CN108424486A - 氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液及其制备方法 - Google Patents

氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液及其制备方法 Download PDF

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CN108424486A
CN108424486A CN201810135845.XA CN201810135845A CN108424486A CN 108424486 A CN108424486 A CN 108424486A CN 201810135845 A CN201810135845 A CN 201810135845A CN 108424486 A CN108424486 A CN 108424486A
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vinyl chloride
vinyl acetate
acrylic acid
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项洪伟
李福增
卢遥
孙立坤
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WUXI HONGHUI NEW MATERIALS TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种氯乙烯‑醋酸乙烯‑丙烯酸丁酯‑丙烯酸六氟丁酯共聚乳液及其制备方法。具体说，是PVC人造革表面处理剂用水性树脂的制备方法。这种氯乙烯‑醋酸乙烯‑丙烯酸丁酯‑丙烯酸六氟丁酯共聚乳液是用氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯、乳化剂、反应型乳化剂、碳酸氢钠、保胶剂、引发剂、消泡剂和去离子水等原料，经混合、反应而成。采用这种方法制备的氯乙烯‑醋酸乙烯‑丙烯酸丁酯‑丙烯酸六氟丁酯共聚乳液，成膜后，不易剥离、脱落，耐水性能好，能保证PVC人造革的产品质量。

Description

氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液及 其制备方法
技术领域
本发明涉及一种水性乳液及其制备方法。具体说，是PVC人造革表面处理剂用水性树脂及其制备方法。
背景技术
在人造革生产行业都知道，PVC人造革是由PVC树脂、增塑剂和稳定剂等助剂先制成表面处理剂，再经过刮涂或贴合工艺将该表面处理剂复合在织物表面而制成的仿真皮材料。其中的表面处理剂多为溶剂型体系，使用时需添加大量的有机溶剂。由于表面处理剂中含有大量的有机溶剂，在生产过程中，有机溶剂会挥发，不仅会对周围环境造成污染，还会危害工人的健康。又由于表面处理剂中含有大量的有机溶剂，有机溶剂会残留在人造革表面，不利于使用者的健康。为减少溶剂挥发对人体和周围环境带来的危害，人们开发了水性处理剂。目前，PVC人造革所用的表面处理剂主要有水性丙烯酸树脂和水性聚氨酯。虽然采用水性处理剂可避免对人体和周围环境带来的危害，但也存在一些问题。一是由于水性处理剂采用水作为溶剂，其表面张力太大，使得处理剂难以在织物表面铺展即流平性差，难以保证产品的质量。二是水性丙烯酸树脂和水性聚氨酯在织物表面粘结力差，使得成膜后易剥离、脱落。三是水性丙烯酸树脂和水性聚氨酯含有亲水基团，使得成膜后耐水性能差。
发明内容
本发明要解决的问题是提供一种氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液及其制备方法。采用这种方法制备的氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液，成膜后，不易剥离、脱落，耐水性能好，能保证PVC人造革的产品质量。
本发明要解决的以上问题由以下技术方案实现：
本发明的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法依次包括以下步骤：
先选取以下份数的原料：
氯乙烯60~120重量份；
醋酸乙烯30~60重量份；
丙烯酸丁酯10~50重量份；
丙烯酸六氟丁酯4~20重量份；
乳化剂1~4重量份；
反应型乳化剂2~6重量份；
碳酸氢钠0.4~1.6重量份；
保胶剂0.2~0.8重量份；
引发剂0.4~1重量份；
消泡剂0.2~0.8重量份；
去离子水150重量份；
然后，将上述氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯和乳化剂投入预乳化釜内，在常温下搅拌0.8~1.2小时，得到单体溶液；
之后，将上述反应型乳化剂、碳酸氢钠、保胶剂和去离子水中的120重量份放在一起，经充分搅拌，混合均匀，得到助剂溶液；
之后，将上述助剂溶液加入上述单体溶液中，并混合均匀，得到预乳化单体溶液；
之后，将上述引发剂和余下的30重量份去离子水放在一起，经充分溶解，得到引发剂溶液；
之后，将上述预乳化单体溶液中的1/6投入反应釜中，均匀搅拌30~50分钟，并升温至74~76摄氏度；
之后，加入上述引发剂溶液中的1/5，开始聚合反应；待反应釜内压力由初始压力降至0.2 Mpa时，开始在4~6小时内连续补加完余下的5/6的预乳化单体溶液和4/5的引发剂溶液；
之后，将反应温度升至78~82摄氏度，继续反应至反应釜内压力低于0.1Mpa；
之后，通冷却水，使反应釜温度降至40摄氏度以下，加入消泡剂；之后，对反应釜进行抽真空，使反应釜内的压力降至0Mpa；
最后，采用冷凝方法回收未反应的氯乙烯，得到氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
其中：
所述乳化剂是壬基酚聚氧乙烯醚；所述反应型乳化剂是烯丙基烷基醇醚硫酸盐；所述保胶剂是聚乙烯吡咯烷酮；所述引发剂是过硫酸铵；所述消泡剂是有机消泡剂。
由上述方案可以看出，由于本发明中含有氯乙烯，使得处理剂与织物间相溶性好，有利于处理剂的扩散和渗透，从而使处理剂与织物间更加牢固的结合在一起，使得成膜后不易剥离、脱落。又由于本发明含有丙烯酸六氟丁酯，而含氟的聚合物表面能很低，既不亲油，也不亲水，可大大降低其表面的张力，因此，具有优异的防水、防粘污性、热稳定性和耐腐蚀性等特点。
具体实施方式
实施例一
先选取以下重量份数的原料：
氯乙烯60重量份；
醋酸乙烯60重量份；
丙烯酸丁酯50重量份；
丙烯酸六氟丁酯20重量份；
乳化剂1重量份；
反应型乳化剂2重量份；
碳酸氢钠0.4重量份；
保胶剂0.2重量份；
引发剂0.4重量份；
消泡剂0.2重量份；
去离子水150重量份。
然后，将上述氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯和乳化剂投入预乳化釜内，在常温下搅拌0.8小时，得到单体溶液。
之后，将上述反应型乳化剂、碳酸氢钠、保胶剂和去离子水中的120重量份放在一起，经充分搅拌，混合均匀，得到助剂溶液；
之后，将上述助剂溶液加入上述单体溶液中，并混合均匀，得到预乳化单体溶液；
之后，将上述引发剂和余下的30重量份去离子水放在一起，经充分溶解，得到引发剂溶液；
之后，将上述预乳化单体溶液中的1/6投入反应釜中，均匀搅拌30分钟，并升温至74摄氏度；
之后，加入上述引发剂溶液中的1/5，开始聚合反应；待反应釜内压力由初始压力降至0.2 Mpa时，开始在4小时内连续补加完余下的5/6的预乳化单体溶液和4/5的引发剂溶液；
之后，将反应温度升至78摄氏度，继续反应至反应釜内压力低于0.1Mpa；
之后，通冷却水，使反应釜温度降至40摄氏度以下，加入消泡剂。之后，对反应釜进行抽真空，使反应釜内的压力降至0Mpa；
最后，采用冷凝方法回收未反应的氯乙烯，得到氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
本实施例中：
所述乳化剂是壬基酚聚氧乙烯醚；
所述反应型乳化剂是烯丙基烷基醇醚硫酸盐；
所述保胶剂是聚乙烯吡咯烷酮；
所述引发剂是过硫酸铵。
所述消泡剂是有机消泡剂（AFE-3168，道康宁）。
实施例二
先选取以下重量份数的原料：
氯乙烯120重量份；
醋酸乙烯30重量份；
丙烯酸丁酯10重量份；
丙烯酸六氟丁酯4重量份；
乳化剂4重量份；
反应型乳化剂6重量份；
碳酸氢钠1.6重量份；
保胶剂0.8重量份；
引发剂1重量份；
消泡剂0.5重量份；
去离子水300重量份。
然后，将上述氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯和乳化剂投入预乳化釜内，在常温下搅拌1小时，得到单体溶液。
之后，将上述反应型乳化剂、碳酸氢钠、保胶剂和去离子水中的250重量份放在一起，经充分搅拌，混合均匀，得到助剂溶液；
之后，将上述助剂溶液加入上述单体溶液中，并混合均匀，得到预乳化单体溶液；
之后，将上述引发剂和余下的50重量份去离子水放在一起，经充分溶解，得到引发剂溶液；
之后，将上述预乳化单体溶液中的1/6投入反应釜中，均匀搅拌40分钟，并升温至75摄氏度；
之后，加入上述引发剂溶液中的1/5，开始聚合反应；待反应釜内压力由初始压力降至0.2 Mpa时，开始在5小时内连续补加完余下的5/6的预乳化单体溶液和4/5的引发剂溶液；
之后，将反应温度升至80摄氏度，继续反应至反应釜内压力低于0.1Mpa；
之后，通冷却水，使反应釜温度降至40摄氏度以下，加入消泡剂。之后，对反应釜进行抽真空，使反应釜内的压力降至0Mpa；
最后，采用冷凝方法回收未反应的氯乙烯，得到氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
本实施例中：
所述乳化剂是壬基酚聚氧乙烯醚；
所述反应型乳化剂是烯丙基烷基醇醚硫酸盐；
所述保胶剂是聚乙烯吡咯烷酮；
所述引发剂是过硫酸铵。
所述消泡剂是有机消泡剂（AFE-3168，道康宁）。
实施例三
先选取以下重量份数的原料：
氯乙烯100重量份；
醋酸乙烯40重量份；
丙烯酸丁酯40重量份；
丙烯酸六氟丁酯8重量份；
乳化剂3重量份；
反应型乳化剂4重量份；
碳酸氢钠1重量份；
保胶剂0.6重量份；
引发剂0.8重量份；
消泡剂0.8重量份；
去离子水120重量份。
然后，将上述氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯和乳化剂投入预乳化釜内，在常温下搅拌1.2小时，得到单体溶液。
之后，将上述反应型乳化剂、碳酸氢钠、保胶剂和去离子水中的96重量份放在一起，经充分搅拌，混合均匀，得到助剂溶液；
之后，将上述助剂溶液加入上述单体溶液中，并混合均匀，得到预乳化单体溶液；
之后，将上述引发剂和余下的24重量份去离子水放在一起，经充分溶解，得到引发剂溶液；
之后，将上述预乳化单体溶液中的1/6投入反应釜中，均匀搅拌50分钟，并升温至76摄氏度；
之后，加入上述引发剂溶液中的1/5，开始聚合反应；待反应釜内压力由初始压力降至0.2 Mpa时，开始在6小时内连续补加完余下的5/6的预乳化单体溶液和4/5的引发剂溶液；
之后，将反应温度升至82摄氏度，继续反应至反应釜内压力低于0.1Mpa；
之后，通冷却水，使反应釜温度降至40摄氏度以下，加入消泡剂。之后，对反应釜进行抽真空，使反应釜内的压力降至0Mpa；
最后，采用冷凝方法回收未反应的氯乙烯，得到氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
本实施例中：
所述乳化剂是壬基酚聚氧乙烯醚；
所述反应型乳化剂是烯丙基烷基醇醚硫酸盐；
所述保胶剂是聚乙烯吡咯烷酮；
所述引发剂是过硫酸铵。
所述消泡剂是有机消泡剂（AFE-3168，道康宁）。

Claims (7)

1.制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于依次包括以下步骤：
先选取以下份数的原料：
氯乙烯60~120重量份；
醋酸乙烯30~60重量份；
丙烯酸丁酯10~50重量份；
丙烯酸六氟丁酯4~20重量份；
乳化剂1~4重量份；
反应型乳化剂2~6重量份；
碳酸氢钠0.4~1.6重量份；
保胶剂0.2~0.8重量份；
引发剂0.4~1重量份；
消泡剂0.2~0.8重量份；
去离子水150重量份；
然后，将上述氯乙烯、醋酸乙烯、丙烯酸丁酯、丙烯酸六氟丁酯和乳化剂投入预乳化釜内，在常温下搅拌0.8~1.2小时，得到单体溶液；
之后，将上述反应型乳化剂、碳酸氢钠、保胶剂和去离子水中的120重量份放在一起，经充分搅拌，混合均匀，得到助剂溶液；
之后，将上述助剂溶液加入上述单体溶液中，并混合均匀，得到预乳化单体溶液；
之后，将上述引发剂和余下的30重量份去离子水放在一起，经充分溶解，得到引发剂溶液；
之后，将上述预乳化单体溶液中的1/6投入反应釜中，均匀搅拌30~50分钟，并升温至74~76摄氏度；
之后，加入上述引发剂溶液中的1/5，开始聚合反应；待反应釜内压力由初始压力降至0.2 Mpa时，开始在4~6小时内连续补加完余下的5/6的预乳化单体溶液和4/5的引发剂溶液；
之后，将反应温度升至78~82摄氏度，继续反应至反应釜内压力低于0.1Mpa；
之后，通冷却水，使反应釜温度降至40摄氏度以下，加入消泡剂；之后，对反应釜进行抽真空，使反应釜内的压力降至0Mpa；
最后，采用冷凝方法回收未反应的氯乙烯，得到氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
2.据权利要求1所述的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于乳化剂是壬基酚聚氧乙烯醚。
3.根据权利要求1所述的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于所述反应型乳化剂是烯丙基烷基醇醚硫酸盐。
4.根据权利要求1所述的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于所述保胶剂是聚乙烯吡咯烷酮。
5.根据权利要求1所述的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于引发剂是过硫酸铵。
6.根据权利要求1所述的制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法，其特征在于所述消泡剂是有机消泡剂。
7.根据权利要求1~6中任一项所述制备氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液的方法所制备的氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液。
CN201810135845.XA 2018-02-10 2018-02-10 氯乙烯-醋酸乙烯-丙烯酸丁酯-丙烯酸六氟丁酯共聚乳液及其制备方法 Pending CN108424486A (zh)

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