CN107446530B - 一种水性丙烯酸酯粉末压敏胶及其制备方法 - Google Patents
一种水性丙烯酸酯粉末压敏胶及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种水性丙烯酸酯粉末压敏胶及其制备方法;该制备方法先将乳化剂加入水中,再加入软单体、硬单体、功能性单体混合均匀,搅拌形成预乳液。然后将预乳液分成两部分,首先在第一部分预乳液中加入引发剂,在缓冲溶液中回流反应,维持70~83℃保温;然后滴加另一部分预乳液,同时引发剂;结束后,83~90℃保温1~2h降温出料;在所得的压敏胶中加入压敏胶5‐20wt%的疏水性SiO2,搅拌,形成SiO2包覆的丙烯酸酯压敏胶微球;将产物置于‐20℃~‐10℃下冷冻,冷冻干燥,得到丙烯酸酯粉末压敏胶。本发明对水性丙烯酸酯压敏胶制备方法进行改进,制备方法简单,获得低成本、水性丙烯酸酯粉末压敏胶。
Description
技术领域
本发明涉及胶粘剂领域,特别是涉及一种水性丙烯酸酯粉末压敏胶及其制备方法。
背景技术
水性丙烯酸酯压敏胶耐光、耐老化性较好,无毒无污染,成本低廉,而且具有优良的压敏性和粘接性,性能稳定,因此它在很多领域得到了广泛的应用。其用量占整个压敏胶65%以上。但是由于水性丙烯酸酯压敏胶以水作为溶剂,在低温条件下,粘接性能降低,限制了水性丙烯酸酯压敏胶在低温条件下的使用。
发明内容
本发明的目的在于克服现有技术的缺陷,对水性丙烯酸酯压敏胶制备方法进行改进,获得低成本、水性丙烯酸酯粉末压敏胶的制备方法。
为了实现上述发明目的,本发明采用了以下技术:
一种水性丙烯酸酯粉末胶的制备方法,包括如下步骤:
1)将乳化剂加入水中,再加入软单体、硬单体和功能性单体混合均匀,搅拌形成预乳液;
所述乳化剂为十二烷基硫酸钠和OP-10中的一种或者两种复合;所述软单体为丙烯酸月桂酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸正丙酯和丙烯酸-2-羟基乙酯中的一种或多种;所述硬单体为甲基丙烯酸甲酯、醋酸乙烯酯、苯乙烯和丙烯腈中的一种或多种;所述功能性单体为衣康酸、丙烯酸、甲基丙烯酸、丙烯酰胺、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种;
2)将预乳液分成两部分,第一部分预乳液为预乳液质量的20%-40%,另一部分预乳液为预乳液质量的60%-80%;首先在第一部分预乳液中加入单体总质量的0.1%-0.5%的引发剂,在缓冲溶液中回流反应,维持70~83℃保温;然后滴加另一部分预乳液,同时滴加单体总质量的0.1%-0.6%引发剂;所述引发剂为过硫酸铵、过硫酸钾、亚硫酸氢钠和偶氮二异丁腈的一种或两种以上;
3)滴加结束后,83~90℃保温1~2h降温出料;
4)在步骤3)所得的压敏胶中加入压敏胶5-20wt%的疏水性SiO2,搅拌,形成SiO2包覆的丙烯酸酯压敏胶微球;
5)将产物置于-20℃~-10℃下冷冻,冷冻干燥,得到丙烯酸酯粉末压敏胶。
为进一步实现本发明目的,优选地,步骤(1)中,所述软单体添加量为单体总质量的60~83%;所述硬单体添加量为单体总质量的10~15%;所述功能性单体添加量为单体总量的1~4%。
优选地,步骤(2)中所述缓冲溶液为0.5wt%-0.7wt%的NaHCO3水溶液。
优选地,步骤1)和4)中搅拌的速率为100~300r/min。
优选地,所述维持70~83℃保温的时间为20-50min。
优选地,所述搅拌形成预乳液是磁力搅拌30-60min形成预乳液。
优选地,所述将产物置于-20℃~-10℃下冷冻的时间为12~48h。
优选地,所述冷冻干燥是在冷冻干燥器中-50℃~-30℃下冷冻干燥12~48h。
优选地,步骤4)所述搅拌为磁力搅拌,搅拌的时间为2-4h;步骤2)滴加总时间为1~5h。
一种由上述制备方法制备得到的水性丙烯酸酯粉末压敏胶,该压敏胶是粉末状,初粘力为14-18#,剥离力为9.6-13.5N/25mm,持粘力为123-347h;吸水率为1.5%-15.8%,固含量为63%-72%。
与现有技术相比,本发明有如下优点:
1)本发明首次反应后期采用疏水性SiO2包覆丙烯酸酯压敏胶形成微球。利用疏水的SiO2包覆丙烯酸酯压敏胶之后,可制成与普通基底不浸润的微球,微球的静态有效表面张力及其动态特性可通过SiO2的疏水性进行调控,从而得到丙烯酸酯粉末压敏胶。首次创新了制备固体粉末压敏胶的方法,得到高固含、高压敏性、低吸水率的粉末胶,可以用于精密设备的密封。
2)本发明最后采用冷冻法,将疏水性SiO2包覆的丙烯酸酯压敏胶微球经过冷冻形成固体胶乳,在低温高真空的条件下使样品中的水分由冰直接升华达到干燥的目的;在干燥的过程中不受表面张力的作用,样品不变形,保持原来的化学组成和胶体性质,同时疏水性SiO2与压敏胶中高聚物共价键结合,保证了产品的粘接性能。
3)本发明的水性丙烯酸酯压敏胶乳液固含量高达63~72%,乳化剂在体系中含量较低,提高了耐水性能。
4)本发明的丙烯酸酯粉末压敏胶,其粉末既保证了粘接性能,也可以在精密仪器条件下使用,生产成本低,操作简单,应用前景广泛。
具体实施方式
为更好的理解本发明,下面结合实施例对本发明作进一步的描述,但本发明的实施方式不限于此。
实施例1(对比例)
向锥形瓶中加入1.5g十二烷基硫酸钠,再加入35g去离子水磁力搅拌至乳化剂溶解,依次加入丙烯酸丁酯80g、丙烯酸异辛酯80g、丙烯酸羟乙酯5g、醋酸乙烯酯8g、甲基丙烯酸甲酯20g、甲基丙烯酸羟乙酯2g,搅拌(搅拌速度300r/min)30min形成预乳液。
向装有温度计、冷凝管、搅拌装置的500mL四口烧瓶中加入0.3g NaHCO3,再加入去离子水40mL,反应温度78℃,搅拌至溶解;将预乳液分成两部分,第一部分预乳液(占总乳液的20wt%)和7g过硫酸铵水溶液同时缓慢加入四口烧瓶,30min滴完后保温30min;再同时滴加剩余80%的预乳液和18g过硫酸铵水溶液,3.5h滴加完毕。反应温度升至85℃,在搅拌条件下保温1h,得到水性丙烯酸酯压敏胶。
在得到的压敏胶中加入压敏胶总量5wt%的疏水性SiO2(上海展云化工有限公司),磁力搅拌2h,形成SiO2包覆的丙烯酸酯压敏胶微球。
将得到的产品在-12℃冷冻24h,迅速置于冷冻干燥器在-38℃干燥24h,得水性丙烯酸酯粉末压敏胶。
实施例2
向锥形瓶中加入1.5g十二烷基硫酸钠,再加入45g去离子水磁力搅拌至乳化剂溶解,依次加入丙烯酸丁酯80g、丙烯酸异辛酯80g、丙烯酸羟乙酯5g、醋酸乙烯酯8g、甲基丙烯酸甲酯20g、甲基丙烯酸羟乙酯2g,搅拌(搅拌速度300r/min)30min形成预乳液。
向装有温度计、冷凝管、搅拌装置的500mL四口烧瓶中加入0.3gNaHCO3,再加入去离子水40mL,反应温度78℃,搅拌至溶解;将预乳液分成两部分,第一部分预乳液(总乳液的25wt%)和7g过硫酸铵水溶液同时缓慢加入四口烧瓶,30min滴完后保温30min;再同时滴加剩余75%预乳液和18g过硫酸铵水溶液,3.5h滴加完毕。
反应温度升至85℃,在搅拌条件下保温1h,得到水性丙烯酸酯压敏胶。
在得到的压敏胶中加入压敏胶总量10wt%的疏水性SiO2(上海展云化工有限公司),磁力搅拌2h,形成SiO2包覆的丙烯酸酯压敏胶微球。
将得到的产品在-14℃冷冻26h,迅速置于冷冻干燥器在-40℃干燥26h,得水性丙烯酸酯粉末压敏胶。
实施例3
向锥形瓶中加入1.5g十二烷基硫酸钠,再加入55g去离子水磁力搅拌至乳化剂溶解,依次加入丙烯酸丁酯80g、丙烯酸异辛酯80g、丙烯酸羟乙酯5g、醋酸乙烯酯8g、甲基丙烯酸甲酯20g、甲基丙烯酸羟乙酯2g,搅拌(搅拌速度300r/min)30min形成预乳液。
向装有温度计、冷凝管、搅拌装置的500mL四口烧瓶中加入0.3gNaHCO3,再加入去离子水40mL,反应温度78℃,搅拌至溶解;将预乳液分成两部分,第一部分预乳液(占总乳液的30wt%)和7g过硫酸铵水溶液同时滴加,30min滴完后保温30min;再同时滴加剩余预70%乳液和18g过硫酸铵水溶液,3.5h滴加完毕。
反应温度升至85℃,在搅拌条件下保温1h,得到水性丙烯酸酯压敏胶。
在得到的压敏胶中加入压敏胶总量15wt%的疏水性SiO2(上海展云化工有限公司),磁力搅拌2h,形成SiO2包覆的丙烯酸酯压敏胶微球。
将得到的产品在-16℃冷冻28h,迅速置于冷冻干燥器在-42℃干燥24h,得水性丙烯酸酯粉末胶。
实施例4
向锥形瓶中加入1.5g十二烷基硫酸钠,再加入65g去离子水磁力搅拌至乳化剂溶解,依次加入丙烯酸丁酯80g、丙烯酸异辛酯80g、丙烯酸羟乙酯5g、醋酸乙烯酯8g、甲基丙烯酸甲酯20g、甲基丙烯酸羟乙酯2g,搅拌(搅拌速度300r/min)30min形成预乳液。
向装有温度计、冷凝管、搅拌装置的500mL四口烧瓶中加入0.3gNaHCO3,再加入去离子水40mL,反应温度78℃,搅拌至溶解;将预乳液分成两部分,第一部分预乳液(总乳液的35wt%)和7g过硫酸铵水溶液同时滴加,30min滴完后保温30min;再同时滴加剩余65%预乳液和18g过硫酸铵水溶液,3.5h滴加完毕。
反应温度升至85℃,在搅拌条件下保温1h,得到水性丙烯酸酯压敏胶。
在得到的压敏胶中加入压敏胶总量20wt%的疏水性SiO2(上海展云化工有限公司),磁力搅拌2h,形成SiO2包覆的丙烯酸酯压敏胶微球。
将得到的产品在-18℃下冷冻36h,迅速置于冷冻干燥器在-44℃下干燥30h,得水性丙烯酸酯粉末压敏胶。
实施例5
向锥形瓶中加入1.5g十二烷基硫酸钠,再加入75g去离子水磁力搅拌至乳化剂溶解,依次加入丙烯酸丁酯80g、丙烯酸异辛酯80g、丙烯酸羟乙酯5g、醋酸乙烯酯8g、甲基丙烯酸甲酯20g、甲基丙烯酸羟乙酯2g,搅拌(搅拌速度300r/min)30min形成预乳液。
向装有温度计、冷凝管、搅拌装置的500mL四口烧瓶中加入0.3gNaHCO3,再加入去离子水40mL,反应温度78℃,搅拌至溶解;将预乳液分成两部分,第一部分预乳液(占预乳液的40wt%)和7g过硫酸铵水溶液同时滴加,30min滴完后保温30min;再同时滴加剩余60%预乳液和18g过硫酸铵水溶液,3.5h滴加完毕。
反应温度升至85℃,在搅拌条件下保温1h,得到水性丙烯酸酯压敏胶。
在得到的压敏胶中加入压敏胶总量25wt%的疏水性SiO2(上海展云化工有限公司),磁力搅拌2h,形成SiO2包覆的丙烯酸酯压敏胶微球。
将得到的产品在-20℃冷冻24h,迅速置于冷冻干燥器在-46℃干燥32h,得水性丙烯酸酯粉末压敏胶。
对上述实施例所得产品进行性能测试,结果如表1所示。
表1产品进行性能测试
表1中固含量按下式计算:
X=m1/m×100%
式中:X-固含量(wt%);m1-单体总质量(g);m-乳液总质量(g)
吸水率按下式计算:
A=(a2-a1)/a1×100%
式中:A-吸水率(wt%);a1-粉末胶吸水前的质量(g);a2-粉末胶吸水后的质量(g);
初粘力测试:根据GB/T 4852-2002标准,测胶粘剂初粘力;
剥离力测试:根据GB/T 2792-1998标准,测胶粘剂剥离力;
持粘力测试:根据GB/T 485-1998标准,测胶粘剂持粘力。
本发明首次反应后期采用疏水性SiO2包覆丙烯酸酯压敏胶形成微球。利用疏水的SiO2包覆丙烯酸酯压敏胶之后,可制成与普通基底不浸润的微球,微球的静态有效表面张力及其动态特性可通过SiO2的疏水性进行调控,从而得到丙烯酸酯粉末压敏胶。
本发明最后采用冷冻法,将疏水性SiO2包覆的丙烯酸酯压敏胶微球经过冷冻形成固体胶乳,在低温高真空的条件下使样品中的水分由冰直接升华达到干燥的目的;在干燥的过程中不受表面张力的作用,样品不变形,既保持原来的化学组成和胶体性质,又保证了产品的粘接性能。如表1,与原水性丙烯酸酯压敏胶(实施例1作为对比例)相比,实施例2-5中随着疏水性SiO2含量的增加,粉末胶的初粘力、剥离力和持粘力都提高,耐水性(吸水率)得到很大的提高,包括初粘力:14-18#,剥离力:9.6-13.5N/25mm,持粘力:123-347h,吸水率:1.5%-15.8%,以及较高的固含量:63%-72%。但是当SiO2含量为25%时,由于SiO2含量过多,造成微球包覆的压敏胶过少,粉末胶的三大力学性能降低。
本发明的水性丙烯酸酯压敏胶乳液固含量高达63~69%,乳化剂在体系中含量较低,提高了耐水性能。
本发明的丙烯酸酯粉末压敏胶,其粉末既保证了粘接性能(初粘力、剥离力、初粘力),也可以在精密仪器条件下使用,生产成本低,操作简单,应用前景广泛。
Claims (10)
1.一种水性丙烯酸酯粉末压敏 胶的制备方法,其特征在于包括如下步骤:
1)将乳化剂加入水中,再加入软单体、硬单体和功能性单体混合均匀,搅拌形成预乳液;
所述乳化剂为十二烷基硫酸钠;所述软单体为丙烯酸月桂酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸正丙酯和丙烯酸-2-羟基乙酯中的一种或多种;所述硬单体为甲基丙烯酸甲酯、醋酸乙烯酯、苯乙烯和丙烯腈中的一种或多种;所述功能性单体为衣康酸、丙烯酸、甲基丙烯酸、丙烯酰胺、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种;
2)将预乳液分成两部分,第一部分预乳液为预乳液质量的20%-40%,另一部分预乳液为预乳液质量的60%-80%;首先在第一部分预乳液中加入单体总质量的0.1%-0.5%的引发剂,在缓冲溶液中回流反应,维持70-83℃保温,然后滴加另一部分预乳液,同时滴加单体总质量的0.1%-0.6%引发剂,所述引发剂为过硫酸铵、过硫酸钾、亚硫酸氢钠和偶氮二异丁腈的一种或两种以上;
3)滴加结束后,83-90℃保温1-2h降温出料;
4)在步骤3)所得的压敏胶中加入压敏胶5-20wt%的疏水性SiO2包覆的丙烯酸酯压敏胶微球;
5)将产物置于-20℃~-10℃下冷冻,冷冻干燥,得到丙烯酸酯粉末压敏胶。
2.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,步骤(1)中所述软单体添加量为单体总质量的60-83%;所述硬单体添加量为单体总质量的10-15%;所述功能性单体添加量为单体总量的1-4%。
3.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,步骤(2)所述缓冲溶液为0.5wt%-0.7wt%的NaHCO3水溶液。
4.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,步骤(1)和(4)中搅拌的速率为100-300r/min。
5.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,所述维持70-83℃保温的时间为20-50min。
6.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,所述搅拌形成预乳液是磁力搅拌30-60min形成预乳液。
7.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,所述将产物置于-20℃~-10℃下冷冻的时间为12-48h。
8.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,所述冷冻干燥是在冷冻干燥器中-50℃~-30℃下冷冻干燥12-48h。
9.根据权利要求1所述的水性丙烯酸酯 粉末压敏胶的制备方法,其特征在于,步骤(4)所述搅拌为磁力搅拌,搅拌的时间为2-4h;步骤(2)滴加总时间为1-5h。
10.一种由权利要求1-9任一项所述制备方法制备得到的水性丙烯酸酯粉末压敏胶,该压敏胶是粉末状,初粘力为14-18#,剥离力为9.6-13.5N/25mm,持粘力为123-347h;吸水率为1.5%-15.8%。
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