CN108485399B - 一种涂布用pvdc水性乳液 - Google Patents

一种涂布用pvdc水性乳液 Download PDF

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CN108485399B
CN108485399B CN201810174488.8A CN201810174488A CN108485399B CN 108485399 B CN108485399 B CN 108485399B CN 201810174488 A CN201810174488 A CN 201810174488A CN 108485399 B CN108485399 B CN 108485399B
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sodium
emulsion
pvdc
carboxylate
acrylate
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尹作柱
吴志刚
苏兰辉
吴宇鹏
吕颖琦
赵鑫犇
马从礼
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Electrochemical Factory Of Zhejiang Juhua Co ltd
Zhejiang Quzhou Jusu Chemical Industry Co ltd
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Abstract

本发明公开了一种涂布用PVDC水性乳液，按重量份数，由以下组份制备而成：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。本发明的PVDC水性乳液涂布在PVC、PET、尼龙、PCT等硬片上制成复合硬片，具有抗冲击强度高，不易产生裂纹，阻隔性好，不会溶出有害物质，能与药品直接接触，热稳定性高抗黄变能力强等优点。

Description

一种涂布用PVDC水性乳液
技术领域
本发明属高分子材料领域，具体涉及一种涂布用PVDC水性乳液。
背景技术
PVC、PET、尼龙、PCT等硬片具有厚薄均匀、密封性能好、热合快、易成型、价格低廉、抗紫外线及抗辐射，已经广泛应用于片剂、胶囊、注射液、口服液等药品的内外包装，但PVC硬片也有致命的缺陷：会溶出有害物质及阻隔性能差。PVDC作为一种塑料包装材料具有便携、不会溶出有害物质可与食品药品直接接触、高阻隔性、价格低廉及方便推广等优点，已经广泛应用于药品和食品包装领域。目前食品及药品包装领域都广泛的使用了PVDC乳液，将PVDC乳液涂布在PVC、PET、尼龙、PCT等材料上，明显改善了这些材料的阻隔性且使这些材料变得绿色环保，可以直接与食品及药品接触。
如中国专利公开号CN104114585A，公开日2014年10月22日，发明名称：偏二氯乙烯系共聚乳液和泡罩包装用膜。该发明提供了一种耐冲击性、热稳定性优异、且兼具阻隔性的泡罩包装用膜及适用于制造该膜的偏二氯乙烯系共聚物乳液。上述泡罩包装用膜涂层以及上述乳液包含重均分子量Mw为12万～30万的偏二氯乙烯系共聚物，所述偏二氯乙烯共聚物是将70～95质量份数的偏二氯乙烯和30～5质量份数的能和偏二氯乙烯共聚的一种及一种以上的单体(偏二氯乙烯和其他单体合计为100质量份)乳液共聚得到。不足之处是抗冲击强度偏低。
又如中国专利公开号CN 102876149A，公开日2013年1月16日，发明名称：一种涂布用自粘性聚偏二氯乙烯乳液及其制备方法。该涂料由含有下述重量含量的原料制成：改性PVDC共聚乳液65-80％、附着力促进剂0.5-5％、滑爽剂3-5％、防粘剂3-5％、软化水13.5-20％；所述改性PVDC共聚乳液是由含有下述重量含量的原料配制成：偏二氯乙烯45-60％、丙烯酸1-3％、丙烯酸丁酯2-5％、甲基丙烯酸乙酯0.5-5％、丙烯腈0.5-3％、链引发剂0.3-0.5％、乳化剂0.1-1％、软化水35.5-37％、消泡剂0.1-0.5％。不足之处是热稳定性和抗黄变能力较差。
发明内容
为了克服现有技术的缺陷，本发明提供一种涂布用PVDC水性乳液，本发明的PVDC水性乳液涂布在PVC、PET、尼龙、PCT等硬片上制成复合硬片，具有抗冲击强度高，不易产生裂纹，阻隔性好，不会溶出有害物质，能与药品直接接触，热稳定性高抗黄变能力强等优点。
为了解决上述技术问题，本发明采用的技术方案为：一种涂布用PVDC水性乳液，按重量份数，由以下组份制备而成：
Figure BDA0001586866880000021
所述种子单体优选为丙烯酸甲酯、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，所述种子单体更优选为丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸甲酯、醋酸羟乙烯酯、醋酸乙烯酯、醋酸乙酯、丙烯腈、甲基丙烯腈、丙烯酸中的一种或几种的混合物。
所述共聚单体优选为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸羟乙酯、醋酸乙烯酯、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，所述共聚单体更优选为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸羟乙酯、醋酸乙烯酯、丙烯酸-2-乙基己酯、丙烯酸、衣康酸中的一种或几种的混合物。
本发明可选用过硫酸盐类引发剂，所述引发剂优选为过硫酸铵、过硫酸钠、过硫酸钾中的一种或几种的混合物。
本发明的种子乳化剂可选用阴离子乳化剂，所述种子乳化剂优选为十二烷基硫酸钠、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，所述种子乳化剂更优选为十二烷基硫酸钠、十五烷基硫酸钠、十八烷基硫酸钠、十五烷基苯磺酸钠、醇醚羧酸盐、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。
本发明的乳化剂可选用阴离子乳化剂，所述乳化剂优选为十二烷基硫酸钠、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、十五烷基羧酸钾、十八烷基羧酸钠中的一种或几种的混合物。所述乳化剂更优选为十二烷基硫酸钠、十八烷基硫酸钠、十五烷基苯磺酸钠、醇醚羧酸盐、十二烷基羧酸钾、十五烷基羧酸钾、十八烷基羧酸钠中的一种或几种的混合物。
所述其他助剂优选为碳酸氢钠、碳酸氢钾、醋酸铵、冰醋酸中的一种或者几种的混合物。
所述改性助剂优选为二甲基硅油、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。
种子乳化剂和乳化剂的用量对乳胶粒子的粒径的大小有影较大影响，其用量太大则乳胶粒子粒径较小，乳液稳定性好，反之则乳胶粒子的粒径较大，乳液稳定性差，因此本发明中种子乳化剂的重量份数为0.1～0.5份，优选为0.3～0.4份；乳化剂重量份数为0.5～3.0份，优选为1.2～2.5份，制得的PVDC乳液的乳胶粒子的粒径在140-190nm之间，既保障了乳液的稳定性，又节约了成本。
PVDC聚合物为结晶性聚合物，当PVDC开始结晶以后，其硬度和阻隔性能都会随着结晶度的增加而增加，但韧性和抗冲击强度会随着结晶度的增加而减少，在加工成成品时会产生裂纹，从而失去阻隔能力。PVDC聚合物中VDC的含量越高，最终其结晶度也越高，阻隔性能也越好，但抗冲击强度会越低。因此，本发明中VDC单体的重量份数为45～55份，优选48-52份，既保证了乳液制得的涂膜的阻隔性能又兼顾了其抗冲击强度。
PVDC聚合物的分子量对聚合物的性质有很大的影响，聚合物的分子量越高，PVDC聚合物的强度和力学性能会提高，耐冲击强度也会提高。反应温度对聚合物的分子量有较大的影响，聚合物的分子量随反应温度的增加而降低。本发明中选择氧化还原体系为引发体系可有效的降低聚会反应温度，从而保障了聚合物较高的分子量，提高了PVDC聚合物的强度和力学性能。
纯PVDC聚合物的热稳定性能比较差，在加热或碰到碱、活泼金属及lewis酸时，很容易脱去氯化氢形成共轭双键。当体系中存在一个共轭双键，很快就在主链上形成更多的不饱和单元，通常采用共聚的方法来阻断这种诱发作用。一般当不饱和单元超过4，聚合物就有可能变色。这里选择VDC单体与其他单体共聚。假设共聚单体均匀嵌套在PVDC分子链中，VDC含量越高，共聚单体的含量越低，那么对应PVDC分子链中VDC链段长度越高，越容易形成单元数超过4的不饱和单元，热稳定性能越差，若VDC单体的含量过低则阻隔性能达不到要求。因此，本发明中VDC单体的重量份数为45～55份，共聚单体为4～10份，既保证了乳液制得的涂膜的阻隔性能又兼顾了其热稳定性。
其他助剂的种类和用量直接影响上述引发剂的自由基活性及偏氯乙烯单体的稳定性。本发明中的其他助剂可以使用碳酸氢钠、碳酸氢钾、醋酸铵、冰醋酸的一种或几种，优选碳酸氢钠。其他助剂用量太大易降低引发剂活性，用量太小则降低偏氯乙烯单体的稳定性，因此，本发明中其他助剂的重量份数为0.01～0.05份，优选为0.03～0.04。
本发明通过优化聚合配方，得到的PVDC水性乳液涂布在PVC、PET、尼龙、PCT等硬片上制成复合硬片，改善了硬片的抗冲击强度、阻隔性、热稳定性和抗黄变等性能。
与现有技术相比，本发明的优点为：
本发明的PVDC水性乳液粒径在142.4～194.3nm之间，含固量在59.8～61.1％之间，粘度在23.2～25.7mPa.S之间，表面张力在38.5～46.6之间，特别适用于涂布在PVC、PET、尼龙、PCT等硬片上制成复合硬片，具有抗冲击强度高，不易产生裂纹，阻隔性好，不会溶出有害物质，能与药品直接接触，热稳定性高抗黄变能力强等优点。
具体实施方式
以下通过实施例对本发明进行更具体的说明，但本发明并不限于所述的实施例。
实施例1
一种涂布用水性PVDC乳液，其原料配方如下：
Figure BDA0001586866880000051
Figure BDA0001586866880000061
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的偏氯乙烯单体、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0.875kg的甲基丙烯酸甲酯、0.7kg的丙烯酸丁酯、0.07kg的丙烯酸、0.105kg的丙烯腈、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。乳液的性能参数见表1。
实施例2
一种涂布用水性PVDC乳液，其原料配方如下：
Figure BDA0001586866880000071
Figure BDA0001586866880000081
制备方法同实施例1，乳液的性能参数见表1。
实施例3
一种涂布用水性PVDC乳液，其原料配方如下：
Figure BDA0001586866880000082
Figure BDA0001586866880000091
制备方法同实施例1，乳液的性能参数见表1。
实施例4
一种涂布用水性PVDC乳液，其原料配方如下：
Figure BDA0001586866880000092
Figure BDA0001586866880000101
制备方法同实施例1，乳液的性能参数见表1。
实施例5
一种涂布用水性PVDC乳液，其原料配方如下：
Figure BDA0001586866880000102
Figure BDA0001586866880000111
制备方法同实施例1，乳液的性能参数见表1。
对比例
按照中国专利公开号CN104114585A实施例1的方法制备得到的产品。
性能测试：
1、耐冲击性评价PVDC/PVC复合硬片的制作
将PVC硬片(厚底约为250um)表面经过电晕放电处理，在表面面涂一层2g/m2的粘合剂(该粘合剂为聚氨酯溶于醋酸乙酯中形成的溶液)，热风干燥20S，面涂80g/m2实施例1～5及对比例制得的水性PVDC乳液，然后经过红外线干燥，即完成了耐冲击性评价PVDC/PVC复合硬片的制作。
耐冲击性按YBB00222005-2015标准执行。性能评价的结果见表2和表3。
2、阻隔性评价PVDC/PVC复合硬片的制作
将PVC硬片(厚底约为250um)表面经过电晕放电处理，在表面面涂一层2g/m2的粘合剂(该粘合剂为聚氨酯溶于醋酸乙酯中形成的溶液)，热风干燥20S，面涂80g/m2实施例1～5及对比例制得的水性PVDC乳液，然后经过红外线干燥，接着置于烘房内于50℃熟化48h，即完成了阻隔性评价PVDC/PVC复合硬片的制作。
水蒸气透过量检测方法按GB1037-1988《塑料薄膜和片材透水蒸气性试验方法杯式法》标准执行；氧气透过量检测方法按GB/T1038-2000《塑料薄膜和薄片气体透过性试验方法压差法》标准执行。性能评价结果见表4。
3、热稳定性评价PVDC/PVC复合硬片的制作
在表面面涂一层2g/m2的粘合剂(该粘合剂为聚氨酯溶于醋酸乙酯中形成的溶液)，热风干燥20S，面涂80g/m2实施例1～5及对比例制得的水性PVDC乳液，然后经过红外线干燥，即完成了热稳定性评价PVDC/PVC复合硬片的制作。
热稳定性评价测试方法：将PVDC/PVC复合片在不同温度下放置一定时间，观察表面颜色有否有变化。性能评价结果见表5。
表1实施例1～5及对比例制得的水性PVDC乳液性能参数
Figure BDA0001586866880000121
表2PVDC/PVC复合硬片的耐冲击性能测试结果
(PVDC乳液常温放置2周)
Figure BDA0001586866880000122
Figure BDA0001586866880000131
表3PVDC/PVC复合硬片的耐冲击性能测试结果
(PVDC乳液常温放置3月)
Figure BDA0001586866880000132
表4PVDC/PVC复合硬片的阻隔性能测试结果
Figure BDA0001586866880000141
表5PVDC/PVC复合硬片热稳定性测试结果
Figure BDA0001586866880000151

Claims (8)

1.一种涂布用PVDC水性乳液，其特征在于，按重量份数，由以下组份制备而成：
Figure FDA0002466821530000011
制备的PVDC水性乳液粒径在142.4～194.3nm之间，含固量在59.8～61.1％之间，粘度在23.2～25.7mPa.S之间，表面张力在38.5～46.6mN/m之间，适用于涂布在PVC硬片上制成复合硬片，乳液常温放置3月涂布半年后复合硬片的耐冲击性433～461KJ/m2，上述涂布后的复合硬片放置半年后的氧气透过率0.74～0.97g/m2·day，水蒸气透过率0.74～0.95g/m2·day。
2.根据权利要求1所述的涂布用PVDC水性乳液，其特征在于，所述种子单体为丙烯酸甲酯、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所述的涂布用PVDC水性乳液，其特征在于，所述共聚单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸羟乙酯、醋酸乙烯酯、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。
4.根据权利要求1所述的涂布用PVDC水性乳液，其特征在于，所述引发剂为过硫酸铵、过硫酸钠、过硫酸钾中的一种或几种的混合物。
5.根据权利要求1所述的涂布用PVDC水性乳液，其特征在于，所述种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。
6.根据权利要求1所述的涂布用PVDC水性乳液，其特征在于，所述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、十五烷基羧酸钾、十八烷基羧酸钠中的一种或几种的混合物。
7.根据权利要求1所述的涂布用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。
8.根据权利要求1所述的涂布用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。
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