CN111253779B - 颗粒稳泡剂及其制备方法和应用 - Google Patents
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Abstract
本发明公开一种颗粒稳泡剂及其制备方法和应用。该颗粒稳泡剂包括粒径为0.1~5μm的亲水固体颗粒,其表面通过物理吸附作用修饰有疏水分子链。其制备方法为:先将亲水固体颗粒加入乙醇‑水溶液中,配成固体颗粒悬浮液;然后加入含疏水分子链的修饰剂,搅拌,使疏水分子链修饰到亲水固体颗粒表面;最后将所得产物抽滤分离,固相物料干燥,即得颗粒稳泡剂。该颗粒稳泡剂可有效提高泡沫稳定性,而且,稳泡剂本身的稳定性较好,制备方便,没有刺激性气味更加绿色环保;该颗粒稳泡剂用于聚氨酯发泡涂层中,一方面可替代传统的硬脂酸铵稳泡剂,另一方面,固体颗粒也可充当聚氨酯发泡涂层的填料或功能助剂,提升涂层性能的同时降低了生产成本。
Description
技术领域
本发明涉及一种稳泡剂及其应用,特别涉及一种颗粒稳泡剂及其制备方法和用作聚氨酯发泡涂层稳泡剂的应用,属于化工助剂技术领域。
背景技术
水性聚氨酯涂层因在生产过程中对人体无害,现已广泛用于合成革、广告布等发泡涂层的制备中,目前生产中添加的稳泡剂为硬脂酸铵乳液,该稳泡剂制备过程中需要大量的氨水,氨水极易挥发,所以硬脂酸铵的生产及使用过程都会对环境造成污染。且硬脂酸铵乳液的稳定性较差,长时间放置后会出现团聚、增稠的现象,不利于使用。此外,硬脂酸铵的耐热性差,在发泡涂层烘干过程中易分解出硬脂酸,影响产品质量。
聚氨酯涂层制备过程中常常会加入固体颗粒,以提高涂层的机械度、遮光率等性能。
基于此,发明人形成了本发明技术。
发明内容
发明目的:针对现有聚氨酯发泡涂层使用的稳泡剂存在的问题,本发明提供一种颗粒稳泡剂及其制备方法,还提供了一种该颗粒稳泡剂用作聚氨酯发泡涂层稳泡剂的应用。
技术方案:本发明所述的颗粒稳泡剂包括粒径为0.1~5μm的亲水固体颗粒,该亲水固体颗粒表面通过物理吸附作用修饰有疏水分子链。
亲水固体颗粒可为钛白粉、碳酸钙、二氧化硅、高岭土、膨润土等中的至少一种。
疏水分子链可由含疏水分子链的修饰剂提供,优选的,亲水固体颗粒表面吸附有含疏水分子链的修饰剂,该含疏水分子链的修饰剂的量可为亲水固体颗粒质量的5~20%。其中,含疏水分子链的修饰剂可为十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、十六烷基硫酸钠、十八烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、脂肪酸甲酯磺酸钠、失水山梨醇单硬脂酸酯、失水山梨醇单油酯、失水山梨醇单棕榈酸酯、失水山梨醇单月桂酸酯、脂肪醇聚氧乙烯醚、二甲基聚硅氧烷聚醚、烷基糖苷、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵中的至少一种。
本发明所述的颗粒稳泡剂的制备方法,包括如下步骤:
(1)将亲水固体颗粒加入乙醇-水溶液中,配成固体颗粒悬浮液;
(2)将含疏水分子链的修饰剂加入上述固体颗粒悬浮液中,搅拌,使疏水分子链修饰到亲水固体颗粒表面;
(3)将步骤(2)所得产物抽滤分离,固相物料干燥,即得颗粒稳泡剂。
步骤(1)中,乙醇-水溶液的浓度优选为10~50%。
较优的,步骤(2)中,搅拌温度为5~60℃,搅拌时间为2~8h。
步骤(3)中,干燥温度优选为40~60℃。
本发明所述的颗粒稳泡剂的应用,是将该颗粒稳泡剂用作聚氨酯发泡涂层的稳泡剂。以聚氨酯发泡涂层中的聚氨酯乳液的量为标准,颗粒稳泡剂与聚氨酯乳液的质量比优选为6~10:100。
发明原理:本发明的颗粒稳泡剂为两亲性颗粒,生成泡沫的过程中具有两亲性的细小颗粒吸附在气液相界面上,形成一层致密的粒子膜,防止气泡之间的聚并和歧化,从而大幅提高泡沫稳定性。
有益效果:与现有技术相比,本发明的优点在于:(1)本发明的颗粒稳泡剂可有效提高泡沫稳定性,而且,稳泡剂本身的稳定性较好,有效的解决了皂类稳泡剂高温烘干后表面有白色固体析出的问题;另外,该固体颗粒稳泡剂制备方便,没有刺激性气味更加绿色环保;(2)将本发明的颗粒稳泡剂用于聚氨酯发泡涂层中,一方面可替代传统的硬脂酸铵稳泡剂,另一方面,固体颗粒也可充当聚氨酯发泡涂层的填料或功能助剂,有效减少了填料、功能助剂的外加量,提升了涂层的机械强度,同时大大降低了生产成本。
具体实施方式
下面对本发明的技术方案作进一步说明。
本发明的颗粒稳泡剂包括亲水固体颗粒,该亲水固体颗粒表面通过物理吸附作用修饰有疏水分子链,其中,亲水固体颗粒的粒径为0.1~5μm。该颗粒稳泡剂可用作聚氨酯发泡涂层的稳泡剂,其作为稳泡剂的同时还可充当聚氨酯发泡涂层的填料或功能助剂。本发明的稳泡剂克服了现有硬脂酸铵稳泡剂的缺陷,通过对聚氨酯发泡涂层中常用的固体颗粒进行修饰,使其具备两亲性,两亲性的细小颗粒在生成泡沫的过程中吸附在气液相界面上,形成一层致密的粒子膜,提高泡沫稳定性。
实施例1
按质量分数计,颗粒稳泡剂原料包括:碳酸钙(粒径5微米)30份,十二烷基硫酸钠1.5份,10%乙醇-水溶液200份。
该颗粒稳泡剂制备步骤如下:
1)称取30份碳酸钙颗粒于反应釜中,加入200份10%乙醇-水溶液,控制温度为40℃,搅拌均匀配成悬浮液;
2)再将1.5份十二烷基硫酸钠加入到碳酸钙悬浮液中,40℃下继续搅拌2小时;
3)停止搅拌,产物抽滤分离,在40℃下干燥,得到碳酸钙颗粒稳泡剂。
实施例2
按质量分数计,颗粒稳泡剂原料包括:碳酸钙(粒径1微米)30份,十二烷基苯磺酸钠3份,20%乙醇-水溶液200份。
该颗粒稳泡剂的制备步骤如下:
1)称取30份碳酸钙颗粒于反应釜中,加入200份20%乙醇-水溶液,控制温度为20℃,搅拌均匀配成悬浮液;
2)再将3份十二烷基苯磺酸钠加入到碳酸钙悬浮液中,20℃下继续搅拌3小时;
3)停止搅拌,产物抽滤分离,在60℃下干燥,得到碳酸钙颗粒稳泡剂。
实施例3
按质量分数计,颗粒稳泡剂原料包括:钛白粉(粒径0.1微米)30份,十六烷基三甲基溴化铵1.5份,40%乙醇-水溶液200份。
该颗粒稳泡剂的制备步骤如下:
1)称取30份钛白粉于反应釜中,加入200份40%乙醇-水溶液,控制温度为60℃,搅拌均匀配成悬浮液;
2)再将1.5份十六烷基三甲基溴化铵加入到钛白粉悬浮液中,60℃下继续搅拌4小时;
3)停止搅拌,产物抽滤分离,在60℃下干燥,得到钛白粉颗粒稳泡剂。
实施例4
按质量分数计,颗粒稳泡剂原料包括:二氧化硅(粒径0.5微米)15份,膨润土(粒径3微米)15份,脂肪醇聚氧乙烯醚6份,50%乙醇-水溶液200份。
该颗粒稳泡剂的制备步骤如下:
1)称取15份二氧化硅及15份膨润土于反应釜中,加入200份50%乙醇-水溶液,控制温度为5℃,搅拌均匀配成悬浮液;
2)再将6份脂肪醇聚氧乙烯醚加入到颗粒悬浮液中,5℃下继续搅拌8小时;
3)停止搅拌,产物抽滤分离,在50℃下干燥,得到二氧化硅/膨润土颗粒稳泡剂。
分别取实施例1~4制备的固体颗粒稳泡剂用作聚氨酯发泡涂层的稳泡剂,固体颗粒稳泡剂的具体用量如下表1,根据如下步骤分别制成聚氨酯发泡涂层:
S1、取200g聚氨酯乳液,12~20g颗粒稳泡剂,1g增稠剂(聚丙烯酸类水性增稠剂)混合均匀;
S2、使用电动发泡机快速搅拌,控制发泡倍率为2,制成发泡浆料;
S3、使用刮膜器将发泡浆料涂敷在离型纸上,涂敷完成后,置于100℃烘箱中烘干,得到聚氨酯发泡涂层。
作为对比,采用20g硬脂酸铵乳液(固含量25%)稳泡剂替代颗粒稳泡剂,根据上述步骤S1~S3制备聚氨酯发泡涂层。
通过显微观察实施例1~4制得的聚氨酯发泡涂层的表面孔径,并与传统硬脂酸铵乳液制备的聚氨酯发泡涂层表面孔径进行对比,测试结果表1。
表1不同发泡剂的聚氨酯发泡涂层平均孔径及气孔分布
由表1可知,与硬脂酸铵乳液制做的涂层比较,用实施例1、实施例2、实施例3、实施例4制成的颗粒稳泡剂制作的涂层,其泡沫孔径更小,且PDI数值更低,说明发泡涂层的孔径分布更均匀,即本发明的颗粒稳泡剂的稳泡性能较传统的硬脂酸铵稳泡剂更优。
Claims (8)
1.一种用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,该颗粒稳泡剂的制备方法,包括如下步骤:
(1)将亲水固体颗粒加入乙醇-水溶液中,配成固体颗粒悬浮液;
(2)将含疏水分子链的修饰剂加入所述固体颗粒悬浮液中,搅拌,使疏水分子链修饰到亲水固体颗粒表面;
(3)将步骤(2)所得产物抽滤分离,固相物料干燥,即得颗粒稳泡剂;所制备得到的颗粒稳泡剂包括粒径为0.1~5μm的亲水固体颗粒,该亲水固体颗粒表面通过物理吸附作用修饰有疏水分子链。
2.根据权利要求1所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,所述亲水固体颗粒为钛白粉、碳酸钙、二氧化硅、高岭土、膨润土中的至少一种。
3.根据权利要求1所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,所述亲水固体颗粒表面吸附有含疏水分子链的修饰剂,该含疏水分子链的修饰剂的量为亲水固体颗粒质量的5~20%。
4.根据权利要求3所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,所述含疏水分子链的修饰剂为十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、十六烷基硫酸钠、十八烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、脂肪酸甲酯磺酸钠、失水山梨醇单硬脂酸酯、失水山梨醇单油酯、失水山梨醇单棕榈酸酯、失水山梨醇单月桂酸酯、脂肪醇聚氧乙烯醚、二甲基聚硅氧烷聚醚、烷基糖苷、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵中的至少一种。
5.根据权利要求1所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,步骤(1)中,所述乙醇-水溶液的浓度为10~50%。
6.根据权利要求1所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,步骤(2)中,所述搅拌温度为5~60℃,搅拌时间为2~8h。
7.根据权利要求1所述的用于聚氨酯发泡涂层的颗粒稳泡剂的制备方法,其特征在于,步骤(3)中,所述干燥温度为40~60℃。
8.一种采用权利要求1的制备方法得到的颗粒稳泡剂的聚氨酯发泡涂层,其特征在于,所述聚氨酯发泡涂层包括聚氨酯乳液和颗粒稳泡剂,其中,颗粒稳泡剂与聚氨酯乳液的质量比为6~10:100。
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