CN108047833A - 一种无需底胶的阻隔胶及其制备方法 - Google Patents

一种无需底胶的阻隔胶及其制备方法 Download PDF

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CN108047833A
CN108047833A CN201711442439.XA CN201711442439A CN108047833A CN 108047833 A CN108047833 A CN 108047833A CN 201711442439 A CN201711442439 A CN 201711442439A CN 108047833 A CN108047833 A CN 108047833A
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朱清梅
宋军军
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Hainan Kai Kai Shui New Material Co Ltd
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Abstract

本发明公开了一种无需底胶的阻隔胶及其制备方法,通过在PVDC胶乳里添加阻隔性更好的PVOH产品,提高阻隔性(≤2cc/m2.24hr),再进一步调整聚合工艺,最终制备了不需要底胶的PVDC乳液,保证良好阻隔效果的前提下,减少了涂布膜底胶工序,避免在生产过程中产生有机溶剂,且不会产生产品溶剂残余风险。

Description

一种无需底胶的阻隔胶及其制备方法
技术领域
本发明涉及一种无需底胶的阻隔胶及其制备方法,属于新型高分子材料领域。
背景技术
截至目前,PVDC是目前高阻隔且透明的软包装行业中应用最广泛,使用量最大的高阻隔薄膜,尤其是国内。常规高阻隔PVDC乳液是需要涂布底胶,目前市场上普遍使用溶剂型底胶,产生大量的有机气体。随着国家对环保监管力度的加大,软包装生产商在减少有害材料的使用以及使用更环保材料两方面倾注了很多研发。在新材料方面,比如开发了AlOx/SiOx镀膜,但其制造设备非常昂贵,且AlOx/SiOx镀层很容易机械划伤,需要涂层保护;再比如开发了聚乙烯醇(以下简称PVOH)材料,但PVOH自身粘度高的特点,在现有市场上普遍使用的PVDC涂布设备上,很难干燥,需要改造设备。
发明内容
为了克服上述问题,本发明的目的在于提供一种无需底胶的阻隔胶及其制备方法,创新点在于:1、通过聚合工艺制备了不需要底胶的PVDC乳液,减少了底胶工序,避免在生产过程中产生有机溶剂,且不会产生产品溶剂残余风险;2、通过在胶乳里添加阻隔性更好的PVOH产品,进一步达到高阻隔性(≤2cc/m2.24hr)。
本发明提供一种无需底胶的阻隔胶,该阻隔胶的固含量为24.4~35.2%,是由重量含量为99.88~99.94%的阻隔乳液、0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂混配制成;所述阻隔乳液为PVDC水性乳液与PVOH溶液按照重量比例1:1-7:3混配而成;所述的消泡剂为有机硅乳液;所述的杀菌剂为氯甲基异噻唑啉酮;
所述PVDC水性乳液的固含量为49.5-53.2%,由含有下述重量含量的原料配比制成:偏二氯乙烯单体35-45%,甲基丙烯酸甲酯4.2-8%,丙烯酸类单体3-4.2%,丙烯腈类单体0.5-1.5%,缓冲剂0.01-0.1%,引发剂0.1-0.5%,阴离子乳化剂0.05-0.2%,反应型乳化剂0.1-0.4%,络合剂0.1-0.2%,去离子水46.8-50.5%;
所述的丙烯酸类单体为甲基丙烯酸或丙烯酸;
所述的丙烯腈类单体为丙烯腈或甲基丙烯腈;
所述的缓冲剂为碳酸氢钠;
所述的引发剂为过硫酸铵;
所述的阴离子乳化剂为十二烷基二苯醚二磺酸钠、十二烷基苯磺酸钠、十二仲烷基磺酸钠中的一种或任何组合;
所述的反应型乳化剂为2-丙烯酰胺基-2-甲基丙磺酸钠;
所述的络合剂为乙二胺四乙酸盐;
所述的PVOH溶液的固含量为5-12%,由含有下述重量含量的原料配比制成:PVOH5-12%,小分子醇类5-15%,去离子水73-90%;
所述PVOH的聚合度400-1700,醇解度97-99%;
所述小分子醇类为异丙醇或乙醇;
本发明还提供一种无需底胶的阻隔胶的制备方法,包括如下步骤:
A.PVDC乳液的制备:
a)按照重量比例,分别取偏二氯乙烯单体35-45%,甲基丙烯酸甲酯4.2-8%,丙烯酸类单体3-4.2%,丙烯腈类单体0.5-1.5%,缓冲剂0.01-0.1%,引发剂0.1-0.5%,阴离子乳化剂0.05-0.2%,反应型乳化剂0.1-0.4%,络合剂0.1-0.2%,去离子水46.8-50.5%,待用;
b)混合单体的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸类单体、丙烯腈类单体置于反应釜中,搅拌均匀,待用;
c)引发剂溶液准备:用去离子水总量的15-25%,将引发剂总量的90-95%溶解,待用;
d)乳化剂稀释液准备:用去离子水总量的15-25%,将混合乳化剂总量的90-95%稀释均匀,待用;
e)络合剂稀释液准备:用去离子水总量的5%-10%,将络合剂稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、引发剂,及缓冲剂加入到反应釜中,常温开启搅拌,搅拌速度为50-100转/分钟,密封,抽真空,添加混合单体总量的5-10%。加温至50-55℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.5-1h后关闭加热装置及搅拌装置,降到室温,出料,待下步使用;
B.PVOH溶液的制备:将73-90%的去离子水倒入搅拌釜,开启搅拌,倒入5-12%的PVOH固体,持续搅拌30分钟,加热到90-95℃保持2-4小时,降温到80℃,添加5-15%小分子醇类,搅拌均匀后,降到室温,出料,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液按照重量比例1:1-7:3加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200-300转/min,搅拌0.5-0.8小时后静置出料,制得阻隔乳液,待下步使用;
D.取99.88-99.94%的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200-300转/min,0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂混配制成然后缓慢添加0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂,再搅拌1-1.5小时后静置出料。
本发明制得的无需底胶的阻隔胶,在19-30μm的BOPP基材上进行涂布试验,涂层涂布量为2.0-4.0g/m2,下机固化后,对涂布膜的附着力、氧气透过量进行检测,附着力好,涂层未脱落,且氧气透过量最低达到0.8ml/m2·day。参照表1中,对比阻隔胶1(专利申请:201210450807.6)、对比阻隔胶2(专利申请:201510385639.0)在保持薄膜基材、涂布量、涂布工艺等条件均相同的情况下得到的性能数据对比可知,本发明无需底胶的阻隔胶较对比阻隔胶1的阻氧更优异;而对比阻隔胶2虽具备更高的阻氧性能,但随着湿度的提高,其阻隔效果大幅下降。因此,本发明无需底胶的阻隔胶与上述两类阻隔胶相比都有较明显的进步。不仅涂布后,省去底胶涂布工序,附着力极好,涂层未脱落,且具备更好的阻氧性能且受湿度影响较小,尤其适用于BOPP/PET/PA等基材涂布,应用于面包、蛋糕、月饼等包装。
表1本发明无需底胶的阻隔胶与对比阻隔胶1、2经涂布BOPP基材后的性能对比
具体实施方式
下面结合具体实施例对本发明的一种无需底胶的阻隔胶及其制备方法作进一步说明。
实施例一
A.PVDC乳液的制备:
a)分别取偏二氯乙烯单体7kg,甲基丙烯酸甲酯1.48kg,丙烯酸0.84kg,甲基丙烯腈0.3kg,碳酸氢钠0.02kg,过硫酸铵0.1kg,十二烷基二苯醚二磺酸钠0.04kg,2-丙烯酰胺基-2-甲基丙磺酸钠0.08kg,乙二胺四乙酸盐0.04kg,去离子水10.1kg,待用;
b)混合单体及混合乳化剂的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸、甲基丙烯腈置于反应釜中,搅拌均匀制成9.62kg的混合单体,再将上述准备好的十二烷基二苯醚二磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸钠置于容器中,搅拌均匀制成0.12kg混合乳化剂,待用;
c)引发剂溶液准备:用1.52kg的去离子水将0.09kg过硫酸铵溶解,待用;
d)乳化剂稀释液准备:用1.62kg去离子水将0.11kg上述制成的混合乳化剂稀释均匀,待用;
e)络合剂稀释液准备:用0.02kg将乙二胺四乙酸盐稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、过硫酸铵,及碳酸氢钠加入到反应釜中,常温开启搅拌,搅拌速度为50r/min,密封,抽真空,添加0.48kg混合单体,加温至50℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.5h后关闭加热装置及搅拌装置,降到室温出料,制得固含量为49.5%的PVDC乳液20kg,待下步使用;
B.PVOH溶液的制备:将18kg的去离子水倒入搅拌釜,开启搅拌,倒入1kg的PVOH固体,持续搅拌30min,加热到90℃保持2h,降温到80℃,添加1kg异丙醇,搅拌均匀后,降到室温,出料,制得固含量为5%的PVOH溶液20kg,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200r/min,搅拌0.5h后静置出料,制得40kg阻隔乳液,待下步使用;
D.取上述制得的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200r/min,然后缓慢添加0.04kg的有机硅乳液及0.01kg的氯甲基异噻唑啉酮,再搅拌1h后静置出料,制得固含量为27.35%的无需底胶的阻隔胶;
E.取上述制得的无需底胶的阻隔胶在19μm的BOPP基材上进行涂布,涂布量为2.5g/m2,烘干固化后测试其涂层未脱落,氧气透过量为2.0ml/m2·day·Pa。
实施例二
A.PVDC乳液的制备:
a)分别取偏二氯乙烯单体15.2kg,甲基丙烯酸甲酯3.2kg,甲基丙烯酸1.54kg,丙烯腈0.49kg,碳酸氢钠0.03kg,过硫酸铵0.12kg,十二烷基苯磺酸钠0.06kg,2-丙烯酰胺基-2-甲基丙磺酸钠0.12kg,乙二胺四乙酸盐0.04kg,去离子水19.2kg,待用;
b)混合单体及混合乳化剂的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸、丙烯腈置于反应釜中,搅拌均匀制成20.43kg的混合单体,再将上述准备好的十二烷基苯磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸钠置于容器中,搅拌均匀制成0.18kg混合乳化剂,待用;
c)引发剂溶液准备:用3.46kg的去离子水将0.11kg过硫酸铵溶解,待用;
d)乳化剂稀释液准备:用2.88kg去离子水将0.17kg上述制成的混合乳化剂稀释均匀,待用;
e)络合剂稀释液准备:用0.03kg将乙二胺四乙酸盐稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、过硫酸铵,及碳酸氢钠加入到反应釜中,常温开启搅拌,搅拌速度为70r/min,密封,抽真空,添加1.23kg混合单体,加温至52℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.6h后关闭加热装置及搅拌装置,降到室温出料,制得固含量为52%的PVDC乳液40kg,待下步使用;
B.PVOH溶液的制备:将20.4kg的去离子水倒入搅拌釜,开启搅拌,倒入1.68kg的PVOH固体,持续搅拌30min,加热到94℃保持2.5h,降温到80℃,添加1.92kg乙醇,搅拌均匀后,降到室温,出料,制得固含量为7%的PVOH溶液24kg,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为230r/min,搅拌0.7h后静置出料,制得64kg阻隔乳液,待下步使用;
D.取上述制得的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为250r/min,然后缓慢添加0.04kg的有机硅乳液及0.01kg的氯甲基异噻唑啉酮,再搅拌1.2h后静置出料,制得固含量为35.19%的无需底胶的阻隔胶;
E.取上述制得的无需底胶的阻隔胶在30μm的BOPP基材上进行涂布,涂布量为3.0g/m2,烘干固化后测试其涂层未脱落,氧气透过量为1.0ml/m2·day·Pa。
实施例三
A.PVDC乳液的制备:
a)分别取偏二氯乙烯单体24kg,甲基丙烯酸甲酯4.08kg,丙烯酸2.1kg,甲基丙烯腈0.6kg,碳酸氢钠0.04kg,过硫酸铵0.02kg,十二仲烷基磺酸钠0.06kg,2-丙烯酰胺基-2-甲基丙磺酸钠0.12kg,乙二胺四乙酸盐0.12kg,去离子水28.86kg,待用;
b)混合单体及混合乳化剂的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸、甲基丙烯腈置于反应釜中,搅拌均匀制成30.78kg的混合单体,再将上述准备好的十二仲烷基磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸钠置于容器中,搅拌均匀制成0.18kg混合乳化剂,待用;
c)引发剂溶液准备:用3.46kg的去离子水将0.11kg过硫酸铵溶解,待用;
d)乳化剂稀释液准备:用2.88kg去离子水将0.17kg上述制成的混合乳化剂稀释均匀,待用;
e)络合剂稀释液准备:用0.03kg将乙二胺四乙酸盐稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、过硫酸铵,及碳酸氢钠加入到反应釜中,常温开启搅拌,搅拌速度为60r/min,密封,抽真空,添加1.23kg混合单体,加温至54℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.7h后关闭加热装置及搅拌装置,降到室温出料,制得固含量为51.9%的PVDC乳液60kg,待下步使用;
B.PVOH溶液的制备:将31.24kg的去离子水倒入搅拌釜,开启搅拌,倒入3.47kg的PVOH固体,持续搅拌30min,加热到93℃保持3h,降温到80℃,添加3.86kg异丙醇,搅拌均匀后,降到室温,出料,制得固含量为9%的PVOH溶液38.57kg,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为250r/min,搅拌0.6h后静置出料,制得98.49kg阻隔乳液,待下步使用;
D.取上述制得的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为260r/min,然后缓慢添加0.05kg的有机硅乳液及0.01kg的氯甲基异噻唑啉酮,再搅拌1.3h后静置出料,制得固含量为35.2%的无需底胶的阻隔胶;
E.取上述制得的无需底胶的阻隔胶在30μm的PET上进行涂布,涂布量为4.0g/m2,烘干固化后测试其涂层未脱落,氧气透过量为0.8ml/m2·day·Pa。
实施例四
A.PVDC乳液的制备:
a)分别取偏二氯乙烯单体33.36kg,甲基丙烯酸甲酯4.4kg,甲基丙烯酸2.4kg,甲基丙烯腈0.64kg,碳酸氢钠0.03kg,过硫酸铵0.02kg,十二烷基二苯醚二磺酸钠0.06kg,2-丙烯酰胺基-2-甲基丙磺酸钠0.16kg,乙二胺四乙酸盐0.08kg,去离子水38.61kg,待用;
b)混合单体及混合乳化剂的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸、甲基丙烯腈置于反应釜中,搅拌均匀制成41.04kg的混合单体,再将上述准备好的十二烷基二苯醚二磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸钠置于容器中,搅拌均匀制成0.22kg混合乳化剂,待用;
c)引发剂溶液准备:用8.88kg的去离子水将0.01kg过硫酸铵溶解,待用;
d)乳化剂稀释液准备:用8.88kg去离子水将0.21kg上述制成的混合乳化剂稀释均匀,待用;
e)络合剂稀释液准备:用0.05kg将乙二胺四乙酸盐稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、过硫酸铵,及碳酸氢钠加入到反应釜中,常温开启搅拌,搅拌速度为80r/min,密封,抽真空,添加3.69kg混合单体,加温至53℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.8h后关闭加热装置及搅拌装置,降到室温出料,制得固含量为51.74%的PVDC乳液80kg,待下步使用;
B.PVOH溶液的制备:将41.6kg的去离子水倒入搅拌釜,开启搅拌,倒入5.33kg的PVOH固体,持续搅拌30min,加热到91℃保持3.5h,降温到80℃,添加6.4kg乙醇,搅拌均匀后,降到室温,出料,制得固含量为10%的PVOH溶液53.33kg,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为280r/min,搅拌0.7h后静置出料,制得133.19kg阻隔乳液,待下步使用;
D.取上述制得的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为220r/min,然后缓慢添加0.12kg的有机硅乳液及0.03kg的氯甲基异噻唑啉酮,再搅拌1.4h后静置出料,制得固含量为35.15%的无需底胶的阻隔胶;
E.取上述制得的无需底胶的阻隔胶在25μm的PA上进行涂布,涂布量为2.0g/m2,烘干固化后测试其涂层未脱落,氧气透过量为1.2ml/m2·day·Pa。
实施例五
A.PVDC乳液的制备:
a)分别取偏二氯乙烯单体45kg,甲基丙烯酸甲酯4.2kg,丙烯酸3.14kg,丙烯腈0.5kg,碳酸氢钠0.01kg,过硫酸铵0.1kg,十二仲烷基磺酸钠0.05kg,2-丙烯酰胺基-2-甲基丙磺酸钠0.1kg,乙二胺四乙酸盐0.1kg,去离子水46.8kg,待用;
b)混合单体及混合乳化剂的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸、丙烯腈置于反应釜中,搅拌均匀制成52.84kg的混合单体,再将上述准备好的十二仲烷基磺酸钠和2-丙烯酰胺基-2-甲基丙磺酸钠置于容器中,搅拌均匀制成0.15kg混合乳化剂,待用;
c)引发剂溶液准备:用11.7kg的去离子水将0.09kg过硫酸铵溶解,待用;
d)乳化剂稀释液准备:用9.36kg去离子水将0.14kg上述制成的混合乳化剂稀释均匀,待用;
e)络合剂稀释液准备:用0.05kg将乙二胺四乙酸盐稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、过硫酸铵,及碳酸氢钠加入到反应釜中,常温开启搅拌,搅拌速度为100r/min,密封,抽真空,添加5.28kg混合单体,加温至55℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌1h后关闭加热装置及搅拌装置,降到室温出料,制得固含量为53.2%的PVDC乳液100kg,待下步使用;
B.PVOH溶液的制备:将170.33kg的去离子水倒入搅拌釜,开启搅拌,倒入28kg的PVOH固体,持续搅拌30min,加热到95℃保持4h,降温到80℃,添加35kg异丙醇,搅拌均匀后,降到室温,出料,制得固含量为12%的PVOH溶液233.33kg,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为300r/min,搅拌0.8h后静置出料,制得333.13kg阻隔乳液,待下步使用;
D.取上述制得的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为300r/min,然后缓慢添加0.17kg的有机硅乳液及0.03kg的氯甲基异噻唑啉酮,再搅拌1.5h后静置出料,制得固含量为24.42%的无需底胶的阻隔胶;
E.取上述制得的无需底胶的阻隔胶在21μm的PET上进行涂布,涂布量为2.0g/m2,烘干固化后测试其涂层未脱落,氧气透过量为1.5ml/m2·day·Pa。

Claims (9)

1.一种无需底胶的阻隔胶,其特征在于,固含量为24.4-35.2%,是由重量含量为99.88-99.94%的阻隔乳液、0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂混配制成。
2.如权利要求1所述的一种无需底胶的阻隔胶,其特征在于,所述的阻隔乳液为PVDC水性乳液与PVOH溶液按照重量比例1:1-7:3混配而成。
3.如权利要求2所述的一种无需底胶的阻隔胶,其特征在于,所述的PVDC水性乳液的固含量为49.5-53.2%,由含有下述重量含量的原料配比制成:偏二氯乙烯单体35-45%,甲基丙烯酸甲酯4.2-8%,丙烯酸类单体3-4.2%,丙烯腈类单体0.5-1.5%,缓冲剂0.01-0.1%,引发剂0.1-0.5%,阴离子乳化剂0.05-0.2%,反应型乳化剂0.1-0.4%,络合剂0.1-0.2%,去离子水46.8-50.5%。
4.如权利要求2所述的一种无需底胶的阻隔胶,其特征在于,所述的PVOH溶液的固含量为5-12%,由含有下述重量含量的原料配比制成:PVOH 5-12%,小分子醇类5-15%,水73-90%。
5.如权利要求1所述的一种无需底胶的阻隔胶,其特征在于,所述的消泡剂为有机硅乳液,所述的杀菌剂为氯甲基异噻唑啉酮。
6.如权利要求3所述的一种无需底胶的阻隔胶,其特征在于,所述的丙烯酸类单体为甲基丙烯酸或丙烯酸,所述的丙烯腈类单体为丙烯腈或甲基丙烯腈。
7.如权利要求3所述的一种无需底胶的阻隔胶,其特征在于,所述的缓冲剂为碳酸氢钠;所述的引发剂为过硫酸铵;所述的阴离子乳化剂为十二烷基二苯醚二磺酸钠、烷基苯磺酸钠、仲烷基磺酸钠中的一种或任何比例组合;所述的反应型乳化剂为2-丙烯酰胺基-2-甲基丙磺酸钠,所述的络合剂为乙二胺四乙酸盐。
8.如权利要求4所述的一种无需底胶的阻隔胶,其特征在于,所述PVOH的聚合度400-1700,醇解度97-99%,所述小分子醇类为异丙醇或乙醇。
9.如权利要求1所述的一种无需底胶的阻隔胶的制备方法,其特征在于,包括如下步骤:
A.PVDC乳液的制备:
a)按照重量比例,分别取偏二氯乙烯单体35-45%,甲基丙烯酸甲酯4.2-8%,丙烯酸类单体3-4.2%,丙烯腈类单体0.5-1.5%,缓冲剂0.01-0.1%,引发剂0.1-0.5%,阴离子乳化剂0.05-0.2%,反应型乳化剂0.1-0.4%,络合剂0.1-0.2%,去离子水46.8-50.5%,待用;
b)混合单体的制备:将上述准备好的偏二氯乙烯单体、甲基丙烯酸甲酯、丙烯酸类单体、丙烯腈类单体置于反应釜中,搅拌均匀,待用;
c)引发剂溶液准备:用去离子水总量的15-25%,将引发剂总量的90-95%溶解,待用;
d)乳化剂稀释液准备:用去离子水总量的15-25%,将混合乳化剂总量的90-95%稀释均匀,待用;
e)络合剂稀释液准备:用去离子水总量的5%-10%,将络合剂稀释均匀,待用;
f)种子反应:依次将剩余的去离子水、混合乳化剂、引发剂,及缓冲剂加入到反应釜中,常温开启搅拌,搅拌速度为50-100转/分钟,密封,抽真空,添加混合单体总量的5-10%,加温至50-55℃,保持0.5h;
g)聚合反应:同时滴加剩余的混合单体、b)步骤准备的引发剂溶液及c)步骤准备的乳化剂稀释液,15h内滴完,并确保混合单体和乳化剂稀释液比引发剂溶液早滴完0.5h;
h)最后添加d)步骤准备的络合剂稀释液,保持搅拌0.5-1h后关闭加热装置及搅拌装置,降到室温,出料,待下步使用;
B.PVOH溶液的制备:将73-90%的去离子水倒入搅拌釜,开启搅拌,倒入5-12%的PVOH固体,持续搅拌30分钟,加热到90-95℃保持2-4小时,降温到80℃,添加5-15%小分子醇类,搅拌均匀后,降到室温,出料,待下步使用;
C.取上述制备好的PVDC乳液、PVOH溶液按照重量比例1:1-7:3加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200-300转/min,搅拌0.5-0.8小时后静置出料,制得阻隔乳液,待下步使用;
D.取99.88-99.94%的阻隔乳液加入到搅拌釜内,然后开启搅拌装置,设置搅拌速度为200-300转/min,0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂混配制成然后缓慢添加0.05-0.1%的消泡剂和0.01-0.02%的杀菌剂,再搅拌1-1.5小时后静置出料。
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