CN106479095B - 一种超软蛋白质湿法树脂及制备方法和应用 - Google Patents

一种超软蛋白质湿法树脂及制备方法和应用 Download PDF

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CN106479095B
CN106479095B CN201610858935.2A CN201610858935A CN106479095B CN 106479095 B CN106479095 B CN 106479095B CN 201610858935 A CN201610858935 A CN 201610858935A CN 106479095 B CN106479095 B CN 106479095B
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钱建中
钱洪祥
巩倩
邹佳娜
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Abstract

本发明涉及超软蛋白质湿法树脂，其由聚酯/聚醚多元醇5％～10％、双端羟基聚醚改性硅油0.3％～0.7％、乙二醇0.3％～1％、二苯基甲烷‑4，4‵‑二异氰酸酯2％～5％、聚乙烯醇粉末15％～20％、聚酰胺蜡0.15％～0.25％、N，N‑二甲基甲酰胺68％～73％制备而成。本发明还公开了该超软蛋白质湿法树脂的制备方法。用上述配方和工艺合成的聚氨酯聚乙烯醇共混湿法树脂制作的湿法合成革贝斯，海绵感强、有蜂窝网状类似真皮蛋白质纤维的泡孔结构、折痕细，并且具有类似真皮蛋白质纤维的轻柔、舒适、自然、保暖的特点。

Description

一种超软蛋白质湿法树脂及制备方法和应用
技术领域
本发明涉及共混改性聚氨酯树脂制备技术领域，更具体的说，涉及一种超软类似蛋白质纤维手感的聚氨酯/聚乙烯醇共混湿法树脂及制备方法和应用。
背景技术
合成革用聚氨酯树脂是用来部分替代天然真皮的新型高分子材料，随着自然资源的日益枯竭，天然真皮资源会日显不足，无法满足日益增长的市场需求，而随着合成革行业的竞争日趋激烈化，人们对合成革用聚氨酯树脂的要求也越来越高，普通聚氨酯树脂已不能满足人们的要求，随之一些仿真皮的合成革材料成为市场的焦点。
通常市场上的聚氨酯合成革产品，由于其泡孔结构一般都是泡孔密度低、小泡孔、或者是细长型的泡孔，泡孔密度与动物皮中蛋白质纤维网状结构相差较大，于是形成的合成革手感没有天然动物皮那种柔软，自然。为了形成类似真皮蛋白质纤维的网状结构，制作仿真皮类合成革产品的一个方向是形成蜂窝状的微孔结构，单独使用聚氨酯一种材料制作合成革湿法贝斯(注：将聚氨酯树脂中加入DMF溶剂及其它填料、助剂制成混合液，真空机脱泡后，浸渍或涂覆于基布上，然后放入水中置换溶剂，聚氨酯树脂逐渐凝固，从而形成微孔聚氨酯粒面层，再通过辊压、烘干定型制成湿法贝斯)虽然能形成微孔，但微孔数量和密度都有一定的局限性。本发明主要选用另一种材料——聚乙烯醇和聚氨酯共混改性，使两种聚合物混合制成均匀的材料，再用来制作类似真皮结构的合成革湿法贝斯。
发明内容
本发明所要解决的技术问题之一在于针对现有技术所存在的不足而提供一种超软蛋白质湿法树脂，用其制成的湿法合成革贝斯，海绵感强、有蜂窝网状类似真皮的泡孔结构、折痕细，并且具有类似真皮蛋白质纤维的轻柔、舒适、自然、保暖的特点。
本发明所要解决的技术问题之二在于提供上述超软蛋白质湿法树脂的制备方法。
本发明所要解决的技术问题之三在于提供上述超软蛋白质湿法树脂的应用。
本发明所要解决的技术问题可以通过以下技术方案来实现：
一种超软蛋白质湿法树脂，该聚氨酯树脂主要由以下重量百分含量的原料制备而成：
Figure BDA0001122069280000021
在本发明的一优选实施例中，所述聚酯/聚醚多元醇为数均分子量为2000～4000g/mol的聚己二酸乙二醇-1,4丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸乙二醇缩二乙二醇酯二醇、聚四氢呋喃醚二醇中的一种或任意两种的混合。
在本发明的一优选实施例中，所述双端羟基聚醚改性硅油为数均分子量为2000～3000g/mol的双端羟基聚醚改性硅油。
在本发明的一优选实施例中，所述双端羟基聚醚改性硅油的质量和聚酯/聚醚多元醇的总质量比为1:20～1:10。
在本发明的一优选实施例中，所述聚乙烯醇粉末为平均聚合度为300～2400的聚乙烯醇粉末一种或两种。
在本发明的一优选实施例中，所述聚乙烯醇粉末为醇解度86％的聚乙烯醇粉末、醇解度88％的聚乙烯醇粉末中的一种或两种的混合。
在本发明的一优选实施例中，所述聚乙烯醇粉末的质量和聚氨酯固形份的总质量的质量比为：2.5:1～1:1；所述聚氨酯固形份的总质量是指：聚酯/聚醚多元醇、乙二醇、双端羟基聚醚改性硅油、异氰酸酯的质量和。
作为本发明第二方面的一种超软蛋白质湿法树脂的制备方法，具有以下步骤组成：
(1)在反应釜中投入聚酯/聚醚多元醇、双端羟基聚醚改性硅油、二苯基甲烷-4，4‵-二异氰酸酯和部分溶剂进行预聚反应，控制反应液中异氰酸酯基和羟基的摩尔比为0.95:1～0.98:1，反应温度控制在75～85℃，反应液固含量控制在40～60％，反应2～3h后，反应液粘度达到10～150Pa·s/50℃时，第一步反应结束；
(2)在反应釜中投入乙二醇、二苯基甲烷-4，4‵-二异氰酸酯和剩余溶剂进行扩链反应，控制反应温度50～80℃，反应至反应液粘度达到50℃时，5～30Pa·s时，加入聚乙烯醇粉末、聚酰胺蜡进行共混反应，反应4～6h，测试反应液粘度达到10～200Pa·s/50℃时，结束反应。
作为本发明第三方面的上述超软蛋白质湿法树脂的应用，是用于制作合成革湿法贝斯，并且制成的湿法贝斯有类似真皮蛋白质纤维的蜂窝状泡孔结构。
本发明的超软蛋白质湿法树脂，主要是采用聚氨酯和聚乙烯醇进行物理共混制成的。聚合物的共混，可以获取新的特性，本发明的共混材料的能够改变传统聚氨酯合成革的泡孔结构。
在本发明中，聚氨酯作为主体聚合物，主要选用了聚酯/聚醚多元醇和双端羟基聚醚改性硅油作为软段大分子多元醇。由于聚氨酯/聚乙烯醇共混材料在制革工艺中往往遇到流平不良等问题，将双端羟基聚醚改性硅油反应到大分子链上，这样能通过改变聚氨酯大分子的表面张力，使其和聚乙烯醇粉末共混时相容性提高。另外，聚酰胺蜡的加入，主要是为了防止聚乙烯醇沉降，保证体系的稳定性。
由于本发明的超软蛋白质湿法树脂是一种聚氨酯/聚乙烯醇的共混材料，将其应用于制革方面，利用制革工艺中凝固时溶胀并分散均匀的聚乙烯醇粉末占用空间，而水洗时，溶于水而留下微孔的特点，可以改变传统的泡孔结构，形成蜂窝状的微孔结构，更接近真皮蛋白质纤维的网状结构，不仅海绵感强、折痕细，并且具有轻柔、舒适、自然、保暖的特点。
附图说明
图1为本发明实施例1和2的超软蛋白质湿法树脂所制湿法贝斯的横截面的泡孔结构示意图。
图2为本发明实施例3和4的超软蛋白质湿法树脂所制湿法贝斯的横截面的泡孔结构示意图。
图3为本发明实施例5的超软蛋白质湿法树脂所制湿法贝斯的横截面的泡孔结构和对比例1所制湿法贝斯的横截面的泡孔结构示意图。
具体实施方式
下面结合具体实施例对本发明进一步详细说明。
实施例1
1、配方
Figure BDA0001122069280000041
2、制备方法
在反应釜中投入聚己二酸乙二醇-1,4丁二醇酯二醇(数均分子量4000g/mol)100kg、聚四氢呋喃醚二醇(数均分子量2000g/mol)50kg、双端羟基聚醚改性硅油(数均分子量2000)10kg、二苯基甲烷-4，4‵-二异氰酸酯(MDI)13.1kg和N，N-二甲基甲酰胺260kg进行预聚反应，反应温度控制在75～85℃，反应2～3h后，反应液粘度达到10～20Pa·s/50℃时，在反应釜中投入乙二醇11.81kg、二苯基甲烷-4，4‵-二异氰酸酯48.26kg和N，N-二甲基甲酰胺1892kg进行扩链反应，控制反应温度60～70℃，反应至反应液粘度达到50℃时，5～10Pa·s时，加入聚乙烯醇0388粉末597kg、聚酰胺蜡6kg进行共混反应，反应4～6h，测试反应液粘度达到170～200Pa·s/50℃时，结束反应。
实施例2
1、配方
Figure BDA0001122069280000051
2、制备方法
在反应釜中投入聚己二酸乙二醇酯二醇(数均分子量3000g/mol)188kg、双端羟基聚醚改性硅油(数均分子量3000g/mol)10kg、二苯基甲烷-4，4‵-二异氰酸酯(MDI)16.11kg和N，N-二甲基甲酰胺143kg进行预聚反应，反应温度控制在75～85℃，反应2～3h后，反应液粘度达到130～150Pa·s/50℃时，在反应釜中投入乙二醇18.25kg、二苯基甲烷-4，4‵-二异氰酸酯74kg和N，N-二甲基甲酰胺1305kg进行扩链反应，控制反应温度50～60℃，反应至反应液粘度达到50℃时，20～30Pa·s时，加入聚乙烯醇0588粉末207kg和聚乙烯醇2488粉末103.5kg、聚酰胺蜡4kg进行共混反应，反应4～6h，测试反应液粘度达到10～30Pa·s/50℃时，结束反应。
实施例3
1、配方
Figure BDA0001122069280000052
Figure BDA0001122069280000061
2、制备方法
在反应釜中投入聚四氢呋喃醚二醇(数均分子量3000g/mol)180kg、双端羟基聚醚改性硅油(数均分子量2000g/mol)18kg、二苯基甲烷-4，4‵-二异氰酸酯(MDI)16.6kg和N，N-二甲基甲酰胺198kg进行预聚反应，反应温度控制在75～85℃，反应2～3h后，反应液粘度达到50～70Pa·s/50℃时，在反应釜中投入乙二醇14.55kg、二苯基甲烷-4，4‵-二异氰酸酯59.3kg和N，N-二甲基甲酰胺2195kg进行扩链反应，控制反应温度70～80℃，反应至反应液粘度达到50℃时，8～12Pa·s时，加入聚乙烯醇1788粉末296.5kg和聚乙烯醇0386粉末296.5kg、聚酰胺蜡8kg进行共混反应，反应4～6h，测试反应液粘度达到150～190Pa·s/50℃时，结束反应。
实施例4
1、配方
Figure BDA0001122069280000062
2、制备方法
在反应釜中投入聚己二酸乙二醇缩二乙二醇酯二醇(数均分子量4000g/mol)180kg、双端羟基聚醚改性硅油(数均分子量2000g/mol)15kg、二苯基甲烷-4，4‵-二异氰酸酯(MDI)12.8kg和N，N-二甲基甲酰胺310kg进行预聚反应，反应温度控制在75～85℃，反应2～3h后，反应液粘度达到20～30Pa·s/50℃时，在反应釜中投入乙二醇14.02kg、二苯基甲烷-4，4‵-二异氰酸酯56.87kg和N，N-二甲基甲酰胺1154kg进行扩链反应，控制反应温度60～70℃，反应至反应液粘度达到50℃时，15～20Pa·s时，加入聚乙烯醇0588粉末405.3kg、聚酰胺蜡5kg进行共混反应，反应4～6h，测试反应液粘度达到100～120Pa·s/50℃时，结束反应。
实施例5
1、配方
Figure BDA0001122069280000071
2、制备方法
在反应釜中投入聚己二酸乙二醇-1,4丁二醇酯二醇(数均分子量4000g/mol)200kg、双端羟基聚醚改性硅油(数均分子量2000g/mol)10kg、二苯基甲烷-4，4‵-二异氰酸酯(MDI)13.2kg和N，N-二甲基甲酰胺273kg进行预聚反应，反应温度控制在75～85℃，反应2～3h后，反应液粘度达到10～20Pa·s/50℃时，在反应釜中投入乙二醇13.95kg、二苯基甲烷-4，4‵-二异氰酸酯56.8kg和N，N-二甲基甲酰胺1587kg进行扩链反应，控制反应温度50～60℃，反应至反应液粘度达到50℃时，5～10Pa·s时，加入聚乙烯醇1788粉末498kg、聚酰胺蜡5kg进行共混反应，反应4～6h，测试反应液粘度达到60～80Pa·s/50℃时，结束反应。
发明人将本发明实施例1-5制备所得的超软蛋白质湿法树脂和对比例HDW-20一起进行了检测试验，比较用上述树脂制作合成革贝斯的泡孔差异。
实验步骤：
(1)将实施例1～5制备的软质全聚醚型耐水解低泡湿法聚氨酯树脂加入色浆、填充和溶剂搅匀配成粘度为8～15Pa·s/25℃的工作浆；将对比例上海汇得科技有限公司的普通软质湿法树脂HDW-30加入色浆、填充、溶剂配成8～15Pa·s/25℃的工作浆。
(2)将0.9mm厚的仿棉绒基布机织布上进行涂刮，经凝固、水洗、烘干后得到湿法贝斯。
试验结果
本发明的超软蛋白质湿法树脂实施例1-5与对比例HDW-30所制湿法贝斯的横截面的泡孔结构对比如图1至图3(数码显微镜放大100倍)：
如图1至图3所示，明显可见，本发明的超软蛋白质湿法树脂制成贝斯的横截面泡孔呈蜂窝状，贝斯厚度更厚，而普通湿法树脂制成贝斯的泡孔呈竖直状并有一定的堆积层，贝斯厚度薄，用普通湿法树脂加填充是无法调节出实施例1-5这样的蜂窝状泡孔。因此，用本发明的共混树脂材料制成的湿法贝斯，具有不同于传统湿法树脂的蜂窝状泡孔结构，更接近真皮蛋白质纤维的网状结构，不仅海绵感强、折痕细，并且具有轻柔、舒适、自然、保暖的特点。

Claims (3)

1.一种超软蛋白质湿法树脂，该聚氨酯树脂主要由以下重量百分含量的原料制备而成：
Figure FDF0000008651860000011
其中，所述聚酯/聚醚多元醇为数均分子量为2000～4000g/mol的聚己二酸乙二醇-1,4丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸乙二醇缩二乙二醇酯二醇、聚四氢呋喃醚二醇中的一种或任意两种以上混合，所述双端羟基聚醚改性硅油为数均分子量为2000～3000g/mol的双端羟基聚醚改性硅油；
所述聚乙烯醇的质量和聚氨酯固形份的总质量的质量比为：2.5:1～1:1；所述聚氨酯固形份的总质量是指：聚酯/聚醚多元醇、乙二醇、双端羟基聚醚改性硅油、异氰酸酯的质量和；所述聚氨酯固形物和聚乙烯醇进行物理共混，制革凝固时所述聚乙烯醇粉末进行溶胀占据空间，并在水洗后溶胀后的聚乙烯醇粉末溶于水而留下微孔；所述聚乙烯醇粉末为平均聚合度为300～2400的聚乙烯醇粉末中一种或两种的混合；所述聚乙烯醇粉末为醇解度86％的聚乙烯醇粉末、醇解度88％的聚乙烯醇粉末中的一种或两种的混合；
所述的超软蛋白质湿法树脂的制备方法，其特征在于，具有以下步骤组成：
(1)在反应釜中投入聚酯/聚醚多元醇、双端羟基聚醚改性硅油、二苯基甲烷-4，4‵-二异氰酸酯和部分溶剂进行预聚反应，控制反应液中异氰酸酯基和羟基的摩尔比为0.95:1～0.98:1，反应温度控制在75～85℃，反应液固含量控制在40～60％，反应2～3h后，反应液粘度达到10～150Pa·s/50℃时，第一步反应结束；
(2)在反应釜中投入乙二醇、二苯基甲烷-4，4‵-二异氰酸酯和剩余溶剂进行扩链反应，控制反应温度50～80℃，反应至反应液粘度达到50℃时，5～30Pa·s时，加入聚乙烯醇粉末、聚酰胺蜡，进行共混反应并使得聚乙烯醇粉末进行溶胀，反应4～6h，测试反应液粘度达到10～200Pa·s/50℃时，结束反应。
2.根据权利要求1所述的超软蛋白质湿法树脂，其特征在于，所述双端羟基聚醚改性硅油的质量和聚酯/聚醚多元醇的总质量比为1:20～1:10；
3.权利要求1至2任一项权利要求所述的超软蛋白质湿法树脂的应用，该超软蛋白质湿法树脂用于制作合成革湿法贝斯所述合成革湿法贝斯有类似真皮蛋白质纤维结构的蜂窝状泡孔结构。
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