanediyl group, C_7-18Alkane arene diyl, substituted C_7-18Alkane-arene diyl, C_4-18Alkanecycloalkanediyl, and substituted C_4-18Alkanecycloalkanediyl.

13. The terminal-modified sulfur-containing polymer of claim 9, wherein each R is⁵An epoxy-terminated group selected from formula (n):

wherein:

each R¹¹Independently is C_1-6An alkanediyl group.

14. The terminal-modified sulfur-containing polymer of claim 9, wherein each R is⁵A thiol-terminated group selected from formula (o), formula (p), formula (q), formula (r), formula(s), formula (t), formula (u), and formula (v):

wherein:

each R⁶Selected from the group consisting of diisocyanate-derived moieties and ethylenically unsaturated monoisocyanates-derived moieties;

each R⁷Is selected from C_2-14Alkanediyl and C_2-14A heteroalkanediyl group; and

15. The terminal-modified sulfur-containing polymer of claim 9, wherein each R is⁵An isocyanate-terminated group selected from formula (w) and formula (x):

wherein:

each R¹²Is a group derived from a diisocyanate.

16. A composition comprising the terminal-modified sulfur-containing polymer of claim 5; and a curing agent reactive with the terminal-modified sulfur-containing polymer of claim 5.

17. An aperture sealed with a sealant comprising the composition of claim 16.

18. A composition comprising the terminal-modified sulfur-containing polymer of claim 9; and a curing agent reactive with the terminal-modified sulfur-containing polymer of claim 9.

19. An aperture sealed with a sealant comprising the composition of claim 18.