CN106702756B - 一种水性pu合成革半成品及其浆料的制备方法 - Google Patents

一种水性pu合成革半成品及其浆料的制备方法 Download PDF

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CN106702756B
CN106702756B CN201611097101.0A CN201611097101A CN106702756B CN 106702756 B CN106702756 B CN 106702756B CN 201611097101 A CN201611097101 A CN 201611097101A CN 106702756 B CN106702756 B CN 106702756B
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mass parts
water
slurry
chain alkyl
base fabric
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CN106702756A (zh
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李桂军
向以俊
杨运波
张锋
王桦
卢海峰
倪伶俐
高晓燕
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Jiangsu Huayuan High Tech Co.,Ltd.
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Abstract

本发明公开了一种水性PU合成革半成品及其浆料的制备方法，包括如下步骤：步骤一、将基布用清水浸湿透；步骤二、轧除基布中的水分；步骤三、将基布表面轧光，再用烫平辊把基布烫平；步骤四、将发泡好的浆料涂覆在步骤三处理好的基布上；步骤五、将涂覆好的基布进入特制烘箱进行干燥，本发明涂布用的浆料由自制水性聚氨酯树脂100质量份，填料10‑20质量份，水性稳泡剂0.5‑2质量份，水性色浆1‑3质量份，水1‑10质量份混合配制而成。本发明的制备方法工艺简单、成本低。本发明制备的水性PU合成革半成品表面平整，泡孔均匀细密，促进水性聚氨酯合成革的快速良性发展。

Description

一种水性PU合成革半成品及其浆料的制备方法
技术领域
本发明涉及合成革制造领域，具体涉及一种水性PU合成革半成品及其浆料的制备方法。
背景技术
传统PU合成革半成品（或称BASE/贝斯）的生产主要采用所谓的湿法加工方式，使用溶剂型聚氨酯为主要载体原料，并且在生产过程中都需要大量使用二甲基甲酰胺（DMF）作为稀释剂，不但造成污染环境、危害生产工人的健康、生产过程不安全，而且成品中会有较多的溶剂残留，对使用者也有一定的危害。
水性聚氨酯合成革以水为分散介质，无毒无害，生产过程不使用任何有机溶剂，对环境没有污染、对人无伤害、生产过程安全性高，成品中也无任何有害物质残留，是溶剂型产品的理想替代品，是合成革行业的发展方向。
水性聚氨酯合成革品质的好坏，很大程度上取决于水性聚氨酯半成品的质量，中国专利申请号为“201110260990.9”，专利名称为“一种水性聚氨酯合成革贝斯的制备方法”缺陷有1、用氯化钠溶液处理基布不仅增加成本也无必要；2、普通烘箱烘干，会造成革表面出现裂纹；3、其浆料中含有部分水性丙烯酸树脂，非真正意义上的水性聚氨酯树脂；4、浆料发泡后还要再进行30分钟的搅拌，造成工艺复杂等。中国专利申请号为“201210331044.3”，专利名称为“水性聚氨酯合成革贝斯的制备方法”缺陷有1、用氯化钙等溶液处理基布不仅增加成本也无必要；2、普通烘箱烘干，会造成革表面出现裂纹；3、其浆料中含有部分水性丙烯酸树脂，非真正意义上的水性聚氨酯树脂。因此造成多年水性聚氨酯合成革的发展进展相当缓慢。中国专利申请号为“201010607207.7”，专利名称为“一种水性聚氨酯合成革贝斯的制造方法”，提供了一种水性聚氨酯合成革贝斯的制备方法，该方法提供的浆料中虽然不含有水性丙烯酸树脂，但此方法生产出来的产品存在以下缺陷： 1、底布浸渍水性聚氨酯浆料后再进行表面涂覆水性聚氨酯浆料，不仅工艺复杂，而且相当增加成本；2、普通烘箱烘干，会造成革表面出现裂纹，无法保证产品质量。
发明内容
针对上述现有技术的缺陷，本发明的目的在于，提供一种水性PU合成革半成品及其浆料的制备方法，以克服产品表面平整度低、生产成本高等问题。
本发明是通过以下技术方案实现的：
一种水性PU合成革半成品及其浆料的制备方法，包括如下步骤：
步骤一、将基布用清水浸湿透；
步骤二、轧除基布中的水分；
步骤三、将基布表面轧光，再用烫平辊把基布烫平；
步骤四、将发泡好的浆料涂覆在步骤三处理好的基布上；
步骤五、将涂覆好的基布将涂覆好的基布以8-18m/h的速度进入烘箱进行干燥，烘箱内温度沿着由前向后的顺序逐渐增加，前段温度范围为70℃-90℃，后段温度范围为100℃-140℃，布料经过烘箱的时候由传动链传送，基布干燥后进行压平、检验收卷；
步骤四中所述浆料的制备步骤如下：
步骤A、制备水性聚氨酯浆料
取水性聚氨酯树脂100质量份，填料10-20质量份，水性稳泡剂0.5-2质量份，水性色浆1-3质量份，水1-10质量份配制成乳白色均一粘稠液体待用；
步骤B、对步骤A制备好的水性聚氨酯浆料进行机械发泡，搅拌速度为100-200转/分钟，所得浆料粘度控制为1000-5000mPa.S。
本发明的进一步改进方案为：
步骤四将浆料涂覆在基布上时的涂布厚度为0.20-0.60mm。
所述烘箱出风口与布料之间设有设有挡风板，出风口吹出的热风的风向为水平方向或者吹向远离布料的一侧。
本发明的更进一步改进方案为：
所述水性聚氨酯树脂的制备步骤为：
步骤1：制备羟基聚醚封端的烷基聚硅氧烷中间体
取丙烯醇聚氧乙烯醚、双硅氢基封端的甲基长链烷基聚二甲基硅氧烷和铂金speier催化剂置入反应釜中搅拌升温至80～160℃反应3～5h, 得羟基聚醚封端的长链烷聚硅氧烷中间体；丙烯醇聚氧乙烯醚和双硅氢基封端的甲基长链烷基聚二甲基硅氧烷物质的量的比为1:0.5，铂金speier催化剂投料量占体系总质量的10-20ppm；
步骤2：制备长链烷基聚硅氧烷改性水性PU树脂预聚体
取150质量份的羟基聚醚封端的长链烷聚硅氧烷中间体、290质量份的PTMG2000、120质量份的TDI、10质量份的乙二醇、50质量份的二羟甲基丙酸（DMPA）和0.4质量份有机铋催化剂, 80～90℃下反应至预聚体粘度增为8000～10000mPa.S时,添加50质量份的丙酮，80～90℃下保持丙酮回流反应3小时,冷却到50℃以下，加入38质量份的三乙胺进行中和反应0.5-1小时，得长链烷基聚硅氧烷改性水性PU树脂预聚体；
步骤3：长链烷基聚硅氧烷改性水性PU树脂扩链反应
将500长链烷基聚硅氧烷改性水性PU树脂预聚体流加入搅拌速度为1000～1500转/分的1300质量份的纯水中，加入10质量份的扩链剂，进行扩链反应4-6小时，得长链烷基聚硅氧烷改性水性PU树脂；所述扩链剂为乙二胺或联肼；
步骤4：脱除丙酮
长链烷基聚硅氧烷改性水性PU树脂在50～60℃、10～30KPa下减压蒸馏脱除丙酮，添加纯水使得到的长链烷基聚硅氧烷改性水性PU树脂固含量为30-35%。
本发明的再进一步改进方案为：
所述水性PU树脂的制备方法步骤1中丙烯醇聚氧乙烯醚的分子式为CH2=CH-CH2O(C2H4O)nH，其中n为8-12的整数；
双硅氢基封端的甲基长链烷基聚二甲基硅氧烷的分子式为H-Si（CH3）2-O-[ Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si-H，其中m为10-20的整数，a为5-20的整数，b为5-10的整数；
羟基聚醚封端的长链烷聚硅氧烷中间体的分子式为H(OH4C2)nOH6C3-Si（CH3）2-O-[ Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si- C3 H6O(C2 H4O)nH，其中m为10-20的整数，n为8-12的整数，a为5-20的整数，b为5-10的整数。
本发明的有益效果为：
1、本发明采用分段干燥的工艺，烘箱内温度沿着由前向后的顺序逐渐增加，避免了因为温度突然升高而使产品表面出现裂痕、部分水性物质残留在图层中难以除去的问题；同时干燥所用的烘箱内的出风口的风向不直接吹向布料，保证涂层快速干燥的同时避免未凝固的涂层在风力作用下产生凹凸不平的现象。
2、本发明使用的涂覆浆料配方中没有使用传统的起泡剂、增稠剂和交联剂，在这种情况下浆料的粘度可达到1000-5000，发泡率可达到0.5-4倍，均优于市售涂覆浆料。
附图说明：
图1为本发明的工艺流程图。
具体实施方式
实施例1
水性PU树脂的制备
步骤1：制备羟基聚醚封端的烷基聚硅氧烷中间体
在2000ml四口玻璃反应釜中，加入1mol分子式为CH2=CH-CH2O(C2H4O)nH的丙烯醇聚氧乙烯醚，其中n为8-12的整数，0.5mol分子式为H-Si（CH3）2-O-[ Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si-H 的双硅氢基封端的甲基长链烷基聚二甲基硅氧烷，其中m为10-20的整数，a为5-20的整数，b为5-10的整数，开动搅拌并加入占体系总质量的10-20ppm的铂金speier催化剂搅拌升温至80～160℃反应3～5h,得分子式为H(OH4C2)nOH6C3-Si（CH3）2-O-[Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si- C3 H6O(C2 H4O)nH的羟基聚醚封端的长链烷聚硅氧烷中间体，其中m为10-20的整数，n为8-12的整数，a为5-20的整数，b为5-10的整数。
步骤2：制备长链烷基聚硅氧烷改性水性聚氨酯树脂预聚体
在装有搅拌器、温度计、回流冷凝器的500ml玻璃聚合反应瓶中加入150质量份上述步骤1的羟基聚醚封端的长链烷聚硅氧烷中间体,290质量份的PTMG2000, 120质量份的TDI, 10质量份的乙二醇, 50质量份的二羟甲基丙酸（DMPA）,0.4质量份有机铋催化剂,常温混合搅拌均匀，逐步加热升温到80～90℃，随着反应的进行粘度逐步增加，预聚体粘度增至8000～10000mPa.S时,添加50g丙酮，保持丙酮回流温度反应3小时,取样检测异氰酸根含量合格后停止加热,将反应体系冷却到50℃以下，加入38g三乙胺进行中和反应0.5-1小时，得长链烷基聚硅氧烷改性水性聚氨酯树脂预聚体。
步骤3：长链烷基聚硅氧烷改性水性聚氨酯树脂扩链反应
将上述步骤2的长链烷基聚硅氧烷改性水性聚氨酯树脂预聚体，缓慢流加入高速搅拌（1000～1500转/分）下的1300质量份的纯水中，然后加入10质量份的乙二胺或联肼等后扩链剂，进行扩链反应4-6小时。
步骤4：脱除丙酮
在具有冷凝回收装置的2000ml减压蒸馏釜中，加入1500g上述步骤4制备的长链烷基聚硅氧烷改性水性聚氨酯树脂,加热至50～60℃后在真空度10～30KPa下减压蒸馏脱除丙酮，并适当补充纯水，即得固体份为30-35%的长链烷基聚硅氧烷改性水性聚氨酯树脂。
实施列2
步骤一、将基布用清水浸湿透；
步骤二、轧除基布中的水分；
步骤三、将基布表面轧光，再用烫平辊把基布烫平；
步骤A、制备水性聚氨酯浆料
取水性聚氨酯树脂100质量份，填料10质量份，水性稳泡剂0.5质量份，水性色浆1质量份，水1质量份配制成乳白色均一粘稠液体待用；
步骤B、对步骤A制备好的水性聚氨酯浆料进行机械发泡，搅拌速度为100转/分钟，所得浆料粘度控制为1000mPa.S。
步骤四、将发泡好的浆料涂覆在步骤三处理好的基布上，涂布厚度为0.60mm；
步骤五、将涂覆好的基布以18m/h的速度进入烘箱进行干燥，烘箱内温度沿着由前向后的顺序逐渐增加，前段温度范围为70℃-90℃，后段温度范围为100℃-140℃，布料经过烘箱的时候由传动链传送，基布干燥后进行压平、检验收卷。
实施列3
步骤一、将基布用清水浸湿透；
步骤二、轧除基布中的水分；
步骤三、将基布表面轧光，再用烫平辊把基布烫平；
步骤A、制备水性聚氨酯浆料
取水性聚氨酯树脂100质量份，填料15质量份，水性稳泡剂1.2质量份，水性色浆2质量份，水5质量份配制成乳白色均一粘稠液体待用；
步骤B、对步骤A制备好的水性聚氨酯浆料进行机械发泡，搅拌速度为200转/分钟，所得浆料粘度控制为5000mPa.S。
步骤四、将发泡好的浆料涂覆在步骤三处理好的基布上，涂布厚度为0.20mm；
步骤五、将涂覆好的基布以8m/h的速度进入烘箱进行干燥，烘箱内温度沿着由前向后的顺序逐渐增加，前段温度范围为70℃-90℃，后段温度范围为100℃-140℃，布料经过烘箱的时候由传动链传送，基布干燥后进行压平、检验收卷。
实施列4
步骤一、将基布用清水浸湿透；
步骤二、轧除基布中的水分；
步骤三、将基布表面轧光，再用烫平辊把基布烫平；
步骤A、制备水性聚氨酯浆料
取水性聚氨酯树脂100质量份，填料20质量份，水性稳泡剂2质量份，水性色浆3质量份，水10质量份配制成乳白色均一粘稠液体待用；
步骤B、对步骤A制备好的水性聚氨酯浆料进行机械发泡，搅拌速度为150转/分钟，所得浆料粘度控制为2500mPa.S。
步骤四、将发泡好的浆料涂覆在步骤三处理好的基布上，涂布厚度为0.40mm；
步骤五、将涂覆好的基布以12m/h的速度进入烘箱进行干燥，烘箱内温度沿着由前向后的顺序逐渐增加，前段温度范围为70℃-90℃，后段温度范围为100℃-140℃，布料经过烘箱的时候由传动链传送，基布干燥后进行压平、检验收卷。

Claims (2)

1.一种水性PU合成革浆料的制备方法，其特征在于，包括如下步骤：步骤A、取水性聚氨酯树脂100质量份，填料10-20质量份，水性稳泡剂0.5-2质量份，水性色浆1-3质量份，水1-10质量份配制成乳白色均一粘稠液体待用；步骤B、对步骤A制备好的水性聚氨酯浆料进行机械发泡，搅拌速度为100-200转/分钟，所得浆料粘度控制为1000-5000mPa.S；
所述水性聚氨酯树脂的制备步骤为：
步骤1：制备羟基聚醚封端的烷基聚硅氧烷中间体
取丙烯醇聚氧乙烯醚、双硅氢基封端的甲基长链烷基聚二甲基硅氧烷和铂金speier催化剂置入反应釜中搅拌升温至80～160℃反应3～5h, 得羟基聚醚封端的长链烷聚硅氧烷中间体；丙烯醇聚氧乙烯醚和双硅氢基封端的甲基长链烷基聚二甲基硅氧烷物质的量的比为1:0.5，铂金speier催化剂投料量占体系总质量的10-20ppm；
步骤2：制备长链烷基聚硅氧烷改性水性聚氨酯树脂预聚体
取150质量份的羟基聚醚封端的长链烷聚硅氧烷中间体、290质量份的PTMG2000、120质量份的TDI、10质量份的乙二醇、50质量份的二羟甲基丙酸和0.4质量份有机铋催化剂, 80～90℃下反应至预聚体粘度增为8000～10000mPa.S时,添加50质量份的丙酮，80～90℃下保持丙酮回流反应3小时,冷却到50℃以下，加入38质量份的三乙胺进行中和反应0.5-1小时，得长链烷基聚硅氧烷改性水性聚氨酯树脂预聚体；
步骤3：长链烷基聚硅氧烷改性水性聚氨酯树脂扩链反应
将500长链烷基聚硅氧烷改性水性PU树脂预聚体流加入搅拌速度为1000～1500转/分的1300质量份的纯水中，加入10质量份的扩链剂，进行扩链反应4-6小时，得长链烷基聚硅氧烷改性水性PU树脂；所述扩链剂为乙二胺或联肼；
步骤4：脱除丙酮
长链烷基聚硅氧烷改性水性PU树脂在50～60℃、10～30KPa下减压蒸馏脱除丙酮，添加纯水使得到的长链烷基聚硅氧烷改性水性聚氨酯树脂固含量为30-35%。
2.根据权利要求1所述的一种水性PU合成革浆料的制备方法，其特征在于：所述水性聚氨酯树脂的制备方法步骤1中丙烯醇聚氧乙烯醚的分子式为CH2=CH-CH2O(C2H4O)nH，其中n为8-12的整数；双硅氢基封端的甲基长链烷基聚二甲基硅氧烷的分子式为H-Si（CH3）2-O-[ Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si-H，其中m为10-20的整数，a为5-20的整数，b为5-10的整数；羟基聚醚封端的长链烷聚硅氧烷中间体的分子式为H(OH4C2)nOH6C3-Si（CH3）2-O-[ Si（CH3）2]a-[ Si（CH3）（CmH2m+1）O]b-（CH3）2 Si- C3 H6O(C2 H4O)nH，其中m为10-20的整数，n为8-12的整数，a为5-20的整数，b为5-10的整数。
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