CN110218288A - 一种硅改性零voc水性聚酯丙烯酸树脂及其制备方法 - Google Patents
一种硅改性零voc水性聚酯丙烯酸树脂及其制备方法 Download PDFInfo
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- CN110218288A CN110218288A CN201910607153.5A CN201910607153A CN110218288A CN 110218288 A CN110218288 A CN 110218288A CN 201910607153 A CN201910607153 A CN 201910607153A CN 110218288 A CN110218288 A CN 110218288A
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- waterborne polyester
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4241—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols from dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明属于水性涂料技术领域,其公开了一种硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,该树脂由以下重量百分比通过聚合杂化反应制备得到:聚酯中间体10‑30%;功能单体20‑40%;丙烯酸单体20‑60%;硅溶胶5‑15%;异氰酸酯固化剂5‑10%;引发剂1‑5%;催化剂0.1‑0.5%,中和剂3‑5%,所述的聚酯中间体为多元醇与多元酸及缩水甘油酯合成得到,所述的硅溶胶为有机硅单体与无机硅单体通过溶胶凝胶法合成得到;所述的功能单体为N‑羟甲基丙烯酰胺、N‑丁氧基甲基丙烯酰胺、叔碳酸缩水甘油酯、甲基丙烯酸异冰片酯中的一种或几种。同时,本发明还公开了该树脂的制备方法。本发明的树脂制得的漆膜具有较高的饱满度、光泽高、硬度高、手触感好等优异性能。
Description
技术领域
本发明涉及水性涂料技术领域,具体涉及一种硅改性零VOC水性聚酯丙烯酸树脂及其制备方法。
背景技术
世界各国环保意识逐渐加强,相继制定相关法规限制VOC的排放,市面上的水性涂料依然含有较大量的VOC。
申请人广东华兹卜新材料科技有限公司于2017年申报了一项发明专利CN201711148011.4,其公开了一种抗老化水性木器涂料,其原料由按重量份计的以下成分组成:水性羟基丙烯酸分散体30-50份;水性聚氨酯树脂乳液25-40份;硅溶胶11-35份;无机复合物14-33份;高枝化聚乙烯亚胺10-25份;聚四氟乙烯1-2份;己二酸二酰肼15-25份;硅烷偶联剂0.5-1份;成膜助剂5-10份;消泡剂0.5-1份;增稠剂1-2份;去离子水30-50份;在该案说明书第7页21、22段记载:硅溶胶具有比表面积大、吸附能力强、羟基密集的特点,能够提高固化速度;硅溶胶对悬浮物有一定的吸附作用,使得涂料容易出现絮凝的缺陷,通过高枝化聚乙烯亚胺(PEI)的吸附作用,其所带电荷由于静电斥力作用,防止了颗粒的聚沉,大大减少絮凝和变白的情况。可以理解的,该方案的硅溶胶仅仅起着提高固化速度、防止絮凝的作用。
申请人福建钢泓金属科技股份有限公司于2016年申请了一项发明专利ZL201610008028.9,其公开了一种抗污、耐指纹不锈钢板水性涂料及其制备方法。由重量百分比的55-70%羟基改性水性聚酯树脂,8-15%甲醚化氨基树脂,3-5%改性硅溶胶,2-4%中和剂,0.1-0.3%润湿剂,0-0.2%流变助剂,0.1-1.5%消泡剂,0.1-0.5%流平剂,3-6%水性聚乙烯蜡和聚四氟乙烯蜡混合浆,1-3%附着力促进剂,1-3%纳米无机盐,0.2-0.5%催化剂,3-5%助溶剂,1-8.5%去离子水制备得到。其通过羟基改性水性聚酯树脂、甲醚化氨基树脂、改性硅溶胶、水性聚乙烯蜡和聚四氟乙烯蜡混合浆组合反应,有优异的抗指纹印迹性能,疏水疏油性能优异,抗指纹涂层水接触角、油接触角大,低滑动角;易于油污滑落;耐磨性,和抗老化性优异。但是该方案并未在此同时改善漆膜的光泽性能、手感。
发明内容
本发明旨在提供一种硅改性零VOC水性聚酯丙烯酸树脂;本发明的树脂中的羟基与异氰酸酯固化以及有机无机硅进一步水解缩合交联,得到的硅改性水性聚酯丙烯酸具有零VOC、高固体分,漆膜具有较高的饱满度、光泽高、硬度高、手触感好等优异性能。同时,本发明还公开了该分散体的制备方法。
其具体方案为:一种硅改性零VOC水性聚酯丙烯酸树脂,该树脂由以下重量百分比通过聚合杂化反应制备得到:聚酯中间体10-30%;功能单体20-40%;丙烯酸单体20-60%;硅溶胶5-15%;异氰酸酯固化剂5-10%;引发剂1-5%;催化剂0.1-0.5%,中和剂3-5%,所述的聚酯中间体为多元醇与多元酸及缩水甘油酯合成得到,所述的硅溶胶为有机硅单体与无机硅单体通过溶胶凝胶法合成得到;
所述的功能单体为N-羟甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、叔碳酸缩水甘油酯、甲基丙烯酸异冰片酯中的一种或几种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的多元醇为季戊四醇、三羟甲基丙烷、新戊二醇、1,3-丙二醇、1,4-丁二醇中的一种或几种;
所述的多元酸为己二酸、苯酐、六氢苯酐、偏苯三酸酐、均苯四甲酸酐中的一种或几种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的缩水甘油酯为叔碳酸缩水甘油酯、缩水甘油丁酯中的至少一种。
优选地,多元醇、多元酸、缩水甘油酯的重量比为:0.5-1.2:1-2.9:1。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的丙烯酸单体为甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸、丙烯酸羟丙酯、苯乙烯中的一种或几种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的有机硅单体为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、n-辛基三乙氧基硅烷中的一种或几种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的无机硅单体为正硅酸乙酯、三甲氧基硅氧烷中的至少一种。
优选地,有机硅单体和无机硅单体的比例为:0.07-0.11:1。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的异氰酸酯固化剂为拜耳的HDI三聚体、TDI三聚体、IPDI三聚体中的一种或几种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的引发剂为过氧化苯甲酰、过氧化苯甲酸叔丁酯、二叔丁基过氧化物、二叔戊基过氧化物中的一种或几种;所述的催化剂为二丁基锡二月桂酸酯、二(十二烷基硫)二丁基锡、辛酸亚锡中的一种。
在上述的硅改性零VOC水性聚酯丙烯酸树脂中,所述的中和剂为N,N-2-甲基乙醇胺、三乙胺中的一种。
同时,本发明还提供一种如上所述的硅改性零VOC水性聚酯丙烯酸树脂的制备方法,包括如下步骤:
步骤1:在带有控温、搅拌、冷凝器的反应釜中,加入至少一种多元酸与多元醇单体,加入催化剂,缓慢升温,至200-250℃,当酸值到30-40mg KOH/g的时,加入缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至120-150℃;
步骤2:在带有控温、搅拌、冷凝器的反应釜中,加入至少一种有机硅单体与无机硅单体,加入无水乙醇或丁醇,升温至50-80℃,滴加去离子水与盐酸的混合物,滴加1-2h,然后保温5-8h;
步骤3:将功能性单体、丙烯酸单体、硅溶胶、缩水甘油酯以及引发剂混合后,滴加至聚酯中间体中,滴加时间2-4h;
步骤4:一次性加入适量的引发剂消除未反应的单体,保温3-4h,降温至80℃,加入中和剂,搅拌10-30min,加入去离子水调节至一定的固含后出料;
步骤5:应用时可将树脂与异氰酸酯固化剂3-10:1重量比例混合均匀,在40-80℃下烘烤或自然干燥成膜。
本发明的有益效果在于:
本发明的树脂中的羟基与异氰酸酯固化以及有机无机硅进一步水解缩合交联,得到的硅改性水性聚酯丙烯酸具有零VOC、高固体分,漆膜具有较高的饱满度、光泽高、硬度高、手触感好等优异性能。
具体实施方式
下面结合具体实施方式,对本发明的技术方案作进一步的详细说明,但不构成对本发明的任何限制。
实施例1
一种硅改性零VOC水性聚酯丙烯酸树脂,制备方法如下:
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入130.86g间苯二甲酸,145.27g新戊二醇,34.65g六氢苯酐,11.32g季戊四醇,加入0.32g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入53.47g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至120℃。
步骤2:硅溶胶的合成,在带有控温、搅拌、冷凝器的反应釜中,加入12.8g乙烯基三甲氧基硅烷,146.17g正硅酸乙酯、26.56g三甲氧基硅氧烷,84.22g无水乙醇,升温至50℃,滴加36.88g去离子水与2.1g盐酸的混合物,滴加1.5h,然后保温8h。
步骤3:称量48.25g叔碳酸缩水甘油酯,79.65g甲基丙烯酸甲酯、28.66g丙烯酸,57.26g丙烯酸羟丙酯,3.57g硅溶胶及8.26g过氧化苯甲酸叔丁酯混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤4:一次性加入2.34g的过氧化苯甲酸叔丁酯消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入510g去离子水调节至一定的固含后出料。
步骤5:应用时可将树脂与异氰酸酯固化剂3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
实施例2
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入118.46g间苯二甲酸,54.21g新戊二醇,18.24g六氢苯酐,6.42g季戊四醇,加入0.28g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入62.26g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至145℃。
步骤2:硅溶胶的合成,在带有控温、搅拌、冷凝器的反应釜中,加入23.47g乙烯基三甲氧基硅烷,183.16g正硅酸乙酯、26.56g三甲氧基硅氧烷,84.22g无水乙醇,升温至50℃,滴加36.88g去离子水与2.1g盐酸的混合物,滴加1.5h,然后保温8h。
步骤3:称量48.25g叔碳酸缩水甘油酯,247.37g甲基丙烯酸甲酯、34.75g丙烯酸,86.92g丙烯酸羟丙酯,247.37g苯乙烯,18.57g硅溶胶及18.34g二叔丁基过氧化物混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤4:一次性加入4.28g的二叔丁基过氧化物消除未反应的单体,保温4h,降温至80℃,加入27.63g二甲基乙醇胺,搅拌10min,加入1100g去离子水调节至一定的固含后出料。
步骤5:应用时可将树脂与(拜耳的HDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
实施例3
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入64.23g己二酸,37.14g1,4-丁二醇,34.65g六氢苯酐,11.32g季戊四醇,加入0.32g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入53.47g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至140℃。
步骤2:硅溶胶的合成,在带有控温、搅拌、冷凝器的反应釜中,加入12.8g乙烯基三甲氧基硅烷,178.42g正硅酸乙酯、84.22g无水乙醇,升温至50℃,滴加36.88g去离子水与2.1g盐酸的混合物,滴加1.5h,然后保温8h。
步骤3:称量72.75g叔碳酸缩水甘油酯,59.65g甲基丙烯酸甲酯、57.66g丙烯酸,49.61g丙烯酸羟乙酯,6.54g硅溶胶及9.26g二叔戊基过氧化物混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤4:一次性加入2.34g的二叔戊基过氧化物消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入420g去离子水调节至一定的固含后出料。
步骤5:应用时可将树脂与(拜耳的TDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
实施例4
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入118.56g间苯二甲酸,122.47g新戊二醇,53.46g六氢苯酐,22.64g季戊四醇,加入0.32g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入53.47g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至125℃。
步骤2:硅溶胶的合成,在带有控温、搅拌、冷凝器的反应釜中,加入12.8g乙烯基三甲氧基硅烷,146.17g正硅酸乙酯、26.56g三甲氧基硅氧烷,84.22g无水乙醇,升温至50℃,滴加36.88g去离子水与2.1g盐酸的混合物,滴加1.5h,然后保温8h。
步骤3:称量48.25g叔碳酸缩水甘油酯,199.65g甲基丙烯酸甲酯、28.66g丙烯酸,57.26g丙烯酸羟丙酯,199.65苯乙烯,24.26g硅溶胶及24.26g过氧化苯甲酰混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤4:一次性加入2.34g的过氧化苯甲酰消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入1200g去离子水调节至一定的固含后出料。
步骤5:应用时可将树脂与(拜耳的TDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
对比例1
一种水性聚酯丙烯酸树脂,制备方法如下:
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入130.86g间苯二甲酸,45.27g新戊二醇,34.65g六氢苯酐,11.32g季戊四醇,加入0.32g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入53.47g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至120℃。
步骤2:称量48.25g叔碳酸缩水甘油酯,109.65g甲基丙烯酸甲酯、28.66g丙烯酸,57.26g丙烯酸羟丙酯,18.57g及9.26g过氧化苯甲酸叔丁酯混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤3:一次性加入2.34g的过氧化苯甲酸叔丁酯消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入510g去离子水调节至一定的固含后出料。
步骤4:应用时可将树脂与(拜耳的IPDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
对比例2
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入64.23g己二酸,37.14g1,4-丁二醇,34.65g六氢苯酐,11.32g季戊四醇,加入0.32g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到35mg KOH/g左右时,加入53.47g叔碳酸缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至145℃。
步骤2:称量72.75g叔碳酸缩水甘油酯,59.65g甲基丙烯酸甲酯、57.66g丙烯酸,49.61g丙烯酸羟乙酯,6.54g及9.26g二叔丁基过氧化物混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤3:一次性加入2.34g的二叔丁基过氧化物消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入420g去离子水调节至一定的固含后出料。
步骤4:应用时可将树脂与(拜耳的HDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
对比例3
步骤1:聚酯中间体的合成,在带有控温、搅拌、冷凝器的反应釜中,加入167.49新戊二醇,68.51g己二酸,46.17g1,2-丙二醇,17.45g六氢苯酐,11.32g季戊四醇,加入0.35g二丁基锡二月桂酸酯缓慢升温至230℃,当酸值到7mg KOH/g左右时,降温至145℃。
步骤2:称量39.9g叔碳酸缩水甘油酯,59.65g苯乙烯、57.66g丙烯酸,49.61g丙烯酸羟乙酯及9.26g二叔丁基过氧化物混合后,滴加至步骤1聚酯中间体中,滴加时间约4h。
步骤3:一次性加入2.34g的二叔丁基过氧化物消除未反应的单体,保温4h,降温至80℃,加入16.74g二甲基乙醇胺,搅拌10min,加入420g去离子水调节至一定的固含后出料。
步骤4:应用时可将树脂与(拜耳的HDI三聚体)3:1重量比例混合均匀,在80℃下烘烤或自然干燥成膜。
对上述实施例1-实施例4中制备的硅改性零VOC水性聚酯丙烯酸树脂的各项性能参数进行测试后。
对上述对比例1-对比例3制备的水性聚酯丙烯酸树脂的各项性能参数与之对比,测试结果如下表1:
表1测试结果
与一般的水性聚酯丙烯酸树脂对比,可以看出,本发明实施例制备的硅改性零VOC水性聚酯丙烯酸树脂具有以下优点:(1)漆膜饱满度好,清漆光泽可达到95,DOI大于95;(2)硬度高,有机无机硅改性后的漆膜,充分交联后硬度可达4H;(3)耐溶剂擦拭好,通过基团反应交联及自交联形成网状结构,用酒精擦拭>200下,不失光、没有擦痕,耐水、酸、碱特别优异。
以上所述的仅为本发明的较佳实施例,凡在本发明的精神和原则范围内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,该树脂由以下重量百分比通过聚合杂化反应制备得到:聚酯中间体10-30%;功能单体20-40%;丙烯酸单体20-60%;硅溶胶5-15%;异氰酸酯固化剂5-10%;引发剂1-5%;催化剂0.1-0.5%,中和剂3-5%,所述的聚酯中间体为多元醇与多元酸及缩水甘油酯合成得到,所述的硅溶胶为有机硅单体与无机硅单体通过溶胶凝胶法合成得到;
所述的功能单体为N-羟甲基丙烯酰胺、N-丁氧基甲基丙烯酰胺、叔碳酸缩水甘油酯、甲基丙烯酸异冰片酯中的一种或几种。
2.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的多元醇为季戊四醇、三羟甲基丙烷、新戊二醇、1,3-丙二醇、1,4-丁二醇中的一种或几种;
所述的多元酸为己二酸、苯酐、六氢苯酐、偏苯三酸酐、均苯四甲酸酐中的一种或几种。
3.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的缩水甘油酯为叔碳酸缩水甘油酯、缩水甘油丁酯中的至少一种。
4.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的丙烯酸单体为甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯、丙烯酸、丙烯酸羟丙酯、苯乙烯中的一种或几种。
5.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的有机硅单体为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、n-辛基三乙氧基硅烷中的一种或几种。
6.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的无机硅单体为正硅酸乙酯、三甲氧基硅氧烷中的至少一种。
7.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的异氰酸酯固化剂为拜耳的HDI三聚体、TDI三聚体、IPDI三聚体中的一种或几种。
8.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的引发剂为过氧化苯甲酰、过氧化苯甲酸叔丁酯、二叔丁基过氧化物、二叔戊基过氧化物中的一种或几种;所述的催化剂为二丁基锡二月桂酸酯、二(十二烷基硫)二丁基锡、辛酸亚锡中的一种。
9.根据权利要求1所述的硅改性零VOC水性聚酯丙烯酸树脂,其特征在于,所述的中和剂为N,N-2-甲基乙醇胺、三乙胺中的一种。
10.一种如权利要求1-9中任一项所述的硅改性零VOC水性聚酯丙烯酸树脂的制备方法,其特征在于,包括如下步骤:
步骤1:在带有控温、搅拌、冷凝器的反应釜中,加入至少一种多元酸与多元醇单体,加入催化剂,缓慢升温,至200-250℃,当酸值到30-40mg KOH/g的时,加入缩水甘油酯,直到酸值降至5mgKOH/g左右,降温至120-150℃;
步骤2:在带有控温、搅拌、冷凝器的反应釜中,加入至少一种有机硅单体与无机硅单体,加入无水乙醇或丁醇,升温至50-80℃,滴加去离子水与盐酸的混合物,滴加1-2h,然后保温5-8h;
步骤3:将功能性单体、丙烯酸单体、硅溶胶、缩水甘油酯以及引发剂混合后,滴加至聚酯中间体中,滴加时间2-4h;
步骤4:一次性加入适量的引发剂消除未反应的单体,保温3-4h,降温至80℃,加入中和剂,搅拌10-30min,加入去离子水调节至一定的固含后出料;
步骤5:应用时可将树脂与异氰酸酯固化剂3-10:1重量比例混合均匀,在40-80℃下烘烤或自然干燥成膜。
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