CN110305328A - 树枝状可见光引发剂及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种树枝状可见光引发剂及其制备方法和应用,本发明将生色团苝单酸酐单钾盐与6‑氨基己酸结合,获得了一种可见光敏引发体系,将其引入到树枝状化合物,得到树枝状可见光引发剂,作为可见光引发剂,用于含不饱和双键水溶性单体的光固化体系的聚合反应。该引发剂极大地提高了可见光引发效率,同时具备绿色环保、相容性好、能耗低等特点。
Description
技术领域
本发明涉及光引发技术,具体涉及一种引发含不饱和双键水溶性单体树枝状可见光引发剂及其制备方法和应用。
背景技术
光固化技术已成为聚合物科学与技术领域的主要组成部分。光引发不仅能耗小,聚合效率高,同时对环境友好,现在已成为光固化技术的关键组成部分。由于紫外光的能量远远高于可见光,所以目前紫外光引发剂的发展更为成熟。然而紫外光引发存在许多不容忽视的问题,当紫外光作用于人体,会令人头痛、头晕,对眼部造成刺激,易引起皮炎,严重的更可引起皮肤癌。相对比于紫外光,可见光可以直接利用太阳光作可见光源,节能环保;具有较长的波长范围,对某些材料来说,它的穿透性相比紫外光更强,固化能力也更强时,可见光对人体无害,且能量较低不会二次引发。
尽管小分子引发剂种类众多,发展较为成熟,但是小分子可见光引发剂存在气味重、挥发度高、抗迁移能力弱、环境兼容性差、树脂相容性差、功能单一等缺点。而树枝状大分子作为一种前沿高分子材料。结构规整、表面密度高,端基具备众多可供修饰的活性基团。由此可见,如何将可见光引发剂接入大分子,使活性单元光照后产生自由基,引发体系光固化,成为交联度、相容性更好的高聚物,是本领域迫切希望解决的问题。
发明内容
本发明的目的是提供一种绿色、高效的,可引发含不饱和双键水溶性单体可见光聚合的树枝状可见光引发剂及其制备方法和应用。
为达到以上发明目的,本发明的技术方案如下:本发明所述的树枝状可见光引发剂,其结构式如式I所示:
首先合成端基为胺基的树枝状大分子,然后引入单酸酐的非对称苝酰亚胺作为光引发基团,制备引发含不饱和双键水溶性单体光固化体系中的树枝状可见光引发剂,用于引发水溶性单体的聚合反应。
本发明所述的树枝状可见光引发剂的制备方法,包括如下步骤:
将PAE(NH2)8、苝盐Ⅱ和反应溶剂咪唑,在100-140℃下发生酰胺化反应,冷却,加入乙醇和盐酸溶液,搅拌,离心分离,洗涤,旋蒸,得到紫红色粘稠状液体,反应式如下:
在本发明的一个优选实施方式中,PAE(NH2)8与苝盐Ⅱ的摩尔比为1:8。
在本发明的一个优选实施方式中,反应时间为6-14小时,优选10小时。
本发明制备的可见光引发剂用于含不饱和双键水溶性单体的光固化体系中聚合反应的用途,所述含不饱和双键水溶性单体为丙烯酰胺或(甲基)丙烯酸-β-羟乙酯、(甲基)丙烯酸-β-羟丙酯、N-乙烯基吡咯烷酮中的一种或几种。
采用的可见光的波长范围为400-780nm,光照强度为20-80mW/cm2,聚合时间为5-30min。
本发明与现有技术相比,具有下列优点:
1.本发明制备的可见光引发剂,光源便宜、绿色安全、穿透能力强。
2.本发明制备的树枝状光引发剂,引发效率高。
3.本发明制备的光引发剂是一种大分子光引发剂,本身无毒,无需添加助引发剂,绿色环保。
具体实施方式
下面的实施例是对本发明的进一步阐述,但本发明的内容不限于此。本发明说明书中的实施方式仅用于对本发明进行说明,其并不对本发明的保护范围起到限定作用。本发明的保护范围仅由权利要求限定,本领域技术人员在本发明公开的实施方式的基础上所做的任何省略、替换或修改都将落入本发明的保护范围。
本发明从分子结构设计出发,将生色团非对称的苝单酸酐单钾盐与6-氨基己酸结合制备单酸酐的非对称苝酰亚胺;在此基础上将其引入到树枝状大分子,其吸收光谱在500nm,制备了树枝状苝酰亚胺可见光引发剂。这类光引发剂在水中有良好的水溶性,在可见光的照射下,不额外添加助剂就可以有效地引发含不饱和双键水溶性单体发生聚合。且多个活性基团在树枝状大分子端基,有利于提高光引发效率。
本发明所述的树枝状苝酰亚胺可见光引发剂的制备方法,包括如下步骤:
(1)中间体端基为8个丙烯酸酯的树枝状大分子(PAE(=)8)的合成:将三羟甲基丙烷三丙烯酸酯、乙二胺、无水甲醇混合,加热到30℃,反应6小时,反应完毕用无水甲醇洗涤,得到无色透明的粘稠液体,反应式如下:
(2)中间体端基为8个伯胺基的树枝状大分子(PAE(NH2)8)的合成:将PAE(=)8和乙二胺混合,加热到30℃,反应24小时,减压蒸馏,用乙酸乙酯洗涤,得到淡黄色透明粘稠液体,反应式如下:
(3)中间体3,4,9,10-苝四羧-3,4,-酸酐-9-羧酸-10-羧酸钾的合成:将3,4,9,10-苝四羧酸酐在KOH水溶液中水解为苝四羧酸钾盐,用盐酸调节pH值至4-6之间,生成3,4,9,10-苝四羧-3,4-酸酐-9-羧酸-10-羧酸钾,反应式如下:
(4)中间体N-己酸-3,4,9,10-苝四羧-3,4-酸酐-9,10-酰亚胺(苝盐Ⅱ)的合成:将6-氨基己酸提前混合于异丙醇:水体积比为7:3的混合溶液,加入1.0g苝单酸酐单钾盐。常温反应6小时,升温至90℃,反应3小时,加入20%的稀盐酸酸化2小时,离心,水洗,加入KOH溶液室温搅拌2小时,抽滤,得到红色滤液,加入饱和KCl溶液,离心,洗涤,加热溶解,抽滤,滤液加入稀盐酸酸化1小时,离心,得到紫红色固体粉末,反应式如下:
(5)水溶性树枝状苝酰亚胺大分子(PAE-PDI-AA)的合成:PAE(NH2)8、苝盐Ⅱ和咪唑,在100-140℃下反应10小时。冷却,加入乙醇和盐酸溶液,搅拌,离心分离,洗涤,旋蒸,得到紫红色粘稠状液体,反应式如下:
实施例1:可见光引发剂的制备
(1)中间体端基为8个丙烯酸酯的树枝状大分子(PAE(=)8)的合成:将60g三羟甲基丙烷三丙烯酸酯、2.4g乙二胺、30mL无水甲醇混合,加热到30℃,反应6小时,用无水甲醇洗涤,得到无色透明的粘稠液体。
(2)中间体端基为8个伯胺基的树枝状大分子(PAE(NH2)8)的合成:将4.665g PAE(=)8和108g乙二胺混合,加热到30-50℃,反应24小时,减压蒸馏,用乙酸乙酯洗涤,得到淡黄色透明粘稠液体。
(3)中间体3,4,9,10-苝四羧-3,4-酸酐-9-羧酸-10-羧酸钾的合成:将3,4,9,10-苝四羧酸酐加入KOH溶液中,铝箔纸包裹避光,加热到90℃,反应至pH值在10.5左右。滴加10%的盐酸水溶液至pH值在4.5-5.5之间。反应1小时,冷却,洗涤至滤液成中性,抽滤,干燥,得到紫红色固体粉末。
(4)中间体N-己酸-3,4,9,10-苝四羧-3,4-酸酐-9,10-酰亚胺的合成:将1.3117g6-氨基己酸提前混合于异丙醇:水体积比为7:3的混合溶液100mL中。向混合溶液中加入1.0g3,4,9,10-苝四羧-3,4-酸酐-9-羧酸-10-羧酸钾。常温,反应6小时,升温至90℃后反应3小时。加入20%的稀盐酸酸化2小时,离心,水洗至中性。加入约60mL5%的KOH溶液室温搅拌2小时,抽滤,滤液中加入100mL饱和KCl溶液,离心分离,用饱和KCl溶液洗涤至滤液无色。60℃热水溶解固体,抽滤,滤液加入20%的稀盐酸在90℃酸化1小时,离心分离,得到紫红色固体粉末。
(5)水溶性树枝状苝酰亚胺大分子(PAE-PDI-AA)的合成:5g咪唑在氮气保护下在100℃熔化成液体,加入0.9g PAE(NH2)8和0.3g苝盐Ⅱ,加热到100℃,反应4小时,升温至120℃,反应3小时,再升至140℃,反应3小时。冷却至室温,加入40mL乙醇和10mL20%盐酸溶液搅拌过夜。离心分离,用20mL乙醚洗涤滤液,旋蒸,得到紫红色粘稠状液体,产率为57.83%。
FT-IR(KBr,cm-1):ν=3415,2980,1692,1654,1594,1437,1250,812,755,627.1H-NMR(D2O,400MHz,δ/ppm)核磁谱图中各峰与PAE-PDI-AA结构中的质子峰对应:δ8.173(d,32H),6.986(d,32H),4.704(t,16H),3.987(m,32H),3.374(m,32H),3.286(m,8H),3.102(d,24H),2.964(t,8H),2.559(t,20H),1.798(m,48H),1.240(m,8H),0.761(t,12H)。13C-NMR(D2O,400MHz,δ/ppm)核磁谱图中各峰与PAE-PDI-AA结构中的质子峰对应:δ175.421,172.516,158.234,154.146,132.594,119.634,115.582,109.158,102.421,62.459,53.963,47.832,44.126,39.789,37.864,22.742,21.572,9.862,8.029。
实施例2:PAE-PDI-AA用量对丙烯酰胺引发性能的影响
取2.0g丙烯酰胺(单体)和一定量的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm,光照时长30min。光照结束后用甲醇洗涤出聚合物,干燥,称重,计算单体转化率。结果如表1。
表1 PAE-PDI-AA用量对丙烯酰胺引发性能的影响
注:PAE-PDI-AA用量/%中的用量是指PAE-PDI-AA占单体含量的百分数。
实施例3:光照时间对丙烯酰胺引发性能的影响
称取2.0g丙烯酰胺(单体)和0.02g的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm。光照结束后用甲醇洗涤出聚合物,干燥,称重,计算单体转化率。结果如表2。
表2光照时长对丙烯酰胺引发性能的影响
实施例4:PAE-PDI-AA用量对甲基丙烯酸-β-羟乙酯引发性能的影响
取2.0g甲基丙烯酸-β-羟乙酯(单体)和一定量的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm,光照时长30min。光照结束后用丙酮洗涤出聚合物,干燥,称重,计算单体转化率。结果如表3。
表3 PAE-PDI-AA用量对甲基丙烯酸-β-羟乙酯引发性能的影响
注:PAE-PDI-AA用量/%中的用量是指PAE-PDI-AA占单体含量的百分数。。
实施例5:光照时间对甲基丙烯酸-β-羟乙酯引发性能的影响
称取2.0g甲基丙烯酸-β-羟乙酯(单体)和0.02g的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm。光照结束后用丙酮洗涤出聚合物,干燥,称重,计算单体转化率。结果如表4。
表4光照时长对甲基丙烯酸-β-羟乙酯引发性能的影响
实施例5:PAE-PDI-AA用量对N-乙烯基吡咯烷酮引发性能的影响
取2.0gN-乙烯基吡咯烷酮(单体)和一定量的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm,光照时长30min。光照结束后用丙酮洗涤出聚合物,干燥,称重,计算单体转化率。结果如表5。
表5PAE-PDI-AA用量对N-乙烯基吡咯烷酮引发性能的影响
注:PAE-PDI-AA用量/%中的用量是指PAE-PDI-AA占单体含量的百分数。。
实施例6:光照时间对N-乙烯基吡咯烷酮引发性能的影响
称取2.0gN-乙烯基吡咯烷酮(单体)和0.02g的PAE-PDI-AA溶于2mL水中,在混匀仪上震荡均匀后置于100W可见光源下,与光源距离15cm。光照结束后用丙酮洗涤出聚合物,干燥,称重,计算单体转化率。结果如表4。
表6光照时长对N-乙烯基吡咯烷酮引发性能的影响
Claims (10)
1.树枝状可见光引发剂,其特征在于,其结构式如下式所示:
2.树枝状可见光引发剂的制备方法,其特征在于,包括如下步骤:
将PAE(NH2)8和N-己酸-3,4,9,10-苝四羧-3,4-酸酐-9,10-酰亚胺在100-140℃下发生酰胺化反应制备目标产物的步骤,
3.如权利要求1所述的方法,其特征在于,PAE(NH2)8与N-己酸-3,4,9,10-苝四羧-3,4-酸酐-9,10-酰亚胺的摩尔比为1:8。
4.如权利要求1所述的方法,其特征在于,反应时间为6-14小时,优选10小时。
5.如权利要求1所述的方法,其特征在于,反应溶剂为咪唑。
6.一种光固化体系,其特征在于,包含:
a)0.12至1.0重量%的如权利要求1所述的光引发剂;
b)49.5至49.9重量%的至少一种含不饱和双键水溶性单体。
7.如权利要求6所述的光固化体系,其特征在于,还包括49.5至49.9重量%的水。
8.如权利要求6所述的光固化体系,其特征在于,所述含不饱和双键水溶性单体为丙烯酰胺或(甲基)丙烯酸-β-羟乙酯、(甲基)丙烯酸-β-羟丙酯、N-乙烯基吡咯烷酮中的一种或几种。
9.如权利要求1所述的光引发剂用于在含不饱和双键水溶性单体光固化体系中聚合反应的用途。
10.如权利要求9所述的用途,其特征在于,采用的可见光的波长范围为400-780nm,光照强度为20-80mW/cm2,聚合时间为5-30min。
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