CN112126079A - 自分层水性树脂及其制备、应用方法 - Google Patents
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Abstract
本发明涉及自分层水性树脂及其制备、应用方法,原材料由丙烯酸类单体、引发剂、乳化剂、液体环氧树脂、改性剂和去离子水组成;以丙烯酸类单体、引发剂、乳化剂和去离子水为原料,采用乳液聚合的方法制备丙烯酸酯乳液;以液体环氧树脂、改性剂和去离子水为原料,采用相反转工艺制备环氧乳液;将丙烯酸酯乳液和水性环氧乳液混合,制得自分层水性树脂。本发明制备的自分层水性树脂,热塑性乳液能够和环氧树脂长期稳定存在,保留了环氧树脂的特性,能够与环氧固化剂开环交联形成连续的致密的膜。
Description
技术领域
本发明属于涂料化工技术领域,具体涉及一种自分层水性树脂及其制备、应用方法。
背景技术
近年来,环保成为工业发展的热点。工业的发展能够为人类的生活提供便利,但同时对大自然的影响也最终会影响到人类自身。随着气候变暖、空气质量下降等自然现象的出现,人类逐步意识到,人与自然是息息相关的。所以,人们也越来越关注对环境的保护。而在涂料行业,环保型涂料逐渐进入人们的视野。水性涂料作为环保型涂料的一种,其发展也日新月异。
水性涂料与溶剂型涂料相比,溶剂使用量少,低VOC排放,对环境友好,使其正在逐步替代溶剂型涂料。虽然越来越多的成功应用案例证明,即使在恶劣的环境条件下,水性涂料也可为钢材提供良好的防腐蚀性能,但水性涂料的性能与溶性型涂料的性能相比,仍无法完全达到或超越溶剂型涂料,使得水性涂料的发展应用受到限制。
环氧树脂因其优异的性能而被广泛应用于防护涂料中。丙烯酸酯类树脂因其优良的耐候性、耐水性和保光性,被广泛用于面漆等装饰涂料中。在配套涂料中,通常需要进行两/三次的涂覆,才能达到防护和装饰的效果。每一层的涂覆都需要较长的适用期和固化过程,这会加重环境垃圾的产生、污染物增多,同时也会造成能源的浪费。为了克服这些缺点,市场迫切需要一种能够结合防护性能和装饰效果的涂料,不仅减少涂层的数量,也能够提供与配套涂料相同或更好的性能。在一次涂装后,涂覆在底材上的涂料能够一次成型,自发分层呈梯度结构,形成底涂和面凃。为满足上述自分层涂料和环保的要求,需要研发一种能够在成膜过程中自分层的水性树脂。
发明内容
本发明的目的在于提供一种自分层水性树脂及其制备、应用方法,能一次成型、自发分层,实现防护性能和装饰效果。
为了达到上述的目的,本发明提供一种自分层水性树脂,由丙烯酸酯乳液和水性环氧乳液混合而成,其中,水性环氧乳液的重量百分比为30~60%,其余为丙烯酸酯乳液;所述丙烯酸酯乳液由丙烯酸类单体预乳液采用乳液聚合的方式制备,制备中乳化剂选用阴离子乳化剂和非离子乳化剂组成的复合乳化剂。
上述自分层水性树脂,其中,所述丙烯酸酯乳液为乳液聚合的热塑性聚合物,所述丙烯酸酯乳液中丙烯酸酯的分子量>5000。
本发明提供的另一技术方案是一种自分层水性树脂制备方法,包括:
配料:原材料由丙烯酸类单体、引发剂、乳化剂、液体环氧树脂、改性剂和去离子水组成,各组份重量百分比为:丙烯酸类单体20~24%,引发剂0.03~0.06%,乳化剂0.2~0.4%,液体环氧树脂20~24%,改性剂2~4%,去离子水45~60%;
制备丙烯酸酯乳液:以丙烯酸类单体、引发剂、乳化剂和去离子水为原料,采用乳液聚合的方法制备丙烯酸酯乳液;
制备水性环氧乳液:以液体环氧树脂、改性剂和去离子水为原料,采用相反转工艺制备环氧乳液;
将丙烯酸酯乳液和水性环氧乳液混合,制得自分层水性树脂。
上述自分层水性树脂制备方法,其中,所述丙烯酸类单体为丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸、丙烯酸乙酯、苯乙烯、苯乙烯磺酸钠和丙烯酸丁酯中的一种或两种以上组合;所述引发剂为过硫酸盐类。
上述自分层水性树脂制备方法,其中,所述乳化剂为阴离子乳化剂和非离子乳化剂组成的复合乳化剂。
上述自分层水性树脂制备方法,其中,所述液体环氧树脂为当量160~200的双酚A型环氧树脂;所述改性剂为含有EO链段的聚醚类化合物。
上述自分层水性树脂制备方法,其中,所述制备丙烯酸酯乳液包括:将丙烯酸类单体、部分乳化剂和去离子水混合均匀,制成单体预乳液;采用乳液聚合的方法,将剩余乳化剂和去离子水混合并加热至70~80℃,同时滴加引发剂和单体预乳液,4~5h滴加完毕,保温20~40min。
上述自分层水性树脂制备方法,其中,所述制备水性环氧乳液包括:将液体环氧树脂和改性剂在110~130℃下反应2~3h,得到改性环氧树脂;在改性环氧树脂中加入去离子水,通过相反转工艺,制备水性环氧乳液。
上述自分层水性树脂制备方法,其中,所述将丙烯酸酯乳液和水性环氧乳液混合,制得自分层水性树脂包括:将丙烯酸酯乳液滴加到40~60℃的水性环氧乳液中,2~3h加完,保温熟化20~40min,得到自分层水性树脂。
本发明还提供了上述自分层水性树脂制备方法制得的自分层水性树脂的应用方法,用作水性涂料的基料。
与现有技术相比,本发明有益技术效果是:
本发明制备的自分层水性树脂,在丙烯酸酯乳液的单体选择中,选择了硬单体与软单体配合,并选择同时具备非离子特性和离子特性的乳化剂,在引发剂的作用下,通过乳液聚合,制备了热塑性乳液;该热塑性乳液能够和环氧树脂长期稳定存在,环氧树脂中的环氧基团未发生反应,保留了环氧树脂的特性;该自分层水性树脂与环氧固化剂配合后,能够交联形成连续的致密的膜。
本发明的自分层水性树脂所得漆膜光泽高、附着力强、耐腐蚀性好等特点。
具体实施方式
以下对本发明的自分层水性树脂及其制备、应用方法作进一步的详细描述。
本发明的自分层水性树脂由丙烯酸酯乳液和水性环氧乳液混合而成,其中,水性环氧乳液的重量百分比为30~60%,其余为丙烯酸酯乳液;所述丙烯酸酯乳液由丙烯酸类单体预乳液采用乳液聚合的方式制备,制备中乳化剂选用阴离子乳化剂和非离子乳化剂组成的复合乳化剂。
本发明的自分层水性树脂综合了丙烯酸酯和环氧树脂的优点,且两者能够在乳液中长时间稳定共存,不发生团聚凝胶现象。
所述丙烯酸酯乳液为乳液聚合的热塑性聚合物,不含硬化剂;所述丙烯酸酯乳液中丙烯酸酯的分子量>5000,能够自行成膜。所述水性环氧乳液由改性环氧树脂通过相反转工艺制备。
本发明的自分层水性树脂制备方法包括:
1)配料
原材料成份及各组份重量百分比如表1所示:
表1原材料成份及各组份重量
丙烯酸类单体 | 20-24% |
引发剂 | 0.03-0.06% |
乳化剂 | 0.2-0.4% |
液体环氧树脂 | 20-24% |
改性剂 | 2-4% |
去离子水 | 45-60% |
较佳地,所述丙烯酸类单体为丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸、丙烯酸乙酯、苯乙烯、苯乙烯磺酸钠和丙烯酸丁酯中的一种或两种以上组合;所述引发剂为过硫酸盐类,如过硫酸铵、过硫酸钾和过硫酸钠中的一种或两种以上组合;所述乳化剂为阴离子乳化剂和非离子乳化剂组成的复合乳化剂;所述液体环氧树脂为当量160-200的双酚A型环氧树脂,如YD-128;所述改性剂为含有EO链段的聚醚类化合物,如聚醚胺、聚乙二醇类;
2)制备丙烯酸酯乳液
以丙烯酸类单体、引发剂、乳化剂和适量去离子水为原料,采用乳液聚合的方法制备丙烯酸酯乳液,具体为:
2-1)将丙烯酸类单体、部分乳化剂和适量去离子水混合均匀,制成单体预乳液;
2-2)采用乳液聚合的方法,将剩余乳化剂和适量去离子水混合并加热至70~80℃,同时滴加引发剂和单体预乳液,4~5h滴加完毕,保温20~40min,再降温待用;
3)制备水性环氧乳液
以液体环氧树脂、改性剂和适量去离子水为原料,采用相反转工艺制备环氧乳液,具体为:
3-1)将液体环氧树脂和改性剂在110~130℃下反应2~3h,得到改性环氧树脂;
3-2)在改性环氧树脂中加入去离子水,通过相反转工艺,制备水性环氧乳液;
4)将丙烯酸酯乳液滴加到40~60℃的水性环氧乳液中,2~3h加完,保温熟化20~40min,得到自分层水性树脂。
以上述自分层水性树脂为基料,加入涂料,制得自分层水性涂料。使用该自分层水性涂料涂敷于底材,在漆膜干燥过程中,丙烯酸酯和环氧树脂自发分层,形成致密的涂膜,不仅对底材进行保护,且漆膜光泽高,有很好的装饰性。
本发明制备的自分层水性树脂,在丙烯酸酯乳液的单体选择中,选择了硬单体与软单体配合,制备的热塑性乳液能够和环氧树脂长期稳定存在,保留了环氧树脂的特性,能够与环氧固化剂开环交联形成连续的致密的膜。
实施例1
A)单体预乳液和引发剂溶液的制备
将丙烯酸丁酯162.9g、甲基丙烯酸甲酯183.2g、苯乙烯140.6g和苯乙烯磺酸钠6.5g、去离子水212.3g和乳化剂4.8g,加入至容器中,搅拌均匀,制成单体预乳液待用;
将1.1g引发剂溶于131.5g去离子水中;
B)丙烯酸酯乳液的制备
在2000ml装有搅拌和温度计的四口烧瓶中,加入156.3g去离子水和0.8g乳化剂,搅拌均匀后,升温至80℃,滴加单体预乳液和引发剂溶液,4h滴加完,并保温30min,再降温待用;
C)水性环氧乳液的制备
将441g液体环氧树脂与59g改性剂加入四口烧瓶中,升温至120℃,反应2h;然后降温至室温,滴加500g去离子水;
D)自分层水性树脂的制备
将水性环氧乳液升温至50℃,然后将丙烯酸酯乳液滴加入反应釜中,3h滴加完,保温熟化30min。
此时,该自分层水性树脂固含量为50%,粒径d(90)=0.1um,当量884。
实施例2
A)单体预乳液和引发剂溶液的制备
将丙烯酸10g、丙烯酸丁酯79g、甲基丙烯酸甲酯89g、苯乙烯65.4g和苯乙烯磺酸钠3.2g、去离子水106.2g和乳化剂2.4g,加入至容器中,搅拌均匀,制成单体预乳液待用;
将0.6g引发剂溶于66g去离子水中;
B)丙烯酸酯乳液的制备
在1000ml装有搅拌和温度计的四口烧瓶中,加入78g去离子水和0.4g乳化剂,搅拌均匀后,升温至80℃,滴加单体预乳液和引发剂溶液,4h滴加完,并保温30min,再降温待用;
C)水性环氧乳液的制备
将200g液体环氧树脂与25g改性剂加入四口烧瓶中,升温至120℃,反应2h;然后降温至室温,滴加225g去离子水;
D自分层水性树脂的制备
将水性环氧乳液升温至50℃,然后将丙烯酸酯乳液滴加入反应釜中,3h滴加完,保温熟化30min。
此时,该自分层水性树脂固含量为49.99%,粒径d(90)=0.1um,当量730。
实施例3
A)单体预乳液和引发剂溶剂的制备
将甲基丙烯酸5g、丙烯酸乙酯50g、甲基丙烯酸丁酯70g、甲基丙烯酸乙酯50g、苯乙烯50g和苯乙烯磺酸钠4g、去离子水100g和乳化剂3g,加入至容器中,搅拌均匀,制成单体预乳液待用;
将0.7g引发剂溶于70g去离子水中;
B)丙烯酸酯乳液的制备
在1000ml装有搅拌和温度计的四口烧瓶中,加入73g去离子水和0.6g乳化剂,搅拌均匀后,升温至80℃,滴加单体预乳液和引发剂溶液,4h滴加完,并保温30min,再降温待用;
C)水性环氧乳液的制备
将100g液体环氧树脂与10g改性剂加入四口烧瓶中,升温至120℃,反应2h;然后降温至室温,滴加110g去离子水;
D)自分层水性树脂的制备
将水性环氧乳液升温至50℃,然后将丙烯酸酯乳液滴加入反应釜中,3h滴加完,保温熟化30min。
此时,该自分层水性树脂固含量为49.99%,粒径d(90)=0.1um,当量1347。
实施例4
将上述实施例中制备的自分层水性树脂应用于涂料的应用中。
按照表2进行涂料制备。
表2涂料成份
A部分 | 重量百分比% |
AERS7013/30(无锡洪汇) | 40 |
R298钛白粉 | 23 |
NB-45重晶石粉 | 25 |
6208分散剂 | 1.5 |
H<sub>2</sub>O | 10.5 |
总计 | 100 |
B部分 | 重量百分比(占A重量) |
BYK-024 | 0.1 |
BYK-347 | 0.4 |
WT-202 | 0.4 |
将A部分砂磨至细度后,加入B部分,制成与自分层水性树脂配合使用的涂料,将涂料加入上述实施例制备的自分层水性树脂中制得自分层水性涂料,进行样板检测,样板规格为150mm×75mm×2mm冷轧钢板,漆膜厚度为40~60um。检测结果见表3:
表3检测结果
实验例1 | 实验例2 | 实验例3 | |
铅笔硬度 | H | H | H |
附着力 | 0 | 0 | 0 |
耐盐雾性 | 500h | 450h | 300h |
50℃热储7天 | 好 | 好 | 好 |
检测结果说明,本发明的自分层水性树脂具有附着力强、漆膜耐腐蚀性好和铅笔硬度高等特点。
Claims (10)
1.自分层水性树脂,其特征在于,由丙烯酸酯乳液和水性环氧乳液混合而成,其中,水性环氧乳液的重量百分比为30~60%,其余为丙烯酸酯乳液;所述丙烯酸酯乳液由丙烯酸类单体预乳液采用乳液聚合的方式制备,制备中乳化剂选用阴离子乳化剂和非离子乳化剂组成的复合乳化剂。
2.如权利要求1所述的自分层水性树脂,其特征在于,所述丙烯酸酯乳液为乳液聚合的热塑性聚合物,所述丙烯酸酯乳液中丙烯酸酯的分子量>5000。
3.自分层水性树脂制备方法,其特征在于,包括:
配料:原材料由丙烯酸类单体、引发剂、乳化剂、液体环氧树脂、改性剂和去离子水组成,各组份重量百分比为:丙烯酸类单体20~24%,引发剂0.03~0.06%,乳化剂0.2~0.4%,液体环氧树脂20~24%,改性剂2~4%,去离子水45~60%;
制备丙烯酸酯乳液:以丙烯酸类单体、引发剂、乳化剂和去离子水为原料,采用乳液聚合的方法制备丙烯酸酯乳液;
制备水性环氧乳液:以液体环氧树脂、改性剂和去离子水为原料,采用相反转工艺制备环氧乳液;
将丙烯酸酯乳液和水性环氧乳液混合,制得自分层水性树脂。
4.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述丙烯酸类单体为丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸、丙烯酸乙酯、苯乙烯、苯乙烯磺酸钠和丙烯酸丁酯中的一种或两种以上组合;所述引发剂为过硫酸盐类。
5.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述乳化剂为阴离子乳化剂和非离子乳化剂组成的复合乳化剂。
6.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述液体环氧树脂为当量160~200的双酚A型环氧树脂;所述改性剂为含有EO链段的聚醚类化合物。
7.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述制备丙烯酸酯乳液包括:
将丙烯酸类单体、部分乳化剂和去离子水混合均匀,制成单体预乳液;
采用乳液聚合的方法,将剩余乳化剂和去离子水混合并加热至70~80℃,同时滴加引发剂和单体预乳液,4~5h滴加完毕,保温20~40min。
8.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述制备水性环氧乳液包括:
将液体环氧树脂和改性剂在110~130℃下反应2~3h,得到改性环氧树脂;
在改性环氧树脂中加入去离子水,通过相反转工艺,制备水性环氧乳液。
9.如权利要求3所述的自分层水性树脂制备方法,其特征在于,所述将丙烯酸酯乳液和水性环氧乳液混合,制得自分层水性树脂包括:将丙烯酸酯乳液滴加到40~60℃的水性环氧乳液中,2~3h加完,保温熟化20~40min,得到自分层水性树脂。
10.采用权利要求3至9中任一权利要求所述的自分层水性树脂制备方法制得的自分层水性树脂的应用方法,其特征在于,用作水性涂料的基料。
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