CN112457174B - 一种棱柱芳烃引发剂及其制备方法 - Google Patents
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Abstract
本发明涉及光引发剂技术领域,提供了一种棱柱芳烃作为光聚合引发剂的应用及其制备方法。棱柱芳烃具有亚甲基桥连萘环而形成的大环结构,是一种新型的光引发剂。在光辐照条件下,棱柱芳烃大环分子断裂形成双自由基的直链寡聚物,可以高效引发单体的光聚合反应。与我们开发的柱芳烃引发剂相比,棱柱芳烃吸收波长较长,在200~400nm之间均具有较强的光吸收,可以实现长波长的光引发聚合。与传统商业光引发剂相比,本发明提供的光引发剂本身安全无毒,光辐照后无小分子碎片生成,可以极大的降低光引发剂的迁移,从而避免光聚合固化产物的毒性、气味等问题。
Description
技术领域:
本发明属于光聚合和光固化领域,具体涉及一种棱柱芳烃作为光引发剂的应用及其制备方法。
背景技术:
近年来随着LED光源在光聚合领域中的普及使用,对商业光引发剂的吸收波长有了新的要求,将商业光引发剂的吸收波长延长并使其与LED光源相匹配是光引发剂领域中需要解决的一项重大技术问题。另外目前商业化的多种I型裂解型和II型夺氢型自由基光引发剂面临的如毒性大、气味强、光解后有害物质的浸出等问题,限制了光引发剂在食品包装或生物医学方面的应用。
针对这些问题,本发明提出利用棱柱芳烃作为光引发剂。在光辐照条件下,棱柱芳烃环状分子断裂形成双自由基的直链寡聚物,可以高效引发单体的光聚合反应。棱柱芳烃在200~400nm之间具有较强的光吸收,这就使它可以匹配利用365nm和405nm的LED光源。另外棱柱芳烃本身安全无毒,不需要任何其他助剂,在光辐照断裂后形成直链寡聚物,并在引发光聚合后被固定到聚合物中,无小分子碎片生成,可以极大的减小光引发剂的迁移,从而避免光聚合固化产物的毒性、气味等问题。而棱柱芳烃两端R基团的改变,可以调节棱柱芳烃的亲疏水性,开发出水溶性和脂溶性棱柱芳烃引发剂。
发明内容
本发明目的在于提供一种棱柱芳烃类光引发剂,该引发剂具有较长的吸收波长,可以匹配LED光源,可通过修饰实现水溶性和脂溶性。具有较低的迁移率,可避免光聚合固化产物的毒性、气味等问题,是一种新型的光引发剂。
一种棱柱芳烃类光引发剂,其特征在于具有亚甲基桥连苯单元形成的大环结构,并且可通过R基团的变化实现脂溶性和水溶性。具有如图1中通式I所示结构:
通式I中:脂溶性棱柱芳烃:R可以是烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基,以及含有卤素取代基、带氧取代基、带氮取代基、带硫取代基的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基。其中n=5,6,7,8,9,10。
通式I中:水溶性棱柱芳烃:R可以是氢、不同聚合物度的聚乙二醇、聚乙烯醇或者包括但不限于羧基、氨基、季铵、磺酸基、单糖、二糖等可溶性基团取代的烷基、芳香基、杂环芳香基、烯基、烷氧基、炔基。其中n=5,6,7,8,9,10。
棱柱芳烃在200~400nm之间具有较强的光吸收,这就可以使它可以匹配利用365nm和405nm的LED光源。
在光辐照条件下,棱柱芳烃环状分子断裂形成双自由基的直链寡聚物,可以高效引发单体的光聚合反应。柱芳烃安全无毒,迁移率低,从而避免光聚合固化产物的毒性、气味等问题。
本发明提供了上述方案所述脂溶性棱柱芳烃类光引发剂的制备方法,包括以下步骤:
萘单体和多聚甲醛,加入适量模板分子,在路易斯酸催化下聚合反应得到棱柱芳烃。
优选的,反应溶剂选择二氯乙烷,萘单体配成2.5mM溶液,萘单体、多聚甲醛和模板分子摩尔比为1:1.2:1。
优选的,路易斯酸选择三氟乙酸,用量是单体质量的6倍。
优选的,反应温度为70℃,反应时间22h。
优选的,用硅胶色谱柱分离洗脱剂采用石油醚:二氯甲烷=1:9。
本发明提供了上述方案所述水溶性棱柱芳烃类光引发剂的制备方法,包括一下步骤:
将甲氧基棱柱芳烃溶于二氯甲烷溶液中,加适量三溴化硼,室温下搅拌,制备得到羟基棱柱芳烃。
羟基棱柱芳烃、X-R、K2CO3溶于乙腈中,氮气保护,将混合物在三颈烧瓶中加热回流2天。将冷却的反应混合物过滤,并用氯仿洗涤。真空蒸发滤液,残余物通过在甲醇和氯仿的混合物中结晶而纯化。过滤收集产物,用甲醇洗涤,并在真空下干燥。
附图说明:
图1为棱柱芳烃的化学结构通式及光引发示意图。
图2为两端带有甲氧基的棱柱[5]芳烃(NP5OCH3)的合成结构式。
图3为水溶性棱柱芳烃的制备过程。
图4为两端带有甲氧基的棱柱[5]芳烃(P6OC2H5)作为光引发剂的示意图和不同单体的化学结构式。
图5是添加不同浓度的NP5OCH3作为光引发剂引发PEG200DA单体的光聚合动力学曲线。
图6是NP5OCH3作为光引发剂引发不同单体的光聚合动力学曲线。
下面结合实施例对本发明提供的方案进行详细的说明。但是不能把它们理解为对本发明保护范围的限定。
实施例1
取250mg二甲氧基萘(NOCH3),溶于530mL干燥二氯乙烷中,配成2.5mM溶液,加入48mg多聚甲醛和267mg四甲基碘化铵,再加入1.5mL三氟乙酸,70℃搅拌反应22h。旋干溶剂后,加入30mL二氯甲烷溶解,20mL饱和食盐水和碳酸氢钠溶液洗两次。旋转蒸发除去溶剂,用硅胶色谱柱分离得到棱柱芳烃(NP5OCH3)。洗脱剂采用石油醚:二氯甲烷=1:9。
优选的,我们选择两端带有甲氧基的棱柱芳烃(NP5OCH3)作为引发剂,选择带有两个双键的PEGDA作为单体。称取10mg NP5OCH3,溶于1g PEGDA单体中,配置质量分数为1%的引发剂-单体混合体系。然后在365nm和405nm LED灯辐照下,用实时红外测定其光聚合动力学曲线。
实验结果表明,NP5OCH3在光辐照下,HEA,PEGD,TMPTA单体的双键发生快速的转化,且最终的转化率较高。说明NP5OCH3作为光引发剂,可以高效的引发不同单体的光聚合。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种棱柱芳烃类光引发剂,其特征在于具有亚甲基桥连萘单元形成的大环结构,可通过改变R基团实现脂溶性或水溶性,具有通式I所示结构:
通式I中:脂溶性棱柱芳烃:R可以是烷基。其中n=5,6,7,8,9,10。
2.根据权利要求1所述的棱柱芳烃类光引发剂,其特征在于,所述棱柱芳烃类光引发剂光吸收波长的范围为200~400nm,在光辐照下,可以高效的引发光聚合反应,可以利用长波长光引发光聚合,并且棱柱芳烃安全无毒,迁移率低,从而避免光聚合固化产物的毒性、气味问题。
3.权利要求1中任一项所述脂溶性棱柱芳烃光引发剂的制备方法,其特征包括以下步骤:
取权利要求1所示的当量的单体,溶于二氯乙烷中,配成2.5mM溶液,加入1.2当量的多聚甲醛和1当量模板,加入6倍单体质量的三氟乙酸,70℃搅拌反应22h,旋干溶剂后,加入一定量二氯甲烷溶解,饱和食盐水和碳酸氢钠溶液洗两次,旋转蒸发除去溶剂,用硅胶色谱柱分离得到棱柱芳烃,洗脱剂采用石油醚:二氯甲烷=1:9。
4.根据权利要求3所述棱柱芳烃的制备方法,其特征在于,当n=5,所用模板分子是四甲基碘化铵,当n=6,7,8,9,10时,所用模板分子是四乙基碘化铵。
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