Graft copolymer and curable thermosetting composition containing same

Abstract

The graft copolymers include a hydrocarbon backbone having phenylene ether oligomers grafted thereto. The graft copolymers can be particularly useful in curable compositions, thermoset compositions, and articles formed therefrom.

Description

[Technical field]

[0001] The present disclosure relates to graft copolymers, curable thermoset compositions containing same, and articles derived therefrom.

[0002] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of European Patent Application No. 21204237.8, filed October 22, 2021, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0003] Thermosets are materials that cure to form extremely hard plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosets are used in protective coatings, adhesives, electronic laminates (such as those used in the manufacture of computer circuit boards), flooring and paving applications, fiberglass reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components).

[0004] Poly(phenylene ether) oligomers can improve the dielectric performance, heat resistance, flame retardancy and moisture absorption of thermoset materials, making them particularly well suited for a variety of applications, especially electronic applications. Hydrocarbon resins are also known for their excellent dielectric performance, but suffer from limitations in adhesion, flame retardancy and thermal performance. Poly(phenylene ether) oligomers have been combined with hydrocarbon resins, but the compatibility of the materials remains technically limited. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, it would be advantageous to provide poly(phenylene ether) oligomer / hydrocarbon compositions with improved suitability for use in curable thermoset compositions. [Means for solving the problem]

[0006] The graft copolymer comprises a hydrocarbon backbone having a phenylene ether oligomer comprising repeating units derived from a substituted or unsubstituted monohydric phenol grafted from the hydrocarbon backbone, the graft copolymer comprising a linking group -L between the hydrocarbon backbone and the phenylene ether oligomer. 1 -(R) n -L 2 -[In formula, L 1 is a substituted or unsubstituted C 1~6 R is an alkylene group, a substituted or unsubstituted phenylene group, or -(C=O)-; n is 0 or 1; L 2 is a single bond or C 1~6 an alkylene group, preferably a single bond or a methylene group; 1 When is a substituted or unsubstituted phenylene group, n is 0.

[0007] Methods for making the graft copolymers represent another aspect of the present disclosure.

[0008] The curable thermoset composition comprises a graft copolymer.

[0009] A cured thermoset composition includes the cured product of a curable thermoset composition.

[0010] The article comprises a cured thermoset composition.

[0011] The above-mentioned and other features are illustrated by the figures and detailed description that follow. [Brief description of the drawings]

[0012] The following diagram is an exemplary embodiment.

[0013] [Figure 1] FIG. 1 shows a chemical scheme of the preparation of a graft copolymer. [Diagram 2] FIG. 1 shows a chemical scheme of the preparation of a graft copolymer. [Diagram 3] FIG. 1 shows a chemical scheme of the preparation of a graft copolymer. [Figure 4] FIG. 1 shows a chemical scheme of the preparation of a graft copolymer. [Diagram 5] FIG. 1 shows a chemical scheme of the preparation of a graft copolymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present inventors have discovered that graft copolymers can be prepared from phenylene ether oligomers and hydrocarbon resins. The graft copolymers can be advantageously used to provide curable thermoset compositions having a desirable combination of dielectric properties, flame retardancy and thermal performance while maintaining compatibility between the phenylene ether oligomer and the hydrocarbon resin.

[0015] Thus, an embodiment of the present disclosure is a graft copolymer. As used herein, the term "graft copolymer" refers to a branched copolymer structure in which a linear main polymer chain has one or more polymer side chains attached thereto. The polymer side chains are different in chemical nature from the main polymer chain. The polymer side chains may be randomly distributed along the main chain. A graft copolymer having a main polymer chain A and one or more polymer side chains B is represented as A(B) m where m represents the number of polymer side chains B per main polymer chain A. In some embodiments, at least one polymer side chain B is grafted to a repeat unit of the main polymer chain A that is not a terminal repeat unit (i.e., at the chain end of the main polymer chain A).

[0016] The graft copolymers of the present disclosure comprise a hydrocarbon backbone having one or more phenylene ether oligomers grafted therefrom. The phenylene ether oligomers have the structure -L 1 -(R) n -L 2 - is grafted to the hydrocarbon backbone via a linking group having L1 is directly attached to the hydrocarbon chain, and L 2 is positioned so that it is directly attached to the phenylene ether oligomer. 1 is a substituted or unsubstituted C 1~6 It can be an alkylene group, a substituted or unsubstituted phenylene group, or -(C=O)-. 1 is C 1~2 Alkylene group or -(C=O)-, preferably C 1~2 The linking group R is a substituted or unsubstituted phenylene group or -(C=O)-, and n is 0 or 1. In some embodiments, n is 0 and R is absent. 1 When R is a substituted or unsubstituted phenylene group, n is 0. In some embodiments, n is 1 and R is a substituted phenylene group, preferably a dimethyl-substituted phenyl group. In some embodiments, R can be a substituted phenylene group derived from 2-methoxyphenol. 2 is a single bond or C 1~6 An alkylene group, for example a divalent ethylene or methylene group. 2 is a single bond, R (if present) or L 1 It will be understood that (when R is absent) is attached directly to the phenylene ether oligomer by a single covalent bond.

[0017] A variety of exemplary linking groups are described. In some embodiments, L 1 can be an ethylene group, n is 0, and L 2 is a single bond (i.e., L 1 The -CH2- group is directly attached to the phenylene ether oligomer. Such linking groups can be seen in FIG. 1. In one embodiment, L 1 can be an ethylene group, n is 1, R is an unsubstituted phenylene group, and L 2 is a methylene group. Such linking groups can be seen in Figure 2a. In one embodiment, L 1 can be an ethylene group (e.g., a substituted ethylene group, preferably containing a methyl group substituent), n is 1, R is -(C=O)-, and L2 is a single bond. Such linking groups can be seen in FIG. 2b. In some embodiments, L 1 can be a substituted or unsubstituted phenylene group, preferably an unsubstituted phenylene group, n is 0, L 2 is a methylene group. Such linking groups can be seen in Figure 3a. In some embodiments, L 1 can be -(C=O)-, n is 0, and L 2 is a single bond. Such linking groups can be seen in Figure 3b. In some embodiments, L 1 can be a substituted or unsubstituted ethylene group (e.g., a hydroxyl-substituted ethylene group), n is 0, and L 2 is a single bond. Such linking groups can be seen in FIG. 4. In some embodiments, L 1 can be a substituted or unsubstituted ethylene group (e.g., a carboxylic acid substituted ethylene group), n is 0, and L 2 is a single bond. Such linking groups can be seen in Figure 5. It is to be understood that the present disclosure is not limited to the foregoing exemplary linking groups, and that -L 1 -(R) n -L 2 It will be understood that any linking group within the broad meaning of - can be used and will depend on the method of making the graft copolymer as further explained in the examples below.

[0018] Thus, the graft copolymer has the structure A(-L 1 -(R) n -L 2 -B) m [In the formula, L 1 , L 2 , R and n are as defined above, A is a hydrocarbon backbone, B is a phenylene ether oligomer, and m is 1 to 50, preferably 1 to 25, and most preferably 1 to 10.

[0019] The hydrocarbon resin backbone of the graft copolymer comprises carbon and hydrogen atoms and excludes atoms other than carbon and hydrogen. The hydrocarbon resin can be saturated or unsaturated. In some embodiments, the hydrocarbon resin comprises unsaturation, for example in the form of carbon-carbon double bonds. In some embodiments, the hydrocarbon resin used to prepare the graft copolymer can initially comprise unsaturation, and after grafting the phenylene ether oligomer, the hydrocarbon resin can have a reduced amount of unsaturation or can be fully saturated by reaction with the phenylene ether oligomer. The unsaturation can be in the main chain (i.e., polymer backbone) of the hydrocarbon resin (e.g., as in poly(1,4-butadiene) repeat units), as pendent groups along the hydrocarbon resin (e.g., as in poly(1,2-butadiene) repeat units), at the chain ends of the hydrocarbon resin, or a combination thereof. The hydrocarbon resin preferably does not comprise aromatic groups or cyclic hydrocarbons.

[0020] In one embodiment, the hydrocarbon resin is an unsaturated C 4~12 Hydrocarbons, preferably C 4~6 The repeating units of the hydrocarbon resin are derived from a diene-containing hydrocarbon and combinations thereof. Representative examples of such hydrocarbons may include, but are not limited to, substituted or unsubstituted butenes (e.g., 2-methyl-1-butene, 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, 3,3-dimethyl-1-butene); substituted or unsubstituted pentenes (e.g., 1-pentene, 2-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene); substituted or unsubstituted hexenes (e.g., 2-hexene); substituted or unsubstituted dienes (e.g., 1,3-butadiene and isoprene). In an embodiment, the hydrocarbon resin includes repeating units derived from a substituted or unsubstituted diene, such as polybutadiene, polyisoprene, or combinations thereof. In an embodiment, the hydrocarbon resin can include poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, or a combination thereof.

[0021] In one embodiment, the hydrocarbon resin is an unsaturated C 4~12 Hydrocarbons and C 4~12 It can be a copolymer containing repeat units derived from a monomer other than the hydrocarbon, such as an alkenyl aromatic monomer. An exemplary alkenyl aromatic monomer is styrene. Thus, in one embodiment, the hydrocarbon resin is a copolymer containing repeat units derived from an alkenyl aromatic and an unsaturated C 4~12 It can be a copolymer of hydrocarbons. For example, the hydrocarbon resin can include poly(styrene-co-butadiene), poly(styrene-co-isoprene), etc. In an embodiment, the hydrocarbon resin can include a block copolymer of styrene and butadiene (e.g., 1,2-butadiene, 1,4-butadiene, or a combination thereof).

[0022] In addition to the hydrocarbon polymer backbone, the graft copolymer comprises at least one phenylene ether oligomer grafted to the hydrocarbon polymer backbone. The phenylene ether oligomer comprises repeat units derived from a substituted or unsubstituted monohydric phenol. The substituted or unsubstituted monohydric phenol has the structure [ka] [In the formula, Q 1 Each occurrence of is independently a halogen, an unsubstituted or substituted C 1~12 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and the oxygen atom; Q 2 Each occurrence of is independently hydrogen, halogen, unsubstituted or substituted C 1~12 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms. In some embodiments, the substituted or unsubstituted monohydric phenol may have a 2,6-(di-C 1~6 In one embodiment, Q 1 Each occurrence of is methyl and Q 2 is hydrogen, and the monohydric phenol is 2,6-xylenol (also called 2,6-dimethylphenol or "DMP").

[0023] Thus, the phenylene ether oligomer has the formula [ka] [In the formula, Q 1 and Q 2 can be as described above. In some embodiments, the phenylene ether oligomer comprises a repeat unit of 2,6-(di-C 1~18 alkyl)phenol or 2,6-diphenylphenol, 2-phenyl-6-(C 1~18 alkyl)phenols, 2-phenyl-6-(cycloalkyl)phenols, 2,6-(dicycloalkyl)phenols, 2-(C 1~18 In one embodiment, the phenylene ether oligomer comprises repeat units derived from 2,6-dimethylphenol, 6-(cycloalkyl)-6-(alkyl)-phenol, or a combination thereof.

[0024] The phenylene ether oligomers may have a number average molecular weight of less than 20,000 grams per mole, or less than 10,000 grams per mole, or less than 5,000 grams per mole, or from 600 to 4,500 grams per mole. The molecular weight may be determined by gel permeation chromatography (GPC) against polystyrene standards. Those skilled in the art will recognize that if the linear block copolymer is prepared by a method that includes oxidative polymerization of phenylene ether oligomers from a hydrocarbon resin, molecular weight characterization of the phenylene ether oligomers using GPC will not be possible. In such cases, the number average molecular weight may be calculated from the degree of polymerization determined using nuclear magnetic resonance (NMR) spectroscopy.

[0025] The phenylene ether oligomer comprises one free chain end. As used herein, the term "free chain end" refers to a chain end that is not attached to the hydrocarbon backbone. The free chain end may comprise a functional group, such as a vinylbenzene ether end group, a methacrylate end group, an acrylate end group, an epoxy end group, a hydroxyl end group, a cyanate ester end group, an amine end group, a maleimide end group, an allyl end group, a styrenic end group, an activated ester end group, or an anhydride end group. In an embodiment, the chain end of the phenylene ether oligomer comprises a methacrylate group. In an embodiment, the graft copolymer may comprise a vinylbenzene ether end group, a methacrylate end group, an acrylate end group, an epoxy end group, a hydroxyl end group, a cyanate ester end group, an amine end group, a maleimide end group, an allyl end group, a styrenic end group, an activated ester end group, or an anhydride end group that is covalently bonded to the hydrocarbon resin.

[0026] In one embodiment, the graft copolymer preferably comprises a backbone comprising a linear hydrocarbon resin derived from poly(1,2-butadiene), poly(1,4-butadiene), butyl rubber, polyisoprene, or a combination thereof, and at least one grafted phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol.

[0027] The graft copolymers may be prepared by a variety of methods. In one embodiment, the graft copolymers may be prepared by oxidative polymerization of a substituted or unsubstituted monohydric phenol from a phenol-functionalized hydrocarbon resin to obtain the graft copolymer.

[0028] The oxidative polymerization may be carried out in the presence of an organic solvent. Suitable organic solvents may include alcohols, ketones, aliphatic and aromatic hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, mixed ether-esters, sulfoxides, and the like, provided that they do not interfere with or participate in the oxidation reaction. High molecular weight poly(phenylene ether) can greatly increase the viscosity of the reaction mixture. Therefore, it is sometimes desirable to use a solvent system that will precipitate lower molecular weight polymers while allowing them to remain in solution until they form higher molecular weight polymers. The organic solvent may include, for example, toluene, benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, trichloroethylene, ethylene dichloride, dichloromethane, chloroform, or combinations thereof. Preferred solvents include aromatic hydrocarbons. In some embodiments, the organic solvent includes toluene, benzene, xylene, chloroform, chlorobenzene, or combinations thereof, preferably toluene.

[0029] The monohydric phenol may be present in the oxidative polymerization reaction mixture in an amount of 5 to 90 weight percent, or 10 to 85 weight percent, or 40 to 60 weight percent, based on the total weight of the monohydric phenol, the hydrocarbon resin, and the solvent. The molar ratio of the monohydric phenol to the phenol-terminated hydrocarbon resin may be determined based on the desired molecular weight of the phenylene ether oligomer. For example, the molar ratio of the monohydric phenol to the phenol-terminated hydrocarbon resin may be 1:1 to 50:1.

[0030] The oxidative polymerization is further carried out in the presence of a copper-amine catalyst. The copper source for the copper-amine catalyst may include salts of cupric or cuprous ions, including halides, oxides, and carbonates. Alternatively, the copper may be provided in the form of a preformed salt of an alkylenediamine ligand. Preferred copper salts include cuprous halides, cupric halides, and combinations thereof. Particularly preferred are cuprous bromide, cupric bromide, and combinations thereof.

[0031] Preferred copper-amine catalysts contain a secondary alkylenediamine ligand. Suitable secondary alkylenediamine ligands are described in U.S. Pat. No. 4,028,341 to Hay and have the formula R b -NH-R a -NH-R c [In the formula, R a is a substituted or unsubstituted divalent residue in which two or three aliphatic carbon atoms form the nearest link between the two diamine nitrogen atoms; R b and R c are each independently isopropyl or a substituted or unsubstituted C 4~8 R is a tertiary alkyl group. a Examples of R include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, the various pentylene isomers having from 2 to 3 carbon atoms separating the two free valences, phenylethylene, tolylethylene, 2-phenyl-1,2-propylene, cyclohexylethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, etc. Preferably, R a is ethylene. b and R cExamples of R may include isopropyl, t-butyl, 2-methyl-but-2-yl, 2-methyl-pent-2-yl, 3-methyl-pent-3-yl, 2,3-dimethyl-but-2-yl, 2,3-dimethylpent-2-yl, 2,4-dimethyl-pent-2-yl, 1-methylcyclopentyl, 1-methylcyclohexyl, and the like. b and R c A highly preferred example of is t-butyl. An exemplary secondary alkylenediamine ligand is N,N'-di-t-butylethylenediamine (DBEDA). Suitable molar ratios of copper to secondary alkylenediamine are from 1:1 to 1:5, preferably from 1:1 to 1:3, more preferably from 1:1.5 to 1:2.

[0032] Preferred copper-amine catalysts containing a secondary alkylenediamine ligand may further contain a secondary monoamine. Suitable secondary monoamine ligands are described in commonly assigned U.S. Pat. No. 4,092,294 to Bennett et al. and have the formula R d -NH-R e [In the formula, R d and R e are each independently a substituted or unsubstituted C 1~12 Alkyl groups, and preferably substituted or unsubstituted C 3~6 The alkyl group is represented by the formula: . Examples of secondary monoamines include di-n-propylamine, di-isopropylamine, di-n-butylamine, di-sec-butylamine, di-t-butylamine, N-isopropyl-t-butylamine, N-sec-butyl-t-butylamine, di-n-pentylamine, bis(1,1-dimethylpropyl)amine, and the like. A highly preferred secondary monoamine is di-n-butylamine (DBA). The preferred molar ratio of copper to secondary monoamine is 1:1 to 1:10, preferably 1:3 to 1:8, more preferably 1:4 to 1:7.

[0033] Preferred copper-amine catalysts containing secondary alkylenediamine ligands may further contain a tertiary monoamine. Suitable tertiary monoamine ligands are described in the aforementioned Hay U.S. Pat. No. 4,028,341 and Bennett U.S. Pat. No. 4,092,294 patents, and include heterocyclic amines and certain trialkylamines, characterized by having an amine nitrogen bonded to at least two groups having a small cross-sectional area. In the case of trialkylamines, at least two of the alkyl groups are methyl and the third is a primary C 1~8 Alkyl group or secondary C 3~8 It is preferably an alkyl group. It is especially preferred that the third substituent does not have more than 4 carbon atoms. A highly preferred tertiary amine is dimethylbutylamine (DMBA). The preferred molar ratio of copper to tertiary amine is less than 1:20, preferably less than 1:15, preferably from 1:1 to less than 1:15, more preferably from 1:1 to 1:12.

[0034] Suitable molar ratios (measured as moles of metal) of copper-amine catalyst to poly(phenylene ether) oligomer starting material are from 1:50 to 1:400, preferably from 1:100 to 1:200, more preferably from 1:100 to 1:180.

[0035] The reaction carried out in the presence of copper-amine catalyst may optionally be carried out in the presence of bromide ions. It has already been mentioned that bromide ions may be provided as cuprous or cupric bromide salts. Bromide ions may also be provided by the addition of 4-bromophenols such as 2,6-dimethyl-4-bromophenol. Additional bromide ions may be provided in the form of hydrobromic acid, alkali metal bromides or alkaline earth metal bromides. Sodium bromide and hydrobromic acid are highly preferred sources of bromide. The suitable ratio of bromide ions to copper ions is 2 to 20, preferably 3 to 20, more preferably 4 to 7.

[0036] In one embodiment, each of the above-mentioned components of the copper-amine catalyst are added simultaneously to the oxidative polymerization reactant.

[0037] The oxidative polymerization may optionally be carried out in the presence of one or more additional components including a lower alkanol or glycol, a small amount of water, or a phase transfer agent. Generally, it is not necessary to remove the reaction by-product water during the reaction.

[0038] In some embodiments, a phase transfer agent is present. Suitable phase transfer agents may include, for example, quaternary ammonium compounds, quaternary phosphonium compounds, tertiary sulfonium compounds, or combinations thereof. Preferably, the phase transfer agent is a compound represented by the formula (R 3 )4Q + X [where each R 3 are the same or different, C 1~10 alkyl; Q is a nitrogen or phosphorus atom; X is a halogen atom or C 1~8 Alkoxy or C 6~18 aryloxy. Exemplary phase transfer catalysts include (CH3(CH2)3)4NX, (CH3(CH2)3)4PX, (CH3(CH2)5)4NX, (CH3(CH2)6)4NX, (CH3(CH2)4)4NX, CH3(CH3(CH2)3)3NX and CH3(CH3(CH2)2)3NX, where X is Cl. - , Br - , C 1~8 Alkoxy or C 6~18 aryloxy. An effective amount of phase transfer agent can be 0.1 to 10 wt%, or 0.5 to 2 wt%, each based on the weight of the reaction mixture. In some embodiments, the phase transfer agent is present and comprises N,N,N'N'-didecyldimethylammonium chloride.

[0039] The oxidative polymerization may be carried out at a temperature of from 20 to 70° C., preferably from 30 to 60° C., more preferably from 45 to 55° C. Depending on the exact reaction conditions selected, the total polymerization reaction time - i.e. the time elapsed between initiating the oxidative polymerization and terminating the oxidative polymerization - may vary, but is typically from 100 to 250 minutes, specifically from 145 to 210 minutes.

[0040] The method further includes terminating the oxidative polymerization to form a terminated reaction mixture. The reaction is terminated when the flow of oxygen to the reaction vessel is stopped. Residual oxygen in the reaction vessel headspace is removed by flushing with an oxygen-free gas, such as nitrogen.

[0041] After the polymerization reaction is completed, the copper ions of the polymerization catalyst are separated from the reaction mixture. This is accomplished by combining a chelating agent with the completed reaction mixture to form a chelated mixture. The chelating agent comprises an alkali metal salt of an aminopolycarboxylic acid, preferably an alkali metal salt of aminoacetic acid, more preferably an alkali metal salt of nitrilotriacetic acid, ethylenediaminetetraacetic acid, or a combination thereof, even more preferably a sodium salt of nitrilotriacetic acid, a sodium salt of ethylenediaminetetraacetic acid, or a combination thereof. In one embodiment, the chelating agent comprises an alkali metal salt of nitrilotriacetic acid. In one embodiment, the chelating agent is a sodium or potassium salt of nitrilotriacetic acid, specifically trisodium nitrilotriacetate. After agitation of the chelation mixture, the mixture comprises an aqueous phase containing chelated copper ions and an organic phase containing dissolved poly(phenylene ether). The chelating mixture may exclude the dihydric phenols required by Cooper et al., U.S. Patent No. 4,110.311, the aromatic amines required by Cooper et al., U.S. Patent No. 4,116,939, and the mild reducing agents of Cooper et al., U.S. Patent No. 4,110.311, which include sulfur dioxide, sulfurous acid, sodium bisulfite, sodium thionite, tin(II) chloride, iron(II) sulfate, chromium(II) sulfate, titanium(III) chloride, hydroxylamine and its salts, phosphates, glucose, and mixtures thereof. The chelating mixture is maintained at a temperature of 40 to 55° C., specifically 45 to 50° C., for a period of 5 to 100 minutes, specifically 10 to 60 minutes, and more specifically 15 to 30 minutes. This temperature and time combination is effective for copper sequestration while also minimizing molecular weight degradation of the poly(phenylene ether). The chelation step includes (and is completed by) separating the aqueous and organic phases of the chelation mixture. This separation step is carried out at a temperature of 40 to 55° C., specifically 45 to 50° C. The 5 to 100 minute time interval for maintaining the chelation mixture at 40-55° C. is measured from the time the terminated reaction mixture is first combined with the chelating agent to the time separation of the aqueous and organic phases is complete.

[0042] In an embodiment, the graft copolymer can be made by a method that includes covalently coupling a hydrocarbon resin and a phenylene ether oligomer, where the hydrocarbon resin and the phenylene ether oligomer contain complementary reactive groups. In an embodiment, the hydrocarbon resin can include at least one terminal carbon-carbon double bond, the phenylene ether oligomer can include a terminal group having ethylenic unsaturation, and a cross-metathesis reaction can be used to couple the hydrocarbon resin and the phenylene ether oligomer.

[0043] In one aspect, the graft copolymers can be made by a process that includes the step of copolymerizing an unsaturated hydrocarbon monomer with a phenylene ether oligomer that contains a polymerizable group at the chain end, such as a methacrylate end group, an acrylate end group, an allyl end group, a styrenic end group, or a vinylbenzene ether end group.

[0044] The graft block copolymer can be isolated, for example, by precipitation into a suitable non-solvent for the block copolymer, such as methanol.

[0045] The method of making the graft copolymer may further include reacting a block copolymer containing at least one grafted phenylene ether oligomer (e.g., a hydroxyl-terminated phenylene ether oligomer) with a selected compound to obtain a desired functional group at the chain end of the phenylene ether oligomer graft, such as a vinylbenzene ether end group, a methacrylate end group, an acrylate end group, an epoxy end group, a hydroxyl end group, a cyanate ester end group, an amine end group, a maleimide end group, an allyl end group, a styrenic end group, an activated ester end group, or an anhydride end group. Suitable compounds containing the desired functional group and a group reactive with the hydroxyl-terminated phenylene ether oligomer may be readily determined by one of ordinary skill in the art. The reaction may be carried out in a solvent. In some embodiments, the graft copolymer may be obtained as a powder and then combined with a compound containing the desired functional group and a solvent. In some embodiments, the graft copolymer may be obtained as a solution from the polymerization without removing the solvent, and the graft copolymer is not isolated before carrying out the reaction.

[0046] Various methods for the preparation of the graft copolymers are further described in the examples below.

[0047] Also provided is a curable thermoset composition comprising the graft copolymer. For example, the graft copolymer can be present in the curable thermoset composition in an amount of 1 to 95 weight percent (wt%), or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, or 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermoset composition.

[0048] In addition to the graft copolymer, the curable thermosetting composition of the present disclosure may further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. In an embodiment, the curable thermosetting composition may further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof. For example, the curable thermosetting composition may further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof, and may further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0049] There is considerable overlap between thermosetting resins, crosslinkers and coupling agents. As used herein, the term "crosslinker" includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or combinations thereof. For example, in some cases, a compound that is a thermosetting resin can also be used as a crosslinker, coupling agent, or both.

[0050] The thermosetting resin is not particularly limited, and the thermosetting resin may be used alone or in combination of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins). Exemplary thermosetting resins include epoxy resins, cyanate ester resins, (bis)maleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., vinylbenzyl ether resins), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers or polymers with curable unsaturation (e.g., vinyl functional groups), and the like, or combinations thereof.

[0051] The epoxy resin may be any epoxy resin that is generally suitable for use in thermosetting resins. The term "epoxy resin" in this context refers to a curable composition of oxirane ring-containing compounds as described, for example, in CA May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. Epoxy resins include bisphenol A type epoxy resins, such as those obtained from bisphenol A and resins obtained by substituting at least one of the 2-, 3- and 5-positions of bisphenol A with a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; bisphenol F type epoxy resins, such as those obtained from bisphenol F and resins obtained by substituting at least one of the 2-, 3- and 5-positions of bisphenol F with a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)methane. glycidyl ether compounds derived from dihydric or trihydric or higher phenols such as 2,3-dimethylphenylethane; novolak type epoxy resins derived from novolak resins which are reaction products between phenols such as phenol and o-cresol and formaldehyde, including bisphenol A novolak type epoxy resins and cresol novolak type epoxy resins; cycloaliphatic epoxy compounds such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; dicyclopentadiene-containing polyepoxides;Aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-amino-phenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2 amine-type epoxy resins derived from, for example, 4-toluenediamine, 2,6-toluenediamine, p-xylylene-diamine, m-xylylenediamine, 1,4-cyclohexane-bis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, and the like; heterocyclic epoxy compounds, and glycidyl ester-type epoxy compounds, such as those derived from glycidyl esters of aromatic carboxylic acids, for example, p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid. "Epoxy resin" may also include the reaction product of a compound containing two or more epoxy groups with an aromatic dihydroxy compound, which may be optionally halogen-substituted, either alone or in combination of two or more;

[0052] The cyanate ester is not limited, and any resin composed of a cyanate ester monomer that polymerizes to form a polymer containing multiple cyanate ester (-OCN) functional groups can be used. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or mixtures of cyanate ester monomers), homopolymers and copolymers, and combinations of these compounds made using cyanate ester precursors. For example, cyanate esters can be prepared according to the methods disclosed in "Chemistry and Technology of Cyanate Ester Resins," by Ian Hamerton, Blackie Academic and Professional; U.S. Pat. No. 3,553,244 and JP-A-7-53497. Exemplary cyanate ester resins include 2,2-bis(4-cyanatophenyl)-propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanatophenyl)-m-diisopropyl-benzene, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). Cyanate ester prepolymers can be homopolymers or copolymers incorporating other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical Company, Inc., such as BT2160 and BT2170, which are prepolymers made with cyanate ester and bismaleimide monomers. Other cyanate ester polymers, monomers, prepolymers, and blends of cyanate ester monomers with other non-cyanate ester monomers are disclosed in US Pat. No. 7,393,904, US Pat. No. 7,388,057, US Pat. No. 7,276,563, and US Pat. No. 7,192,651.

[0053] Bismaleimide resins can be prepared by reaction of monomeric bismaleimides with nucleophiles such as diamines, aminophenols or aminobenzhydrazides, or by reaction of bismaleimides with diallyl bisphenol A.Exemplary bismaleimide resins include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimido-benzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimido-diphenylether, 3,3'-bismaleimidodiphenylsulfone, 4,4'-bismaleimido-diphenylsulfone, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6- Bismaleimido-pyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citracon-imido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimido-phenyl)ethane, N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazole N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane bismaleimide No. 3,562,223, U.S. Pat. No. 4,211,860 and U.S. Pat. No. 4,211,861 or prepared by the methods described, for example, in U.S. Pat. No. 3,018,290.

[0054] Benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared by the reaction of an aldehyde, a phenol, and a primary amine, with or without a solvent. Phenolic compounds for forming benzoxazines include phenols and polyphenols. The use of polyphenols with two or more hydroxyl groups that are reactive in forming benzoxazines can result in branched, crosslinked, or combinations of branched and crosslinked products. The group connecting the phenol group to the phenol can be a branch point or a connecting group in the polybenzoxazine.

[0055] Exemplary phenols for use in preparing the benzoxazine monomers are phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2-methyl-phenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol). 4,4'-(1,4-phenylenediisopropylidene)-bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)-bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, isopropylidene-bis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi-[indene]5,6'-diol, dihy hydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxy-phenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(ortho-cresol), dicyclopentadienyl bisphenol, etc.

[0056] The aldehyde used to form the benzoxazine can be any aldehyde, such as an aldehyde having 1 to 10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic or an aromatic-substituted alkyl amine. The amine can be a polyamine, for example, to prepare a multifunctional benzoxazine monomer for crosslinking.

[0057] The amines for forming the benzoxazines contain from 1 to 40 carbon atoms, and may contain from 6 to 40 carbon atoms, provided they do not contain aromatic rings. Di- or polyfunctional amines may be branching points for connecting one polybenzoxazine with another.

[0058] In some cases, thermal polymerization at 150 to 300° C. can be used to polymerize the benzoxazine monomers. Polymerization can be done in bulk, from solution, or by other methods. Catalysts such as carboxylic acids can be used to reduce the polymerization temperature or accelerate the polymerization rate at the same temperature.

[0059] Vinylbenzyl ether resins can be prepared by condensation of phenols with vinylbenzyl halides such as vinylbenzyl chloride. Bisphenol-A and trisphenols and polyphenols are commonly used to produce poly(vinylbenzyl ethers) which can be used to produce crosslinked thermoset resins. Exemplary vinylbenzyl ethers are the condensation of vinylbenzyl halides such as resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2'6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidenediphenol, 4,4'- Isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'-sulfinyl-diphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloro-ethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(Cyclopentylidene)diphenol, 4,4'-(Cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)-isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, dihydroxybenzophenone, tris(4-hydro The vinyl benzyl ethers may include those produced by reaction with tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)-propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxy-phenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)-ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienyl-bis(2,6-dimethylphenol), dicyclopentadienyl bisphenol, and the like.

[0060] Arylcyclobutenes have the structure [ka] [wherein B is an organic or inorganic radical having a valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidenedialkylsilanyl, arylalkylsilanyl, diarylsilanyl and C 6~20 Each occurrence of X is independently selected from hydroxy and C 1~24each occurrence of Z is independently hydrogen, halogen or C 1~12 n is 1 to 1000, or 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods of arylcyclobutene synthesis can be found in U.S. Pat. Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, 4,724,260, and 5391,650.

[0061] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, followed by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. By this route, bis, tris and other polyphenols can produce bis, tris and poly(perfluorovinyl ethers). Phenols useful in these syntheses include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynapthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetra-methylbiphenol, 3,3'-dibromo-2,2' ,6,6'-Tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)-bisphenol, 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)-bisphenol, 4,4'-ethylidene diphenol, 4,4'oxydiphenol, 4,4'thiodiphenol, 4,4'thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)-bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)-methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(Cyclopentylidene)diphenol, 4,4'-(Cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)-diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone, Tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)-phenylphosphine oxide, dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(2-methylphenol), dicyclopentadienyl bisphenol, etc.

[0062] The crosslinking agent, including the auxiliary crosslinking agent, is not particularly limited. The crosslinking agent may be used alone or in combination with two or more different crosslinking agents. Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with vinyl functional groups that can be cured. Such materials include oligomers and polymers with crosslinkable unsaturation. Examples include styrene butadiene rubber (SBR), butadiene rubber (BR) and nitrile butadiene rubber (NBR) with unsaturation based on butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR) and halogenated butyl rubber with unsaturation based on isoprene; ethylene-α-olefin copolymer elastomers with unsaturation based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB) or 1,4-dihexadiene (1,4-HD) (for example ethylene-α-olefin copolymers obtained by copolymerizing ethylene, α-olefins and dienes, for example ethylene-propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM)). Examples include hydrogenated nitrile rubber, fluorocarbon rubber, for example vinylidene fluoride-hexafluoropropene copolymer and vinylidene fluoride-pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber prepared from epichlorohydrin and ethylene oxide (ECO), epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T) and also ethylene acrylic rubber. Further examples include various liquid rubbers, such as several types of liquid butadiene rubber, and liquid atactic butadiene rubber, which is a butadiene polymer with 1,2-vinyl connections prepared by anionic living polymerization.It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc., manufactured by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymers, and polynorbornene (such as those sold by Elf Atochem).

[0063] Polybutadiene resins containing increasing levels of 1,2 addition are desirable for thermoset matrices. Examples include functionalized polybutadiene and poly(butadiene-styrene) random copolymers sold by Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins. These include butadienes containing low vinyl content, such as RICON 130, 131, 134, 142; polybutadienes containing high vinyl content, such as RICON 150, 152, 153, 154, 156, 157, and P30D; random copolymers of styrene and butadiene, including RICON 100, 181, 184, and maleic anhydride grafted polybutadienes and alcohol condensates derived therefrom, such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6, and RICON 156MA17. Polybutadienes that may be used to improve adhesion include RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500; polybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene) and RICON 257 (35% polybutadiene in styrene); (meth)acrylic functionalized polybutadienes, such as polybutadiene diacrylate and polybutadiene dimethacrylate, are also included. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500 and RICACRYL 3801. Also included are powder dispersions of functional polybutadiene derivatives including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 0 1731 HS, and RICOBOND 1756HS.Additional butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those having a molecular weight of 3,000 to 50,000 g / mol, and polybutadiene homopolymers having a molecular weight of 3,000 to 50,000 g / mol. Also included are polybutadiene, polyisoprene and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethylmaleic acid or hydroxyl functional groups.

[0064] Further examples of curable vinyl-functional oligomers and polymers include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid and citraconic acid; unsaturated epoxy (meth)acrylate resins containing acryloyl or methacryloyl groups; unsaturated epoxy resins containing vinyl or allyl groups, urethane (meth)acrylate resins, polyether (meth)acrylate resins, polyalcohol (meth)acrylate resins, alkyd acrylate resins, polyester acrylate resins, spiroacetal acrylate resins, diallyl phthalate resins, diallyl tetrabromophthalate resins, diethylene glycol bisallyl carbonate resins and polyethylene polythiol resins. For example, crosslinking agents. Other exemplary crosslinking agents further include multifunctional crosslinking monomers such as (meth)acrylate monomers having two or more (meth)acrylate moieties per monomer molecule. Exemplary multifunctional monomers include di(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, and the like; Tri(meth)acrylates, for example, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyls, for example, tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl ester of citric acid, tri(meth)allyl ester of phosphoric acid, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; tetra(meth)acrylates, for example, pentaerythritol tetra(meth)acrylate, etc.;Penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate; hexa(meth)acrylates, such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate; glycidyl compounds, such as glycidyl(meth)acrylate, (meth)allyl glycidyl ether, 1-chloro-2,3-epoxypropyl(meth)acrylate, 2-bromo-3,4-epoxybutyl(meth)acrylate, 2-(epoxyethyloxy)-ethyl(meth)acrylate, 2-(3,4-epoxybutyloxy)-ethyl(meth)acrylate; polythiol compounds, such as trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate); silanes, such as and tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloxyimino)silane, vinyltris-(acetoxime)silane, methyltris(methylethyloxyimino)silane, methyltris(acetoxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxy-silane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-t-butoxy-diacetoxysilane, methyltris(ethyllactate)silane, vinyltris(ethyllactate)silane, and the like; carbodiimides, such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, and the like; or combinations thereof. The curable thermosetting composition may optionally include a crosslinking catalyst, such as a carboxylate salt;

[0065] When the curable thermoset composition includes a crosslinking agent, the crosslinking agent may be included in an amount of 1 to 60 wt%, or 5 to 45 wt%, or 10 to 30 wt%, based on the total weight of the curable thermoset composition.

[0066] Curable thermosetting compositions may include one or more curing agents. As used herein, the term "curing agent" includes compounds variously described as curing agents, hardeners, etc., or both.

[0067] Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenol-based hardeners include novolac-type phenolic resins, resole-type phenolic resins, cresol novolac resins, aralkyl-type phenolic resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene-type phenolic resins, terpene-modified phenolic resins, biphenyl-type phenolic resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane-type phenolic resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, aminotriazine-modified phenolic resins, or combinations thereof. Examples of anhydride hardeners include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymer (SMA) and olefin-maleic anhydride copolymers, such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof. Other hardeners and hardeners include compounds such as dicyandiamide, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combination thereof. Other exemplary hardeners include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.

[0068] When the curable thermoset composition includes a curing agent, the curing agent can be included in an amount of 0.01 to 50 wt%, or 0.1 to 30 wt%, or 0.1 to 20 wt%, based on the total weight of the curable thermoset composition.

[0069] The curable thermosetting composition may include a curing catalyst. As used herein, the term "curing catalyst" includes compounds variously described as cure accelerators, cure promoters, cure catalysts, and cure cocatalysts.

[0070] Exemplary cure accelerators include substituted or unsubstituted C 3~6Heterocyclic accelerators include heterocyclic accelerators such as heterocycles, where each heteroatom is independently the same or different and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic accelerators include benzotriazoles; triazines; piperazines, such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, and the like; imidazoles, such as 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethyl ...2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole, 2-ethylimidazole n-Propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole Imidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole midazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole; cyclic amidines, such as, for example, 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline, and the like; N,N-dimethylaminopyridine; sulfamidates; or combinations thereof.

[0071] Amine cure accelerators include isophorone diamine, triethylenetetraamine, diethylenetriamine, 1,2- and 1,3-diaminopropane, 2,2-dimethylpropylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane, 4-azaheptamethylenediamine, N,N'-bis(3-aminopropyl)butane- 1,4-diamine, dicyanamide, diamide diphenylmethane, diamide diphenylsulfonic acid (amine adduct), 4,4'-methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde resin, urea formaldehyde resin, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3'-iminobispropylamine, 2,4-bis(p-aminobenzyl)amine diphenylamine, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,2- and 1,3-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1,2-diamino-4-ethylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1-cyclohexyl-3,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyltoluenediamine; or a tertiary amine hardening accelerator. accelerators, for example triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tri(N,N-dimethylaminomethyl)phenol; or combinations thereof.

[0072] The cure accelerator can be a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonate esters, sulfonate esters, carboxylate esters, phosphonic acid ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, and the like, or combinations thereof. Diaryliodonium salts are those having the structure [(R 10 )(R 11 )I] + X - R 10 and R 11 are each independently 1~20 Alkyl, C 1~20 C optionally substituted with one to four monovalent radicals selected from alkoxy, nitro and chloro; 6~14 is a monovalent aromatic hydrocarbon radical; X- is an anion. Additional cure accelerators include those having the structure [(R 10 )(R 11 )I] + SbF6 - R 10 and R 11 are each independently 1 to 4 C 1~20 Alkyl, C 1~20 C optionally substituted with alkoxy, nitro or chloro 6~14 Monovalent aromatic hydrocarbons; for example, 4-octyloxyphenylphenyliodonium hexafluoroantimonate.

[0073] The cure accelerator may be a metal salt complex such as copper(II), aluminum(III), zinc, cobalt, tin salts of aliphatic or aromatic carboxylic acids selected from copper(II), tin(II) and aluminum(III) salts of acetates, stearates, gluconates, citrates, benzoates, and mixtures thereof. For example, the cure accelerator may be a copper(II) or aluminum(III) salt of a β-diketonate; a copper(II), iron(II), iron(III), cobalt(II), cobalt(III) or aluminum(III) salt of an acetylacetonate; a zinc(II), chromium(II) or manganese(II) salt of an octoate; or a combination thereof.

[0074] When the curable thermoset composition includes a curing catalyst, the curing catalyst may be included in an amount of 0.01 to 5 wt%, or 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermoset composition.

[0075] The curable thermosetting composition may optionally include a cure initiator such as a peroxide compound. Exemplary peroxide cure initiators are benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, t-butyl peroxybenzoate, t-butyl peroxy 2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butyl peroxide, and t-butyl cumyl peroxide. peroxides, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di(t-butylperoxyisophthalate), t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, and the like, or combinations thereof.

[0076] When the curable thermoset composition includes a curing initiator, the curing initiator may be included in an amount of 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, based on the total weight of the curable thermoset composition.

[0077] Flame retardants include, for example, organic compounds that contain phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organic phosphates and organic compounds that contain phosphorus-nitrogen bonds, may be preferred in certain applications for regulatory reasons.

[0078] Examples of phosphorus flame retardants include phosphates, phosphazenes, phosphites, phosphines, phosphinates, polyphosphates, and phosphonium salts. Phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)phosphate, phenyl bis(3,5,5'-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolylphosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl)phosphate, trimethyl ... cresyl-diphenyl phosphate; 1,3-phenylenebis(di-2,6-xylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), condensed phosphate compounds, such as aromatic condensed phosphate compounds; and cyclic phosphate ester compounds, bis(diphenyl)phosphate of hydroquinone, bis(diphenyl)phosphate of bisphenol A, and the like, or their oligomeric or polymeric counterparts, or combinations thereof.

[0079] Examples of phosphazene compounds include cyclic and linear phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazenes) have a cyclic structure in which the phosphorus-nitrogen double bond is present in the molecule. Examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum tris-(diethylphosphinate), aluminum tris-(methylethylphosphinate), aluminum tris-(diphenylphosphinate), zinc bis-(diethylphosphinate), zinc bis-(methylphosphinate), zinc bis-(diphenylphosphinate), titanyl bis-(diethylphosphinate), titanyl bis-(methylethylphosphinate) and titanyl bis-(diphenylphosphinate). Examples of polyphosphate compounds include melamine polyphosphate, melam polyphosphate and melem polyphosphate. Examples of phosphonium salt compounds include tetraphenylphosphonium tetraphenylborate. Examples of phosphite compounds include trimethylphosphite and triethylphosphite. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chlorides, phosphoric ester amides, phosphoric amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0080] Halogenated materials, such as bisphenols, for example 2,2-bis-(3,5-dichlorophenyl)-propane, bis-(2-chlorophenyl)-methane, bis(2,6-dibromophenyl)-methane, 1,1-bis-(4-iodophenyl)-ethane, 1,2-bis-(2,6-dichlorophenyl)-ethane, 1,1-bis-(2-chloro-4-iodophenyl)ethane, 1,1-bis-(2-chlorophenyl)ethane, 2,2-bis-(3-bromo-4-hydroxyphenyl)-ethane, 1,1-bis-(3,5-dichlorophenyl)-ethane, 2,2-bis-(3-phenyl-4-bromophenyl)-ethane, 2,6-bis-(4,6-dichloronaphthyl)-propane, and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2 bis-(3-bromo-4-hydroxyphenyl)-propane may also be used as flame retardants. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl and 2,4'-dichlorobiphenyl, as well as decabromodiphenyl ether, decabromodiphenylethane, and oligomeric and polymeric halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or copolycarbonates of bisphenol A and tetrabromobisphenol A, and carbonate precursors such as phosgene. Metal synergists such as antimony oxide may also be used in conjunction with the flame retardants.

[0081] Inorganic flame retardants, such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate, to name a few. 1~16Salts of alkylsulfonates; such as Na2CO3, K2CO3, MgCO3, CaCO3 and BaCO3, or fluoro-anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6 or Na3AlF6 may also be used.

[0082] When the curable thermoset composition includes a flame retardant, the flame retardant may be included in an amount of greater than 1 wt%, or from 1 to 20 wt%, or from 5 to 20 wt%, based on the total weight of the curable thermoset composition.

[0083] The curable thermosetting composition may further include inorganic or organic fillers, such as, for example, particulate fillers, fibrous fillers, and the like, or combinations thereof. Any inorganic and organic fillers may be used, including, but not limited to, those known in the art.

[0084] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B or Sn based fillers, such as zinc borate, zinc stannate and zinc hydroxystannate; metal oxides, such as zinc oxide and tin oxide, alumina, silica (including fused silica, fumed silica, spherical silica and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (chopped, milled or cloth), glass mat, small glass spheres, hollow glass microspheres, aramid fibers, quartz, etc., or combinations thereof. Other exemplary inorganic fillers include powdered titanium ceramics, such as any one of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, etc. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolites, and hydrotalcites, hi an embodiment, the filler may be treated with a coupling agent as disclosed herein.

[0085] Glass fibers include those based on E, A, C, ECR, R, S, D and NE glasses, as well as quartz. The glass fibers can have any suitable diameter, such as 2 to 30 micrometers (μm), or 5 to 25 μm, or 5 to 15 μm. The length of the glass fibers before compounding is not limited and can be 2 to 7 millimeters (mm), or 1.5 to 5 mm. Alternatively, longer glass fibers or continuous glass fibers can be used. Suitable glass fibers are commercially available from suppliers such as Owens Corning, Nippon Electric Glass Co., Ltd., PPG, and Johns Manville.

[0086] The organic filler can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, and the like, or combinations thereof.

[0087] The filler may be selected based on the requirements of coefficient of thermal expansion (CTE) and thermal conductivity. For example, Al2O3, BN, AlN, or combinations thereof may be used for electronic modules with high thermal conductivity. For example, MgO may be used for increased thermal conductivity and increased CTE. For example, SiO2 (e.g., amorphous SiO2) may be used for lightweight modules with low CTE and small dielectric constant.

[0088] When the curable thermoset composition includes a filler, the filler can be included in an amount of greater than 1 wt%, or from 1 to 50 wt%, or from 1 to 30 wt%, or from 10 to 30 wt%, based on the total weight of the curable thermoset composition.

[0089] Coupling agents, also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, and the like. Exemplary olefin-maleic anhydride copolymers may include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof. Exemplary silanes may include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0090] Examples of aminosilane coupling agents are γ-aminopropyltrimethoxy-silane, γ-aminopropyltriethoxysilane, N-beta(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-beta(aminoethyl)γ-aminopropyltrimethoxysilane, and N-beta(aminoethyl)γ-aminopropyltriethoxysilane. Illustrative epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0091] Other exemplary silane coupling agents include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl tri-ethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxy ... -dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthio-carbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, and the like, or combinations thereof. The silane coupling agent can be a polysulfide silane coupling agent having 2 to 4 sulfur atoms forming a polysulfide bridge. For example, the coupling agent can be bis(3-triethoxysilylpropyl) di, tri or tetrasulfide.

[0092] When the curable thermoset composition includes a coupling agent, the coupling agent may be included in an amount of 0.01 to 5 wt%, or 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermoset composition.

[0093] The curable thermosetting composition may optionally include a solvent. The solvent may be, for example, 3~8 Ketone, C3~8 N,N-Dialkylamides, C 4~16 Dialkyl ether, C 6~12 Aromatic Hydrocarbons, C 1~3 Chlorinated hydrocarbons, C 3~6 Alkyl alkanoates, C 2~6 Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. 4~8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvent can be non-halogenated. Specific C 3~6 Alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. 2~6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. 2~6The alkyl cyanide includes, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent can be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl ketone, methyl ethyl ... The solvent may be sanone, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picoline, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, ionic liquids, or combinations thereof.

[0094] When a solvent is utilized, the curable thermoset composition may comprise 2 to 99 wt% of the solvent, based on the total weight of the curable thermoset composition. For example, the amount of solvent may be 5 to 80 wt%, or 10 to 60 wt%, or 20 to 50 wt%, based on the total weight of the curable thermoset composition. The solvent may be selected, in part, to adjust the viscosity of the curable thermoset composition. Thus, the amount of solvent may depend on variables including the type and amount of graft block copolymer, the type and amount of other ingredients such as curing additives, the type and amount of any supplemental thermoset resin, and the processing temperature used for any subsequent processing of the curable thermoset composition, such as impregnation of a reinforcing structure with the curable thermoset composition for preparation of a composite. The solvent may be anhydrous. For example, the solvent may comprise less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water, based on the total weight of the solvent.

[0095] The curable thermosetting composition can further include a curable unsaturated monomer composition, which can include, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, and the like, or a combination thereof. For example, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne-containing monomers include those described in U.S. Pat. No. 6,627,704 to Yeager et al., and include (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidones, and vinylazalactones as disclosed in U.S. Pat. No. 4,304,705 to Heilman et al. Exemplary monofunctional monomers include mono(meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, and the like, or combinations thereof.

[0096] The curable thermosetting composition may optionally further comprise one or more additional additives. Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow improvers, anti-drip agents, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, stress relief additives, and the like, or combinations thereof. When present, the additional additives may be included in any effective amount, for example, in an amount of 0.01 to 20 wt%, or 0.01 to 10 wt%, or 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the curable thermosetting composition.

[0097] The curable thermoset composition may be prepared by combining the graft copolymer and other optional components disclosed herein using any suitable method.

[0098] Cured thermosetting compositions are also provided, including the cured product of the curable thermosetting composition. There is no particular restriction on the manner in which the curable thermosetting composition may be cured. The curable composition may be cured, for example, thermally or by using irradiation techniques, including UV or electron beam irradiation. For example, the cured product may be obtained by heating the curable thermosetting composition as defined herein for a time and temperature sufficient to evaporate the solvent and achieve curing. If heat curing is used, the temperature may be 30 to 400°C, or 50 to 250°C, or 100 to 250°C. Heating may range from 1 minute to 24 hours, or 1 minute to 6 hours, or 3 hours to 5 hours. Curing may be staged to produce a partially cured and often tack-free resin, which is then fully cured by heating for a longer period of time or at a temperature within the aforementioned range. As used herein, the term "cured" encompasses partially cured or fully cured products.

[0099] The cured thermosetting composition may have one or more desirable properties. For example, the thermosetting composition may have a glass transition temperature of 165° C. or more, preferably 170° C. or more, more preferably 165 to 180° C. The thermosetting composition may also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df) and reduced moisture absorption. For example, the thermosetting composition may have a dielectric constant of less than 3.0, preferably less than 2.75, more preferably less than 2.6 at a frequency of 10 GHz. The thermosetting composition may have a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz. Thus, the thermosetting composition comprising the linear block copolymer of the present disclosure may be particularly well suited for use in electronics applications.

[0100] The curable thermosetting compositions and cured thermosetting compositions can be used in a variety of applications and uses, including any application where conventional thermosetting compositions are used. For example, useful articles comprising the curable thermosetting compositions or the cured thermosetting compositions can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, cast components, prepregs, casings, laminates, metal clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather resistant coatings, scratch resistant coatings, and electrical insulating coatings; adhesives; binders; glues; composites such as those using carbon fiber and glass fiber reinforcements. When utilized as coatings, the disclosed compounds and compositions can be deposited on the surface of a variety of underlying substrates. For example, the compositions can be deposited on the surface of metals, plastics, glass, fiber sidings, ceramics, masonry, wood, or any combination thereof. The disclosed compositions may be used as coatings on the surface of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and storage in the paint and surface coating industries. The curable thermoset compositions and cured thermoset compositions derived therefrom may also be particularly well suited for use in forming electrical and computer components.

[0101] The method of forming a composite may include impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and stacking a plurality of prepregs. The reinforcing structure may be a porous substrate, such as a fiber preform or substrate, or other porous material including ceramic, polymer, glass, carbon, or combinations thereof. For example, the porous substrate may be a woven or nonwoven glass fabric, a fiberglass fabric, or a carbon fiber. When the article includes a fiber preform, the method of manufacturing the article may include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fiber preform may be shaped, optionally before or after removing the solvent. In some embodiments, the curable thermosetting composition layer may further include a woven or nonwoven glass fabric. For example, the curable layer may be prepared by impregnating a glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), "Prepreg Technology", March 2005, Publication No. FGU 017b; Anonymous (Hexcel Corporation), "Advanced Fibre Reinforced Matrix Products for Direct Processes", June 2005, Publication No. ITA 272; and Bob Griffiths, "Farnborough Airshow Report 2006", CompositesWorld.com, September 2006. The weight and thickness of the reinforcing structure are selected according to the intended use of the composite, using criteria well known to those skilled in the art of producing fiber reinforced resin composites. The reinforcing structure can contain various finishes that are suitable for the thermoset component of the curable thermoset composition.

[0102] Methods for producing articles from curable thermosetting compositions may include partially curing the curable thermosetting composition to form a prepreg or fully curing the curable thermosetting composition to form a composite article. References herein to the property of a "cured composition" refer to a composition that is substantially fully cured. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. Those skilled in the art of thermosetting can determine whether a sample is partially cured or substantially fully cured without undue experimentation. Curing may occur before or after removal of the solvent from the curable composition. In addition, the article may be further shaped, for example by thermoforming, before or after removal of the solvent, before curing, after partial curing, or after full curing. In some embodiments, the article is formed and the solvent is removed; the article is partially cured (B-staged); optionally shaped; and then further cured.

[0103] Commercial-scale methods for forming composites are known in the art, and the curable thermosetting compositions described herein are easily adaptable to existing processes and equipment. For example, prepregs are often produced in a treater. The main components of a treater include a feeder roller, a resin impregnation tank, a treater oven, and a receiver roller. The reinforcing structure (e.g., E-glass) is usually wound onto a large spool. The spool is then placed on a feeder roller, which rotates and slowly rolls the reinforcing structure. The reinforcing structure then travels through a resin impregnation tank containing the curable thermosetting composition. The curable composition impregnates the reinforcing structure. After emerging from the tank, the coated reinforcing structure travels upward through a vertical treater oven, which is typically at a temperature of 175 to 200° C., and the solvent evaporates. The resin begins to polymerize at this point. When the composite emerges from the tower, it is sufficiently cured so that the web is not wet or sticky. However, the curing process is stopped short of completion to allow additional curing to occur when the laminate is made. The web then wraps the prepreg around a receiver roll.

[0104] Electrical and electronic articles comprising or derived from the curable thermosetting composition are also provided. Articles include those comprising printed circuits, such as those used in the medical or aerospace industries. Other articles include antennas and similar articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic notepads, and similar devices, or office automation equipment. For example, electrical components can be placed on the printed circuit board, including the laminate. Other exemplary articles prepared from the curable composition for various applications can include copper clad laminates (CCLs), such as metal core copper clad laminates (MCCCLs), composite articles, and coated articles, such as multilayer articles.

[0105] The dielectric layer can be prepared from a curable thermosetting composition and can be useful in circuit assemblies, for example, metal clad laminates, such as copper clad laminates. For example, the laminate can include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally, a heat dissipating metal matrix layer disposed on the dielectric layer opposite the conductive metal layer. The dielectric layer can optionally include a fiber preform (e.g., a cloth layer). For example, the dielectric layer can further include a glass cloth layer.

[0106] The conductive metal layer can be in the form of a circuit and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, etc., or combinations thereof. Other metals include copper-molybdenum alloys, nickel-cobalt-iron alloys such as KOVAR available from Carpenter Technology Corporation, nickel-iron alloys such as INVAR available from National Electronic Alloys, Inc., bimetals, trimetals, trimetals derived from two layers of copper and one layer of INVAR, and trimetals derived from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or copper alloys. Alternatively, rolled copper foil can be used. The conductive metal layer can have a thickness of 2 to 200 micrometers (μm), or 5 to 50 μm, or 5 to 40 μm.

[0107] The heat-dissipating metal matrix layer can be a thermally conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof. Any thermally conductive, electrically conductive metal can be used, provided that the metal is electrically insulated from the metal circuit layer. A preferred supporting metal matrix layer can have a thickness of 0.1 to 20 millimeters (mm), or 0.5 to 10 mm, or 0.8 to 2 mm.

[0108] The conductive metal layer and the supporting metal matrix layer can be pretreated to have a high surface roughness for enhanced adhesion to the dielectric layer. Treatment methods include, for example, cleaning, flame treatment, plasma discharge, corona discharge, etc., to enhance adhesion of the metal layer. The dielectric layer can be firmly bonded to the conductive metal layer or heat dissipation layer without the use of adhesives, or adhesives can be used to improve the adhesion of the dielectric layer to the conductive metal layer or heat dissipation layer. Exemplary adhesives used to bond the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxies, etc., or combinations thereof.

[0109] Copper clad laminates can be made without the use of thermosetting adhesives by thermal lamination of one or more dielectric layers, one or more conductive metal layers and a supporting metal matrix layer under pressure. The dielectric layer can be prepared from a curable thermosetting composition and can be prepared by a solvent casting process to form a layer before the thermal lamination step. For example, the dielectric layer, the conductive metal layer and the heat dissipating layer can be thermally laminated together by an adhesive-free process under pressure to form a laminate. The conductive metal layer can optionally be in the form of a circuit before lamination, or the conductive metal layer can optionally be etched after lamination to form an electrical circuit. The lamination can be by hot pressing or roll calendaring methods, such as roll-to-roll methods. The conductive metal layer in the copper clad laminate can be further patterned to obtain a printed circuit board. Furthermore, the copper clad laminate can be shaped to obtain a circuit board having the shape of a sheet, tube or rod.

[0110] Alternatively, laminates for circuit assemblies can be made by solution casting techniques in which the curable thermosetting composition is cast directly onto a conductive metal layer, followed by lamination to a heat dissipating metal matrix layer. For example, the curable thermosetting composition can be cast directly onto a heat dissipating metal matrix layer, followed by lamination to a conductive metal layer.

[0111] Multi-layer laminates containing additional layers can also be made by thermal lamination in one step or two or more successive steps by processes such as hot pressing or roll calendaring. For example, there can be up to seven layers, or up to 16 layers in a laminate. In one embodiment, a laminate can be formed in one step or two or more successive steps with sequential layers of fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil or subcombinations thereof with fewer layers, such that the laminate includes a layer of thermoset film between any layer of metal foil and any layer of fabric. In another embodiment, a first laminate can be formed in one step or two or more successive steps with a layer of fabric between two layers of thermoset, for example a layer of woven glass fabric between two layers of thermoset. A second laminate can then be prepared by laminating a metal foil to the thermoset side of the first laminate.

[0112] The printed circuit board prepared from the curable thermosetting composition can have a total thickness of 0.1 to 20 mm, specifically 0.5 to 10 mm, the total thickness referring to the assembly including each layer of the dielectric layer, the conductive metal layer and the supporting metal matrix layer. The circuit assembly can have a total thickness of 0.5 to 2 mm, specifically 0.5 to 1.5. There is no specific limit to the thickness of the dielectric layer, which can be 5 to 1500 μm, or 5 to 750 μm, or 10 to 150 μm, or 10 to 100 μm. For example, the printed circuit board can be a metal core printed circuit board (MCPCB) for use in light emitting diode (LED) applications.

[0113] The curable thermosetting composition can be used as a coating, for example in the preparation of multi-layer articles. A method of making a coating can include combining the curable thermosetting composition and optionally a fluoropolymer, and forming a coating on a substrate. For example, a multilayer article can be made by forming a layer comprising a curable thermoset composition, removing solvent from the layer and optionally curing to obtain a primer layer, forming a second layer over the primer layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, YO3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, etc.), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, etc.), or a combination thereof to obtain a multilayer article, and optionally thermally treating the multilayer article to cure the curable thermoset composition. In some embodiments, the second layer can further comprise a curable thermoset composition.

[0114] Additional uses for the curable thermoset compositions include, for example, acid bath vessels; neutralization tanks; aircraft components; bridge girders; bridge decks; electrolytic cells; exhaust stacks; scrubbers; athletic equipment; stairs; walkways; automotive exterior panels such as hoods and trunk lids; floor pans; air intakes; pipes and ducts, including heater ducts; industrial fans, fan housings and blowers; industrial mixers; ship hulls and decks; fenders for marine terminals; tiles and coatings; architectural panels; business machine housings; trays, including cable trays; concrete modifiers; dishwashers and refrigeration. storage components;electrical encapsulants;electrical panels;tanks and tank linings, including electrolytic refining tanks, water softener tanks, fuel tanks and various filament wound tanks;furniture;garage doors;gratings;protective body gear;luggage;outdoor vehicles;pressure tanks;optical waveguides;radomes;handrails;railroad components such as tank cars;hopper car covers;car doors;truck bed liners;satellite dishes;signage;solar energy panels;telephone switch housings;tractor components;transformer covers;truck components such as fenders, hoods, bodies, cabs and berths;connectors Insulation for rotating machines, including ground, turn and phase isolation insulation; commutators; core insulation and cord and racing tape; drive shaft couplings; propeller blades; missile components; rocket motor cases; wing sections; sucker rods; fuselage sections; wing skins and flaring; engine nacelles; cargo doors; tennis racquets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; lateral leaf springs; pumps, such as automotive smog pumps; electrical components, such as power cable connections, recessed and tooling wire wound and densely packed multi-element assemblies; electromechanical device encapsulations; battery cases; resistors; fuses and thermal cut-off devices; coatings for printed wiring boards; casting items such as capacitors, transformers and crankcase heaters; miniature molded electronic components including coils, capacitors, resistors and semiconductors; as steel replacement in chemical processing, pulp and paper, power generation and wastewater treatment; scrubbers; pultruded parts for structural applications including structural members, grates and safety rails; swimming pools, swimming pool slides, hot tubs and saunas;drive shafts for under hood applications;dry toner resins for copiers;marine tooling and composites;heat shields;submarine hulls;prototype production;laboratory model development;laminate trim;drilling fixtures;jointing jigs;inspection fixtures;industrial metal forming dies;aircraft stretch block and hammer formwork;vacuum molding tools;flooring including flooring for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, coolers and outdoor loading docks;conductive compositions for antistatic applications;for decorative flooring;expansion joints for bridges;injectable mortar for patching and repairing cracks in structural concrete;tile grouting;machine rails;metal dowels;bolts and supports;repair of oil and fuel storage tanks, as well as numerous other applications.

[0115] Useful processes for preparing articles and materials include those generally known in the art for processing thermoset resins. Such processes are described in such references as, for example, Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal, Senior Ed, pp. 105-168 and 497-533, and “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.), Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include resin transfer molding; sheet molding; bulk molding; pultrusion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting, open mold casting; lamination, including wet or dry layup and spray layup; contact molding, including cylindrical contact molding; compression molding; including vacuum assisted resin transfer molding and chemically assisted resin transfer molding; conformal tool molding; autoclave curing; heat curing in air; vacuum bagging; pultrusion; Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP); open molding, sequential combination of resin and glass; and filament winding, including cylindrical filament winding. For example, the article can be prepared by a resin transfer molding process.

[0116] Articles are provided that are derived from the curable thermosetting composition, and are composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded components, prepregs, casings, cast articles, laminates, or combinations thereof; or the article is a metal clad laminate, electronic composite, structural composite, or combinations thereof. The article can be manufactured as disclosed herein, for example, by casting, molding, extruding, etc., and removing the solvent from the formed article. In an embodiment, the article can be a layer and can be formed by casting the curable composition onto a substrate to form a cast layer. The solvent can be removed by any number of means, including by heating the cast layer, heating the cast layer under heat and pressure, for example, by laminating the cast layer to another substrate. In some embodiments, the article prepared by the above-described method can include an adhesive, packaging material, capacitor film, or circuit board layer. In some embodiments, the article prepared from the curable composition can be a dielectric layer, or a coating disposed on a substrate, such as a wire or cable coating. For example, the article can be a dielectric layer in a circuit material, such as a printed circuit board, for example, used in lighting or communication applications. Another exemplary article prepared from the curable composition can be one or more coating layers. The curable composition can be used to prepare articles as disclosed herein for other curable thermosetting compositions. EXAMPLES

[0117] The present disclosure is further illustrated by the following non-limiting examples.

[0118] Prophetic Example 1: Preparation of Polyphenylene Ether Grafted Polybutadiene (PPE-g-PBD) The preparation of polyphenylene ether grafted polybutadiene using the grafting from approach is illustrated in FIG.

[0119] Synthesis of 2,6-dimethylphenol grafted polybutadiene (I): Alkylation of 2,6-dimethylphenol with polybutadiene is achieved using a Lewis acid catalyst such as AlCl3. Other catalysts that may be used include boron trifluoride phenol complex, p-toluenesulfonic acid, methanesulfonic acid, cation exchange catalysts, sulfuric acid, phosphoric acid, etc. Polybutadiene is dissolved in excess of 2,6-dimethylphenol and the catalyst is added. The reaction temperature is increased to 140-150°C and maintained for 4-6 hours. The material is isolated by precipitation into methanol.

[0120] Synthesis of polyphenylene ether grafted polybutadiene (II): 2,6-Dimethylphenol grafted polybutadiene (I) is polymerized with 2,6-dimethylphenol by oxidative coupling polymerization. 2,6-Dimethylphenol grafted polybutadiene and 2,6-dimethylphenol are dissolved in toluene in a 500 ml glass reactor. To this solution are added dimethylbutylamine, dibutylamine, ditert-butylethylamine, Maquat™ and a mixture of Cu2O and HBr (aqueous solutions). Oxygen is bubbled through the reaction for 2 hours at a temperature of 25-40°C. After stopping the oxygen flow, an aqueous solution of the trisodium salt of trinitriloacetic acid is added. The temperature is increased to 60°C and maintained for 2 hours. The toluene phase is separated and the PPE-g-PBD copolymer is isolated by precipitation into methanol. The product is dried under vacuum and nitrogen.

[0121] Synthesis of methacrylate-capped polyphenylene ether grafted polybutadiene (III): Dissolve PPE-g-PBD copolymer in toluene. Increase temperature to 120°C to perform azeotropic distillation. Reduce temperature to 75°C and add dimethylaminopyridine to the reaction solution. Once DMAP is dissolved, add methacrylic anhydride slowly (20 min) to the reaction mixture. After addition, increase temperature to 110°C for gentle reflux. Isolate material by precipitation into methanol.

[0122] Alternatively, the PPE-g-PBD copolymer can be capped with vinylbenzyl chloride or allyl bromide in the presence of a strong base catalyst.

[0123] Prophetic Example 2: Preparation of Polyphenylene Ether Grafted Polybutadiene (PPE-g-PBD) The preparation of polyphenylene ether grafted polybutadiene using the grafting to approach is shown in FIG.

[0124] Synthesis of styrene-capped polyphenylene ether (Ia): The monofunctional low molecular weight polyphenylene ether copolymer is dissolved in toluene. To this solution, 50% NaOH(aq) solution and a phase transfer agent are added. Vinylbenzyl chloride is added dropwise at room temperature. The temperature is raised to 75° C. and maintained for 4 hours. After cooling to room temperature, the solution is transferred to an extraction funnel and neutralized with 0.1N HCl aqueous solution, followed by washing with DI water. The organic phase is separated and the product is isolated by precipitation into methanol. The product is dried under vacuum and nitrogen at room temperature.

[0125] Synthesis of polyphenylene ether grafted polybutadiene (IIa) via free radical coupling: The styrene-capped polyphenylene ether and polybutadiene are dissolved in toluene. The reaction temperature is increased to 140°C under pressure and maintained for 5 hours. The product is precipitated in methanol, filtered and dried.

[0126] Alternatively, acrylate, methacrylate or allyl capped polyphenylene ethers can be synthesized and used as (I). For example, a methacrylate capped phenylene ether oligomer used for grafting to polybutadiene is shown in Figure 2b.

[0127] Prophetic Example 3: Preparation of Polyphenylene Ether Grafted Polybutadiene (PPE-g-PBD) The preparation of polyphenylene ether grafted polybutadiene using copolymerization is shown in FIG. 3a.

[0128] Synthesis of styrene-capped polyphenylene ether (Ia): The monofunctional low molecular weight polyphenylene ether copolymer is dissolved in toluene. To this solution, 50% NaOH(aq) solution and a phase transfer agent are added. Vinylbenzyl chloride is added dropwise at room temperature. The temperature is raised to 75° C. and maintained for 4 hours. After cooling to room temperature, the solution is transferred to an extraction funnel and neutralized with 0.1N HCl aqueous solution, followed by washing with DI water. The organic phase is separated and the product is isolated by precipitation into methanol. The product is dried under vacuum and nitrogen at room temperature.

[0129] Synthesis of polyphenylene ether grafted copolymer (IIa): The anionic copolymerization of styrene-capped polyphenylene ether (Ia) and butadiene is carried out at different compositions at 50 °C under dry nitrogen in a glass tube equipped with a three-way valve. Purified butadiene is added to a 5-10 wt% solution of styrene-capped polyphenylene ether (I) in dry toluene to which the required amount of THF has been added. The copolymerization is then initiated by adding the required amount of s-BuLi solution to the resulting mixture, after which the polymerization mixture is stirred for different reaction times depending on the targeted conversion. The copolymerization is terminated by adding a small amount of methanol, and the final product is isolated by precipitating the polymerization mixture in excess methanol and then drying in a vacuum oven.

[0130] Alternatively, acrylate, methacrylate or allyl-capped polyphenylene ethers can be synthesized and used as (I). Isoprene can be used as a comonomer and the copolymerization reaction can be carried out using free radical or nitroxide mediated polymerization. An example of a methacrylate-capped phenylene ether oligomer used for copolymerization with butadiene is shown in Figure 3b.

[0131] Prophetic Example 4: Preparation of Polyphenylene Ether Grafted Polybutadiene Using a Grafting-to Approach The preparation of polyphenylene ether grafted polybutadiene from epoxidized polybutadiene is shown in FIG.

[0132] Synthesis of polyphenylene ether grafted polybutadiene: Epoxidized polybutadiene and polyphenylene ether oligomers (either monofunctional or difunctional) are dissolved in a solvent (toluene, chloroform). To this solution, a catalyst is added at room temperature. The reaction is carried out under reflux for 4 hours. The polyphenylene ether grafted polybutadiene is isolated by precipitation into a non-solvent (e.g., methanol).

[0133] Prophetic Example 5: Preparation of Polyphenylene Ether Grafted Polybutadiene Using a Grafting-to Approach The preparation of polyphenylene ether grafted polybutadiene from maleic anhydride functionalized polybutadiene is shown in FIG.

[0134] Synthesis of polyphenylene ether grafted polybutadiene: Maleic anhydride grafted polybutadiene and polyphenylene ether oligomers (either monofunctional or difunctional) are dissolved in a solvent (toluene, chloroform). To this solution, a catalyst is added at room temperature. The reaction is carried out under reflux for 4 hours. The polyphenylene ether grafted polybutadiene is isolated by precipitation into a non-solvent (methanol).

[0135] The present disclosure further includes the following aspects.

[0136] Aspect 1: A graft copolymer comprising a hydrocarbon backbone having a phenylene ether oligomer comprising repeat units derived from a substituted or unsubstituted monohydric phenol grafted from the hydrocarbon backbone, the graft copolymer comprising a linking group -L between the hydrocarbon backbone and the phenylene ether oligomer.1 -(R) n -L 2 -[In formula, L 1 is a substituted or unsubstituted C 1~6 R is an alkylene group, a substituted or unsubstituted phenylene group, or -(C=O)-; n is 0 or 1; L 2 is a single bond or C 1~6 an alkylene group, preferably a single bond or a methylene group; 1 When is a substituted or unsubstituted phenylene group, n is 0.

[0137] Embodiment 2: The graft copolymer of embodiment 1, comprising the structure A(-L 1 -(R) n -L 2 -B) m [In the formula, A is a hydrocarbon skeleton, and L 1 is C 1~6 Alkylene group or -C(O)-, preferably C 1~2 is an alkylene group, n is 0 or 1, R is a substituted or unsubstituted phenylene group, L 2 is a single bond or C 1~6 A is an alkylene group, preferably a single bond or a methylene group, B is a phenylene ether oligomer; and m is 1 to 50, preferably 1 to 25, most preferably 1 to 10.

[0138] Embodiment 3: The graft copolymer of embodiment 1 or 2, wherein the phenylene ether oligomer has a weight average molecular weight of less than 20,000 grams per mole, preferably less than 10,000, and more preferably between 600 and 4,500 grams per mole, as measured by nuclear magnetic resonance spectroscopy.

[0139] Embodiment 4: The graft copolymer of any of embodiments 1 to 3, wherein the phenylene ether oligomer is 2,6-(di-C 1~18alkyl)phenol, or 2,6-diphenylphenol, 2-phenyl-6-(C 1~18 alkyl)phenols, 2-phenyl-6-(cycloalkyl)phenols, 2,6-(dicycloalkyl)phenols, 2-(C 1~18 a graft copolymer comprising repeat units derived from a cyclic alkyl (alkyl)-6-(cycloalkyl)phenol, or a combination thereof;

[0140] Embodiment 5: The graft copolymer of any of embodiments 1 to 4, wherein the hydrocarbon resin contains unsaturation. Preferably, the hydrocarbon resin is selected from the group consisting of polybutadiene, polyisoprene, alkenyl aromatics and unsaturated C 4~12 A copolymer of a hydrocarbon, or a combination thereof, more preferably poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, poly(styrene-co-butadiene), poly(styrene-co-isoprene), or a combination thereof, and even more preferably a graft copolymer comprising poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, or a combination thereof.

[0141] Example 6: The graft copolymer of any of Examples 1 to 5, comprising at least one end group comprising a vinylbenzene ether end group, a methacrylate end group, an acrylate end group, an epoxy end group, a hydroxyl end group, a cyanate ester end group, an amine end group, a maleimide end group, an allyl end group, a styrenic end group, an activated ester end group, or an anhydride end group.

[0142] Embodiment 7: The graft copolymer of embodiment 1, comprising: a linear hydrocarbon backbone; and phenylene ether oligomers grafted onto the chain ends of the hydrocarbon backbone.

[0143] Embodiment 8: The graft copolymer of embodiment 7, wherein the hydrocarbon backbone is selected from the group consisting of poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, alkenyl aromatics and unsaturated C 4~12a copolymer of a hydrocarbon, butyl rubber, or a combination thereof; and a graft copolymer in which the phenylene ether oligomer comprises repeat units derived from 2,6-dimethylphenol and has a weight average molecular weight of less than 6,000 grams per mole.

[0144] Embodiment 9: A method of making the graft copolymer of any of embodiments 1 to 8, comprising the steps of: oxidatively polymerizing a substituted or unsubstituted monohydric phenol from a phenol-functionalized hydrocarbon resin to obtain the graft copolymer; or covalently coupling a hydrocarbon resin and a phenylene ether oligomer, wherein the hydrocarbon resin and the phenylene ether oligomer comprise complementary reactive groups; or copolymerizing an ethylenically unsaturated monomer and a polymerizable phenylene ether oligomer, wherein the polymerizable phenylene ether oligomer comprises a methacrylate end group, an acrylate end group, an allyl end group, a styrenic end group, or a vinyl benzene ether end group.

[0145] Embodiment 10: A curable thermoset composition comprising the graft copolymer of any of embodiments 1 to 8.

[0146] Example 11: The curable thermosetting composition of example 10, further comprising a crosslinker, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0147] Example 12: The curable thermoset composition of example 10 or 11, further comprising one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0148]

[0031] Embodiment 13: A cured thermoset composition comprising the cured product of the curable thermoset composition of any of embodiments 10-12.

[0149] Example 14: An article comprising the cured thermoset composition of Example 13, the article being a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; or an article being a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0150] Example 15: An article made from a varnish composition comprising the curable thermoset composition of any of Examples 10 to 12 and a solvent, the article being preferably a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate; or a metal clad laminate.

[0151] The compositions, methods and articles can alternatively comprise, consist of or consist essentially of any suitable material, step or ingredient disclosed herein. The compositions, methods and articles can additionally or alternatively be formulated to be devoid of or substantially free of any material (or species), step or ingredient that is not otherwise necessary to achieve the function or purpose of the compositions, methods and articles.

[0152] All ranges disclosed herein are inclusive of the endpoints, which are combinable independently of each other. "Combinations" are inclusive of admixtures, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a," "an," and "the" do not denote limitations of quantity, and should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. References throughout the specification to "embodiments" mean that the particular element described in connection with that embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. The term "combinations thereof," as used herein, includes one or more of the listed elements and is open, allowing for the presence of one or more similar elements not named. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.

[0153] Unless otherwise specified herein to the contrary, all test standards are the latest standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0154] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs.All cited patents, patent applications and other references are incorporated herein by reference in their entirety.However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term from this application shall take precedence over the conflicting term from the incorporated reference.

[0155] Compounds are described using standard nomenclature. For example, any position that is not substituted by any indicated group is understood to have its valency satisfied by a bond or hydrogen atom as indicated. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0156] As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, suffix or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated or unsaturated. It can also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as being substituted, it can optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, when specifically described as being substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., and can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to a branched or straight-chain, saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" refers to a straight or branched, monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH2). "Alkoxy" refers to an alkyl group linked through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a straight or branched, saturated, divalent aliphatic hydrocarbon group, such as methylene (-CH2-) or propylene (-(CH2)3-). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, all of the ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing the specified number of carbon atoms, for example, phenyl, tropone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound containing one or more of fluoro, chloro, bromo, or iodo substituents. Combinations of different halo atoms (e.g., bromo and fluoro) or only chloro atoms may be present. The prefix "hetero" means that the compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2 or 3 heteroatoms), each of which is independently N, O, S, Si, or P. "Substituted" means that the compound or group contains, each of which is independently, C, H, or C, in place of a hydrogen. 1~9 Alkoxy, C 1~9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3~12 Cycloalkyl, C 2~12 Alkenyl, C 5~12 Cycloalkenyl, C 6~12 Aryl, C 7~13 Aryl alkylene, C 4~12 Heterocycloalkyl and C 3~12It means that it is substituted with at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl, provided that the valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with nitrile.

[0157] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that may not be presently foreseen or foreseeable may become apparent to applicants or others skilled in the art. Accordingly, the appended claims are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents as filed and as they may be amended.

Claims

1. A graft copolymer comprising a hydrocarbon backbone having phenylene ether oligomers comprising repeat units derived from a substituted or unsubstituted monohydric phenol grafted from the hydrocarbon backbone, The graft copolymer has a linking group -L between the hydrocarbon backbone and the phenylene ether oligomer. １ - (R) ｎ -L ２ - [In the formula, L １ is a substituted or unsubstituted C １～６ an alkylene group, a substituted or unsubstituted phenylene group, or —(C═O)—; R is a substituted or unsubstituted phenylene group or —(C═O)—; n is 0 or 1; L ２ is a single bond or C １～６ an alkylene group, preferably a single bond or a methylene group; However, L １ is a substituted or unsubstituted phenylene group, then n is 0. A graft copolymer comprising:

2. 10. The graft copolymer of claim 1, having the structure A(-L １ -(R) ｎ -L ２ -B) ｍ [In the formula, A is a hydrocarbon skeleton, L １ is C １～６ Alkylene group or —C(O)—, preferably C １～２ is an alkylene group, n is 0 or 1; R is a substituted or unsubstituted phenylene group; L ２ is a single bond or C １～６ an alkylene group, preferably a single bond or a methylene group; B is a phenylene ether oligomer; m is 1 to 50, preferably 1 to 25, and most preferably 1 to 10. A graft copolymer characterized in that it is

3. 10. The graft copolymer of claim 1, wherein the phenylene ether oligomer has a number average molecular weight of less than 20,000 grams per mole, preferably less than 10,000, and more preferably from 600 to 4,500 grams per mole, as measured by nuclear magnetic resonance spectroscopy.

4. 2. The graft copolymer of claim 1, wherein the phenylene ether oligomer is 2,6-(di-C １～１８ alkyl)phenol, or 2,6-diphenylphenol, 2-phenyl-6-(C １～１８ alkyl)phenols, 2-phenyl-6-(cycloalkyl)phenols, 2,6-(dicycloalkyl)phenols, 2-(C １～１８ 1. A graft copolymer comprising repeating units derived from a 6-(cycloalkyl)-1,1-dimethyl-2,2-dimethyl-4-(methylphenyl ...

5. 10. The graft copolymer of claim 1, wherein the hydrocarbon backbone contains unsaturation. Preferably, the hydrocarbon resin is selected from the group consisting of polybutadiene, polyisoprene, alkenyl aromatics and unsaturated C ４～１２ A graft copolymer characterized by comprising a copolymer of hydrocarbons, or a combination thereof, more preferably poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, poly(styrene-co-butadiene), poly(styrene-co-isoprene), or a combination thereof, and even more preferably poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, or a combination thereof.

6. 10. The graft copolymer of claim 1, comprising at least one end group comprising a vinyl benzene ether end group, a methacrylate end group, an acrylate end group, an epoxy end group, a hydroxyl end group, a cyanate ester end group, an amine end group, a maleimide end group, an allyl end group, a styrenic end group, an activated ester end group, or an anhydride end group.

7. 10. The graft copolymer of claim 1, a linear hydrocarbon skeleton; a phenylene ether oligomer grafted onto the chain end of the hydrocarbon backbone; A graft copolymer comprising:

8. 8. The graft copolymer of claim 7, The hydrocarbon backbone may be selected from poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, alkenyl aromatics and unsaturated C ４～１２ hydrocarbon copolymer, butyl rubber, or a combination thereof; The graft copolymer is characterized in that the phenylene ether oligomer comprises repeating units derived from 2,6-dimethylphenol and has a weight average molecular weight of less than 6,000 grams per mole.

9. 9. A method for making the graft copolymer of any one of claims 1 to 8, comprising: oxidatively polymerizing a substituted or unsubstituted monohydric phenol from a phenol-functionalized hydrocarbon resin to obtain said graft copolymer; or covalently coupling a hydrocarbon resin and the phenylene ether oligomer, wherein the hydrocarbon resin and the phenylene ether oligomer contain complementary reactive groups; or copolymerizing an ethylenically unsaturated monomer and a polymerizable phenylene ether oligomer, wherein the polymerizable phenylene ether oligomer comprises a methacrylate end group, an acrylate end group, an allyl end group, a styrenic end group, or a vinyl benzene ether end group; A method comprising:

10. A curable thermosetting composition comprising the graft copolymer of any one of claims 1 to 8.

11. 11. The curable thermosetting composition of claim 10, further comprising a crosslinker, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

12. 11. The curable thermoset composition of claim 10, further comprising one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

13. A cured thermoset composition comprising the cured product of the curable thermoset composition of claim 10.

14. 14. An article comprising the cured thermoset composition of claim 13, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; Or, an article characterized as being a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

15. 11. An article made from a varnish composition comprising the curable thermosetting composition of claim 10 and a solvent, the article being preferably a fiber, layer, coating, cast article, prepreg, composite, or laminate; or a metal clad laminate.

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