CN110240688A - 一种表处剂用水性聚氨酯树脂及其制备方法 - Google Patents

一种表处剂用水性聚氨酯树脂及其制备方法 Download PDF

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CN110240688A
CN110240688A CN201910436793.4A CN201910436793A CN110240688A CN 110240688 A CN110240688 A CN 110240688A CN 201910436793 A CN201910436793 A CN 201910436793A CN 110240688 A CN110240688 A CN 110240688A
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waterborne polyurethane
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李维虎
赵学庭
孙之龙
朱保凌
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Lnzhou Ketian Aqueous Polymer Material Co Ltd
Hefei Scisky Technology Co Ltd
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Hefei Scisky Technology Co Ltd
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Abstract

本发明公开了一种表处剂用水性聚氨酯树脂,所述合成革表处剂包括组分A和组分B,所述组分A包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂,700~900质量份乳化水,3~4质量份后扩链试剂;所述组分B包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂。采用本发明的水性聚氨酯树脂所制备的合成革特黑特雾表处剂,长时间贮存稳定性好,合成革雾度和黑度效果优异,能达到自消光效果;本发明树脂制备过程中采用一步投料法,可大大降低人力物力成本。

Description

一种表处剂用水性聚氨酯树脂及其制备方法
技术领域
本发明属于材料技术领域,具体涉及一种表处剂用水性聚氨酯树脂及其制备方法。
背景技术
目前,合成革类用品越来越普遍,已大量取代资源不足的天然皮革,用以制作箱、包、鞋、汽车内饰和家具装饰等。随着人们生活水平改善和对环保要求的提高,合成革制品不仅需要优异的外观和触感,还需要无毒无污染,这不仅对合成革提出更高要求,同时对合成革表处剂提出了更高要求,其中,特黑特雾作为一种新风格逐渐被广大消费者所喜爱,但目前市场上特黑特雾表处剂主要以油性树脂为主,无法做到无毒无污染,部分水性特黑特雾表处剂因加入大量消光粉导致乳液稳定性较差,长时间存放容易出现沉淀。因此,亟需研究出一种实现合成革表面特黑特雾效果、无毒无污染且性能稳定的新型合成革表处剂。
本发明针对上述缺陷,提出一种水性聚氨酯树脂用于制备特黑特雾表处剂,很好地解决了上述问题。
发明内容
本发明旨在提供一种表处剂用水性聚氨酯树脂及其制备方法,主要目的是实现合成革表面特黑特雾效果、无毒无污染且性能稳定。
为解决上述问题,本发明是通过以下技术方案实现的:
一种表处剂用水性聚氨酯树脂,所述合成革表处剂包括组分A和组分B,
所述组分A包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂,700~900质量份乳化水,3~4质量份后扩链试剂;
所述组分B包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂。
可选地,所述组分A和组分B中的亲水扩链剂包括2,2-二羟甲基丙酸。
可选地,所述组分A的状态包括透明乳液、半透明乳液和乳白乳液。
可选地,所述透明乳液的粒径小于0.001微米,半透明乳液的粒径0.001-0.1微米,乳白乳液的粒径大于0.1微米。
可选地,所述有机硅改性剂包括胺基硅烷偶联剂。
可选地,所述后扩链试剂选自乙二胺、异丁二胺、己二胺、对苯二甲胺、邻苯二甲胺、异氟尔酮二胺、环己二甲胺中的一种或多种。
可选地,所述中和剂包括三乙胺。
可选地,所述乳化水包括去离子水。
可选地,所述催化剂为辛酸铋、辛酸锌的一种或两种。
可选地,所述大分子多元醇选自聚己二酸2-甲基丙二醇酯二醇、蓖麻油、聚异戊二烯二醇、聚异丁烯二醇、聚己二酸异戊二醇酯二醇、聚环氧丙烷二醇和聚四氢呋喃醚中的一种或多种。
一种表处剂用水性聚氨酯树脂的制备方法,包括以下步骤,
制备组分A:将大分子多元醇、多异氰酸酯、亲水扩链剂和催化剂混合反应;调温至30~40℃,加入有机硅改性剂;降温至0~25℃,加入中和剂,加乳化水和后扩链剂,获得组份A;
制备组分B:将大分子多元醇、多异氰酸酯、亲水扩链剂和催化剂混合反应;调温至30~40℃,加入有机硅改性剂;降温至0~25℃,加入中和剂,获得组份B;
将组份A加入组份B中乳化,获得所述表处剂用水性聚氨酯树脂。
种表处剂用水性聚氨酯树脂的应用,所述表处剂用水性聚氨酯树脂应用于特黑特特雾表处剂。
采用本发明的水性聚氨酯树脂所制备的合成革特黑特雾表处剂,长时间贮存稳定性好,合成革雾度和黑度效果优异,耐水耐酒精性能好,能达到自消光效果;本发明树脂制备过程中采用一步投料法,可大大降低人力物力成本,本发明的特黑特雾水性聚氨酯树脂,环保无毒,长时间贮存稳定性好。
具体实施方式
下面通过几个具体的实施例对本发明作进一步的说明,但需要指出的是本发明的实施例中所描述的具体的物料配比、工艺条件及结果等仅用于说明本发明,并不能以此限制本发明的保护范围,凡是根据本发明的精神实质所作的等效变化或修饰,都应该涵盖在本发明的保护范围内。
本发明中,采用一步法将大分子多元醇、多异氰酸酯、亲水扩链剂和催化剂在70~80℃进行混合反应6h;将温度调节至30~40℃,加入有机硅改性剂,混合反应0.5h;调节温度至0~25℃,加入中和剂,反应1~5min后在高速搅拌下加乳化水高速乳化1min,加入后扩链剂继续反应10min,获得组份A;
采用一步法将大分子多元醇、多异氰酸酯、亲水扩链剂和催化剂在70~80℃进行混合反应6h;将温度调节至30~40℃,加入有机硅改性剂,混合反应0.5h;调节温度至0~25℃,加入中和剂,反应1~5min后获得组份B;
在高速搅拌下将组份A加入组份B中高速乳化1min,获得具有自消光性能的特黑特雾表处剂树脂。
下面结合实施例进一步阐述本发明。应理解,实施例仅用于说明本发明,而非限制本发明的范围。
在一实施例中:
制备组份A:将聚氧化丙烯二醇60g、聚己二酸异戊二醇酯二醇90g、异佛尔酮二异氰酸酯IPDI 35g、4,4'-二环己基甲烷二异氰酸酯HMDI 15g、2,2-二羟甲基丙酸DMPA 2g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至40℃,加入有机硅改性剂2g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺1.5g进行中和,中和时间2min后在高速搅拌下加乳化水700g,使得分散成乳液状态后添加乙二胺1g反应时间10min,获得组份A。
制备组份B:将聚四氢呋喃醚50g、聚己二酸异戊二醇酯二醇100g、异佛尔酮二异氰酸酯IPDI 52g、2,2-二羟甲基丙酸DMPA 3g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至40℃,加入有机硅改性剂2g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺2.2g进行中和,中和时间2min后获得组份B。
在高速搅拌条件下将组份A加入到组份B中,高速乳化1min,在45℃、抽真空-0.07MPa的条件下进行减压蒸馏,搅拌2h后,测试结果为无丙酮味无臭味,且测试固含量达标,进而获得所述表处剂用水性聚氨酯树脂,样品1。
在一实施例中:
制备组份A:将聚氧化丙烯二醇60g、聚己二酸异戊二醇酯二醇90g、异佛尔酮二异氰酸酯IPDI 35g、4,4'-二环己基甲烷二异氰酸酯HMDI 15g、2,2-二羟甲基丙酸DMPA 4g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至30℃,加入有机硅改性剂3g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺3g进行中和,中和时间2min后在高速搅拌下加乳化水700g,使得分散成乳液状态后添加乙二胺1g反应时间10min,获得组份A。
制备组份B:将聚四氢呋喃醚50g、聚己二酸异戊二醇酯二醇100g、异佛尔酮二异氰酸酯IPDI 52g、2,2-二羟甲基丙酸DMPA 3g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至30℃,加入有机硅改性剂3g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺2.2g进行中和,中和时间2min后获得组份B。
在高速搅拌条件下将组份A加入到组份B中,高速乳化1min,在45℃、抽真空-0.07MPa的条件下进行减压蒸馏,搅拌2h后,测试结果为无丙酮味无臭味,且测试固含量达标,进而获得所述表处剂用水性聚氨酯树脂,样品2。
在一实施例中:
制备组份A:将聚氧化丙烯二醇60g、聚己二酸异戊二醇酯二醇90g、异佛尔酮二异氰酸酯IPDI 35g、4,4'-二环己基甲烷二异氰酸酯HMDI 15g、2,2-二羟甲基丙酸DMPA 6g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至30℃,加入有机硅改性剂1g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺4.5g进行中和,中和时间2min后在高速搅拌下加乳化水700g,使得分散成乳液状态后添加乙二胺1g,反应时间10min,获得组份A。
制备组份B:将聚四氢呋喃醚50g、聚己二酸异戊二醇酯二醇100g、异佛尔酮二异氰酸酯IPDI 52g、2,2-二羟甲基丙酸DMPA 3g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至30℃,加入有机硅改性剂1g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺2.2g进行中和,中和时间2min后获得组份B。
在高速搅拌条件下将组份A加入到组份B中,高速乳化1min,在45℃、抽真空-0.07MPa的条件下进行减压蒸馏,搅拌2h后,测试结果为无丙酮味无臭味,且测试固含量达标,进而获得所述表处剂用水性聚氨酯树脂,样品3。
在一实施例中:
制备组份A:将聚氧化丙烯二醇60g、聚己二酸异戊二醇酯二醇90g、异佛尔酮二异氰酸酯IPDI 35g、4,4'-二环己基甲烷二异氰酸酯HMDI 15g、2,2-二羟甲基丙酸DMPA 8g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至40℃,加入有机硅改性剂1.5g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺6g进行中和,中和时间2min后在高速搅拌下加乳化水700g,使得分散成乳液状态后添加乙二胺1g反应时间10min,获得组份A,样品4。
制备组份B:将聚四氢呋喃醚50g、聚己二酸异戊二醇酯二醇100g、异佛尔酮二异氰酸酯IPDI 52g、2,2-二羟甲基丙酸DMPA 3g、辛酸铋0.4g以及稀释剂丙酮5g,在75℃进行混合反应6h;调节温度至40℃,加入有机硅改性剂1.5g,混合反应0.5h;调节温度至需要的乳化温度15℃,添加三乙胺2.2g进行中和,中和时间2min后获得组份B。
在高速搅拌条件下将组份A加入到组份B中,高速乳化1min,在45℃、抽真空-0.07MPa的条件下进行减压蒸馏,搅拌2h后,测试结果为无丙酮味无臭味,且测试固含量达标,进而获得所述表处剂用水性聚氨酯树脂。
测试结果:
对上述4个实施例水性聚氨酯树脂进行性能参数测试,结果如表1所示:
表1水性聚氨酯树脂的基本特征参数测试结果
将各实施例水性聚氨酯树脂配置成表处剂进行性能测试,结果如表2所示:
表2合成革表处剂的性能测试结果
实验过程中通过调节亲水扩链剂的用量来调节组份A乳液粒径的大小,从而获得具有不同粒径的水性聚氨酯乳液,外观上组份A乳液状态依次为透明无明显蓝光、半透明有蓝光、乳白有蓝光、乳白无蓝光,所述透明乳液的粒径小于0.001微米,半透明乳液的粒径0.001-0.1微米,乳白乳液的粒径大于0.1微米。
本发明采用不同粒径大小的水性聚氨酯乳液(组份A)代替水性聚氨酯乳化时所用的乳化水对水性聚氨酯预聚体(组份B)进行高速分散,由于组份A的乳液粒径具有可调节性,在对组份B高速分散后可形成具有粒径大小不等的水性聚氨酯乳液,该乳液在成膜过程中由于粒径大小的不均一可形成不规则的表面,从而达到自消光效果,所合成乳液的粒径越不均一,自消光效果越明显。使用该树脂配置的特黑特雾表处剂在不使用消光粉的前提下可获得较好的特黑特雾效果。此处需要说明的是,本发明的乳液状组分A加入到预聚体组分B中,从而获得了自消光效果,若是两个预聚体相互混合分散,则达不到本发明中的效果。
此外,本发明加入有机硅改性的胺基硅烷偶联剂,在不影响原有特黑特雾效果的前提下,可显著提高树脂的耐水耐酒精性能。在加入原料1-3质量份的有机硅改性的胺基硅烷偶联剂时,树脂的耐水耐酒精性能最佳,加入多于或少于这个范围的量,耐水耐酒精性能均较差,且本发明中是在30-40℃时加入有机硅改性剂,此处需要说明的是,在条件为30-40℃时加入1-3质量份的有机硅改性剂,才能达到显著的耐水耐酒精性能,其余条件均较差。
由此可见,采用本发明的水性聚氨酯树脂所制备的合成革特黑特雾表处剂,长时间贮存稳定性好,合成革雾度和黑度效果优异,耐水耐酒精性能好,树脂制备过程中采用一步投料法,可大大降低人力物力成本。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种表处剂用水性聚氨酯树脂,其特征在于,所述合成革表处剂包括组分A和组分B,
所述组分A包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂,700~900质量份乳化水,3~4质量份后扩链试剂;
所述组分B包括170~190质量份大分子多元醇,30~40质量份多异氰酸酯,1~8质量份亲水扩链剂,0.3~0.4质量份催化剂,1~3质量份有机硅改性剂,2~4质量份中和剂。
2.根据权利要求1所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述组分A和组分B中的亲水扩链剂包括2,2-二羟甲基丙酸。
3.根据权利要求2所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述组分A的状态包括透明乳液、半透明乳液和乳白乳液。
4.根据权利要求3所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述透明乳液的粒径小于0.001微米,半透明乳液的粒径0.001-0.1微米,乳白乳液的粒径大于0.1微米。
5.根据权利要求4所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述中和剂包括三乙胺。
6.根据权利要求5所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述乳化水包括去离子水。
7.根据权利要求6所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述催化剂为辛酸铋、辛酸锌的一种或两种。
8.根据权利要求7所述的一种表处剂用水性聚氨酯树脂,其特征在于:所述大分子多元醇选自聚己二酸2-甲基丙二醇酯二醇、蓖麻油、聚异戊二烯二醇、聚异丁烯二醇、聚己二酸异戊二醇酯二醇、聚环氧丙烷二醇和聚四氢呋喃醚中的一种或多种。
9.如权利要求1-8任一项所述的一种表处剂用水性聚氨酯树脂的制备方法,其特征在于,将组份A加入组份B中乳化,获得所述表处剂用水性聚氨酯树脂。
10.如权利要求1-8任一项所述的一种表处剂用水性聚氨酯树脂的应用,其特征在于,所述表处剂用水性聚氨酯树脂应用于特黑特特雾合成革表处剂的制备。
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