Curable poly(polyphenylene ether) oligomer composition for coating

Abstract

The ultraviolet photocurable coating composition comprises 5-40 weight percent of ultraviolet photocurable poly(polyphenylene ether) oligomer; 60-95 weight percent of ultraviolet photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3 weight percent of photoinitiator.

Description

Background Technology

[0001] Cross-citation of the present application

[0002] This application claims the benefit of U.S. application no. 62 / 841182 filed on April 30, 2019, the entirety of which is incorporated herein by reference.

[0003] background

[0004] The present disclosure relates to a curable coating composition, in particular a curable coating composition comprising a poly(polyphenylene ether) oligomer.

[0005] Coatings for substrates may need to possess high heat resistance, high impact strength, and low moisture absorption depending on the end application. Poly(polyphenylene ether) generally has excellent electrical properties, high heat resistance, and moisture resistance, but low impact strength. There is a need for poly(polyphenylene ester) coating compositions that possess high glass transition temperatures and low moisture absorption, along with improved excellent hardness. Such coating compositions would be even more useful for coating various thermal substrates if UV curing is possible. means of solving the problem

[0006] Simple explanation

[0007] An ultraviolet photocurable poly(polyphenylene ether) oligomer is disclosed comprising 5-40 weight percent of an ultraviolet photocurable poly(polyphenylene ether) oligomer; 60-95 weight percent of a co-curable ultraviolet photoreactive monomer, oligomer, polymer, or combination thereof; and 0.01-3 weight percent of a photoinitiator.

[0008] A method for forming an ultraviolet photo-curable coating composition is disclosed.

[0009] In addition, a thermosetting composition comprising a cured product of an ultraviolet photo-curable coating composition is disclosed.

[0010] Additionally, a method for forming a coated article by coating an article with a coating composition, and an article comprising the coating composition are disclosed.

[0011] The features described above and other features are exemplified by the following drawings and detailed description. Specific details for implementing the invention

[0012] The present invention discloses a curable coating composition, in particular a UV-curable coating composition comprising a poly(polyphenylene ether) oligomer, a process for manufacturing the curable coating composition, and an article coated with the curable coating composition. The composition has desirable properties including an improved glass transition temperature, excellent hardness, and low hygroscopicity, and consequently produces a higher performance composition for a coating substrate.

[0013] The coating composition is UV-curable and comprises an ultraviolet photocurable poly(polyphenylene ether) oligomer as described below; a co-curable monomer, oligomer, polymer, or combination thereof as described below; and a UV photoinitiator. The functional monomer contains an ethylene-based unsaturated terminal functional group that is UV-curable, i.e., reactive in the presence of free radicals generated by the action of ultraviolet light on the photoinitiator. The co-curable monomer, oligomer, polymer, or combination thereof also contains an ethylene-based unsaturated terminal functional group that is UV-curable, i.e. reactive in the presence of free radicals generated by the action of ultraviolet light on the photoinitiator. As used herein, "curable" and "cured" refer to both polymerization and crosslinking reactions between the components of the UV-curable coating composition.

[0014] The poly(polyphenylene ether) oligomer comprises repeating structural units of the chemical formula (1).

[0015]

[0016] Here, Z 1Each case independently involves halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2- C 12 halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; and Z 2 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms.

[0017] In a preferred embodiment of chemical formula (1), Z 1 Each case independently involves halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2- C7 halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; and Z 2 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-7 It is a halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms.

[0018] In a more preferred embodiment, Z 1Each case independently involves halogens, or unsubstituted or substituted primary C 1-6 Hydrocarbil; and Z 2 Each case independently involves hydrogen, halogen, or unsubstituted or substituted primary C 1-6 Hydrocarbil; and in the present embodiment, even more preferably, Z 1 Each case of is the same and Z 2 Each case is the same or different. The poly(polyphenylene ether) oligomer may typically comprise a unit having terminal group(s) containing an aminoalkyl group located at an ortho position with respect to the hydroxyl group. Additionally, tetramethyldiphenoquinone (TMDQ) terminal groups are frequently present, which are obtained from reaction mixtures generally containing 2,6-dimethylphenol, where tetramethyldiphenoquinone (TMDQ) byproducts are present. Therefore, Z 1 and Z 2 Each may independently be hydrogen, cyclohexyl, phenyl, di-n-butylaminomethyl, morpholinomethyl, or a combination thereof. In a preferred aspect, the poly(polyphenylene ether) oligomer comprises a 2,6-dimethyl-1,4-phenylene ether unit, a 2,3,6-trimethyl-1,4-phenylene ether unit, or a combination thereof. In some aspects, the poly(polyphenylene ether) oligomer comprises a poly(2,6-dimethyl-1,4-phenylene ether) unit.

[0019] Poly(polyphenylene ether) oligomers can be monofunctional or bifunctional. In some aspects, poly(polyphenylene ether) oligomers can be monofunctional. For example, they can be monofunctional having a UV photocurable functional group at one end of the oligomer chain. The functional group can be, for example, a vinyl, allyl, or (meth)acrylate group, preferably a methacrylate group. Alternatively, the poly(polyphenylene ether) oligomer can be bifunctional having UV photocurable functional groups at both ends of the oligomer chain. The functional group can be a vinyl, allyl, or (meth)acrylate group, preferably a methacrylate group.

[0020] In some aspects, the poly(polyphenylene ether) oligomer comprises a monofunctional or difunctional poly(polyphenylene ether) oligomer of formula (2).

[0021]

[0022] Here, Q 1 and Q 2 is independently a halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; Q 3 and Q 4 In each case, hydrogen, halogen, unsubstituted or substituted C1-C 12 Primary or secondary hydrocarbil, C1-C 12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12halohydrocarbyloxy, where at least two carbon atoms separate halogen and oxygen atoms; each Z is independently hydrogen, allyl, vinyl, or (meth)acrylate and at least one Z is allyl, vinyl, or (meth)acrylate; x and y have average values, each independently 0-30, or 0-20, preferably 0-15, more preferably 0-10, even more preferably 0-8, provided that the sum of x and y is at least 2, preferably at least 3, more preferably at least 4.

[0023] Also, in chemical formula (2), L is represented by the following chemical formula (3) or chemical formula (4). L can be chemical formula (3) and

[0024]

[0025] Here, R 3 , R 4 , R 5 , and R 6 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; w is 0 or 1; and Y is

[0026] Igo

[0027] Here, R 7 Each case is independently hydrogen or C 1-12 Hydrocarbyl, R 8 and R 9 Each case is independently hydrogen, hydrocarbyl, or R 8 and R 9 together with carbon atoms and C 4-12It forms cyclohydrocarbylene. In a preferred aspect of chemical formula (3), R 3 , R 4 , R 5 , and R 6 is independently hydrogen, halogen, substituted or unsubstituted C 1-6 It is a primary or secondary hydrocarbyl; and w is 0 or 1.

[0028] In another aspect, L in chemical formula (3) is chemical formula (4)

[0029] Igo

[0030] Here, E is 6–100, or 11–80, or 11–60; and in each case of R, independently unsubstituted or substituted C 1-13 Alkyl, C 1-13 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aril, C 6-10 Aryloxy, C 7-13 Arylalkylene, or C 7-13 It is an alkylarylene. The group may be completely or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Also, in formula (4), each p and q is independently 0 or 1; R 1 is 2-valent C 2-8 It is an aliphatic group, and in each case of M, independently 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 Aril, C 6-10 Aryloxy, C 7-12 Aralkill, C 7-12 Aralkoxy, C 7-12 Alkylaryl, or C 7-12It is an alkylaryloxy, where each n is independently 0, 1, 2, 3, or 4. Preferably, in Formula 4, E is 5-60; and in each case of R, C is independently 1-6 Alkyl, C 3-6 Cycloalkyl, or C 6-14 It is aryl, more preferably methyl; p and q are each 1; and R 1 is 2-valent C 2-8 It is an aliphatic group, and M is halogen, cyano, C 1-4 Alkyl, C 1-4 Alkoxy, C 6-10 Aril, C 7-12 Aralkyl, or C 7-12 alkylaryl, more preferably methyl or methoxy; and each n is independently 0, 1, or 2.

[0031] In some respects, L is the chemical formula (4a)

[0032] Igo

[0033] Here, n has an average value of 5–100, or 10–80, or 10–60.

[0034] In one aspect, the poly(polyphenylene ether) oligomer comprises a difunctional poly(polyphenylene ether) oligomer of formula (2a).

[0035]

[0036] Here, Q 1 , Q 2 , Q 3 , Q 4 , L, x and y are as defined in formula (2), (3), or (4) and R 10 It is methyl or hydrogen. In one aspect, Q 1 , Q 2 , Q 3 , or Q 4is hydrogen, methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl, or a combination thereof.

[0037] In some aspects, the poly(polyphenylene ether) oligomer comprises a difunctional poly(polyphenylene ether) oligomer of formula (2b).

[0038]

[0039] Here, Q 5 and Q 6 Each case of is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl; and each case of a and b is independently 0-20, provided that the sum of a and b is at least 2; and R 10 Each case is independently methyl or hydrogen. Preferably, in formula (2b), Q 5 and Q 6 Each case of is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl, and each R 10 It is methyl. Suitable poly(polyphenylene ether) oligomers of this type, for example NORYL SA9000, are commercially available from SABIC.

[0040] The difunctional poly(polyphenylene ether) oligomer of formula (2) may be prepared by derivatization of a hydroxyl-terminated poly(polyphenylene ether) oligomer prepared by the oxidative polymerization of at least one monovalent phenol in the presence of a polymerization catalyst comprising a catalytic metal ion, a catalytic amine ligand, oxygen, and a solvent, optionally in combination with at least one divalent or polyvalent phenol. The polymerization catalyst may be prepared in situ by mixing the catalytic metal ion and the catalytic amine ligand. The solvent may be benzene, toluene, xylenes, mesitylene, chlorobenzene, dichlorobenzenes, chloroform, or a combination thereof. In some aspects, the solvent comprises toluene. Molecular oxygen may be provided, for example, in a purified form or as air. Derivatization of one or both of the terminal hydroxyl groups to provide the Z group can be carried out by methods known in the art.

[0041] The poly(polyphenylene ether) oligomer may further comprise a block copolymer comprising a poly(phenylene ether) block comprising an aryloxy-terminated polysiloxane block having a unit described in formula (1), a terminal group Z described in formula (2), and repeating siloxane units of formula (5).

[0042]

[0043] Here, R 3 Each case of C independently 1-12 Hydrocarbyl or C 1-12 halohydrocarbyl; and the polysiloxane block further comprises terminal units of formula (6).

[0044]

[0045] Here, Y is hydrogen, halogen, C 1-12 Hydrocarbyl, or C1-12 Hydrocarbiloxy, and R 3 Each case of independently hydrogen, C 1-12 Hydrocarbyl, or C 1-12 It is halohydrocarbyl. Preferably, Y is hydrogen, halogen, C 1-6 Hydrocarbyl, or C 1-6 Hydrocarbiloxy, and R 3 Each case is independently hydrogen, C 1-6 Hydrocarbyl, or C 1-6 It is halohydrocarbyl. More preferably, Y is hydrogen, methyl, or methoxy, and each R 3 is methyl. In some respects, the polysiloxane block is formula (7)

[0046] Igo

[0047] Here, n has an average value of 5–80 or 10–60. In one aspect, the block copolymer is a poly(2,6-dimethyl-1,4-phenylene ether) block, a poly(2,6-dimethyl-1,4-phenylene ether-co-2,3,6-trimethyl-1,4-phenylene ether- co -2,3,6-trimethyl-1,4-phenylene ether)) block, or a combination thereof; a polysiloxane block of the formula comprising, on average, 10 to 100 siloxane repeating units of formula (7); and a terminal Z group as described in formula (2), preferably a (meth)acrylate group. The preparation of the hydroxyl-terminal block copolymer is described, for example, in US 8722837. Derivatizing one or both of the terminal hydroxyl groups to provide the Z group may be done by methods known in the art.

[0048] In some respects, poly(polyphenylene ether) oligomers are essentially free of incorporated diphenoquinone residues. In the context, "essentially free" means that less than 1 weight percent (weight%) of poly(polyphenylene ether) oligomer molecules contain diphenoquinone residues. As described in Hay’s US 3306874, the synthesis of poly(polyphenylene ether) oligomers by the oxidative polymerization of monovalent phenols produces diphenoquinone as a byproduct as well as the desired poly(polyphenylene ether) oligomer. For example, when the monovalent phenol is 2,6-dimethylphenol, 3,3',5,5'-tetramethyldiphenoquinone is produced. Typically, the diphenoquinone is "reequilibrated" into a poly(polyphenylene ether) oligomer by heating the polymerization mixture to produce a poly(phenylene ether) oligomer containing terminal or internal diphenoquinone residues (i.e., the diphenoquinone is incorporated into the poly(polyphenylene ether) oligomer structure). For example, when a poly(polyphenylene ether) oligomer is prepared by the oxidative polymerization of 2,6-dimethylphenol to produce poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone, the reequilibration of the reaction mixture can produce a poly(polyphenylene ether) oligomer having terminal and internal residues of the incorporated diphenoquinone. However, this reequilibration reduces the molecular weight of the poly(polyphenylene ether) oligomer. Therefore, if a higher molecular weight poly(polyphenylene ether) oligomer is required, it may be preferable to separate the diphenoquinone from the poly(polyphenylene ether) oligomer rather than reequilibrating the diphenoquinone into the poly(polyphenylene ether) oligomer chain.This separation can be achieved, for example, by precipitating the poly(polyphenylene ether) oligomer in a solvent or solvent mixture in which the poly(polyphenylene ether) oligomer is insoluble and diphenoquinone is soluble. For example, poly(polyphenylene ether) oligomers are prepared by the oxidative polymerization of 2,6-dimethylphenol in toluene to produce a toluene solution containing poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone, while poly(2,6-dimethyl-1,4-phenylene ether) that is essentially free of diphenoquinone is obtained by mixing 1 volume of the toluene solution with 1-4 volumes of methanol or a methanol / water mixture. Alternatively, the amount of diphenoquinone byproducts generated during oxidative polymerization can be minimized (e.g., oxidation in the presence of 10 wt% or less of monovalent phenol). The re-equilibration of diphenoquinone into poly(polyphenylene ether) oligomer chains can be minimized by initiating polymerization and adding at least 95 weight percent of monovalent phenol over a process of at least 50 minutes, and / or by separating the poly(polyphenylene ether) oligomers within 200 minutes after the completion of oxidative polymerization (e.g., by separating the poly(polyphenylene ether) oligomers). This approach is described in International Patent Application No. WO2009 / 104107 A1 by Delsman et al. In an alternative approach using the temperature-dependent solubility of diphenoquinone in toluene, a toluene solution containing diphenoquinone and poly(polyphenylene ether) oligomers can be adjusted to a temperature of 25°C, at which diphenoquinone is poorly soluble but the poly(polyphenylene ether) oligomers are soluble, and this insoluble diphenoquinone can be removed by solid-liquid separation (e.g., filtration).

[0049] The poly(polyphenylene ether) oligomers useful herein are low molecular weight poly(polyphenylene ether) oligomers. The poly(polyphenylene ether) oligomers may have a number average molecular weight of 500-7,000 grams per mole (g / mol) and a weight average molecular weight of 500-15,000 g / mol when measured by gel permeation chromatography using polystyrene standards. In some aspects, when measured by gel permeation chromatography using polystyrene standards, the number average molecular weight may be 750-4,000 g / mol and the weight average molecular weight may be 1,500-9,000 g / mol.

[0050] In some aspects, poly(polyphenylene ether) oligomers have an intrinsic viscosity of 0.03 to 1 deciliter per gram. For example, poly(polyphenylene ether) oligomers may have an intrinsic viscosity of 0.25 to 1 deciliter per gram (dl / g), or 0.25 to 0.7 dl / g, or 0.35 to 0.55 dl / g, or 0.35 to 0.50 dl / g when measured in chloroform at 25 °C using an Ubérod viscometer. In other aspects, poly(polyphenylene ether) oligomers may have an intrinsic viscosity of 0.03 to 0.13 dl / g, or 0.05 to 0.1 dl / g, or 0.1 to 0.15 dl / g when measured in chloroform at 25 °C using an Ubérod viscometer. The poly(phenylene ether)-polysiloxane block copolymer may have an intrinsic viscosity of at least 0.1 dlo / g when measured in chloroform at 25 °C. In some embodiments, the intrinsic viscosity is 0.1-0.5 dl / g.

[0051] A UV photocurable coating composition comprises a poly(polyphenylene ether) oligomer and a co-curable monomer, oligomer, polymer, or combination thereof. The co-curable monomer, oligomer, polymer, or combination thereof may include straight- or branched-chain alkyl, cyclic, or aromatic, or partially aromatic groups, and the type and amount thereof are selected to provide a desired degree of curability (polymerization or crosslinking), a desired viscosity of the coating composition, and desired properties of the cured coating.

[0052] Oligomers or polymer (meth)acrylates such as polyester acrylate, amine-modified polyether acrylate, aliphatic urethane acrylate, and polyurethane acrylate may be present.

[0053] In one aspect, UV photocurable monomers are used. (Meth)acrylate-containing UV photocurable monomers that may be included in such vinyl, allyl, or UV photocurable coating compositions include mono-, di-, tri-, tetra-, and higher functional group vinyl, allyl, or (meth)acrylates, and many specific examples well known in the art. The monomers may be straight-chain or branched-chain alkyl, cyclic, or partially aromatic.

[0054] The UV photocurable monomer may be a (meth)acrylate monomer having one or more acrylate or methacrylate moieties per monomer molecule. The (meth)acrylate monomer may have mono-, di-, tri-, tetra-, or penta- functional groups. In one aspect, a di-functional monomer is used to obtain the desired flexibility and adhesion of the cured coating. The (meth)acrylate monomer may be straight- or branched-chain alkyl, cyclic, or partially aromatic. The UV photocurable monomer may also comprise a combination of monomers that, when balanced, yields the desired adhesion to a coating composition on a substrate, wherein the coating composition can be cured to form a hard, flexible material having the desired properties.

[0055] Useful (meth)acrylate monomers are mono-(meth)acrylates, particularly substituted or unsubstituted C 1-36(Meth)acrylate esters of a hydrocarbyl group, e.g., 2-(2-ethoxyethoxy)ethyl acrylate, 2-2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, alkoxylated lauryl acrylate, alkoxylated phenol acrylate, alkoxylated phenol methacrylate, alkoxylated tetrahydrofurfuryl acrylate, butyl acrylate, butyl methacrylate, caprolactone acrylate, cyclic trimethylolpropane formal acrylate trimethylolpropane formal acrylate), dicyclopentadienyl methacrylate, ethoxylated hydroxyethyl methacrylate, ethoxylated nonyl phenol acrylate, ethoxylated nonyl phenol methacrylate, ethoxylated nonyl phenyl acrylate, ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isodecyl acrylate,Isodecyl methacrylate, isooctyl acrylate, lauryl acrylate, lauryl methacrylate, methoxy polyethylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, methyl acrylate, methyl methacrylate, octyldecyl acrylate, polypropylene glycol monomethacrylate, polyurethane acrylate, polyurethane methacrylate, propoxylated allyl methacrylate, propyl acrylate, propyl propyl methacrylate, stearyl acrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tridecyl acrylate, tridecyl methacrylate, and similar substituted or unsubstituted C, 1-36 It includes (meth)acrylate esters of hydrocarbyl groups.

[0056] Useful polyfunctional (di-, tri-, tetra-, or penta- functional groups) (meth)acrylates are C2-12 Hydrocarbon diol di(meth)acrylates, e.g., 1,6-hexanediol diacrylate (HDTA), 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate C such as di(meth)acrylate (neopentyl glycol ethoxylate di(meth)acrylate), polyethylene glycol poly(meth)acrylate (polyethylene glycol poly(meth)acrylate), and similar substances 2-12 It contains hydrocarbon diol di(meth)acrylate.

[0057] For example, the (meth)acrylate monomer may be 1,6-hexanediol diacrylate (HDDA) alone or in combination with other monomers such as tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), or octyl / decyl acrylate (ODA).

[0058] In certain aspects, the UV photocurable monomer, oligomer, or polymer is dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, polyether acrylate, amine-modified polyether acrylate, polyester acrylate, polyurethane acrylate, aliphatic urethane acrylate, or a combination thereof.

[0059] Curable coating compositions can provide a coating that hardens over time, but optimal results are achieved in the presence of a free radical curing agent activated by UV light. There are no particular limitations on the properties of a useful photoinitiator as long as it generates radicals upon energy absorption. Therefore, the curable coating composition includes a photoinitiator. Optional additional types of free radical initiators may be present; for example, a heat-activated free radical initiator that provides two-part curing by UV light and heat may be present. Generally, a photoinitiator may be used when the coating composition is UV-cured.

[0060] The photoinitiator is present in an effective amount to promote UV photocuring at a suitable curing rate without causing premature gelation of the coating composition.The photoinitiators are α-hydroxyketone, hydroxycyclohexylphenyl ketone, hydroxymethylphenylpropanone, dimethoxyphenylacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one. 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone), diethoxyacetophenone, 2,2-di-sec-butoxyacetophenone, diethoxy-phenyl acetophenone, bis(2,6-dimethoxybenzoyl)-2,4-,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide It may include, but is not limited to, an oxide (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), or a combination thereof.

[0061] A UV photocurable coating composition may comprise, to provide a total of 100% by weight based on the total weight of the curable composition, 5-40% by weight of each poly(polyphenylene ether) oligomer; 60-95% by weight of an ultraviolet photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3% by weight of a UV photoactivator. In another aspect, to provide a total of 100% by weight based on the total weight of the curable composition, the UV photocurable coating composition may comprise, to provide a total of 100% by weight based on the total weight of the curable composition, 10-40% by weight of each poly(polyphenylene ether) oligomer; 60-90% by weight of an ultraviolet photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3% by weight of a UV photoactivator. In another aspect, the UV photocurable coating composition may comprise, to provide a total of 100 weight% based on the total weight of the curable composition, 20-40 weight% of each poly(polyphenylene ether) oligomer; 60-80 weight% of UV photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3 weight% of UV photoactivator. In a slightly different aspect, the UV photocurable coating composition may comprise, to provide a total of 100 weight% based on the total weight of the curable composition, 25-35 weight% of each poly(polyphenylene ether) oligomer; 55-75 weight% of UV photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3 weight% of UV photoactivator.

[0062] The curable coating composition may optionally further comprise one or more additives known in the art, e.g., stabilizers, release agents, lubricants, processing aids, dropping agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, foaming agents, mineral oils, metal inerts, anti-blocking agents, or combinations thereof. If present, such additives may be used in a total amount of 10% by weight or less, specifically 5% by weight or less, more specifically 1% by weight or less, based on the total weight. A solvent may be present in the coating composition, but is preferably not used.

[0063] A method for forming a coated substrate comprises providing a substrate; coating the substrate with a UV photocurable coating composition to provide a coated substrate; and exposing the coated substrate to UV light to cure the coating composition to provide a cured coating. The choice of substrate is not critical and may be organic or inorganic, for example, a polymer, glass, ceramic, metal, or metal alloy. The substrate may be any shape suitable for coating. The coating is applied at an effective thickness to provide a desired thickness of the cured coating, for example, a cured thickness of 0.01 to 10 millimeters. The intensity and duration of exposure of the UV light are selected to provide the desired degree of curing. As mentioned above, using UV photocuring allows for the use of heat-sensitive substrates. Meanwhile, if a thermal initiator is present, the cured coating may be thermally cured after photocuring.

[0064] Depending on the type and relative amount of poly(phenylene ether) oligomer; curable monomer, oligomer, polymer, or combination thereof; and photoinitiator, the glass transition temperature of the cured composition may be 100-200°C, specifically 120-200°C, and more specifically 120-170°C. In some aspects, the glass transition temperature is 120-150°C.

[0065] The cured coating may exhibit excellent impact strength. In some respects, the composition exhibits an unnotched Izod impact strength of at least 400 joules per meter, specifically 400-600 joules per meter, more specifically 450-550 joules per meter, and slightly more specifically 480-520 joules per meter, when measured by 2 foot-pounds of hammer energy at 23°C according to ASTM D 4812-06.

[0066] The cured coating may exhibit an absorption rate of 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less, measured after being immersed in deionized water at 25 ℃ for 24 hours.

[0067] The cured coating may also exhibit a number of advantageous properties simultaneously. In some aspects, the cured composition may exhibit at least one of the following properties: a glass transition temperature of 120-200°C; and an absorption rate of 1% by weight or less measured after immersion in deionized water at 25°C for 24 hours. In some aspects, the cured composition may exhibit both properties.

[0068] The coating composition is useful for a wide range of applications, such as optical fibers, medical devices, and industrial and construction applications, e.g., electrical and electronic products. The coating can be used for adhesive bonding and assembly of components, component marking, gasketing and sealing, potting, masking, encapsulation, and coating for alloy wheels and hood parts. Coatings for industrial and construction applications, such as metal panels, plastics, and metal pipes, and wood primers may be mentioned.

[0069] Articles are further disclosed in this specification having at least one surface coated with a cured coating. The coating may be in the form of a layer, an encapsulating agent, an adhesive, a sealant, a molded coating, a prepreg, a casing, or a laminate. The article may be a device or a component of a device for use in electronic, medical, industrial, construction, automotive, telecommunications, consumer applications, etc.

[0070] The present specification is further explained by the following non-limiting examples.

[0071] Examples

[0072] The materials used in these examples are shown in Table 1.

[0073] Table 1.

[0074]

[0075] The poly(phenylene ether) oligomer used in this example comprises repeating units derived from 2,6-dimethylphenol and tetramethylbisphenol A, having vinyl end groups, an intrinsic viscosity of 0.09 dl / g, and a number average molecular weight of 2,300 g / mol.

[0076] The formulations and characteristics of Comparative Example 1 (CE1) and Examples 1-10 (E1-E10) are shown in Table 2.

[0077] Table 2.

[0078]

[0079] A formulation was prepared by dissolving PPE and a photoinitiator in each acrylate at 80 °C. After complete dissolution, the solutions were applied between two glass plates and placed under a UV lamp (featuring 100 watts of 365 nm longwave UV) for 10 minutes. The film was removed from the glass plates and immersed in chloroform to test for swelling. If the film is insoluble in chloroform, it indicates the formation of a three-dimensional (3D) network structure.

[0080] Examples 1, 2, 5, 7, 9, and 10 were insoluble in chloroform, indicating that these compositions formed a 3D network structure. This may be due to a larger amount of photoindicator present in the reaction mixture (0.2 g). In the case of Examples 9 and 10, the cured material was at least partially soluble because I-1 and I-2 are monofunctional groups.

[0081] The formulations and characteristics of Comparative Example 1 (CE1-CE5) and Examples 11-14 (E11-E14) are shown in Table 3.

[0082] Table 3.

[0083]

[0084] The amount of initiator was kept constant for Comparative Examples (CE1-CE5) and Examples 11-14 (E11-E14). For example, 0.1 g of initiator was used for 10 g of resin, and 0.2 g of initiator was used for 20 g of resin. In Comparative Examples 2-5, no PPE resin was present. As shown in Table 3, when PPE was present, the Tg measured by differential scanning calorimetry (DSC) improved. For example, comparisons of CE2 and E11, CE3 and E12, CE4 and E13, and CE5 and E14 showed increases of 29, 92, and 53 °C, respectively. The Tg of CE4 and E14 could not be measured by DSC because the PPE dissolved in PA-4.

[0085] The disclosure of this specification further includes the following aspects.

[0086] Aspect 1: A UV photocurable coating composition comprising 5-40 wt% of a UV photocurable poly(polyphenylene ether) oligomer; 60-95 wt% of a UV photocurable monomer, oligomer, polymer, or combination thereof; and 0.01-3 wt% of a photoinitiator activated by ultraviolet light.

[0087] Aspect 2: In Aspect 1, the difunctional poly(polyphenylene ether) oligomer has the following chemical formula

[0088] including

[0089] Here, Q 1 and Q 2 Each case independently involves halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; Q 3 and Q 4 In the case of independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; x and y are each independently 0–30; Z is a halogen, allyl, vinyl, or (meth)acrylate, and at least one Z is an allyl, vinyl, or (meth)acrylate; L is the following chemical formula

[0090] Igo

[0091] Here, R 3 , R4 , R 5 , and R 6 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; w is 0 or 1; and Y is

[0092] Igo

[0093] Here, R 7 Each case is independently hydrogen or C 1-12 It is hydrocarbyl, and R 8 and R 9 Each case of independently hydrogen, C 1-12 Hydrocarbyl, or R 8 and R 9 together with carbon atoms and C 4-12 Forming cyclohydrocarbylene; or L is the following chemical formula

[0094] Igo

[0095] Here, E is 6–100, and in each case, R is independently unsubstituted or substituted C 1-13 Alkyl, C 1-13 Alkoxy, C 3-6 Cycloalkyl, C 3-6 Cycloalkoxy, C 6-14 Aril, C 6-10 Aryloxy, C 7-13 Arylalkylene, or C 7-13 It is an alkylarylene, where each p and q is independently 0 or 1, and R 1 2 valence C 2-8 It is an aliphatic group, and in each case of M, it is independently halogen, cyano, nitro, C 1-8 Alkylthio, C 1-8 Alkyl, C 1-8 Alkoxy, C 2-8 Alkenyl, C2-8 Alkenyloxy, C 3-8 Cycloalkyl, C 3-8 Cycloalkoxy, C 6-10 Aril, C 6-10 Aryloxy, C 7-12 Aralkyl, C 7-12 Aralkoxy, C 7-12 Alkylaryl, or C 7-12 A UV photo-curable coating composition, wherein the alkylaryloxy is and each n is independently 0, 1, 2, 3, or 4.

[0096] Aspect 3: In Aspect 1, the UV photocurable poly(polyphenylene ether) oligomer comprises at least one allyl, vinyl, or (meth)acrylate terminal group; a poly(polyphenylene ether) block; and a polysiloxane block, wherein the poly(polyphenylene ether) block has the following chemical formula

[0097] Igo

[0098] Here, Z 1 Each case independently involves halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2- C 12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom, and Z 2 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2- C 12 It is a halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom; and the polysiloxane block comprises a repeating unit of the following chemical formula.

[0099]

[0100] Here, R 3 Each case of C independently 1-12 Hydrocarbyl or C 1-12 It is a halohydrocarbyl, and the polysiloxane block further comprises a terminal unit of the following chemical formula (6).

[0101]

[0102] Here, Y is hydrogen, halogen, C 1-12 Hydrocarbyl, or C 1-12 Hydrocarbiloxy, and R 3 Each case of independently hydrogen, C 1-12 Hydrocarbyl, or C 1-12 It is halohydrocarbyl, preferably where Y is hydrogen, halogen, C 1-6 Hydrocarbyl, or C 1-6 It is hydrocarbyloxy, and R 3 Each case of independently, C 1-6 Hydrocarbyl, or C 1-6 It is halohydrocarbyl, more preferably where Y is hydrogen, methyl, or methoxy, and each R 3 is methyl, ultraviolet photo-curable coating composition.

[0103] Aspect 4: In Aspect 1, the difunctional poly(polyphenylene ether) oligomer comprises a polysiloxane block of the following chemical formula.

[0104]

[0105] Here, n is an ultraviolet photo-curable coating composition having an average value of 5-100, or 10-80 or 10-60.

[0106] Aspect 5: An ultraviolet photocurable coating composition according to Aspect 1, wherein the poly(polyphenylene ether) oligomer comprises at least one terminal (meth)acrylate group, preferably two terminal methacrylate groups.

[0107] Side 6: In Side 1, the UV photocurable poly(polyphenylene ether) is of the following chemical formula

[0108] including

[0109] Here, Q 1 and Q 2 Each case independently involves halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; Q 3 and Q 4 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; x and y are each independently 0–30; and L is the following chemical formula

[0110] Igo

[0111] Here, R 3 , R 4 , R 5 , and R 6 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; w is 0 or 1; and R 10 is methyl or halogen; and Y is

[0112] Igo

[0113] Here, R 7 Each case is independently hydrogen or C 1-6 It is hydrocarbyl, and R 8 and R 9 Each case of independently hydrogen, C 1-6 It is hydrocarbil, or R 8 and R 9 Together with carbon atoms and C 4-6 UV photo-curable coating composition forming cyclohydrocarbylene.

[0114] Side 7: In Side 1, the UV photocurable poly(polyphenylene ether) oligomer has the following chemical formula

[0115] Igo

[0116] Here, Q 5 and Q 6 Each case of is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl; each case of a and b is independently 0-20, provided that the sum of a and b is at least 2; and R 10 Each case of is methyl or hydrogen; preferably, the above Q 5 and Q 6 Each case is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl, and each R 10 UV photo-curable coating composition containing methyl phosphate.

[0117] Aspect 8: A UV photocurable coating composition according to Aspect 1, wherein the UV photocurable poly(polyphenylene ether) has a number average molecular weight of 500-7,000 g / mol and a weight average molecular weight of 500-15,000 g / mol as measured by gel permeation chromatography using a polystyrene standard.

[0118] Aspect 9: An ultraviolet photocurable coating composition according to Aspect 1, wherein the ultraviolet photocurable monomer, oligomer, or polymer is a (meth)acrylate.

[0119] A UV photo-curable coating composition according to Aspect 1, wherein the curable monomer, oligomer, or polymer is dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate polyether acrylate, amine-modified polyether acrylate, polyester acrylate, polyurethane acrylate, aliphatic urethane acrylate, or a combination thereof.

[0120] Aspect 11: An ultraviolet photocurable coating composition according to Aspect 1, comprising 20-40 wt% of an ultraviolet photocurable poly(polyphenylene ether) oligomer; 60-80 wt% of an ultraviolet photocurable monomer, oligomer, polymer, or combination thereof; and 0.1-3 wt% of a photoinitiator.

[0121] Aspect 12: The ultraviolet photo-curable coating composition comprising, in aspect 1, 20-40 wt% of a meth(acrylate)-terminated poly(polyphenylene ether) oligomer; 60-80 wt% of a combination of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, polyether acrylate, amine-modified polyether acrylate, polyester acrylate, polyorethane acrylate, aliphatic urethane acrylate, isobornyl acrylate, and isobornyl methacrylate; and 0.1-3 wt% of a photoinitiator.

[0122] Aspect 13: A cured product of a curable composition according to Aspect 1, having a glass transition temperature of 120-200°C; an absorption rate of 1 wt% or less measured after immersion in deionized water at 25°C for 24 hours; or a combination thereof.

[0123] Aspect 14: A method for forming a coated substrate, the method comprising: providing a substrate; coating the substrate with an ultraviolet photocurable coating composition of any one of Aspects 1 to 12 to provide a coated substrate; and curing the coating composition with ultraviolet light.

[0124] Aspect 15: An article comprising a thermosetting composition according to Aspect 13, wherein the coating comprises a thermosetting composition in the form of a layer, an encapsulating agent, an adhesive, a sealant, a molding coating, a prepreg, a casing, or a laminate.

[0125] Compositions, methods, and articles may alternatively include, be composed of, or be substantially composed of any suitable material, step, or component disclosed herein. Compositions, methods, and articles may additionally or alternatively be formulated without or substantially without any material (or species), step, or component that is not necessary to achieve the function or purpose of the composition, method, and article.

[0126] All ranges disclosed herein include endpoints, and endpoints may be combined independently of one another (e.g., a range of “up to 25 wt%, or 5 wt%–20 wt%” includes endpoints of the “5 wt%–25 wt%” range and all intermediate values). “Combinations” include blends, mixtures, alloys, reaction products, and similar items. Terms such as “first,” “second,” etc., are used to distinguish one element from another, rather than indicating order, quantity, or importance. The terms “a,” “an,” and “the” do not indicate a limitation of quantity and should be interpreted to include both singular and plural forms unless otherwise indicated herein or clearly contradictory in the context. “Or” means “and / or” unless otherwise specified. Throughout the specification, references to “some aspect,” “one aspect,” etc., mean that a specific element described in relation to that aspect is included in at least one aspect described herein and may or may not be present in another aspect. Additionally, it should be understood that the described elements may be combined in any appropriate manner in various aspects. "Combinations of these" include any combination that optionally includes at least one of the listed components or attributes, along with similar or equivalent components or attributes that are disclosed and not listed.

[0127] Unless otherwise specified herein, all test standards are the most recent standards valid 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 standards appear.

[0128] Unless otherwise defined, technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, in the event that the terms of this application contradict or conflict with the terms of the integrated reference, the terms of this application shall prevail over the conflicting terms of the integrated reference.

[0129] Compounds are described using standard nomenclature. For example, any position not substituted with any indicated group is understood to have a valence filled by a bond or hydrogen atom as indicated. A dash ("-") not between two letters or symbols is used to indicate the attachment point for a substituent. For example, -CHO is attached through the carbon of the carbonyl group. "(Meth)acrylate" contains both acrylate and methacrylate groups.

[0130] As used herein, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used alone or as a prefix, suffix, or fragment of another term. The residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also include a combination of aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated hydrocarbon portions. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms on the carbon and hydrogen members of the substituent residue. Thus, when specifically described as 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. For example, Z of Formula 1. 1It may be a di-n-butylaminomethyl group formed by the reaction of a terminal 3,5-dimethyl-1,4-phenyl group with a di-n-butylamine component of an oxidative polymerization catalyst.

[0131] The term "alkyl" refers to a branched or straight-chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-phenyl, s-pentyl, and n- and s-hexyl. "Alkenyl" refers to a straight-chain or branched-chain, monovalent hydrocarbon group having one or more carbon-carbon double bonds. "Alkoxy" refers to an alkyl group connected via oxygen (i.e., alkyl-O-), e.g., methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a straight-chain or branched-chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x It means, where x is the number of hydrogens replaced by cyclization. The prefix "halo" means a group or compound containing one or more of fluoro, chloro, bromo, or iodo substituents. A combination of other halo groups (e.g., bromo and fluoro) or only chloro groups may be present. The prefix "hetero" means that the compound or group contains one or more ring members that are heteroatoms (e.g., 1, 2, or 3 heteroatom(s)), where each heteroatom(s) is independently N, O, S, Si, or P. "Substituted" means that the compound or group contains at least one (e.g., 1, 2, 3, or 4) of C, each independently, instead of hydrogen. 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkyl sulfonyl (-S(=O)2-alkyl), C 6-12Aryl sulfonyl (-S(=O)2-aryl) thiol (-SH), thiocyano (hiocyan, -SCN), tosyl (tosyl, CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aril, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 This means that it is substituted with a substituent that may be heteroaryl, provided that the normal valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituent. For example, the -CH2CH2CN group is a C2 alkyl group substituted with a nitrile.

[0132] Although certain aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or may not be anticipated may arise to the applicant or those skilled in the art. Accordingly, the submitted and attached claims and claims subject to modification are intended to include all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

Claim 1 A UV photocurable coating composition comprising 5-39.99 weight percent of a UV photocurable poly(polyphenylene ether) oligomer; 60-94.99 weight percent of a UV photocurable monomer, oligomer, polymer, or combination thereof comprising terminal units derived from (meth)acrylate or allyl monomers; and 0.01-3 weight percent of a photoinitiator activated by UV light, wherein the UV photocurable monomer, oligomer, or polymer is different from the UV photocurable poly(polyphenylene ether) oligomer. Claim 2 In claim 1, the ultraviolet photocurable poly(polyphenylene ether) oligomer has the following structure Includes and here Q 1 and Q 2 Each case independently involves halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; Q 3 and Q 4 Each case independently involves hydrogen, halogen, unsubstituted or substituted C1-C 12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom; x and y are each independently 0–30; Z is a halogen, allyl, vinyl, or (meth)acrylate, provided that at least one Z is allyl, vinyl, or (meth)acrylate; and L is the following chemical formula And here R 3 , R 4 , R 5 , and R 6 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2-12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; w is 0 or 1; and Y is And here R 7 Each case is independently hydrogen or C 1-12 It is hydrocarbil, and R 8 and R 9 Each case of independently hydrogen, C 1-12 It is hydrocarbil, or R 8 and R 9 together with carbon atoms and C 4-12 Forming cyclohydrocarbylene; or L is the following chemical formula Here, E is 6–100, and in each case, R is independently 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 arylalkylene, or C 7-13 It is an alkylarylene (alkylarylene); each p and q is independently 0 or 1, and R 1 2 valence C 2-8 It is an aliphatic group, and in each case of M, it is independently 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 aralkoxy, C 7-12 alkylaryl, or C 7-12 A UV photocurable coating composition that is an alkylaryloxy, and each n is independently 0, 1, 2, 3, or 4. Claim 3 In claim 1, the UV photocurable poly(polyphenylene ether) oligomer comprises at least one allyl, vinyl, or (meth)acrylate terminal group; a poly(polyphenylene ether) block; and a polysiloxane block, wherein the poly(polyphenylene ether) block has the following chemical formula And here Z 1 Each case independently involves halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2- C 12 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom, and Z 2 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-12 Primary or secondary hydrocarbil, C 1-12 Hydrocarbilthio, C 1-12 Hydrocarbiloxy, or C 2- C 12 It is a halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom; and the polysiloxane block comprises a repeating unit of the following chemical formula. Here R 3 Each case of C independently 1-12 Hydrocarbyl or C 1-12 It is a halohydrocarbyl, and the polysiloxane block further comprises a terminal unit of the following chemical formula (6). Here, Y is hydrogen, halogen, C 1-12 Hydrocarbyl, or C 1-12 It is hydrocarbyloxy, and R 3 Each case of independently hydrogen, C 1-12 Hydrocarbyl, or C 1-12 Halohydrocarbyl, UV photocurable coating composition. Claim 4 In claim 1, the ultraviolet photocurable poly(polyphenylene ether) oligomer comprises a polysiloxane block of the following chemical formula. Here, n is an ultraviolet photo-curable coating composition having an average value of 5-100, or 10-80 or 10-60. Claim 5 A UV photocurable coating composition according to claim 1, wherein the poly(polyphenylene ether) oligomer comprises at least one terminal (meth)acrylate group. Claim 6 In claim 1, the ultraviolet photocurable poly(polyphenylene ether) is of the following chemical formula Includes and here Q 1 and Q 2 Each case independently involves halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; Q 3 and Q 4 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; x and y are each independently 0–30; and L is the following chemical formula (3) and here R 3 , R 4 , R 5 , and R 6 Each case independently involves hydrogen, halogen, unsubstituted, or substituted C 1-6 Primary or secondary hydrocarbil, C 1-6 Hydrocarbilthio, C 1-6 Hydrocarbiloxy, or C 2-6 It is a halohydrocarbyloxy, where at least two carbon atoms separate a halogen and an oxygen atom; w is 0 or 1; and R 10 is methyl or hydrogen; and Y is And here R 7 Each case is independently hydrogen or C 1-6 It is hydrocarbil, and R 8 and R 9 Each case of independently hydrogen, C 1-6 Hydrocarbyl, UV photo-curable coating composition. Claim 7 In claim 1, the ultraviolet photocurable poly(polyphenylene ether) oligomer has the following chemical formula And here Q 5 and Q 6 Each case of is independently methyl, cyclohexyl, phenyl, di-n-butylaminomethyl, or morpholinomethyl; each case of a and b is independently 0-20, provided that the sum of a and b is at least 2; R 10 Each case is a UV photo-curable coating composition, which is methyl or hydrogen. Claim 8 A UV photocurable coating composition according to claim 1, wherein the UV photocurable poly(polyphenylene ether) has a number average molecular weight of 500-7,000 g / mol and a weight average molecular weight of 500-15,000 g / mol as measured by gel permeation chromatography using a polystyrene standard. Claim 9 A UV photocurable coating composition according to claim 1, wherein the UV photocurable monomer, oligomer, or polymer is a (meth)acrylate. Claim 10 A UV-curable coating composition according to claim 9, wherein the curable monomer, oligomer, or polymer is dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, polyether acrylate, amine-modified polyether acrylate, polyester acrylate, polyurethane acrylate, aliphatic urethane acrylate, or a combination thereof. Claim 11 A UV photocurable coating composition according to claim 1, comprising 20-39.9 weight percent of a UV photocurable poly(polyphenylene ether) oligomer; 60-79.9 weight percent of a UV photocurable monomer, oligomer, polymer, or combination thereof; and 0.1-3 weight percent of a photoinitiator. Claim 12 In claim 1, 20-39.9 weight percent of meth(acrylate)-terminated capped poly(polyphenylene ether) oligomer; 60-79.9 weight percent of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, polyether acrylate, amine-modified polyether acrylate, polyester acrylate, polyurethane acrylate, aliphatic urethane acrylate, isobornyl acrylate, isobornyl methacrylate, or a combination thereof; UV photo-curable coating composition comprising 0.1-3 weight percent of photoinitiator. Claim 13 A cured product of the curable composition of claim 1, having a glass transition temperature of 120-200°C; an absorption rate of 1 weight percent or less measured after immersion in deionized water at 25°C for 24 hours; or a combination thereof. Claim 14 A method for forming a coated substrate, the method comprising: providing a substrate; providing a coated substrate by coating the substrate with an ultraviolet photocurable coating composition of any one of claims 1 to 12; and curing the coating composition with ultraviolet light. Claim 15 An article comprising a thermosetting composition according to paragraph 13, wherein the coating is in the form of a layer, an encapsulating adhesive, a sealant, a molding coating, a prepreg, a casing, or a laminate.

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