TWI490251B - Containing unsaturated polyphenylene ether resin and its composition, thermosetting resin composition - Google Patents
Containing unsaturated polyphenylene ether resin and its composition, thermosetting resin composition Download PDFInfo
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本發明提供一種含不飽和基聚苯醚樹脂及其組成物、熱固化樹脂組成物，該含不飽和基聚苯醚樹脂含有一個以上烯丙基官能基，可以再含有乙烯基官能基，該含不飽和基聚苯醚樹脂數量平均分子量在2500以上時，有高溶劑溶解度，溶劑選擇多元化、高樹脂相溶性之特性，因此提高聚苯醚樹脂分子量，同時也達到低介電常數、低介電損失、高玻璃轉移溫度、易加工性之目的。The present invention provides an unsaturated group-containing polyphenylene ether resin and a composition thereof, and a thermosetting resin composition. The unsaturated group-containing polyphenylene ether resin contains one or more allyl functional groups, and may further contain a vinyl functional group. When the number average molecular weight of the unsaturated polyphenylene ether resin is more than 2,500, the solvent solubility is high, the solvent is diversified, and the resin is highly soluble, so that the molecular weight of the polyphenylene ether resin is increased, and the low dielectric constant and low are also achieved. Dielectric loss, high glass transition temperature, easy processing.
本發明在於提供一種含不飽和基聚苯醚樹脂及其組成物、熱固化樹脂組成物，可以經由熱固化達到低介電常數、低介電損失、高玻璃轉移溫度，可應用於積層板、UV塗料、光阻劑、半導體封裝材、塗布劑、玻璃纖維預浸物、印刷電路板、覆銅積層板、彩色濾光片、顯示器密封等不同用途。The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, etc.
熱可塑性聚苯醚樹脂具有優異的電氣特性及良好的耐酸鹼特性，但應用在印刷電路板基材時，耐高溫性、耐溶劑性不佳，溶解度低、高結晶性、熔融黏度高，熔點與玻璃轉移點溫度相差甚小，使得聚苯醚樹脂在電子材料上應用受到限制。The thermoplastic polyphenylene ether resin has excellent electrical properties and good acid and alkali resistance, but when applied to a printed circuit board substrate, it has high temperature resistance and solvent resistance, low solubility, high crystallinity, and high melt viscosity. The temperature difference between the melting point and the glass transition point is very small, which limits the application of polyphenylene ether resin to electronic materials.
傳統聚苯醚樹脂分子量愈高，電性愈佳，但溶解性愈差，一般甲苯是最佳溶劑，常見改善聚苯醚樹脂溶解度方法有：The higher the molecular weight of the traditional polyphenylene ether resin, the better the electrical property, but the worse the solubility, the general toluene is the best solvent, and the common methods for improving the solubility of the polyphenylene ether resin are:
1.低分子量化：聚苯醚樹脂數量平均分子量控制在2500以下，如中華民國專利I363770號、583221號，該低分子量聚苯醚樹脂，可完全溶解於甲苯，部份溶解於甲基乙基酮。1. Low molecular weight: The number average molecular weight of the polyphenylene ether resin is controlled below 2,500. For example, the Republic of China Patent No. I363770, No. 583221, the low molecular weight polyphenylene ether resin can be completely dissolved in toluene and partially dissolved in methyl ethyl group. ketone.
2.官能基化：環氧基聚苯醚樹脂，如中華民國專利I227249號；丙烯酸酯聚苯醚樹脂，如中華民國專利I264440號；亞甲基苯乙烯基聚苯醚樹脂，如中華民國專利279418號、250995號、357420號、342886號，雖然可以改善溶解度，但分子量仍限制在數量平均分子量2500以下，當數量平均分子量在2500以上時溶劑溶解性仍不盡理想，不能滿足產業殷切需求。2. Functionalization: epoxy polyphenylene ether resin, such as the Republic of China patent I227249; acrylate polyphenylene ether resin, such as the Republic of China patent I264440; methylene styrene-based polyphenylene ether resin, such as the Republic of China patent 279418, 250995, 357420, and 342886, although the solubility can be improved, the molecular weight is still limited to the number average molecular weight of 2,500 or less. When the number average molecular weight is above 2,500, the solvent solubility is still not satisfactory, and the industrial demand is not satisfied.
目前公知技術之聚苯醚樹脂，其顯然存在的問題在於無法達到數量平均分子量在2500以上時，具高溶解度、多元化溶劑選擇、樹脂相溶性高之要求，其仍不足以滿足產業實際需求。The polyphenylene ether resin of the prior art has a problem in that it cannot meet the requirement of high solubility, diversified solvent selection, and high resin compatibility when the number average molecular weight is more than 2,500, which is still insufficient to meet the actual needs of the industry.
本發明所欲解決之問題，在於提供一種含不飽和基聚苯醚樹脂，其含有一個以上烯丙基官能基，可以再含有乙烯基官能基，該含不飽和基聚苯醚樹脂數量平均分子量在2500以上時，有高溶劑溶解度，多元化溶劑選擇、高樹脂相溶性之要求，當聚苯醚樹脂分子量提高時，同時也達到低介電常數、低介電損失、高玻璃轉移溫度、易加工性之目的The problem to be solved by the present invention is to provide an unsaturated polyphenylene ether resin containing one or more allyl functional groups, which may further contain a vinyl functional group, and the number average molecular weight of the unsaturated polyphenylene ether-containing resin Above 2500, it has high solvent solubility, diversified solvent selection, high resin compatibility, and when the molecular weight of polyphenylene ether resin increases, it also achieves low dielectric constant, low dielectric loss, high glass transition temperature, and easy Processability
鑑於上述問題，本發明之解決問題之技術手段在提供一種含不飽和基聚苯醚樹脂，其化學結構如式(一)所示：
本發明提供一種含不飽和基聚苯醚樹脂組成物，其係至少包含一種含不飽和基聚苯醚樹脂；本發明提供一種熱固化樹脂組成物，其係包含一種含不飽和基聚苯醚樹脂組成物及熱聚合起始劑。The present invention provides an unsaturated polyphenylene ether-containing resin composition comprising at least one unsaturated polyphenylene ether-containing resin; the present invention provides a thermosetting resin composition comprising an unsaturated polyphenylene ether Resin composition and thermal polymerization initiator.
對照先前技之功效，本發明提供一種含不飽和基聚苯醚樹脂，其數量平均分子量在2500以上時，有高溶劑溶解度，溶劑選擇多元化、 高樹脂相溶性之特性，當聚苯醚樹脂分子量提高時，同時也達到低介電常數、低介電損失、高玻璃轉移溫度、易加工性之目的。Compared with the efficacy of the prior art, the present invention provides an unsaturated polyphenylene ether resin having a high solvent solubility and a solvent selection diversity when the number average molecular weight is above 2,500. The high resin compatibility property, when the molecular weight of the polyphenylene ether resin is increased, also achieves the purposes of low dielectric constant, low dielectric loss, high glass transition temperature, and easy processability.
本發明在於提供一種含不飽和基聚苯醚樹脂及其組成物、熱固化樹脂組成物，可以經由熱固化達到低介電常數、低介電損失、高玻璃轉移溫度，可應用於積層板、UV塗料、光阻劑、半導體封裝材、塗布劑、玻璃纖維預浸物、印刷電路板、覆銅積層板、彩色濾光片、顯示器密封等不同用途。The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, etc.
本發明之目的在提供一種含不飽和基聚苯醚樹脂，其化學結構如式(一)所示：
本發明提供一種含不飽和基聚苯醚樹脂，其中X之單體可以來自於：二氯甲基苯、二氯甲基聯苯、二氯甲基苯醚等；其中Y之單體為含烯丙基雙酚類可以來自於：二烯丙基酚雙酚A、二烯丙基酚雙酚B、二烯丙基酚雙酚F、二烯丙基酚雙酚M、二烯丙基酚雙酚Z、甲基烯丙基酚雙酚A、甲基烯丙基酚雙酚B、甲基烯丙基酚雙酚F、甲基烯丙基酚雙酚M、甲基烯丙基酚雙酚Z、丁基烯丙基酚雙酚A、丁基烯丙基酚雙酚B、丁基烯丙基酚雙酚F、丁基烯丙基酚雙酚M、丁基烯丙基酚雙酚Z、苯基烯丙基酚雙酚A、苯基烯丙基酚雙酚B、苯基烯丙基酚雙酚F、苯基烯丙基酚雙酚M、苯基烯丙基酚雙酚Z等；其中分子中乙烯基單體可以來自於：鄰氯甲基苯乙烯、間氯甲基苯乙烯、對氯甲基苯乙烯之一或群族；本發明合成一種含不飽和基聚苯醚樹脂使用之含烯丙基單酚類為鄰烯丙基酚；本發明合成一種含不飽和基 聚苯醚樹脂使用之酚基聚苯醚，其數量平均分子量在500~7000較佳，其數量平均分子量在2500~5000最佳；本發明合成一種含不飽和基聚苯醚樹脂使用之酚基聚苯醚，可以是單酚基聚苯醚、雙酚基聚苯醚；本發明合成一種含不飽和基聚苯醚樹脂在溶劑中以鹼進行脫鹽縮合醚化反應該鹼包括：甲醇鈉、氫氧化鈉、氫氧化鉀、三甲胺三乙胺、三丁胺、碳酸鈉、碳酸鉀、乙醇鈉等，較佳縮合溫度為20℃~150℃，可以加入四級銨鹽或四級磷鹽之相轉移劑或不加相轉移劑等。The present invention provides an unsaturated polyphenylene ether resin, wherein the monomer of X can be derived from: dichloromethylbenzene, dichloromethylbiphenyl, dichloromethylphenyl ether, etc.; wherein the monomer of Y is contained Allyl bisphenols can be derived from: diallyl phenol bisphenol A, diallyl phenol bisphenol B, diallyl phenol bisphenol F, diallyl phenol bisphenol M, diallyl Phenol bisphenol Z, methallyl phenol bisphenol A, methallyl phenol bisphenol B, methallyl phenol bisphenol F, methallyl phenol bisphenol M, methallyl Phenol bisphenol Z, butyl allyl phenol bisphenol A, butyl allyl phenol bisphenol B, butyl allyl phenol bisphenol F, butyl allyl phenol bisphenol M, butyl allyl Phenol bisphenol Z, phenyl allyl phenol bisphenol A, phenyl allyl phenol bisphenol B, phenyl allyl phenol bisphenol F, phenyl allyl phenol bisphenol M, phenyl allyl Phenol bisphenol Z or the like; wherein the vinyl monomer in the molecule may be derived from: one or a group of o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene; the invention synthesizes an unsaturated group The allyl monophenols used in the polyphenylene ether resin are o-allyl phenols; Synthesis of an unsaturated group The phenolic polyphenylene ether used in the polyphenylene ether resin preferably has a number average molecular weight of 500 to 7,000, and the number average molecular weight thereof is preferably 2500 to 5000. The present invention synthesizes a phenol group used for an unsaturated polyphenylene ether resin. The polyphenylene ether may be a monophenolic polyphenylene ether or a bisphenol polyphenylene ether; the present invention synthesizes an unsaturated polyphenylene ether resin in a solvent to perform a desalting condensation etherification reaction with a base. The base includes: sodium methoxide, Sodium hydroxide, potassium hydroxide, trimethylamine triethylamine, tributylamine, sodium carbonate, potassium carbonate, sodium ethoxide, etc., preferably having a condensation temperature of 20 ° C to 150 ° C, may be added with a quaternary ammonium salt or a quaternary phosphonium salt The phase transfer agent or the phase transfer agent is not added.
本發明合成一種含不飽和基聚苯醚樹脂使用之有機溶劑至少包括含一選自：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2吡咯啶酮、二甲基亞碸、二甲基磷醯胺、甲乙基酮、甲基異丁基酮、二異丁基酮、甲基異戊基酮、環戊酮、環己酮、二異丁酮、四氫夫喃、四甲脲、二咢烷、γ-丁內酯、氯仿、二氯甲烷、二乙二醇單己基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、乙酸正丁酯、二乙二醇單丁基醚乙酸酯、甲苯、二甲苯等。The organic solvent used in the synthesis of an unsaturated polyphenylene ether resin of the present invention comprises at least one selected from the group consisting of: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- 2 pyrrolidone, dimethyl hydrazine, dimethyl phosphoniumamine, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone, Diisobutyl ketone, tetrahydrofuran, tetramethyl urea, dioxane, γ-butyrolactone, chloroform, dichloromethane, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, n-butyl acetate, diethylene glycol monobutyl ether acetate, toluene, xylene, and the like.
本發明提供一種熱固化樹脂組成物，其係包含一種含不飽和基聚苯醚樹脂及熱聚合起始劑，其使用之熱聚合起始劑包括：偶氮二異丁腈、偶氮二(2-異丙基)丁腈、偶氮二異庚腈、過氧化二苯甲醯、過氧化乙醯異丁醯、過氧化二乙醯、過氧化(2,4-二氯苯甲醯)、過氧化(2-二甲基苯甲醯)、過氧化十二醯、過氧化二碳酸二異丙酯、過氧化雙(3,5,5-三甲基己醯)、過氧化環己酮、過氧化甲乙酮、過氧化二碳酸二環己丙酯、過氧化二碳酸二環己酯、過氧化二碳酸二(4-叔丁基環己酯)、過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸雙(2-苯基乙氧基)酯、過氧化二碳酸雙十六烷基酯、過氧 化苯甲酸特丁酯、過氧化苯乙酸特丁酯、過氧乙酸、過氧化特戊酸叔丁酯、過氧化特戊酸叔己酯、過氧化新癸酸異丙苯酯、過氧化苯甲酸叔丁酯、叔丁基過氧化氫、叔丁基過氧化苯甲酸酯、叔丁基過氧化特戊酸酯、異丙苯過氧化氫、對孟烷過氧化氫、過氧化二特丁基、過氧化二異丙苯、過氧化二叔丁基、過氧化氫、過硫酸銨、過硫酸鉀、過氧化物-烷基金屬、氧-烷基金屬等。The present invention provides a thermosetting resin composition comprising an unsaturated polyphenylene ether resin and a thermal polymerization initiator, and the thermal polymerization initiator used therein comprises: azobisisobutyronitrile, azobis ( 2-isopropyl)butyronitrile, azobisisoheptanenitrile, benzammonium peroxide, isobutyl hydrazine peroxide, diethyl hydrazine peroxide, peroxidation (2,4-dichlorobenzidine) , (2-dimethylbenzhydrazide) peroxide, dodecyl peroxide, diisopropyl peroxydicarbonate, bis(3,5,5-trimethylhexyl) peroxide, peroxycyclohexane Ketone, methyl ethyl ketone peroxide, dicyclohexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl peroxydicarbonate), di(2-diethyl peroxydicarbonate) Ethyl) ester, bis(2-phenylethoxy) peroxydicarbonate, dihexadecyl peroxydicarbonate, peroxygen Butyl benzoate, tert-butyl benzoate, peroxyacetic acid, t-butyl peroxypivalate, t-hexyl peroxypivalate, cumene peroxy neodecanoate, benzoyl peroxide Tert-butyl formate, tert-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, cumene hydroperoxide, para-hydrogen peroxide, peroxide Butyl, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkyl metal, oxy-alkyl metal, and the like.
本發明提供一種一種含不飽和基聚苯醚樹脂組成物，其係至少包含一種含不飽和基聚苯醚樹脂，可再包含無機纖維補強材包括：E玻璃纖維、NE玻璃纖維、D玻璃纖維、S玻璃纖維、T玻璃纖維、矽氧玻璃纖維、碳纖維、鋁纖維、碳化矽纖維、石棉、岩絨其織物或非織物或其混合物；有機纖維補強材包括：全芳香族聚醯胺纖維、聚醯亞胺纖維、液晶聚酯、聚酯纖維、含氟纖維、聚苯并咢坐纖維、棉纖維、亞麻纖維其織物或非織物或其混合物。The present invention provides an unsaturated polyphenylene ether-containing resin composition comprising at least one unsaturated polyphenylene ether resin, and further comprising inorganic fiber reinforcing materials including: E glass fiber, NE glass fiber, and D glass fiber. , S glass fiber, T glass fiber, xenon glass fiber, carbon fiber, aluminum fiber, tantalum carbide fiber, asbestos, rock wool fabric or non-woven fabric or a mixture thereof; organic fiber reinforcing material comprises: wholly aromatic polyamide fiber, Polyimide fibers, liquid crystal polyesters, polyester fibers, fluorine-containing fibers, polybenzopyrene fibers, cotton fibers, flax fibers, woven or non-woven fabrics or mixtures thereof.
本發明提供一種一種含不飽和基聚苯醚樹脂組成物，其係至少包含一種含不飽和基聚苯醚樹脂組成物，可再包含無機填充劑包括：矽氧、融合矽氧、合成矽氧、球狀矽氧、中空矽氧、勃姆石、水菱鎂礦、碳酸鈣鎂石、滑石、煅燒滑石、高嶺土、矽礦石、氫氧化鋁、非鹼性玻璃、熔融玻璃碳化矽、氧化鋁、氮化鋁、氧化矽鋁、氮化硼、二氧化鈦、雲母、合成雲母、石膏、碳酸鈣、碳酸鎂、氫氧化鎂、氧化鎂等。The present invention provides a composition containing an unsaturated polyphenylene ether resin, which comprises at least one unsaturated polyphenylene ether resin composition, and further comprises an inorganic filler comprising: helium oxygen, fusion helium oxygen, synthetic helium oxygen , globular helium oxygen, hollow helium oxygen, boehmite, hydromagnesite, calcium carbonate, talc, calcined talc, kaolin, strontium ore, aluminum hydroxide, non-alkaline glass, molten glass tantalum carbide, alumina , aluminum nitride, yttrium aluminum oxide, boron nitride, titanium dioxide, mica, synthetic mica, gypsum, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, and the like.
將3,3’5,5’-四甲基-4,4’-雙酚F 12.8g(0.05mole)、聚苯醚 130g(Asahi製S202A)、甲苯300g加入裝有機械攪拌、冷凝管之四口反應瓶中，加熱至80℃~90℃，分批加入過氧化苯甲醯2g，反應24小時後水洗三次，減壓蒸餾脫除甲苯及水份，可得到雙官能酚基聚苯醚P-1，以FT-IR測酚性OH當量重為1305g/mole，以GPC測數量平均分子量為3735。3,3'5,5'-tetramethyl-4,4'-bisphenol F 12.8 g (0.05 mole), polyphenylene ether 130g (Ssa A made by Asahi) and 300g of toluene were added to a four-reaction reaction flask equipped with mechanical stirring and condensation tube, heated to 80 ° C ~ 90 ° C, 2 g of benzamidine peroxide was added in batches, and washed three times after 24 hours. The toluene and water were removed by pressure distillation to obtain a bifunctional phenolic polyphenylene ether P-1 having a phenolic OH equivalent weight of 1,305 g/mole by FT-IR and a number average molecular weight of 3,735 by GPC.
將單官能酚基聚苯醚235.6g(GE製SA-120/酚性OH當量重為2356g/mole)、4,4’-二氯甲基聯苯24.5g(0.1mole)，加入二甲基甲醯胺300g溶解之，再分批加入甲醇鈉5.4g(0.10mole)，溫度控制50℃~55℃，反應5小時後，加入2,2’-二烯丙基雙酚A 30.8g(0.1mole)、氯甲基苯乙烯15.25g(0.1mole)，再分批加入甲醇鈉11.88g(0.22mole)，溫度控制45℃~50℃，反應8小時後，將反應溶液滴入水中以獲得固體，再以蒸餾水水洗三次，甲醇洗淨一次後乾燥，可得到單乙烯基聚苯醚SA120-V，收率96%，以GPC測數量平均分子量為4217，以離子層析儀測總氯含量為70ppm。235.6 g of monofunctional phenolic polyphenylene ether (SA-120/phenolic OH equivalent weight of 2356 g/mole made by GE) and 24.5 g (0.1 mole) of 4,4'-dichloromethylbiphenyl were added to dimethyl group. 300 g of methotrexate was dissolved, and 5.4 g (0.10 mole) of sodium methoxide was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After 5 hours of reaction, 2,2'-diallyl bisphenol A 30.8 g (0.1) was added. Mole), chloromethylstyrene 15.25g (0.1mole), and then added 11.88g (0.22mole) of sodium methoxide in batches, the temperature is controlled at 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution is dropped into water to obtain a solid Then, it is washed three times with distilled water, and once washed with methanol, the monovinyl polyphenylene ether SA120-V is obtained in a yield of 96%. The average molecular weight measured by GPC is 4217, and the total chlorine content measured by ion chromatography is 70ppm.
將聚苯醚P1/261.0g、4,4’-二氯甲基聯苯24.5g(0.1mole)、2,2’-二烯丙基雙酚A 30.8g(0.1mole)，加入二甲基甲醯胺350g溶解之，再分批加入甲醇鈉10.8g(0.20mole)，溫度控制50℃~55℃，反應5小時後，加入氯甲基苯乙烯30.5g(0.2mole)，再分批加入甲醇鈉11.88g(0.22mole)，溫度控制45℃~50℃，反應8小時後，將反應溶液滴入水中以獲得固體，再以蒸餾水水洗三次，甲醇洗淨一次後乾燥，可得到雙乙烯基聚苯醚PI-2V，收率95 %，以GPC測數量平均分子量為4760，以離子層析儀測總氯含量為80ppm。Polyphenylene ether P1/261.0g, 4,4'-dichloromethylbiphenyl 24.5g (0.1mole), 2,2'-diallyl bisphenol A 30.8g (0.1mole), added to dimethyl Melamine 350g was dissolved, and then added sodium methoxide 10.8g (0.20mole) in batches, temperature control 50 ° C ~ 55 ° C, after 5 hours of reaction, add chloromethyl styrene 30.5g (0.2mole), and then added in batches Sodium methoxide 11.88g (0.22mole), temperature control 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution was dripped into water to obtain a solid, and then washed three times with distilled water, methanol washed once and dried to obtain a double vinyl Polyphenylene ether PI-2V, yield 95 %, the average molecular weight measured by GPC was 4760, and the total chlorine content by ion chromatography was 80 ppm.
將聚苯醚P1/261.0g、4,4’-二氯甲基聯苯24.5g(0.1mole)、2-烯丙基酚13.4g(0.1mole)，加入二甲基甲醯胺350g溶解之，再分批加入甲醇鈉10.8g(0.20mole)，溫度控制50℃~55℃，反應5小時後，加入氯甲基苯乙烯15.25g(0.1mole)，再分批加入甲醇鈉5.94g(0.11mole)，溫度控制45℃~50℃，反應8小時後，將反應溶液滴入水中以獲得固體，再以蒸餾水水洗三次，甲醇洗淨一次後乾燥，可得到雙乙烯基聚苯醚PI-VA，收率96%，以GPC測數量平均分子量為4380，以離子層析儀測總氯含量為76ppm。Polyphenylene ether P1/261.0g, 4,4'-dichloromethylbiphenyl 24.5g (0.1mole), 2-allylphenol 13.4g (0.1mole), added to dimethylformamide 350g dissolved Then add 10.8g (0.20mole) of sodium methoxide in batches, control the temperature from 50 °C to 55 °C, and react for 5 hours, add 15.25g (0.1mole) of chloromethylstyrene, and add 5.94g (0.11) of sodium methoxide in batches. Mole), temperature control 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution was dropped into water to obtain a solid, and then washed three times with distilled water, methanol washed once and dried to obtain divinyl polyphenylene ether PI-VA The yield was 96%, the average molecular weight measured by GPC was 4380, and the total chlorine content by ion chromatography was 76 ppm.
將聚苯醚P1/261.0g、對二氯甲基苯35.0g(0.2mole)，加入二甲基甲醯胺450g溶解之，再分批加入甲醇鈉10.8g(0.20mole)，溫度控制50℃~55℃，反應5小時後，加入2,2’-二烯丙基雙酚A 61.6g(0.2mole)，再分批加入甲醇鈉10.8g(0.20mole)，溫度控制50℃~55℃，反應5小時後，加入對二氯甲基苯35.0g(0.2mole)，再分批加入甲醇鈉10.8g(0.20mole)，溫度控制50℃~55℃，反應5小時後，加入2-烯丙基酚26.8g(0.2mole)，再分批加入甲醇鈉15.21g(0.28mole)，溫度控制45℃~50℃，反應8小時後，將反應溶液滴入水中以獲得固體，再以蒸餾水水洗三次，甲醇洗淨一次後乾燥，可得到雙烯丙基聚苯醚PI-2A，收率94%，以GPC測數量平均分子量為5590，以離子層析儀測總氯含量為96ppm。Polyphenylene ether P1/261.0g, p-dichloromethylbenzene 35.0g (0.2mole), dissolved in dimethylformamide 450g, and then added sodium methoxide 10.8g (0.20mole) in batches, temperature control 50 ° C After ~5 ° C, 5 hours after the reaction, 2,2'-diallyl bisphenol A 61.6 g (0.2 mole) was added, and then sodium methoxide 10.8 g (0.20 mole) was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After reacting for 5 hours, 35.0 g (0.2 mole) of p-dichloromethylbenzene was added, and 10.8 g (0.20 mole) of sodium methoxide was added in portions, and the temperature was controlled at 50 ° C to 55 ° C. After reacting for 5 hours, 2-allyl was added. 26.8g (0.2mole) of phenol, adding 15.21g (0.28mole) of sodium methoxide in batches, the temperature is controlled at 45 ° C ~ 50 ° C, after 8 hours of reaction, the reaction solution is dripped into water to obtain a solid, and then washed three times with distilled water. After methanol was washed once and dried, bisallyl polyphenylene ether PI-2A was obtained in a yield of 94%. The average molecular weight measured by GPC was 5590, and the total chlorine content by ion chromatography was 96 ppm.
實施例6~9依序為：聚苯醚SA120-V、P1-2V、P1-VA、P1-2A各取10g及過氧化二異丙苯0.01g ，溶於10g甲苯中，在150℃下烘烤2小時，再150℃下脫氣壓鑄成形3小時，最後以220℃下固化6小時，得到固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表一所示。Examples 6 to 9 are: 10 g of polyphenylene ether SA120-V, P1-2V, P1-VA, and P1-2A, and 0.01 g of dicumyl peroxide , dissolved in 10 g of toluene at 150 ° C. After baking for 2 hours, the pressure was cast at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours to obtain a cured product. The glass transition temperature, dielectric constant and dielectric loss were measured. The data are shown in Table 1. .
將市售雙乙烯基聚苯醚〔OPE-St-2200/MGC製〕取10g，在150℃下脫氣壓鑄成形3小時，最後以220℃下固化6小時，得到固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表一所示。10 g of commercially available divinyl polyphenylene ether [OPE-St-2200/MGC] was taken, and subjected to degassing molding at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours to obtain a cured product, and the glass transition was measured. Temperature, dielectric constant, and dielectric loss are shown in Table 1.
將聚苯醚P1、SA120-V、P1-2V、P1-VA、PI-2A、OPE-St-2200各取10g，分別溶於10g之甲苯(TOL)、10g之甲基乙基酮(MEK)、10g之丙二醇甲醚乙酸酯(PMA)，觀察其溶解性，其數據如表二所示。10 g of each of polyphenylene ether P1, SA120-V, P1-2V, P1-VA, PI-2A, and OPE-St-2200 were dissolved in 10 g of toluene (TOL) and 10 g of methyl ethyl ketone (MEK). 10 g of propylene glycol methyl ether acetate (PMA) was observed for solubility, and the data are shown in Table 2.
○：表示 完全溶解 ○: a case completely dissolved
△：表示 部份溶解 △: indicates partial dissolution
×：表示 不溶解 ×: indicates that it does not dissolve
實施例11~14依序為：聚苯醚SA120-V、P1-2V、P1-VA、P1-2A各取50g及二(3-乙基-5-甲基-4-順丁烯醯亞胺苯基)甲烷〔BMI-5100/大和化學製〕50g ，經研磨後混合均勻，在150℃下烘烤2小時，再150℃下脫氣壓鑄成形3小時，最後以220℃下固化6小時，得到固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表三所示。Examples 11 to 14 were sequentially obtained: 50 g of polyphenylene ether SA120-V, P1-2V, P1-VA, and P1-2A, and bis(3-ethyl-5-methyl-4-cis-butenylene) Amine phenyl)methane [BMI-5100/Dahe Chemical] 50g , uniformly mixed after grinding, baked at 150 ° C for 2 hours, then degassed at 150 ° C for 3 hours, and finally cured at 220 ° C for 6 hours The cured product was obtained, and its glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 3.
將二(3-乙基-5-甲基-4-順丁烯醯亞胺苯基)甲烷〔BMI-5100/大和化學製〕100g ，經研磨均勻，在150℃下烘烤2小時，再150℃下脫氣壓鑄成形3小時，最後以220℃下固化6小時，得到固化物，測量其玻璃轉移溫度、介電常數、介電損失，其數據如表三所示。 100 g of bis(3-ethyl-5-methyl-4-succinimide phenyl)methane [BMI-5100/Dahe Chemical] was uniformly ground and baked at 150 ° C for 2 hours. After degassing at 150 ° C for 3 hours, and finally curing at 220 ° C for 6 hours, a cured product was obtained, and the glass transition temperature, dielectric constant, and dielectric loss were measured, and the data are shown in Table 3.
由表一可知實施例6~9之SA120-V、PI-2V、PI-VA、PI-2A相對與比較例1之OPE-St-2200，加入熱聚合起始劑，經熱固化表現出較高之玻璃轉移溫度、較低之介電常數、較低之介電損失；由表二可知SA120-V、PI-2V、PI-VA、PI-2A之數量平均分子量大於PI、OPE-St-2200之數量平均分子量，溶劑溶解性SA120-V、PI-2V、PI-VA、PI-2A優於PI、OPE-St-2200； 由表三可知實施例11~14中SA120-V、PI-2V、PI-VA、PI-2A與BMI-5100共混固化後相對與比較例2單獨BMI-5100固化，表現出較低之介電常數、較低之介電損失特性。It can be seen from Table 1 that SA120-V, PI-2V, PI-VA, and PI-2A of Examples 6 to 9 are relatively compared with OPE-St-2200 of Comparative Example 1, and a thermal polymerization initiator is added, which is thermally cured. High glass transition temperature, lower dielectric constant, lower dielectric loss; Table 2 shows that the number average molecular weight of SA120-V, PI-2V, PI-VA, PI-2A is greater than PI, OPE-St- The average molecular weight of 2200, solvent solubility SA120-V, PI-2V, PI-VA, PI-2A is better than PI, OPE-St-2200; It can be seen from Table 3 that the blending of SA120-V, PI-2V, PI-VA, PI-2A and BMI-5100 in Examples 11-14 is relatively solidified with that of Comparative Example 2 alone BMI-5100, showing a lower level. Electrical constant, low dielectric loss characteristics.
本發明在提供一種含不飽和基聚苯醚樹脂及其組成物、熱固化樹脂組成物，可以經由熱固化達到低介電常數、低介電損失、高玻璃轉移溫度，可應用於積層板、UV塗料、光阻劑、半導體封裝材、塗布劑、玻璃纖維預浸物、印刷電路板、覆銅積層板、彩色濾光片、顯示器密封等不同用途。The invention provides an unsaturated polyphenylene ether resin and a composition thereof, and a thermosetting resin composition, which can achieve low dielectric constant, low dielectric loss and high glass transition temperature through thermal curing, and can be applied to laminated boards, UV coatings, photoresists, semiconductor packaging materials, coating agents, glass fiber prepregs, printed circuit boards, copper clad laminates, color filters, display seals, etc.
本發明已經配合上述具體實施例、比較例描述，熟悉本項技藝人士將可基於以上描述作出多種變化，不因此而限制本發明之申請專利範圍。The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.
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| US20090247032A1 (en) * | 2008-04-01 | 2009-10-01 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg and metal-foil-clad laminate |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
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| US20090247032A1 (en) * | 2008-04-01 | 2009-10-01 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg and metal-foil-clad laminate |
| CN102807658A (en) * | 2012-08-09 | 2012-12-05 | 广东生益科技股份有限公司 | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite |
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