CN107778419B - 一种poss改性自阻燃型丙烯酸乳液及其制备方法 - Google Patents

一种poss改性自阻燃型丙烯酸乳液及其制备方法 Download PDF

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CN107778419B
CN107778419B CN201711065451.3A CN201711065451A CN107778419B CN 107778419 B CN107778419 B CN 107778419B CN 201711065451 A CN201711065451 A CN 201711065451A CN 107778419 B CN107778419 B CN 107778419B
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谢义鹏
许钧强
康伦国
姚东生
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CANGZHOU JICHUN NEW MATERIAL Co.,Ltd.
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Abstract

本发明涉及一种POSS改性自阻燃型丙烯酸乳液,其成分有软硬丙烯酸单体、硼酸衍生物交联单体、六丙烯酸酯基POSS、乳化剂、多胺或联吡啶配体、铜化合物催化剂、卤代化合物引发剂和去离子水;本发明还提供一种POSS改性自阻燃型丙烯酸乳液的制备方法,所述的制备方法为乳液型ATRP聚合法,具有工艺简便、聚合体系稳定、分子量分布窄、均匀的特点;本发明制得的一种POSS改性自阻燃型丙烯酸乳液,具有优良的耐水解和贮存稳定性,制成的涂膜具有优异的耐磨性、耐老化性、自洁性、柔韧性、耐腐蚀性和自阻燃性。

Description

一种POSS改性自阻燃型丙烯酸乳液及其制备方法
技术领域
本发明涉及一种改性丙烯酸乳液,尤其涉及到一种POSS改性自阻燃型丙烯酸乳液及其制备方法,属于水性树脂合成技术领域。
技术背景
国内外相继制定了严厉的环保法规来限制挥发性有机化合物(VOC)向大气排放,水性化、高性能、环保化已成为涂料发展的方向;丙烯酸乳液是各种丙烯酸类单体的共聚物的通称,广泛用于各行各业中,其在木器漆行业中尤为重要;木器漆不仅具有装饰美化作用,而且对木材具有保护作用,可以延长木材使用寿命,但是在我国市场上销售的木器漆多数还是溶剂性型的,这些木器漆涂料中含有大量有毒的有机挥发物,严重危害生产和施工人员的身体健康,及污染大气。随着人们环保意识的日益增强,溶剂型涂料的使用范围已日益受到限制,而水性木器漆因其具有无环境污染、毒性小及无火灾隐患等优点越来越受到人们的关注和重视。近年来,低污染高性能的环保型水性木器漆已越来越受到人们的重视。
目前市场常见的水性木器漆有水性醇酸树脂、水性聚氨酯、水性丙烯酸乳液,满足不了防火涂料的阻燃性能。
中国专利CN105968255A公开了一种自阻燃型丙烯酸乳液,其特征在于:所述的自阻燃型改性苯丙乳液,是利用反应型含卤阻燃型乙烯基单体,可与丙烯酸酯类单体发生乳液共聚合反应,通过化学键方式把阻燃基团固定在树脂分子结构上,不会解析脱落,合成后的丙烯酸乳液具有自阻燃性能,制备涂料时不需要另外添加其它阻燃剂就可起到持久阻燃性能;该发明制得的自阻燃型丙烯酸乳液具有良好的附着力、耐水性,耐久性,制成的涂膜具有耐水性、耐碱性、耐擦洗性和持久自阻燃性能,广泛用于室内外木器、钢结构、建筑的阻燃涂料,既起到装饰作用,又起到保护作用。但是所述丙烯酸乳液的合成方法存在效率差、乳液稳定性低的缺点。
发明内容
本发明旨在提供一种POSS改性自阻燃型丙烯酸乳液及其制备方法。
POSS又称笼型聚倍半硅氧烷,是由Si-O交替连接的硅氧骨架组成的无机内核,其形状如同一个“笼子”,属于纳米化合物。POSS基团的多样性、高活性以及较好的聚合物相容性使之既可以通过物理共混又可以通过化学共聚的方法将其引入到聚合物材料中。
POSS改性聚合物能显著改善聚合物材料的表面光滑性、耐磨性、透明性和柔韧性;利用POSS的八臂结构和具有反应活性的官能团以及高度对称性,来制备星形树枝状聚合物,降低树脂的粘度,提高固含量。
本发明所述的POSS改性高硬度耐水性醇酸树脂,是在水性醇酸树脂分子结构上引入硼酸衍生物交联单体和六丙烯酸酯基POSS,使得丙烯酸分子骨架中含有硼氧键、硅氧键,具有星形树枝状结构,有效提高丙烯酸乳液的耐水性、自洁性、耐磨性、耐腐蚀性和阻燃性。
为克服现有技术的缺点和不足,本发明采取以下技术方案,所述的一种POSS改性自阻燃型丙烯酸乳液,按质量份数计,其成分为:30.0~45.0份软单体、5.0~10.0份硬单体、3.0~5.0份硼酸衍生物交联单体、4.0~8.0份六丙烯酸酯基POSS、0.5~2.0份乳化剂、0.6~1.2份配体、1.3~2.5份催化剂、0.7~1.5份引发剂、50.0~55.0份去离子水。
其中,所述的硼酸衍生物交联单体为对乙烯基苯基硼酸、对乙烯基苄基硼酸、烯丙基硼酸、二对乙烯基苯基硼酸、二对乙烯基苄基硼酸、二烯丙基硼酸中的至少一种。
所述的六丙烯酸酯基POSS,其分子结构式如下:
所述的软单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸异辛酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸异辛酯中的至少一种。
所述的硬单体为苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯中的至少一种。
所述的乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、油酸钾、油酸钠或琥珀酸酯磺酸钠、甘油硬脂酸酯、甘油油酸酯、月桂醇聚氧乙烯醚、月桂酸聚氧乙烯酯、双十二烷基苯基醚二磺酸钠、月桂酸钠、OP-10、苯乙基酚聚氧乙烯醚、吐温中的至少一种。
所述的配体为N,N,N’,N’-四甲基乙二胺、N,N,N’,N’,N”-五甲基丙烯酸甲酯基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸正丁酯基三乙烯基四胺、2,2’-联吡啶、N,N,N’,N’,N”-五甲基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸甲酯基三乙烯基四胺中的至少一种。
所述的催化剂为溴化亚铜、氯化亚铜、溴化亚铜、溴化铜中的至少一种。
所述的引发剂为4-[2-(2-溴-2-甲基丙酰氧基)乙氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)癸氧基]-4-氧代-2-磺酸基丁酸二钠、4-[6-(2-溴-2-甲基丙酰氧基)己氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)辛氧基]-4-氧代-2-磺酸基丁酸二钠、2-氯丙酰胺、2-溴丙酰胺、2-碘代丙烯酸甲酯、2-氯代丙腈、2-溴丙烯酸乙酯、2-溴丙烯酸甲酯、二溴丙烯酸乙酯、1-溴代乙腈、2-甲基-2-溴代丙烯酸乙酯、2-溴代异丁酸乙酯、2-溴丙烯酸乙酯、N,N-二乙基-2-溴代丙烯酰胺中的至少一种。
所述的一种POSS改性自阻燃型丙烯酸乳液,其制备方法如下:按配方量计,依次向反应釜中加入催化剂、软单体、硬单体、硼酸衍生物交联单体、六丙烯酸酯基POSS、乳化剂、配体和去离子水,在N2保护下,在转速800~1000rpm转速下搅拌0.5~1h至乳化均匀,然后加热到70~100℃,控制搅拌速度200~300rpm,逐滴滴加10%的引发剂水溶液,保持恒温反应8~12h,得所述的POSS改性自阻燃型丙烯酸乳液。
本发明的制备方法为一种乳液型ATRP聚合法,具有工艺简便、聚合体系稳定、分子量分布窄、均匀的特点。
本发明制得的一种POSS改性自阻燃型丙烯酸乳液,具有优良的耐水解和贮存稳定性,制成的涂膜具有优异的耐磨性、耐老化性、自洁性、柔韧性、耐腐蚀性和自阻燃性。
具体实施方式
下面结合实施例对本发明的一种POSS改性自阻燃型丙烯酸乳液及其制备方法做进一步的描述。可以理解的是,此处所描述的具体实施例仅仅用于解释相关发明,而非对该发明的限定。
实施例1
一种POSS改性自阻燃型丙烯酸乳液,采取乳液型ATRP聚合法制备,其步骤如下:按配方量计,依次向反应釜中加入10.0份丙烯酸正丙酯、20.0份甲基丙烯酸叔丁酯、10.0份甲基丙烯酸甲酯、3.0份硼对乙烯基苄基硼酸、8.0份六丙烯酸酯基POSS、0.3份月桂醇聚氧乙烯醚、0.2份月桂酸钠、1.2份N,N,N’,N’,N”,N”-六甲基丙烯酸正丁酯基三乙烯基四胺、1.3份溴化亚铜和36.5份去离子水,在N2保护下,在转速800~1000rpm转速下搅拌45min至乳化均匀,然后加热到85~90℃,控制搅拌速度200~300rpm,逐滴滴加10%的4-[10-(2-溴-2-甲基丙酰氧基)癸氧基]-4-氧代-2-磺酸基丁酸二钠水溶液15.0份,保持恒温反应8h,得所述的POSS改性自阻燃型丙烯酸乳液。
实施例2
一种POSS改性自阻燃型丙烯酸乳液,采取乳液型ATRP聚合法制备,其步骤如下:按配方量计,依次向反应釜中加入2.0份丙烯酸乙酯、25.0份丙烯酸异辛酯、5.0份苯乙烯、5.0份二对乙烯基苄基硼酸、4.0份六丙烯酸酯基POSS、1.0份月桂酸聚氧乙烯酯、1.0份双十二烷基苯基醚二磺酸钠、0.6份N,N,N’,N’,N”-五甲基二乙烯基三胺、2.5份溴化铜和去离子水48.7份,在N2保护下,在转速800~1000rpm转速下搅拌40min至乳化均匀,然后加热到70~75℃,控制搅拌速度200~300rpm,逐滴滴加10%的4-[10-(2-溴-2-甲基丙酰氧基)辛氧基]-4-氧代-2-磺酸基丁酸二钠水溶液7.0份,保持恒温反应10h,得所述的POSS改性自阻燃型丙烯酸乳液。
实施例3
一种POSS改性自阻燃型丙烯酸乳液,采取乳液型ATRP聚合法制备,其步骤如下:按配方量计,依次向反应釜中加入42.0份丙烯酸正丙酯、7.0份甲基丙烯酸乙酯、4.0份二烯丙基硼酸、5.0份六丙烯酸酯基POSS、0.8份琥珀酸酯磺酸钠、1.0份N,N,N’,N’-四甲基乙二胺、2.0份溴化亚铜和去离子水43.9份,在N2保护下,在转速800~1000rpm转速下搅拌45min至乳化均匀,然后加热到80~85℃,控制搅拌速度200~300rpm,逐滴滴加10%的4-[10-(2-溴-2-甲基丙酰氧基)癸氧基]-4-氧代-2-磺酸基丁酸二钠水溶液9.0份,保持恒温反应11h,得所述的POSS改性自阻燃型丙烯酸乳液。
将本发明的实施例配制成水性防火涂料与市面上的自阻燃型丙烯酸防火涂料(对比例)进行性能对比测试,按照相关标准进行检测,其测试数据如表1所示:
表1水性防火涂料性能技术指标
尽管本发明已作了详细说明并引用了实施例,但对于本领域的普通技术人员,显然可以按照上述说明而做出的各种方案、修改和改动,都应该包括在权利要求的范围之内。

Claims (5)

1.一种POSS改性自阻燃型丙烯酸乳液,其特征在于:所述的POSS改性自阻燃型丙烯酸乳液,按质量份数计,其成分为:30.0~45.0份软单体、5.0~10.0份硬单体、3.0~5.0份硼酸衍生物交联单体、4.0~8.0份六丙烯酸酯基POSS、0.5~2.0份乳化剂、0.6~1.2份配体、1.3~2.5份催化剂、0.7~1.5份引发剂、50.0~55.0份去离子水;
其中,所述的硼酸衍生物交联单体为对乙烯基苯基硼酸、对乙烯基苄基硼酸、烯丙基硼酸、二对乙烯基苯基硼酸、二对乙烯基苄基硼酸、二烯丙基硼酸中的至少一种;
所述的六丙烯酸酯基POSS,其分子结构式如下所示:
所述的配体为N,N,N’,N’-四甲基乙二胺、N,N,N’,N’,N”-五甲基丙烯酸甲酯基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸正丁酯基三乙烯基四胺、2,2’-联吡啶、N,N,N’,N’,N”-五甲基二乙烯基三胺、N,N,N’,N’,N”,N”-六甲基丙烯酸甲酯基三乙烯基四胺中的至少一种;
所述的催化剂为溴化亚铜、氯化亚铜、溴化亚铜、溴化铜中的至少一种;
所述的引发剂为4-[2-(2-溴-2-甲基丙酰氧基)乙氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)癸氧基]-4-氧代-2-磺酸基丁酸二钠、4-[6-(2-溴-2-甲基丙酰氧基)己氧基]-4-氧代-2-磺酸基丁酸二钠、4-[10-(2-溴-2-甲基丙酰氧基)辛氧基]-4-氧代-2-磺酸基丁酸二钠、2-氯丙酰胺、2-溴丙酰胺、2-碘代丙烯酸甲酯、2-氯代丙腈、2-溴丙烯酸乙酯、2-溴丙烯酸甲酯、二溴丙烯酸乙酯、1-溴代乙腈、2-甲基-2-溴代丙烯酸乙酯、2-溴代异丁酸乙酯、2-溴丙烯酸乙酯、N,N-二乙基-2-溴代丙烯酰胺中的至少一种。
2.根据权利要求1所述的POSS改性自阻燃型丙烯酸乳液,其特征在于:所述的软单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸异辛酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸异辛酯中的至少一种。
3.根据权利要求1所述的POSS改性自阻燃型丙烯酸乳液,其特征在于:所述的硬单体为苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯中的至少一种。
4.根据权利要求1所述的POSS改性自阻燃型丙烯酸乳液,其特征在于:所述的乳化剂为十二烷基硫酸钠、十二烷基苯磺酸钠、油酸钾、油酸钠或琥珀酸酯磺酸钠、甘油硬脂酸酯、甘油油酸酯、月桂醇聚氧乙烯醚、月桂酸聚氧乙烯酯、双十二烷基苯基醚二磺酸钠、月桂酸钠、OP-10、苯乙基酚聚氧乙烯醚、吐温中的至少一种。
5.一种根据权利要求1所述的POSS改性自阻燃型丙烯酸乳液的制备方法,其特征在于:所述的制备方法为乳液型ATRP聚合法,其步骤如下:按配方量计,依次向反应釜中加入催化剂、软单体、硬单体、硼酸衍生物交联单体、六丙烯酸酯基POSS、乳化剂、配体和去离子水,在N2保护下,在转速800~1000rpm转速下搅拌0.5~1h至乳化均匀,然后加热到70~100℃,控制搅拌速度200~300rpm,逐滴滴加10%的引发剂水溶液,保持恒温反应8~12h,得所述的POSS改性自阻燃型丙烯酸乳液。
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