CN109970727B - 一种长波长可聚合光引发剂及其制备方法 - Google Patents
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- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种长波长可聚合光引发剂,涉及光聚合领域中光引发剂的合成技术领域,基于传统的光引发剂引发波长较短,小分子光引发剂在光聚合过程中易有小分子残留进而迁移的问题而提出,本发明公开的长波长可聚合光引发剂,其结构式通式如下:其制备方法主要是利用N‑乙烯基吡咯烷酮与无α‑H的醛的缩合反应来制备。本发明的有益效果在于:N‑乙烯基吡咯烷酮本身就是一种光固化单体,其N上连着双键,用其反应得到的产物中由于含有可光聚合的双键,光聚合时可光引发又可光聚合;这类光引发剂在光聚合过程中被聚合在体系当中,所以在固化体系当中就没有小分子光引发剂的残留,从而达到低迁移;这类结构的引发剂最大吸收波长达到430nm,可应用于LED灯源引发光聚合。
Description
技术领域
本发明涉及光聚合领域中光引发剂的合成技术领域,具体涉及一种长波长可聚合光引发剂及其制备方法。
背景技术
光引发剂是光聚合最核心的组成部分,它关系到配方体系在光照射时低聚物及稀释剂能否迅速由液态转变固态。按照引发机理不同,光引发剂可分为自由基聚合光引发剂和阳离子光引发剂,其中自由基聚合光引发剂应用最为广泛。
光引发剂的发展和紫外光源的发展有着密不可分的关系,由于传统的光源——汞灯,污染大而被逐渐禁止使用,取而代之的是新型的LED光源。但是LED光源受到封装技术与材料的限制,短波长的LED光源制备技术尚不成熟,而配合传统汞灯光源的引发剂往往引发波长较短,并且传统的小分子光引发剂及其光解碎片容易迁移和挥发,且在光聚合过程中易有小分子残留产生毒性,因此,设计和合成可聚合适应LED光源的自由基型光引发剂已是光聚合技术发展的迫切需求。
发明内容
本发明解决的技术问题在于传统的光引发剂引发波长较短,在光聚合过程中易有小分子残留产生毒性。
本发明是采用以下技术方案解决上述技术问题的:
一种长波长可聚合光引发剂,其结构通式如下:
其中:
1)X为O、S、N、C或Se;
2)R1-R4为H、卤素取代基、带O的取代基、带N的取代基、带S的取代基或含有上述取代基的烷烃、烯烃、炔烃、芳烃整链或支链;其中卤素取代基为-F、-Cl、-Br或-I;带O的取代基为-CHO、-COOH、-CO或-OH;带N的取代基为-NH3、-NO2或-CN;带S的取代基为-HS、-SO3H或-CH2S;
本发明还提供一种长波长可聚合光引发剂的制备方法,包括以下步骤:
将无α-H的醛和N-乙烯基吡咯烷酮加入到乙酸乙酯中溶解,以质量分数为1%-5%的碱溶液,调节pH值为13,通入氮气反应,与20-50℃反应3-5h后,冰浴3h,析出晶体后,使用有机溶剂洗涤,除去溶剂,得到提纯后的产物。
优选的,无α-H的醛的结构通式如下:
优选的,其反应方程式如下:
其中:
1)X为O、S、N、C或Se;
2)R1-R4为H、卤素取代基、带O的取代基、带N的取代基、带S的取代基或含有上述取代基的烷烃、烯烃、炔烃、芳烃整链或支链;其中卤素取代基为-F、-Cl、-Br或-I;带O的取代基为-CHO、-COOH、-CO或-OH;带N的取代基为-NH3、-NO2或-CN;带S的取代基为-HS、-SO3H或-CH2S;
优选的,所述碱溶液为氨水、氢氧化钠、氢氧化钾或碳酸氢钠。
优选的,所述有机溶剂为甲醇、乙醇、乙酸乙酯、二氯甲烷、三氯甲烷、乙腈或丙酮。
本发明的有益效果在于:
(1)N-乙烯基吡咯烷酮中N上连的双键可以聚合,反应得到的产物中由于含有可聚合的双键,可光引发又可光聚合,在反应过程中,不会有小分子残留,具有低迁移和低毒性;
(2)可以根据反应物的选择得到最大吸收波长在345nm-450nm范围内的不同吸收波长的光敏产物,即可匹配不同波长的LED灯源使用;
(3)光引发剂杂化五元环结构上的O、S、N、Se原子具有孤立电对,与苯环相比,能与双键结构形成大共轭体系,从而使引发剂最大吸收波长达到450nm;
(4)光引发剂与丙烯酸酯类单体在不添加助引发剂的条件下,具有较高的反应速率,600s内双键转化率能够达到80%左右,且光引发剂的含量仅仅达到单体质量的0.01%;
(5)光引发剂在紫外光照射下,具有光漂白的效果。
附图说明
图1为本发明实施例1中产物4-乙烯基噻吩-N-乙烯基吡咯烷酮的紫外吸收光谱图;
图2为本发明实施例1中产物4-乙烯基噻吩-N-乙烯基吡咯烷酮引发单体PEGDA聚合的双键实时转化率图。
具体实施方式
为使对本发明的结构特征及所达成的功效有更进一步的了解与认识,用以较佳的实施例对本发明进行详细的说明。
本发明中,所涉及的组分和原料均为常规市售产品,或可通过本领域的常规技术手段获得。
实施例1
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol噻吩甲醛和1mol N-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:如图1和图2所示,本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到400nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,600s内对单体PEGDA的双键转化率为80%,具有光漂白的效果。
实施例2
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol噻唑甲醛和1molN-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)中获得的淡黄色晶体使用乙醇洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到400nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,300s内对单体PEGDA的双键转化率为82%,具有光漂白的效果。
实施例3
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol吡咯甲醛和1molN-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)中获得的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到420nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,300s内对单体PEGDA的双键转化率为80%,具有光漂白的效果。
实施例4
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol咪唑甲醛和1mol N-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)中获得的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到430nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,600s内对单体PEGDA的双键转化率为83%,具有光漂白的效果。
实施例5
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol芘甲醛和1mol N-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到430nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,600s内对单体PEGDA的双键转化率为88%,具有光漂白的效果。
实施例6
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol萘甲醛和1mol N-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合。
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体。
(3)将步骤2)的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到415nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,300s内对单体PEGDA的双键转化率为80%,具有光漂白的效果。
实施例7
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol乙烯基咔唑甲醛和1mol N-乙烯基吡咯烷酮溶于20mL的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物;
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到430nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,500s内对单体PEGDA的双键转化率为88%,具有光漂白的效果。
实施例8
一种长波长可聚合光引发剂的制备方法,包括以下步骤:
(1)称取1mol水杨醛和1mol N-乙烯基吡咯烷酮溶于20ml的乙酸乙酯中,在搅拌下均匀混合;
(2)在步骤(1)所制备的混合溶液滴加3-5滴质量分数为5%的NaOH水溶液(0.5gNaOH,9.5g水),调节pH值为13,30℃下反应3h后,通入氮气,使用冰浴继续反应3h,析出淡黄色晶体;
(3)将步骤(2)的淡黄色晶体使用二氯甲烷洗涤,真空干燥除去溶剂,得到纯净的淡黄色产物。
对本实施例中制备的引发剂的性能的测试如下:
(1)将合成产物溶于乙腈溶剂当中,摩尔浓度为3*10-5mol L-1,进行紫外光谱测试得到其紫外光谱。
(2)将合成产物溶解在单体中,双盐片进行实时红外测试,设置不同的质量浓度梯度(1%,0.5%,0.25%,0.1%,0.02%,0.01%),得到不同引发剂浓度的双键实时转化率。
实验结果:本实施例中制备的长波长可聚合光引发剂的最大吸收波长达到425nm,在不添加助引发剂的条件下,且引发剂含量仅为0.01wt%,300s内对单体PEGDA的双键转化率为86%,具有光漂白的效果。
实施例9
以0.01%质量分数将实施实例1-9得到的合成产物分别加入到PEGDA单体中,分别编号1,2,3,4,5,6,7,8,9,在365nm的LED灯源下固化之后,将固化好的块状聚合物在乙腈中浸泡24h,超声处理2h。取浸提液去测紫外光谱。
实验结果:如表1所示,浸提液在250nm-450nm波段没有紫外吸收,即这种引发剂在引发体系中没有小分子迁移。
表1为本发明实施例9中编号1-9的浸提液在250nm-450nm波长范围的最大吸收峰值的数据表格:
实施例10
不符合无α-H的醛的结构通式归纳如下:
其中X为O、S、N、C或Se;Y为C、N、O或S;
R10-R49为H、卤素取代基、带O的取代基、带N的取代基、带S的取代基或含有上述取代基的烷烃、烯烃、炔烃、芳烃整链或支链;其中卤素取代基为-F、-Cl、-Br或-I;带O的取代基为-CHO、-COOH、-CO或-OH;带N的取代基为-NH3、-NO2或-CN;带S的取代基为-HS、-SO3H或-CH2S;
以上仅是本发明的优选实施方式,本发明的保护范围并不仅限于上述实施例,与本发明构思无差异的各种工艺方案均在本发明的保护范围内。
Claims (6)
2.制备如权利要求1所述的长波长可聚合光引发剂的制备方法,其特征在于:包括以下步骤:将无α-H的醛和N-乙烯基吡咯烷酮加入到乙酸乙酯中溶解,以质量分数为1%-5%的碱溶液,调节pH值为13,通入氮气反应,与20-50℃反应3-5h后,冰浴3h,析出晶体后,使用有机溶剂洗涤,除去溶剂,得到提纯后的产物。
5.根据权利要求2所述的长波长可聚合光引发剂的制备方法,其特征在于:所述碱溶液为氨水、氢氧化钠、氢氧化钾或碳酸氢钠。
6.根据权利要求2所述的长波长可聚合光引发剂的制备方法,其特征在于:所述有机溶剂为甲醇、乙醇、乙酸乙酯、二氯甲烷、三氯甲烷、乙腈或丙酮。
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