CN106189640B - 一种改性水性丙烯酸树脂涂料的制备方法 - Google Patents

一种改性水性丙烯酸树脂涂料的制备方法 Download PDF

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CN106189640B
CN106189640B CN201610572579.8A CN201610572579A CN106189640B CN 106189640 B CN106189640 B CN 106189640B CN 201610572579 A CN201610572579 A CN 201610572579A CN 106189640 B CN106189640 B CN 106189640B
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孟宪龙
孟宪林
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Hong Hengda waterproof material Co., Ltd.
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Abstract

本发明公开了一种改性水性丙烯酸树脂涂料的制备方法,属于涂料技术领域。本发明以二氧化硅为原料,加入乙醇溶液中超声分散,并用偶联剂进行改性,经离心、干燥制得改性二氧化硅,再制备聚甲基倍半硅氧烷粉末备用,然后将甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸缩水甘油酯混合均匀,加入引发剂反应制得改性丙烯酸乳液,最后将聚甲基倍半硅氧烷粉末、改性二氧化硅、乳化剂、改性丙烯酸乳液、去离子水以及消泡剂高速分散制得改性水性丙烯酸树脂涂料,本发明制备的改性水性丙烯酸树脂涂料解决了传统涂料的吸水性较高不易长期储存和使用的缺陷,可投入大批量工业生产,具有较佳的经济前景。

Description

一种改性水性丙烯酸树脂涂料的制备方法
技术领域
本发明公开了一种改性水性丙烯酸树脂涂料的制备方法,属于涂料技术领域。
背景技术
涂料,旧称油漆,是指可涂覆于物件表面,与基体结合牢固、形成具有一定强度固态薄膜的物质。随着国民经济的科技的不断发展,涂料逐渐被应用于其他领域,发展出多种新功能,广泛应用于光学、热能、物理化学方面。涂料工业的发展间接反映了其他行业的发展。我国涂料工业历史悠久,生产量和消费量均处于世界领先地位,发展前景广阔,正在逐渐成为国民经济新的增长点。
涂料按形态可分为水性涂料、溶剂型涂料、粉末涂料、高固体份涂料等。传统的溶剂型涂料排放的有机化合物是现代社会中重要的污染源。VOC排放到空气与氮氧化物在日光的作用下形成地面臭氧,有刺激性气味,能引起人体呼吸系统感染发炎,同时空气中VOC能够直接吸入到人体内或者刺激眼睛、皮肤等,损害人体的健康。因此,随着各国环境保护法规的出台和人们环境保护意识的逐渐增强,传统的溶剂型涂料由于其较高的VOC排放量逐渐退出历史的舞台,高性能、低污染、多功能的环保型涂料受到大家的青睐,发展率的环保型涂料逐渐成为未来涂料技术的发展趋势,其中水性涂料以其优异的综合性能脱颖而出。但是传统的水性丙烯酸树脂涂料具有易失光、吸水性较高、热粘冷脆等缺点,因而限制了其在某些领域的应用。
发明内容
本发明主要解决的技术问题:针对传统水性丙烯酸树脂涂料易失光、吸水性较高、热粘冷脆等问题,提供了一种改性水性丙烯酸树脂涂料的制备方法。本发明以二氧化硅为原料,加入乙醇溶液中超声分散,并用偶联剂进行改性,经离心、干燥制得改性二氧化硅,再制备聚甲基倍半硅氧烷粉末备用,然后将甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸缩水甘油酯混合均匀,加入引发剂反应制得改性丙烯酸乳液,最后将聚甲基倍半硅氧烷粉末、改性二氧化硅、乳化剂、改性丙烯酸乳液、去离子水以及消泡剂高速分散制得改性水性丙烯酸树脂涂料,本发明制备的改性水性丙烯酸树脂涂料解决了传统涂料的吸水性较高不易长期储存和使用的缺陷,可投入大批量工业生产,具有较佳的经济前景。
为了解决上述技术问题,本发明所采用的技术方案是:
(1)称取200~300g二氧化硅,置于鼓风干燥箱中,在200~210℃下干燥20~24h后,加入1.0~1.2L质量分数为75%乙醇溶液中,用300W超声波超声分散2~3h,加入40~60g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.0~3.5,在75~80℃恒温水浴下,以300~400r/min搅拌3~4h,转入离心机中离心分离,将沉淀置于60~65℃真空干燥箱中干燥4~6h,得改性二氧化硅,备用;
(2)量取1~2mL甲基三甲氧基硅烷,加入10~20mL去离子水中,在60~70℃恒温水浴下,以300~400r/min搅拌20~30min,加入0.5~1.0mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌2~3h,转入离心机中离心分离,用无水乙醇洗涤沉淀2~4次,将沉淀置于70~80℃干燥箱中干燥3~5h,得聚甲基倍半硅氧烷粉末,备用;
(3)量取20~40mL甲基丙烯酸甲酯、10~20mL丙烯酸丁酯、2~6mL甲基丙烯酸缩水甘油酯、4~9mL甲基丙烯酸、4~8mL乙烯基硅油,混合均匀,将混合液滴加入90~150mL去离子水中,并以800~1000r/min搅拌1~2h,用200W超声波超声15~20min,加入1~2g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至70~75℃,保温1~2h,继续加热至80~85℃,保温2~3h,冷却至室温,出料,得改性丙烯酸乳液;
(4)按重量份数计,称取200~220份去离子水、380~400份上述改性丙烯酸乳液、200~220份钛白粉、100~120份上述步骤(1)制备的改性二氧化硅、3~5份上述步骤(2)制备的聚甲基倍半硅氧烷粉末、1~2份乳化剂双甘油聚丙二醇醚、0.3~1.2份消泡剂聚硅氧烷,加入高速剪切分散仪中,以10000~12000r/min剪切分散,得改性水性丙烯酸树脂涂料。
本发明的应用方法是:将所需铺贴的铺层与基层胶粘贴紧实,排除气泡后将本发明制得的改性水性丙烯酸树脂涂料与水按质量比1:2进行均匀混合涂抹于金属管材内表层,随后静置固化,所制备的涂层干燥时间缩短1~2h,漆膜厚度为0.5~1.0cm,表面光滑无气孔,粘弹性较佳,金属管材的使用寿命延长5~7年。
本发明的有益效果是:
(1)本发明制得成品吸水性降低,不易失光,稳定性提高,易于长期使用和储存,使金属管材的使用寿命延长5~7年;
(2)有效降低传统涂料对人体的危害性,涂装后的膜具有优异的耐水性和柔韧性,且能够进行生物降解,减少对环境的污染。
(3)本发明生产容易,对设备要求低,生产稳定性好,能够大规模生产。
具体实施方式
首先称取200~300g二氧化硅,置于鼓风干燥箱中,在200~210℃下干燥20~24h后,加入1.0~1.2L质量分数为75%乙醇溶液中,用300W超声波超声分散2~3h,加入40~60g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.0~3.5,在75~80℃恒温水浴下,以300~400r/min搅拌3~4h,转入离心机中离心分离,将沉淀置于60~65℃真空干燥箱中干燥4~6h,得改性二氧化硅,备用;量取1~2mL甲基三甲氧基硅烷,加入10~20mL去离子水中,在60~70℃恒温水浴下,以300~400r/min搅拌20~30min,加入0.5~1.0mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌2~3h,转入离心机中离心分离,用无水乙醇洗涤沉淀2~4次,将沉淀置于70~80℃干燥箱中干燥3~5h,得聚甲基倍半硅氧烷粉末,备用;量取20~40mL甲基丙烯酸甲酯、10~20mL丙烯酸丁酯、2~6mL甲基丙烯酸缩水甘油酯、4~9mL甲基丙烯酸、4~8mL乙烯基硅油,混合均匀,将混合液滴加入90~150mL去离子水中,并以800~1000r/min搅拌1~2h,用200W超声波超声15~20min,加入1~2g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至70~75℃,保温1~2h,继续加热至80~85℃,保温2~3h,冷却至室温,出料,得改性丙烯酸乳液;按重量份数计,称取200~220份去离子水、380~400份上述改性丙烯酸乳液、200~220份钛白粉、100~120份上述制备的改性二氧化硅、3~5份上述制备的聚甲基倍半硅氧烷粉末、1~2份乳化剂双甘油聚丙二醇醚、0.3~1.2份消泡剂聚硅氧烷,加入高速剪切分散仪中,以10000~12000r/min剪切分散,得改性水性丙烯酸树脂涂料。
实例1
首先称取200g二氧化硅,置于鼓风干燥箱中,在200℃下干燥20h后,加入1.0L质量分数为75%乙醇溶液中,用300W超声波超声分散2h,加入40g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.0,在75℃恒温水浴下,以300r/min搅拌3h,转入离心机中离心分离,将沉淀置于60℃真空干燥箱中干燥4h,得改性二氧化硅,备用;量取1mL甲基三甲氧基硅烷,加入10mL去离子水中,在60℃恒温水浴下,以300r/min搅拌20min,加入0.5mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌2h,转入离心机中离心分离,用无水乙醇洗涤沉淀2次,将沉淀置于70℃干燥箱中干燥3h,得聚甲基倍半硅氧烷粉末,备用;量取20mL甲基丙烯酸甲酯、10mL丙烯酸丁酯、2mL甲基丙烯酸缩水甘油酯、4mL甲基丙烯酸、4mL乙烯基硅油,混合均匀,将混合液滴加入90mL去离子水中,并以800r/min搅拌1h,用200W超声波超声15min,加入1g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至70℃,保温1h,继续加热至80℃,保温2h,冷却至室温,出料,得改性丙烯酸乳液;按重量份数计,称取200份去离子水、380份上述改性丙烯酸乳液、200份钛白粉、100份上述制备的改性二氧化硅、3份上述制备的聚甲基倍半硅氧烷粉末、1份乳化剂双甘油聚丙二醇醚、0.3份消泡剂聚硅氧烷,加入高速剪切分散仪中,以10000r/min剪切分散,得改性水性丙烯酸树脂涂料。
本发明的应用方法是:将所需铺贴的铺层与基层胶粘贴紧实,排除气泡后将本发明制得的改性水性丙烯酸树脂涂料与水按质量比1:2进行均匀混合涂抹于金属管材内表层,随后静置固化,所制备的涂层干燥时间缩短1h,漆膜厚度为0.5cm,表面光滑无气孔,粘弹性较佳,金属管材的使用寿命延长5年。
实例2
首先称取250g二氧化硅,置于鼓风干燥箱中,在205℃下干燥22h后,加入1.1L质量分数为75%乙醇溶液中,用300W超声波超声分散2.5h,加入50g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.3,在77℃恒温水浴下,以350r/min搅拌3.5h,转入离心机中离心分离,将沉淀置于63℃真空干燥箱中干燥5h,得改性二氧化硅,备用;量取1.5mL甲基三甲氧基硅烷,加入15mL去离子水中,在65℃恒温水浴下,以350r/min搅拌25min,加入0.7mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌2.5h,转入离心机中离心分离,用无水乙醇洗涤沉淀3次,将沉淀置于75℃干燥箱中干燥4h,得聚甲基倍半硅氧烷粉末,备用;量取30mL甲基丙烯酸甲酯、15mL丙烯酸丁酯、4mL甲基丙烯酸缩水甘油酯、6mL甲基丙烯酸、6mL乙烯基硅油,混合均匀,将混合液滴加入120mL去离子水中,并以900r/min搅拌2h,用200W超声波超声17min,加入1.5g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至72℃,保温1.5h,继续加热至82℃,保温2h,冷却至室温,出料,得改性丙烯酸乳液;按重量份数计,称取210份去离子水、390份上述改性丙烯酸乳液、210份钛白粉、110份上述制备的改性二氧化硅、4份上述制备的聚甲基倍半硅氧烷粉末、1.5份乳化剂双甘油聚丙二醇醚、0.7份消泡剂聚硅氧烷,加入高速剪切分散仪中,以11000r/min剪切分散,得改性水性丙烯酸树脂涂料。
本发明的应用方法是:将所需铺贴的铺层与基层胶粘贴紧实,排除气泡后将本发明制得的改性水性丙烯酸树脂涂料与水按质量比1:2进行均匀混合涂抹于金属管材内表层,随后静置固化,所制备的涂层干燥时间缩短2h,漆膜厚度为0.8cm,表面光滑无气孔,粘弹性较佳,金属管材的使用寿命延长6年。
实例3
首先称取300g二氧化硅,置于鼓风干燥箱中,在210℃下干燥24h后,加入1.2L质量分数为75%乙醇溶液中,用300W超声波超声分散3h,加入60g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.5,在80℃恒温水浴下,以400r/min搅拌4h,转入离心机中离心分离,将沉淀置于65℃真空干燥箱中干燥6h,得改性二氧化硅,备用;量取2mL甲基三甲氧基硅烷,加入20mL去离子水中,在70℃恒温水浴下,以400r/min搅拌30min,加入1.0mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌3h,转入离心机中离心分离,用无水乙醇洗涤沉淀4次,将沉淀置于80℃干燥箱中干燥5h,得聚甲基倍半硅氧烷粉末,备用;量取40mL甲基丙烯酸甲酯、20mL丙烯酸丁酯、6mL甲基丙烯酸缩水甘油酯、9mL甲基丙烯酸、8mL乙烯基硅油,混合均匀,将混合液滴加入150mL去离子水中,并以1000r/min搅拌2h,用200W超声波超声20min,加入2g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至75℃,保温2h,继续加热至85℃,保温3h,冷却至室温,出料,得改性丙烯酸乳液;按重量份数计,称取220份去离子水、400份上述改性丙烯酸乳液、220份钛白粉、120份上述制备的改性二氧化硅、5份上述制备的聚甲基倍半硅氧烷粉末、2份乳化剂双甘油聚丙二醇醚、1.2份消泡剂聚硅氧烷,加入高速剪切分散仪中,以12000r/min剪切分散,得改性水性丙烯酸树脂涂料。
本发明的应用方法是:将所需铺贴的铺层与基层胶粘贴紧实,排除气泡后将本发明制得的改性水性丙烯酸树脂涂料与水按质量比1:2进行均匀混合涂抹于金属管材内表层,随后静置固化,所制备的涂层干燥时间缩短1h,漆膜厚度为1.0cm,表面光滑无气孔,粘弹性较佳,金属管材的使用寿命延长7年。

Claims (1)

1.一种改性水性丙烯酸树脂涂料的制备方法,其特征在于具体制备步骤为:
(1)称取200~300g二氧化硅,置于鼓风干燥箱中,在200~210℃下干燥20~24h后,加入1.0~1.2L质量分数为75%乙醇溶液中,用300W超声波超声分散2~3h,加入40~60g硅烷偶联剂KH﹣570,并用冰醋酸调节pH至3.0~3.5,在75~80℃恒温水浴下,以300~400r/min搅拌3~4h,转入离心机中离心分离,将沉淀置于60~65℃真空干燥箱中干燥4~6h,得改性二氧化硅,备用;
(2)量取1~2mL甲基三甲氧基硅烷,加入10~20mL去离子水中,在60~70℃恒温水浴下,以300~400r/min搅拌20~30min,加入0.5~1.0mL摩尔浓度为0.1mol/L氢氧化钠溶液,继续恒温搅拌2~3h,转入离心机中离心分离,用无水乙醇洗涤沉淀2~4次,将沉淀置于70~80℃干燥箱中干燥3~5h,得聚甲基倍半硅氧烷粉末,备用;
(3)量取20~40mL甲基丙烯酸甲酯、10~20mL丙烯酸丁酯、2~6mL甲基丙烯酸缩水甘油酯、4~9mL甲基丙烯酸、4~8mL乙烯基硅油,混合均匀,将混合液滴加入90~150mL去离子水中,并以800~1000r/min搅拌1~2h,用200W超声波超声15~20min,加入1~2g引发剂2,2'-偶氮二异丁基脒二盐酸盐,在氮气氛围下,加热至70~75℃,保温1~2h,继续加热至80~85℃,保温2~3h,冷却至室温,出料,得改性丙烯酸乳液;
(4)按重量份数计,称取200~220份去离子水、380~400份上述改性丙烯酸乳液、200~220份钛白粉、100~120份上述步骤(1)制备的改性二氧化硅、3~5份上述步骤(2)制备的聚甲基倍半硅氧烷粉末、1~2份乳化剂双甘油聚丙二醇醚、0.3~1.2份消泡剂聚硅氧烷,加入高速剪切分散仪中,以10000~12000r/min剪切分散,得改性水性丙烯酸树脂涂料。
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