CN112142901A - 一种拒水拒油涂布膜用pvdc水性乳液及其制备方法 - Google Patents

一种拒水拒油涂布膜用pvdc水性乳液及其制备方法 Download PDF

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CN112142901A
CN112142901A CN202010985667.7A CN202010985667A CN112142901A CN 112142901 A CN112142901 A CN 112142901A CN 202010985667 A CN202010985667 A CN 202010985667A CN 112142901 A CN112142901 A CN 112142901A
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pvdc
emulsion
sodium
water
repellent
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邵春明
孙洪阳
肖瑞厚
高艳林
王海连
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Zhejiang Juhua Technology Center Co Ltd
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Abstract

本发明公开了一种拒水拒油涂布膜用PVDC水性乳液及其制备方法，通过引入含氟烯丙基醚类单体与VDC单体进行共聚反应，将含氟侧链引入到PVDC聚合物上。乳液成膜时利用表面势能动力使含氟侧链迁移向表面，实现表面氟元素的聚集，使得PVDC膜表面具有低表面自由能。本发明的PVDC水性乳液可以涂布在塑料膜或硬片上，形成的PVDC膜具有高阻隔性的同时具有拒水、拒油、防污和耐候性能。

Description

一种拒水拒油涂布膜用PVDC水性乳液及其制备方法
技术领域
本发明属高分子材料领域，具体涉及一种拒水拒油涂布膜用PVDC水性乳液。
背景技术
涂布膜是在基材膜的表面涂覆上一层功能性涂料而形成的。在塑料包装行业，涂布膜因厚度小、柔性好、成本低等优点越来越具有竞争力。PVDC乳液涂布膜同时对水蒸气和氧气具有非常优异的阻隔性，且具有安全环保，无毒的特点，广泛应用于薄膜类食品包装行业。但PVDC膜表面自由能较低，不拒水拒油且不防污、不耐候，使得其在某些使用场合受到了限制。
发明内容
本发明的目的在于提供一种能制备同时具有拒水、拒油、防污和耐候性能的高阻隔性涂布膜的含氟PVDC水性乳液。
为了解决上述技术问题，本发明采用如下技术方案：
一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：将含氟烯丙基醚类单体作为聚合单体中的一种与VDC单体进行共聚反应，按重量份数，反应原料组成为：种子单体1～5份，VDC单体45～55份，共聚单体4～10份，引发剂0.01～0.05份，种子乳化剂0.1～0.5份，乳化剂0.5～3份，其他助剂0.01～0.05份，改性助剂0.001～0.01份，去离子水35～40份；其中，含氟烯丙基醚类单体作为种子单体的一种占0.1～5份。
优选的，种子单体还包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸羟乙酯、醋酸羟乙烯酯、醋酸乙烯酯、醋酸乙酯、丙烯酸-2-乙基己酯、丙烯腈、甲基丙烯腈、丙烯酸、甲基丙烯酸、衣康酸中的一种或几种的混合物。
优选的，种子乳化剂包括含氟乳化剂和阴离子乳化剂，所述阴离子乳化剂为十二烷基硫酸钠、十五烷基硫酸钠、十八烷基硫酸钠、十二烷基苯磺酸钠、十五烷基苯磺酸钠、十八烷基磺酸钠、醇醚羧酸盐、十二烷基羧酸钾、十五烷基羧酸钠、十八烷基羧酸钾中的一种或几种的混合物。
优选的，含氟烯丙基醚类单体为全氟聚醚烯丙基醚类单体。
优选的，引发剂为过硫酸盐类。
优选的，其他助剂为碳酸氢钠、碳酸氢钾、醋酸铵、冰醋酸中的一种或者几种的混合物。
优选的，改性助剂为二甲基硅油、聚硅氧烷、苯乙醇油酸酯、磷酸三丁酯、苯乙酸月桂醇酯、聚乙烯醚中的一种或几种的混合物。
制备如权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液的方法，其特征在于，包括如下步骤：
(1)配置引发剂水溶液：称取过硫酸铵，用去离子水配成过硫酸铵水溶液Ⅰ，备用；称取焦亚硫酸钠，用去离子水配成焦亚硫酸钠水溶液，备用；称取过硫酸铵，用去离子水配成过硫酸铵水溶液Ⅱ，备用；
(2)配置预混液：将VDC单体、丙烯酸甲酯、丙烯酸丁酯、衣康酸、丙烯酸、十八烷基硫酸钠、十二烷基羧酸钾、十五烷基苯磺酸钠、碳酸氢钠、醋酸铵及去离子水投入混液槽，在5℃，170rpm搅拌转速下分散30min，得到预混液，备用；
(3)种子乳液聚合：将全氟己基烯丙基醚单体、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、十二烷基硫酸钠、醇醚羧酸盐及去离子水投入聚合釜内，在100rpm搅拌转速下预分散30分钟后，将聚合釜的温度升至75℃，加入步骤(1)配置得到的过硫酸铵水溶液Ⅰ进行反应，反应1.5h后结束反应，得到种子乳液；
(4)PVDC乳液聚合：用氮气将聚合釜置换两次后抽真空，压力为-0.08Mpa，抽真空完成后将聚合釜温度调整至55℃，加入步骤(1)配置得到的焦亚硫酸钠水溶液、过硫酸铵水溶液Ⅱ，以及步骤(2)配置得到的预混液进行反应，控制搅拌转速为110rpm，反应12h后，升温至70℃保温2h，得到PVDC乳液；
(5)乳液的脱吸：向步骤(4)得到的PVDC乳液中加入二甲基硅油及聚乙烯醚，将氮气管的出口没在PVDC乳液液面以下，鼓入氮气并抽真空，整个脱吸过程中压力控制在-0.02Mpa，温度控制在65℃，搅拌转速为20rpm，脱吸时间为4h，脱吸完成后冷却过滤，即得到产品。
由于采用上述技术方案，本发明具有以下有益效果：
本发明通过引入含氟烯丙基醚类单体与VDC单体进行共聚反应，将含氟侧链引入到PVDC聚合物上，乳液成膜时利用表面势能动力使含氟侧链迁移向表面，实现表面氟元素的聚集，使得PVDC膜表面具有低表面自由能。本发明的PVDC水性乳液可以涂布在塑料膜或硬片上，形成的PVDC膜具有高阻隔性的同时具有拒水、拒油、防污和耐候性能。制备过程中，种子乳液促进PVDC乳液聚合，乳液的脱吸可分离未反应的单体，提高产品的纯度。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
实施例1
一种拒水拒油涂布膜用PVDC水性乳液，其原料配方如下：
种子单体：全氟己基烯丙基醚单体0.1kg、甲基丙烯酸甲酯0.88kg、丙烯酸丁酯0.7kg、丙烯酸0.07kg；
VDC单体：49.51kg；
共聚单体：丙烯酸甲酯2.91kg、丙烯酸丁酯2.91kg、衣康酸2.33kg、丙烯酸0.58kg；
引发剂：过硫酸铵0.022kg、焦亚硫酸钠0.02kg；
种子乳化剂：十五烷基硫酸钠0.07kg、醇醚羧酸盐0.07kg；
乳化剂：十二烷基硫酸钠0.41kg、十二烷基羧酸钾0.41kg、十五烷基苯磺酸钠0.0.82kg；
其他助剂：碳酸氢钠0.02kg、醋酸铵0.02kg；
改性助剂：二甲基硅油0.002kg、聚乙烯醚0.002kg；
去离子水：38.2kg。
制备步骤如下：
(1)配置引发剂水溶液：称取0.005kg的过硫酸铵(APS)，用2kg去离子水配成过硫酸铵水溶液Ⅰ，备用；称取0.02kg的焦亚硫酸钠(SMBS)，用3kg去离子水配成焦亚硫酸钠水溶液，备用；称取0.017kg过硫酸铵(APS)，用3kg去离子水配成过硫酸铵水溶液Ⅱ，备用；
(2)配置预混液：将49.51kg的VDC单体、2.91kg的丙烯酸甲酯、2.91kg的丙烯酸丁酯、2.33kg的衣康酸、0.58kg的丙烯酸、0.41kg的十八烷基硫酸钠、0.41kg的十二烷基羧酸钾、0.82kg的十五烷基苯磺酸钠、0.02kg的碳酸氢钠、0.02kg的醋酸铵及7.2kg去离子水投入混液槽，在5℃，170rpm搅拌转速下分散30min，得到预混液，备用；
(3)种子乳液聚合：将0.1kg全氟己基烯丙基醚单体、0.88kg的甲基丙烯酸甲酯、0.7kg的丙烯酸丁酯、0.07kg的丙烯酸、0.07kg十二烷基硫酸钠、0.07kg的醇醚羧酸盐及23kg的去离子水投入聚合釜内，在100rpm搅拌转速下预分散30分钟后，将聚合釜的温度升至75℃，加入步骤(1)配置得到的过硫酸铵水溶液Ⅰ进行反应，反应1.5h后结束反应，得到种子乳液；
(4)PVDC乳液聚合：用氮气将聚合釜置换两次后抽真空，压力为-0.08Mpa，抽真空完成后将聚合釜温度调整至55℃，加入步骤(1)配置得到的焦亚硫酸钠水溶液、过硫酸铵水溶液Ⅱ，以及步骤(2)配置得到的预混液进行反应，控制搅拌转速为110rpm，反应12h后，升温至70℃保温2h，得到PVDC乳液；
(5)乳液的脱吸：向步骤(4)得到的PVDC乳液中加入0.002kg的二甲基硅油及0.002kg的聚乙烯醚，将氮气管的出口没在PVDC乳液液面以下，鼓入氮气并抽真空，整个脱吸过程中压力控制在-0.02Mpa，温度控制在65℃，搅拌转速为20rpm，脱吸时间为4h，脱吸完成后冷却过滤，即得到产品。
实施例2
一种拒水拒油涂布膜用PVDC水性乳液，其原料配方如下：
种子单体：全氟聚醚烯丙基醚5kg；
VDC单体：49.2kg；
共聚单体：丙烯酸-2-乙基己酯1.1kg、甲基丙烯酸甲酯2.0kg、衣康酸2.0kg、丙烯酸0.57kg；
引发剂：过硫酸铵0.025kg、焦亚硫酸钠0.01kg；
种子乳化剂：十五烷基硫酸钠0.1kg、醇醚羧酸盐0.1kg、十八烷基羧酸钾0.1kg、全氟辛酸铵0.1kg；
乳化剂：十二烷基硫酸钠0.34kg、醇醚羧酸盐0.34kg、十二烷基羧酸钾0.34kg；
其他助剂：碳酸氢钠0.02kg、冰醋酸0.005kg；
改性助剂：苯乙酸月桂醇酯0.003kg、聚乙烯醚0.002kg；
去离子水：38.55kg。
制备方法同实施例1。
实施例3
一种拒水拒油涂布膜用PVDC水性乳液，其原料配方如下：
种子单体：甲基丙烯酸甲酯1.26kg、醋酸乙烯酯0.61kg、甲基丙烯腈0.1kg、丙烯酸0.06kg；
VDC单体：49.6kg；
共聚单体：十三氟辛基烯丙基醚4kg、甲基丙烯酸乙酯0.6kg、衣康酸0.7kg、醋酸乙烯酯1.0kg；
引发剂：过硫酸铵0.019kg、焦亚硫酸钠0.014kg；
种子乳化剂：十八烷基硫酸钠0.09kg、十五烷基苯磺酸钠0.09kg；
乳化剂：全氟己酸铵0.2kg、醇醚羧酸盐0.5kg、十五烷基羧酸钾0.7kg；
其他助剂：碳酸氢钾0.02kg、醋酸铵0.01kg；
改性助剂：苯乙醇油酸酯0.003kg、磷酸三丁酯0.003kg；
去离子水：38.4kg。
制备方法同实施例1。
实施例4
一种拒水拒油涂布膜用PVDC水性乳液，其原料配方如下：
种子单体：全氟聚醚甲基烯丙基醚0.11kg、醋酸乙酯0.74kg、丙烯腈0.14kg、丙烯酸甲酯1.86kg；
VDC单体：52kg；
共聚单体：全氟丁基烯丙基醚2.9kg、甲基丙烯酸乙酯1.74kg、衣康酸1.13kg、丙烯酸甲酯0.58kg；
引发剂：过硫酸铵0.025kg、焦亚硫酸钠0.014kg；
种子乳化剂：十八烷基硫酸钠0.1kg、十五烷基苯磺酸钠0.1kg、全氟己酸铵0.1kg；
乳化剂：醇醚羧酸盐1.0kg、全氟-3，6-二氧杂辛酸铵0.7kg、十五烷基羧酸钾0.7kg；
其他助剂：碳酸氢钾0.02kg、醋酸铵0.01kg；
改性助剂：苯乙醇油酸酯0.003kg、磷酸三丁酯0.003kg；
去离子水：38.4kg。
制备方法同实施例1。
实施例5
一种拒水拒油涂布膜用PVDC水性乳液，其原料配方如下：
种子单体：三氟丙基烯丙基醚1.36kg、丙烯酸丁酯0.85kg、丙烯酸0.17kg、甲基丙烯酸甲酯1.02kg；
VDC单体：49.2kg；
共聚单体：丙烯酸-2-乙基己酯1.7kg、甲基丙烯酸甲酯2.5kg、衣康酸2.5kg、全氟聚醚烯丙基醚0.57kg；
引发剂：过硫酸铵0.025kg、焦亚硫酸钠0.01kg；
种子乳化剂：十五烷基硫酸钠0.1kg、醇醚羧酸盐0.2kg、十八烷基羧酸钾0.1kg；
乳化剂：十二烷基硫酸钠0.34kg、醇醚羧酸盐0.34kg、十二烷基羧酸钾0.34kg；
其他助剂：碳酸氢钠0.02kg、冰醋酸0.005kg；
改性助剂：苯乙酸月桂醇酯0.003kg、聚乙烯醚0.002kg；
去离子水：38.55kg。
制备方法同实施例1。
将实施例1-5制备好的PVDC水性乳液进行测试，测试方法如下：
水接触角按照GB/T 30693-2014《塑料薄膜与水接触角的测量》规定的方法进行。
耐候性测试按照ASTM G154-16《非金属材料荧光紫外曝露设备的操作标准》规定的方法进行。
测试结果如表1所示。
表1实施例1～5获得的PVDC乳液涂布膜的性能
实施例 1 2 3 4 5
水接触角/° 73 128 112 106 93
耐候性(不粉化) 300h 1000h 850h 700h 580h
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所作出地简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。

Claims (8)

1.一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：将含氟烯丙基醚类单体作为聚合单体中的一种与VDC单体进行共聚反应，按重量份数，反应原料组成为：种子单体1～5份，VDC单体45～55份，共聚单体4～10份，引发剂0.01～0.05份，种子乳化剂0.1～0.5份，乳化剂0.5～3份，其他助剂0.01～0.05份，改性助剂0.001～0.01份，去离子水35～40份；其中，含氟烯丙基醚类单体作为种子单体的一种占0.1～5份。
2.根据权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述种子单体还包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸羟乙酯、醋酸羟乙烯酯、醋酸乙烯酯、醋酸乙酯、丙烯酸-2-乙基己酯、丙烯腈、甲基丙烯腈、丙烯酸、甲基丙烯酸、衣康酸中的一种或几种的混合物。
3.根据权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述种子乳化剂包括含氟乳化剂和阴离子乳化剂，所述阴离子乳化剂为十二烷基硫酸钠、十五烷基硫酸钠、十八烷基硫酸钠、十二烷基苯磺酸钠、十五烷基苯磺酸钠、十八烷基磺酸钠、醇醚羧酸盐、十二烷基羧酸钾、十五烷基羧酸钠、十八烷基羧酸钾中的一种或几种的混合物。
4.根据权利要求3所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述含氟烯丙基醚类单体为全氟聚醚烯丙基醚类单体。
5.根据权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述引发剂为过硫酸盐类。
6.根据权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述其他助剂为碳酸氢钠、碳酸氢钾、醋酸铵、冰醋酸中的一种或者几种的混合物。
7.根据权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液，其特征在于：所述改性助剂为二甲基硅油、聚硅氧烷、苯乙醇油酸酯、磷酸三丁酯、苯乙酸月桂醇酯、聚乙烯醚中的一种或几种的混合物。
8.制备如权利要求1所述一种拒水拒油涂布膜用PVDC水性乳液的方法，其特征在于，包括如下步骤：
(1)配置引发剂水溶液：称取过硫酸铵，用去离子水配成过硫酸铵水溶液Ⅰ，备用；称取焦亚硫酸钠，用去离子水配成焦亚硫酸钠水溶液，备用；称取过硫酸铵，用去离子水配成过硫酸铵水溶液Ⅱ，备用；
(2)配置预混液：将VDC单体、丙烯酸甲酯、丙烯酸丁酯、衣康酸、丙烯酸、十八烷基硫酸钠、十二烷基羧酸钾、十五烷基苯磺酸钠、碳酸氢钠、醋酸铵及去离子水投入混液槽，在5℃，170rpm搅拌转速下分散30min，得到预混液，备用；
(3)种子乳液聚合：将全氟己基烯丙基醚单体、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、十二烷基硫酸钠、醇醚羧酸盐及去离子水投入聚合釜内，在100rpm搅拌转速下预分散30分钟后，将聚合釜的温度升至75℃，加入步骤(1)配置得到的过硫酸铵水溶液Ⅰ进行反应，反应1.5h后结束反应，得到种子乳液；
(4)PVDC乳液聚合：用氮气将聚合釜置换两次后抽真空，压力为-0.08Mpa，抽真空完成后将聚合釜温度调整至55℃，加入步骤(1)配置得到的焦亚硫酸钠水溶液、过硫酸铵水溶液Ⅱ，以及步骤(2)配置得到的预混液进行反应，控制搅拌转速为110rpm，反应12h后，升温至70℃保温2h，得到PVDC乳液；
(5)乳液的脱吸：向步骤(4)得到的PVDC乳液中加入二甲基硅油及聚乙烯醚，将氮气管的出口没在PVDC乳液液面以下，鼓入氮气并抽真空，整个脱吸过程中压力控制在-0.02Mpa，温度控制在65℃，搅拌转速为20rpm，脱吸时间为4h，脱吸完成后冷却过滤，即得到产品。
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US20070049687A1 (en) * 2005-08-29 2007-03-01 Masayuki Hashimoto Emulsifier for emulsion polymerization, production method of polymer emulsion and polymer emulsion
CN101633715A (zh) * 2009-05-07 2010-01-27 大连理工大学 一种含氟树脂乳液及其制备方法
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