CN112390903B - 一种以惰性双烯内酯为引发剂制备pmma的方法 - Google Patents
一种以惰性双烯内酯为引发剂制备pmma的方法 Download PDFInfo
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Abstract
本发明公开了一种以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,将惰性双烯内酯作为引发剂加入到MMA中,在空气氛围或含氧气氛中搅拌、加热反应,实现MMA的耐氧本体自由基聚合。与传统自由基聚合体系相比,本发明中惰性双烯内酯与氧气的共引发体系可实现常用PMMA聚合温度下的耐氧自由基聚合,避免了繁琐的除氧步骤,可适用于1%~21%的氧气含量范围,且该惰性双烯内酯性质稳定,储运要求低。
Description
技术领域
本发明涉及一种基于二氧化碳基惰性双烯内酯作为引发剂耐氧引发MMA自由基聚合的方法,属于高分子合成工艺技术领域。
背景技术
自由基聚合的引发剂是控制聚合速率和分子量的重要因素,传统自由基聚合常用偶氮类和过氧类化合物作引发剂,这类引发剂高热或撞击可能引起爆炸,需要低温等储运条件;氧化还原体系中氧化剂通常也是氢过氧化物,而还原剂如常用于引发MMA共聚合的N,N-二甲基苯胺也对高热敏感,受高热有爆炸风险且会放出有毒的氧化氮烟气,无机还原剂中常含金属元素,使所制得聚合物的应用受限。开发较安全的非金属自由基引发剂可降低引发剂的储运要求,避免在聚合产物中引入金属杂质,减少对聚合物应用的限制。
传统自由基聚合通常需要除氧,因为氧气会阻聚、消耗引发剂、使可控聚合无法得到理论聚合度的高分子,目前仅有少数体系可实现耐氧气的自由基聚合,但通常也都需要加入酶或光活性染料等耗氧的添加剂。Pan等人2018年报道了有机硼试剂与氧气共引发的机理,可实现MMA在空气氛围中的自由基聚合;Endo等人2014年报道了降冰片双烯酸乙酯与催化剂量的氧气共引发MMA自由基聚合的例子。本发明提出将一种惰性的双烯内酯分子与氧气共引发MMA的耐氧自由基聚合的方法,引发剂本身惰性,方便储运,且安全无毒;其与氧气共引发因此可使MMA在含氧环境中聚合,避免了繁琐的除氧步骤。这种共引发体系应用条件简单,单体储运方便,可耐氧引发MMA自由基聚合。
发明内容
本发明所要解决的技术问题是:提供一种安全、无毒、方便储运、耐氧的自由基引发剂,将其用于MMA的自由基聚合。
为了解决上述技术问题,本发明通过以下技术方案实现:
一种以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,将惰性双烯内酯作为引发剂加入到MMA中,在空气氛围或含氧气氛中搅拌、加热反应,实现MMA的耐氧本体自由基聚合。
优选地,所述惰性双烯内酯的结构式如式Ⅰ所示:
优选地,所述惰性双烯内酯与MMA的摩尔比为1:100~1:9。
优选地,所述含氧气氛中氧气的摩尔含量为MMA摩尔的1%。
优选地,所述加热反应的温度为60~90℃,时长为24h。
优选地,所述PMMA的数均分子量为44~81.4kDa,分子量分布为2.39~5.59。
与传统自由基聚合体系相比,本发明中惰性双烯内酯与氧气的共引发体系可实现常用PMMA聚合温度下的耐氧自由基聚合,避免了繁琐的除氧步骤,可适用于1%~21%的氧气含量范围,且该惰性双烯内酯性质稳定,储运要求低。
附图说明
图1为实施例1中产物的1H核磁谱图;
图2为实施例1中产物的GPC图;
图3为实施例2中产物的1H核磁谱图;
图4为实施例2中产物的GPC图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
实施例1
将5.8微升(0.04mmol)惰性双烯内酯()与424.7微升(4mmol)甲基丙烯酸甲酯混合于Schlenk管,加入磁子,支口通大气,冷却水回流,90℃加热24h。反应结束后将粗产物溶于4毫升二氯甲烷,重沉淀于30毫升石油醚,离心得沉淀,所得沉淀在60℃下真空干燥过夜。称重产率为66%,所得聚合物数均分子量为44kDa,分子量分布为2.39。
实施例2
Claims (5)
2.根据权利要求1所述的以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,所述惰性双烯内酯与MMA的摩尔比为1:100~1:9。
3.根据权利要求1所述的以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,所述含氧气氛中氧气的摩尔含量为MMA摩尔的1%。
4.根据权利要求1所述的以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,所述加热反应的温度为60~90℃,时长为24h。
5.根据权利要求1所述的以惰性双烯内酯为引发剂制备PMMA的方法,其特征在于,所述PMMA的数均分子量为44~81.4kDa,分子量分布为2.39~5.59。
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US4125695A (en) * | 1977-01-06 | 1978-11-14 | Pennwalt Corporation | Polymerization process with reduced cycle time employing polyfunctional free radical initiators |
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