CN110790875B - 一种有机硅改性丙烯酸乳液粘合剂及其制备方法 - Google Patents
一种有机硅改性丙烯酸乳液粘合剂及其制备方法 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09J151/085—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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Abstract
本发明属于胶粘剂技术领域,具体涉及一种有机硅改性丙烯酸乳液粘合剂,按重量份数,包括如下配方组成:丙烯酸甲酯20‑40份、丙烯酸异辛酯35‑60份、丙烯酸3‑8、醋酸乙烯酯7‑10份、十二烷基硫酸钠2‑5份、烷基酚聚氧乙烯醚3‑5份、过硫酸钾0.2‑2份、亚硫酸氢钠0.1‑1份、碳酸氢钠0.2‑3份、改性纳米二氧化硅5‑12份、去离子水80‑150份、多乙烯基硅氧烷笼型倍半硅氧烷2‑5份、氨水0.5‑3份;该胶粘剂具有较强的力学性能和耐湿性能。
Description
技术领域
本发明属于粘合剂技术领域,具体涉及一种有机硅改性丙烯酸乳液粘合剂及其制备方法。
背景技术
聚丙烯酸酯是一类具有多种性能、用途广泛的聚合物,其乳液一般是以丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯为主要单体,与甲基丙烯酸酯单体、苯乙烯、丙烯腈等共聚物形成的乳液。丙烯酸酯乳液胶粘剂具有价格便宜、毒性小、工艺性好、单体选择性广、粘度变化范围宽、流变性可控性强等诸多优点。产品种类有包装胶带、电气绝缘胶带、表面保护胶带、双面胶带、医用胶带、商标纸和压敏标签等,已广泛应用于木材加工、材料包装、织物整理、压敏胶、建筑用胶以及纸张制造等各行业。
通过对聚合物的结构或聚合方法加以改进,可得到性能更加优异的改性丙烯酸酯胶粘剂。近年来,一些研究者通过在聚合过程中加入改性剂等合成丙烯酸胶粘剂。如专利CN101735753A公开了一种特殊结构的丙烯酸酯乳液粘合剂及其制备方法。配比包括(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸、丙烯酰胺、低温自交联反应单体、混合乳化剂(脂肪醇聚氧乙稀醚、十二烷基硫酸钠),过硫酸铵引发剂、低温自交联促进剂、去离子水等组成。然而现有丙烯酸酯胶粘剂胶膜的耐水性、耐候性、耐湿热性能等还不够理想,急需开展丙烯酸酯结构的改性或聚合工艺研究,提升丙烯酸酯粘合剂的综合性能。
发明内容
为解决现有技术的不足,本发明提供一种有机硅改性丙烯酸乳液粘合剂及其制备方法,具体研究方案如下:
一种有机硅改性丙烯酸乳液粘合剂,按重量份数,包括如下配方组成:丙烯酸甲酯20-40份、丙烯酸异辛酯35-60份、丙烯酸3-8、醋酸乙烯酯7-10份、十二烷基硫酸钠2-5份、烷基酚聚氧乙烯醚3-5份、过硫酸钾0.2-2份、亚硫酸氢钠0.1-1份、碳酸氢钠0.2-3份、改性纳米二氧化硅5-12份、去离子水80-150份、多乙烯基硅氧烷笼型倍半硅氧烷2-5份、氨水0.5-3份。
所述多乙烯基硅氧烷有机倍半硅氧烷的结构式如下:
该结构通过对笼型倍半硅氧烷(POSS)进行多乙烯基硅氧烷(DVS)的接枝改性形成多乙烯基硅氧烷笼型倍半硅氧烷(DVS-POSS)树脂。由于在有机分子中引入了多个不饱和双键参与共聚合反应,形成网络结构,提高力学性能。同时,该结构属于有机/无机杂化材料,制成的胶膜还具有较优的耐湿热性能。
所述丙烯酸甲酯、丙烯酸异辛酯、丙烯酸、醋酸乙烯酯为聚合单体,通过多种单体的组合可以形成共聚结构,提高其综合性能;
所述十二烷基硫酸钠为阴离子型乳化剂,为液体产品,氯磺酸含量小于0.5%,氯磺酸具有一定的氧化性,当其含量较高时制备出的乳液长期放置会变色,降低了使用寿命。
所述烷基酚聚氧乙烯醚为非离子型乳化剂,优选壬基酚聚氧乙烯醚系列,包括OP-10、OP-15、OP-20、OP-25、OP-30、OP-35中的至少一种;
进一步的,所述阴离子型乳化剂与非离子型乳化剂复合使用,其中阴离子型乳化剂主要与无机添加剂相互作用,非离子型乳化剂主要与聚合单体相互作用,两者相互协同提高乳化效果。
所述改性纳米二氧化硅由纳米二氧化硅与乙烯基硅氧烷按一定质量比混合后,充分研磨形成的表面含有一层双键的二氧化硅纳米粒子。纳米粒子在配方中主要起到增加强度,提高耐热性能的作用;
所述过硫酸钾为引发剂,所述亚硫酸氢钠主要起到中和过量过硫酸钾的作用,碳酸氢钠起到调节pH值的作用,氨水起到调节pH值和增稠的作用;
所述DVS-POSS树脂的制备方法,包括如下步骤:
(1)氮气保护下,向三口烧瓶中依次加入三氯化铁25g、浓盐酸10mL、甲醇20mL、甲苯25mL和正己烷175mL,50-60℃下,充分搅拌后将溶有三氯硅烷(10mL)的正己烷(75mL)溶液缓慢滴加到混合液中,滴加完毕后继续搅拌反应1-2h,反应完毕后加入,分离正己烷层,过滤除去正己烷层中的少量固体,滤液干燥结晶得白色含八氢基的笼形倍半硅氧烷(T8H8)。
(2)将T8H8与DVS按质量比1:3.5加入无水四氢呋喃中,然后滴加一定量的Pt催化剂,70℃回流反应12h,冷却至室温,加入三苯基磷继续搅拌反应1h后过滤除去Pt催化剂,滤液旋蒸除溶剂得无色粘稠液体。
本发明还提供所述有机硅改性丙烯酸乳液粘合剂的制备方法,具体制备步骤如下:
(1)二氧化硅粒子的表面改性:将纳米二氧化硅粒子用5%的稀硝酸浸泡24h,然后在120℃下干燥2h后与乙烯基硅氧烷按质量比充分混合,研磨30-50min后得表面覆盖有含双键的硅氧烷的纳米SiO2;
(2)在氮气气氛下,将部分去离子水加入反应釜中,然后加入引发剂,改性纳米二氧化硅、十二烷基硫酸钠,部分碳酸氢钠,调节pH值7-8,逐步升高温度至35℃,持续搅拌;
(3)将剩余去离子水,全部多乙烯基硅氧烷有机倍半硅氧烷、丙烯酸聚合单体,烷基酚聚氧乙烯醚,剩余碳酸氢钠加入搅拌釜中充分搅拌形成均一乳状液;
(4)将步骤(3)所得乳状液逐滴加入到步骤(2)反应釜中,滴加完毕后35℃下保温反应2h,然后升高温度至45-50℃再保温反应2h,最后升高温度至60-70℃,继续反应3-5h,反应完毕后降温至30-40℃;
(5)向步骤(4)所得反应液中缓慢滴加还原剂,滴加完毕后,保温反应30-40min,然后加入氨水调节pH值,增稠,降温得有机硅改性的丙烯酸粘合剂。
本发明的有益效果在于:(1)有机硅改性的丙烯酸乳液胶膜具有较高的力学性能和耐湿热性能;(2)改性二氧化硅纳米粒子进一步提高了胶膜的力学性能和耐湿性;(3)本发明所述丙烯酸粘合剂的制备工艺简单,可操作性强。
具体实施方式
下面以实施例对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
需要指出的是,本发明实施例所用二氧化硅粒子为改性纳米二氧化硅,具体改性方法为:将纳米二氧化硅粒子用5%的稀硝酸浸泡24h,然后在120℃下干燥2h后与乙烯基硅氧烷按质量比充分混合,研磨30-50min后得表面覆盖有含双键的硅氧烷的纳米SiO2;稀硝酸浸泡的目的在于除去表面的无机杂质,使颗粒表面更为粗糙有利于乙烯基硅氧烷的吸附。
本发明实施例所用多乙烯基硅氧烷有机倍半硅氧烷的结构式如下:
该结构通过对笼型倍半硅氧烷(POSS)进行多乙烯基硅氧烷(DVS)的接枝改性形成多乙烯基硅氧烷笼型倍半硅氧烷(DVS-POSS)树脂。由于在有机分子中引入了多个不饱和双键参与共聚合反应,形成网络结构,提高力学性能。同时,该结构属于有机/无机杂化材料,制成的胶膜还具有较优的耐湿热性能。
所述DVS-POSS树脂的制备方法,包括如下步骤:
(1)氮气保护下,向三口烧瓶中依次加入三氯化铁25g、浓盐酸10mL、甲醇20mL、甲苯25mL和正己烷175mL,50-60℃下,充分搅拌后将溶有三氯硅烷(10mL)的正己烷(75mL)溶液缓慢滴加到混合液中,滴加完毕后继续搅拌反应1-2h,反应完毕后加入,分离正己烷层,过滤除去正己烷层中的少量固体,滤液干燥结晶得白色含八氢基的笼形倍半硅氧烷(T8H8)。
(2)将T8H8与DVS按质量比1:3.5加入无水四氢呋喃中,然后滴加一定量的Pt催化剂,70℃回流反应12h,冷却至室温,加入三苯基磷继续搅拌反应1h后过滤除去Pt催化剂,滤液旋蒸除溶剂得无色粘稠液体。
实施例1.
本实施例提供一种有机硅改性丙烯酸乳液粘合剂,按重量份数,包括如下配方组成:丙烯酸甲酯40份、丙烯酸异辛酯45份、丙烯酸5份、醋酸乙烯酯8份、十二烷基硫酸钠3份、OP-103份、过硫酸钾0.3份、亚硫酸氢钠0.2份、碳酸氢钠0.2份、改性纳米二氧化硅8份、去离子水100份、多乙烯基硅氧烷笼型倍半硅氧烷3份、氨水1份。
本发明还提供所述有机硅改性丙烯酸乳液粘合剂的制备方法,具体制备步骤如下:
(1)在氮气气氛下,将300g去离子水加入反应釜中,然后加入引发剂过硫酸钾3g,改性纳米二氧化硅80g、十二烷基硫酸钠30g,碳酸氢钠0.5g,逐步升高温度至35℃,持续搅拌;
(2)将剩余去离子水700g,乙烯基硅氧烷有机倍半硅氧烷30g、丙烯酸甲酯400g、丙烯酸异辛酯450g、丙烯酸50g、醋酸乙烯酯80g、OP-10 30g、剩余碳酸氢钠1.5g加入搅拌釜中充分搅拌形成均相乳状液;
(3)将步骤(2)所得乳状液逐滴加入到步骤(1)反应釜中,滴加完毕后35℃下保温反应2h,然后升高温度至45-50℃再保温反应2h,最后升高温度至60-70℃,继续反应3-5h,反应完毕后降温至30-40℃;
(4)向步骤(3)所得反应液中缓慢滴加亚硫酸氢钠水溶液(2g亚硫酸氢钠+10g水),滴加完毕后,保温反应30-40min,然后加入氨水10g调节pH值至8-9,增稠,降温得有机硅改性的丙烯酸粘合剂。
实施例2.
本实施例提供一种有机硅改性丙烯酸乳液粘合剂,按重量份数,包括如下配方组成:丙烯酸甲酯30份、丙烯酸异辛酯50份、丙烯酸4份、醋酸乙烯酯9份、十二烷基硫酸钠4份、OP-153份、过硫酸钾1份、亚硫酸氢钠0.8份、碳酸氢钠1份、改性纳米二氧化硅10份、去离子水120份、多乙烯基硅氧烷笼型倍半硅氧烷4份,氨水2份。
本发明还提供所述有机硅改性丙烯酸乳液粘合剂的制备方法,具体制备步骤如下:
(1)在氮气气氛下,将400g去离子水加入反应釜中,然后加入引发剂过硫酸钾10g,改性纳米二氧化硅100g、十二烷基硫酸钠40g,碳酸氢钠3g,逐步升高温度至35℃,持续搅拌;
(2)将剩余去离子水800g,乙烯基硅氧烷有机倍半硅氧烷40g、丙烯酸甲酯300g、丙烯酸异辛酯500g、丙烯酸40g、醋酸乙烯酯90g,OP-15 30g,剩余碳酸氢钠7g加入搅拌釜中充分搅拌形成均相乳状液;
(3)将步骤(2)所得乳状液逐滴加入到步骤(1)反应釜中,滴加完毕后35℃下保温反应2h,然后升高温度至45-50℃再保温反应2h,最后升高温度至60-70℃,继续反应3-5h,反应完毕后降温至30-40℃;
(4)向步骤(3)所得反应液中缓慢滴加亚硫酸氢钠水溶液(8g亚硫酸氢钠+40g水),滴加完毕后,保温反应30-40min,然后加入氨水20g调节pH值至8-9,增稠,降温得有机硅改性的丙烯酸粘合剂。
对比例
为进一步验证本发明的技术效果,以现有专利技术CN201710300161.6制备类似粘合剂,所述粘合剂包括甲基丙烯酸甲酯10份、丙烯酸7份、丙烯酸缩水甘油酯2份、八甲基丙烯酸甲酯基倍半硅氧烷12份、纳米二氧化硅粒子4份、有机化纳米氢氧化锌3份、马来酸硅聚氧乙烯醚单酯羧酸盐7份、2-丙烯酰胺基-2-甲基丙磺酸3份、丙烯酸辛酯8份、引发剂1份、去离子水60份。
对上述实施例和对比例制备的粘合剂分别测试其剥离强度和吸水性,其中剥离强度按照GB/T 2790-1995,采用微机控制电子拉力试验机测定,将胶粘剂涂布在聚乙烯膜上干燥后测定;吸水性测试是将干燥后的胶膜浸泡在水中,浸泡48h,测试吸水率;具体结果如表1所示,可见本发明制备的粘合剂的的耐湿性能和力学性能均有显著提高。
表1.丙烯酸乳液粘合剂性能参数
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
2.根据权利要求1所述一种有机硅改性丙烯酸乳液粘合剂,其特征在于,所述十二烷基硫酸钠为阴离子型乳化剂,为液体产品,氯磺酸含量小于0.5%。
3.根据权利要求1所述一种有机硅改性丙烯酸乳液粘合剂,其特征在于,所述烷基酚聚氧乙烯醚为非离子型乳化剂,包括OP-10、OP-15、OP-20、OP-25、OP-30、OP-35中的至少一种。
4.根据权利要求1所述一种有机硅改性丙烯酸乳液粘合剂,其特征在于,所述改性纳米二氧化硅的制备方法为:将纳米二氧化硅粒子用5%的稀硝酸浸泡24h,然后在120℃下干燥2h后与乙烯基硅氧烷按质量比充分混合,研磨30-50min后得表面覆盖有含双键的硅氧烷的纳米SiO2。
5.根据权利要求1所述一种有机硅改性丙烯酸乳液粘合剂,其特征在于,所述多乙烯基硅氧烷有机倍半硅氧烷的制备方法,包括如下步骤:
(1)氮气保护下,向三口烧瓶中依次加入三氯化铁25g、浓盐酸10mL、甲醇20mL、甲苯25mL和正己烷175mL,50-60℃下,充分搅拌后将溶有三氯硅烷10mL的正己烷75mL溶液缓慢滴加到混合液中,滴加完毕后继续搅拌反应1-2h,反应完毕后,分离正己烷层,过滤除去正己烷层中的少量固体,滤液干燥结晶得白色含八氢基的有机倍半硅氧烷T8H8;
(2)将T8H8与DVS按质量比1:3.5加入无水四氢呋喃中,然后滴加一定量的Pt催化剂,70℃回流反应12h,冷却至室温,加入三苯基磷继续搅拌反应1h后过滤除去Pt催化剂,滤液旋蒸除溶剂得无色粘稠液体。
6.权利要求1所述的一种有机硅改性丙烯酸乳液粘合剂的制备方法,具体制备步骤如下:
(1)二氧化硅粒子的表面改性:将纳米二氧化硅粒子用5%的稀硝酸浸泡24h,然后在120℃下干燥2h后与乙烯基硅氧烷按质量比充分混合,研磨30-50min后得表面覆盖有含双键的硅氧烷的纳米SiO2;
(2)在氮气气氛下,将部分去离子水加入反应釜中,然后加入过硫酸钾,改性纳米二氧化硅、十二烷基硫酸钠,部分碳酸氢钠,调节pH值7-8,逐步升高温度至35℃,持续搅拌;
(3)将剩余去离子水,全部多乙烯基硅氧烷有机倍半硅氧烷、丙烯酸甲酯、丙烯酸异辛酯、丙烯酸、醋酸乙烯酯、烷基酚聚氧乙烯醚,剩余碳酸氢钠加入搅拌釜中充分搅拌形成均相乳状液;
(4)将步骤(3)所得乳状液逐滴加入到步骤(2)反应釜中,滴加完毕后35℃下保温反应2h,然后升高温度至45-50℃再保温反应2h,最后升高温度至60-70℃,继续反应3-5h,反应完毕后降温至30-40℃;
(5)向步骤(4)所得反应液中缓慢滴加亚硫酸氢钠水溶液,滴加完毕后,保温反应30-40min,然后加入氨水调节pH值,增稠,降温得有机硅改性的丙烯酸粘合剂。
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