WO2019214121A1 - 聚丙烯酸酯类大分子光引发剂及其合成方法与应用 - Google Patents

聚丙烯酸酯类大分子光引发剂及其合成方法与应用 Download PDF

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WO2019214121A1
WO2019214121A1 PCT/CN2018/105392 CN2018105392W WO2019214121A1 WO 2019214121 A1 WO2019214121 A1 WO 2019214121A1 CN 2018105392 W CN2018105392 W CN 2018105392W WO 2019214121 A1 WO2019214121 A1 WO 2019214121A1
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photoinitiator
initiator
formula
molecular weight
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PCT/CN2018/105392
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French (fr)
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王辰龙
赵文超
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北京英力科技发展有限公司
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Priority to DE112018007592.3T priority Critical patent/DE112018007592T5/de
Priority to US17/042,967 priority patent/US11608395B2/en
Publication of WO2019214121A1 publication Critical patent/WO2019214121A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the invention relates to a macromolecular photoinitiator, in particular to a polyacrylate type macromolecular photoinitiator and a synthesis method and application thereof.
  • UV curing technology is widely used in coatings, inks, adhesives, photoresists, laser 3D printing, etc., without volatile organic solvents, fast curing speed, low energy consumption, and good curing properties.
  • the residual small molecule photoinitiator or its photolyzed fragments easily migrate from the cured coating to the surface, causing the product to produce odor and even toxic during use.
  • One way to avoid the above problems is to introduce an unsaturated double bond, that is, a polymerizable photoinitiator, into the small molecule photoinitiator.
  • the small molecule photoinitiator is anchored to the crosslinked network by participating in the polymerization.
  • Another approach is to directly synthesize a macromolecular photoinitiator that anchors the photoinitiating group to the macromolecular chain.
  • Macromolecular photoinitiators are typically prepared by copolymerization of small molecular photoinitiators containing polymerizable double bonds with other monomers. Among them, benzophenone is inexpensive, and as a hydrogen abstraction type photoinitiator does not produce photolysis fragments like the cleavage type, so much research has been conducted. For example, as shown in Formula IV, Carlini et al. obtain a polymeric photoinitiator containing a benzophenone unit by radical copolymerization (Polymer, 1983, 24: 101):
  • Li Hao et al. (Photosensing Science and Photochemistry, 2007, 25(6)) synthesized a series of water-soluble macromolecular photoinitiators PTX by copolymerization and epoxy ring-opening to introduce thioxanthone and glucosamine onto the same molecule.
  • These three photoinitiators can achieve good results in photopolymerization of acrylamide, and the curing rate is PTX-GA3>PTX-GA2>PTX-GA1, and the structure is as shown in Formula V.
  • Zeng Zhaohua et al. synthesized a macromolecular photoinitiator containing both a benzophenone group and a hydrogen donor group as shown in Formula VI.
  • Such macroinitiators immobilize two benzophenone groups on both sides of the rigid triazine ring, reducing the probability of adjacent free radical binding and increasing the efficiency of initiation.
  • the macroinitiator contains an amine-based hydrogen supply unit without the need to additionally add a hydrogen-donating component.
  • 3-ketocoumarin is used as a photoinitiator, which is particularly suitable for long-wave UV curing, but it is only a small molecule photoinitiator and has not been subjected to macromolecularization.
  • the invention provides a polyacrylate type macromolecular photoinitiator and a preparation method thereof, and the obtained product does not contain a component having a molecular weight of less than 1000, and can effectively avoid introduction of a small molecular weight substance and migration pollution generated thereby.
  • the present invention provides a polyacrylate type macromolecular photoinitiator, in particular, which does not contain a component having a molecular weight of less than 1000, and has the general formula of Formula I:
  • PI is a hydrogen abstraction photoinitiator group
  • R 1 and R 2 are each H or CH 3
  • R 3 is a C 1 -C 8 alkyl group, a C 1 -C 8 alkane substituted by a hydroxy group
  • group, a tip is C 5 -C 6 cycloalkyl substituted C 1 -C 3 alkyl, C 5 -C 6 cycloalkyl or H
  • n 1 is an integer value of 1
  • n 2 is greater than the value An integer equal to 0.
  • the PI of the formula I described in the present invention is selected from a benzophenone photoinitiator group, a coumarin photoinitiator group or a thioxanthone photoinitiator group.
  • the PI of the formula I in the present invention is selected from one or more of the formulae II-1 to II-11:
  • R 4 and R 5 in the formula II-11 are each a C 1 -C 4 alkyl group.
  • the mass percentage of the polyacrylate type macromolecular photoinitiator PI group of the present invention is between 20% and 85% of the polyacrylate type macromolecular photoinitiator.
  • the preparation method of the polyacrylate type macromolecular photoinitiator in the invention is characterized in that: in step 1, the compound of the formula III-1 and the compound of the formula III-2, the molecular weight regulator and the thermal initiator are dissolved in a solvent to be polymerized. Reaction; Step 2, after the completion of the polymerization reaction, the reaction solution is dropped into the post-treatment solvent, stirred, and then left to stand for separation, and the lower layer polymer is separated, and the solvent is removed under reduced pressure to obtain a product.
  • the thermal initiator in the present invention is selected from an azo initiator or an organic peroxy initiator, wherein the azo initiator is selected from the group consisting of azobisisobutyronitrile and azobisisoheptanenitrile;
  • the agent is selected from the group consisting of dibenzoyl peroxide, dodecyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di(2-ethylhexyl) peroxydicarbonate, and diperoxydicarbonate Isopropyl ester, dicyclohexyl peroxydicarbonate.
  • the molecular weight modifier in the present invention is dodecyl mercaptan; the post-treatment solvent is methanol or ethanol.
  • the present invention also provides a photocurable composition
  • a photocurable composition comprising:
  • ethylenically unsaturated compounds include: epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane Acrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound; monomer is monofunctional, difunctional or polyfunctional acrylate Or methacrylate.
  • the photocurable composition further contains at least one reactive amine-based initiator which can participate in polymerization, such as an acrylated amine-based initiator, such as IGM's Photomer 4250, Photomer 4775, etc.; or a polymerization having a molecular weight greater than 1000.
  • a reactive amine-based initiator which can participate in polymerization, such as an acrylated amine-based initiator, such as IGM's Photomer 4250, Photomer 4775, etc.; or a polymerization having a molecular weight greater than 1000.
  • Type tertiary amine promoter is a reactive amine-based initiator which can participate in polymerization.
  • the photocurable composition provided by the invention is used in the fields of food packaging printing, pharmaceutical packaging printing, furniture coating and the like, which have strict requirements on material migration, for example, using the light curing composition as a glazing oil printed on a paper bag, having a pole Low odor perception.
  • the product 170 g is a macromolecular photoinitiator containing an initiator group as shown in II-4. The molecular weight of the initiator was between 1000 and 100000 and the initiator group content was 42% by GPC. The data are shown in Table 1 and Figure 1.
  • the product 142 g is a macromolecular photoinitiator containing an initiator group as shown in II-4. The molecular weight of the initiator was between 1000 and 13000 and the initiator group content was 42% by GPC. The data is shown in Table 1.
  • the product 102 g was a macromolecular photoinitiator containing an initiator group as shown in II-4, and the initiator group content was 24%.
  • the data is shown in Table 1.
  • the product 178 g is a macromolecular photoinitiator containing an initiator group as shown in II-4, and the initiator group content is 73%.
  • the data is shown in Table 1.
  • the concentrated reaction solution was added dropwise with stirring. After stirring for 30 minutes, the mixture was allowed to stand for liquid separation. The lower layer of the resin was decomposed and dehydrated at 80 ° C for 1 hour to obtain a pale yellow color.
  • the product 11g is a macromolecular photoinitiator containing an initiator group as shown in Formula II-6, and the initiator group content is 38%.
  • the data is shown in Table 1.
  • 13 g is a macromolecular photoinitiator containing an initiator group as shown in Formula II-8, and the initiator group content is 43%.
  • the data is shown in Table 1.
  • the product, 11 g was a macromolecular photoinitiator containing an initiator group as shown in Formula II-1, and the initiator group content was 40%.
  • the data is shown in Table 1.
  • step 2 Add 5g of the first step product to the 250ml four-necked bottle, step 2 product 5g, butyl acrylate 10g, toluene 30g, nitrogen gas in the bottle, add 10g toluene, 0.6g azobisisobutyronitrile and 0.2g at 80 °C
  • a mixture of dodecanethiol was reacted for 6 h, and then warmed to 100 ° C for 2 h and then cooled to room temperature.
  • 80 g of methanol was placed in a 250 ml four-necked flask, and the temperature was lowered to 10 ° C. The concentrated reaction solution was added dropwise with stirring.
  • the product 18 g, is a macromolecular photoinitiator containing an initiator group as shown in Formula II-11, with an initiator group content of 43%, as shown in Table 1.
  • Figure 1 is a graph showing the molecular weight distribution of the GPC test of the product of Example 1.

Abstract

一种聚丙烯酸酯型大分子光引发剂及其合成方法与应用，不含有分子量小于1000的组分，能有效避免光引发剂中小分子量物质的引入及其所产生的气味及迁移污染，其通式如式I所示。

Description

[根据细则37.2由ISA制定的发明名称]　聚丙烯酸酯类大分子光引发剂及其合成方法与应用 技术领域
本发明涉及大分子光引发剂，尤其是一种聚丙烯酸酯型大分子光引发剂及其合成方法与应用。
技术背景
紫外光固化技术具有不含挥发性有机溶剂、固化速度快、能耗低、固化产物性能好等特点，因而广泛应用于涂料、油墨、粘合剂、光刻胶、激光3D打印等领域。
传统的光固化体系中，残留的小分子光引发剂或其光解碎片易从固化涂层中迁移到表面，导致产品在使用过程中发生产生气味，甚至有毒。避免上述问题的途径之一，就是向小分子光引发剂中引入不饱和双键，也就是可聚合光引发剂。通过参与聚合，把小分子光引发剂锚固在交联网络上。另一个途径是直接合成大分子型的光引发剂，把光引发基团锚固在大分子链上。与小分子光引发剂相比，大分子光引发剂具有挥发性低、气味小、迁移率小、与树脂的相容性好、功能多样性等优点，它是比可聚合光引发剂效果更显著的一类光引发剂。大分子光引发剂通常可利用含可聚合双键的小分子光引发剂与其它单体通过共聚制备。其中二苯甲酮价格低廉，而且作为夺氢型光引发剂不像裂解型那样产生光解碎片，因而研究较多。例如式Ⅳ所示，Carlini等通过自由基共聚合得到含二苯甲酮单元的高分子光引发剂(Polymer,1983,24:101)：
Figure PCTCN2018105392-appb-000001
李浩等人(感光科学与光化学,2007,25(6))通过共聚以及环氧开环将硫 杂蒽酮和葡萄糖胺引入到同一分子上合成了一系列水溶性的大分子光引发剂PTX-GA1、PTX-GA2、PTX-GA3。这3种光引发剂引发丙烯酰胺光聚合都能获得较好的效果，且固化速率PTX-GA3＞PTX-GA2＞PTX-GA1，结构如式Ⅴ所示。
Figure PCTCN2018105392-appb-000002
曾兆华等人合成一种如式Ⅵ所示的同时含有二苯甲酮基团和供氢胺基的大分子光引发剂。此类大分子引发剂将两个二苯甲酮基团固定在刚性三嗪环两侧，减少临近自由基结合的机率，提高引发效率。同时大分子引发剂含有胺基供氢单元，无需额外加入供氢组分。
Figure PCTCN2018105392-appb-000003
美国专利9951034中有使用3-酮香豆素作为光引发剂，其特别适用于长波UV固化，但其只是小分子光引发剂，并未进行大分子化。
总体来看，目前公布的大分子引发剂均未对产物的分子量进行要求。那么就不能保证产物中不包含未反应的小分子原料，或者分子量较低的低聚物。这些小分子原料和低聚物在使用时仍然是易于迁移的，或成为迁移污染的来源之一。EuPIA(欧洲印刷油墨协会)的有关规范是在印刷油墨中使用添加物时分子量大于1000Dt的物质可以免于风险测试，也就是说，小于1000Dt的物质要做风险测试，当测试迁移率小于10ppb时，被认定可以使用。本发明提出了一种聚丙烯酸酯型的大分子光引发剂及其制造方法，所得到的产物不含有分子量小于1000的组分，能有效避免小分子量物质的引入及其所产生的迁移污染。
发明内容
本发明提供一种聚丙烯酸酯型大分子光引发剂，特别是其不含有分子量小于1000的组分，其通式如式I所示：
Figure PCTCN2018105392-appb-000004
式I中，PI为夺氢型光引发剂基团；R 1、R 2各自分别为H或者CH 3；R 3为C 1—C 8的烷基、被羟基取代的C 1—C 8烷基、末端被C 5—C 6环烷基取代的C 1—C 3烷基、C 5—C 6环烷基或H；n 1取值为大于等于1的整数；n 2取值为大于等于0的整数。
本发明中所述式Ⅰ的PI选自二苯甲酮类光引发剂基团、香豆素类光引发剂基团或硫杂蒽酮类光引发剂基团。
本发明中所述式Ⅰ的PI选自式Ⅱ-1～Ⅱ-11之中的一种或几种：
Figure PCTCN2018105392-appb-000005
Figure PCTCN2018105392-appb-000006
其中，式Ⅱ-11中所述R 4、R 5分别为C 1-C 4的烷基。
本发明所述聚丙烯酸酯型大分子光引发剂PI基团的质量百分比占所述聚丙烯酸酯型大分子光引发剂的20％—85％之间。
本发明中所述聚丙烯酸酯型大分子光引发剂的制备方法，特征是：步骤一，将式Ⅲ-1化合物和式Ⅲ-2化合物、分子量调节剂、热引发剂溶于溶剂中发生聚合反应；步骤二，聚合反应完成后，将反应液滴入后处理溶剂中，搅拌后静置分液，分出下层聚合物，经减压脱除溶剂得到产物，
Figure PCTCN2018105392-appb-000007
式Ⅲ-1和式Ⅲ-2中PI、R 1、R 2、R 3定义如权利要求1所述。
本发明中所述热引发剂选自偶氮类引发剂或有机过氧类引发剂，其中偶氮类引发剂选自偶氮二异丁腈、偶氮二异庚腈；有机过氧类引发剂选自过氧化二苯甲酰、过氧化双十二酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二碳酸二(2-乙基己基)酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯。
本发明中所述分子量调节剂为十二硫醇；所述后处理溶剂为甲醇或乙醇。
本发明还提供一种光固化组合物，含有：
a.至少一种式Ⅰ所示的聚丙烯酸酯类大分子光引发剂；
b.至少一种可参与自由基聚合的烯键式不饱和化合物。
其中，烯键式不饱和化合物包括：环氧丙烯酸酯树脂、聚氨酯丙烯酸酯树脂、聚酯丙烯酸酯树脂、聚醚丙烯酸酯树脂、丙烯酸酯化聚丙烯酸酯、环氧甲基丙烯酸酯树脂、聚氨酯甲基丙烯酸酯树脂、聚酯甲基丙烯酸酯树脂、聚醚甲基丙烯酸酯树脂、丙烯酸酯化聚甲基丙烯酸酯、烯丙基醚化合物；单体为单官能团、双官能团或多官能团的丙烯酸酯或甲基丙烯酸酯。
上述光固化组合物进一步含有至少一种可参与聚合的活性胺类助引发剂，例如丙烯酸化的胺类助引发剂，如IGM公司的Photomer 4250、Photomer 4775等；或一种分子量大于1000的聚合型叔胺类助引发剂。
本发明提供的的光固化组合物用于食品包装印刷、药品包装印刷、家具涂装等对物质迁移有严格要求的领域，例如利用本光固化组合物作为上光油印刷在纸袋上，具有极低的气味感知。
具体实施方式
原料制备例一4-(2-羟基乙氧基)二苯甲酮的制备
步骤一：
在2500ml四口瓶中加入400g无水三氯化铝750g二氯乙烷，降至5℃，滴加250g乙二醇苯醚醋酸酯，反应4h，将反应液滴入1000ml水中，水洗3次，有机相脱溶后得产物[2-(4-苯甲酰基)苯氧基]乙醇醋酸酯350g。
步骤二：
在2000ml四口瓶中放入上步产物[2-(4-苯甲酰基)苯氧基]乙醇醋酸酯350g和1000g甲苯，滴加350g 20％氢氧化钠水溶液，50℃反应4h后，每次用500ml水，50℃水洗3次，降至-15℃结晶得4-(2-羟基乙氧基)二苯甲酮250g。
原料制备例二2-(4-苯甲酰基)苯氧基乙氧基乙醇的制备
步骤一：
在250ml四口瓶中加入100g 2-(2-苯氧基乙氧基)乙醇和60g醋酐，120℃反应4h后减压脱溶，得到乙酸2-(2-苯氧基乙氧基)乙酯120g。
步骤二：
在500ml四口瓶中加入80g无水三氯化铝，150g二氯乙烷，降至5℃，滴加50g上步产物乙酸2-(2-苯氧基乙氧基)乙酯，反应4h，将反应液滴入200ml水中，水洗3次，有机相脱溶后得产物[2-(4-苯甲酰基)苯氧基乙氧基]乙醇醋酸酯70g。
步骤三：
在500ml四口瓶中放入上步产物[2-(4-苯甲酰基)苯氧基乙氧基]乙醇醋酸酯70g和100g异丙醇，滴加70g 20％氢氧化钠水溶液，室温反应4h后，每次用100ml20％氯化钠水溶液，水洗3次，有机相旋蒸脱溶得产物2-(4-苯甲酰基)苯氧基乙氧基乙醇50g。
实施例一
步骤一：
在500ml四口瓶中放入原料制备例1的产物4-(2-羟基乙氧基)二苯甲酮90g，丙烯酸57g，对甲苯磺酸1.5g，对苯二酚0.045g，甲苯150g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状液体丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯112g。
步骤二：
1L四口瓶中放入上步产物丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯100g，丙烯酸丁酯100g，甲苯300g，氮气置换瓶内气体，80℃滴加100g甲苯、12g偶氮二异丁腈和4g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。70℃减压旋蒸去除溶剂200g。在1L四口瓶中放入400g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物170g，为含如Ⅱ-4所示引发剂基团的大分子光引发剂。经GPC测试引发剂分子量在1000～100000之间,引发剂基团含量42％，数据见表1及图1。
实施例二
步骤一：
在500ml四口瓶中放入4-(2-羟基乙氧基)二苯甲酮90g，丙烯酸57g，对甲苯磺酸1.5g，对苯二酚0.045g，甲苯150g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状液体丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯112g。
步骤二：
1L四口瓶中放入上步产物丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯100g，丙烯酸丁酯100g，甲苯300g，氮气置换瓶内气体，80℃滴加100g甲苯、24g偶氮二异庚腈和10g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。70℃减压旋蒸去除溶剂200g。在1L四口瓶中放入400g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物142g，为含如Ⅱ-4所示引发剂基团的大分子光引发剂。经GPC测试引发剂分子量在1000～13000之间,引发剂基团含量42％，数据见表1。
实施例三
步骤一：
在500ml四口瓶中放入4-(2-羟基乙氧基)二苯甲酮90g，丙烯酸57g，对甲苯磺酸1.5g，对苯二酚0.045g，甲苯150g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状液体丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯112g。
步骤二：
1L四口瓶中放入上步产物丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯60g，丙烯酸丁酯140g，甲苯300g，氮气置换瓶内气体，80℃滴加100g甲苯、24g偶氮二异庚腈和10g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。70℃减压旋蒸去除溶剂200g。在1L四口瓶中放入400g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物102g，为含如Ⅱ-4所示引发剂基团的大分子光引发剂,引发剂 基团含量24％，数据见表1。
实施例四
步骤一：
在500ml四口瓶中放入4-(2-羟基乙氧基)二苯甲酮90g，丙烯酸57g，对甲苯磺酸1.5g，对苯二酚0.045g，甲苯150g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状液体丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯112g。
步骤二：
1L四口瓶中放入上步产物丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯180g，丙烯酸丁酯420g，甲苯300g，氮气置换瓶内气体，80℃滴加100g甲苯、24g偶氮二异庚腈和10g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。70℃减压旋蒸去除溶剂200g。在1L四口瓶中放入400g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物178g，为含如Ⅱ-4所示引发剂基团的大分子光引发剂,引发剂基团含量73％，数据见表1。
实施例五
步骤一：
在500ml四口瓶中放入原料制备例二的产物2-(4-苯甲酰基苯氧基乙氧基)乙醇20g，丙烯酸15g，对甲苯磺酸0.35g，对苯二酚0.005g，甲苯75g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状丙烯酸[2-(4-苯甲酰基)苯氧基乙氧基]乙酯27g。
步骤二：
在250ml四口瓶中加入上步产物丙烯酸[2-(4-苯甲酰基)苯氧基乙氧基]乙酯10g，丙烯酸丁酯10g，甲苯30g，氮气置换瓶内气体，100℃滴加10g甲苯、0.6g过氧化苯甲酰和0.2g十二硫醇的混合液，反应6h后升温至120℃保持2h后降至室温。在250ml四口瓶中放入80g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡 黄色产物11g为含如式Ⅱ-6所示引发剂基团的大分子光引发剂,引发剂基团含量38％，数据见表1。
实施例六
步骤一：
在250ml四口瓶中放入2-羟基硫杂蒽酮10g，丙烯酸8g，甲苯20g，对甲苯磺酸0.2g，对苯二酚0.005g，回流脱水反应12h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得13g黄色油状液体。
步骤二：
在250ml四口瓶中加入上步产物10g，丙烯酸丁酯10g，甲苯30g，氮气置换瓶内气体，80℃滴加10g甲苯、0.6g偶氮二异丁腈和0.2g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。在250ml四口瓶中放入80g甲醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到黄色产物13g，为含如式Ⅱ-8所示引发剂基团的大分子光引发剂,引发剂基团含量43％，数据见表1。
实施例七
步骤一：
在250ml四口瓶中放入10g 4-羟基二苯甲酮，5g丙烯酰氯，10g碳酸钾，20g DMF，80℃反应4h后减压脱溶，30g乙醇溶解后结晶，得12g白色固体粉末状的丙烯酸(4-苯甲酰基)苯酯。
步骤二：
在250ml四口瓶中加入上步产物10g，丙烯酸丁酯10g，甲苯30g，氮气置换瓶内气体，80℃滴加10g甲苯、0.6g偶氮二异丁腈和0.2g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。在250ml四口瓶中放入80g乙醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物11g，为含如式Ⅱ-1所示引发剂基团的大分子光引发剂，引发剂基团含量40％，数据见表1。
实施例八
步骤一：
在250ml四口瓶中放入2-羟基硫杂蒽酮10g，丙烯酸8g，甲苯20g，对甲苯磺酸0.2g，对苯二酚0.005g，回流脱水反应12h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得13g黄色油状液体。
步骤二：
在500ml四口瓶中放入原料制备例1的产物4-(2-羟基乙氧基)二苯甲酮90g，丙烯酸57g，对甲苯磺酸1.5g，对苯二酚0.045g，甲苯150g，回流脱水反应24h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得黄色油状液体丙烯酸[2-(4-苯甲酰基)苯氧基]乙酯112g。
步骤三：
在250ml四口瓶中加入上步骤一产物5g，步骤二产物5g，丙烯酸丁酯10g，甲苯30g，氮气置换瓶内气体，80℃滴加10g甲苯、0.6g偶氮二异丁腈和0.2g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。在250ml四口瓶中放入80g甲醇，降至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到黄色产物13g，为同时含如式Ⅱ-4和Ⅱ-8所示引发剂基团的大分子光引发剂,引发剂基团含量43％，数据见表1。
实施例九
步骤一：
在250ml四口瓶中放入3-[4'-(2”-羟乙基)苯甲酰基)-5,7-二甲氧基香豆素10g，丙烯酸8g，甲苯20g，对甲苯磺酸0.2g，对苯二酚0.005g，回流脱水反应12h后，每次使用50ml水，水洗3次，至水相pH≈6～7，分液后减压脱溶，得12g黄色油状液体。
步骤二：
在250ml四口瓶中加入上步产物10g，丙烯酸丁酯10g，甲苯30g，氮气置换瓶内气体，80℃滴加10g甲苯、0.6g偶氮二异丁腈和0.2g十二硫醇的混合液，反应6h后升温至100℃保持2h后降至室温。在250ml四口瓶中放入80g乙醇，降 至10℃，在搅拌下滴入浓缩后的反应液，搅拌30min后静置分液，下层树脂80℃减压旋蒸脱溶1h，得到淡黄色产物18g，为含如式Ⅱ-11所示引发剂基团的大分子光引发剂，引发剂基团含量43％，数据见表1。
表1 GPC法测量分子量数据
样品名称 测试项目 Mn Mw 分子量分布最小值
实施例一产物 分子量 7711.9 15819 ＞1000
实施例二产物 分子量 3262.6 5214.7 ＞1000
实施例三产物 分子量 5276.8 8365.2 ＞1000
实施例四产物 分子量 9535.1 19833 ＞1000
实施例五产物 分子量 9022.0 18332 ＞1000
实施例六产物 分子量 8532.1 16255 ＞1000
实施例七产物 分子量 6522.4 9521.2 ＞1000
实施例八产物 分子量 8032.8 15997 ＞1000
实施例九产物 分子量 9032.1 16322.1 ＞1000
表1
应用例
实施例九聚丙烯酸酯型大分子的应用
按表2质量比例配制10组配方，使用25μm线棒涂布于白卡纸板上，2000W高压汞灯4m/min带速固化1遍后，得到F1-F10共10组样板，指触干法测试固化效果；人为感测固化表面的气味。测试结果如表3所示，含有本发明提供的聚丙烯酸酯型大分子光引发剂固化性能良好，而且气味低于市售小分子光引发剂和大分子光引发剂。
表2光固化组合物配方表
Figure PCTCN2018105392-appb-000008
表2
表3光固化组合物的应用检测结果
实验配方 光引发剂 固化效果 固化后表面气味
F1 实施例一产物 固化良好 几乎无气味
F2 实施例二产物 固化良好 几乎无气味
F3 实施例三产物 固化良好 几乎无气味
F4 实施例四产物 固化良好 几乎无气味
F5 实施例五产物 固化良好 几乎无气味
F6 实施例六产物 固化良好 几乎无气味
F7 实施例七产物 固化良好 几乎无气味
F8 实施例八产物 固化良好 几乎无气味
F9 实施例九产物 固化良好 几乎无气味
F10 二苯甲酮 固化良好 有明显气味
F11 Omnipol BP 固化良好 略有气味
表3
附图说明
图1为实施例一产物的GPC测试分子量分布图。

Claims (14)

  1. 一种聚丙烯酸酯型大分子光引发剂，其特征是不含有分子量小于1000的组分，其通式如式I所示：
    Figure PCTCN2018105392-appb-100001
    式I中，PI为夺氢型光引发剂基团；R 1、R 2各自分别为H或者CH 3；R 3为C 1—C 8的烷基、被羟基取代的C 1—C 8烷基、末端被C 5—C 6环烷基取代的C 1—C 3烷基、C 5—C 6环烷基或H；n 1取值为大于等于1的整数；n 2取值为大于等于0的整数。
  2. 权利要求1中所述式Ⅰ的PI选自二苯甲酮类光引发剂基团、香豆素类光引发剂基团或硫杂蒽酮类光引发剂基团。
  3. 权利要求2中所述式Ⅰ的PI选自式Ⅱ-1～Ⅱ-11之中的一种或几种：
    Figure PCTCN2018105392-appb-100002
    Figure PCTCN2018105392-appb-100003
    其中，式Ⅱ-11中所述R 4、R 5分别为C 1‐C 4的烷基。
  4. 权利要求1中所述聚丙烯酸酯类大分子光引发剂PI基团质量百分比占聚丙烯酸酯型大分子光引发剂的20％—85％之间。
  5. 权利要求1中所述聚丙烯酸酯型大分子光引发剂的制备方法，其特征是：步骤一，将式Ⅲ-1化合物和、化合物、分子量调节剂、热引发剂溶于溶剂中发生聚合反应；步骤二，聚合反应完成后，将反应液滴入后处理溶剂中，静置分液，分出下层聚合物及所含的溶剂，经减压脱除溶剂得到产物，
    Figure PCTCN2018105392-appb-100004
    式Ⅲ-1和式Ⅲ-2中PI、R 1、R 2、R 3定义如权利要求1所述。
  6. 权利要求5中所述后处理溶剂为甲醇或乙醇。
  7. 权利要求5中所述分子量调节剂为十二硫醇。
  8. 权利要求5中所述热引发剂选自偶氮类引发剂或有机过氧类引发剂。
  9. 权利要求8中所述偶氮类引发剂选自偶氮二异丁腈、偶氮二异庚腈。
  10. 权利要求8中所述有机过氧类引发剂选自过氧化二苯甲酰、过氧化双十二酰、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二碳酸二(2-乙基己基)酯、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯。
  11. 一种光固化组合物，含有：
    a.至少一种权利要求1所述的聚丙烯酸酯类大分子光引发剂；
    b.至少一种可参与自由基聚合的烯键式不饱和化合物。
  12. 权利要求11的光固化组合物进一步含有至少一种可参与聚合的活性胺类助引发剂，或一种分子量大于1000的聚合型叔胺类助引发剂。
  13. 权利要求11所述的光固化组合物用于食品包装印刷、药品包装印刷、家具涂装。
  14. 一种由将权利要求11的组合物涂覆并固化在基材上所形成的物品。
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