LINEAR BLOCK COPOLYMERS AND CURABLE THERMOSETTING COMPOSITIONS COMPRISING LINEAR BLOCK COPOLYMERS - Patent application

Abstract

The linear block copolymer comprises at least one block A comprising a phenylene ether oligomer containing repeat units derived from a substituted or unsubstituted monohydric phenol, and at least one block B comprising a hydrocarbon resin. The linear block copolymers may be particularly useful in curable compositions, thermoset compositions, and articles formed therefrom.

Description

[Technical field]

[0001] This disclosure relates to linear block copolymers, methods of forming same, curable thermoset compositions containing same, and articles derived therefrom.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and benefit of European Patent Application No. 21204234.5, 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 ultra-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 making 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 electronics 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, however, technical limitations remain in the compatibility of the materials. Summary of the Invention [Problem to be solved by the invention]

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

[0006] The linear block copolymer comprises at least one block A comprising a phenylene ether oligomer containing repeat units derived from a substituted or unsubstituted monohydric phenol, and at least one block B comprising a hydrocarbon resin.

[0007] A method for making a linear block copolymer includes oxidatively polymerizing a substituted or unsubstituted monohydric phenol derived from a phenol-terminated hydrocarbon resin to provide a linear block copolymer, or polymerizing an ethylenically unsaturated monomer derived from a phenylene ether macroinitiator to provide a linear block copolymer, or covalently coupling a hydrocarbon resin and a phenylene ether oligomer, wherein the hydrocarbon resin and the phenylene ether oligomer contain complementary reactive groups.

[0008] The curable thermosetting composition comprises a linear block copolymer having an intrinsic viscosity of 0.15 deciliters per gram or less as determined by an Ubbelohde viscometer in chloroform at 25° C., and optionally further comprises one or more of a crosslinker, a curing agent, a curing catalyst, a curing initiator, or combinations thereof, a flame retardant, a filler, a coupling agent, or combinations thereof, or both.

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

[0010] The article comprises a cured thermoset composition.

[0011] The article may be made from a varnish composition that includes a curable thermosetting composition and a solvent.

[0012] These and other features are illustrated in the figures and detailed description that follow.

[0013] The following figure is an exemplary embodiment. [Brief description of the drawings]

[0014] [Figure 1] 1 shows a chemical scheme of a method for preparing a phenylene ether-polybutadiene-phenylene ether (ABA) triblock copolymer. [Diagram 2] FIG. 1 shows a chemical scheme of a method for the preparation of methacrylate-capped phenylene ether-polybutadiene-phenylene ether (ABA) triblock copolymers. [Diagram 3] 1 shows a chemical scheme of a method for preparing polyisoprene-phenylene ether-polyisoprene (BAB) triblock copolymer. [Figure 4] FIG. 1 shows a chemical scheme of a method for the preparation of methacrylate-capped phenylene ether-butyl rubber (AB) block copolymers. [Diagram 5] 1 shows a chemical scheme of a method for preparing a phenylene ether-butyl rubber (AB) block copolymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present inventors have discovered that linear block copolymers can be prepared from phenylene ether oligomers and hydrocarbon resins. Linear block copolymers can conveniently provide a desirable combination of dielectric properties, flame retardancy, and thermal performance while maintaining compatibility between the phenylene ether oligomers and the hydrocarbon resins. Linear block copolymers can be particularly useful in curable thermosetting compositions.

[0016] Thus, one aspect of the present disclosure is a linear block copolymer. As used herein, the term "linear block copolymer" refers to a copolymer in which the blocks are linked end-to-end in a linear sequence. For example, the linear block copolymer of the present disclosure can include AB linear diblock copolymers, ABA linear triblock copolymers, BAB linear triblock copolymers, and the like. In one embodiment, additional A and B blocks can be present, for example, an ABABA linear pentablock copolymer is provided. In one embodiment, the A and B blocks are linked in a regular alternating sequence. The terminal positions of the block copolymer can be occupied by A blocks, B blocks, or A and B blocks. Other block sequences and compositions (e.g., block C derived from a third monomer different from the phenylene ether and the hydrocarbon resin, for example, to provide an ABC triblock copolymer) are also contemplated by the present disclosure.

[0017] The linear block copolymers of the present disclosure include at least one block A comprising a phenylene ether oligomer. The phenylene ether oligomer comprises repeat units derived from a substituted or unsubstituted monohydric phenol. The substituted or unsubstituted monohydric phenol can have the structure: [ka] In the formula, Q 1 Each event is independently halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2-12 halohydrocarbyloxy (at least two carbon atoms separate the halogen atom and the oxygen atom), and Q 2 Each event 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 (at least two carbon atoms separate the halogen atom and the oxygen atom). In one embodiment, the substituted or unsubstituted monohydric phenol is a 2,6-(di-C 1-6 In one embodiment, Q 1 Each event in is methyl, and Q 2 where each event is hydrogen and the monohydric phenol is 2,6-xylenol (also called 2,6-dimethylphenol or "DMP").

[0018] Thus, the phenylene ether oligomer block A comprises a repeat unit of the formula: [ka] In the formula, Q 1 and Q 2 can be as described above. In one embodiment, 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 In one embodiment, the phenylene ether oligomer comprises repeat units derived from a monohydric phenol, including 2,6-dimethylphenol, 2,6-dimethylphenyl ...

[0019] The phenylene ether oligomers can have a number average molecular weight of less than 10,000 grams / mole, or less than 5,000 grams / mole, or from 600 to 4,500 grams / mole. Molecular weights can be determined by gel permeation chromatography (GPC) against polystyrene standards. Those skilled in the art will recognize that molecular weight characterization of phenylene ether oligomers cannot be performed using GPC when linear block copolymers are prepared by a process that includes oxidative polymerization of phenylene ether oligomers derived from a hydrocarbon resin. In such cases, the number average molecular weight can be calculated from the degree of polymerization determined using nuclear magnetic resonance (NMR) spectroscopy.

[0020] The phenylene ether oligomers have an intrinsic viscosity of 0.15 deciliters / gram or less, preferably 0.02 to 0.15 deciliters / gram, and more preferably 0.12 to 0.13 deciliters / gram. Intrinsic viscosity can be determined by an Ubbelohde viscometer in chloroform at 25°C. The intrinsic viscosity refers to the intrinsic viscosity of the phenylene ether oligomer prior to coupling with the hydrocarbon resin. As with molecular weight determination, those skilled in the art will recognize that intrinsic viscosity characterization of phenylene ether oligomers cannot be performed when linear block copolymers are prepared by a process involving oxidative polymerization of phenylene ether oligomers derived from a hydrocarbon resin.

[0021] In addition to the phenylene ether oligomer A block, the linear block copolymer comprises at least one block B comprising a hydrocarbon resin. The hydrocarbon resin comprises carbon and hydrogen atoms and excludes atoms other than carbon and hydrogen. The hydrocarbon resin can be saturated or unsaturated. In one embodiment, the hydrocarbon resin comprises unsaturation, for example in the form of carbon-carbon double bonds. The unsaturation can be present in the main chain (i.e., polymer backbone) of the hydrocarbon resin, as pendant groups along the hydrocarbon resin, or combinations thereof. In one embodiment, the hydrocarbon resin does not comprise aromatic groups or saturated or unsaturated cyclic hydrocarbons.

[0022] 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 hydrocarbon. In one embodiment, the repeating units of the hydrocarbon resin are derived from diene-containing hydrocarbons and combinations thereof. Representative examples of such hydrocarbons 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 one embodiment, the hydrocarbon resin comprises substituted or unsubstituted dienes, such as polybutadiene, polyisoprene, or combinations thereof. In one embodiment, the hydrocarbon resin can include poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, or a combination thereof.

[0023] 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 of an alkenyl aromatic hydrocarbon 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 one aspect, the hydrocarbon resin can include a block copolymer of styrene and butadiene (e.g., 1,2-butadiene, 1,4-butadiene, or a combination thereof).

[0024] In one embodiment, the linear block copolymer comprises at least one block A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol, and at least one block B comprising a linear hydrocarbon resin containing unsaturation, preferably poly(1,2-butadiene), poly(1,4-butadiene), or a combination thereof.

[0025] In one embodiment, the linear block copolymer can be a multiblock copolymer. For example, the linear block copolymer can include at least two blocks A, including phenylene ether oligomers, including repeat units derived from, for example, 2,6-dimethylphenol, and a block B, including a linear hydrocarbon resin including unsaturation, preferably poly(1,2-butadiene), poly(1,4-butadiene), or a combination thereof, and the linear block copolymer is an ABA triblock copolymer. In one embodiment, the linear block copolymer can include at least two B blocks, and preferably, the copolymer is a linear BAB triblock copolymer, and the A and B blocks can be as described above.

[0026] In one embodiment, at least one terminal position of the linear block copolymer can be occupied by an A block comprising a phenylene ether oligomer, and at least one end group of the linear block copolymer can 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 styrene end group, an activated ester end group, or an anhydride end group covalently bonded to the A block of the linear block copolymer. In one embodiment, at least one end group of the linear block copolymer can comprise a methacrylate group covalently attached to the A block.

[0027] In one embodiment, at least one terminal position of the linear block copolymer can be occupied by a B block comprising a hydrocarbon resin, and at least one end group of the linear block copolymer can comprise 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 styrene end group, an activated ester end group, or an anhydride end group covalently bonded to the B block of the linear block copolymer.

[0028] In one embodiment, the linear block copolymers can be prepared by a process that includes the steps of oxidatively polymerizing a substituted or unsubstituted monohydric phenol derived from a phenol-terminated hydrocarbon resin to provide a linear block copolymer, for example as shown in FIG.

[0029] The oxidative polymerization can be carried out in the presence of an organic solvent. Suitable organic solvents include alcohols, ketones, aliphatic and aromatic hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, mixed ether-esters, sulfoxides, etc., provided that they do not interfere with or participate in the oxidation reaction. High molecular weight poly(phenylene ether)s can significantly increase the viscosity of the reaction mixture. Therefore, it is sometimes desirable to use a solvent system that can precipitate them while leaving low molecular weight polymers in solution until they form high molecular weight polymers. Organic solvents can include, for example, toluene, benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, trichloroethylene, ethylene dichloride, dichloromethane, chloroform, or combinations thereof. Preferred solvents include aromatic hydrocarbons. In one embodiment, the organic solvent includes toluene, benzene, xylene, chloroform, chlorobenzene, or combinations thereof, preferably toluene.

[0030] The monohydric phenol can 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 phenol-terminated hydrocarbon resin can be present in the oxidative polymerization reaction mixture in an amount of 15 to 90 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 can 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 can be 1:1 to 50:1.

[0031] The oxidative polymerization is further carried out in the presence of a copper-amine catalyst. The copper source for the copper-amine catalyst can include salts of cupric or cuprous ions, including halides, oxides, and carbonates. Alternatively, the copper can be provided in the form of a preformed salt of an alkylenediamine ligand. Preferred copper salts include cuprous halides, cupric halides, and combinations thereof. Cuprous bromide, cupric bromide, and combinations thereof are particularly preferred.

[0032] 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 are represented by 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 bond between the two diamine nitrogen atoms, and R b and R c each independently represents isopropyl or a substituted or unsubstituted C 4-8 R is a tertiary alkyl group. aExamples of R include: ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, the various pentylene isomers having 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 c Examples of R 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 1:1 to 1:5, preferably 1:1 to 1:3, more preferably 1:1.5 to 1:2.

[0033] 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 (Bennett et al.) and are represented by the formula: R d -NH-R e In the formula, R d and R e each independently represents a substituted or unsubstituted C 1-12 Alkyl groups, preferably substituted or unsubstituted C 3-6It is an alkyl group. 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.

[0034] Preferred copper-amine catalysts containing secondary alkylenediamine ligands may further contain a tertiary monoamine. Suitable tertiary monoamine ligands are described in the above-mentioned U.S. Patents Hay, 4,028,341 and Bennett, 4,092,294, and include heterocyclic amines and certain trialkylamines, which are characterized by having an amine nitrogen bonded to at least two groups having a small cross-sectional area. In the case of trialkylamines, it is preferred that 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 an alkyl group. It is especially preferred that the third substituent has 4 or less 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.

[0035] 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.

[0036] The reaction carried out in the presence of copper-amine catalyst can optionally be carried out in the presence of bromide ions. It has already been mentioned that bromide ions can be provided as cuprous bromide or cupric bromide salts. Bromide ions can also be provided by adding 4-bromophenol, for example 2,6-dimethyl-4-bromophenol. Additional bromide ions can be provided in the form of hydrobromic acid, alkali metal bromides, or alkaline earth metal bromides. Sodium bromide and hydrobromic acid are highly preferred bromide sources. The preferred ratio of bromide ions to copper ions is 2 to 20, preferably 3 to 20, more preferably 4 to 7.

[0037] In one embodiment, each of the above components of the copper-amine catalyst are added simultaneously to the oxidative polymerization reactant.

[0038] The oxidative polymerization can optionally be carried out in the presence of one or more additional components, such as 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.

[0039] In one embodiment, a phase transfer agent is present. Suitable phase transfer agents include, for example, a quaternary ammonium compound, a quaternary phosphonium compound, a tertiary sulfonium compound, or a combination thereof. Preferably, the phase transfer agent is 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, and X is a halogen atom or C 1-8 Alkoxy or C 6-18 Exemplary phase transfer catalysts include (CH(CH))NX, (CH(CH)PX, (CH(CH))NX, (CH(CH))NX, (CH(CH))NX, (CH(CH))NX, CH(CH(CH))NX, and CH(CH(CH)NX), where X is Cl. - , Br - , C 1-8Alkoxy or C 6-18 aryloxy. An effective amount of the 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 one embodiment, the phase transfer agent is present and comprises N,N,N',N'-didecyldimethylammonium chloride.

[0040] The oxidative polymerization can 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 the start of the oxidative polymerization and the end of the oxidative polymerization - can vary, but is typically from 100 to 250 minutes, particularly from 145 to 210 minutes.

[0041] 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 reactor is stopped. Residual oxygen in the reactor headspace is removed by flushing with an oxygen-free gas, such as nitrogen.

[0042] After the polymerization reaction is terminated, the copper ions of the polymerization catalyst are separated from the reaction mixture. This is accomplished by combining a chelating agent with the terminated reaction mixture to form a chelate 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 stirring the chelate mixture, the mixture comprises an aqueous phase containing chelated copper ions and an organic phase containing dissolved poly(phenylene ether). The chelating mixture is capable of eliminating the dihydric phenols required by Cooper et al., U.S. Pat. No. 4,110,311, the aromatic amines required by Cooper et al., U.S. Pat. No. 4,116,939, and the weak reducing agents of Cooper et al., U.S. Pat. No. 4,110,311, including 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 combination of temperature and time is effective for copper sequestration while also minimizing molecular weight degradation of the poly(phenylene ether). The chelation process includes (and is completed by) separating the aqueous and organic phases of the chelation mixture. This separation process 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.

[0043] In one embodiment, the linear block copolymer can be produced by a method comprising polymerizing an ethylenically unsaturated monomer from a phenylene ether macroinitiator to provide a linear block copolymer. The phenylene ether macroinitiator comprises at least one chain end comprising a functional group capable of initiating polymerization of an unsaturated hydrocarbon. For example, the phenylene ether oligomer can comprise at least one chain end comprising a 2,2,6,6-tetramethylpiperidinyl group capable of polymerizing an unsaturated hydrocarbon monomer using nitroxide mediated polymerization (NMP). Other polymerization techniques are also contemplated by the present disclosure, such as free radical polymerization, atom transfer radical polymerization (ATRP), and the like. A suitable chain end functional group for the phenylene ether macroinitiator can be selected by one skilled in the art according to the polymerization technique used as guided by the present disclosure.

[0044] In one embodiment, linear block copolymers can be prepared by a process 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. For example, a hydrocarbon resin that contains at least one reactive group (e.g., a tosyl group) at at least one chain end of the hydrocarbon resin can be reacted with an alkali metal (e.g., sodium) salt of a hydroxyl-terminated phenylene ether oligomer under suitable conditions to provide the desired block copolymer. In one embodiment, the hydrocarbon resin can contain at least one terminal carbon-carbon double bond, the phenylene ether oligomer can contain a terminal group having ethylenic unsaturation, and a cross-metathesis reaction can be used to couple the hydrocarbon resin and the phenylene ether oligomer to form an AB-type linear block copolymer.

[0045] The linear block copolymer can be isolated, for example, by precipitation into a suitable non-solvent for the block copolymer, such as methanol.

[0046] The method for producing a linear block copolymer can further include reacting a block copolymer having at least one A block occupying a terminal position of the block copolymer (e.g., a hydroxyl-terminated phenylene ether oligomer) with a compound selected to provide a desired functional group, such as a methacrylate group, at the chain end of the block copolymer. Suitable compounds containing the desired functional group and a group reactive with the hydroxyl-terminated phenylene ether oligomer can be readily determined by those skilled in the art. The reaction can be carried out in a solvent. In one embodiment, the linear block copolymer can be obtained as a powder, which is then combined with a compound containing the desired functional group and a solvent. In one embodiment, the linear block copolymer can be obtained as a solution without removing the solvent from the polymerization or coupling reaction, and the linear block copolymer is not isolated before carrying out the reaction. Exemplary syntheses are further described in the examples below.

[0047] Various methods for the preparation of the linear block copolymers are further described in the Examples below.

[0048] Also provided are curable thermoset compositions comprising the linear block copolymer. For example, the linear block 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.

[0049] 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. In one 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 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.

[0050] There is considerable overlap between thermosetting resins, crosslinkers, and coupling agents. As used herein, the term "crosslinker" includes compounds that can be used as a thermosetting resin, a crosslinker, a coupling agent, or a combination thereof. For example, in some cases, a compound that is a thermosetting resin could also be used as a crosslinker, a coupling agent, or both.

[0051] The thermosetting resin is not particularly limited, and the thermosetting resin can 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 (having curable unsaturation (e.g., vinyl functional groups)), and the like, or combinations thereof.

[0052] The epoxy resin can generally be any epoxy resin suitable for use in thermosetting resins. The term "epoxy resin" in this context refers to a curable composition of oxirane ring-containing compounds, for example, as described in CA May, Epoxy Resins, 2nd Edition Supplement, (New York & Basle: Marcel Dekker Inc.), 1988. Examples of epoxy resins include bisphenol A type epoxy resins, such as those obtained from bisphenol A and those 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 those 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; glycidyl ether compounds derived from divalent, trivalent or higher phenols, such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols and hormones such as phenol and o-cresol; novolac type epoxy resins derived from novolac resins which are reaction products between aldehydes, e.g., bisphenol A novolac type epoxy resins and cresol novolac 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'-diaminodiphenyl-ethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene,Amine-type epoxy resins derived from 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, 2,4-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-trimethyl-indane, etc., heterocyclic epoxy compounds, and glycidyl ester-type epoxy compounds, for example, those derived from the glycidyl esters of aromatic carboxylic acids, such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid. "Epoxy resin" can also include the reaction product of a compound containing two or more epoxy groups with an aromatic dihydroxy compound, which can be optionally halogen-substituted, and can be used alone or in combination of two or more.

[0053] The cyanate ester is not limited, and any resin made of cyanate ester monomers that polymerize 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 blends of cyanate ester monomers), homopolymers, and copolymers made from cyanate ester precursors, and combinations of these compounds. 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 those prepared from 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, dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). The cyanate ester prepolymers can be homopolymers or can be copolymers incorporating other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical, 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 US7393904, US7388057, US7276563, and US7192651.

[0054] Bismaleimide resins can be formed 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)propane, 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'-diphenyl ether bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide Nos. 3,562,223, 4,211,860, and 4,211,861 or prepared by the method described, for example, in U.S. Pat. No. 3,018,290.

[0055] Benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared from the reaction of aldehydes, phenols, and primary amines with or without solvent. Phenolic compounds for forming benzoxazines include phenols and polyphenols. The use of polyphenols with two or more reactive hydroxyl groups in forming benzoxazines can result in branched products, crosslinked products, or a combination of branched and crosslinked products. The group that links the phenolic group in the phenol can be a branch point or a linking group in polybenzoxazines.

[0056] Exemplary phenols for use in preparing the benzoxazine monomers include: 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'-isopropylidene 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. .

[0057] 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 alkylamine. The amine can be a polyamine, for example, to prepare a multifunctional benzoxazine monomer for crosslinking.

[0058] The amines for forming the benzoxazines have 1 to 40 carbon atoms, provided they do not contain aromatic rings, and then they can have 6 to 40 carbon atoms. Di- or polyfunctional amines can be branching points for linking one polybenzoxazine to another.

[0059] In some embodiments, thermal polymerization at 150 to 300° C. can be used to polymerize the benzoxazine monomers. The polymerization can be carried out in bulk, from solution, or otherwise. A catalyst, such as a carboxylic acid, can be used to reduce the polymerization temperature or to accelerate the polymerization rate at the same temperature.

[0060] Vinylbenzyl ether resins can be prepared from the 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 thermosetting resins. Exemplary vinylbenzyl ethers include those produced from the reaction of vinylbenzyl halides with the following: 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-dimethyl Phenol) (tetramethylbisphenol 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-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, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbisphenol, etc. ,

[0061] Arylcyclobutenes include those derived from compounds having the following structure: [ka] where B is an organic or inorganic radical of valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidenedialkylsilanyl, arylalkylsilanyl, diarylsilanyl and C 6-20 phenolic compounds), each occurrence of X is independently hydroxy or C1-24 is hydrocarbyl (including straight chain and branched alkyl and cycloalkyl), and each occurrence of Z is independently hydrogen, halogen, or C 1-12 hydrocarbyl, and 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 US 4,743,399, US 4,540,763, US 4,642,329, US 4,661,193, US 4,724,260, and 391,650.

[0062] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, followed by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. Bis-, tris-, and other polyphenols can be used to produce bis-, tris-, and poly(perfluorovinyl ethers) by this route. Phenols useful in their synthesis include: 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'-diphenyl-2,2 ... '-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 (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'-(hexafluoroisoproylidene)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 (spirobiindan), 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. ,

[0063] The crosslinking agent also includes auxiliary crosslinking agents, and is not particularly limited. The crosslinking agent can be used alone or in combination of 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) (having unsaturated bonds based on butadiene), natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber (having unsaturated bonds based on isoprene), ethylene-α-olefin copolymer elastomers (having unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD)) (e.g., ethylene-α-olefin copolymers obtained by copolymerizing ethylene, α-olefins, and dienes, such as ethylene-propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM)). Examples also include hydrogenated nitrile rubber, fluorocarbon rubber, such as 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 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 linkages prepared by anionic living polymerization.It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc., by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbon polymers, and polynorbornene (sold, for example, by Elf Atochem).

[0064] Polybutadiene resins containing high levels of 1,2 addition are desirable for thermosetting matrices. Examples include functionalized polybutadiene and poly(butadiene-styrene) random copolymers (sold under the trade names RICON, RICACRYL, and RICOBOND resins by Ricon Resins, Inc.). These include butadienes containing low vinyl contents such as RICON 130, 131, 134, 142, polybutadienes containing high vinyl contents such as RICON 150, 152, 153, 154, 156, 157, and P30D, random copolymers of styrene and butadiene such as 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. Also included are polybutadienes that can be used to improve adhesion, such as 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. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Powder dispersions of functional polybutadiene derivatives are also included, such as RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 01731 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 hydroxylated functional groups.

[0065] 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, for example (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, such as trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyls, such as 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, such as pentaerythritol tetra(meth)acrylate, etc.; penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, etc.; hexa(meth)acrylates, such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc.; 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, etc.; polythiol compounds, for example, trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc.; silanes, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloximine)silane, vinyltris-(acetoxime)silane, methyltris(methylethyloximine)silane, methyltris(acetoxime)silane, etc. Silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-t-butoxy-diacetoxysilane, methyltris(ethyllactate)silane, vinyltris(ethyllactate)silane, etc., carbodiimides such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, etc., or combinations thereof. The curable thermosetting composition can optionally include a crosslinking catalyst, such as a carboxylate.

[0066] When the curable thermosetting composition includes a crosslinking agent, the crosslinking agent can 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 thermosetting composition.

[0067] Curable thermosetting compositions can include one or more curing agents. As used herein, the term "curing agent" includes compounds variously described as curing agents, hardeners, etc., or both.

[0068] Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenolic hardeners include the following: 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.

[0069] When the curable thermosetting 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 thermosetting composition.

[0070] 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.

[0071] Exemplary cure accelerators include heterocyclic accelerators, such as substituted or unsubstituted C 3-6Heterocycles include those in which 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, etc., imidazoles such as 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-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 Midazole, 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, 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 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline, and the like, N,N-dimethylaminopyridine, sulfamidate, or combinations thereof.

[0072] 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, diphenylmethane, diaminodi ... Amidodiphenylsulfonic 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)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,2- and 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 tertiary amine cure accelerators, such as 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.

[0073] The cure accelerator can be a latent cationic cure catalyst, such as 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 - wherein R 10 and R 11 are each independently optional, C 1-20 Alkyl, C 1-20 C substituted with one to four monovalent radicals selected from alkoxy, nitro, and chloro 6-14 is a monovalent aromatic hydrocarbon radical, and X - is an anion. Additional cure accelerators include those having the structure [(R 10 )(R 11 )I] + SbF6 - wherein R 10 and R 11 each independently represents, optionally, 1 to 4 C 1-20 Alkyl, C 1-20 Alkoxy, nitro, or chloro substituted C 6-14 It is a monovalent aromatic hydrocarbon, for example, 4-octyloxyphenylphenyliodonium hexafluoroantimonate.

[0074] The cure accelerator can be a metal salt complex, for example, a copper(II), aluminum(III), zinc, cobalt, tin salt of an aliphatic or aromatic carboxylic acid selected from copper(II), tin(II), and aluminum(III) salts of acetate, stearate, gluconate, citrate, benzoate, and mixtures thereof. For example, the cure accelerator can 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.

[0075] When the curable thermosetting composition includes a curing catalyst, the curing catalyst can 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 thermosetting composition.

[0076] The curable thermosetting composition can optionally include a cure initiator, such as a peroxide compound. Exemplary peroxide cure initiators include: 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, ... -butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di(t-butylperoxy)isophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, and the like, or combinations thereof.

[0077] When the curable thermosetting composition includes a curing initiator, the curing initiator can 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 thermosetting composition.

[0078] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred for regulatory reasons in certain applications, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0079] Examples of phosphorus-based 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-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p -tolyl bis(2,5,5'-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl-diphenyl phosphate, cresyl-diphenyl phosphate, 1,3-phenylene bis(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, as well as cyclic phosphate compounds, bis(diphenyl)phosphate of hydroquinone, bis(diphenyl)phosphate of bisphenol A, and the like, or their oligomeric or polymeric counterparts, or combinations thereof.

[0080] 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 the following: 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 chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0081] Halogenated materials can also be used as flame retardants, for example bisphenols such as 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-chloro-4-methylphenyl)-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. 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 and carbonate precursors of bisphenol A and tetrabromobisphenol A, such as phosgene. Metal synergists such as antimony oxide can also be used with the flame retardants.

[0082] Inorganic flame retardants can also be used, e.g. 1-16Alkyl sulfonates such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate salts, salts of Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoro-anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6.

[0083] When the curable thermosetting composition includes a flame retardant, the flame retardant can be included in an amount greater than 1 wt%, or from 1 to 20 wt%, or from 5 to 20 wt%, based on the total weight of the curable thermosetting composition.

[0084] The curable thermosetting composition can further include inorganic or organic fillers, such as particulate fillers, fibrous fillers, and the like, or combinations thereof. Any inorganic and organic fillers, including those known in the art, can be used without limitation.

[0085] 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 quartz, 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, crushed, or cloth), glass mat, glass spheres, hollow glass microspheres, aramid fibers, quartz, and the like, 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, and the like. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolites, and hydrotalcites. In one aspect, the fillers can be treated with the coupling agents disclosed herein.

[0086] 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, for example, 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 or continuous glass fibers can be used. Suitable glass fibers are commercially available from sources such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0087] 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.

[0088] The filler can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al2O3, BN, AlN, or a combination thereof can be used for electronics modules with high thermal conductivity. For example, MgO can be used for increased thermal conductivity and increased CTE. For example, SiO2 (e.g., amorphous SiO2) can be used for lightweight modules with low CTE and small dielectric constant.

[0089] When the curable thermosetting 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 thermosetting composition.

[0090] Coupling agents, also called adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, etc. Exemplary olefin-maleic anhydride copolymers include: maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof. Exemplary silanes include: epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0091] Examples of aminosilane coupling agents are γ-aminopropyltrimethoxy-silane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)γ-aminopropyltriethoxysilane. Exemplary epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0092] 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-triethoxysilylpropyl Silane coupling agents include, for example, silane-N,N-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-mercaptopropyl dimethoxymethyl silane, 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.

[0093] When the curable thermosetting composition includes a coupling agent, the coupling agent can 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 thermosetting composition.

[0094] The curable thermosetting composition can optionally include a solvent. The solvent can be, for example, C 3-8 Ketone, C 3-8 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 The specific ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof. 4-8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Particular dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Particular aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvent can be non-halogenated. Particular 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. 2-6Examples of the alkyl cyanide include acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent may 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, cyclohexanone, diglyme, trimethylsilyl ether, methyl ethyl ketone ... The solvent may be glyme, 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, an ionic liquid, or a combination thereof.

[0095] If a solvent is used, the curable thermosetting composition can include 2 to 99 wt% of the solvent based on the total weight of the curable thermosetting composition. For example, the amount of solvent can be 5 to 80 wt%, or 10 to 60 wt%, or 20 to 50 wt%, based on the total weight of the curable thermosetting composition. The solvent can be selected in part to adjust the viscosity of the curable thermosetting composition. Thus, the amount of solvent can depend on variables such as the type and amount of the linear block copolymer, the type and amount of other ingredients such as curing additives, the type and amount of any auxiliary thermosetting resin(s), and the processing temperature used for any subsequent processing of the curable thermosetting composition, such as impregnation of a reinforcing structure with the curable thermosetting composition for preparation of a composite. The solvent can be anhydrous. For example, the solvent can include 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.

[0096] The curable thermosetting composition can further include a curable unsaturated monomer composition, such as a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or 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 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.

[0097] The curable thermosetting composition can optionally further comprise one or more additional additives, such as, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow modifiers, anti-drip agents, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage agents, stress relief additives, and the like, or combinations thereof. If present, the additional additives can be included in any effective amount, such as, for example, from 0.01 to 20 wt%, or from 0.01 to 10 wt%, or from 0.01 to 5 wt%, or from 0.01 to 1 wt%, based on the total weight of the curable thermosetting composition.

[0098] The curable thermosetting composition can be prepared by combining the linear block copolymer and other optional ingredients disclosed herein using any suitable method.

[0099] 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 can be cured. The curable composition can be cured, for example, thermally or by using irradiation techniques, such as UV or electron beam irradiation. For example, the cured product can be obtained by heating the curable thermosetting composition as defined herein for a time and temperature sufficient to evaporate the solvent and effect curing. If thermal curing is used, the temperature can be 30 to 400°C, or 50 to 250°C, or 100 to 250°C. Heating can be between 1 minute and 24 hours, or 1 minute and 6 hours, or 3 hours and 5 hours. Curing can be done in stages, producing a partially cured, often tack-free resin, which is then fully cured by heating for a longer period or temperature within the ranges. As used herein, the term "cured" encompasses partially cured or fully cured products.

[0100] The cured thermoset composition can have one or more desirable properties. For example, the thermoset composition can have a glass transition temperature of 165° C. or more, preferably 170° C. or more, more preferably 165 to 180° C. The thermoset composition can also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df), and reduced moisture absorption. For example, the thermoset composition can 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 thermoset composition can have a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz. Thus, the thermoset composition comprising the linear block copolymer of the present disclosure can be particularly well suited for use in electronics applications.

[0101] The curable thermosetting composition and the cured thermosetting composition can be used in a variety of applications and uses, for example, in any application where conventional thermosetting compositions are used. For example, useful articles comprising the curable thermosetting composition or the cured thermosetting composition can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded parts, prepregs, casings, laminates, metal clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary applications and uses 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 reinforcement. When used as coatings, the disclosed compounds and compositions can be deposited on the surface of various underlying substrates. For example, the compositions can be deposited on the surface of metal, plastic, glass, fiber sizing, ceramic, stone, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surface of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface coating industries. The curable thermosetting compositions and cured thermosetting compositions derived therefrom may also be particularly well suited for use in forming electrical and computer components.

[0102] The method of forming a composite can include impregnating a reinforcing structure with a curable thermosetting composition, partially curing the curable thermosetting composition to form a prepreg, and laminating a plurality of prepregs. The reinforcing structure can be a porous base material, such as a fiber preform or substrate, or other porous material including ceramic, polymer, glass, carbon, or combinations thereof. For example, the porous base material can be a woven or non-woven glass cloth, glass fiber cloth, or carbon fiber. When the article includes a fiber preform, the method of making the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fiber preform can optionally be molded before or after removing the solvent. In some aspects, the curable thermosetting composition layer can further include a woven or non-woven glass cloth. For example, the curable layer can be prepared by impregnating a glass cloth with the curable composition and removing the solvent from the impregnated glass cloth. 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 is selected according to the intended use of the composite, using criteria well known to those skilled in the art of making fiber reinforced resin composites. The reinforcing structure can include a variety of finishes suitable for the thermosetting component of the curable thermosetting composition.

[0103] A method of making an article from a curable thermosetting composition can 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 substantially fully cured composition. 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 can be before or after removal of the solvent from the curable composition. Additionally, the article can be further shaped, for example by thermoforming, before or after removal of the solvent, before curing, after partial curing, or after full curing. In one embodiment, an article is formed, the solvent is removed, the article is partially cured (B-staged), optionally shaped, and then further cured.

[0104] Commercial-scale methods of 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 treaters. 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 gradually spreads the reinforcing structure. The reinforcing structure then travels through a resin impregnation tank containing a 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 is evaporated. The resin begins to polymerize at this point. When the composite emerges from the tower, it is fully cured, so that the web is not wet or sticky. However, the curing process is stopped short of completion, so that additional curing can occur as the laminate is produced. The web then winds the prepreg onto a receiver roll.

[0105] Electrical and electronic articles comprising or derived from the curable thermosetting composition are also provided. Articles include those comprising printed circuits used in the medical or aerospace industries. Still 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 organizers, and similar devices, or office automation equipment. For example, electrical components can be placed on printed circuit boards, including laminates. Other exemplary articles prepared from the curable composition for various applications include copper clad laminates (CCLs), such as metal core copper clad laminates (MCCCLs), composite articles, and coated articles, such as multi-layer articles.

[0106] 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.

[0107] 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, wrought 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.

[0108] The heat dissipating metal matrix layer can be a thermally conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, etc., or a combination thereof. Thermally conductive, electrically conductive metals 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.

[0109] The conductive metal layer and the supporting metal matrix layer can be pretreated to have a high surface roughness to enhance 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 adhered to the conductive metal layer or heat dissipating layer without the use of adhesives, or adhesives can be used to improve adhesion of the dielectric layer to the conductive metal layer or heat dissipating layer. Exemplary adhesives used to adhere the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxies, etc., or combinations thereof.

[0110] Copper clad laminates can be produced by thermal lamination under pressure of one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer without the use of a thermosetting adhesive. The dielectric layer can be prepared from a curable thermosetting composition and can be prepared by a solution casting process to form the layers before the thermal lamination step. For example, the dielectric layer, the conductive metal layer, and the heat dissipating layer can be thermally laminated together under pressure by an adhesive-free process 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, for example, by a roll-to-roll process. The conductive metal layer in the copper clad laminate can be further patterned to provide a printed circuit board. Furthermore, the copper clad laminate can be shaped to provide a circuit board having the shape of a sheet, tube, or rod.

[0111] Alternatively, laminates for circuit assemblies can be produced by a solution casting process, where 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.

[0112] Multi-layer laminates containing additional layers can also be produced in one step by thermal lamination or in two or more successive steps by processes such as hot pressing or roll calendering. For example, up to seven layers, or up to 16 layers can be present in a laminate. In one embodiment, a laminate can be formed in one step or in two or more successive steps with a fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil sequence or a subcombination 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 in 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.

[0113] 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, where the total thickness refers to the assembly including each of the layers, 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 particular limit to the thickness of the dielectric layer, and it 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.

[0114] The curable thermosetting composition can be used, for example, as a coating in the preparation of multi-layer articles. A method of making a coating can include combining the curable thermosetting composition and, optionally, a fluoropolymer to form a coating on a substrate. For example, a multilayer article can be made by forming a layer comprising a curable thermosetting composition, removing solvent from the layer, and optionally curing to provide 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 provide a multilayer article, and optionally heat treating the multilayer article to cure the curable thermosetting composition. In some embodiments, the second layer can further comprise a curable thermosetting composition.

[0115] Additional applications for the curable thermosetting compositions include, for example, acid bath vessels, neutralization tanks, aircraft components, bridge girders, bridge decks, electrolytic cells, exhaust stacks, scrubbers, sporting goods, stairs, walkways, automotive exterior panels, such as hoods and trunk lids, floor pans, air scoops, pipes and ducts, such as heater ducts, industrial fans, fan housings, and blowers, industrial mixers, boat hulls and decks, marine terminal fenders, tiles and coatings, siding, business machine housings, trays, such as cable trays, concrete modifiers, dishwasher and refrigerator parts, electrical sealants, electrical panels, tanks, such as electrolytic refining tanks, water softener tanks, fuel tanks, and various filament wound tanks and and tank linings, furniture, garage doors, gratings, protective clothing, luggage, outdoor motor vehicles, pressure tanks, optical waveguides, radomes, handrails, railway components such as tank cars, hopper car covers, car doors, truck bed liners, satellite television antennas, signs, solar energy panels, telephone switchgear housings, tractor components, transformer covers, truck components such as fenders, bonnets, bodies, cabs, and beds, insulation for rotating machinery such as ground insulation, turn insulation, and phase isolation insulation, commutators, core insulation and cord and racing tape, drive shaft couplings, propeller blades, missile structural components, rocket motor cases, wings, sucker rods, fuselage sections, wing skins and flares, engine nucleinarcelle), cargo hatches, tennis racquets, golf club shafts, fishing rods, skis and ski poles, bicycle parts, transverse leaf springs, pumps such as automotive smog pumps, electrical components, fittings, and tools such as electrical cable joints, windings and high density packing multi-element assemblies, sealing of electromechanical devices, battery cases, resistors, fuses and thermal cut-off devices, coatings for printed wiring boards, castings such as capacitors, transformers, crankcase heaters, small molded electronic components such as coils, capacitors, resistors, and semiconductors, as a replacement for steel in chemical processing, pulp and paper, power generation, and wastewater treatment, scrub towers, pultruded parts for structural applications such as structural members, grates, and guard rails, swimming pools, swimming pool slides, hot tubs, and and saunas, drive shafts for under the hood applications, dry toner resins for copiers, marine tools and composites, heat shields, submarine hulls, prototyping, laboratory model development, laminate trim, drilling fixtures, bonding fixtures, inspection fixtures, industrial metal forming dies, aircraft stretch block and hammer dies, vacuum forming dies, flooring, e.g., for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, chillers, and outside loading docks, conductive compositions for static protection, decorative flooring, expansion joints for bridges, injection mortars for patching and repairing cracks in structural concrete, grout for tiles, machine rails, metal dowels, bolts and posts, repair of oil and fuel storage tanks, and many other uses.

[0116] Useful processes for preparing articles and materials include those generally known in the art for the processing of thermosetting resins. Such processes are described in the literature, for example, in 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 in "Polyesters and Their Applications", 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, such as reaction injection molding (RIM), atmospheric pressure molding (APM), casting, such as centrifugal and static casting open mold casting, lamination, such as wet or dry lay-up and spray lay-up, also including contact molding, such as cylindrical contact molding, compression molding, such as vacuum assisted resin transfer molding and chemically assisted resin transfer molding, matched tool molding, autoclave curing, heat curing in air, vacuum bagging, pultrusion, Seaman Composite Resin Infusion Manufacturing Processing (SCRIMP), continuous combination open molding of resin and glass, and filament winding, such as cylindrical filament winding. For example, the article can be prepared by a resin transfer molding process.

[0117] Also provided are articles derived from the curable thermosetting compositions, the articles being composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded parts, prepregs, casings, castings, laminates, or combinations thereof, or the articles being metal clad laminates, electronic composites, structural composites, or combinations thereof. The articles can be manufactured, for example, by casting, molding, extrusion, or the like, as disclosed herein, and by removing the solvent from the formed article. In one embodiment, the article can be a layer and can be formed by casting the curable composition onto a substrate and forming a cast layer. The solvent can be removed by any number of means, for example, by heating the cast layer, heating the cast layer under heat and pressure, for example, by laminating the cast layer to another substrate. In one embodiment, the articles prepared by the above methods can include adhesives, packaging materials, capacitor films, or circuit board layers. In one embodiment, the articles prepared from the curable compositions can be a dielectric layer, or a coating disposed on a substrate, for example, 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

[0118] This disclosure is further illustrated by the following non-limiting examples.

[0119] Prophetic Example 1: Preparation of Phenylene Ether-Polybutadiene-Phenylene Ether (ABA) Triblock Copolymers Phenylene ether-polybutadiene-phenylene ether (ABA) triblock copolymers are prepared according to FIG.

[0120] Hydroxyl-functionalized polybutadiene resin (Krasol 2000, Cray Valley) is dissolved in toluene in a four-neck round-bottom flask equipped with an overhead stirrer, thermocouple, and condenser. Aqueous sodium hydroxide (50%) is added to the solution and water is removed by azeotropic distillation at 120-166°C. The temperature is reduced to 25°C and 4-(2-bromoethyl)phenol is added to the reaction mixture. The temperature is increased to 100°C and maintained for 4 hours. The solution is neutralized with aqueous HCl (3.5%), followed by a deionized water wash. The toluene phase is separated and evaporated to isolate the phenol-terminated polybutadiene.

[0121] Phenol-terminated polybutadiene is polymerized with 2,6-dimethylphenol by oxidative coupling polymerization. Phenol-terminated polybutadiene and 2,6-dimethylphenol are dissolved in toluene in a 500 ml glass reactor. To this solution is added dimethylbutylamine, dibutylamine, ditert-butylethylamine, Maquat™ and a mixture of Cu2O and HBr(aq). Oxygen is bubbled through the reaction for 2 hours at a temperature of 25-40°C. The oxygen flow is stopped and 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-PBD-PPE block copolymer is isolated by precipitation into methanol. The product is dried under vacuum and nitrogen.

[0122] Prophetic Example 2: Preparation of Methacrylate-Capped PPE-PBD-PPE Triblock Copolymers Methacrylate-capped PPE-PBD-PPE triblock copolymers are prepared according to FIG.

[0123] The PPE-PBD-PPE block copolymer is dissolved in toluene. The temperature is increased to 120° C. and azeotropic distillation is performed. The temperature is reduced to 75° C. and dimethylaminopyridine (DMAP) is added to the reaction mixture. Once the DMAP has dissolved, methacrylic anhydride is slowly added (e.g., over 20 minutes) to the reaction mixture. After addition, the temperature is increased to 110° C. for gentle reflux. The methacrylate-capped PPE-PBD-PPE triblock copolymer is isolated by precipitation into methanol.

[0124] Prophetic Example 3: Preparation of Polyisoprene-Phenylene Ether-Polyisoprene (BAB) Triblock Copolymer Polyisoprene-phenylene ether-polyisoprene (BAB) triblock copolymers are prepared according to FIG.

[0125] A bifunctional low molecular weight poly(phenylene ether) is dissolved in toluene. To this solution is added aqueous NaOH (50%) and Adogen326 as a phase transfer catalyst. 1-(1-(4-(chloromethyl)phenyl)ethoxy)-2,2,6,6-tetramethylpiperidine is slowly added and the temperature is increased to 75°C. After completion of the reaction, the reaction mixture is neutralized with aqueous HCl (3.5%) and subsequently washed with deionized water. The toluene phase is separated and the PPE macroinitiator is isolated by precipitation into methanol. Alternatively, the PPE macroinitiator is synthesized using diethyl(1-(tert-butyl(1-(4-(chloromethyl)phenyl)ethoxy)amino)-2,2-dimethylpropyl)phosphonate and N-(tert-butyl)-O-(1-(4-(chloromethyl)phenyl)ethyl)-N-(2-methyl-1-phenylpropyl)hydroxylamine.

[0126] Nitroxide-mediated polymerization of isoprene from PPE macroinitiator is carried out in bulk to give PI-PPE-PI triblock copolymer. The PPE macroinitiator and isoprene prepared above are added to a Schlenk flask. The mixture is degassed by multiple freeze-thaw cycles and subsequently stirred at 120°C until the reaction mixture reaches the target conversion. The resulting solution is cooled and then diluted with chloroform and precipitated into methanol to isolate the triblock copolymer.

[0127] Prophetic Example 4: Preparation of Butyl Rubber-Phenylene Ether (AB) Copolymer The preparation of butyl rubber-phenylene ether (AB) copolymers using a cross-metathesis reaction is shown in FIG.

[0128] Synthesis of phenol-functionalized butyl rubber (I) by cross metathesis reaction: To a solution of butyl rubber in chloroform, eugenol and Grubbs' catalyst are added at room temperature. The reaction mixture is refluxed for 3 hours and the product is obtained by precipitation into methanol.

[0129] Synthesis of butyl rubber-phenylene ether (AB) block copolymer (II): Eugenol grafted butyl rubber is polymerized with 2,6-dimethylphenol by oxidative coupling polymerization. Eugenol grafted butyl rubber and 2,6-dimethylphenol are dissolved in toluene in a 500 ml glass reactor. To this solution is added a mixture of dimethylbutylamine, dibutylamine, ditert-butylethylamine, Maquat™ and Cu2O and HBr(aq). Oxygen is bubbled through the reaction for 2 hours at a temperature between 25-40°C. After the oxygen flow is stopped, 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-block-butyl rubber copolymer is isolated by precipitation into methanol. The product is dried under vacuum and nitrogen.

[0130] Synthesis of Methacrylate Capped Butyl Rubber-Phenylene Ether (AB) Copolymer (III): Dissolve PPE-block-Butyl Rubber Copolymer in toluene. Increase temperature to 120°C and perform azeotropic distillation. Reduce temperature to 75°C and add dimethylaminopyridine to the reaction solution. Once DMAP is dissolved, add methacrylic anhydride slowly into the reaction mixture (20 min). After addition, increase temperature to 110°C for gentle reflux. Isolate material by precipitation into methanol.

[0131] Prophetic Example 5: Preparation of Butyl Rubber-Polyphenylene Ether Copolymer The preparation of butyl rubber-polyphenylene ether (AB) copolymers using a cross-metathesis approach is shown in FIG.

[0132] Synthesis of allyl-capped polyphenylene ether (I): A 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. Allyl bromide is added dropwise at room temperature. Stirring is maintained at room temperature for 8 hours. The solution is transferred to an extraction funnel and neutralized with 0.1N HCl aqueous solution, followed by DI water washes. The organic phase is separated and the product is isolated by precipitation into methanol. The particles are dried under vacuum and nitrogen at room temperature. Alternatively, acrylate, allyl or styrene capped polyphenylene ethers can be synthesized and used as (I). Synthesis of polyphenylene ether butyl rubber (AB) block copolymers (II) by cross metathesis reaction: To a solution of butyl rubber in chloroform, allyl- or eugenol-capped PPE and Grubbs catalyst are added at room temperature. The reaction mixture is refluxed for 3 hours and the product is obtained by precipitation into methanol.

[0133] The disclosure further includes the following aspects.

[0134] Aspect 1: A linear block copolymer comprising at least one block A comprising a phenylene ether oligomer comprising repeat units derived from a substituted or unsubstituted monohydric phenol, and at least one block B comprising a hydrocarbon resin, the block A having an intrinsic viscosity of 0.15 deciliters / gram or less as determined by an Ubbelohde viscometer at 25° C. in chloroform.

[0135] Embodiment 2: The linear block copolymer of embodiment 1, wherein the copolymer is a linear AB diblock copolymer.

[0136] Embodiment 3: The linear block copolymer of embodiment 1, wherein the copolymer is a linear multiblock copolymer comprising at least two A blocks, preferably the copolymer is a linear ABA triblock copolymer, or at least two B blocks, preferably the copolymer is a linear BAB triblock copolymer.

[0137] Embodiment 4: The linear block copolymer of any of embodiments 1-3, wherein the phenylene ether oligomer has a molecular weight of less than 10,000, more preferably from 600 to 4,500 grams / mole, as determined by nuclear magnetic resonance spectroscopy.

[0138] Embodiment 5: The linear block copolymer of any of embodiments 1-4, wherein the substituted or unsubstituted monohydric phenol 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 linear block copolymers comprising 1-(cycloalkyl)-6-(alkyl)-phenols, 1-(cycloalkyl)-6-(alkyl)-phenols, or combinations thereof.

[0139] Embodiment 6: The linear block copolymer of any of embodiments 1-5, wherein the hydrocarbon resin comprises unsaturation, preferably the hydrocarbon resin is polybutadiene, polyisoprene, alkenyl aromatic, and unsaturated C 4-12 A linear block copolymer comprising a hydrocarbon copolymer or combination thereof, more preferably poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, poly(styrene-co-butadiene), poly(styrene-co-isoprene), or combination thereof, and even more preferably poly(1,2-butadiene), poly(1,4-butadiene), polyisoprene, or combination thereof.

[0140] Embodiment 7: The linear block copolymer of any of embodiments 1-6, comprising at least one block A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol, and at least one block B comprising a linear hydrocarbon resin comprising unsaturation.

[0141] Embodiment 8: The linear block copolymer of embodiment 1, comprising at least two blocks A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol, and a block B comprising a linear hydrocarbon resin comprising unsaturation, wherein the linear block copolymer is an ABA triblock copolymer.

[0142] Embodiment 9: The linear block copolymer of embodiment 1, comprising a block A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol and at least two blocks B comprising a linear hydrocarbon resin comprising unsaturation, wherein the linear block copolymer is a BAB triblock copolymer.

[0143] Embodiment 10: The linear block copolymer of claim 1, wherein at least one end group of the linear block copolymer comprises 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 styrene end group, an activated ester end group, or an anhydride end group.

[0144] Embodiment 11: A method of making the linear block copolymer of any of Embodiments 1-10, the method comprising: oxidatively polymerizing a substituted or unsubstituted monohydric phenol derived from a phenol-terminated hydrocarbon resin to provide a linear block copolymer; or polymerizing an ethylenically unsaturated monomer derived from a phenylene ether macroinitiator to provide a linear block 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.

[0145] Example 12: A curable thermosetting composition comprising the linear block copolymer of any of Examples 1-10, and optionally further comprising one or more of a crosslinker, a curing agent, a curing catalyst, a curing initiator, or combinations thereof, a flame retardant, a filler, a coupling agent, or combinations thereof, or combinations thereof.

[0146]

[0036] Example 13: A cured thermoset composition comprising the cured product of the curable thermoset composition of Example 12.

[0147] Example 14: An article comprising the cured thermoset composition of example 13, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded part, a prepreg, a casing, a casting, a laminate, or a combination thereof, or the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0148] Example 15: An article made from a varnish composition comprising the curable thermosetting composition of Example 12 and a solvent, preferably the article is a fiber, a layer, a coating, a casting, a prepreg, a composite, or a laminate, or the article is a metal clad laminate.

[0149] The compositions, methods, and articles may optionally comprise, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The compositions, methods, and articles may additionally, or alternatively, be formulated to be devoid of, or substantially free of, any materials (or species), steps, or components that are not otherwise required for the function or achievement of the purpose of the compositions, methods, and articles.

[0150] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "Combinations" include blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like do not denote an order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a," "an," and "the" do not denote a limitation of quantity, and should be construed to encompass both the singular and the plural, unless otherwise stated herein or clearly contradicted by context. "Or" means "and / or," unless expressly stated otherwise. Throughout the specification, reference to "an embodiment" means 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" includes one or more of the elements recited herein and is not limited, acknowledging the presence of one or more similar elements not named. In addition, it should be understood that the elements described can be combined in any suitable manner in the various embodiments.

[0151] Unless specified to the contrary herein, 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.

[0152] Unless otherwise specified, 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 patents, patent applications, and other references cited 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 in this application shall take precedence over the conflicting term in the incorporated reference.

[0153] Compounds are described using standard nomenclature. For example, any position that is not substituted by any indicated group is understood to have its valence filled by the indicated bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment for a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0154] As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, subscript, 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 substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to branched or straight-chain, saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH2). "Alkoxy" means an alkyl group linked through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group, such as methylene (-CH2-) or propylene (-(CH2)3-). "Cycloalkylene" means a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization(s). "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, all ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "Arylalkylene" means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. A combination of different halo atoms (e.g., bromo and fluoro) or only chloro atoms can 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), where the heteroatom(s) are each independently N, O, S, Si, or P. "Substituted" means that the compound or group contains, each 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 3-12 It means substituted with at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl, provided that the standard valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0155] While particular embodiments have been described, presently unanticipated or unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or those skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, shall cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. at least one block A having an intrinsic viscosity of 0.15 deciliters per gram or less as determined by an Ubbelohde viscometer in chloroform at 25°C and comprising a phenylene ether oligomer comprising repeat units derived from a substituted or unsubstituted monohydric phenol; at least one block B comprising a hydrocarbon resin; A linear block copolymer comprising:

2. The linear block copolymer of claim 1, wherein the copolymer is a linear AB diblock copolymer.

3. The copolymer is At least two A blocks, or At least two B blocks, 2. The linear block copolymer of claim 1, which is a linear multi-block copolymer comprising:

4. 10. The linear block copolymer of claim 1, wherein the phenylene ether oligomer has a number average molecular weight of less than 10,000 grams per mole as determined by nuclear magnetic resonance spectroscopy.

5. The substituted or unsubstituted monohydric phenol is a 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 10. The linear block copolymer of claim 1, comprising a 6-(cycloalkyl)-6-(alkyl)phenol, a 6-(cycloalkyl)-6-(alkyl)phenol, or a combination thereof.

6. The linear block copolymer of claim 1 , wherein the hydrocarbon resin comprises unsaturation.

7. at least one block A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol; at least one block B comprising a linear hydrocarbon resin containing unsaturation; 2. The linear block copolymer of claim 1, comprising:

8. at least two blocks A comprising a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol; Block B comprising a linear hydrocarbon resin containing unsaturation; Including, The linear block copolymer of claim 1, wherein the linear block copolymer is an ABA triblock copolymer.

9. Block A comprises a phenylene ether oligomer comprising repeat units derived from 2,6-dimethylphenol; at least two blocks B comprising a linear hydrocarbon resin containing unsaturation; 2. The linear block copolymer of claim 1, comprising:

10. 2. The linear block copolymer of claim 1, wherein at least one end group of the linear block copolymer comprises 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 styrene end group, an activated ester end group, or an anhydride end group.

11. A method for producing the linear block copolymer of any one of claims 1 to 10, comprising the steps of: oxidatively polymerizing a substituted or unsubstituted monohydric phenol derived from a phenol-terminated hydrocarbon resin to provide said linear block copolymer; or polymerizing ethylenically unsaturated monomers derived from a phenylene ether macroinitiator to provide said linear block copolymer; or covalently coupling a hydrocarbon resin and a phenylene ether oligomer, wherein said hydrocarbon resin and said phenylene ether oligomer contain complementary reactive groups; A method comprising:

12. A curable thermosetting composition comprising the linear block copolymer of any one of claims 1 to 10, optionally comprising: a crosslinker, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; or one or more of a flame retardant, a filler, a coupling agent, or a combination thereof; 1. A curable thermosetting composition, further comprising:

13. A cured thermoset composition comprising the cured product of the curable thermoset composition of claim 12.

14. 14. An article comprising the cured thermoset composition of claim 13, the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded part, a prepreg, a casing, a casting, a laminate, or a combination thereof; or The article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

15. 13. An article made from a varnish composition comprising the curable thermosetting composition of claim 12 and a solvent.

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