CN113698831A - 一种高氧气阻隔涂料 - Google Patents

一种高氧气阻隔涂料 Download PDF

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CN113698831A
CN113698831A CN202111053389.2A CN202111053389A CN113698831A CN 113698831 A CN113698831 A CN 113698831A CN 202111053389 A CN202111053389 A CN 202111053389A CN 113698831 A CN113698831 A CN 113698831A
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oxygen barrier
high oxygen
barrier coating
percent
crosslinking monomer
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白永平
钟文
李卫东
殷晓芬
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Wuxi Haite New Material Research Institute Co Ltd
Harbin Institute of Technology of Wuxi Research Institute of New Materials
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Wuxi Haite New Material Research Institute Co Ltd
Harbin Institute of Technology of Wuxi Research Institute of New Materials
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    • C09D133/04—Homopolymers or copolymers of esters
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract

本发明公开了一种高氧气阻隔涂料，如下重量百分比的组分制备而成：主单体：15‑60％；交联单体：0.05％‑8％；后交联单体：1‑35％；引发剂：0.1‑1.5％；溶剂：30‑70％；固化剂：0.02‑3％。本发明的有益效果为：交联单体使聚合物在聚合过程中形成部分网状结构，增加分子链段的刚性。后交联单体为含有羟基基团的单体，能够为合成后的聚合物提供交联点，羟基基团与后续添加的固化剂的特征基团反应，在固化过程中形成致密的网状交联结构，极大的限制分子链段的运动并减小链段之间的间隙，从而使得涂层聚合物的分子链段热运动受到限制，自由体积分数减小，最终使得氧气的渗透路径减少或闭塞、氧气的渗透率下降。因此，本发明的涂料形成的涂层达到了对氧气的高阻隔效果。

Description

一种高氧气阻隔涂料
技术领域
本发明涉及涂料制备领域，特别是涉及一种高氧气阻隔涂料。
背景技术
高氧气阻隔的需求是薄膜包装材料领域面临的一项重大挑战。薄膜改性最有效的方式就是涂布改性。目前工业化用于涂布改性的高氧气阻隔涂料主要为PVA和PVDC。二者均为结晶型聚合物，存在有脆性大，难溶解的的特点，且结晶程度高，与基材的附着力差，改性后的薄膜存在诸多使用条件限制。因此，有必要开发了一种非结晶性的高氧气阻隔涂料。
发明内容
了实现上述目标，本发明首先提供了一种高氧气阻隔涂料，其技术方案如下：
一种高氧气阻隔涂料，由如下重量百分比的组分制备而成：
主单体：15-60％；
交联单体：0.05％-8％；
后交联单体：1-35％；
引发剂：0.1-1.5％；
溶剂：30-70％；
固化剂：0.02-3％。
在一些实施例中，所述主单体为甲基丙烯酸甲酯、苯乙烯、丙烯酸异冰片酯种的一种或几种。
在一些实施例中，所述交联单体为马来酸二烯丙酯、二乙烯基苯、四甲基四乙烯基环四硅氧烷、N-环己基马来酰胺。
在一些实施例中，所述后交联单体为丙烯酸羟乙酯，1.4丁烯二醇，2,3丁烯二醇，甲基丙烯酸羟乙酯中的一种或几种。
在一些实施例中，所述的引发剂为过氧化苯酰或偶氮二异丁腈。
在一些实施例中，所述固化剂为L75或L25。
在一些实施例中，所述溶剂为乙酸乙酯、乙酸丙酯、乙酸丁酯、乙二醇、异丙醇、正丁醇、丙酮、丁酮、四氢呋喃、二甲基亚砜、N-甲基吡咯烷酮、2-甲基-4戊酮、环己酮种的一种或几种。
在一些实施例中，所述固化剂在聚合完成后再加入。
本发明还提供了一种如上述任一项所述的高氧气阻隔涂料的使用方法，所述高氧气阻隔涂料在完成涂布后在35-60℃的熟化室熟化12-48h。
本发明的有益效果为：
交联单体使聚合物在聚合过程中形成部分网状结构，增加分子链段的刚性。后交联单体为含有羟基基团的单体，能够为合成后的聚合物提供交联点，羟基基团与后续添加的固化剂的特征基团反应，在固化过程中形成致密的网状交联结构，极大的限制分子链段的运动并减小链段之间的间隙，从而使得涂层聚合物的分子链段热运动受到限制，自由体积分数减小，最终使得氧气的渗透路径减少或闭塞、氧气的渗透率下降。因此，本发明的涂料形成的涂层达到了对氧气的高阻隔效果。
此外，本发明使用的功能单体材料的玻璃化转变温度低，可以防止涂层出现龟裂。
具体实施方式
下面结合具体实例，进一步阐明本说明。本部分的描述仅是示范性和解释性，不应对本发明的保护范围有任何的限制作用。
实施例1
将60g丙烯酸异冰片酯、0.05g N-环己基马来酰胺、1g 1-4顺丁烯二醇、0.1g过氧化苯甲酰、38.8g乙酸丁酯聚合得到丙烯酸酯涂料。
在使用前添加0.05g L75固化剂。
实施例2
将15g苯乙烯、5g二乙烯基苯马来酸二烯丙酯、7.5g 2，3丁烯二醇、1g偶氮二异丁腈及70g正丁醇聚合得到丙烯酸酯涂料。
在使用前添加1.5g L75固化剂。
实施例3
将32.5g甲基丙烯酸甲酯、8g马来酸二烯丙酯、25g丙烯酸羟乙酯、1.5g过氧化苯甲酰及30g二甲基亚砜聚合得到丙烯酸酯涂料。
在使用前添加3g L25固化剂。
性能测试：
对比例1：PET基膜。
对比例2：普通丙烯酸酯涂料
测试方法：将对比例2及本发明三个实施例的涂料分别倒入特定容器后干燥成指定厚度的涂层。然后通过压制法经由设备测试其氧气透过率。氧气透过率单位为e-15cm3·cm/cm2·S·Pa。测试数值越低表明氧气阻隔效率越高。
测试样品 氧气透过率e<sup>-15</sup>cm<sup>3</sup>·cm/cm<sup>2</sup>·S·Pa
实施例一 1.232
实施例二 1.276
实施例三 1.186
对比例一 1.450
对比例二 7.336
从表中结果可见，与PET基膜及普通的丙烯酸酯涂料相比，本发明实施例制备的高阻氧涂料的氧气阻隔效果得到显著提升。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下,还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (9)

1.一种高氧气阻隔涂料，其特征在于，所述高氧气阻隔涂料由如下重量百分比的组分制备而成：
主单体：15-60％；
交联单体：0.05％-8％；
后交联单体：1-35％；
引发剂：0.1-1.5％；
溶剂：30-70％；
固化剂：0.02-3％。
2.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述主单体为甲基丙烯酸甲酯、苯乙烯、丙烯酸异冰片酯种的一种或几种。
3.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述交联单体为马来酸二烯丙酯、二乙烯基苯、四甲基四乙烯基环四硅氧烷、N-环己基马来酰胺。
4.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述后交联单体为丙烯酸羟乙酯，1.4丁烯二醇，2,3丁烯二醇，甲基丙烯酸羟乙酯中的一种或几种。
5.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述的引发剂为过氧化苯酰或偶氮二异丁腈。
6.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述固化剂为L75或L25。
7.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述溶剂为乙酸乙酯、乙酸丙酯、乙酸丁酯、乙二醇、异丙醇、正丁醇、丙酮、丁酮、四氢呋喃、二甲基亚砜、N-甲基吡咯烷酮、2-甲基-4戊酮、环己酮种的一种或几种。
8.如权利要求1所述的高氧气阻隔涂料，其特征在于，所述固化剂在聚合完成后再加入。
9.一种如权利要求1所述的高氧气阻隔涂料的使用方法，其特征在于，所述高氧气阻隔涂料在完成涂布后在35-60℃的熟化室熟化12-48h。
CN202111053389.2A 2021-09-09 2021-09-09 一种高氧气阻隔涂料 Pending CN113698831A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276721A (zh) * 2021-12-21 2022-04-05 无锡海特新材料研究院有限公司 一种高阻氧涂料及制备方法及使用方法

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Publication number Priority date Publication date Assignee Title
CN1749288A (zh) * 2004-09-14 2006-03-22 比克化学股份有限公司 共聚物、其制备、和作为润湿剂与分散剂的用途
CN102060954A (zh) * 2010-11-23 2011-05-18 广州慧谷化学有限公司 一种丙烯酸乳液及其制备方法与应用
CN103059313A (zh) * 2012-12-17 2013-04-24 中山大桥化工集团有限公司 有机硅改性丙烯酸树脂的制备方法
CN105175615A (zh) * 2015-08-28 2015-12-23 广州市恒珑宇化工科技有限公司 一种应用于钢材紧固件表面的水性环保型成膜材料及其制备方法与应用
CN110003753A (zh) * 2019-04-25 2019-07-12 哈尔滨工业大学无锡新材料研究院 一种用于双向拉伸聚酯薄膜的高阻隔涂料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1749288A (zh) * 2004-09-14 2006-03-22 比克化学股份有限公司 共聚物、其制备、和作为润湿剂与分散剂的用途
CN102060954A (zh) * 2010-11-23 2011-05-18 广州慧谷化学有限公司 一种丙烯酸乳液及其制备方法与应用
CN103059313A (zh) * 2012-12-17 2013-04-24 中山大桥化工集团有限公司 有机硅改性丙烯酸树脂的制备方法
CN105175615A (zh) * 2015-08-28 2015-12-23 广州市恒珑宇化工科技有限公司 一种应用于钢材紧固件表面的水性环保型成膜材料及其制备方法与应用
CN110003753A (zh) * 2019-04-25 2019-07-12 哈尔滨工业大学无锡新材料研究院 一种用于双向拉伸聚酯薄膜的高阻隔涂料及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276721A (zh) * 2021-12-21 2022-04-05 无锡海特新材料研究院有限公司 一种高阻氧涂料及制备方法及使用方法

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Application publication date: 20211126