CN108047104B - 一种可降低体积收缩的可聚合的二硫化合物的制备及用途 - Google Patents
一种可降低体积收缩的可聚合的二硫化合物的制备及用途 Download PDFInfo
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- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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- C08F128/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
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Abstract
本发明涉及一种可降低体积收缩的可聚合的二硫化合物的合成及应用,其合成包括如下步骤:将带有活泼氢的脂肪族巯基化物和碘化钠加入反应器中,在磁力搅拌的情况下滴加双氧水反应得产物A;将产物A和有机碱放入反应瓶中,在磁力搅拌的作用下滴加酰氯类化合物,得到可聚合的二硫化合物。发明的有益效果是:(1)可聚合的二硫化合物可以显著降低光聚合过程中的体积收缩,为降低体积收缩提供了一个新方法;(2)可聚合的二硫化合物不仅可以参与光聚合还可以引发光聚合。
Description
技术领域
本发明涉及一种可降低体积收缩的可聚合的二硫化合物的制备方法及用途,属于高分子化学材料技术领域。
背景技术
紫外光固化技术是20世纪60年代发展起来的一种新型的固化技术。紫外光固化以紫外光为固化能源,光引发剂吸收辐射能量后,其分子外层电子发生跃迁生成活性中心,与树脂中的反应基团发生作用,继而引发体系的自由基聚合或离子聚合,实现迅速固化。与传统的热固化不同,紫外光固化无需进行高温加热,具有速度快,工艺、设备简单,投资少,安全,环保等特点,因而被广泛应用于涂料、胶黏剂、油墨和电子产品等诸多领域。然而在光聚合中,尤其是广泛应用的自由基光聚合中,由于聚合前单体或预聚物分子之间的范德华作用力距离,被聚合后的共价键长度所取代,以及分子间的快速交联限制了链段的运动,自由体积变小,而不可避免地会产生聚合收缩。这种聚合收缩对材料的应用性能造成很大的影响,严重地限制了该技术在要求高性能、高精密度的材料(例如3D打印材料)、生物材料(例如齿科修复材料)等领域的应用。因而探索降低光固化过程中的聚合收缩的新方法,提高光固化材料性能,实现对材料性能的控制是一直致力于研究解决的难题。
二硫键是一个动态可逆变化的键,二硫化合物被广泛应用于自修复材料和可逆表面功能材料中。事实上,二硫键在紫外光照射下也可发生均裂形成硫自由基,形成的硫自由基可重新互相结合或与碳结合恢复为共价键。在碳-碳双键的光聚合过程中部分二硫键随之断裂,就必然会增加聚合体系中的自由体积,进而降低光固化过程中的体积收缩。同时在光固化过程中伴随着二硫键的可逆的“断裂-恢复”过程,可以对固化过程中的自由体积产生一个反复的调整来降低体积收缩。将二硫键与可光聚合的基团相结合,制备可聚合的二硫化合物,利用其二硫键的动态可逆特性来降低光聚合过程中体积收缩,为提高光固化材料性能提供一种新的途径。
发明内容
本发明提供一种可降低体积收缩的可聚合的二硫化合物的制备方法及用途,为降低光固化过程中的体积收缩提供了一个简便,快捷,高效的新方法。本发明通过广泛而深入地探究,从分子结构出发,通过分子设计,将二硫键引入与光聚合基团相结合,从而合成可以聚合的二硫化合物,利用其二硫键的动态可逆特性降低自由基光聚合过程中的体积收缩。本发明还提供一种包含可聚合的二硫化合物的组合物。
具体而言,本发明包括:
1.一种通式为(I)的可聚合的二硫化合物:
(I)
其中n1和n2相同或相异,并独立地取自0~10,优选2~6,更优选2~3;
R1和R2相同或相异,并选自:氢原子、甲基、乙基、正丙基、异丙基。
2.一种制备项1中所述的可聚合二硫化合物的方法,其特征在于包括如下步骤:
a)将带有活泼氢的脂肪族巯基化合物和碘化钠按一定摩尔比加入反应器中,溶于有机溶剂1,在磁力搅拌的情况下缓慢滴加过氧化氢溶液。滴加完毕后,在温度为10~60℃的条件下,继续反应0.5~2h。然后加入饱和硫代硫酸钠水溶液,用有机溶剂1洗涤水相,合并有机相。有机相用饱和食盐水洗涤,加入干燥剂干燥,然后,旋蒸除去溶剂得到产物A;
b)取产物A和有机碱放入反应瓶中,溶于有机溶剂2中,将烧瓶置于冰水浴5~30min,而后在磁力搅拌的作用下滴加酰氯类化合物。滴加完毕后,移除冰水浴,在温度为25~50℃的条件下,继续反应8~36h,然后先除去有机溶剂2得到棕色油状液体,再加入有机溶剂3。用无机碱溶液洗涤有机相,分液取有机相,而后用去离子水洗涤得到的有机相,加入干燥剂干燥;最后,旋蒸除去溶剂得到可聚合的二硫化合物。
3.根据项2中所述方法,其特征在于步骤a中带有活泼氢的脂肪族巯基化合物选自C1~C10的巯基醇、巯基羧酸和巯基乙胺,优选β-巯基乙醇、3-巯基-1-丙醇、6-巯基己-1-醇、巯基乙酸;有机溶剂1可以是任意能溶解反应物的有机溶剂,优选乙酸乙酯。
4.根据项2中所述方法,其特征在于步骤a中碘化钠与脂肪族巯基化合物的摩尔比为0.005~0.02:1;双氧水与脂肪族巯基化合物的摩尔比为1:0.5~3。
5.根据项2中所述方法,其特征在于步骤b中有机溶剂2可以是任意能溶解反应物的无水有机溶剂,优选无水四氢呋喃和二氯甲烷;有机溶剂3可以是任意能溶解反应物的有机溶剂,优选三氯甲烷。
6.根据项2中所述方法,其特征在于步骤a和b中干燥剂可以是无水硫酸钠、无水硫酸镁、无水氯化钙;步骤b中无机碱可以选自碳酸钾、碳酸钠、碳酸氢钠。
7.根据项2中所述方法,其特征在于步骤b中所述有机碱选自三乙胺、二乙胺、三乙醇胺、吡啶;酰氯类化合物选自丙烯酰氯、甲基丙烯酰氯、2-丁烯酰氯,优选丙烯酰氯、甲基丙烯酰氯。
8.根据项2中所述方法,其特征在于所述产物A与酰氯类物质的摩尔比为1:1~5;所述三乙胺的摩尔量为产物A的1~10倍。
9.一种可自由基光固化的组合物,其特征在于包含项1所述的可聚合二硫化合物。
10.根据项9所述的组合物,其特征在于,该组合物包含1%~30%的所述可聚合的二硫化合物,1%~5%的光引发剂以及65%~98%的光反应性树脂或活性单体,基于该组合物的总重量。
11.根据项10所述的组合物,其特征在于,所述光反应性树脂选自环氧(甲基)丙烯酸树脂、聚氨酯(甲基)丙烯酸树脂、聚酯(甲基)丙烯酸树脂、聚醚(甲基)丙烯酸树脂、丙烯酸酯化聚(甲基)丙烯酸树脂一种或多种;所述的活性单体为单官能团,双官能团或多官能团(甲基)丙烯酸酯单体一种或多种;所述光引发剂选自由基型光引发剂一种或多种。
发明详述
在下文对本发明的描述中,除另有明确说明,本申请中的数值均可视为被措词“大约”修饰。但是,本发明人已尽可能精确地报道了实施例中的数值,尽管这些数值不可避免地包括一定的误差。
在本申请中,除非明确排除,本发明的具体或者优选实施方案可以组合。另外,本申请实施例的各项要素是与其对应的上位技术特征的具体的优选选择。如果所述上位技术特征可以与其它上位特征进行组合,则实施例的所述要素,即所述具体的优选选择,也可以与所述其它上位特征进行组合。这些组合应被视为本申请原始记载内容的一部分。
发明的有益效果是:(1)可聚合的二硫化合物可以显著降低光聚合过程中的体积收缩,为降低体积收缩提供了一个新方法;(2)可聚合的二硫化合物不仅可以参与光聚合还可以引发光聚合。
具体实施方式
下面结合实施例对本发明所述的可聚合的二硫化合物及其制备方法和用途予以进一步的说明,但本发明并不局限于此。
原料来源
双氧水:北京化工厂,化学级
碘化钠:天津福晨化学试剂厂,化学级
乙酸乙酯:北京化工厂,分析级
石油醚:北京化工厂,分析级
乙腈:北京化工厂,分析级
三氯甲烷:北京化工厂,分析级
四氢呋喃:北京化工厂,分析级
碳酸钾:北京化工厂,化学级
五水合硫代硫酸钠:北京化工厂,化学级
无水硫酸镁:北京化工厂,化学级
巯基乙醇:天津福晨化学试剂厂,化学级
3-巯基-1-丙醇:萨恩化学技术有限公司,化学级
丙烯酰氯:北京偶合科技有限公司,化学级
三乙胺:北京化工厂,化学级
二缩三丙二醇二丙烯酸酯 (TPGDA):长兴化学材料(珠海)有限公, 工业级
2-羟基-2-甲基-1-苯基-1-丙酮(1173):Ciba-Geigy,化学级。
附图说明
图1,图2分别是实施例1中产物DSDA的1H NMR、13C-NMR谱图。
图3,图4分别是实施例2中产物DSTA的1H NMR、13C-NMR谱图。
【实施例1】
可聚合的二硫化合物DSDA的制备
第一步:将原料β-巯基乙醇(0.78g,1mmol)和碘化钠(1.5mg,0.01mmol)放入三口烧瓶中,加入3mL乙酸乙酯作为溶剂,在磁力搅拌缓慢滴加30%双氧水(0.11mL,1mmol)。滴加完毕后,在30℃下,继续搅拌半个小时。搅拌完毕后,加入15mL饱和硫代硫酸钠水溶液,用15mL乙酸乙酯萃取水相,合并有机相。萃取液用15mL饱和食盐水洗涤,然后用无水硫酸钠干燥,最后,旋蒸除去溶剂得到产物2,2′-二硫二乙醇。产率为98%,反应式如下:
第二步:将中间体2,2′-二硫二乙醇(7.7g,50mmol)和三乙胺(50mL,400mmol)放入烧瓶中,加入150mL无水四氢呋喃作为溶剂,将烧瓶置于冰水浴中15min,而后在磁力搅拌的作用下缓慢滴加丙烯酰氯(18.1g,200mmol)。待滴加完毕后,移除冰水浴,在30℃下搅拌24h。反应完毕,先旋蒸除去四氢呋喃得到棕色油状液体,然后加入150mL三氯甲烷溶解,用碳酸钾溶液(0.1mol/L)洗涤,而后用去离子水洗涤,加入无水硫酸钠干燥,最后,旋蒸除去溶剂得到淡黄色透明液体为产物可聚合二硫化合物DSDA,产率为95%。反应式如下:
【实施例2】
可聚合的二硫化合物DSTA的制备
第一步:将原料3-巯基-1-丙醇(0.92g,1mmol)和碘化钠(1.5mg,0.01mmol)放入三口烧瓶中,加入3mL乙酸乙酯作为溶剂,在磁力搅拌的情况下缓慢滴加30%双氧水(0.11mL,1mmol)。滴加完毕后,在30℃下,继续搅拌半个小时。搅拌完毕后,加入15mL饱和硫代硫酸钠水溶液,用15mL乙酸乙酯萃取。然后萃取液用15mL饱和食盐水洗涤,然后用无水硫钠干燥,最后,旋蒸除去溶剂得到产物3,3′-二硫二丙醇。产率为98%,反应式如下:
第二步:取中间体3,3'-二硫二丙醇(9.1g,50mmol)和三乙胺(50mL,400mmol)放入烧瓶中,加入150mL无水四氢呋喃作为溶剂,将烧瓶置于冰水浴中15min,而后在磁力搅拌的作用下缓慢滴加丙烯酰氯(18.1g,200mmol)。待滴加完毕后,移除冰水浴,在30℃下搅拌24h。反应完毕,先旋蒸除去四氢呋喃得到棕色油状液体,然后加入150mL三氯甲烷溶解,用碳酸钾溶液(0.1mol/L)洗涤,而后用去离子水洗涤,加入无水硫酸钠干燥,最后,旋蒸除去溶剂得到淡黄色透明液体为产物可聚合得二硫化合物DSTA,产率为94%。反应式如下:
【实施例3】
本实施例的目的在于说明实施例1所制备的可聚合的二硫化合物(DSDA)能够降低光聚合过程中的体积收缩。按表1中配方配置DSDA与二缩三丙二醇二丙烯酸酯(TPGDA)组成的感光液,基于该感光液的总重量添加2wt%1173作为光引发剂,将感光液涂布于载玻片上形成0.4mm厚液膜,阻氧,在光强为5mW cm-2的紫外灯下曝光,然后采用激光测位移法(LDS)对光固化时体积收缩进行监测,结果见表1。加入DSDA能够明显降低体积收缩。
表1 含有DSDA的光固化配方及体积收缩
【实施例4】
本实施例的目的在于说明实施例2所制备的可聚合的二硫化合物(DSTA)能够降低光聚合过程中的体积收缩。按表2中配方配置DSTA与二缩三丙二醇二丙烯酸酯(TPGDA)组成的感光液,基于该感光液的总重量添加2wt%1173作为光引发剂,将感光液涂布于载玻片上形成0.4mm厚液膜,阻氧,在光强为5mW cm-2的紫外灯下曝光,然后采用激光测位移法(LDS)对光固化时体积收缩进行监测,结果见表2。加入DSTA能够明显降低体积收缩。
表2 含有DSTA的光固化配方及体积收缩
【实施例5】
本实施例的目的在于说明实施例1所制备的DSDA具有引发光聚合能力,在光聚合体系中能够不添加光引发剂,即可引发光聚合,得到光聚合物。取适量可聚合的二硫化合物DSDA的移入直径为6mm,高为80mm的圆柱形玻璃瓶中,然后将装有澄清透明的二硫化合物DSDA的圆柱形玻璃瓶置于波长365nm,光强为5mW cm-2的紫外灯下曝光,使其发生光化学反应,曝光10分钟,可得到透明聚合物棒。
Claims (1)
1.一种可降低体积收缩的可自由基光固化的组合物,其特征在于,
该组合物包含1%~30%的可聚合的二硫化合物,1%~5%的光引发剂以及65%~98%的活性单体,基于该组合物的总重量;
所述可聚合的二硫化合物为DSDA或DSTA;
DSDA和DSTA的结构式如下:
所述光引发剂为1173光引发剂;
所述活性单体为二缩三丙二醇二丙烯酸酯;
所述可聚合的二硫化合物通过以下步骤制备:
a)将β-巯基乙醇或3-巯基-1-丙醇和碘化钠按一定摩尔比加入反应器中,溶于乙酸乙酯中,在磁力搅拌的情况下缓慢滴加过氧化氢溶液,滴加完毕后,在温度为30℃的条件下,继续反应0.5h,然后加入饱和硫代硫酸钠水溶液,用乙酸乙酯洗涤水相,合并有机相,有机相用饱和食盐水洗涤,加入无水硫酸钠干燥,然后,旋蒸除去溶剂得到产物A;
b)取产物A和三乙胺放入反应瓶中,溶于无水四氢呋喃中,将烧瓶置于冰水浴15min,而后在磁力搅拌的作用下滴加丙烯酰氯,滴加完毕后,移除冰水浴,在温度为30℃的条件下,继续反应24h,然后先除去四氢呋喃得到棕色油状液体,再加入三氯甲烷,用碳酸钾溶液洗涤有机相,分液取有机相,而后用去离子水洗涤得到的有机相,加入无水硫酸钠干燥;最后,旋蒸除去溶剂得到可聚合的二硫化合物;
其中,所述碘化钠与β-巯基乙醇或3-巯基-1-丙醇的摩尔比为0.01:1;双氧水与β-巯基乙醇或3-巯基-1-丙醇的摩尔比为1:1;
所述产物A与丙烯酰氯的摩尔比为1:4;所述三乙胺的摩尔量为产物A的8倍。
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