CN104447325A - Ultraviolet-curable yellowing-resistant epoxy acrylate and preparation method thereof - Google Patents

Ultraviolet-curable yellowing-resistant epoxy acrylate and preparation method thereof Download PDF

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CN104447325A
CN104447325A CN 201410632414 CN201410632414A CN104447325A CN 104447325 A CN104447325 A CN 104447325A CN 201410632414 CN201410632414 CN 201410632414 CN 201410632414 A CN201410632414 A CN 201410632414A CN 104447325 A CN104447325 A CN 104447325A
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reactor
acrylate
step
temperature
yellowing
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林星星
颜极
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洞头县恒立印刷材料有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10Epoxy resins modified by unsaturated compounds

Abstract

The invention relates to ultraviolet-curable yellowing-resistant epoxy acrylate and a preparation method thereof. The preparation method comprises the following steps: adding dicarboxylic anhydride, hydroxyethyl acrylate or hydroxyethyl methacrylate, a catalyst, an antioxidant and a polymerization inhibitor into a reactor, starting stirring and heating, controlling the temperature of the materials in the reactor to be 95-100 DEG C, and cooling when the acid value of the materials in the reactor meets a requirement; when the temperature of the materials in the reactor is lowered to 80 DEG C, stopping cooling, then adding glycidyl acrylate or glycidyl methacrylate and a catalyst; continuously heating the materials in the reactor, controlling the temperature to be 108-112 DEG C, and vacuumizing for 30 minutes when the acid value of the materials in the reactor is less than or equal to 5mgKOH/g, cooling and adding the polymerization inhibitor; and when the temperature of the materials in the reactor is lowered to 70 DEG C, filtering and discharging. The ultraviolet-curable yellowing-resistant epoxy acrylate provided by the invention has the advantages that the synthetic method is simple, the used raw materials are low in price, the product is good in weathering resistance and appropriate in price, and the viscosity of a finished product is low.

Description

一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法 An anti-yellowing UV-curable epoxy acrylate and preparation method

技术领域 FIELD

[0001] 本发明涉及一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法。 [0001] The present invention relates to an epoxy acrylate of yellowing and method for preparing anti-UV-curable.

背景技术 Background technique

[0002] 紫外光固化树脂是一种分子量相对较低的感光性树脂,具有可以进行光固化反应的基团,如各类不饱和双键或环氧基等。 [0002] The ultraviolet-curable resin is a relatively low molecular weight of a photosensitive resin having a group of photo-curing reaction, such as various types of unsaturated double bond or an epoxy group. 在光固化最终的产品各组分中,紫外光固化树脂是光固化的主体,它的性能基本决定了固化后材料的主要性能,因此,紫外光固化树脂的合成和选择无疑是光固化产品配方设计的重要环节。 In the photocuring the final product of the components, the UV curable resin is a photo-curable body, its performance substantially determines the main properties of the cured material, and therefore, ultraviolet-curable resin is undoubtedly the choice of synthesis and light-cured product formulations an important part of the design.

[0003] 自从80年代初我国紫外线光固化(UV)开始研究,到95年才真正进入我国,所有的产品和原材料都依靠进口。 [0003] Since the early 1980s of ultraviolet light-cured (UV) began to study, to 95 years to truly enter our country, all products and raw materials are imported. 然而在这近二十年的时间里;紫外线光固化行业得到迅速的发展,根据中国辐射固化协会不完全统计,到2012年底中国紫外线光固化产值每年的增长率都超过20%。 However, in the nearly two decades of time; UV light curing industry developed rapidly, according to the China Association of radiation curing incomplete statistics, by the end of 2012 the output value of China ultraviolet light curing annual growth rate of over 20%. 由于这几年紫外线光固化行业应用的范围在不断的拓宽,技术在不断的成熟,以及社会各界人士对环保的日益重视,对经济效益的关注,对能源的节约,使光固化的优势得以明显的体现。 As the ultraviolet light-cured in recent years in the range of industry applications continue to broaden, the technology continues to mature, and the community's increasing emphasis on environmental protection, focusing on economic efficiency, saving energy, and light curing advantage is obvious expression. 有专家预测在今后的这几年中UV行业的年增长率最少15%。 Some experts predict that in the next few years in the UV industry annual growth rate of at least 15%. 由于树脂是影响产品最终性能的最重要成份,因此该产业的大力发展自然而然对光固化树脂从数量和品种上要求会更多。 Since the resin is the most important ingredient affecting the performance of the final product, and therefore to develop the industry of natural light - cured resin from the quantity and variety of requirements will be more. 现有光固化树脂品种主要有环氧丙烯酸酯、聚氨酯丙烯酸、聚酯丙烯酸酯等、聚醚丙烯酸酯、丙烯酸酯化聚丙烯酸酯等等,这些现有的紫外光固化树脂有些户外耐候性差,易黄变,不耐高温,限制了其使用范围,在合成反应中所用原料中有带有苯环结构的环氧树脂,有价格非常昂贵的脂环族环氧树脂。 Conventional photo-curable resin varieties are epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates, acrylated polyacrylates, etc., some of these resins is poor outdoor durability conventional UV curing, easy to yellowing, not high temperature, limiting its use in the synthesis of the raw material used in the reaction with the epoxy ring structure, it is very expensive cycloaliphatic epoxy resins.

发明内容 SUMMARY

[0004] 本发明针对以上问题,提供一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法。 [0004] The present invention is directed to the above problems, there is provided an epoxy acrylate UV curable and preparation method yellowing resistance.

[0005] 本发明的发明目的通过以下方案实现: 一种可紫外光固化耐黄变环氧丙烯酸酯,通过以下方法制备得到: 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到要求时,降温。 [0005] The invention object of the present invention is achieved by the following scheme: An anti-yellowing UV-curable epoxy acrylates, be prepared by the following method: Step a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate esters, the catalyst , the antioxidant and polymerization inhibitor added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material within the reactor to meet the requirements, cooling.

[0006] 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C, 直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入阻聚剂。 [0006] The second step when the temperature of the reactor contents dropped to 80 ° C, cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor, the temperature control 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and add a polymerization inhibitor.

[0007] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0007] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0008] -种可紫外光固化耐黄变环氧丙烯酸酯,二元酸酐为丁二酸酐、戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯中的一种或几种;所述丙烯酸缩水甘油酯又称丙烯酸-2, 3-环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、N,N-二甲基苄胺、苄基三乙氯化胺、四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、对羟基苯甲醚、特丁基对苯二酚、 对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、 亚磷酸三苯酯、次磷酸中的一种或几种。 [0008] - kind of anti-yellowing UV-curable epoxy acrylate, a dibasic acid anhydride as succinic anhydride, glutaric anhydride of one or two; the hydroxy acrylate ester is hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate in one or more of; the methacrylic hydroxy ester is hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane dimethacrylate , pentaerythritol trimethacrylate of one or more; also known as glycidyl acrylate, said acrylate-2,3-epoxy propyl methacrylate, glycidyl methacrylate, -2 also known as, 3-glycidoxy propyl; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetrabutylammonium bromide, triphenylphosphine, one or several; the polymerization inhibitor is hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, tert-butyl catechol in one or more of; the antioxidant is antioxidant 1010 agent, antioxidant 1076, antioxidant 264, triphenyl phosphite, hypophosphorous acid of one or more.

[0009] -种可紫外光固化耐黄变环氧丙烯酸酯,第一步添加的催化剂的量与第二步添加的催化剂的量一致。 [0009] - consistent with the amount of catalyst the amount of catalyst species UV curable epoxy acrylate yellowing resistance, the first step and second step of adding added.

[0010] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到设计要求时,降温。 [0010] A method of preparing UV-curable epoxy acrylate yellowing resistance, the first step will be a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate ester, a catalyst, a polymerization inhibitor and an antioxidant was added to the reactor , heated up at the start of stirring, temperature control of the reactor in 95~KKTC, until the acid value of the material in the reactor to meet the design requirements, cooling.

[0011] 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C, 直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入阻聚剂。 [0011] The second step when the temperature of the reactor contents dropped to 80 ° C, cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor, the temperature control 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and add a polymerization inhibitor.

[0012] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0012] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0013] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,二元酸酐为丁二酸酐、戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯中的一种或几种;所述丙烯酸缩水甘油酯又称丙烯酸-2, 3-环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、N,N-二甲基苄胺、苄基三乙氯化胺、 四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、对羟基苯甲醚、特丁基对苯二酚、对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、亚磷酸三苯酯、次磷酸中的一种或几种 [0013] A method of preparing UV-curable epoxy acrylate yellowing resistance, the dibasic acid anhydride is succinic anhydride, glutaric anhydride of one or two; the acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl propyl, trimethylolpropane diacrylate, pentaerythritol triacrylate in one or more of; the methacrylic hydroxy ester is hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylol propane di one or more methacrylate, pentaerythritol trimethacrylate ester; also known as glycidyl acrylate, said acrylate-2,3-epoxy propyl methacrylate, glycidyl methacrylate, also known as -2,3-epoxy-propyl; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetrabutylammonium bromide, triphenylphosphine in one or more; and the polymerization inhibitor as hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, tert-butyl catechol in one or more of; the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, hypophosphorous acid of one or more .

[0014] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第一步添加的催化剂的量与第二步添加的催化剂的量一致。 [0014] A method of preparing UV-curable epoxy acrylate yellowing resistance, the same amount of catalyst added to the first step and the second step of the catalyst added.

[0015] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,130g丙烯酸羟丙酯,0. 9g三苯基磷,0. 7g抗氧剂264,0. 8g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料酸值彡250mgK0H/g时,降温。 [0015] A method of preparing UV-curable epoxy acrylate yellowing resistance, the first step will IOOg succinic anhydride, 130g hydroxypropyl acrylate, 0. 9g triphenylphosphine, 0. 7g antioxidant 264,0 . 8g was added to the reactor hydroxy anisole, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the reactor San 250mgK0H / g, cool. 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及0. 9g三苯基磷,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入0. Ig对轻基苯甲醚。 When the second stage reactor batch temperature of 80 ° C, was added 145g of glycidyl methacrylate and 0. 9g triphenylphosphine, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, was evacuated for 30 minutes to cool and added to 0. Ig light anisole.

[0016] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0016] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0017] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,300g季戊四醇三丙烯酸酯,2g四丁基溴化胺,I. 4g抗氧剂亚磷酸三苯酯,〇. 7g次磷酸,I. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜100°C,直到反应器内物料酸值< 100mgK0H/g时,降温。 [0017] A anti-yellowing UV-curable epoxy acrylate preparation process, the first step IOOg succinic anhydride, 300g of pentaerythritol triacrylate, 2g tetrabutylammonium bromide, I. 4g antioxidant tris phenyl ester, square. 7g hypophosphorous acid, I. 2g was added to the reactor hydroxy anisole, stirring was started to heat up of the reactor temperature was controlled at 95~100 ° C, until the acid value of the reactor <100mgK0H when / g, cooling.

[0018] 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇. 2g对羟基苯甲醚。 [0018] When the second stage reactor batch temperature of 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium bromide, amine 2g, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and added square. 2g p-hydroxy anisole.

[0019] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0019] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0020] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,500g季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物, 2g四丁基溴化胺,I. 4g抗氧剂亚磷酸三苯酯,0. 7g次磷酸,I. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料酸值彡100mgK0H/g时,降温。 [0020] - method of producing an anti-yellowing cured epoxy acrylate ultraviolet light, the first step the mixture IOOg succinic anhydride, 500 g of pentaerythritol triacrylate and pentaerythritol tetraacrylate, 2g tetrabutylammonium bromide, I. 4g triphenyl phosphite antioxidant, 0. 7g hypophosphorous acid, I. 2g hydroxyanisole was added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the reactor material acid value of San 100mgK0H / g, when cooling.

[0021] 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇. 2g对羟基苯甲醚。 [0021] When the second stage reactor batch temperature of 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium bromide, amine 2g, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and added square. 2g p-hydroxy anisole.

[0022] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0022] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0023] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物为季戊四醇三丙烯酸酯含量在60〜65%和季戊四醇四丙烯酸酯含量在35〜40%的一种混合物。 [0023] - method of producing an anti-yellowing cured epoxy acrylate ultraviolet light, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate is pentaerythritol triacrylate content of 60~65% and the content of pentaerythritol tetraacrylate 35~40 % of a mixture.

[0024] 本发明提供的一种可紫外光固化耐黄变环氧丙烯酸酯及其制备方法,合成方法简单,所用原料价格低廉,成品耐候性优良,价格适宜,耐黄变性好,且成品的粘度低。 [0024] The present invention provides an anti-yellowing UV curable epoxy acrylate and its preparation method, the synthesis method is simple, inexpensive raw materials used, finished product excellent in weatherability, affordable, good yellowing resistance, and low viscosity of the finished product . 解决了环氧丙烯酸酯黄变明显、粘度高,脂环族环氧丙烯酸酯价格昂贵和脂肪族聚氨酯丙烯酸酯粘度高、价格高的缺点,在工业上具有广泛的应用前景,丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯代替环氧树脂。 The epoxy acrylate solution becomes clear yellow, high-viscosity alicyclic epoxy acrylate is expensive and aliphatic urethane acrylates high viscosity, the disadvantage of high price, has wide application prospect in industrial, glycidyl acrylate or glycidyl methacrylate instead of epoxy.

具体实施方式 detailed description

[0025] 实施例1 : 一种可紫外光固化耐黄变环氧丙烯酸酯,通过以下方法制备得到: 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到要求时,降温。 [0025] Example 1: A UV-curable epoxy acrylate yellowing resistance, be prepared by the following method: Step a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate esters, catalysts, antioxidants and hindered cohesive added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material within the reactor to meet the requirements, cooling.

[0026] 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C, 直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入阻聚剂。 [0026] The second step when the temperature of the reactor contents dropped to 80 ° C, cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor, the temperature control 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and add a polymerization inhibitor.

[0027] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0027] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0028] -种可紫外光固化耐黄变环氧丙烯酸酯,其中二元酸酐、丙烯酸羟基酯、催化剂、 抗氧剂、阻聚剂、甲基丙烯酸缩水甘油酯的质量比值为1000 : 1300 : 18 : 7 : 9 : 1450。 [0028] - kind of anti-yellowing UV-curable epoxy acrylates, wherein the dibasic acid anhydride, acrylic hydroxy ester, a catalyst, an antioxidant, a polymerization inhibitor, glycidyl methacrylate ester mass ratios of 1000: 1300: 18: 7: 9: 1450.

[0029] -种可紫外光固化耐黄变环氧丙烯酸酯,其中二元酸酐、季戊四醇三丙烯酸酯、催化剂、抗氧剂、阻聚剂、甲基丙烯酸缩水甘油酯的质量比值为1000 : 3000 : 40 : 21 : 14 : 1450。 [0029] - kind of anti-yellowing UV-curable epoxy acrylates, wherein the dibasic acid anhydride, pentaerythritol triacrylate, a catalyst, an antioxidant, a polymerization inhibitor, glycidyl methacrylate ester mass ratios of 1000: 3000: 40 : 21: 14: 1450.

[0030] 一种可紫外光固化耐黄变环氧丙烯酸酯,第一步添加的阻聚剂的质量与第二步添加的阻聚剂的质量比为8 : 1〜6 : 1。 [0030] An anti-yellowing UV-curable epoxy acrylates, mass polymerization inhibitor and a second step the quality of the first step to add the polymerization inhibitor added is 8: 1~6: 1.

[0031] 一种可紫外光固化耐黄变环氧丙烯酸酯,第一步反应器内物料的酸值为彡250mgK0H/g。 [0031] An anti-yellowing UV-curable epoxy acrylate, the material in the first step is an acid value of San 250mgK0H / g.

[0032] -种可紫外光固化耐黄变环氧丙烯酸酯,第一步反应器内物料的酸值为彡100mgK0H/g。 [0032] - kind of anti-yellowing UV-curable epoxy acrylate, the material in the first step is an acid value of San 100mgK0H / g.

[0033] -种可紫外光固化耐黄变环氧丙烯酸酯,所述二元酸酐为丁二酸酐、戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯中的一种或几种; 所述丙烯酸缩水甘油酯又称丙烯酸-2, 3-环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、N,N-二甲基苄胺、苄基三乙氯化胺、四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、对羟基苯甲醚、特丁基对苯二酚、对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、亚磷酸三苯酯、次磷酸中的一种或几种。 [0033] - kind of anti-yellowing UV-curable epoxy acrylates, said dibasic acid anhydride is succinic anhydride, glutaric anhydride of one or two; the hydroxy acrylate ester is hydroxyethyl acrylate, hydroxypropyl acrylate, one or more esters, trimethylol propane diacrylate, pentaerythritol triacrylate; said hydroxy ester is methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylol propane dimethyl one or more acrylate, pentaerythritol trimethacrylate ester; also known as glycidyl acrylate, said acrylate-2,3-epoxy propyl methacrylate, glycidyl methacrylate, known as - 2, 3-epoxypropyl ester; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetrabutylammonium bromide, triphenylphosphine in a one or several; the polymerization inhibitor is hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, tert-butyl catechol in one or more of; the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, hypophosphorous acid of one or more.

[0034] 一种可紫外光固化耐黄变环氧丙烯酸酯,第一步添加的催化剂的量与第二步添加的催化剂的量一致。 [0034] An anti-yellowing UV-curable epoxy acrylates, consistent amount of catalyst added to the first step and second step of adding a catalyst.

[0035] -种可紫外光固化耐黄变环氧丙烯酸酯,丙烯酸缩水甘油酯又称丙烯酸_2, 3-环氧丙基酯,甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2,3_环氧丙基酯。 [0035] - kind of anti-yellowing UV-curable epoxy acrylate, glycidyl acrylate, also known _2, 3-glycidoxy propyl methacrylate, glycidyl methacrylate, known as ring -2,3_ oxopropyl ester.

[0036] -种可紫外光固化耐黄变环氧丙烯酸酯,所述第一步中的开始搅拌加热升温中搅拌转速为90-300转/分钟,优选项90-150转/分钟和200-300转/分钟;加热升温方式为反应器外部油浴加热。 [0036] - kind of anti-yellowing UV-curable epoxy acrylates, initiating the first step in a stirred heated up with stirring speed of 90-300 rev / min, preference 90-150 revolutions / min and 200-300 rpm / min; temperature rise embodiment the reactor was heated externally in an oil bath heating.

[0037] 实施例2 :-种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到设计要求时,降温。 [0037] Example 2: - Preparation types of UV-curable epoxy acrylate yellowing resistance, the first step will be a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate ester, a catalyst, a polymerization inhibitor and an antioxidant added into the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material within the reactor to meet the design requirements, cooling.

[0038] 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C, 直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入阻聚剂。 [0038] The second step when the temperature of the reactor contents dropped to 80 ° C, cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor, the temperature control 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and add a polymerization inhibitor.

[0039] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0039] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0040] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,所述二元酸酐为丁二酸酐、 戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯中的一种或几种;所述丙烯酸缩水甘油酯又称丙烯酸-2, 3-环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、N,N-二甲基苄胺、苄基三乙氯化胺、四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、对羟基苯甲醚、特丁基对苯二酚、对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、 抗氧剂264、亚磷酸三苯酯、次磷酸中的一种 [0040] A method of preparing UV-curable epoxy acrylate yellowing resistance of the dibasic acid anhydride is succinic anhydride, glutaric anhydride of one or two; the hydroxy acrylate ester is hydroxyethyl acrylate, one or more of hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate; said hydroxy ester is methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane propane dimethacrylate, pentaerythritol trimethacrylate of one or more; also known as glycidyl acrylate, said acrylate-2,3-epoxy propyl acrylate, glycidyl methacrylate, also known as a based acrylic -2,3-epoxy propyl; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetrabutylammonium bromide, triphenylphosphine of one or more; and the polymerization inhibitor as hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, tert-butyl catechol in one or more of; the anti- 1010 antioxidant agent is oxygen, antioxidant 1076, antioxidant 264, triphenyl phosphite, hypophosphorous acid of one 几种。 Several.

[0041] 一种可紫外光固化耐黄变环氧丙烯酸酯,其中二元酸酐、丙烯酸羟基酯、催化剂、 抗氧剂、阻聚剂、甲基丙烯酸缩水甘油酯的质量比值为1000 : 1300 : 18 : 7 : 9 : 1450。 [0041] An anti-yellowing UV-curable epoxy acrylates, wherein the dibasic acid anhydride, acrylic hydroxy ester, a catalyst, an antioxidant, a polymerization inhibitor, glycidyl methacrylate ester mass ratios of 1000: 1300: 18: 7: 9: 1450. [0042] 一种可紫外光固化耐黄变环氧丙烯酸酯,其中二元酸酐、季戊四醇三丙烯酸酯、催化剂、抗氧剂、阻聚剂、甲基丙烯酸缩水甘油酯的质量比值为1000 : 3000 : 40 : 21 : 14 : 1450。 [0042] An anti-yellowing UV-curable epoxy acrylates, wherein the dibasic acid anhydride, pentaerythritol triacrylate, a catalyst, an antioxidant, a polymerization inhibitor, glycidyl methacrylate ester mass ratios of 1000: 3000: 40 : 21: 14: 1450.

[0043] -种可紫外光固化耐黄变环氧丙烯酸酯,第一步添加的阻聚剂的质量与第二步添加的阻聚剂的质量比为8 : 1〜6 : 1。 [0043] - kind of anti-yellowing UV-curable epoxy acrylates, and the mass ratio of mass of the polymerization inhibitor added in the second step of the first step of the polymerization inhibitor added is 8: 1~6: 1.

[0044] 一种可紫外光固化耐黄变环氧丙烯酸酯,第一步添加的催化剂的量与第二步添加的催化剂的量一致。 [0044] An anti-yellowing UV-curable epoxy acrylates, consistent amount of catalyst added to the first step and second step of adding a catalyst.

[0045] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,所述第一步中的开始搅拌加热升温中搅拌转速为90-300转/分钟,优选项90-150转/分钟和200-300转/分钟;加热升温方式为反应器外部油浴加热。 [0045] A method of preparing UV-curable epoxy acrylate yellowing resistance of starting the first step in a stirred heated up with stirring speed of 90-300 rev / min, preference 90-150 revolutions / min and 200 -300 rpm / min; temperature rise embodiment the reactor was heated externally in an oil bath heating.

[0046] -种可紫外光固化耐黄变环氧丙烯酸酯,第一步反应器内物料的酸值为彡250mgK0H/g。 [0046] - kind of anti-yellowing UV-curable epoxy acrylate, the material in the first step is an acid value of San 250mgK0H / g.

[0047] -种可紫外光固化耐黄变环氧丙烯酸酯,第一步反应器内物料的酸值为彡100mgK0H/g。 [0047] - kind of anti-yellowing UV-curable epoxy acrylate, the material in the first step is an acid value of San 100mgK0H / g.

[0048] 实施例3 :-种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,130g丙烯酸羟丙酯,0. 9g三苯基磷,0. 7g抗氧剂264,0. 8g对羟基苯甲醚全部加到反应器内,然后开始搅拌加热升温,将反应器内物料温度控制在95〜 100°C,直到反应器内物料酸值彡250mgK0H/g时,降温。 [0048] Example 3: -. Preparation species UV curable epoxy acrylate-yellowing resistance, the first step IOOg succinic anhydride, 130g hydroxypropyl acrylate, 0 9g triphenylphosphine, 0 7g Antioxidant agent 264,0. 8g hydroxyanisole was added to all the reactor, stirring was then started to heat up the contents of the reactor temperature was controlled at 95~ 100 ° C, until the acid value of the reactor San 250mgK0H / g when , cool. 第二步当反应器物料温度降为为80°C时,加入145g甲基丙烯酸缩水甘油酯及0.9g 三苯基磷,然后加热反应器内物料,将温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,将反应器抽真空30分钟,降温并加入0. Ig对羟基苯甲醚。 When the second stage reactor contents temperature was reduced to 80 ° C, was added 145g of glycidyl methacrylate and 0.9g of triphenylphosphine, followed by heating of the reactor, controlling the temperature at 108~112 ° C, until reactor contents acid value <5mgK0H / g, when the reactor is evacuated for 30 minutes to cool and added to 0. Ig hydroxyanisole.

[0049] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0049] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0050] 所述产品的分子式为:C17H2409。 [0050] The product of the formula: C17H2409.

[0051] 所述产品的结构式为: [0051] The product has a structural formula:

Figure CN104447325AD00081

[0052] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第一步的化学反应: [0052] - method of producing an anti-yellowing cured epoxy acrylate ultraviolet light, the first step of the chemical reaction:

Figure CN104447325AD00082

[0053] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第二步的化学反应: [0053] - method of producing an anti-yellowing cured epoxy acrylate ultraviolet light, chemical reaction of the second step:

Figure CN104447325AD00083

[0054] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,所述第一步中的开始搅拌加热升温,搅拌转速为90-300转/分钟,优选项90-150转/分钟和200-300转/分钟;加热方式为反应器外部油浴加热。 [0054] - Preparation of UV-curable types can be resistance to yellowing of epoxy acrylate, the start of the first step heated up with stirring, stirring speed of 90-300 rev / min, preference 90-150 revolutions / min and 200 -300 rpm / min; heating the reactor externally heated in an oil bath.

[0055] 实施例4 :一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,300g季戊四醇三丙烯酸酯,2g四丁基溴化胺,I. 4g抗氧剂亚磷酸三苯酯,〇. 7g次磷酸,I. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜100°C,直到反应器内物料酸值< 100mgK0H/g时,降温。 [0055] Example 4: Preparation yellowing an epoxy acrylate UV curable resistance, the first step IOOg succinic anhydride, 300g of pentaerythritol triacrylate, 2g tetrabutylammonium bromide, I 4g antioxidant. agents triphenyl phosphite, square. 7g hypophosphorous acid, I. 2g hydroxyanisole was added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~100 ° C, until the contents of the reactor an acid value of <100mgK0H / g, when cooling.

[0056] 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇. 2g对羟基苯甲醚。 [0056] When the second stage reactor batch temperature of 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium bromide, amine 2g, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and added square. 2g p-hydroxy anisole.

[0057] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0057] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0058] 所述产品的分子式为:C25H32013。 [0058] The product of the formula: C25H32013.

[0059] 所述产品的结构式为: [0059] The product has a structural formula:

Figure CN104447325AD00091

[0060] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,所述第一步中的开始搅拌加热升温,搅拌转速为90-300转/分钟,优选项90-150转/分钟和200-300转/分钟;加热方式为反应器外部油浴加热。 [0060] - Preparation of UV-curable types can be resistance to yellowing of epoxy acrylate, the start of the first step heated up with stirring, stirring speed of 90-300 rev / min, preference 90-150 revolutions / min and 200 -300 rpm / min; heating the reactor externally heated in an oil bath.

[0061] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第一步的化学反应: [0061] A method of preparing UV-curable epoxy acrylate yellowing resistance, the first step of the chemical reaction:

Figure CN104447325AD00092

[0062] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第二步的化学反应: [0062] - method of producing an anti-yellowing cured epoxy acrylate ultraviolet light, chemical reaction of the second step:

Figure CN104447325AD00093

[0063] 实施例5 :-种可紫外光固化耐黄变环氧丙烯酸酯的制备方法, 第一步将IOOg 丁二酸酐,500g季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物, 2g四丁基溴化胺,I. 4g抗氧剂亚磷酸三苯酯,0. 7g次磷酸,I. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料酸值彡100mgK0H/g时,降温。 [0063] Example 5: - preparing Species UV curable epoxy acrylate-yellowing resistance, the first step mixture was IOOg succinic anhydride, 500 g of pentaerythritol triacrylate and pentaerythritol tetraacrylate, 2g tetrabutyl amines, I. 4g triphenyl phosphite antioxidant, 0. 7g hypophosphorous acid, I. 2g hydroxyanisole was added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material San 100mgK0H / g in the reactor, cooling.

[0064] 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇. 2g对羟基苯甲醚。 [0064] When the second stage reactor batch temperature of 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium bromide, amine 2g, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, when vacuum for 30 minutes to cool and added square. 2g p-hydroxy anisole.

[0065] 第三步当反应器内物料温度降到70°C时,过滤出料。 [0065] The third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.

[0066] 一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物为季戊四醇三丙烯酸酯含量在60〜65%和季戊四醇四丙烯酸酯含量在35〜40%的一种混合物。 [0066] A method of preparing UV-curable epoxy acrylate yellowing resistance, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate is pentaerythritol triacrylate content of 60~65% and the content of pentaerythritol tetraacrylate 35~40 % of a mixture.

[0067] -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,所述第一步中的开始搅拌加热升温,搅拌转速为90-300转/分钟,优选项90-150转/分钟和200-300转/分钟;加热方式为反应器外部油浴加热。 [0067] - Preparation of UV-curable types can be resistance to yellowing of epoxy acrylate, the start of the first step heated up with stirring, stirring speed of 90-300 rev / min, preference 90-150 revolutions / min and 200 -300 rpm / min; heating the reactor externally heated in an oil bath.

[0068] 实施例6 :-种可紫外光固化耐黄变环氧丙烯酸酯,在合成反应中所用原料的没有用到带有苯环结构的环氧树脂,也没有用价格非常昂贵的脂环族环氧树脂,因此产品耐候性优良,价格适宜,且成品的粘度低。 [0068] Example 6: - kind of anti-yellowing UV-curable epoxy acrylate, the synthesis reaction in the raw material did not use an epoxy resin having benzene ring structure, with no very expensive cycloaliphatic epoxy resin, and therefore the product is excellent in weatherability, affordable, and low viscosity of the finished product. 解决了环氧丙烯酸酯黄变明显、粘度高、脂环族环氧丙烯酸酯价格昂贵和脂肪族聚氨酯丙烯酸酯粘度高、价格高缺点。 The epoxy acrylate solution becomes clear yellow, high-viscosity alicyclic epoxy acrylate is expensive and aliphatic urethane acrylates high viscosity, high price disadvantage.

[0069] 实施例7 : -种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,第一步添加的阻聚剂的质量与第二步添加的阻聚剂的质量比为8 : 1〜6 : 1。 [0069] Example 7: - UV curable species resistant to yellowing prepared epoxy acrylate, mass than the mass of the polymerization inhibitor added in the first step and the second step of the polymerization inhibitor added is 8: 1~6 : 1.

[0070] 实施例8 :-种可紫外光固化耐黄变环氧丙烯酸酯在制备UV涂料、油墨或粘合剂中的应用。 [0070] Example 8: - application of UV-curable species yellowing resistance in the preparation of an epoxy acrylate UV coatings, inks or adhesives.

[0071] 需要理解到的是:上述实施例虽然对本发明的设计思路作了比较简单的文字描述,但是这些文字描述,只是对本发明设计思路的简单文字描述,而不是对本发明设计思路的限制,任何不超出本发明设计思路的组合、增加或修改,均落入本发明的保护范围内。 [0071] is to be understood to be: the embodiments described above, although the design concept of the present invention is made relatively simple text, but the text description, simply text on the design concept of the present invention will be described, not to limit the design concept of the present invention, any combination of design without departing from the idea of ​​the invention, additions or modifications fall within the scope of the present invention.

Claims (10)

  1. 1. 一种可紫外光固化耐黄变环氧丙烯酸酯,其特征是通过以下方法制备得到: 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到要求时,降温; 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C,直到反应器物料的酸值< 5mgKOH/g时,抽真空30分钟,降温并加入阻聚剂; 第三步当反应器内物料温度降到70°C时,过滤出料。 An anti-yellowing UV-curable epoxy acrylate, which was prepared wherein the following method: Step a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate ester, a catalyst, a polymerization inhibitor and an antioxidant was added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material within the reactor to meet the requirements, cooling; the second step when the reactor temperature of the material drops 80 ° C when cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor temperature was controlled at 108~112 ° C, the reactor contents until the acid value <5mgKOH / g , the vacuum for 30 minutes to cool and adding a polymerization inhibitor; a third step when the reactor temperature dropped when the mass 70 ° C, the material was filtered.
  2. 2. 根据权利要求1所述的一种可紫外光固化耐黄变环氧丙烯酸酯,其特征是:所述二元酸酐为丁二酸酐、戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、季戊四醇三甲基丙烯酸酯中的一种或几种;所述丙烯酸缩水甘油酯又称丙烯酸-2, 3-环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、N,N-二甲基苄胺、苄基三乙氯化胺、四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、 对羟基苯甲醚、特丁基对苯二酚、对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、亚磷酸三苯酯、 According to one of the claims 1 anti-yellowing UV-curable epoxy acrylates, characterized in that: said dibasic acid anhydride is succinic anhydride, glutaric anhydride of one or two; said hydroxy acrylate esters are hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate in one or more of; the methacrylic hydroxy ester is hydroxyethyl methacrylate, methacrylic acid one or more of hydroxypropyl methacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate ester; also known as glycidyl acrylate, said acrylate-2,3-epoxy propyl methacrylate, glycidyl acrylate, also known as methacrylic acid-2,3-epoxypropyl ester; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetrabutylphosphonium amines, one or more of triphenylphosphine; the polymerization inhibitor is hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, t-butylcatechol in the kind of the or more; the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, 次磷酸中的一种或几种。 One or more times phosphate.
  3. 3. 根据权利要求1所述的一种可紫外光固化耐黄变环氧丙烯酸酯,其特征是:所述第一步添加的催化剂的量与第二步添加的催化剂的量一致。 According to one of the claims 1 anti-yellowing UV-curable epoxy acrylates, characterized in that: an amount consistent with the amount of catalyst added to said first step and second step of adding a catalyst.
  4. 4. 根据权利要求1所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是: 第一步将二元酸酐、丙烯酸羟基酯或甲基丙烯酸羟基酯、催化剂、抗氧剂及阻聚剂加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料的酸值达到设计要求时,降温; 第二步当反应器物料的温度降到80°C时,停止降温,后加入丙烯酸缩水甘油酯酯或甲基丙烯酸缩水甘油酯及催化剂;继续加热反应器内的物料,温度控制在108〜112°C,直到反应器物料的酸值< 5mgKOH/g时,抽真空30分钟,降温并加入阻聚剂; 第三步当反应器内物料温度降到70°C时,过滤出料。 The one of the production method according to claim 1, yellowing of epoxy acrylate UV curable resistance, characterized in that: the first step a dibasic acid anhydride, acrylate, hydroxypropyl acrylate, hydroxypropyl acrylate or methacrylate ester, a catalyst, antioxidant the agent and the polymerization inhibitor added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~KKTC, until the acid value of the material within the reactor to meet the design requirements, cooling; the second step when the reactor contents when the temperature dropped to 80 ° C, cooling is stopped, after the addition of glycidyl acrylate, glycidyl methacrylate or acrylate and a catalyst; material heating was continued in the reactor temperature was controlled at 108~112 ° C, until the reactor contents an acid value of <5mgKOH / g, when vacuum for 30 minutes to cool and adding a polymerization inhibitor; a third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.
  5. 5. 根据权利要求4所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是:所述二元酸酐为丁二酸酐、戊二酸酐中的一种或两种;所述丙烯酸羟基酯为丙烯酸羟乙酯、丙烯酸羟丙酯、三羟甲丙烷二丙烯酸酯、季戊四醇三丙烯酸酯中的一种或几种;所述甲基丙烯酸羟基酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、三羟甲丙烷二甲基丙烯酸酯、 季戊四醇三甲基丙烯酸酯中的一种或几种;所述丙烯酸缩水甘油酯又称丙烯酸_2,3_环氧丙基酯、甲基丙烯酸缩水甘油酯又称甲基丙烯酸-2, 3-环氧丙基酯;所述催化剂为三乙胺、 N,N-二甲基苄胺、苄基三乙氯化胺、四丁基溴化胺、三苯基磷中的一种或几种;所述阻聚剂为对苯二酚、对羟基苯甲醚、特丁基对苯二酚、对叔丁基邻苯二酚中的一种或几种;所述抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264、亚磷 4 5. According to one method of preparation according to claim yellowing of epoxy acrylate UV curable resistance, characterized in that: said dibasic acid anhydride is succinic anhydride, glutaric anhydride of one or two; the said hydroxy acrylate is hydroxyethyl acrylate, one or more of ethyl acrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate; said hydroxy ester is methyl methacrylate, hydroxyethyl methacrylate, one or more of hydroxypropyl methacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate ester; also known as a glycidyl acrylate ester of glycidyl acrylate _2,3_ , glycidyl methacrylate, also known as methacrylic acid-2,3-epoxypropyl ester; the catalyst is triethylamine, N, N- dimethylbenzylamine, benzyl triethyl ammonium chloride, tetra butylamine bromide, triphenylphosphine one or several of; the polymerization inhibitor is hydroquinone, p-hydroxyanisole, tertiary-butylhydroquinone, t-butylcatechol in the of It is one or more; the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, phosphoramidites 酸三苯酯、次磷酸中的一种或几种。 Acid triphenyl ester, hypophosphorous acid of one or more.
  6. 6. 根据权利要求4所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是:所述第一步添加的催化剂的量与第二步添加的催化剂的量一致。 6. According to one of claim 4 yellowing preparing an epoxy acrylate UV curable resistance, wherein: an amount consistent with the amount of catalyst added to said first step and second step of adding a catalyst.
  7. 7. 根据权利要求4所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是: 第一步将100g 丁二酸酐,130g丙烯酸羟丙酯,0. 9g三苯基磷,0. 7g抗氧剂264,0. 8g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜KKTC,直到反应器内物料酸值彡250mgK0H/g时,降温; 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及0. 9g三苯基磷,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入0. lg对轻基苯甲醚; 第三步当反应器内物料温度降到70°C时,过滤出料。 4 7. According to one method of preparation according to claim yellowing of epoxy acrylate UV curable resistance, characterized in that: the first step 100g of succinic anhydride, 130g hydroxypropyl acrylate, 0 9g triphenylphosphine , 0. 7g antioxidant 264,0. 8g hydroxyanisole was added to the reactor to start heating up stirring, temperature control of the reactor in 95~KKTC, until the acid value of the reactor San 250mgK0H / g when, cooling; the second step when the temperature of the reactor contents to 80 ° C, was added 145g of glycidyl methacrylate and 0. 9g triphenylphosphine, temperature controlled at 108~112 ° C, the reactor contents until the acid value <5mgK0H / g, the vacuum for 30 minutes and cool to 0. lg light added anisole; a third step of the reactor when the temperature dropped to 70 ° C, the material was filtered.
  8. 8. 根据权利要求4所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是: 第一步将100g 丁二酸酐,300g季戊四醇三丙烯酸酯,2g四丁基溴化胺,1. 4g抗氧剂亚磷酸三苯酯,〇. 7g次磷酸,1. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜100°C,直到反应器内物料酸值< 100mgK0H/g时,降温; 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇.2g对羟基苯甲醚; 第三步当反应器内物料温度降到70°C时,过滤出料。 8. A member according to claim 4, wherein the preparation of yellowing of epoxy acrylate UV curable resistance, characterized in that: the first step 100g of succinic anhydride, 300g of pentaerythritol triacrylate, 2g tetrabutylammonium bromide , 1. 4g triphenyl phosphite antioxidants, square. 7g hypophosphorous acid, 1. 2g hydroxyanisole was added to the reactor, stirring was started to heat up of the reactor temperature was controlled at 95~100 ° C until the acid value of the reactor <100mgK0H / g, when cooling; mass of the second stage when the reactor temperature was 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium bromide 2g, temperature control 108~112 ° C, the reactor contents until the acid value <5mgK0H / g, the vacuum for 30 minutes to cool and added 〇.2g hydroxyanisole; a third step of the reactor when the temperature dropped to 70 ° C when the filtered material.
  9. 9. 根据权利要求4所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是: 第一步将100g 丁二酸酐,500g季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物, 2g四丁基溴化胺,1. 4g抗氧剂亚磷酸三苯酯,0. 7g次磷酸,1. 2g对羟基苯甲醚加到反应器内,开始搅拌加热升温,反应器内物料温度控制在95〜10(TC,直到反应器内物料酸值彡100mgK0H/g时,降温; 第二步当反应器物料温度为80°C时,加入145g甲基丙烯酸缩水甘油酯及2g四丁基溴化胺,温度控制在108〜112°C,直到反应器物料的酸值< 5mgK0H/g时,抽真空30分钟,降温并加入〇.2g对羟基苯甲醚; 第三步当反应器内物料温度降到70°C时,过滤出料。 9. A member according to claim 4, wherein the prepared ultraviolet light curable epoxy acrylate yellowing resistance, characterized in that: the first step and the mixture was 100g of succinic anhydride, 500 g of pentaerythritol triacrylate and pentaerythritol tetraacrylate, 2g tetrabutylammonium bromide, 1. 4g triphenyl phosphite antioxidant, 0. 7g hypophosphorous acid, 1. 2g hydroxyanisole was added to the reactor, stirring was started to heat up the temperature of the reactor control 95~10 (TC, until the acid value of the reactor San 100mgK0H / g, the cooling; the second step when the temperature of the reactor contents to 80 ° C, was added 145g of glycidyl methacrylate and tetrabutylammonium 2g amine bromide, temperature controlled at 108~112 ° C, until the acid value of the reactor contents <5mgK0H / g, the vacuum for 30 minutes to cool and added 〇.2g hydroxyanisole; the third step when the reactor when the batch temperature dropped to 70 ° C, the material was filtered.
  10. 10. 根据权利要求9所述的一种可紫外光固化耐黄变环氧丙烯酸酯的制备方法,其特征是:所述季戊四醇三丙烯酸酯与季戊四醇四丙烯酸酯的混合物为季戊四醇三丙烯酸酯含量在60〜65%和季戊四醇四丙烯酸酯含量在35〜40%的一种混合物。 10. A method according to claim 9 yellowing preparing an epoxy acrylate UV curable resistance, characterized in that: the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate is pentaerythritol triacrylate content 60~ a mixture of 35~40% and 65% pentaerythritol tetraacrylate content.
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CN103342793A (en) * 2013-05-31 2013-10-09 成都彭州立源高分子材料有限公司 Organic fluorine silicon hybrid photosensitive resin and synthesis method thereof

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