CN113930118A - 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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CN113930118A
CN113930118A CN202111368675.8A CN202111368675A CN113930118A CN 113930118 A CN113930118 A CN 113930118A CN 202111368675 A CN202111368675 A CN 202111368675A CN 113930118 A CN113930118 A CN 113930118A
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oxygen barrier
monomer
barrier coating
curing agent
crosslinking
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白永平
钟文
李卫东
殷晓芬
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Wuxi Longchi Fluorine Silicon New Material Co ltd
Wuxi Haite New Material Research Institute Co Ltd
Harbin Institute of Technology of Wuxi Research Institute of New Materials
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Wuxi Longchi Fluorine Silicon New Material Co ltd
Wuxi Haite New Material Research Institute Co Ltd
Harbin Institute of Technology of Wuxi Research Institute of New Materials
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Abstract

本发明提供了一种高氧气阻隔涂料，其特征在于，由主单体，交联单体1，交联单体2，引发剂，溶剂聚合而成。本发明提供的高氧气阻隔涂料，交联单体使聚合物在聚合过程中形成部分网状结构，增加了分子链段的刚性，交联单体1为含有羟基基团的单体，羟基基团与固化剂1在固化过程中形成致密的网状交联结构，交联单体2为含有羧酸基团的单体，羧酸基团与固化剂2在固化过程中形成致密的网状交联结构，两种网状结构的叠加能更好地限制分子链段的运动并减小链段之间的间隙，致使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，氧气的渗透路径减少或闭塞，氧气的渗透率下降，从而对氧气的具有较好的阻隔效果。

Description

一种高氧气阻隔涂料
技术领域
本发明涉及涂料技术领域，尤其涉及一种高氧气阻隔涂料。
背景技术
丙烯酸酯聚合物涂料是对改性PET使用最广的涂料之一，但是由于其为无定型聚合物，不能形成结晶，故在高氧气阻隔性上的使用一直处于相对空白的状态。有鉴于此，有必要开发一种交联型丙烯酸酯聚合物，使的非结晶的丙烯酸酯聚合物涂料也具有高氧气阻隔性，来提升PET膜的氧气阻隔性。
发明内容
本发明的目的在于公开一种高氧气阻隔涂料，交联单体使聚合物在聚合过程中形成部分网状结构，增加了分子链段的刚性，交联单体1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，羟基基团与固化剂1在固化过程中形成致密的网状交联结构，交联单体2为含有羧酸基团的单体，羧酸基团与固化剂2在固化过程中形成致密的网状交联结构，两种网状结构的叠加能更好地限制分子链段的运动并减小链段之间的间隙，致使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，氧气的渗透路径减少或闭塞，氧气的渗透率下降，从而对氧气的具有较好的阻隔效果，提升PET膜的氧气阻隔性。
为实现上述目的，本发明提供了一种高氧气阻隔涂料，由主单体，交联单体1，交联单体2，引发剂，溶剂聚合而成。
在一些实施方式中，由主单体，交联单体1，交联单体2，引发剂，溶剂聚合后再与固化剂1和固化剂2交联而成；各组分的重量份数为：主单体：10-65份，交联单体1：1-25份，交联单体2：1-25份，引发剂：0.1-2份，溶剂：30-70份，固化剂1：0.01-3份，固化剂2:0.01-3份。
在一些实施方式中，所述主单体为甲基丙烯酸甲酯、苯乙烯、醋酸乙烯酯中的一种或多种。
在一些实施方式中，所述交联单体1为丙烯酸、甲基丙烯酸中的一种或两种。
在一些实施方式中，所述交联单体2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多种。
在一些实施方式中，所述引发剂为过氧化苯酰或偶氮二异丁腈。
在一些实施方式中，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、环己酮中的一种或多种。
在一些实施方式中，所述固化剂1为固化剂L75或固化剂L25中的一种或两种。
在一些实施方式中，所述固化剂2为Ga240或氮丙啶中的一种或两种。
与现有技术相比，本发明的有益效果是：本发明提供的高氧气阻隔涂料，交联单体使聚合物在聚合过程中形成部分网状结构，增加了分子链段的刚性，交联单体1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，羟基基团与固化剂1在固化过程中形成致密的网状交联结构，交联单体2为含有羧酸基团的单体，羧酸基团与固化剂2在固化过程中形成致密的网状交联结构，两种网状结构的叠加能更好地限制分子链段的运动并减小链段之间的间隙，致使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，氧气的渗透路径减少或闭塞，氧气的渗透率下降，从而对氧气的具有较好的阻隔效果，提升了PET膜的氧气阻隔性。
具体实施方式
下面结合各实施方式对本发明进行详细说明，但应当说明的是，这些实施方式并非对本发明的限制，本领域普通技术人员根据这些实施方式所作的功能、方法、或者结构上的等效变换或替代，均属于本发明的保护范围之内。
实施例一：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将65g甲基丙烯酸甲酯，2g甲基丙烯酸，2g甲基丙烯酸羟乙酯，2g过氧化苯甲酰，30g乙酸乙酯聚合得到聚合物，在使用前添加0.01g固化剂L75和0.01g氮丙啶，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
实施例二：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将10g苯乙烯，13g丙烯酸，4g 1,4丁烯二醇，1g偶氮二异丁腈，70g丙酮聚合得到聚合物，在使用前添加1g固化剂L25和2g Ga240，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
实施例三：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将12g甲基丙烯酸甲酯，25g丙烯酸，25g丙烯酸羟乙酯，1.5g过氧化苯酰，30.5g四氢呋喃聚合得到聚合物，在使用前添加3g固化剂L75和3g Ga240，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
实施例四：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将25g醋酸乙烯酯，25g丙烯酸，5g丙烯酸羟乙酯，0.5g偶氮二异丁腈，41.5g丁酮酮聚合得到聚合物，在使用前添加0.5g固化剂L25和2.5g Ga240，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
实施例五：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将35g苯乙烯，5g丙烯酸，25g甲基丙烯酸羟乙酯，1g过氧化苯甲酰，36g四氢呋喃聚合得到聚合物，在使用前添加2.5g固化剂L25和0.5g Ga240，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
实施例六：
本实施例公开了一种高氧气阻隔涂料，由下列组分及方法获得：将40g苯乙烯，5g丙烯酸，5g 2,3丁烯二醇，0.2g偶氮二异丁腈，49g乙酸正丁酯聚合得到聚合物，在使用前添加0.3g固化剂L25和0.5g Ga240，得到丙烯酸酯涂料。将丙烯酸酯涂料涂布在PET基膜上，再在35-60℃的熟化室熟化12-48h。
对比例一：PET基膜。
对比例二：将普通丙烯酸酯涂料涂布在PET基膜上。
测试方法：将实施例一～六获得的涂料涂布在PET基膜上干燥固化后，采用压制法经由设备测试其氧气透过率。氧气透过率单位为cm3/m2·24h·0.1MPa，测试数值越低表明氧气阻隔能力越强。测试结果如下表：
Figure BDA0003361519270000041
Figure BDA0003361519270000051
观察可知，实施例一～六获得的丙烯酸酯涂料氧气阻隔效率更高，分析原因为：交联单体使聚合物在聚合过程中形成部分网状结构，增加了分子链段的刚性，交联单体1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，羟基基团与固化剂1在固化过程中形成致密的网状交联结构，交联单体2为含有羧酸基团的单体，羧酸基团与固化剂2在固化过程中形成致密的网状交联结构，两种网状结构的叠加能更好地限制分子链段的运动并减小链段之间的间隙，致使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，氧气的渗透路径减少或闭塞，氧气的渗透率下降，从而对氧气的具有较好的阻隔效果，提升了PET膜的氧气阻隔性。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (9)

1.一种高氧气阻隔涂料，其特征在于，由主单体，交联单体1，交联单体2，引发剂，溶剂聚合而成。
2.根据权利要求1所述的高氧气阻隔涂料，其特征在于，由主单体，交联单体1，交联单体2，引发剂，溶剂聚合后再与固化剂1和固化剂2交联而成；各组分的重量份数为：主单体：10-65份，交联单体1：1-25份，交联单体2：1-25份，引发剂：0.1-2份，溶剂：30-70份，固化剂1：0.01-3份，固化剂2:0.01-3份。
3.根据权利要求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、醋酸乙烯酯中的一种或多种。
4.根据权利要求1所述的高氧气阻隔涂料，其特征在于，所述交联单体1为丙烯酸、甲基丙烯酸中的一种或两种。
5.根据权利要求1所述的高氧气阻隔涂料，其特征在于，所述交联单体2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多种。
6.根据权利要求1所述的高氧气阻隔涂料，其特征在于，所述引发剂为过氧化苯酰或偶氮二异丁腈。
7.根据权利要求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、环己酮中的一种或多种。
8.根据权利要求2所述的高氧气阻隔涂料，其特征在于，所述固化剂1为固化剂L75或固化剂L25中的一种或两种。
9.根据权利要求2所述的高氧气阻隔涂料，其特征在于，所述固化剂2为Ga240或氮丙啶中的一种或两种。
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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
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
CN113604116A (zh) * 2021-09-09 2021-11-05 哈尔滨工业大学无锡新材料研究院 一种高氧气阻隔涂料及其制备方法及其涂布方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN113604116A (zh) * 2021-09-09 2021-11-05 哈尔滨工业大学无锡新材料研究院 一种高氧气阻隔涂料及其制备方法及其涂布方法

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