CN107501505B - 防水透湿合成革用面层聚氨酯树脂及其制备方法 - Google Patents

防水透湿合成革用面层聚氨酯树脂及其制备方法 Download PDF

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CN107501505B
CN107501505B CN201710699429.8A CN201710699429A CN107501505B CN 107501505 B CN107501505 B CN 107501505B CN 201710699429 A CN201710699429 A CN 201710699429A CN 107501505 B CN107501505 B CN 107501505B
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杨银龙
张其斌
孙向浩
段伟东
张�浩
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Abstract

本发明公开了一种防水透湿合成革用面层聚氨酯树脂及其制备方法，所述防水透湿合成革用面层聚氨酯，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂，多元醇包含多元醇A和多元醇B，多元醇A和多元醇B的摩尔数之比为1:1～1:3；多元醇A选自聚四氢呋喃醚二醇、聚四氢呋喃环氧丙烷共聚醚二醇中的一种以上，多元醇B选自聚四氢呋喃环氧乙烷共聚醚二醇、聚环氧丙烷环氧乙烷共聚醚二醇、聚环氧乙烷二醇中的一种以上，扩链剂为双羟基扩链剂和双胺基扩链剂，三官能度化合物为三羟基化合物，封端剂为单胺基硅烷偶联剂。本发明的防水透湿聚氨酯合成革不仅具有优异的防水透湿性能，还具有出色的耐磨性能。

Description

防水透湿合成革用面层聚氨酯树脂及其制备方法
技术领域
本发明涉及一种聚氨酯树脂及其制备方法。
背景技术
随着人们对穿着舒适性、功能性的不断提高，差异化的聚氨酯合成革逐渐得到合成革各企业的广泛关注，如防水透湿型聚氨酯合成革。防水透湿聚氨酯合成革由于其特有的防水性、透汽性，使得其广泛应用于生产高档鞋、高档服装等。根据防水透湿机理，可将防水透湿聚氨酯合成革分为微孔透湿型、无孔亲水导湿型、微孔透湿和亲水导湿结合型等。
由于无孔亲水导湿型聚氨酯合成革具有生产操作方便、生产成本低等原因，是各合成革企业优先选择的生产产品。由于在无孔聚氨酯树脂膜的两边存在湿度梯度，水汽分子则利用树脂分子链中的亲水基团作为介质，通过“吸附-扩散-解吸”过程，从高湿度一侧扩散到低湿度一侧，从而实现透汽性；而由于该合成革表面为致密膜，因此水滴不会穿过革面，从而实现防水功能。
作为防水透湿合成革重要原料的聚氨酯面层树脂，一直是行业内重点开发的对象。中国专利CN101914854B通过聚酯三醇和聚乙二醇(PEG)作为多元醇获得了芳香族感温型防水透湿聚氨酯树脂，其固含量为29-31％。中国专利CN103319687B通过聚碳酸酯二醇、聚四氢呋喃醚二醇、PEG作为多元醇获得了芳香族防水透湿聚氨酯树脂。中国专利CN101381448B通过向防水透湿聚氨酯树脂中引入氯化钾，使得通过该树脂制备的聚氨酯合成革不仅具有亲水导湿性还具有大量的微孔结构，但其树脂仍为芳香族聚氨酯树脂。中国专利申请CN101348552A通过聚氧化丙烯二元醇和聚氧化乙烯二元醇获得了芳香族防水透湿服装用粘接树脂。上述专利都是芳香族聚氨酯树脂，其耐黄变、耐光照性能不够好，不适合做浅色制品。
由于防水透湿聚氨酯树脂常常用于生产浅色劳保革、浅色服装革等，因此使用脂肪族异氰酸酯制备无黄变型聚氨酯树脂是非常有必要的，但无黄变防水透湿聚氨酯的耐磨性通常比较差。中国专利申请CN105693992A可使用脂肪族异氰酸酯通过一步法双螺杆挤出合成生物基透湿热塑性聚氨酯树脂，由于其没有使用溶剂，在加工制备防水透湿合成革时非常困难。中国专利申请CN105017501A通过聚酯多元醇、聚醚多元醇复合使用的方法获得了耐磨性能较好的脂肪族防水透湿聚氨酯树脂，但其使用了聚酯多元醇，产品耐水解性有一定降低。中国专利申请CN102993400A通过聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇中一种或一种以上获得了脂肪族防水透湿聚氨酯树脂，但其产品合格后还需要再次升温至70-80℃，能耗较高，且该产品的耐磨性不佳。中国专利CN103649153B通过偏苯三酸和/或苯均四酸获得了防水透湿聚氨酯树脂，其也可以制备脂肪族组合料，但其拉伸强度不够好。
发明内容
本发明的目的在于提供一种防水透湿合成革用面层聚氨酯树脂及其制备方法，以解决现有的防水透湿聚氨酯树脂存在的技术不足。
本发明所述的防水透湿合成革用面层聚氨酯树脂，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯、助剂、封端剂和溶剂，其中：
(1)所述多元醇包含多元醇A和多元醇B，且多元醇A和多元醇B的摩尔数之比为1:1～1:3。
所述多元醇A选自聚四氢呋喃醚二醇、聚四氢呋喃环氧丙烷共聚醚二醇中的一种或两种，数均分子量为1000～3000；
所述多元醇B选自聚四氢呋喃环氧乙烷共聚醚二醇、聚环氧丙烷环氧乙烷共聚醚二醇、聚环氧乙烷二醇中的一种以上，所述多元醇B的数均分子量为1000～3000；
(2)所述扩链剂包含双羟基扩链剂和双胺基扩链剂，且双胺基扩链剂的摩尔数与扩链剂总摩尔数的比值b等于0.7～0.8；
所述扩链剂总摩尔数与多元醇总摩尔数的比值a等于2～4；
所述双羟基扩链剂为乙二醇、丁二醇中的一种或两种。
所述双胺基扩链剂为异佛尔酮二胺、4,4'-二胺基二环己基甲烷中一种或两种。
(3)所述三官能度化合物的摩尔数为扩链剂总摩尔数的0.1％～0.2％，所述三官能度化合物为三羟基化合物，如三羟甲基丙烷、三羟甲基乙烷、 1,2,6-己三醇、甘油或三羟基聚醚等中的一种或以上；
(4)所述二异氰酸酯的摩尔数为多元醇总摩尔数、扩链剂总摩尔数与 1.5倍的三官能度化合物摩尔数之和，即
n(二异氰酸酯)＝n(多元醇)+n(扩链剂)+1.5n(三官能度化合物)；
所述的二异氰酸酯为脂肪族二异氰酸酯，例如为六亚甲基二异氰酸酯、 4,4'-二环己基甲烷二异氰酸酯或异佛尔酮二异氰酸酯中的一种或以上；
优选，所述的二异氰酸酯为异佛尔酮二异氰酸酯。
(5)所述封端剂的摩尔数为多元醇、扩链剂、三官能度化合物和二异氰酸酯总重量除以50000，即：
Figure BDA0001379971860000041
所述封端剂选自单胺基硅烷偶联剂，如γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷等。
(6)所述助剂包含抗氧剂和光稳定剂，其中抗氧剂占多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂总重量的0.01％～0.03％；光稳定剂占多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂总重量的0.01％～ 0.5％。
所述抗氧剂为受阻酚类抗氧剂，如中国台湾双键化工股份有限公司Chinox 1010、Chinox 1035等。
所述光稳定剂为苯并三唑类紫外线吸收剂或受阻胺类光稳定剂，如中国台湾双键化工股份有限公司的Chisorb 320、Chisorb 292等。
(7)所述溶剂的用量，为多元醇、扩链剂、三官能度化合物、二异氰酸酯、封端剂、助剂和溶剂总重量的65％～75％；
所述的溶剂包括溶剂A，溶剂B和溶剂C，其中溶剂A选自二甲基甲酰胺、二甲基乙酰胺中至少一种，溶剂B选自甲苯、丁酮、醋酸乙酯中至少一种，溶剂C选自异丙醇、异丁醇中至少一种。
优选，所述的溶剂A占溶剂总重量的比例不低于55％，溶剂C占溶剂重量的10％。优选，所述的溶剂A为二甲基甲酰胺，溶剂B为甲苯，溶剂C为异丙醇。
所述的防水透湿合成革用面层聚氨酯树脂的制备方法，包括如下步骤：
(1)将抗氧剂、多元醇A、多元醇B、三官能度化合物、双羟基扩链剂、部分溶剂A在50～60℃混合均匀；
所述的部分溶剂A指的是，溶剂A的加入重量为溶剂A总重量的20～ 30％；
(2)然后加入二异氰酸酯，升温至95～105℃后，预聚2～3小时，然后降温至30～40℃，并加入剩余的溶剂A和溶剂B，搅拌25～30分钟；
(3)加入双氨基扩链剂，30～40℃反应4～5小时，加入溶剂C和封端剂，搅拌30分钟后加入光稳定剂，即可获得所述防水透湿合成革用面层聚氨酯树脂。
与现有技术相比，本发明的有益效果是：
本发明通过加入适量的可控的三官能度化合物，并利用硅烷偶联剂作为封端剂制备了防水透湿合成革用聚氨酯树脂。由于本发明的树脂有交联结构，且制备成合成革后可通过末端偶联剂实现更多的交联结构，使得通过本发明制备的防水透湿聚氨酯合成革不仅具有优异的防水透湿性能，还具有出色的耐磨性能。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应该理解，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整，仍属于本发明的保护范围。以下实施例所用原料均为市售。
实施例1
本实施例所用原料及重量如表1。
表1
Figure BDA0001379971860000061
制备方法如下：
(1)将0.039g Chinox 1010、100g聚四氢呋喃醚二醇、100g聚环氧乙烷二醇、0.1072g三羟甲基丙烷、7.44g乙二醇、79.81g二甲基甲酰胺在60℃混合；
(2)然后加入133.65g异佛尔酮二异氰酸酯，升温至105℃后，预聚3小时，然后降温至40℃，并加入319.24g二甲基甲酰胺和253.94g甲苯，搅拌30 分钟；
(3)加入47.68g异佛尔酮二胺，40℃反应5小时，加入72.55g异丙醇和 1.72gγ-氨丙基三乙氧基硅烷，搅拌30分钟后加入0.039g Chisorb 320，即可获得所述防水透湿合成革用面层聚氨酯树脂。
实施例2
本实施例所用原料及重量如表2。
表2
Figure DEST_PATH_IMAGE001
制备方法如下：
(1)将0.55g Chinox 1035、300g聚四氢呋喃环氧丙烷共聚醚二醇、900g 聚四氢呋喃环氧乙烷共聚醚二醇、6g三羟基聚醚、28.8g丁二醇、998.88g二甲基乙酰胺在50℃混合均匀；
(2)然后加入336.72g六亚甲基二异氰酸酯，升温至95℃后，预聚2小时，然后降温至30℃，并加入2330.72g二甲基乙酰胺和1664.8g丁酮，搅拌25分钟；
(3)加入269.26g 4,4'-二胺基二环己基甲烷，30℃反应4小时，加入 554.93g异丁醇和6.6gγ-氨丙基三甲氧基硅烷，搅拌30分钟后加入1.85g Chisorb 292，即可获得所述防水透湿合成革用面层聚氨酯树脂。
实施例3
本实施例所用原料及重量如表3。
表3
Figure BDA0001379971860000081
制备方法如下：
(1)将0.2g Chinox 1010、200g聚四氢呋喃醚二醇、360g聚四氢呋喃环氧乙烷共聚醚二醇、0.86g三羟基聚醚、20.25g丁二醇、408.34g二甲基甲酰胺在60℃混合均匀；
(2)然后加入267.36g异佛尔酮二异氰酸酯，升温至95℃后，预聚3小时，然后降温至30℃，并加入1225.02g二甲基甲酰胺和466.68g醋酸乙酯，搅拌 25分钟；
(3)加入141.99g 4,4'-二胺基二环己基甲烷，40℃反应4小时，加入 233.34g异丙醇和4.38gγ-氨丙基三乙氧基硅烷，搅拌30分钟后加入4.97g Chisorb 292，即可获得所述防水透湿合成革用面层聚氨酯树脂。
实施例4
为进一步说明本发明的技术创新，选取实施例1至3所得树脂、市售防水透湿合成革用面层聚氨酯树脂样本分别按照下列制样方法制革：
将5份色片、100份上述聚氨酯树脂、40份二甲基甲酰胺、30份丁酮混合均匀并脱泡，得工作浆；用刮刀以0.15mm的厚度将工作浆涂覆于劳保革用离型纸上，经120℃烘箱烘干；再次涂覆0.2mm厚的工作浆，并于130℃烘干；然后涂覆0.2mm的工作浆，并贴合1.4mm的超细纤维合成革基布，烘干并从离型纸上剥离即可得防水透湿合成革。实施例1、2和3，与市售样本所制备的防水透湿合成革分别测试防水透湿性能(QB/T 4044-2010)和10万次马丁代尔耐磨(GB/T 19089-2003)，测试结果见表4。
其中：所述的市售样本为浙江华峰合成树脂有限公司的牌号为WV7020 的产品。
表4
Figure BDA0001379971860000091
Figure BDA0001379971860000101
从表4可知，本发明制备的防水透湿合成革面层聚氨酯树脂具有优异的防水性、透汽性和耐磨性。

Claims (10)

1.防水透湿合成革用面层聚氨酯，其特征在于，由包含以下组分的原料制成：多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂，其中：
(1)所述多元醇包含多元醇A和多元醇B，且多元醇A和多元醇B的摩尔数之比为1:1～1:3；
所述多元醇A选自聚四氢呋喃醚二醇、聚四氢呋喃环氧丙烷共聚醚二醇中的一种或两种；
所述多元醇B选自聚四氢呋喃环氧乙烷共聚醚二醇、聚环氧丙烷环氧乙烷共聚醚二醇、聚环氧乙烷二醇中的一种以上；
(2)所述扩链剂包含双羟基扩链剂和双胺基扩链剂，且双胺基扩链剂的摩尔数与扩链剂总摩尔数的比值b等于0.7～0.8；
(3)所述三官能度化合物的摩尔数为扩链剂总摩尔数的0.1％～0.2％，所述三官能度化合物为三羟基化合物；
(4)所述二异氰酸酯的摩尔数为多元醇总摩尔数、扩链剂总摩尔数与1.5倍的三官能度化合物摩尔数之和；
(5)所述封端剂选自单胺基硅烷偶联剂。
2.根据权利要求1所述的防水透湿合成革用面层聚氨酯，其特征在于，所述多元醇A的数均分子量为1000～3000，所述多元醇B的数均分子量为1000～3000，所述扩链剂总摩尔数与多元醇总摩尔数的比值a等于2～4。
3.根据权利要求2所述的防水透湿合成革用面层聚氨酯，其特征在于，所述双羟基扩链剂为乙二醇、丁二醇中的一种或两种，所述双胺基扩链剂为异佛尔酮二胺、4,4'-二胺基二环己基甲烷中一种或两种。
4.根据权利要求3所述的防水透湿合成革用面层聚氨酯，其特征在于，所述三官能度化合物的摩尔数为扩链剂总摩尔数的0.1％～0.2％，所述三官能度化合物为三羟甲基丙烷、三羟甲基乙烷、1,2,6-己三醇、甘油或三羟基聚醚中的一种或以上。
5.根据权利要求1～4任一项所述的防水透湿合成革用面层聚氨酯，其特征在于，所述的二异氰酸酯为六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯或异佛尔酮二异氰酸酯中的一种或以上。
6.根据权利要求1～4任一项所述的防水透湿合成革用面层聚氨酯，其特征在于，所述封端剂的摩尔数为多元醇、扩链剂、三官能度化合物和二异氰酸酯总重量除以50000。
7.根据权利要求6所述的防水透湿合成革用面层聚氨酯，其特征在于，所述封端剂为γ-氨丙基三乙氧基硅烷或γ-氨丙基三甲氧基硅烷。
8.权利要求1所述的防水透湿合成革用面层聚氨酯，其特征在于，还包括助剂和溶剂，所述助剂包含抗氧剂和光稳定剂，其中抗氧剂占多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂总重量的0.01％～0.03％；光稳定剂占多元醇、扩链剂、三官能度化合物、二异氰酸酯和封端剂总重量的0.01％～0.5％；
所述抗氧剂为受阻酚类抗氧剂；
所述光稳定剂为苯并三唑类紫外线吸收剂或受阻胺类光稳定剂；
所述溶剂的用量，为多元醇、扩链剂、三官能度化合物、二异氰酸酯、封端剂、助剂和溶剂总重量的65％～75％；
所述的溶剂包括溶剂A，溶剂B和溶剂C，其中溶剂A选自二甲基甲酰胺、二甲基乙酰胺中至少一种，溶剂B选自甲苯、丁酮、醋酸乙酯中至少一种，溶剂C选自异丙醇、异丁醇中至少一种。
9.根据权利要求8所述的防水透湿合成革用面层聚氨酯，其特征在于，所述的溶剂A占溶剂总重量的比例不低于55％，溶剂C占溶剂重量的10％，所述的溶剂A为二甲基甲酰胺，溶剂B为甲苯，溶剂C为异丙醇。
10.根据权利要求1～9任一项所述的防水透湿合成革用面层聚氨酯的制备方法，其特征在于包括如下步骤：
(1)将抗氧剂、多元醇A、多元醇B、三官能度化合物、双羟基扩链剂、部分溶剂A在50～60℃混合均匀；
所述的部分溶剂A指的是，溶剂A的加入重量为溶剂A总重量的20～30％；
(2)然后加入二异氰酸酯，升温至95～105℃后，预聚2～3小时，然后降温至30～40℃，并加入剩余的溶剂A和溶剂B，搅拌25～30分钟；
(3)加入双氨基扩链剂，30～40℃反应4～5小时，加入溶剂C和封端剂，搅拌30分钟后加入光稳定剂，即可获得所述防水透湿合成革用面层聚氨酯树脂。
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