CN107383278A - 一种无皂乳液聚合制备阳离子聚合物乳液的方法 - Google Patents
一种无皂乳液聚合制备阳离子聚合物乳液的方法 Download PDFInfo
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Abstract
本发明提供了一种不使用乳化剂和引发剂的合成阳离子聚合物乳液的方法，首先将长链烷基烯丙基二甲基氯化铵分散在水中，分散均匀后缓慢加入（甲基）丙烯酸酯类疏水单体或者不加入疏水单体，机械搅拌进行预乳化，然后用超声波发生器进行乳化，将乳液用γ射线辐射引发聚合，得到只含有水和乳滴两种组份的纯净的阳离子聚合物乳液，可以直接应用于对纯度要求较高的领域，如日用化工、食品、生物医药等领域。
Description
技术领域
本发明涉及高分子化学乳液聚合领域，特别涉及一种γ射线辐照引发的无皂乳液聚合的方法。
背景技术
乳液聚合是高分子合成的传统方法。通常是借助于乳化剂和机械搅拌，将单体分散在水中形成乳液，再加入引发剂引发单体聚合。在聚合体系中至少包括单体、水、乳化剂、引发剂四种主要成分，其中乳化剂用量约占配方总量的0.2%到0.8%。不过，在大多数使用场合，乳化剂会影响乳液的最终使用性能，譬如会导致高分子材料的耐水性下降，电绝缘性下降，防污性下降等，甚至对环境造成污染。而在一些对纯净度要求较高的领域，譬如应用于生物医药方面，还需要进行后处理除去。
基于上述原因，无皂乳液聚合技术应运而生。进行无皂乳液聚合时，在反应过程中不加乳化剂或仅加入微量乳化剂(其浓度小于临界胶束浓度CMC)。由于没有或者很少，在某些场合免去了去除乳化剂的后处理工序，同时也避免了乳化剂对聚合物产品电学性能、光学性能、表面性能以及耐水性、成膜性等产生不良影响，而且制备的乳胶粒子的粒径单分散性好。
CN 103936920 A提供了一种阳离子氟硅聚丙烯酸酯无皂乳液的制备方法。将阳离子单体、乙烯基单体、全氟烷基（甲基）丙烯酸酯、有机硅单体、交联单体溶解到有机溶剂中，加入油溶性引发剂（偶氮二异丁腈、偶氮二异庚䝼或过氧化苯甲酰）后进行预乳化，在一定温度下聚合一定时间。然后，加水后蒸除有机溶剂，再加入水溶性引发剂（过硫酸盐），在更高温度下聚合一定时间，得到阳离子氟硅聚丙烯酸酯无皂乳液。其中，油溶性引发剂与全氟烷基（甲基）丙烯酸酯的质量比为0.005-0.02:1，过硫酸盐与全氟烷基（甲基）丙烯酸酯的质量比为0.01-0.05:1。
CN 103755879 A提供了一种含氟聚丙烯酸酯无皂乳液的制备方法。先用油溶性引发剂偶氮二异丁腈引发混合单体A（含丙烯酸十二氟庚酯或甲基丙烯酸十二氟庚酯、N-烷基二烯丙基胺、N-甲基二烯丙基胺）共聚，然后将该共聚物和水加入到混合单体B（含有机氟单体和丙烯酸酯单体）中，并制得预乳化乳液，用水溶性引发剂偶氮二异丁脒盐酸盐引发聚合。其中，偶氮二异丁腈为混合单体A总质量的1%-5%，偶氮二异丁脒盐酸盐为混合单体B总质量的0.5%-5%。
CN 103275270 A提出了无皂乳液法制备氟碳改性聚丙烯酰胺。以纯水为溶剂，过硫酸钾为引发剂，具有便面活性的新型氟碳/碳氢混合型阳离子表面活性剂单体以胶束形式分散在水中，在无乳化剂条件下与丙烯酰胺共聚。经处理后制得粉剂。其中，过硫酸钾的量为1-3mmol/L。
CN 102775548 A提供了超声波引发无皂乳液聚合制备纳米银-PAAEM复合材料的方法。
将硝酸银溶于蒸馏水中，再加入AAEM（乙酰乙酸基甲基丙烯酸乙酯）和引发剂过硫酸铵。将体系置于超声波反应器中进行反应。经冷藏、破乳、洗涤、干燥，得到纳米银-PAAEM复合物。其中，过硫酸铵和AAEM的质量比为0.05-0.15:8-12。
从以上文献中可以知道，尽管不使用乳化剂，无皂乳液聚合仍需要水溶性引发剂来引发。这些引发剂分解后所形成的残基，要么作为高分子链的链端，要么存在于水溶液中。这些残基含量尽管比较低，但对聚合物性能仍有不良影响。尤其是在要求比较高的场合，需要除去。譬如，应用于生物医药材料时，这些残基的含量应该越低越好。
发明内容
基于以上原因，本发明提供了一种γ射线引发的无皂乳液聚合方法。这种方法既不使用表面活性剂，也不使用引发剂，体系中只含有可聚合单体和蒸馏水两类组份。聚合后，乳液纯净。
所述可聚合单体可以是一种两亲性单体，也可以是一种或多种两亲性单体与一种或多种疏水单体的混合单体。
在本发明中，两亲性单体优选长链烷基烯丙基二甲基氯化铵，所述长链烷基是十四烷基、十六烷基或十八烷基。由于两亲性单体是季铵盐，所制备的乳液是阳离子聚合物乳液。本发明中，所述两亲性单体既带有强亲水性的季铵盐阳离子，又带有疏水性的长链烷基。将两亲性单体分散到蒸馏水中，长链烷基会自动形成疏水微区，而亲水性基团位于疏水微区表面，即形成胶束。胶束的粒径大小和浓度取决于两亲性单体的浓度和分散程度。本发明中，两亲性单体与水的质量比为1:2.5至1:10，优选1:5至1:10。
在本发明中所述疏水单体优选甲基丙烯酸酯和丙烯酸酯，优选甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸丁酯。疏水单体分散到水中时，会进入两亲性单体的胶束中。但，胶束的稳定性取决于胶束的表面电荷和表面亲水性。过多的疏水单体会降低胶束的表面电荷和表面亲水性，进而降低胶束的稳定性。本发明中，两亲性单体与疏水单体的重量比为1:0至1:1，优选1:0至1:0.3。
在本发明中，为提高两亲性单体的分散程度，采用超声波辅助分散。超声波辅助分散时间0.1h至2h，优选0.5h至1h。超声波频率20kHz至120kHz，优选20kHz至40kHz。
在本发明中，在γ射线作用下，水辐射分解形成·H、·OH等自由基，这些自由基由水相进入胶束内，引发单体聚合。γ射线辐照剂量1kGy至30kGy，优选5kGy至20kGy。γ射线本发明中，基本操作步骤是：
（1）将两亲性单体溶于水中，机械搅拌，形成均匀体系；
（2）向容器中缓慢加入疏水单体，机械搅拌，形成预乳化体系；
（3）用超声波发生器对预乳化体系进行处理，得到乳液体系；
（4）将乳液置于容器中，密闭容器，将容器置于γ射线辐照场中辐照。（
本发明提供的一种无皂乳液聚合制备阳离子聚合物乳液的方法具有以下优点：
1.乳液中不含乳化剂和引发剂残留，乳液纯净。可以直接应用于对纯度要求较高的领域，如日用化工、食品、生物医药等领域。
2.原料易得，毒性低，使用安全，贮存方便，绿色环保。
3.加工工艺简单，不需要进行温度控制，节约能源。不管是在单体分散阶段，还是γ射线辐照阶段，都是室温进行。
4. γ射线穿透能力强，体系内水辐射分解产生的自由基浓度分布均匀，可以得到粒径均匀的乳液。
5.只要体系处于γ射线辐照场中，水辐射分解会持续产生自由基，有利于提高单体转化率，单体转化率可以达到100%，无单体残留。
上述诸多特点表明，本发明适于工业化生产，并且具有广泛的应用前景。
具体实施方式
实施例1
称取100mL蒸馏水、10g十六烷基烯丙基二甲基氯化铵和2g丙烯酸甲酯。将蒸馏水加入到烧杯中，在机械搅拌下将十六烷基烯丙基二甲基氯化铵溶解到水中，搅拌2h后全部溶解。在维持搅拌的情况下，将丙烯酸甲酯缓慢地连续滴入烧杯中，1h内滴加完。撤去机械搅拌，用超声波发生器分散0.5h，超声波频率设定为20kHz。将烧杯中的乳液倒入聚乙烯塑料袋内，密封。将塑料袋放到γ射线辐照场内辐照，辐照剂量率1000Gy/h，辐照剂量8kGy。辐照结束后取出，得到乳白色乳液。
实施例2
称取100mL蒸馏水、13g十四烷基烯丙基二甲基氯化铵和1.5g甲基丙烯酸甲酯。将蒸馏水加入到烧杯中，在机械搅拌下将十六烷基烯丙基二甲基氯化铵溶解到水中，搅拌2h后全部溶解。在维持搅拌的情况下，将丙烯酸甲酯缓慢地连续滴入烧杯中，1h内滴加完。撤去机械搅拌，用超声波发生器分散0.5h，超声波频率设定为20kHz。将烧杯中的乳液倒入聚乙烯塑料袋内，密封。将塑料袋放到γ射线辐照场内辐照，辐照剂量率2000Gy/h，辐照剂量15kGy。辐照结束后取出，得到乳白色乳液。
实施例3
称取100mL蒸馏水、16g十八烷基烯丙基二甲基氯化铵和1g丙烯酸甲酯。将蒸馏水加入到烧杯中，在机械搅拌下将十六烷基烯丙基二甲基氯化铵溶解到水中，搅拌2h后全部溶解。在维持搅拌的情况下，将丙烯酸甲酯缓慢地连续滴入烧杯中，1h内滴加完。撤去机械搅拌，用超声波发生器分散0.5h，超声波频率设定为20kHz。将烧杯中的乳液倒入聚乙烯塑料袋内，密封。将塑料袋放到γ射线辐照场内辐照，辐照剂量率2000Gy/h，辐照剂量8kGy。辐照结束后取出，得到乳白色乳液。
Claims (9)
1.一种无皂乳液聚合制备阳离子聚合物乳液的方法，特征在于聚合体系中只含有可聚合单体和蒸馏水两类组份。
2.如权利要求1所述一种无皂乳液聚合制备阳离子聚合物乳液的方法，特征在于采用γ射线引发聚合，特征在于辐照剂量1kGy至30kGy，优选5kGy至20kGy；辐照剂量率100Gy/h至10000Gy/h，优选500 Gy/h至5000Gy/h。
3.如权利要求1所述一种无皂乳液聚合制备阳离子聚合物乳液的方法，特征在于采用超声波发生器辅助乳化，特征在于超声波作用时间0.1h至2h，优选0.5h至1h；超声波频率20kHz至120kHz，优选20kHz至40kHz。
4.如权利要求1所述一种无皂乳液聚合制备阳离子聚合物乳液的方法，特征在于可聚合单体可以是一种两亲性单体，也可以是一种或多种两亲性单体与一种或多种疏水单体的混合单体。
5.如权利要求4所述两亲性单体，特征在于两亲性单体是长链烷基烯丙基二甲基氯化铵，所述长链烷基是十四烷基、十六烷基或十八烷基。
6.如权利要求4所述疏水单体，特征在于疏水单体是甲基丙烯酸酯和丙烯酸酯，优选甲基丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸丁酯。
7.如权利要求1所述一种无皂乳液聚合制备阳离子聚合物乳液的方法，特征在于合成步骤如下：
（1）将两亲性单体溶于水中，机械搅拌，形成均匀体系；
（2）向容器中缓慢加入疏水单体，机械搅拌，形成预乳化体系；
（3）用超声波发生器对预乳化体系进行处理，得到乳液体系；
（4）将乳液置于容器中，密闭容器，将容器置于γ射线辐照场中辐照。
8.如权利要求7所述合成步骤，特征在于两亲性单体与水的质量比为1:2.5至1:10，优选1:5至1:10。
9.如权利要求7所述合成步骤，特征在于疏水单体与两亲性单体的重量比为0:1至1:1，优选0:1至0.3:1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759982A (en) * | 1970-05-26 | 1973-09-18 | Kendall & Co | Anionic complexes of monomeric emulsion stabilizers |
| US4011259A (en) * | 1969-10-20 | 1977-03-08 | The Kendall Company | Monomeric emulsion stabilizers |
| CN102050918A (zh) * | 2010-12-07 | 2011-05-11 | 陕西科技大学 | 一种阳离子聚丙烯酸酯涂饰剂的无皂乳液聚合方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4011259A (en) * | 1969-10-20 | 1977-03-08 | The Kendall Company | Monomeric emulsion stabilizers |
| US3759982A (en) * | 1970-05-26 | 1973-09-18 | Kendall & Co | Anionic complexes of monomeric emulsion stabilizers |
| CN102050918A (zh) * | 2010-12-07 | 2011-05-11 | 陕西科技大学 | 一种阳离子聚丙烯酸酯涂饰剂的无皂乳液聚合方法 |
Non-Patent Citations (1)
| Title |
|---|
| 王新波: ""可聚合乳化剂存在下的乳液聚合研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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