CN102863323A - Method for preparing polymeric benzophenone derivative photoinitiator - Google Patents
Method for preparing polymeric benzophenone derivative photoinitiator Download PDFInfo
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- 150000008366 benzophenones Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LJRIZGQRKVWXSI-UHFFFAOYSA-N [4-(oxiran-2-ylmethoxy)phenyl]-phenylmethanone Chemical compound C=1C=C(OCC2OC2)C=CC=1C(=O)C1=CC=CC=C1 LJRIZGQRKVWXSI-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 18
- 239000012965 benzophenone Substances 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 abstract description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000003999 initiator Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001723 curing Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003384 small molecules Chemical group 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种可聚合二苯甲酮衍生物光引发剂的制备方法The invention relates to a preparation method of a polymerizable benzophenone derivative photoinitiator
背景技术 Background technique
光固化技术是20世纪60年代问世的一种新型环境友好型绿色技术，具有固化速度快、污染少、节能、固化产物性能优异等特点，因此其在光刻胶、光固化涂料、电子封装材料、光固化油墨、粘合剂、印刷材料等方面有广泛的应用。通常光固化体系包括三种主要组分，即低聚物、单体、光引发剂，其中光引发剂是光固化体系的关键组分。根据作用机理，可将光引发剂分为自由基型引发剂和阳离子型引发剂，自由基型引发剂又可分为裂解型和夺氢型两种类型。在自由基聚合中，二苯甲酮是常见的夺氢型光引发剂，结构简单，易于合成，引发活性高，但是其熔点低、分子量小、易挥发，在固化膜中易向表面迁移析出，产生毒性，使其在食品和药物包装方面的应用受到制约。而应用可聚合型二苯甲酮光引发剂成为解决这一问题的有效方法。Photocuring technology is a new type of environmentally friendly green technology that came out in the 1960s. It has the characteristics of fast curing speed, less pollution, energy saving, and excellent performance of cured products. Therefore, it is used in photoresists, photocurable coatings, and electronic packaging materials. , light-curing inks, adhesives, printing materials, etc. have a wide range of applications. Generally, the photocuring system includes three main components, namely oligomer, monomer, and photoinitiator, wherein the photoinitiator is the key component of the photocuring system. According to the mechanism of action, photoinitiators can be divided into free radical initiators and cationic initiators, and free radical initiators can be divided into two types: cleavage type and hydrogen abstraction type. In free radical polymerization, benzophenone is a common hydrogen abstraction photoinitiator. It has a simple structure, is easy to synthesize, and has high initiating activity. However, it has a low melting point, small molecular weight, and is volatile, and it is easy to migrate and precipitate on the surface in the cured film. , resulting in toxicity, which restricts its application in food and drug packaging. The application of polymerizable benzophenone photoinitiator has become an effective method to solve this problem.
可聚合二苯甲酮光引发剂是指在二苯甲酮分子上引入可聚合基团，使其既是含有光活性基团的引发剂，也是具有不饱和基团的单体，在紫外光的照射下，引发单体聚合并参与光交联反应，并且此类引发剂亦可自身引发聚合生成高分子，若含有不同类型光引发基团的可聚合型单体共聚，还可得到引发效率优良的高分子型光引发剂。The polymerizable benzophenone photoinitiator refers to the introduction of a polymerizable group on the benzophenone molecule, making it both an initiator containing a photoactive group and a monomer with an unsaturated group. Under irradiation, monomer polymerization is initiated and participates in the photocrosslinking reaction, and this type of initiator can also initiate polymerization by itself to form polymers. If polymerizable monomers containing different types of photoinitiating groups are copolymerized, excellent initiation efficiency can also be obtained. polymer photoinitiator.
可聚合型光引发剂由于其无小分子残留，与树脂相容性好，引发性能高，安全无毒，能克服常规小分子引发剂的挥发和迁移性问题，可提高产品的耐候性、光泽等优异特点而逐渐成为人们广泛关注的领域。Polymerizable photoinitiators have no small molecule residues, good compatibility with resins, high initiation performance, safety and non-toxicity, can overcome the volatility and migration problems of conventional small molecule initiators, and can improve the weather resistance and gloss of products It has gradually become a field of widespread concern due to its excellent characteristics.
发明内容 Contents of the invention
本发明提供了一种可聚合二苯甲酮衍生物光引发剂的制备方法。本发明通过分子结构设计向二苯甲酮分子中引入不饱和双键，使得该二苯甲酮衍生物光引发剂本身亦可以发生聚合反应，另外，此光引发剂可降低常规小分子光引发剂存在的毒性和表面迁移性的问题。The invention provides a preparation method of a polymerizable benzophenone derivative photoinitiator. The present invention introduces unsaturated double bonds into benzophenone molecules through molecular structure design, so that the photoinitiator itself of benzophenone derivatives can also undergo polymerization reaction. The toxicity and surface migration problems of the agent.
本发明制备的可聚合二苯甲酮衍生物光引发剂，其化学结构式如下：The polymerizable benzophenone derivative photoinitiator prepared by the present invention, its chemical structural formula is as follows:
其中R=H或CH3 where R=H or CH3
本发明的可聚合二苯甲酮衍生物光引发剂的制备方法如下：The preparation method of polymerizable benzophenone derivative photoinitiator of the present invention is as follows:
将1%-1.5%的阻聚剂和1.5%-2%的四丁基溴化铵溶于1.1-1.3摩尔分数的不饱和羧酸或不饱和羧酸酯中，慢慢滴加至1-2摩尔分数的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在85°С-95°С，2h滴加完毕，温度升至100°С-110°С，2h-4h反应完毕，冷至室温，将其溶于二氯甲烷中，用10mL-20mL 2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂。Dissolve 1%-1.5% polymerization inhibitor and 1.5%-2% tetrabutylammonium bromide in 1.1-1.3 mole fraction of unsaturated carboxylic acid or unsaturated carboxylic acid ester, slowly drop to 1- In 2 mole fractions of 4-(2,3-epoxypropoxy)benzophenone (EBP), heat and stir, the temperature is controlled at 85°С-95°С, after 2 hours, the temperature rises to 100°С С-110°С, 2h-4h after the reaction is completed, cool to room temperature, dissolve it in dichloromethane, wash twice with 10mL-20mL 2% NaOH solution and deionized water, and dry overnight with anhydrous sodium sulfate. Filter, remove dichloromethane by rotary evaporation, and dry in vacuum to obtain a polymerizable benzophenone derivative photoinitiator.
本发明的可聚合二苯甲酮衍生物光引发剂的反应式如下：The reaction formula of polymerizable benzophenone derivative photoinitiator of the present invention is as follows:
其中R=H或CH3 where R=H or CH3
其中R=CH2或(CH2)2 where R=CH 2 or (CH 2 ) 2
其中R=H或CH3 where R=H or CH3
其中R=CH2或(CH2)2 where R=CH 2 or (CH 2 ) 2
本发明所述的阻聚剂包括：氯化亚铜、三氯化铁、对羟基苯甲醚。The polymerization inhibitor of the present invention includes: cuprous chloride, ferric chloride, p-hydroxyanisole.
本发明可聚合二苯甲酮衍生物光引发剂的制备方法，通过分子结构设计，将不饱和双键引入二苯甲酮光引发剂分子中，提高了光引发剂与聚合体系的相容性，降低了常规光引发剂的挥发和迁移性。The preparation method of the polymerizable benzophenone derivative photoinitiator of the present invention introduces unsaturated double bonds into the benzophenone photoinitiator molecule through molecular structure design, thereby improving the compatibility between the photoinitiator and the polymerization system , reducing the volatility and mobility of conventional photoinitiators.
具体实施方式 Detailed ways
实施例1Example 1
将0.05g的对羟基苯甲醚和0.05g的四丁基溴化铵溶于3.3g的丙烯酸中，慢慢滴加至10.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在85°С，2h滴加完毕，温度升至100°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用10mL 2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4—(丙烯酸-2-羟基丙酯-3-氧基)二苯甲酮。结构如结构式1所示：1H NMR（250MHz）in CDCl3：δ2ppm(1H，OH)，3.95ppm(1H，CH)，3.09，4.09ppm(4H，CH2)，6.12-6.37ppm(3H，CH=CH2)，6.87-7.70ppm(9H，苯环)Dissolve 0.05g of p-hydroxyanisole and 0.05g of tetrabutylammonium bromide in 3.3g of acrylic acid, slowly add dropwise to 10.5g of 4-(2,3-epoxypropoxy)diphenyl In ketone (EBP), heat and stir, the temperature is controlled at 85°С, the dropwise addition is completed in 2 hours, the temperature rises to 100°С, the reaction is completed in 2 hours, cooled to room temperature, dissolved in dichloromethane, and mixed with 10mL 2% NaOH solution, deionized water were washed 2 times, anhydrous sodium sulfate dried overnight, filtered, rotary evaporation to remove dichloromethane, vacuum-dried to obtain a polymerizable benzophenone derivative photoinitiator 4—(acrylic acid-2- hydroxypropyl-3-oxy)benzophenone. The structure is shown in Formula 1: 1 H NMR (250MHz) in CDCl 3 : δ2ppm (1H, OH), 3.95ppm (1H, CH), 3.09, 4.09ppm (4H, CH 2 ), 6.12-6.37ppm (3H, CH=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
实施例2Example 2
将0.04g的对羟基苯甲醚和0.05g的四丁基溴化铵溶于3.3g的甲基丙烯酸中，慢慢滴加至10.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在85°С，2h滴加完毕，温度升至100°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用10mL2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4—(甲基丙烯酸-2-羟基丙酯-3-氧基)二苯甲酮。结构如结构式2所示：1H NMR（250MHz）in CDCl3：δ1.93ppm(3H,CH3)，2ppm(1H，OH)，3.95ppm(1H，CH)，3.09，4.09ppm(4H，CH2)，5.90，6.09ppm(2H，C=CH2)，6.87-7.70ppm(9H,苯环)Dissolve 0.04g of p-hydroxyanisole and 0.05g of tetrabutylammonium bromide in 3.3g of methacrylic acid, slowly add dropwise to 10.5g of 4-(2,3-epoxypropoxy) In benzophenone (EBP), heat and stir, the temperature is controlled at 85 ° С, 2h dropwise is completed, the temperature rises to 100 ° С, 2h reaction is completed, cooled to room temperature, it is dissolved in dichloromethane, with 10mL2 % NaOH solution and deionized water were washed 2 times respectively, dried over night with anhydrous sodium sulfate, filtered, rotary evaporated to remove dichloromethane, and dried in vacuum to obtain a polymerizable benzophenone derivative photoinitiator 4—(methacrylic acid -2-hydroxypropyl-3-oxy)benzophenone. The structure is shown in structural formula 2: 1 H NMR (250MHz) in CDCl 3 : δ1.93ppm (3H, CH 3 ), 2ppm (1H, OH), 3.95ppm (1H, CH), 3.09, 4.09ppm (4H, CH 2 ), 5.90, 6.09ppm (2H, C=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
实施例3Example 3
将0.04g的对羟基苯甲醚和0.06g的四丁基溴化铵溶于3.3g的丙烯酸羟乙酯中，慢慢滴加至11.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在90°С，2h滴加完毕，温度升至100°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用10mL 2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4—(丙烯酰氧基-4-羟基-3，5-二氧基)二苯甲酮。结构如结构式3所示：1H NMR（250MHz）in CDCl3：δ2ppm(1H，OH)，3.65，4.26，4.32ppm(6H，CH2)，5.08ppm(1H，CH)，5.80，6.05，6.43ppm(3H，CH=CH2)，6.87-7.70ppm(9H，苯环)Dissolve 0.04g of p-hydroxyanisole and 0.06g of tetrabutylammonium bromide in 3.3g of hydroxyethyl acrylate, and slowly add it dropwise to 11.5g of 4-(2,3-epoxypropoxy ) in benzophenone (EBP), heated and stirred, the temperature was controlled at 90 ° С, the dropwise addition was completed in 2 hours, the temperature rose to 100 ° С, the reaction was completed in 2 hours, cooled to room temperature, dissolved in dichloromethane, and used 10mL of 2% NaOH solution and deionized water were washed twice respectively, dried overnight over anhydrous sodium sulfate, filtered, rotary evaporated to remove methylene chloride, and dried in vacuo to obtain a polymerizable benzophenone derivative photoinitiator 4—(propylene Acyloxy-4-hydroxy-3,5-dioxy)benzophenone. The structure is shown in structural formula 3: 1 H NMR (250MHz) in CDCl 3 : δ2ppm (1H, OH), 3.65, 4.26, 4.32ppm (6H, CH 2 ), 5.08ppm (1H, CH), 5.80, 6.05, 6.43 ppm (3H, CH=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
实施例4Example 4
将0.05g的对羟基苯甲醚和0.06g的四丁基溴化铵溶于4g的甲基丙烯酸羟乙酯中，慢慢滴加至10.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在90°С，2h滴加完毕，温度升至100°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用20mL2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4-(甲基丙烯酰氧基-4-羟基-3，5-二氧基)二苯甲酮。结构如结构式4所示：1H NMR（250MHz）in CDCl3：δ1.93ppm(3H，CH3)，2ppm(1H，OH)，3.65，4.26，4.32ppm(6H，CH2)，5.08ppm(1H，CH)，5.58，6.15ppm(3H，C=CH2)，6.87-7.70ppm(9H，苯环)Dissolve 0.05g of p-hydroxyanisole and 0.06g of tetrabutylammonium bromide in 4g of hydroxyethyl methacrylate, slowly add dropwise to 10.5g of 4-(2,3-epoxypropoxy Base) in benzophenone (EBP), heating and stirring, the temperature is controlled at 90 ° С, 2h dropwise, the temperature rises to 100 ° С, 2h reaction is completed, cooled to room temperature, dissolved in dichloromethane, Wash twice with 20mL of 2% NaOH solution and deionized water, dry overnight over anhydrous sodium sulfate, filter, remove methylene chloride by rotary evaporation, and dry in vacuo to obtain a polymerizable benzophenone derivative photoinitiator 4-(methyl Acryloyloxy-4-hydroxy-3,5-dioxy)benzophenone. The structure is shown in Formula 4: 1 H NMR (250MHz) in CDCl 3 : δ1.93ppm (3H, CH 3 ), 2ppm (1H, OH), 3.65, 4.26, 4.32ppm (6H, CH 2 ), 5.08ppm ( 1H, CH), 5.58, 6.15ppm (3H, C=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
实施例5Example 5
将0.04g的对三氯化铁和0.05g的四丁基溴化铵溶于3.3g的丙烯酸羟丙酯中，慢慢滴加至10.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在90°С，2h滴加完毕，温度升至100°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用20mL 2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4-(丙烯酰氧基-5-羟基-4，6-二氧基)二苯甲酮。结构如结构式5所示：1H NMR（250MHz）in CDCl3：δ2ppm(1H，OH)，1.74，3.37，4.15，4.26ppm(8H，CH2)，5.08ppm(1H，CH)，5.80，6.05，6.43ppm(3H，CH=CH2)，6.87-7.70ppm(9H,苯环)Dissolve 0.04g of p-ferric chloride and 0.05g of tetrabutylammonium bromide in 3.3g of hydroxypropyl acrylate, and slowly add dropwise to 10.5g of 4-(2,3-epoxypropoxy ) in benzophenone (EBP), heated and stirred, the temperature was controlled at 90 ° С, the dropwise addition was completed in 2 hours, the temperature rose to 100 ° С, the reaction was completed in 2 hours, cooled to room temperature, dissolved in dichloromethane, and used 20mL of 2% NaOH solution and deionized water were washed twice respectively, dried overnight with anhydrous sodium sulfate, filtered, rotary evaporated to remove dichloromethane, and dried in vacuum to obtain a polymerizable benzophenone derivative photoinitiator 4-(propylene Acyloxy-5-hydroxy-4,6-dioxy)benzophenone. The structure is shown in Formula 5: 1 H NMR (250MHz) in CDCl 3 : δ2ppm (1H, OH), 1.74, 3.37, 4.15, 4.26ppm (8H, CH 2 ), 5.08ppm (1H, CH), 5.80, 6.05 , 6.43ppm (3H, CH=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
实施例6Example 6
将0.04g的氯化亚铜和0.07g的四丁基溴化铵溶于4g的丙烯酸羟丁酯中，慢慢滴加至10.5g的4-（2,3-环氧丙氧基）二苯甲酮(EBP)中，加热搅拌，温度控制在90°С，2h滴加完毕，温度升至110°С，2h反应完毕，冷至室温，将其溶于二氯甲烷中，用10mL2%的NaOH溶液、去离子水分别洗涤2次，无水硫酸钠干燥过夜，过滤，旋转蒸发去除二氯甲烷，真空干燥，得到可聚合二苯甲酮衍生物光引发剂4—(丙烯酰氧基-6-羟基-5，7-二氧基)二苯甲酮。结构如结构式6所示：1H NMR（250MHz）in CDCl3：δ2ppm(1H，OH)，1.464，1.57，3.37，4.15，4.26ppm(10H，CH2)，5.08ppm(1H，CH)，5.80，6.05，6.43ppm(3H，CH=CH2)，6.87-7.70ppm(9H,苯环)Dissolve 0.04g of cuprous chloride and 0.07g of tetrabutylammonium bromide in 4g of hydroxybutyl acrylate, slowly add dropwise to 10.5g of 4-(2,3-epoxypropoxy) di In benzophenone (EBP), heat and stir, the temperature is controlled at 90 ° С, 2h dropwise is completed, the temperature rises to 110 ° С, 2h reaction is completed, cooled to room temperature, it is dissolved in dichloromethane, with 10mL2% NaOH solution and deionized water were washed twice respectively, dried overnight with anhydrous sodium sulfate, filtered, rotary evaporated to remove methylene chloride, and dried in vacuo to obtain a polymerizable benzophenone derivative photoinitiator 4—(acryloyloxy -6-hydroxy-5,7-dioxy)benzophenone. The structure is shown in Formula 6: 1 H NMR (250MHz) in CDCl 3 : δ2ppm (1H, OH), 1.464, 1.57, 3.37, 4.15, 4.26ppm (10H, CH 2 ), 5.08ppm (1H, CH), 5.80 , 6.05, 6.43ppm (3H, CH=CH 2 ), 6.87-7.70ppm (9H, benzene ring)
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| CN111269336A (en) * | 2020-03-22 | 2020-06-12 | 胥彩虹 | Polymerizable photoinitiator and preparation method thereof |
| CN112796000A (en) * | 2021-01-20 | 2021-05-14 | 东华大学 | A kind of aliphatic polyester with high gel content and high crystallinity and preparation method thereof |
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| CN114805642A (en) * | 2022-03-11 | 2022-07-29 | 广州五行材料科技有限公司 | Polymerizable benzophenone photoinitiator and preparation method thereof |
| CN114957834A (en) * | 2022-05-31 | 2022-08-30 | 马鞍山恒粤塑胶有限公司 | Plastic for washing liquid plastic packaging bottle and preparation method thereof |
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