CN105859985B - 一种可快速固化的柔性聚甲基丙烯酸甲酯材料及其制备方法和应用 - Google Patents
一种可快速固化的柔性聚甲基丙烯酸甲酯材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种可快速固化的柔性聚甲基丙烯酸甲酯材料及其制备方法,是两组分反应型,包括组分A树脂体系和组分B固化体系,其比例为A:B=100:1~8。本发明所述可快速固化的柔性聚甲基丙烯酸甲酯材料在保证快速固化的同时,实现材料的柔韧性、强度、耐磨性等综合性能的提升,另一方面,避免传统配方里面采用柔性单体增韧,气味难闻,增韧效果有限的弊端。本发明得到的产品体系可以应用在混凝土防腐、地坪、铺装等相关领域。
Description
技术领域
本发明属于建筑材料领域,具体涉及一种可快速固化的柔性聚甲基丙烯酸甲酯(MMA)材料。
背景技术
环氧地坪、聚氨酯地坪和聚甲基丙烯酸甲酯(PMMA)地坪是目前通用的地坪材料,得到广泛的应用。然而,环氧地坪涂料一般要求零度以上或是五度以上才能正常固化,限制其在北方寒冷地区的应用,且固化时间比较长,一般2天以后才能完全固化,另一方面,环氧材料耐候性差,光照环境下易粉化,不能在户外使用;聚氨酯地坪铺装材料湿基面固化、耐磨性、力学性能等具有一定的限制,在停车场、车间等环境很难应用。
而以甲基丙烯酸甲酯单体或树脂为主体,丙烯酸、甲基丙烯酸羟乙酯等树脂为交联剂,并加入颜填料、高熔点蜡及其它助剂制备而成的新型地坪材料,具有潮湿基面可固化、低温固化、反应迅速(1h内可投入使用),耐磨性优异,耐紫外性能好的特点,广泛应用于食品、药品、饮料、电子电器、纺织、服装等轻工车间,厨房、冷藏库、停车场、仓库、开放式走廊、场馆、体育馆等室内空间,室外广场、码头等外露环境,尤其适用于工期紧迫,急于使用的场所。
专利CN104046070A一种可快速固化的MMA地坪涂料,提供一种固化时间短、性能优良、绿色环保的MMA地坪涂料,首先合成丙烯酸类MMA预聚体,然后与丙烯酸类单体、交联剂、粉填料、助剂等组合形成快速固化的MMA产品,但是得到的地坪材料的柔韧性不足;
专利CN104449173A一种热塑性弹性体改性的聚甲基丙烯酸甲酯彩色防滑涂料,提供一种三组分反应型高弹性、快固化、喷涂施工的彩色防滑路桥涂料,主要是采用热塑性弹性体B组分中的废旧轮胎橡胶颗粒和交联单体改性固化而成,但其含有的增粘树脂主要为古马隆等石油树脂材料,环保性不足,且使用的TPU材料存在易黄变、耐候性不足的问题。
PMMA树脂材料常规采用的增韧单体味道难闻,且增韧效果有限,附着力不足,导致该体系的应用受到限制,更清洁高效的增韧改性方案建立具有高的应用价值。
发明内容
本发明为解决现有PMMA树脂材料的增韧材料对环境不友好,增韧效果不好以及耐候性不足等问题,本发明提供一种高柔性、快固化、高耐候、高耐磨,气味友好的的可快速固化的柔性聚甲基丙烯酸甲酯材料及其制备方法。
本发明创新性的采用弹性体改性剂,丙烯酸树脂和多官能交联剂共同作用,在保证快速固化的同时,实现材料的柔韧性、强度、耐磨性等综合性能的提升,另一方面,避免传统配方里面采用柔性单体增韧,气味难闻,增韧效果有限的弊端。本发明得到的产品体系可以应用在混凝土防腐、地坪、铺装等相关领域。
本发明所述可快速固化的柔性聚甲基丙烯酸甲酯材料,是两组分反应型,包括组分A树脂体系和组分B固化体系,其比例为A:B=100:1~8。
组分A树脂体系的组成为,以重量份数计:
组分B固化体系为过氧化苯甲酰(BPO),
为了提高PMMA树脂材料的柔韧性,本发明使用的丙烯酸树脂为市售的改性PMMA树脂,如BMA/MMA、EA/MMA等共聚物,IBMA均聚物等,如相应的帝斯曼(DSM)的NeoCrylTMB-891,NeoCrylTMB-722,NeoCrylTMB-731等;
为提高PMMA树脂材料的柔韧性,本发明使用的弹性改性剂为聚氨酯预聚体,甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)等市售的弹性体。
所述聚氨酯预聚体为帝斯曼NeorezTMU-371。
为提高PMMA树脂材料的力学性能、耐磨性,本发明使用的交联单体为1,6-己二醇二丙烯酸酯,二缩三丙二醇二丙烯酸酯,乙氧化双酚A二丙烯酸酯,丙氧化新戊二醇二丙烯酸酯,乙二醇二甲基丙烯酸酯,三羟甲基丙烷三丙烯酸酯,乙氧化三羟甲基丙烷玩丙烯酸酯,丙氧化三羟甲基丙烷三丙烯酸酯,聚乙二醇400二丙烯酸酯的一种或多种;
所述交联单体选自帝斯曼下列代码的产品:SR238,SR306,SR349,SR9003,SR206,SR351,SR454,SR492,SR344。
为提高PMMA树脂材料的环保性,本发明使用的环保性增塑剂为环己烷-1,2-二甲酸二异壬酯(DINCH)、邻苯二甲酸二辛脂(DOP)等本行业通用的环保型增塑剂的任意比例混合。
为提高PMMA树脂材料的力学性能,提高体系颜料的稳定性,本发明使用的填料为触变性无机增强填料,气相二氧化硅、轻质碳酸钙等中的一种或几种任意比例混合。
为适应不同的应用环境需要,本发明使用的颜料为本行业熟知的颜料,如钛白粉、铬绿等行业通用的耐候性各色颜料或色浆。
为提高PMMA树脂材料的力学性能,本发明使用的交联促进剂为异辛酸钴和正丁醛苯胺缩合物。
所述交联促进剂为市售产品促进剂808。
为提高PMMA树脂材料的温度适应性,满足在-15℃以上都可以顺利固化,本发明使用的催化剂为胺类催化剂如对甲苯胺、三乙胺等本行业公知的材料;
为提高PMMA树脂材料的耐磨性能、耐候性,本发明使用的助剂为本行业熟知的石蜡油、抗紫外剂和改性聚硅氧烷消泡剂中的任意一种。
为提高体系的储存稳定性,本发明使用的阻聚剂为本行业熟知的对苯二酚。
本发明所述可快速固化的柔性聚甲基丙烯酸甲酯材料的制备方法,包括以下步骤:
步骤一:A组分制备:
搅拌下将丙烯酸树脂陆续加入到MMA单体、交联单体和环保增塑剂的混合体系里,搅拌并完全溶解;
将弹性改性剂加入①步骤得到的混合溶液里面,并保持体系温度20-60℃以加快溶解速度;
降至室温,将助剂、促进剂、颜料、填料加入步骤②得到的混合溶液里,高速剪切分散20-60min;
加入阻聚剂,搅拌分散均匀得到A组分。
步骤二:将B组分直接包装得到B组分
本发明所述的可快速固化的柔性聚甲基丙烯酸甲酯材料的应用方法:施工时根据环境温度按照A:B=100:1-8混合搅拌,直至B完全溶解,采用滚涂、刮涂施工皆可;固化1-5h后即可投入使用。
有益效果:
本发明得到的树脂体系,固化速度快,潮湿基面可固化;常温实干时间<50min,1-5h可投入使用;
本发明得到的树脂体系,固化后韧性得到显著提升,弥补了甲基丙烯酸树脂的脆性过大的缺陷,且增韧组分对环境友好。
本发明合成工艺简单,施工方便。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
可快速固化的柔性聚甲基丙烯酸甲酯材料的性能测试按照JC/T2251-2014《聚甲基丙烯酸甲酯防水涂料》中相关规定执行;
柔韧性按照JC/T2217-2014《环氧树脂防水涂料》中相关规定执行;
耐磨性采用旋转磨耗仪,750g,500r测试磨损质量;
耐候性采用紫外老化箱,老化辐照时间1500h,表观无粉化、脱落、开裂、黄变。
试样成型与养护温度为23±2℃,相对湿度50±5%。
各实施例可快速固化的柔性聚甲基丙烯酸甲酯材料的制备,包括以下步骤:
(1)A组分制备过程如下:
①搅拌下将丙烯酸树脂陆续加入到MMA单体、交联单体和环保增塑剂的混合体系里,搅拌并完全溶解;
②将弹性改性剂加入①步骤得到的混合溶液里面,并保持体系温度20-60℃以加快溶解速度;
③降至室温,将助剂、促进剂、颜料、填料加入步骤②得到的混合溶液里,高速剪切分散20-60min;
④加入阻聚剂,搅拌分散均匀得到A组分
(2)将B组分直接包装得到B组分
(3)使用时,搅拌下将B组分1-8份,加入到100份A组分里面,B组分完全溶解后,采用滚涂或刮涂的方式施工,固化1-5h。
各实施例和对比例的配方比例与性能数据如表1和表2所示,25℃标准成型环境:
对比例1~3给出了在没有弹性改性剂、触变增强填料,少量丙烯酸树脂的条件下PMMA树脂材料的配方。与实施例1~3对比发现,可快速固化的柔性聚甲基丙烯酸甲酯材料在柔韧性、固化时间、耐磨性等方面具有显著优势。
整个体系仍然是采用自由基固化成型,采用固化剂配比调控体系固化反应速度,保证低温固化性能,保持了自由基固化的快速、高效。
弹性改性剂的加入,在相对刚性的PMMA体系中引入柔性链段,大幅提升PMMA树脂材料的柔韧性,避免出现PMMA树脂材料易脆性断裂的固有缺陷;增强填料和高韧性丙烯酸树脂引入,进一步提升柔韧性的同时,保证足够的强度,且填料作为内润滑材料可以防止基体树脂被划伤或微观的撕裂破坏,从而提升耐磨性能和抗划伤性能。
另外,丙烯酸树脂和弹性改性材料的引入,在固化过程中出现相变,吸收反应放热,另外单位体积内可固化放热的单体数量减少,单位体积放热量减少,温升降低,自由基聚合自加速现象减缓,从而,避免出现爆聚的现象,显著提高最终成型涂层的综合性能。
选用的触变增强填料具有增加最终涂层强度和耐磨抗划伤性能外,还能够调控体系稠度,保证施工性能和颜料在体系内的储存稳定性。
表1 待续实施例、对比例原材料配方表,
续表1 实施例、对比例原材料配方表
备注:颜料、增塑剂、抗滑石蜡油、抗紫外剂、消泡剂和阻聚剂为本行业公知的原材料,相对实施例中MMA为100份固定用量,颜料钛白粉、增塑剂DINCH、抗滑石蜡油15#白油、抗紫外剂UV329、有机硅消泡剂201、阻聚剂对苯二酚分别为6份、3份、3份、1份、1份、0.03份;B组分添加量根据施工温度为A组分的1-8%,以上实施例是在标准温度下成型测试,所以用量为A组分的3%;但本发明相关材料的用量不仅仅限于此用量。
表2 实施例测试结果
Claims (8)
1.一种可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述可快速固化的柔性聚甲基丙烯酸甲酯材料是两组分反应型,所述两组分包括组分A树脂体系和组分B固化体系,其比例为A:B=100:1~8;
组分A树脂体系的组成为,以重量份数计:
组分B固化体系为过氧化苯甲酰(BPO),
所述丙烯酸树脂为市售的改性PMMA树脂;
所述弹性改性剂为聚氨酯预聚体、 甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)或丙烯腈-丁二烯-苯乙烯共聚物(ABS)。
所述交联单体为1,6-己二醇二丙烯酸酯,二缩三丙二醇二丙烯酸酯,乙氧化双酚A二丙烯酸酯,丙氧化新戊二醇二丙烯酸酯,乙二醇二甲基丙烯酸酯,三羟甲基丙烷三丙烯酸酯,丙氧化三羟甲基丙烷三丙烯酸酯,聚乙二醇400二丙烯酸酯的一种或多种;
所述环保型增塑剂为环己烷-1,2-二甲酸二异壬酯(DINCH)、邻苯二甲酸二辛脂(DOP)以任意比例混合;
所述填料为触变性无机增强填料,选自气相二氧化硅、轻质碳酸钙以任意比例混合;
所述促进剂为异辛酸钴和正丁醛苯胺缩合物;
所述催化剂为胺类催化剂,选自对甲苯胺、三乙胺;
所述助剂为石蜡油、抗紫外剂和改性聚硅氧烷消泡剂中的任意一种;
所述阻聚剂为对苯二酚。
2.根据权利要求1所述的可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述丙烯酸树脂选自BMA/MMA、EA/MMA共聚物,IBMA均聚物中的任意一种。
3.根据权利要求2所述的可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述丙烯酸树脂选自相应的帝斯曼(DSM)的NeoCrylTMB-891,NeoCrylTMB-722,NeoCrylTMB-731。
4.根据权利要求1所述的可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述聚氨酯预聚体为帝斯曼NeorezTMU-371。
5.根据权利要求1所述的可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述交联单体选自帝斯曼下列代码的产品:SR238,SR306,SR349,SR9003,SR206,SR351,SR454,SR492,SR344。
6.根据权利要求1所述的可快速固化的柔性聚甲基丙烯酸甲酯材料,其特征在于,所述交联促进剂为市售产品促进剂808。
7.权利要求1-6的任一项所述的可快速固化的柔性聚甲基丙烯酸甲酯材料的制备方法,其特征在于,包括以下步骤:
步骤一:A组分制备:
搅拌下将丙烯酸树脂陆续加入到MMA单体、交联单体和环保增塑剂的混合体系里,搅拌并完全溶解;
将弹性改性剂加入①步骤得到的混合溶液里面,并保持体系温度20-60℃以加快溶解速度;
降至室温,将助剂、促进剂、颜料、填料加入步骤②得到的混合溶液里,高速剪切分散20-60min;
加入阻聚剂,搅拌分散均匀得到A组分;
步骤二:将B组分直接包装得到B组分。
8.权利要求1-6的任一项所述的可快速固化的柔性聚甲基丙烯酸甲酯材料的应用方法,其特征在于,施工时根据环境温度按照A:B=100:1-8混合搅拌,直至B完全溶解,采用滚涂、刮涂施工皆可;固化1-5h后即可投入使用。
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