CN103539920A - 一种合成革用的水性聚氨酯及其制备方法 - Google Patents
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Abstract
本发明提供了一种合成革用的水性聚氨酯,按照重量百分比,该组合物由以下组分组成:20~30%的甲苯二异氰酸酯;1~3%的聚碳酸酯;15~20%的新戊二醇;10~15%的芳基磺酸钠聚酯多元醇;15~20%的多元醇树脂乳液;0.8-3%的沸石粉;0.2~0.8%的有机催干剂;以及其他为水。该组分的水性聚氨酯具有较高的固含量及稳定性。
Description
技术领域
本发明涉及一种聚氨酯,尤其是一种合成革用的水性聚氨酯及其制备方法。
背景技术
水性聚氨酯是一类性能优异的“绿色材料”,其固含量是水性聚氨酯的一种重要指标。此处使用术语“固含量”又称不挥发份含量,是指水性聚氨酯在规定条件下烘干后剩余部分占总量的百分数。因此,固含量不仅是成膜物质,还包括调料、助剂等等。固含量的高低对于生产效率、运输成本,以及使用性能等具有非常重要的影响。
然而,现有的水性聚氨酯的固含量一般较低,一般为30~40%,在严苛的生产条件下,也可以达到50%左右。例如,现有的一种常见的方法可以使用水分散性的聚氨酯胶黏剂与水分散性的多异氰酸酯交联剂混合。其中,聚氨酯胶黏剂的制备包括预聚物的制备,预聚物的中和与分散到去粒子水中得到分散体,然后再阔连生产水性聚氨酯。然而,上述方法生产的水性聚氨酯的固含量仍然较低,其中存在大量的水,使得水性聚氨酯制革困难,无法按照溶剂型聚氨酯的制革工艺完成合成革的制作。
即便在某些实施方式中的水性聚氨酯具有较高的固含量,例如达到55%以上,但其稳定性太差,依然难以应用于合成革的制作当中。因此,在保持其稳定性的前提下,提高水性聚氨酯的固含量是一种急待解决的技术问题。
发明内容
针对现有技术的不足,本发明的目的是要提供一种具有较高固含量且其稳定性较好的合成革用的水性聚氨酯。
本发明的另一目的在于提供一种能耗低、生产效率高的制备上述水性聚氨酯的制备方法。
为了达到本发明的目的,本发明采用以下技术方案实现:
本发明的一种合成革用的水性聚氨酯,按照重量百分比,该组合物由以下组分组成:
甲苯二异氰酸酯 20~30%;
聚碳酸酯 1~3%;
新戊二醇 15~20%;
芳基磺酸钠聚酯多元醇 10~15%;
多元醇树脂乳液 15~20%;
沸石粉 0.8-3%;
有机催干剂 0.2~0.8%;
其他为水。
上述水性聚氨酯中,所述多元醇树脂乳液包括以下按照重量百分比的组分:40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水。
所述多元醇树脂乳液的-OH当量为185~237。
所述芳基磺酸钠聚酯多元醇的分子量Mn为600~1500。
制备本发明的水性聚氨酯的方法依次包括以下步骤:
在反应釜中加入重量百分比为20~30%的甲苯二异氰酸酯、重量百分比为10~15%的芳基磺酸钠聚酯多元醇、重量百分比为15~20%的新戊二醇以及重量百分比为1~3%的聚碳酸酯;然后升温至73摄氏度反应1~1.5小时,进行回流;
升温至85摄氏度反应2~3小时,然后降温至65摄氏度,加入芳基磺酸钠聚酯多元醇,再在60摄氏度下反应2.5~3.5小时制得A反应物;
将上述的A反应物和重量百分比15~20%多元醇树脂乳液、重量百分比为0.8~3%的沸石粉、重量百分比为0.2~0.8%的有机催干剂以及相应分量的水性 固化剂在乳化釜中乳化,乳化3~4小时后即制得水性聚氨酯。
所述多元醇树脂乳液包括以下按照重量百分比的组分:40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水。
所述多元醇树脂乳液的-OH当量为185~237。
所述芳基磺酸钠聚酯多元醇的分子量Mn为600~1500。
与现有技术相比,本发明通过上述配方生产的水性聚氨酯具有较高的固含量,一般情况下的固含量高达56%以上。此外,该水性聚氨酯的稳定性也较好,具有较高的耐醇性、耐酸性和耐碱性。
此外,与普通的水性聚氨酯相比,其可以节省运输成本和烘干过程的能耗,抗Ca2+、Mg2+离子性优良,对水质要求不高,更为适宜作为人造革的生产原料,生产出较高质量的人造革。
具体实施方式
下面例举若干个具体实施方式以对本发明进行详细说明,本部分的描述仅仅是示范性和解释性说明,不应构成对本发明的保护范围产生任何限制作用。
在以下实施例和对比例中,使用以下方法对水性聚氨酯的固含量进行测定:
将一个表面皿洗干净,在高温下进行烘干。用天平称出表面皿的质量m1;称取2~3克乳液于表面皿中,测得质量为m2;在60℃的条件下烘干后,称取此时表面皿的质量,在恒重时得到质量m3,最后,按照下式计算固含量C(%)
式中:C——固含量%;
m1——干燥表面皿的质量,g;
m2——干燥表面皿及未干燥乳液的质量和,g;
m3——干燥表面皿及固形物的质量和,g。
实施例1
1、多元醇树脂乳液的制备
原料:
称取重量百分比为40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水
其制备方法包括如下步骤:
将多元醇树脂加入500ml的烧杯中,加热至20~80℃,加入非离子乳化剂A-3065;
将乳化机分散头置于烧杯内,开启乳化机,越热分散头,将上述的混合溶液分散均匀;
向上述步骤的分散均匀后的混合溶液中加入40~75摄氏度的热水,当混合溶液达到相转化临界点时停止加水,搅拌3~10分钟至混合溶液均匀,加入剩余的水,继续搅拌5~30分钟,即得到多元醇树脂乳液。
2、制备水性聚氨酯。
在反应釜中按照表1加入甲苯二异氰酸酯、芳基磺酸钠聚酯多元醇、新戊二醇以及聚碳酸酯;然后升温至73摄氏度反应1~1.5小时,进行回流;
升温至85摄氏度反应2~3小时,然后降温至65摄氏度,按照表1的组分含量加入芳基磺酸钠聚酯多元醇,再在60摄氏度下反应2.5~3.5小时制得A反应物;
将上述的A反应物和按照表1中的含量加入元醇树脂乳液、沸石粉、有机催干剂以及相应分量的水在乳化釜中乳化,乳化3~4小时后即制得水性聚氨酯。
然后按照上述的方法测定该水性聚氨酯的固含量,在表2中列出了测试结果。
其中,上述的多元醇树脂乳液包括以下按照重量百分比的组分:40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水。
实施例2
按照表1中指定的各组分含量列出的含量重复实施例1的方法,在表2 中列出了测试结果。
实施例3
按照表1中指定的各组分含量列出的含量重复实施例1的方法,在表2中列出了测试结果。
对比例1
原料:
1000g聚酯二元醇(由己二酸,1,4-丁二醇制备,分子量3000);
32.9二羟甲基丙酸(DMPA)
24.8g三乙胺(TEA)
65.7g六亚甲基二异氰酸酯(HDI)
86.8g异佛尔酮二异氰酸酯(IPDI)
8.5g乙二胺(EDA)
0.3g二月桂酸二丁基锡
400g丙酮
1210.0g去离子水。
制备方法:在装有电动搅拌搅拌器,回流冷凝管、热电偶温度计的玻璃反应器中,加入聚酯二元醇、DMPA,于90-100℃下熔化。然后降温至70摄氏度左右加入IPDI和HDI,滴加0.3g二月桂酸二丁基锡催化剂,在400g丙酮存在条件下,于70摄氏度搅拌反应5小时,得到预聚体。预聚体降温至50摄氏度,加入TEA中和成盐。将中和后所得的预聚物在高速剪切下分散到去去离子水中,分散乳化约10min,然后加入EDA扩链1小时,最后减压蒸出丙酮得到一个稳定的乳白色水性聚氨酯分散液,在表2中列出了测试结果。
对比例2
原料:
1000g聚酯二元醇(由己二酸,1,4-丁二醇制备,分子量1000)
42.1g二羟甲基丙酸(DMPA)
31.4g三乙胺(TEA)
107g六亚甲基二异氰酸酯(HDI)
329.9g异佛尔酮二异氰酸酯(IPDI)
34g乙二胺(EDA)
0.3g二月桂酸二丁基锡
450g丙酮
1550g去离子水。
制备方法:见对比例1,得到乳白色的水性聚氨酯分散液,在表2中列出了测试结果。
表1
表2
上述表2中各实施例与对比例中对固含量的测试结果表明,本发明的用于人造革的水性聚氨酯明显地优于各对比物的水性聚氨酯的固含量,并且具有较高的稳定性。
此外,从对比例的制备方法也可以看出,采用本发明所述的制备方法,其制备工艺也更为简化,有效地提高了制备效率。
以上所述仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (8)
1.一种合成革用的水性聚氨酯,按照重量百分比,该组合物由以下组分组成:
甲苯二异氰酸酯 20~30%;
聚碳酸酯 1~3%;
新戊二醇 15~20%;
芳基磺酸钠聚酯多元醇 10~15%;
多元醇树脂乳液 15~20%;
沸石粉 0.8-3%;
有机催干剂 0.2~0.8%;
其他为水。
2.如权利要求1所述的一种合成革用的水性聚氨酯,所述多元醇树脂乳液包括以下按照重量百分比的组分:40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水。
3.如权利要求2所述的一种合成革用的水性聚氨酯,所述多元醇树脂乳液的-OH当量为185~237。
4.如权利要求1所述的一种和成革用的水性聚氨酯,所述芳基磺酸钠聚酯多元醇的分子量Mn为600~1500。
5.一种制备 权利要求1所述合成革用的水性聚氨酯的制备方法,包括以下步骤:
在反应釜中加入重量百分比为20~30%的甲苯二异氰酸酯、重量百分比为10~15%的芳基磺酸钠聚酯多元醇、重量百分比为15~20%的新戊二醇以及重量百分比为1~3%的聚碳酸酯;然后升温至73摄氏度反应1~1.5小时,进行回流;
升温至85摄氏度反应2~3小时,然后降温至65摄氏度,加入芳基磺酸钠聚酯多元醇,再在60摄氏度下反应2.5~3.5小时制得A反应物;
将上述的A反应物和重量百分比15~20%多元醇树脂乳液、重量百分比为0.8~3%的沸石粉、重量百分比为0.2~0.8%的有机催干剂以及相应分量的水在乳化釜中乳化,乳化3~4小时后即制得水性聚氨酯。
6.如权利要求5所述的合成革用的水性聚氨基的制备方法,所述多元醇树脂乳液包括以下按照重量百分比的组分:40%~80%的多元醇树脂,2~10%的非离子乳化剂,以及30~52%的温度为40~75摄氏度的热水。
7.如权利要求6所述的合成革用的水性聚氨基的制备方法,所述多元醇树脂乳液的-OH当量为185~237。
8.如权利要求7所述的合成革用的水性聚氨基的制备方法,所述芳基磺酸钠聚酯多元醇的分子量Mn为600~1500。
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