CN110950768B - 一种可光漂白的可见光引发剂及其制备方法和应用 - Google Patents
一种可光漂白的可见光引发剂及其制备方法和应用 Download PDFInfo
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- CN110950768B CN110950768B CN201911089719.6A CN201911089719A CN110950768B CN 110950768 B CN110950768 B CN 110950768B CN 201911089719 A CN201911089719 A CN 201911089719A CN 110950768 B CN110950768 B CN 110950768B
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- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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Abstract
本发明公开了一种可光漂白的可见光引发剂以及其制备方法和应用，属于可见光光固化领域。现有技术在可见光光固化过程中，存在固化体系会吸收可见光导致可见光的穿透性降低以及固化体系的固化深度降低的问题。本发明的光引发剂可以成功引发可见光自由基光聚合，且聚合完成后的材料可从有色转变为无色透明，拓宽了材料的使用范围，同时也提高其固化深度。本发明还提供了这一类可光漂白的可见光引发剂制备方法，将芳醛与含活泼亚甲基的化合物通过缩合反应制备这类可光漂白的可见光引发剂。该类光引发剂合成方法简单，并且可通过分子结构调节改变其吸收波长以适应不同波长的光源，应用范围广。
Description
技术领域
本发明属于可见光光固化技术领域，具体涉及一种可光漂白的可见光引发剂及其制备方法和应用。
背景技术
光固化技术具有耗能低、污染小、效率高、室温速度快、固化完全等特点，是一类绿色环保技术，可以广泛应用于油墨、涂料、光敏电阻、胶黏剂、印刷电路板、3D打印等领域。光引发剂作为光固化材料的重要组成部分，不仅决定着光固化的速率以及程度，也影响光固化产品的性能。大的光密度和高强度是紫外光固化技术获得商业成功的关键。尽管紫外光固化技术在很多领域都得到广泛的应用，但该技术存在一定的固有缺陷，比如产生臭氧，固化深度不够等，并且在长时间的紫外光照射，对人体会有极大的伤害。
这些问题可以通过使用可见光作为光源来得以解决。可见光光固化技术具有很多优点：第一，可见光比较安全，对人体无害，廉价易得；第二，单体或预聚物一般不会吸收可见光，这样可以减少可见光的能力损失，透光效果比较好，能够穿透较厚的材料，可以改善固化深度。在可见光光引发剂体系中，开发高效、抗氧阻、绿色、多功能性的光引发剂体系已经成为目前研究的重点。为了保证其可见光区的吸收，可见光引发剂必然是带颜色的，因此，形成的光固化材料带有颜色，这将限制可见光引发剂的应用范围；这种颜色体系对可见光有强烈吸收，导致光线不能深层穿透光固化，从而会影响光固化深度。可光漂白的可见光引发剂是新型的可见光引发剂，在可见光光照条件下，光固化体系会的颜色将转变至无色透明，使光固化材料的颜色不受可见光引发剂的颜色的影响。另外，光固化体系转变为无色透明，固化体系并不会再吸收该波段可见光，这样会提高可见光的穿透性，提高可见光的固化深度。刘仁等(ACS Appl.Mater.Interfaces.2018,10,16113-16123.)提出香豆素类的可光漂白的可见光引发剂，该引发剂在单体或预聚物以及溶剂中具有较好的光漂白性能。该引发剂可以提高可见光的穿透性以及巯基-烯烃体系的光固化深度。Robert Liska等(Angew.Chem.Int.Ed.2018,57,12146-12150)报道了一类锡可见光引发剂，该类引发剂可以在522nm和460nm LED下高效引发HDDA聚合且能够有效提高固化深度。
经过查阅文献以及资料，目前有关可光漂白的可见光引发剂的报道较少，本发明主要针对这种现状公开一系列可光漂白的可见光引发剂，该类引发剂具有引发效果好、波长可调、光漂白性能好等特点。
发明内容
为了克服现有技术在可见光光固化过程中，固化体系会吸收可见光导致可见光的穿透性降低以及固化体系的固化深度降低的问题，本发明的目的是提供了一类可光漂白的可见光引发剂。此类光引发剂可以成功引发可见光自由基光聚合，且聚合完成后的材料可从有色转变为无色透明，拓宽了材料的使用范围。同时也提高其固化深度。
本发明的第二个目的是提供可光漂白的可见光引发剂的制备方法，将芳醛与含活泼亚甲基的化合物通过缩合反应制备这类可光漂白的可见光引发剂。该类光引发剂合成方法简单，并且可通过分子结构调节改变其吸收波长以适应不同波长的光源，应用范围广。
本发明的第三个目的是提供可光漂白的可见光引发剂的应用。
为了实现上述目的，本发明采用如下技术方案：
第一方面，提供一种可光漂白的可见光引发剂，其结构式为：
R1，R2为烷基，苯基，烯丙基，丙烯酰基或甲基丙烯酰基；
R3为氢，烷基，烯丙基，二烷基胺基，环烷胺基或烷氧基；
R4，R5，R6为烷基，烯丙基，丙烯酰基或甲基丙烯酰基；
R7为氢，烷基，二烷基胺基，环烷胺基或者烯丙基；
R8为烷基，苯基或者烯丙基；
X为O或S；
A可以分为A1和A2两类；
A1代表
其中
R11，R12，R13为烷基，烯丙基；
A2代表
第二方面，提供上述可光漂白的可见光引发剂的制备方法，将芳醛与含活泼亚甲基的化合物与溶剂混合均匀，以弱碱和弱酸混合物或强碱为催化剂，在一定温度下反应12-48h，减压除去低沸物，纯化后即得可光漂白的可见光引发剂。
优选的，所述弱碱和弱酸混合物中弱碱包括但不局限于环己胺、吡啶、六氢吡啶以及其它一级胺、二级胺等，弱酸包括但不局限于甲酸、乙酸、丙酸；所述强碱催化剂包括但不局限于三级丁醇钾、氨基钠、氢化钠、氢化钾、三苯甲基钠以及二异丙基胺基锂；所使用的溶剂包括但不局限于苯、甲苯、二甲苯、四氢呋喃、乙醚等醚类溶剂、三级丁醇。
优选的，所述的芳醛和活泼亚甲基的化合物的摩尔比为1:1-1:3，溶剂的质量用量依据反应特征为芳醛的10-50倍，催化剂的摩尔用量依据反应特征为芳醛的10％-300％。
优选的，所述反应温度依据反应特征可以从0℃到溶剂沸点。
第三方面，提供本发明可光漂白的可见光引发剂在引发一系列单体发生自由基聚合或交联固化反应中的应用，具体过程如下：将一定量的可光漂白的可见光引发剂和一定量的单体或预聚物混合均匀后平铺于聚四氟乙烯模板或玻璃板上，氩气保护下，可见光LED光照30min即可固化成无色透明膜。
本发明设计基本原理在于，可光漂白的可见光引发剂在可见光的作用下，通过光物理化学作用，分子中的双键断裂，从而产生活性自由基，活性自由基能够引发一系列单体或者预聚物发生自由基聚合或者交联固化，并且聚合完成后体系转变为无色透明。
本发明的优点和有益效果为：
(1)可光漂白的可见光引发剂能够引发单体发生自由基聚合并且聚合前后颜色发生改变，拓展了可见光光引发剂的应用范围，具有更广泛的适用性。
(2)提高可见光光固化体系的光固化深度。
(3)此类可光漂白的可见光引发剂可以通过结构调整来适应不同波长的可见光光源，使得引发剂与光源的匹配性更合理，拓宽了该引发剂的应用范围。
(4)原料廉价易得，合成方法较简单。
附图说明
附图1实例1制备的可光漂白的可见光引发剂的1H NMR图谱。
附图2实例1制备的可光漂白的可见光引发剂的13C NMR图谱。
附图3实例1制备的可光漂白的可见光引发剂在甲苯溶液中的可见光光解图谱。
附图4实例1制备的可光漂白的可见光引发剂在甲苯溶液中光照前后的对比图。
附图5实例1制备的可光漂白的可见光引发剂引发HDDA光聚合曲线。
附图6实例1制备的可光漂白的可见光引发剂引发HDDA光聚合前后变化图片。
具体实施方式
通过以下详细说明结合附图可以进一步理解本发明的特点和优点。所提供的实施例仅是对本发明方法的说明，而不以任何方式限制本发明揭示的其余内容。
【实施例1】式1所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入4-二苯胺基苯甲醛(0.27g，1mmol)，环己胺(0.1g，1mmol)，丙二酸二叔丁酯(0.16g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应48h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到黄色粉末状固体即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ7.37(s,1H,-C＝CH-Ar),7.28(d,J＝8.7Hz,2H,Ar-H),7.20(dd,J＝14.2,6.6Hz,4H,Ar-H),7.02(dd,J＝16.8,7.8Hz,6H,Ar-H),6.88(d,J＝8.7Hz,2H,Ar-H),1.46(d,J＝5.1Hz,18H,-C(CH3)3).
其核磁氢谱、核磁碳谱分别示于附图1以及附图2，由附图1可以看到，在8.02ppm处为双键上的质子峰，6-8ppm处为苯环上质子峰，1.3ppm处分别为叔丁基上的甲基的质子峰，3.0-3.3以及1.1-1.2ppm处分别为乙胺基上的亚甲基以及甲基的质子峰。从附图2可以看出，167.62ppm以及165.02ppm处均为O＝C的碳峰，153.69ppm以及122.48ppm处为肉桂酸酯基团中的C＝C的碳峰，81ppm以及26ppm处分别为叔丁基的季碳以及伯碳的碳峰，这些结果表明4-二苯胺基苯甲醛与丙二酸二叔丁基酯发生缩合反应得到肉桂酸酯类的衍生物。
其在甲苯溶液中的可见光光解谱图如附图3所示，由附图3可以看出，随着可见光光照时间的延长，可光漂白的可见光引发剂的最大吸收波长处的吸光度降低，说明可光漂白的可见光引发剂在甲苯溶液中可以发生光降解，由附图4可以看出，可光漂白的可见光引发剂在甲苯溶液中是黄色透明的，在405nm的LED灯光照下，该溶液由黄色透明转变为无色透明，说明该引发剂可以在溶液中实现可见光光漂白。将其引发HDDA单体聚合的曲线如附图5所示，根据附图5可以看出随着引发剂的浓度的增大，引发剂引发单体聚合的速率以及双键转化率也会提高，当引发剂浓度达到1×10-4mol/g时，双键转化率为72％。
【实施例2】式2所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2-烯丙基-4-二乙基胺基苯甲醛(0.217g，1mmol)，环己胺(0.1g，1mmol)，丙二酸二乙酯(0.216g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应48h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到黄色透明液体即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.62(s,1H,-C＝CH-Ar),7.28(d,J＝8.7Hz,1H,Ar-H),7.20(dd,J＝14.2,6.6Hz,2H,Ar-H),5.92(dd,J＝16.8,7.8Hz,1H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,2H,-CH2CH＝CH2),4.29–4.18(m,4H,-OCH2CH3),3.36(q,J＝7.1Hz,4H,-NCH2CH3),3.14–2.96(m,2H,-CH2CH＝CH2),1.23(dt,J＝11.7,7.1Hz,6H,-OCH2CH3),1.00(t,J＝7.0Hz,6H,-NCH2CH3).
【实施例3】式3所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入氢化钠(0.072g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加2,4-二乙胺基苯甲醛(0.248g，1mmol)，无水乙酸乙酯(0.55g，3mmol)，无水四氢呋喃5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ8.08(d,J＝16.1Hz,1H,-C＝CH-Ar),7.65–7.36(m,1H,Ar-H),6.43–6.33(m,1H,Ar-H),6.30(d,J＝2.6Hz,1H,HC＝C-),6.19(d,J＝16.0Hz,1H,Ar-H),4.35–4.14(m,2H-OCH2CH3),3.37(q,J＝7.1Hz,4H,-NCH2CH3),3.04(q,J＝7.1Hz,4H,NCH2CH3),1.31(q,J＝7.2Hz,3H,-OCH2CH3),1.23–1.12(m,6H,-NCH2CH3),1.10–0.97(m,6H,-NCH2CH3).
【实施例4】式4所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入4-(二烯丙基胺基)-2-哌啶基-苯甲醛(0.284g，1mmol)，环己胺(0.1g，1mmol)，硝基甲烷(0.122g，2mmol)，冰醋酸(0.06g，1mmol)，二甲苯10g，在氩气的室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.13(d,J＝16.1Hz,1H,-C＝CH-Ar),7.97(d,J＝2.6Hz,1H,HC＝C-),7.65–7.36(m,1H,Ar-H),6.43–6.33(m,1H,Ar-H),6.19(d,J＝16.0Hz,1H,Ar-H),5.92(dd,J＝16.8,7.8Hz,2H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,4H,-CH2CH＝CH2),4.02(m,4H,-CH2-CH＝CH2),3.37(q,J＝7.1Hz,4H,-NCH2CH2-),1.7(q,J＝7.1Hz,4H,-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-NCH2CH2CH2-).
【实施例5】式5所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,4-二-(二乙基胺基)苯甲醛(0.248g，1mmol)，环己胺(0.1g，1mmol)，丙三腈(0.066g，1mmol)，冰醋酸(0.06g，1mmol)，10g，在氩气的保护下升温至100℃反应48h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色透明液体即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.29–8.13(d,J＝16.1Hz,1H,-C＝CH-Ar),8.03(s,1H,Ar-H),6.44(dd,J＝9.3,2.5Hz,1H,Ar-H),6.23(d,J＝2.5Hz,1H,Ar-H),3.44(q,J＝7.1Hz,4H,-NCH2CH3),3.05(q,J＝7.1Hz,4H,-NCH2CH3),1.32–1.16(m,6H,-NCH2CH3),1.03(q,J＝7.1Hz,6H,-NCH2CH3).
【实施例6】式6所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,4-二-(二乙胺基)苯甲醛(0.248g，1mmol)，环己胺(0.1g，1mmol)，1,3-茚二酮(0.146g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ9.12–8.87(m,1H,-C＝CH-),8.18(s,1H,Ar-H),7.96–7.69(m,2H,Ar-H),7.69–7.42(m,2H,Ar-H),6.34(dt,J＝22.3,11.2Hz,1H,Ar-H),6.11(dd,J＝12.0,2.5Hz,1H,Ar-H),3.47–3.26(m,4H,-NCH2CH3),3.11(q,J＝7.1Hz,4H,-NCH2CH3),1.22–1.12(m,6H,-NCH2CH3),1.07(t,J＝7.1Hz,6H,-NCH2CH3).
【实施例7】式7所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3,4,5-三甲氧基苯甲醛(0.196g，1mmol)，环己胺(0.1g，1mmol)，丙三腈(0.066g，1mmol)，冰醋酸(0.06g，1mmol),甲苯10g，在氩气的保护下升温至100℃反应48h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到黄色透明液体即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.29–8.13(d,J＝16.1Hz,1H,-C＝CH-Ar),6.91(m,2H,Ar-H),3.71(s,9H,-OCH3).
【实施例8】式8所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入1,2,3-三-(2-甲基丙烯酰基)-5-苯甲醛(0.358g，1mmol)，环己胺(0.1g，1mmol)，硝基甲烷(0.122g，2mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.29–8.13(d,J＝16.1Hz,-C＝CH-Ar,1H),7.97(d,J＝2.6Hz,1H,H-C＝C-),6.81(m,2H,Ar-H),6.4-6.1(d,J＝8.7Hz,6H,-C＝CH2),2.1(m,9H,CH3CH＝CH2).
【实施例9】式9所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入氨基钠(0.072g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加3,4,5-三烯丙基氧基苯甲醛(0.274g，1mmol)，无水丙酮(0.174g，3mmol)，无水乙醚5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ7.6(d,J＝16.1Hz,-C＝CH-Ar,1H),6.7(d,J＝2.6Hz,1H,HC＝C-),6.6(m,2H,Ar-H),5.92(dd,J＝16.8,7.8Hz,3H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,6H,-CH2CH＝CH2),4.7(m,6H,-CH2CH＝CH2).
【实施例10】式10所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3,5-二烯丙基氧基-4-甲氧基苯甲醛(0.248g，1mmol)，环己胺(0.1g，1mmol)，二甲磺酰基甲烷(0.172g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ7.6(d,J＝16.1Hz,-C＝CH-Ar,1H),6.7(m,2H,Ar-H),5.92(dd,J＝16.8,7.8Hz,2H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,4H,-CH2-CH＝CH2),4.7(m,4H,-CH2-CH＝CH2),3.71(s,3H,-OCH3),2.8(s,6H,-SO2CH3).
【实施例11】式11所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3,5-二甲基丙烯酰氧基-4-甲氧基苯甲醛(0.304g，1mmol)，环己胺(0.1g，1mmol)，环己烷-1,3-二酮(0.112g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应48h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,-C＝CH-Ar,1H),6.81(m,2H,Ar-H),6.4-6.1(d,J＝8.7Hz,4H,-C＝CH2),3.71(s,3H,-OCH3),3.2(m,4H,O＝C-CH2-),2.1(m,6H,CH3CH＝CH2),1.5(m,2H,O＝C-CH2-CH2-).
【实施例12】式12所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3,5-二甲基丙烯酰氧基-4-甲氧基苯甲醛(0.304g，1mmol)，环己胺(0.1g，1mmol)，环戊-4-烯-1,3-二酮(0.096g，1mmol)，冰醋酸(0.06g，1mmol)，苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,-C＝CH-Ar,1H),7.4(m,-CH＝CH-,2H),6.81(m,2H,Ar-H),6.4-6.1(d,J＝8.7Hz,4H,-C＝CH2),3.71(s,3H,-OCH3),2.1(m,6H,CH3CH＝CH2).
【实施例13】式13所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3-苯并呋喃甲醛(0.146g，1mmol)，吡啶(0.079g，1mmol)，二甲磺酰基甲烷(0.172g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,-C＝CH-Ar,1H),8.21(m,1H,Ar-H),7.84(m,1H,Ar-H),7.59(m,1H,Ar-H),7.39(m,1H,Ar-H),7.31(m,1H,Ar-H),2.8(s,6H,-SO2CH3).
【实施例14】式14所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入5-二乙基胺基-2-甲基苯并呋喃-3-醛(0.231g，1mmol)，哌啶(0.85g，1mmol)，丙二酸二乙酯(0.216g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,-C＝CH-Ar,1H),7.77(m,1H,Ar-H),7.42(m,1H,Ar-H),6.75(m,1H,Ar-H),4.35–4.14(m,4H-OCH2CH3),3.47–3.26(m,4H,-NCH2CH3),2.57(s,3H,Ar-CH3),1.23(dt,J＝11.7,7.1Hz,6H,-OCH2CH3),1.03(q,J＝7.1Hz,6H,-NCH2CH3).
【实施例15】式15所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入5-哌啶基苯并呋喃-3-醛(0.229g，1mmol)，环己胺(0.1g，1mmol)，1,8-二烯-4,6-壬二酮(0.152g，1mmol)，冰醋酸(0.06g，1mmol)，叔丁醇10g，在氩气的保护下升温至100℃反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,-C＝CH-Ar,1H),8.21(m,1H,Ar-H),7.77(m,1H,Ar-H),7.42(m,1H,Ar-H),6.75(m,1H,Ar-H),5.92(dd,J＝16.8,7.8Hz,2H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,4H,-CH2CH＝CH2),3.6(m,4H,-CH2CH＝CH2),3.37(q,J＝7.1Hz,4H,N-CH2CH2-),1.7(q,J＝7.1Hz,4H,-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-NCH2CH2CH2-).
【实施例16】式16所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入3-苯并噻吩甲醛(0.162g，1mmol)，环己胺(0.1g，1mmol)，环戊-4-烯-1,3-二酮(0.096g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.5(d,J＝16.1Hz,1H,-C＝CH-Ar),8.21(m,1H,Ar-H),8.0(m,1H,Ar-H),7.49(m,1H,Ar-H),7.42(m,1H,Ar-H),7.4(m,-CH＝CH-,2H),6.75(m,1H,Ar-H).
【实施例17】式17所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入氢化钾(0.072g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加5-烯丙基-2-哌啶基苯并噻吩-3-醛(0.285g，1mmol)，无水乙酸叔丁酯(0.174g，3mmol)，无水四氢呋喃5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ8.2(d,J＝16.1Hz,-CH＝CH-Ar,1H),8.21(m,1H,Ar-H),8.0(m,1H,Ar-H),7.49(m,1H,Ar-H),7.42(m,1H,Ar-H),6.3(d,J＝16.1Hz,-CH＝CH-Ar,1H),5.92(dd,J＝16.8,7.8Hz,2H,-CH2CH＝CH2),5.04(d,J＝8.7Hz,4H,-CH2CH＝CH2),3.3(m,4H,-CH2CH＝CH2),3.37(q,J＝7.1Hz,4H,-NCH2CH2-),1.7(q,J＝7.1Hz,4H,-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-NCH2CH2CH2-).
【实施例18】式18所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2-二乙基胺基-5-甲氧基苯并噻吩-3-醛(0.263g，1mmol)，环己胺(0.1g，1mmol)，硝基甲烷(0.061g，1mmol)，甲酸(0.046g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.27(m,1H,Ar-H),8.14(d,J＝16.1Hz,1H,-CH＝CH-Ar),7.86(d,J＝16.1Hz,-CH＝CH-Ar,1H),8.21(m,1H,Ar-H),7.11(m,1H,Ar-H),3.71(s,3H,-OCH3),3.47–3.26(m,4H,-NCH2CH3),1.07(t,J＝7.1Hz,6H,-NCH2CH3).
【实施例19】式19所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入1-甲基吲哚-3-醛(0.159g，1mmol)，环己胺(0.1g，1mmol)，1,3-茚二酮(0.146g，1mmol)，丙酸(0.074g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.7(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.6(m,1H,Ar-H),8.02(m,1H,Ar-H),7.93(m,2H,Ar-H),7.52(m,1H,Ar-H),7.36(m,2H,Ar-H),7.11(m,2H,Ar-H),3.7(s,3H,-NCH3).
【实施例20】式20所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入9-烯丙基吲哚-3-醛(0.235g，1mmol)，环己胺(0.1g，1mmol)，1,3-环戊二酮并萘环(0.198g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.8(m,2H,Ar-H),8.7(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.6(m,1H,Ar-H),8.15(m,2H,Ar-H),8.02(m,1H,Ar-H),7.76(m,2H,Ar-H),7.52(m,1H,Ar-H),7.36(m,1H,Ar-H),7.19(m,1H,Ar-H),6.02(dd,J＝16.8,7.8Hz,2H,-CH2CH＝CH2),5.9(d,J＝8.7Hz,4H,-CH2CH＝CH2),5.2(m,4H,-CH2CH＝CH2).
【实施例21】式21所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入三苯甲基钠(0.072g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加5-二乙胺基-1-苯基吲哚-3-醛(0.292g，1mmol)，乙酰丙酮(0.10g，1mmol)，无水甲苯5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ8.7(d,J＝16.1Hz,-CH＝CH-Ar,1H),7.8(m,1H,Ar-H),7.62(m,2H,Ar-H),7.58(m,1H,Ar-H),7.50(m,2H,Ar-H),7.36(m,1H,Ar-H),7.01(m,1H,Ar-H),6.2(m,1H,Ar-H),3.47–3.26(m,4H,-NCH2CH3),2.37(s,3H,O＝C-CH3,)1.07(t,J＝7.1Hz,6H,-NCH2CH3).
【实施例22】式22所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入叔丁基醇钠(0.288g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加1-烯丙基-5-哌啶基吲哚-3-醛(0.268g，1mmol)，异佛尔酮(0.138g，1mmol)，无水甲苯5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ8.6(m,1H,Ar-H),7.58(m,1H,Ar-H),7.0(d,J＝16.1Hz,-CH＝CH-Ar,1H),6.8(m,1H,Ar-H),6.6(m,1H,Ar-H),6.17(m,1H,-C＝CH-),6.04(m,1H,Ar-H),6.02(dd,J＝16.8,7.8Hz,1H,-CH2CH＝CH2),5.9(d,J＝8.7Hz,2H,-CH2CH＝CH2),5.2(m,2H,-CH2CH＝CH2),3.37(q,J＝7.1Hz,4H,-NCH2CH2-),2.09(s,3H,-CH＝CCH3),1.7(q,J＝7.1Hz,4H,-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-NCH2CH2CH2-),1.24(s,6H,-C(CH3)2).
【实施例23】式23所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入二异丙基胺基锂(0.321g，3mmol)，置于冰水浴中，在氩气的保护下缓慢滴加1-甲基-5-哌啶基吲哚-3-醛(0.242g，1mmol)，1,3-环己二酮(0.112g，1mmol)，，无水甲苯5.0g的混合溶液，30min滴加完毕，冰水浴反应12h，TCL检测原料反应完全，减压除去低沸，加入PE:EA＝10:1稀释，经过硅胶柱(PE:EA＝10:1)得到黄色透明油状液体。1H NMR(400MHz,CDCl3)δ8.6(m,1H,Ar-H),8.5(d,J＝16.1Hz,-CH＝CH-Ar,1H),6.8(m,1H,Ar-H),6.6(m,1H,Ar-H),6.04(m,1H,Ar-H),3.7(s,3H,-NCH3),3.37(q,J＝7.1Hz,4H,-NCH2CH2-),3.16(m,4H,O＝C-CH2-),1.7(q,J＝7.1Hz,4H,-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-NCH2CH2CH2-),1.52(m,2H,-CH2CH2CH2-).
【实施例24】式24所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入1-苯基-5-哌啶基吲哚-3-醛(0.304g，1mmol)，环己胺(0.1g，1mmol)，1H-迫苯并萘-1,3-二酮(0.196g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.7(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.49(m,2H,Ar-H),8.46(m,2H,Ar-H),7.87(m,2H,Ar-H),7.62(m,2H,Ar-H),7.58(m,1H,Ar-H),7.5(m,2H,Ar-H),7.35(m,1H,Ar-H),7.01(m,1H,Ar-H),6.2(m,1H,Ar-H),3.37(q,J＝7.1Hz,4H,-NCH2CH2-),1.7(q,J＝7.1Hz,4H-NCH2CH2-),1.6(q,J＝7.2Hz,2H,-N-CH2CH2CH2-).
【实施例25】式25所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入9-烯丙基-9H-咔唑-3-醛(0.235g，1mmol)，环己胺(0.1g，1mmol)，1H-迫苯并萘-1,3-二酮(0.198g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.7(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.49(m,2H,Ar-H),8.46(m,2H,Ar-H),8.34(m,1H,Ar-H),8.17(m,1H,Ar-H),7.87(m,2H,Ar-H),7.68(m,1H,Ar-H),7.59(m,1H,Ar-H),7.44(m,1H,Ar-H),7.33(m,1H,Ar-H),7.25(m,1H,Ar-H),6.02(dd,J＝16.8,7.8Hz,1H,-CH2CH＝CH2),5.9(d,J＝8.7Hz,2H,-CH2CH＝CH2),5.2(m,2H,-CH2CH＝CH2).
【实施例26】式26所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入9-烯丙基-9H-咔唑-3-醛(0.235g，1mmol)，环己胺(0.1g，1mmol)，1H-环戊烯并[b]蒽-1,3-二酮(0.246g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.80(m,2H,Ar-H),8.7(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.58(m,2H,Ar-H),8.34(m,1H,Ar-H),8.17(m,1H,Ar-H),8.01(m,2H,Ar-H),7.68(m,1H,Ar-H),7.54(m,2H,Ar-H),7.53(m,1H,Ar-H),7.5(m,1H,Ar-H),7.44(m,1H,Ar-H),7.33(m,1H,Ar-H),6.02(dd,J＝16.8,7.8Hz,1H,-CH2CH＝CH2),5.9(d,J＝8.7Hz,2H,-CH2CH＝CH2),5.2(m,2H,-CH2CH＝CH2).
【实施例27】式27所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,7-二-(二乙基胺基)-9-苯基-9H-咔唑-3-醛(0.413g，1mmol)，环己胺(0.1g，1mmol)，乙酰丙酮(0.10g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下升温至100℃12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.8(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.25(m,1H,Ar-H),7.62(m,2H,Ar-H),7.58(m,1H,Ar-H),7.50(m,2H,Ar-H),6.75(m,1H,Ar-H),6.7(m,1H,Ar-H),6.6(m,1H,Ar-H),6.2(m,1H,Ar-H),3.47–3.26(m,8H,-NCH2CH3),2.37(s,6H,O＝C-CH3),1.07(t,J＝7.1Hz,12H,-NCH2CH3).
【实施例28】式28所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,7-二烯丙基-9-苯基-9H-咔唑-3-醛(0.351g，1mmol)，环己胺(0.1g，1mmol)，硝基甲烷(0.061g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1HNMR(400MHz,CDCl3)δ8.43(m,1H,Ar-H),8.34(m,1H,Ar-H),8.26(m,1H,Ar-H),8.13(d,J＝16.1Hz,1H-CH＝CH-Ar),7.62(m,2H,Ar-H),7.58(m,1H,Ar-H),7.52(m,1H,Ar-H),7.51(m,1H,Ar-H),7.5(m,2H,Ar-H),7.16(m,1H,Ar-H),5.92(dd,J＝16.8,7.8Hz,1H,-CH2-CH＝CH2),5.04(d,J＝8.7Hz,2H,-CH2CH＝CH2),3.14–2.96(m,2H,-CH2-CH＝CH2).
【实施例29】式29所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,7-二-(二乙基胺基)-9-苯基-9H-咔唑-3-醛(0.413g，1mmol)，环己胺(0.1g，1mmol)，1,3-环戊二酮并萘环(0.198g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ8.98(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.85(m,2H,Ar-H),8.25(m,1H,Ar-H),8.18(m,1H,Ar-H),8.15(m,2H,Ar-H),7.76(m,2H,Ar-H),7.62(m,2H,Ar-H),7.58(m,1H,Ar-H),7.5(m,2H,Ar-H),6.75(m,1H,Ar-H),6.72(m,1H,Ar-H),6.2(m,1H,Ar-H),3.47–3.26(m,8H,-NCH2CH3),1.07(t,J＝7.1Hz,12H,-NCH2CH3).
【实施例30】式30所示可光漂白的可见光引发剂的制备
100mL单口烧瓶中加入2,7-二哌啶基-9-苯基-9H-咔唑-3-醛(0.437g，1mmol)，环己胺(0.1g，1mmol)，8,10-环戊二酮并菲环(0.246g，1mmol)，冰醋酸(0.06g，1mmol)，甲苯10g，在氩气的保护下室温反应12h，TCL检测原料几乎反应完全，减压除去低沸，加入PE:EA＝10:1稀释，离心，上层清液经过硅胶柱(PE:EA＝10:1)得到红色固体粉末即为可光漂白的可见光引发剂。1H NMR(400MHz,CDCl3)δ9.60(m,1H,Ar-H),8.98(d,J＝16.1Hz,1H,-CH＝CH-Ar),8.86(m,2H,Ar-H),8.84(m,1H,Ar-H),8.25(m,1H,Ar-H),8.17(m,1H,Ar-H),7.9(m,1H,Ar-H),7.75(m,1H,Ar-H),7.68(m,1H,Ar-H),7.63(m,1H,Ar-H),7.62(m,2H,Ar-H),7.58(m,2H,Ar-H),7.5(m,2H,Ar-H),6.76(m,1H,Ar-H),6.7(m,1H,Ar-H),6.2(m,1H,Ar-H),3.37(q,J＝7.1Hz,4H,N-CH2-CH2-),1.7(q,J＝7.1Hz,4H N-CH2-CH2-),1.6(q,J＝7.2Hz,2H,N-CH2-CH2-).
应用实施例1
将一份质量的实施例1所述的可光漂白的可见光引发剂和100份质量的1,6-己二醇二丙烯酸酯(HDDA)或聚氨酯丙烯酸酯(PUA)均匀后平铺于聚四氟乙烯模板或玻璃板上，氩气保护下，可见光LED光照30min即可固化成无色透明膜。附图6所示为引发剂引发HDDA聚合前后变化图，聚合之前体系为黄色透明状液体，用405nm的LED灯光照30min之后体系转变为无色透明固体，说明该引发剂可以引发HDDA聚合并且可以实现可见光光漂白。
Claims (2)
1.一种可光漂白的可见光引发剂，其特征在于，所述可见光引发剂的结构式为式1：
2.权利要求1所述的可光漂白的可见光引发剂在引发一系列单体发生自由基聚合或交联固化反应中的应用，其特征在于，具体过程如下：将一定量的可光漂白的可见光引发剂和一定量的单体或预聚物混合均匀后平铺于聚四氟乙烯模板或玻璃板上，氩气保护下，可见光LED光照30min即可固化成无色透明膜。
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