Bifunctional sizing agent for improved adhesion to substrates

Abstract

A composition comprising a sizing agent comprising a difunctional poly(arylene ether) comprising a silyl-containing group comprising a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally comprising a terminal functional group which is neither a silyl-containing end group nor hydrogen.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This PCT application claims priority to European Patent Application No. 21170719.5, filed April 27, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to sizing agents, particularly bifunctional sizing agents, compositions containing the sizing agents, methods of manufacture, and uses thereof. [Background technology]

[0003] Thermosetting resins are materials that cure to form very hard plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosetting resins are used in protective coatings, adhesives, electronic laminates (such as those used in making computer circuit boards), flooring and paving applications, glass fiber reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components). Poly(arylene ethers) generally have good dielectric properties. Due to their wide use in electronic applications, particularly laminates for printed circuit boards, it is desirable to provide compositions containing poly(arylene ethers) with improved adhesion to substrates, such as copper foil substrates in multilayer laminates. Summary of the Invention [Problem to be solved by the invention]

[0004] Thus, there is a need in the art for poly(arylene ether) compositions that have improved adhesion to substrates, such as copper foil substrates in multi-layer laminates. [Means for solving the problem]

[0005] The above and other deficiencies in the art are addressed by a composition comprising a sizing agent that includes a difunctional poly(arylene ether) that includes a silyl-containing group, including a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally includes a terminal functional group that is neither a silyl-containing end group nor hydrogen.

[0006] In another embodiment, the method of manufacture includes combining the above ingredients to form a sizing agent.

[0007] In another embodiment, the curable composition comprises the composition described above.

[0008] In another embodiment, the thermoset comprises a curable composition.

[0009] In another embodiment, a method of forming a coated substrate comprises coating a substrate with the above-described composition.

[0010] In yet another aspect, the article comprises a thermoset.

[0011] In yet another aspect, a method of making an article includes molding, extruding, or shaping the poly(arylene ether) described above into an article.

[0012] In yet another aspect, a reinforcing agent sized with the above composition is disclosed.

[0013] In yet another aspect, a metal foil coated with the above composition is disclosed.

[0014] These and other features are illustrated by the following detailed description, examples, and claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Poly(arylene ether)s are known to improve the dielectric performance of thermosetting materials for electronic applications. The demand for big data storage and high speed data transmission at higher frequencies is driving the need for the use of high density and multi-layer printed circuit boards in electronic applications. The increasing complexity of boards and shrinking design space with the introduction of wireless units are driving the demand for high performance materials.

[0016] A printed circuit board (PCB) may include a sheet of thermoset resin and a layer of copper foil laminated to a substrate. A PCB may include multiple copper layers. For example, a two-layer board may include copper on both sides of a layer of thermoset resin, and a multi-layer board may include additional copper layers sandwiched between layers of thermoset resin. At high frequencies, current tends to follow the contours of the surface of the conductor (e.g., copper foil), causing signal loss (i.e., "skin effect"). Therefore, to reduce overall insertion loss or loss through a conductor, a smoother conductor (e.g., metal) surface, also referred to as a "low roughness" surface, is preferred. High performance materials that can adhere to smooth metal foils in multi-layer printed circuit boards may increase transmission speeds due to reduced dielectric loss. However, conventional poly(arylene ether) laminates may not readily adhere to smooth metal surfaces, such as the surface of low roughness copper foil. Advantageously, the present inventors have discovered a bifunctional sizing agent that can promote adhesion to smooth metal surfaces, i.e., is soluble in the poly(arylene ether) matrix, and can participate in crosslinking. By including a bifunctional sizing agent in the poly(arylene ether) composition, post-production surface modification may be avoided, thus reducing production costs. The sizing agent comprises a bifunctional poly(arylene ether) containing a silyl-containing group and optionally a terminal functional group excluding both the silyl-containing group and hydrogen. The silyl-containing group may be present as a terminal functional group, a pendant group, or a combination of terminal functional groups and pendant groups. Thus, the silyl-containing group promotes adhesion to the surface, whether it is a pendant group or a terminal group. When the silyl-containing group is present only as a pendant group, both hydroxyl ends are available for functionalization and crosslinking. When the silyl-containing group is present as a terminal group, optionally a pendant group, one hydroxyl end is available for functionalization and crosslinking. This differs from conventional poly(arylene ether)s having silyl-containing end groups, in which both ends of the poly(arylene ether) contain a silyl-containing group, because in this approach, one end is available for crosslinking. The composition may further comprise a supplemental difunctional poly(arylene ether) having any terminal functional group.The bifunctional sizing agents can be used to treat the surfaces of substrates such as glass fibers, alumina fibers, basalt fibers, quartz fibers, inorganic fillers, and metal foils.

[0017] The composition includes a sizing agent and, optionally, a supplemental difunctional poly(arylene ether).

[0018] The sizing agent of the composition includes a difunctional poly(arylene ether) that includes a silyl-containing group and, optionally, a terminal functional group. The silyl-containing group can include a silyl-containing end group, a silyl-containing pendant group, or a combination of a silyl-containing end group and a silyl-containing pendant group. Any terminal functional group is neither a silyl-containing end group nor hydrogen.

[0019] The composition may include a supplemental difunctional poly(arylene ether) in addition to the difunctional poly(arylene ether) of the sizing agent. The supplemental difunctional poly(arylene ether) may include a terminal functional group. Any terminal functional group of the difunctional poly(arylene ether) is neither a silyl-containing end group nor hydrogen.

[0020] The individual components of the composition are discussed in more detail below.

[0021] The poly(arylene ether) and / or the auxiliary difunctional poly(arylene ether) of the sizing agent may contain repeat units derived from a monohydric phenol. The repeat units derived from a monohydric phenol are represented by the formula (1):

[0022] [ka]

[0023] (In the formula, Z 1 is independently in each occurrence a halogen, an unsubstituted or substituted C 1~ C 12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1~ C 12Hydrocarbylthio, C 1~ C 12 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~ C 12 halohydrocarbyloxy, and Z 2 is independently in each occurrence hydrogen, halogen, unsubstituted or substituted C 1~ C 12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1~ C 12 Hydrocarbylthio, C 1~ C 12 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~ C 12 As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. The residue may also contain combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as being substituted, the hydrocarbyl residue may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, when specifically described as being substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z 1 may be a di-n-butylaminomethyl group formed by reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0024] The poly(arylene ether) and / or the supplemental mono- or difunctional poly(arylene ether) of the sizing agent may contain 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In some embodiments, the poly(arylene ether) is poly(2,6-dimethyl-1,4-phenylene ether). In some embodiments, the poly(arylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.03 deciliters per gram to 1 deciliter per gram. For example, the poly(arylene ether) can have an intrinsic viscosity of 0.25 deciliters per gram to 1 deciliter per gram, specifically, 0.25 deciliters per gram to 0.7 deciliters per gram, more specifically, 0.35 deciliters per gram to 0.55 deciliters per gram, and even more specifically, 0.35 deciliters per gram to 0.50 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer.

[0025] The poly(arylene ether) of the sizing agent and / or the supplemental difunctional poly(arylene ether) may comprise molecules having aminoalkyl-containing end group(s) typically located ortho to a hydroxy group. Tetramethyldiphenoquinone (TMDQ) end groups are frequently also present, typically obtained from 2,6-dimethylphenol-containing reaction mixtures in which tetramethyldiphenoquinone by-product is present. The poly(arylene ether) may be in the form of a homopolymer, copolymer, graft copolymer, ionomer, block copolymer, or oligomer, and combinations thereof.

[0026] The poly(arylene ether) and / or the auxiliary difunctional poly(arylene ether) of the sizing agent may be represented by the formula (2):

[0027] [ka]

[0028] (In the formula, Q1 and Q 2 is independently in each occurrence a halogen, an unsubstituted or substituted C 1~15 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 including halohydrocarbyloxy, Q 3 and Q 4 is independently in each occurrence hydrogen, halogen, unsubstituted or substituted C 1~ C 15 Primary or secondary hydrocarbyl, C 1~ C 12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 halohydrocarbyloxy, where x and y have an average value and are each independently 0 to 30 or 0 to 20, preferably 0 to 15, more preferably 0 to 10, and even more preferably 0 to 8, with the proviso that the sum of x and y is at least 2, preferably at least 3, and more preferably at least 4, and where Q 1 ~Q 4 At least one of, or a combination thereof, is unsubstituted or substituted C1- 15 In one embodiment, Q may comprise a poly(arylene ether) of Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 , Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 16 , Q 17 , Q 18 , Q 19 , Q 20 , 1 , Q 2 , Q 3 , or Q 4 is hydrogen, methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl, or a combination thereof.

[0029] Furthermore, in formula (2), L is represented by the following formula (3) or formula (4). L is represented by formula (3)

[0030] [ka]

[0031] (In the formula, R 3 , R 4 , R 5 , and R 6 is independently in each occurrence hydrogen, halogen, unsubstituted or substituted C 1~12 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 halohydrocarbyloxy, and w is 0 or 1, and Y is

[0032] [ka]

[0033] and Here, R 7 is, independently in each occurrence, hydrogen or C 1~12 Contains hydrocarbyl, R 8 and R 9 is, independently in each occurrence, hydrogen, C 1~12 Contains hydrocarbyl or R 8 and R 9 together with the carbon atom C 4~12 In one embodiment of formula (3), R 3 , R 4 , R 5 , and R 6 are each independently hydrogen, halogen, unsubstituted or substituted C 1~6 It includes primary or secondary hydrocarbyl and w is 0 or 1.

[0034] In another embodiment, L in formula (2) is formula (4):

[0035] [ka]

[0036] wherein E is 6 to 100, or 11 to 80, or 11 to 60, and R is, independently in each occurrence, unsubstituted or substituted C 1~13 Alkyl, C 1~13 Alkoxy, C 3~6 Cycloalkyl, C 3~6 Cycloalkoxy, C 6~14 Aryl, C 6~10 Aryloxy, C 7~13 Aryl alkylene or C 7~13 The above groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Furthermore, in formula (4), p and q are each independently 0 or 1, and R 1 is a divalent C 2~8 an aliphatic group; M is, independently in each occurrence, halogen, cyano, nitro, C 1~8 Alkylthio, C 1~8 Alkyl, C 1~8 Alkoxy, C 2~8 Alkenyl, C 2~8 Alkenyloxy, C 3~8 Cycloalkyl, C 3~8 Cycloalkoxy, C 6~10 Aryl, C 6~10 Aryloxy, C 7~12 Aralkyl, C 7~12 Aralkoxi, C 7~12 Alkylaryl or C 7~12 alkylaryloxy, where n is, independently at each occurrence, 0, 1, 2, 3, or 4. Preferably, in formula 4, E is 5 to 60, and R is, independently at each occurrence, C 1~6 Alkyl, C 3~6 Cycloalkyl, or C 6~14 aryl, more preferably methyl; p and q are each 1; R 1 is a divalent C 2~8 is an aliphatic group, M is a halogen, cyano, C 1~4 Alkyl, C 1~4 Alkoxy, C 6~10 Aryl, C 7~12 Aralkyl or C 7~12alkylaryl, more preferably methyl or methoxy; and each n is independently 0, 1, or 2.

[0037] In some embodiments, the poly(arylene ether) of the sizing agent and / or the auxiliary poly(arylene ether) have the formula (2b):

[0038] [ka]

[0039] (In the formula, Q 5 and Q 6 wherein, independently in each occurrence, methyl, di-n-butylaminomethyl, or morpholinomethyl, and a and b are, independently in each occurrence, 0 to 20, provided that the sum of a and b is at least 2.

[0040] The poly(arylene ether) of formula (2) can be prepared by derivatization of a hydroxyl-terminated poly(arylene ether) prepared by oxidative polymerization of at least one monohydric phenol, optionally in combination with at least one dihydric or polyhydric phenol, in the presence of a polymerization catalyst comprising a catalytic metal ion and a catalytic amine ligand, oxygen, and a solvent. The polymerization catalyst can be prepared in situ by mixing the catalytic metal ion and the catalytic amine ligand. The solvent can be benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, chloroform, or combinations thereof. In some embodiments, the solvent comprises toluene. Molecular oxygen can be provided, for example, in purified form or as air.

[0041] As used herein, the term "poly(arylene ether)" may also refer to low molecular weight poly(arylene ether). In some embodiments, the poly(arylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. In some embodiments, the poly(arylene ether) may have an intrinsic viscosity of 0.03 deciliters per gram to 0.13 deciliters per gram, or 0.05 deciliters per gram to 0.1 deciliters per gram, or 0.1 deciliters per gram to 0.15 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer. The poly(arylene ether) may have a number average molecular weight of 500 grams per mole to 7000 grams per mole, and a weight average molecular weight of 500 grams per mole to 15000 grams per mole, as determined by gel permeation chromatography using polystyrene standards. In some embodiments, the number average molecular weight can be from 750 grams per mole to 4000 grams per mole, and the weight average molecular weight can be from 1500 grams per mole to 9000 grams per mole, as determined by gel permeation chromatography using polystyrene standards.

[0042] In some embodiments, the poly(arylene ether) is essentially free of incorporated diphenoquinone residues. In this context, "essentially free" means that less than 1 weight percent (wt%) of the poly(arylene ether) molecules contain residues of diphenoquinone. As described in U.S. Pat. No. 3,306,874 to Hay, the synthesis of poly(arylene ether) by oxidative polymerization of monohydric phenols produces not only the desired poly(arylene ether) but also diphenoquinone as a by-product. For example, when the monohydric phenol is 2,6-dimethylphenol, 3,3',5,5'-tetramethyldiphenoquinone is produced. Typically, the diphenoquinone is "re-equilibrated" to poly(arylene ether) by heating the polymerization reaction mixture (i.e., incorporating diphenoquinone into the poly(arylene ether) structure) to obtain poly(arylene ethers containing terminal or internal diphenoquinone residues. For example, when a poly(arylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol to obtain poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone, re-equilibration of the reaction mixture can produce a poly(arylene ether) having terminal and internal residues of diphenoquinone incorporated therein. However, such re-equilibration reduces the molecular weight of the poly(arylene ether). Thus, when a higher molecular weight poly(arylene ether) is desired, it may be desirable to separate the diphenoquinone from the poly(arylene ether) rather than re-equilibrating the diphenoquinone into a poly(arylene ether) chain. Such separation can be accomplished, for example, by precipitating the poly(arylene ether) in a solvent or solvent mixture in which the poly(arylene ether) is insoluble and the diphenoquinone is soluble.For example, if a poly(arylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol in toluene to obtain a toluene solution containing poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone, poly(2,6-dimethyl-1,4-phenylene ether) essentially free of diphenoquinone can be obtained by mixing one volume of the toluene solution with one to four volumes of methanol or a methanol / water mixture. Alternatively, the amount of diphenoquinone by-product produced during the oxidative polymerization can be minimized (e.g., by initiating the oxidative polymerization in the presence of less than 10 wt. % monohydric phenol and adding at least 95 wt. % monohydric phenol over at least 50 minutes) and / or re-equilibration of diphenoquinone to poly(arylene ether) chains can be minimized (e.g., by isolating the poly(arylene ether) within 200 minutes after the end of the oxidative polymerization). These approaches are described in International Patent Application Publication WO 2009 / 104107 to Delsman et al. In an alternative approach using the temperature-dependent solubility of diphenoquinone in toluene, a toluene solution containing diphenoquinone and poly(arylene ether) can be adjusted to a temperature of 25° C., where diphenoquinone is poorly soluble but poly(arylene ether) is soluble, and the insoluble diphenoquinone can be removed by solid-liquid separation (e.g., filtration).

[0043] The poly(arylene ether) of the sizing agent includes a silyl-containing group and, optionally, a terminal functional group that is not a silyl-containing group or hydrogen. The silyl-containing group of the sizing agent can include a silyl-containing end group, a silyl-containing pendant group, or the silyl-containing group of the sizing agent can be present as both a silyl-containing end group and a silyl-containing pendant group. Examples of pendant silyl-containing groups include those of the formula (CR2): n Si(R a )(OR) 3-a In some embodiments, the pendant silyl-containing group includes a group of formula * -(CR2)n Si(R a )(OR) 3-a wherein the silyl-containing pendant group is of the formula

[0044] [ka]

[0045] (wherein " * " indicates the attachment of a pendant group to the skeleton (i.e., main chain) of the poly(arylene ether). The silyl-containing group that is the terminal functional group may be any of the following formulae:

[0046] [ka]

[0047] (In the ceremony, `` * With respect to the silyl-containing pendant groups and silyl-containing end groups of the sizing agent, R is, independently in each occurrence, hydrocarbyl, a is 0 to 2, n is 2 to 13, g is 0 to 4, and G is, independently in each occurrence, halogen, unsubstituted or substituted C 1~15 Primary or secondary hydrocarbyl, C 1~15 Hydrocarbylthio, C 1~15 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~15 The silyl-containing groups may be the same or different.

[0048] When the silyl-containing group is a terminal functional group, the silyl-containing group can be incorporated as shown in formula S-1. When the silyl-containing group is a pendant group, the silyl-containing group can be incorporated as shown in formula S-2. When the silyl-containing group is a pendant group and a terminal functional group, the silyl-containing group can be incorporated as shown in formula S-3. The poly(arylene ether)s shown below are not so limited, but are included for illustrative purposes only.

[0049] [ka]

[0050] With respect to formulas S-1 to S-3, G, g, R, a, and n are as defined above in each case. G, g, R, a, and n may be the same or different in each case.

[0051] The difunctional poly(arylene ether) of the sizing agent and the auxiliary monofunctional or difunctional poly(arylene ether) may each include a terminal functional group. The terminal functional group of the poly(arylene ether) of the sizing agent is a group that excludes both a silyl-containing end group and hydrogen. Similarly, the auxiliary poly(arylene ether) may include at least one terminal functional group that is not a silyl-containing group or hydrogen.

[0052] In one embodiment, the auxiliary poly(arylene ether) has the structure

[0053] [ka]

[0054] (In the formula, Q 1 , Q 2 , Q 3 , Q 4 , L, x, and y are as defined above, and R 10 is methyl or hydrogen).

[0055] In the above (meth)acrylate terminated poly(arylene ether) structure, there are limitations on the variables x and y, which correspond to the number of phenylene ether repeat units at two different locations in the bifunctional poly(arylene ether). In this structure, x and y are independently 0 to 30, specifically 0 to 20, more specifically 0 to 15, even more specifically 0 to 10, and even more specifically 0 to 8. The sum of x and y is at least 2, specifically at least 3, and more specifically at least 4. The poly(arylene ether) is characterized by proton nuclear magnetic resonance spectroscopy ( 1 H NMR) to determine whether, on average, these constraints are met. 1 H NMR can distinguish between the protons associated with the internal and terminal phenylene ether groups and the protons associated with the internal and terminal residues of the polyhydric phenol as well as the terminal residues. Thus, it is possible to determine the average number of phenylene ether repeat units per molecule as well as the relative abundance of the internal and terminal residues derived from the dihydric phenol.

[0056] In some embodiments, the secondary poly(arylene ether) has the structure

[0057] [ka]

[0058] (In the formula, Q 5 and Q 6 independently in each occurrence, methyl, di-n-butylaminomethyl, or morpholinomethyl; and a and b are independently in each occurrence 0 to 20, with the proviso that the sum of a and b is at least 2; and R 10 is methyl or hydrogen in each instance.

[0059] The difunctional poly(arylene ether) and / or the supplemental mono- or difunctional poly(arylene ether) of the sizing agent may include terminal functional groups, which may include (meth)acrylate, styrene, -CH-(CH)-CH=CH, allyl, cyanate ester, glycidyl ether, anhydride, aniline, maleimide, activated ester, or combinations thereof.

[0060] The sizing agent can be prepared according to a method comprising the steps of: oxidatively polymerizing a monohydric phenol, an alkenyl-substituted monohydric phenol, and optionally a dihydric phenol to obtain a sizing agent precursor having alkenyl pendant groups, alkenyl-substituted phenol terminal functional groups, or a combination thereof, and a hydroxyl-terminated difunctional poly(arylene ether); reacting the alkenyl group of the sizing agent precursor with a silane reagent to obtain a sizing agent having a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and at least one hydroxyl terminus; optionally reacting at least one hydroxyl terminus of the sizing agent to obtain a sizing agent having a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and a terminal functional group that is neither a silyl-containing end group nor hydrogen; and optionally reacting at least one hydroxyl terminus of the difunctional poly(arylene ether) to obtain a difunctional poly(arylene ether) having at least one terminal functional group. The following schemes show examples of sizing agent precursors (P-1 through P-3) in which an alkenyl-substituted monohydric phenol is incorporated into the poly(arylene ether) backbone, as a terminal functional group, or both. The following structures and schemes are for illustrative purposes only and are not intended to limit the compositions and methods of the present disclosure.

[0061] [ka]

[0062] The sizing agent can be prepared using a redistribution method. The poly(arylene ether) used in the redistribution method can be monofunctional or difunctional. The silyl-containing group can be incorporated before or after the redistribution. For example, an alkenyl-substituted monohydric phenol can be added to the redistribution reaction mixture, and the alkenyl group can be converted to a silyl-containing group after the redistribution is completed. Alternatively, the alkenyl group of the alkenyl-substituted monohydric phenol can be converted to a silyl group before the redistribution.

[0063] The redistribution method may include the steps of: adding a redistribution catalyst to a reaction mixture containing an alkenyl-substituted monohydric phenol and a hydroxyl-terminated mono- or difunctional poly(arylene ether) precursor to obtain a sizing agent oligomeric precursor having an alkenyl-substituted phenol end functional group, and a hydroxyl-terminated mono- or difunctional poly(arylene ether); reacting the alkenyl group of the sizing agent oligomeric precursor with a silane reagent to obtain a sizing agent having a hydroxyl terminus and a silyl-containing end group; optionally reacting the hydroxyl terminus of the sizing agent oligomeric precursor to obtain a sizing agent having a silyl-containing end group and a terminal functional group that is neither a silyl-containing end group nor hydrogen; and optionally reacting the hydroxyl terminus of the mono- or difunctional poly(arylene ether) to obtain a difunctional poly(arylene ether) having a terminal functional group.

[0064] The redistribution method may include the steps of: adding a redistribution catalyst to a reaction mixture containing a silyl-substituted monohydric phenol and a hydroxyl-terminated mono- or difunctional poly(arylene ether) precursor to obtain a sizing agent oligomeric precursor having silyl-substituted phenol end functional groups, and a hydroxyl-terminated mono- or difunctional poly(arylene ether), optionally reacting the hydroxyl terminus of the sizing agent oligomeric precursor to obtain a sizing agent having silyl-containing end groups and a terminal functional group that is neither a silyl-containing end group nor hydrogen, and optionally reacting the hydroxyl terminus of the mono- or difunctional poly(arylene ether) to obtain a mono- or difunctional poly(arylene ether) having terminal functional groups.

[0065] As disclosed above, the difunctional poly(arylene ether) and the supplemental monofunctional or difunctional poly(arylene ether) of the sizing agent may have at least one terminal functional group, and the method of making each poly(arylene ether) further includes reacting a poly(arylene ether) having a terminal hydroxyl group with a compound to obtain a poly(arylene ether) having at least one (meth)acrylate, styrene, -CH2-(CH4)-CH=CH2, allyl, cyanate ester, glycidyl ether, anhydride, aniline, maleimide, or activated ester terminal functional group. For example, if a poly(arylene ether) having at least one vinylbenzyl ether terminal group is desired, the method may include reacting a hydroxyl-terminated poly(arylene ether) with a vinylbenzyl halide (e.g., vinylbenzyl chloride). When a functional phenylene ether having at least one (meth)acrylic end group is desired, the method may include reacting a hydroxyl-terminated poly(arylene ether) with a (meth)acrylic acid halide or anhydride. Suitable compounds containing the desired functionality and groups reactive with poly(arylene ether)s having terminal hydroxyl groups may be readily determined by one skilled in the art.

[0066] The poly(arylene ether) of the present disclosure can be a reactive component in a curable composition. In the curable composition, the difunctional poly(arylene ether) of the sizing agent and the auxiliary monofunctional or difunctional poly(arylene ether) each contain a terminal functional group. In addition to the sizing agent and the auxiliary difunctional poly(arylene ether), the curable composition can contain a cure accelerator. The cure accelerator can be selected based on the functional groups present on the poly(arylene ether) and, if present, the auxiliary curable resin or curable unsaturated monomer composition. For example, the cure accelerator can include amines, dicyandiamides, polyamides, amidoamines, Mannich bases, anhydrides, phenol formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate esters, or combinations thereof.

[0067] In some embodiments, the curable composition may further comprise a supplemental curable resin, a curable unsaturated monomeric or polymeric composition, or both. The supplemental curable resin may be a thermosetting resin, such as an epoxy resin, a cyanate ester resin, an isocyanate resin, a maleimide resin, a benzoxazine resin, a vinylbenzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, a curable vinyl-functional oligomer or polymer, or a combination thereof.

[0068] Epoxy resins useful as auxiliary curing resins can be prepared by reacting phenols or polyphenols with epichlorohydrin to form polyglycidyl ethers. Examples of phenols useful for preparing epoxy resins include substituted bisphenol A, bisphenol F, hydroquinone, resorcinol, tris-(4-hydroxyphenyl)methane, and novolac resins derived from phenol or o-cresol. Epoxy resins can also be prepared by reacting aromatic amines such as p-aminophenol or methylenedianiline with epichlorohydrin to form polyglycidylamines. Epoxy resins can be converted to solid, infusible, and insoluble three-dimensional networks by curing with a crosslinking agent, often called a curing agent or hardener. The curing agent is catalytic or co-reactive. Co-reactive curing agents have active hydrogen atoms that can react with the epoxy groups of the epoxy resin to form a crosslinked resin. The active hydrogen atoms can be present in functional groups including primary or secondary amines, phenols, thiols, carboxylic acids, or carboxylic anhydrides. Examples of co-reactive curing agents for epoxy resins include aliphatic and cycloaliphatic amines, as well as amine-functional adducts with epoxy resins, Mannich bases, aromatic amines, polyamides, amidoamines, phenalkamines, dicyandiamides, polycarboxylic acid functional polyesters, carboxylic acid anhydrides, amine-formaldehyde resins, phenol-formaldehyde resins, polysulfides, polymercaptans, or combinations of co-reactive curing agents. Catalytic curing agents function as initiators for the homopolymerization of epoxy resins or as accelerators for co-reactive curing agents. Examples of catalytic curing agents include tertiary amines such as 2-ethyl-4-methylimidazole, Lewis acids such as boron trifluoride, and latent cationic curing catalysts such as diaryliodonium salts.

[0069] The auxiliary curing resin may be a cyanate ester. A cyanate ester is a compound having a cyanate group (-OC≡N) attached to carbon through an oxygen atom, i.e., a COC≡N group. Cyanate esters useful as auxiliary curing resins may be prepared by the reaction of a cyanogen halide with a phenol or a substituted phenol. Examples of useful phenols include bisphenol A, bisphenol F, and bisphenols utilized in the manufacture of epoxy resins such as novolac resins based on phenol or o-cresol. Cyanate ester prepolymers are prepared by polymerization / cyclotrimerization of cyanate esters. Prepolymers prepared from cyanate esters and diamines may also be used.

[0070] The auxiliary curing resin may be a bismaleimide resin, which may be prepared by reaction of a monomeric bismaleimide with a nucleophile such as a diamine, an aminophenol, or an aminobenzhydrazide, or by reaction of a bismaleimide with diallyl bisphenol A.Non-limiting examples of bismaleimide resins include 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 1,3-bismaleimide benzene, 1,4-bismaleimide benzene, 2,4-bismaleimide toluene, 4,4'-bismaleimide diphenyl methane, 4,4'-bismaleimide diphenyl ether, 3,3'-bismaleimide diphenyl sulfone, 4,4'-bismaleimide diphenyl sulfone, 4,4'-bismaleimide Dicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimidopyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citraconimido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl Nyl-1,1-bis(4-maleimidophenyl)ethane, N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazole, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bis Included among these are maleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane bismaleimide, N,N'-m-meta-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, and N,N'-methylenebis(3-chloro-p-phenylene) bismaleimide, as well as the maleimide resins disclosed in U.S. Pat. No. 3,562,223 to Bargain et al. and U.S. Pat. Nos. 4,211,860 and 4,211,861 to Stenzenberger.The bismaleimide resins may be prepared by methods known in the art, for example, as described in U.S. Patent No. 3,018,290 to Sauters et al. In some embodiments, the bismaleimide resin is N,N'-4,4'-diphenylmethane bismaleimide.

[0071] The auxiliary curing resin may be a benzoxazine resin. As is well known, benzoxazine monomers are made from the reaction of three reactants, namely, an aldehyde, a phenol, and a primary amine, with or without the use of a solvent. Ishida, U.S. Pat. No. 5,543,516, describes a solventless method for forming benzoxazine monomers. Ning and Ishida, Journal of Polymer Science, Chemistry Edition, vol. 32, page 1121 (1994), describes a solvent-based procedure. Solvent-based procedures are generally common to the benzoxazine monomer literature.

[0072] The preferred phenolic compounds for forming benzoxazine include phenol and polyphenol.The use of polyphenol with two or more hydroxyl groups that are reactive in forming benzoxazine can lead to branched or crosslinked products.The group that connects the phenol group to the phenol can be the branch point or connecting group in polybenzoxazine.

[0073] Exemplary phenols used in the preparation of benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, and the like. 4,4'-(4-hydroxyphenyl)methane (bisphenol F), 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (bisphenol Z), 4,4'-(cyclododecylidene)diphenol, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(cyclohex ...1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, isopropylidenebis(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 (spirobiindane), dihydro Examples of bisphenol K include tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)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), and dicyclopentadienyl bisphenol.

[0074] The aldehyde used to form the benzoxazine may be any aldehyde. In some embodiments, the aldehyde has 1 to 10 carbon atoms. In some embodiments, the aldehyde is formaldehyde. The amine used to form the benzoxazine may be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic amine, or an aromatic-substituted alkyl amine. The amine may be a polyamine, but in some circumstances the use of a polyamine will result in a multifunctional benzoxazine monomer. Multifunctional benzoxazine monomers are more likely to result in branched and / or crosslinked polybenzoxazines than monofunctional benzoxazines, which is expected to result in a thermoplastic polybenzoxazine.

[0075] Amines for forming benzoxazines generally have 1 to 40 carbon atoms, unless they contain aromatic rings and can have 6 to 40 carbon atoms. Difunctional or polyfunctional amines can also act as branching points connecting one polybenzoxazine to another. Thermal polymerization is the preferred method for polymerizing benzoxazine monomers. The temperature at which thermal polymerization is induced typically varies from 150°C to 300°C. Polymerization is typically carried out in bulk, but can also be carried out from solution or by other methods. Catalysts such as carboxylic acids are known to slightly reduce the polymerization temperature or accelerate the polymerization rate at the same temperature.

[0076] The auxiliary curing resin may be a vinylbenzyl ether resin. Vinylbenzyl ether resins can be readily prepared by condensing phenol with a vinylbenzyl halide, such as vinylbenzyl chloride, to produce the vinylbenzyl ether. Bisphenol A and trisphenols and polyphenols are commonly used to produce poly(vinylbenzyl ethers), which can be used to produce crosslinked thermosetting resins. Vinylbenzyl ethers useful in the present composition include vinylbenzyl chloride or vinylbenzyl bromide in combination with resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3 ... -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 (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4 ,4'-Isopropylidenebis(2,6-dimethylphenol) (tetramethylbisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P), 4,4'-ethylidene diphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'-sulfonyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol (bisphenol AF), 4,4'-(1-phenylethylidene)bisphenol (bisphenol AP), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bisphenol F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (bisphenol Z), 4,4'-(cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol , 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), 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), dicyclopentadienylbis(ortho-cresol), dicyclopentadienylbisphenol, and the like can be mentioned as vinyl benzyl ethers produced by reaction with ,

[0077] The auxiliary curing resin may be an arylcyclobutene resin. Arylcyclobutenes include those having the general structure

[0078] [ka]

[0079] (wherein B is an organic or inorganic group of valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidenedialkylsilanyl, arylalkylsilanyl, diarylsilanyl, and C 6~20 X is, independently in each occurrence, hydroxy or C 1~24 Hydrocarbyl (including linear and branched alkyl and cycloalkyl), Z is, independently at each occurrence, hydrogen, halogen, or C 1~12 and n is 1 to 1000, or 1 to 8, or 2, 3, or 4. Other useful arylcyclobutenes and methods for synthesizing arylcyclobutenes can be found in Kirchhoff et al., U.S. Pat. Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, and 4,724,260, and Brennan et al., U.S. Pat. No. 5,391,650.

[0080] The auxiliary curing resin may include an isocyanate resin, examples of which include, but are not limited to, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), triallyl isocyanurate (TAIC), hydrogenated 1,3-xylylene diisocyanate, and hydrogenated 1,4-xylylene diisocyanate.

[0081] The auxiliary curing resin may be a perfluorovinyl ether resin. Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane followed by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. By this route, bisphenols, trisphenols, and other polyphenols can produce bis(perfluorovinyl ethers), tris(perfluorovinyl ethers), and poly(perfluorovinyl ethers). Non-limiting examples of phenols useful in these syntheses include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)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 (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol) (tetrabromobiphenol), Bisphenol A), 4,4'-isopropylidenebis(2,6-dimethylphenol) (tetramethylbisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)bisphenol (bisphenol P), 4,4'-ethylidene diphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol (bisphenol AF), 4,4'-(1-phenylethylidene)bisphenol (bisphenol AP), bis(4-hydroxyphenyl)-2,2-dichloroethylene (bisphenol C), bis(4-hydroxyphenyl)methane (bisphenol F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, phenol (bisphenol Z), 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3, 4,6-Pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), 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.

[0082] The curable composition may comprise an oligomer or polymer having curable vinyl functionality. Such materials include oligomers and polymers having 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 (copolymer of isobutylene and isoprene, IIR), and halogenated butyl rubber, ethylene-α-olefin copolymer elastomers having unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (i.e., 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)). In some embodiments, EBDM is used. Examples 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 various types of liquid butadiene rubber and liquid atactic butadiene rubber, which is a butadiene polymer with 1,2-vinyl connections prepared by anionic living polymerization.It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (such as CTBN, VTBN, ATBN by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymers, and polynorbornene (sold, for example, by Elf Atochem).

[0083] Polybutadiene resins, typically polybutadienes containing high levels of 1,2 addition, may be desirable in curable compositions. Examples include functionalized polybutadienes and poly(butadiene-styrene) random copolymers sold by RICON RESINS under the trade names RICON resins, RICACRYL resins, and RICOBOND resins. These resins include butadienes with both low vinyl content, such as RICON 130, RICON 131, RICON 134, RICON 142, polybutadienes with high vinyl content, such as RICON 150, RICON 152, RICON 153, RICON 154, RICON 156, RICON 157, and RICON P30D, random copolymers of styrene and butadiene including RICON 100, RICON 181, RICON 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, including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500, polybutadiene 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.Also included are powder dispersions of functionalized polybutadiene derivatives, including, for example, RICON 150D, RICON 152D, RICON 153D, RICON 154D, RICON P30D, RICOBOND 01731 HS, and RICOBOND 1756HS. Additional butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as copolymers having a molecular weight of 3000 grams per mole to 50,000 grams per mole, and polybutadiene homopolymers having a molecular weight of 3000 grams per mole to 50,000 grams per mole. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functionality, 2-hydroxyethyl maleic acid functionality, or hydroxylated functionality.

[0084] Further examples of oligomers and polymers with curable vinyl functionality include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, unsaturated epoxy (meth)acrylate resins with acryloyl or methacryloyl groups, unsaturated epoxy resins with 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.

[0085] In some embodiments, the curable composition comprises a curable unsaturated monomer composition or polymer composition. The curable unsaturated monomer composition can include, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, a multifunctional allylic compound, a multifunctional (meth)acrylate, a multifunctional (meth)acrylamide, a multifunctional styrenic compound, or a combination thereof. For example, in some embodiments, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene-containing and alkyne-containing monomers include those described in U.S. Pat. No. 6,627,704 to Yeager et al. Non-limiting examples of alkene-containing monomers include acrylate, methacrylate, and vinyl ester functionalized materials capable of undergoing free radical polymerization. Of particular use are acrylate and methacrylate materials. These materials can be monomers and / or oligomers such as (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidones, and vinylazalactones as disclosed in US Pat. No. 4,304,705 to Heilman et al.Such monomers include monoacrylates, diacrylates, and polyacrylates, as well as monomethacrylates, dimethacrylates, and polymethacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid, n-hexyl acrylate, tetrahydrofurfuryl acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, acrylonitrile, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate. , trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 2-phenoxyethyl acrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, bis[1-(2-acryloxy)]-p-ethoxyphenyl dimethylmethane, 2,2-bis[1-(3-acryloxy-2-hydroxy)]propoxyphenylpropane, tris(hydroxyethyl)isocyanurate trimethacrylate, bisacrylates and bismethacrylates of polyethylene glycols having a molecular weight average of 200 grams per mole to 500 grams per mole, bisacrylates and bismethacrylates of polybutadiene having a molecular weight average of 1000 grams per mole to 10,000 grams per mole, Boettcher et al. No. 4,652,274 to Zador et al. and copolymerizable mixtures of acrylated monomers such as those disclosed in U.S. Pat. No. 4,652,274 to Zador et al. and acrylated oligomers such as those disclosed in U.S. Pat. No. 4,642,126 to Zador et al.

[0086] It may be desirable to crosslink the alkene- or alkyne-containing monomers. Particularly useful crosslinker compounds include allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol, and the like. Examples of acrylates include acrylates such as butyl ether triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, bis[1-(2-acryloxy)]-p-ethoxyphenyl dimethylmethane, 2,2-bis[1-(3-acryloxy-2-hydroxy)]propoxyphenylpropane, tris(hydroxyethyl)isocyanurate trimethacrylate, and bisacrylates and bismethacrylates of polyethylene glycols having a molecular weight average of 200 grams per mole to 500 grams per mole.

[0087] Also included are allylic and styrenic resins such as triallyl and trimethallyl isocyanurate, trimethallyl cyanurate, triallyl cyanurate, divinylbenzene and dibromostyrene, as well as others described in Yeager et al., U.S. Pat. No. 6,627,704.

[0088] In addition to the poly(arylene ether), the cure accelerator, and, if present, the auxiliary resin or unsaturated monomer composition, the curable composition may optionally include a solvent. The solvent may have an atmospheric boiling point of from 50° C. to 250° C. A boiling point within this range facilitates removal of the solvent from the curable composition while minimizing or eliminating the effects of foaming upon removal of the solvent.

[0089] The solvent is, for example, C 3~8 Ketone, C3~8 N,N-Dialkylamides, C 4~16 Dialkyl ether, C 6~12 Aromatic Hydrocarbons, C 1~3 Chlorinated hydrocarbons, C 3~6 Alkyl alkanoates, C 2~6 The carbon number range refers to the total number of carbon atoms in the solvent molecule. For example, C 4~16 Dialkyl ethers have 4 to 16 total carbon atoms, and the two alkyl groups may be the same or different. As another example, the 3 to 8 carbon atoms in an "N,N-dialkylamide" includes the carbon atom in the amide group, and "C 2~6 The 2 to 6 carbon atoms in the alkyl cyanide include the carbon atoms in the cyanide group. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. 4~8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. In some embodiments, C 4~16 Dialkyl ethers include cyclic ethers such as tetrahydrofuran and dioxane. In some embodiments, C 4~16 The dialkyl ether is acyclic. The dialkyl ether may further optionally include one or more ether oxygen atoms in the alkyl group and one or more hydroxyl group substituents on the alkyl group. The aromatic hydrocarbon solvent may include an ethylenically unsaturated solvent. Exemplary aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvent is preferably non-halogenated. As used herein, the term "non-halogenated" means that the solvent does not contain any fluorine, chlorine, bromine, or iodine atoms. Specific C 3~6Alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. 2~6 The alkyl cyanide can include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. In some embodiments, the solvent is acetone. In some embodiments, the solvent is methyl ethyl ketone. In some embodiments, the solvent is methyl isobutyl ketone. In some embodiments, the solvent is N-methyl-2-pyrrolidone. In some embodiments, the solvent is dimethylformamide. In some embodiments, the solvent is ethylene glycol monomethyl ether.

[0090] When a solvent is utilized, the curable composition may include 2 to 100 parts by weight of the solvent, based on 100 parts by weight of the poly(arylene ether), the accelerator, and any auxiliary resin or unsaturated monomer composition (if present). For example, the amount of the solvent may be 5 to 80 parts by weight, or 10 to 60 parts by weight, or 20 to 40 parts by weight, based on 100 parts by weight of the poly(arylene ether), the accelerator, and any auxiliary resin. The solvent may be selected in part to adjust the viscosity of the curable composition. Thus, the amount of solvent may depend on variables including the type and amount of poly(arylene ether), the type and amount of the accelerator, the type and amount of the auxiliary resin, and any subsequent processing of the curable composition, such as the processing temperature used to impregnate the reinforcing structure with the curable composition to prepare a composite.

[0091] The curable composition may optionally further comprise one or more additives. Exemplary additives include, for example, solvents, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow improvers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, stress relief additives, inorganic fillers, or combinations thereof.

[0092] The curable composition may include the poly(arylene ether) described herein, a curing accelerator, a solvent, and an auxiliary resin, curable unsaturated monomer composition, or polymer composition, or a combination thereof. In some embodiments, the auxiliary curable resin and / or curable unsaturated monomer composition or polymer composition is not present.

[0093] The curable composition can include 1 wt% to 99 wt% of the auxiliary curable resin, curable unsaturated monomer composition, or polymer composition, or both, and 1 wt% to 99 wt% of the poly(arylene ether), each based on the total weight of the curable composition. For example, the composition can include 20 wt% to 99 wt% of the auxiliary curable resin, curable unsaturated monomer composition, or polymer composition, or both, and 1 wt% to 80 wt% of the poly(arylene ether).

[0094] A thermoset composition (i.e., a cured composition) can be obtained using any curing method known in the art, such as moisture curing, thermal curing, and / or UV curing. In some embodiments, a thermoset can be obtained by heating the curable composition as defined herein for a time and temperature sufficient to evaporate the solvent and effect curing. For example, the curable composition can be heated to a temperature of 50°C to 250°C to cure the composition and obtain a thermoset composition. During curing, a crosslinked three-dimensional polymer network is formed. For certain thermosetting resins, such as (meth)acrylate resins, curing can also be achieved by exposure to actinic radiation at a sufficient wavelength and time. In some embodiments, curing the composition can include pouring the curable composition into a mold and curing the poured composition in the mold at 150°C to 250°C.

[0095] The thermosetting compositions described herein may also be particularly well suited for use in forming a variety of articles. For example, useful articles may be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded components, prepregs, casings, laminates, metal clad laminates, electronic composites, structural composites, or combinations thereof. In some embodiments, the articles may be in the form of composites that can be used in a wide variety of applications, such as printed circuit boards.

[0096] Sizing agents can also be used as coatings for reinforcing agents, e.g. for sized reinforcing agents. Possible sized reinforcing agents are, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripolites, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (fibrous talc, modular ... talc, needle talc, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates or (armospheres), kaolin, silicon carbide, alumina, boron carbide, whiskers of iron, nickel, or copper, continuous and chopped carbon or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO2, aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, Natural fillers such as cellulose, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground nut shells or rice hulls, reinforcing organic fibrous fillers such as poly(ether ketones), polyimides, polybenzoxazoles, poly(phenylene sulfide), polyesters, polyethylenes, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, and poly(vinyl alcohol), and combinations thereof. The fillers and reinforcing agents may be coated with a layer of metallic material to promote electrical conductivity or surface treated with silanes to improve adhesion and dispersion with the polymer matrix.

[0097] The sizing agent can also be used as a coating for metal foils, such as copper foils. Metal foils can be characterized by surface roughness (Rz). Rz is measured by measuring the vertical distance from the highest peak to the lowest valley within five sampling lengths and averaging the distances. Rz can be measured using a contact profilometer or optical interferometry according to ASTM D7127, ISO 25178, or a combination thereof.

[0098] The metal foil may include a standard surface. The roughness of the foil may be about 10.2 μm or more, as determined according to Rz ISO, or about 8.5 μm or more, as determined according to Rz JIS, for a foil having a thickness of 35 μm.

[0099] The metal foil may have a smooth surface as classified by IPC-4562. The metal foil may include a low roughness metal foil. The foil roughness may range from about 5.1 μm to about 10.2 μm, as determined according to Rz ISO, or from about 4.2 μm to about 8.5 μm, as determined according to Rz JIS, for a foil having a thickness of 35 μm. The metal foil may include a very low roughness metal foil. The foil roughness may range from about 2.5 μm to about 5.1 μm, as determined according to Rz ISO, or from about 2.0 μm to about 4.2 μm, as determined according to Rz JIS, for a foil having a thickness of 35 μm. The metal foil may include a metal foil with an ultra-flat profile. The foil roughness may range from about 1.25 μm to about 10.2 μm, as determined according to Rz ISO, or from about 4.2 μm to about 8.5 μm, as determined according to Rz JIS, for a foil having a thickness of 35 μm. The metal foil may include a substantially no-profile metal foil. The roughness of the foil may range from about 0 μm to about 1.25 μm, as determined according to Rz ISO, or from about 0 μm to about 1.25 μm, as determined according to Rz JIS, for a foil having a thickness of 35 μm.

[0100] The metal foil can have a thickness of about 10 μm to about 100 μm, about 10 μm to about 75 μm, or about 10 μm to about 50 μm. In some embodiments, the metal foil has a thickness of about 15 μm to greater than 40 μm. EXAMPLES

[0101] The present disclosure is further illustrated by the following non-limiting examples.

[0102] Redistribution of 2-allyl-6-methylphenol to poly(phenylene ether): 120 grams of poly(phenylene ether) was added to a 1 L 4-neck round bottom flask equipped with a condenser, thermocouple, heating mantle, overhead stirrer, and an addition port. 170 mL of toluene was added to the reaction flask to dissolve the poly(phenylene ether) with stirring under a N2 atmosphere. To this solution was added 6.61 g of 2-allyl-6-methylphenol (44.6 mmol) and the temperature was set to 100 °C. At 60 °C-80 °C, 3.81 g of benzoyl peroxide (15.8 mmol) was added. The reaction temperature was maintained at 100 °C for 3.5 hours. The reaction mixture was cooled to ambient temperature under N2.

[0103] Hydrosilylation of 2-allyl-6-methylphenol-containing poly(phenylene ether): 60 ml of toluene was added to the above reaction flask. A Dean-Stark trap was attached to the flask and the temperature was raised to achieve vigorous reflux. After removing 60 mL of azeotrope, the reaction solution was cooled to 100 °C. 7.33 g of triethoxysilane (44.6 mmol) and 0.66 g of Karstedt catalyst (0.69 mmol) were added to the reaction solution and refluxed for 4.5 h. The solvent was removed using a rotary evaporator and the product was further dried in a vacuum oven at 90 °C overnight. The product was 1 Analysis by 1 H NMR spectroscopy confirmed the presence of silyl-containing groups. 1 H NMR (600MHz, CDCl3): (1)δ 1.18(9H,t);(2)δ 3.9(6H,q);(3)δ 0.9(2H,t);(4)δ 1.6(2H,m);(5)δ 2.5(2H,t).

[0104] [ka]

[0105] Redistribution of eugenol to poly(phenylene ether): 120 grams of poly(phenylene ether) was added to a 2 L, 3-neck round bottom flask equipped with a condenser, thermocouple, heating mantle, overhead stirrer, and an addition port. 170 mL of toluene was added to the reaction flask to dissolve the poly(phenylene ether) with stirring under a N2 atmosphere. To this solution, 7.3 g of eugenol (44.6 mmol) was added and the temperature was set to 100 °C. At 60 °C-80 °C, 3.81 g of benzoyl peroxide (15.8 mmol) was added. The reaction temperature was maintained at 100 °C for 3.5 hours. The reaction mixture was cooled to ambient temperature under N2.

[0106] Hydrosilylation of eugenol-containing poly(phenylene ether): 60 ml of toluene was added to the above reaction flask. A Dean-Stark trap was attached to the flask and the temperature was raised to achieve vigorous reflux. After removing 60 mL of azeotrope, the reaction solution was cooled to 100 °C. 7.33 g of triethoxysilane (44.6 mmol) and 0.66 g of Karstedt catalyst (0.69 mmol) were added to the reaction solution and refluxed for 4.5 h. The solvent was removed using a rotary evaporator and the product was further dried in a vacuum oven at 90 °C overnight. The product was 1 Analysis by 1 H NMR spectroscopy confirmed the presence of silyl-containing groups. 1 H NMR (600MHz, CDCl3): (1)δ 1.18(9H,t);(2)δ 3.9(6H,q);(3)δ 0.9(2H,t);(4)δ 1.6(2H,m);(5)δ 2.5(2H,t).

[0107] [ka]

[0108] The present disclosure further includes the following aspects.

[0109] Aspect 1. A composition comprising a sizing agent comprising a difunctional poly(arylene ether) comprising a silyl-containing group comprising a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally comprising a terminal functional group that is neither a silyl-containing end group nor hydrogen.

[0110] Aspect 2. The composition of aspect 1, further comprising a supplemental mono- or difunctional poly(arylene ether) optionally comprising at least one terminal functional group that is neither a silyl-containing end group nor hydrogen.

[0111] Aspect 3. The silyl-containing end group has the formula

[0112] [ka]

[0113] and the silyl-containing pendant group is of the formula (CR2): n Si(R a )(OR) 3-a wherein the silyl-containing pendant group is of the formula

[0114] [ka]

[0115] is derived from a repeat unit comprising wherein R is, independently in each occurrence, hydrocarbyl; a is 0 to 2; n is 2 to 13; g is 0 to 4; and G is, independently in each occurrence, halogen, unsubstituted or substituted C 1~15 Primary or secondary hydrocarbyl, C 1~15 Hydrocarbylthio, C 1~15 Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~15 halohydrocarbyloxy, and * The composition of any one of the preceding embodiments, wherein: indicates attachment to the poly(arylene ether) via a carbon-oxygen bond.

[0116] Aspect 4. The composition of any of Aspects 1-3, wherein the terminal functional group of the difunctional poly(arylene ether) of the sizing agent and at least one terminal functional group of the auxiliary mono- or difunctional poly(arylene ether) each independently comprises a (meth)acrylate, a styrene, -CH2-(C6H4)-CH=CH2, an allyl, a cyanate ester, a glycidyl ether, an anhydride, an aniline, a maleimide, or an activated ester.

[0117] Aspect 5. A sizing agent comprising a difunctional poly(arylene ether) having a silyl-containing group comprising a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally at least one terminal functional group that is neither a silyl-containing end group nor hydrogen, and a supplemental mono- or difunctional poly(arylene ether) having at least one terminal functional group that is neither a silyl-containing end group nor hydrogen, wherein the silyl-containing end group is represented by the formula

[0118] [ka]

[0119] and the silyl-containing end group is of the formula (CR2): n Si(R a )(OR) 3-a wherein the silyl-containing pendant group is of the formula

[0120] [ka]

[0121] is derived from a repeat unit comprising wherein R is, independently in each occurrence, hydrocarbyl; a is 0 to 2; n is 2 to 13; g is 0 to 4; and G is, independently in each occurrence, halogen, unsubstituted or substituted C 1~15 Primary or secondary hydrocarbyl, C 1~15 Hydrocarbylthio, C 1~15Hydrocarbyloxy or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~15 halohydrocarbyloxy, and * The composition of any one of embodiments 1-4, wherein indicates attachment to the poly(arylene ether) via a carbon-oxygen bond.

[0122] Embodiment 6. A method of making a sizing agent according to any of embodiments 1-5, comprising: oxidatively polymerizing a monohydric phenol, an alkenyl-substituted monohydric phenol, and optionally a dihydric phenol to obtain a sizing agent precursor having alkenyl pendant groups, alkenyl-substituted phenol terminal functional groups, or combinations thereof, and a difunctional poly(arylene ether) having at least one hydroxyl terminus; reacting an alkenyl group of the sizing agent precursor with a silane reagent to obtain a sizing agent having a silyl-containing end group, a silyl-containing pendant group, or combinations thereof, and at least one hydroxyl terminus; optionally reacting at least one hydroxyl terminus of the sizing agent to obtain a sizing agent having a silyl-containing end group, a silyl-containing pendant group, or combinations thereof, and a terminal functional group that is neither a silyl-containing end group nor hydrogen; and optionally reacting at least one hydroxyl terminus of the difunctional poly(arylene ether) to obtain a difunctional poly(arylene ether) having at least one terminal functional group.

[0123] Embodiment 7. A method of making a sizing agent according to any of embodiments 1-5, comprising: adding a redistribution catalyst to a reaction mixture comprising an alkenyl-substituted monohydric phenol and a difunctional poly(arylene ether) precursor having at least one hydroxyl terminus to obtain a sizing agent oligomeric precursor having an alkenyl-substituted phenol end functional group, and a hydroxyl-terminated mono- or difunctional poly(arylene ether); reacting an alkenyl group of the sizing agent oligomeric precursor with a silane reagent to obtain a sizing agent having a hydroxyl terminus and a silyl-containing end group; optionally reacting a hydroxyl terminus of the sizing agent oligomeric precursor to obtain a sizing agent having a silyl-containing end group and a terminal functional group which is neither a silyl-containing end group nor hydrogen; and optionally reacting a hydroxyl terminus of the mono- or difunctional poly(arylene ether) to obtain a difunctional poly(arylene ether) having a terminal functional group.

[0124] Embodiment 8. A method of making a sizing agent according to any of Embodiments 1-5, comprising adding a redistribution catalyst to a reaction mixture containing a silyl-substituted monohydric phenol and a hydroxyl-terminated, difunctional poly(arylene ether) precursor to obtain a sizing agent oligomeric precursor having silyl-substituted phenol end functional groups, and a hydroxyl-terminated, difunctional poly(arylene ether); optionally reacting the hydroxyl terminus of the sizing agent oligomeric precursor having silyl-substituted phenol end functional groups to obtain a sizing agent having a silyl-containing end group and a terminal functional group which is neither a silyl-containing end group nor hydrogen; and optionally reacting the hydroxyl terminus of the difunctional poly(arylene ether) to obtain a mono- or difunctional poly(arylene ether) having terminal functional groups.

[0125] Embodiment 9. A curable composition comprising the composition of any of Embodiments 2-6, wherein the difunctional poly(arylene ether) of the sizing agent and the auxiliary monofunctional or difunctional poly(arylene ether) each comprise a terminal functional group, and optionally a cure accelerator.

[0126] Embodiment 10. The curable composition of embodiment 9, further comprising a supplemental curable resin, a curable unsaturated monomer or polymer, or a combination thereof.

[0127] Example 11. A thermosetting composition comprising the curable composition of example 9 or example 10.

[0128] Example 12. A method of forming a coated substrate, comprising: providing a substrate; coating the substrate with a curable composition according to example 8 or 9 to obtain a coated substrate; and curing the curable composition, wherein the curing comprises moisture curing, thermal curing, or UV curing.

[0129] Example 13. An article comprising the thermoset composition of Example 12, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronics composite, or a structural composite, preferably an adhesive, a prepreg, a laminate, or a metal clad laminate.

[0130] Aspect 14. A reinforcing agent sized with the composition of any one of aspects 1-10.

[0131] Embodiment 15. A metal foil coated with the composition of any one of embodiments 1-10.

[0132] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or ingredients disclosed herein. The compositions, methods, and articles can additionally or alternatively be fabricated to be devoid of, or substantially free of, any materials (or species), steps, or ingredients that are not necessary to the function or accomplishment of the purpose of the compositions, methods, and articles.

[0133] All ranges disclosed in this disclosure are inclusive of the endpoints, and the endpoints are combinable independently of one another (e.g., the range "up to 25 wt.%, or more specifically, 5 wt.% to 20 wt.%" includes the endpoints and all intermediate values ​​of the range "5 wt.% to 25 wt.%). "Combination" includes blends, mixtures, alloys, reaction products, and the like. Terms such as "first," "second," and the like do not denote any order, amount, or importance, but rather are used to distinguish one element from another. The terms "a," "an," and "the" do not denote limitations of quantity, and should be construed to include both the singular and the plural, unless otherwise stated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. References throughout the specification to "some embodiments," "an embodiment," and the like mean that the particular element described in connection with that embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. It should further be understood that the described elements can be combined in any suitable manner in the various embodiments. "Combinations thereof" is open-ended and includes any combination that includes at least one of the recited components or features together with, optionally, similar or equivalent unrecited components or features.

[0134] Unless otherwise specified herein, all test standards are the most recent standards in effect as of the filing date of this application or, if priority is claimed, as of the filing date of the earliest priority application in which the test standard appears.

[0135] 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 cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term from this application shall take precedence over the conflicting term from the incorporated reference.

[0136] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have a valency filled by the indicated bond or by a 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.

[0137] The term "alkyl" refers to a branched or straight-chain unsaturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n-hexyl and s-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH2). "Alkoxy" refers to an alkyl group linked through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy. "Alkylene" refers to a straight or branched saturated divalent aliphatic hydrocarbon group, such as methylene (-CH2-), or propylene (-(CH2)3-). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization(s). "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds within the ring, all of the ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing the specified number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro) or only chloro groups may be present. The prefix "hetero" means that the compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where the heteroatom(s) are each independently N, O, S, Si, or P. "Substituted" means that the compound or group contains, each independently, C, in place of a hydrogen, provided that the normal valence of the substituted atom is not exceeded. 1~9 Alkoxy, C 1~9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3~12 Cycloalkyl, C 2~12 Alkenyl, C 5~12 Cycloalkenyl, C 6~12 Aryl, C 7~13 Aryl alkylene, C 4~12 Heterocycloalkyl, and C 3~12It means that it is substituted with at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl. The number of carbon atoms indicated in the group is exclusive of any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0138] While particular embodiments have been described, presently foreseen or foreseeable alternatives, modifications, variations, improvements, and substantial equivalents may occur to applicant or others skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, will embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A sizing agent composition comprising a silyl-containing group including a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally including a terminal functional group that is neither a silyl-containing end group nor hydrogen. The sizing agent composition includes a bifunctional poly(arylene ether).

2. The composition according to claim 1, further comprising an auxiliary monofunctional or bifunctional poly(arylene ether) optionally including at least one terminal functional group that is neither a silyl-containing end group nor hydrogen.

3. The silyl-containing end group is derived from a repeating unit including the formula 【Chemical 1】 comprising, wherein the silyl-containing pendant group has the formula (CR ２ ), ｎ Si(R ａ )(OR) ３－ａ wherein the silyl-containing pendant group has the formula 【Chemical 2】 wherein, in each case independently, R is hydrocarbyl, a is from 0 to 2, n is from 2 to 13, g is from 0 to 4, G is, in each case independently, halogen, unsubstituted or substituted C １～１５ primary or secondary hydrocarbyl, C １～１５ hydrocarbylthio, C １～１５ hydrocarbyloxy, or C in which at least two carbon atoms are separated by a halogen atom and an oxygen atom ２～１５ halohydrocarbyloxy, and ＊ represents a bond to said poly(arylene ether) via a carbon-oxygen bond, the composition according to claim 1 or 2.

4. The terminal functional groups of the bifunctional poly(arylene ether) of the sizing agent and at least one terminal functional group of the auxiliary monofunctional or bifunctional poly(arylene ether) are each independently (meth)acrylate, styrene, -CH ２ -(C ６ H ４ )-CH=CH ２ , allyl, cyanate ester, glycidyl ether, anhydride, aniline, maleimide, or activated ester, the composition according to claim 1 or 2.

5. A bifunctional poly(arylene ether) having a silyl-containing group including a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and optionally at least one terminal functional group that is neither a silyl-containing end group nor hydrogen, and An auxiliary monofunctional or bifunctional poly(arylene ether) having at least one terminal functional group that is neither a silyl-containing end group nor hydrogen, The sizing agent includes the sizing agent, wherein The silyl-containing end group includes the formula 【Chemical Formula 3】 and is derived from a repeating unit including The silyl-containing pendant group has the formula (CR ２ ), ｎ Si(R ａ )(OR) ３－ａ and here, the silyl-containing pendant group has the formula [Chemical Formula 4] wherein, in each case independently, R is hydrocarbyl, a is from 0 to 2, n is from 2 to 13, g is from 0 to 4, G is, in each case independently, halogen, unsubstituted or substituted C １～１５ primary or secondary hydrocarbyl, C １～１５ hydrocarbylthio, C １～１５ hydrocarbyloxy, or C in which at least two carbon atoms are separated by a halogen atom and an oxygen atom ２～１５ is halohydrocarbyloxy, and ＊ represents a bond to said poly(arylene ether) via a carbon-oxygen bond, the composition according to claim 1 or 2.

6. A method for preparing the sizing agent according to claim 1 or 2, comprising: Oxidatively polymerizing a monohydric phenol, an alkenyl-substituted monohydric phenol, and optionally a dihydric phenol to obtain a sizing agent precursor having an alkenyl pendant group, an alkenyl-substituted phenol terminal functional group, or a combination thereof, and a monofunctional or bifunctional poly(arylene ether) having at least one hydroxyl terminal; Reacting the alkenyl group of the sizing agent precursor with a silane reagent to obtain a sizing agent having a silyl-containing end group, a silyl group-containing pendant group, or a combination thereof, and at least one hydroxyl terminal; Optionally reacting at least one hydroxyl terminal of the sizing agent to obtain a sizing agent having a silyl-containing end group, a silyl-containing pendant group, or a combination thereof, and a terminal functional group that is neither a silyl-containing end group nor hydrogen; Optionally reacting at least one hydroxyl terminal of the monofunctional or bifunctional poly(arylene ether) to obtain a monofunctional or bifunctional poly(arylene ether) having at least one terminal functional group; The method includes the above steps.

7. A method for producing the sizing agent according to claim 1 or 2, comprising: adding a redistribution catalyst to a reaction mixture containing an alkenyl-substituted monohydric phenol and a bifunctional poly(arylene ether) precursor having at least one hydroxyl terminus to obtain a sizing agent oligomer precursor having an alkenyl-substituted phenol terminal functional group and a monofunctional or bifunctional poly(arylene ether) having a hydroxyl terminus; reacting the alkenyl group of the sizing agent oligomer precursor with a silane reagent to obtain a sizing agent having a hydroxyl terminus and a silyl-containing terminal group; optionally reacting the hydroxyl terminus of the sizing agent oligomer precursor to obtain a sizing agent having a silyl-containing terminal group and a terminal functional group that is neither a silyl-containing terminal group nor hydrogen; optionally reacting the hydroxyl terminus of the monofunctional or bifunctional poly(arylene ether) to obtain a bifunctional poly(arylene ether) having a terminal functional group; A method comprising the above steps.

8. A method for producing the sizing agent according to claim 1 or 2, comprising: adding a redistribution catalyst to a reaction mixture containing a silyl-substituted monohydric phenol and a monofunctional or bifunctional poly(arylene ether) precursor having a hydroxyl terminus to obtain a sizing agent oligomer precursor having a silyl-substituted phenol terminal functional group and a monofunctional or bifunctional poly(arylene ether) having a hydroxyl terminus; optionally reacting the hydroxyl terminus of the sizing agent oligomer precursor having a silyl-substituted phenol terminal functional group to obtain a sizing agent having a silyl-containing terminal group and a terminal functional group that is neither a silyl-containing terminal group nor hydrogen; optionally reacting the hydroxyl terminus of the monofunctional or bifunctional poly(arylene ether) to obtain a monofunctional or bifunctional poly(arylene ether) having a terminal functional group; A method comprising the above steps.

9. A curable composition, wherein the bifunctional poly(arylene ether) and the auxiliary monofunctional or bifunctional poly(arylene ether) of the sizing agent each contain a terminal functional group; A curable composition comprising the composition according to claim 1 or 2, optionally containing a curing accelerator.

10. The curable composition according to claim 9, further comprising an auxiliary curable resin, a curable unsaturated monomer or polymer, or a combination thereof.

11. A thermosetting composition comprising the curable composition according to claim 9.

12. A method of forming a coated substrate, comprising: preparing a substrate; coating the substrate with the curable composition according to claim 9 to obtain a coated substrate; curing the curable composition; wherein the curing includes moisture curing, thermal curing, or UV curing.

13. An article comprising the thermosetting composition according to claim 12, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded component, prepreg, casing, laminate, metal-clad laminate, composite material for electronics, or structural composite material, preferably an adhesive, prepreg, laminate, or metal-clad laminate.

14. A reinforcing agent sized with the composition according to claim 1 or 2.

15. A metal foil coated with the composition according to claim 1 or 2.

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