CN113106764A - 一种超纤超软质耐刮耐磨面层树脂及其制备方法 - Google Patents

一种超纤超软质耐刮耐磨面层树脂及其制备方法 Download PDF

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CN113106764A
CN113106764A CN202010033595.6A CN202010033595A CN113106764A CN 113106764 A CN113106764 A CN 113106764A CN 202010033595 A CN202010033595 A CN 202010033595A CN 113106764 A CN113106764 A CN 113106764A
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宗军业
鲁明友
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Abstract

本发明公开了一种超纤超软质耐刮耐磨面层树脂及其制备方法，所述超纤超软质耐刮耐磨面层树脂，由以下重量份的原料组成：N，N‑二甲基甲酰胺50‑60份、乙酯10‑15份、抗氧化剂0.1‑0.3份、聚酯多元醇4‑7份、聚醚多元醇10‑15份、异氰酸酯5‑8份、离子交换树脂1‑3份、醋酸丁酸纤维素0.4‑0.8份、扩链剂1.1‑1.8份、丙烯腈‑苯乙烯共聚物1‑2份。本申请的面层树脂在制备时先对原料混匀，再加入异氰酸酯，以此便于原料之间充分反应，其工序简单、操作方便，便于批量生产。其制得的面层树脂具有手感柔软、折纹细致、耐磨耐刮、抗菌抗虫、耐候抗氧化的特点。

Description

一种超纤超软质耐刮耐磨面层树脂及其制备方法
技术领域
本发明涉及一种树脂技术领域，特别涉及一种超纤超软质耐刮耐磨面层树脂及其制备方法。
背景技术
目前，天然皮革的资源有限，随着科学技术进步和人民生活水平提高，开发研制高品质的仿真皮革满足市场需求，成为急需解决的问题。
采用超细纤维(超纤)树脂生产的仿真皮革比天然皮革具有更良好的柔软性、透气性、耐久性、抗霉性、附化学品性、易保养性、加工性以及质量均一性，促使超纤树脂的工厂蓬勃发展。从工业意义上讲，该超纤树脂制成的仿真皮革适用于现代化规模生产，同时又能保护生态、减少环境污染，充分利用了非自然资源。
目前，由于市场上对仿真皮革的仿真度要求越来越高，尤其是对手感和折纹、耐磨耐刮的要求的提高，使得厂家不得不改进原有的配方工艺以进行适应，进而对超纤树脂的要求也随之增加。为此，研发一种手感柔软、折纹细致且耐磨耐刮的超纤树脂是目前急需解决的技术难题。
发明内容
针对现有技术存在的不足，本发明的第一个目的在于提供一种超纤超软质耐刮耐磨面层树脂，具有手感柔软、折纹细致、耐磨耐刮的特点。
本发明的第二个目的在于提供一种超纤超软质耐刮耐磨面层树脂的制备方法，其具有工序简单、操作方便的特点。
为实现上述第一个目的，本发明提供了如下技术方案：
一种超纤超软质耐刮耐磨面层树脂，由以下重量份的原料组成：
N，N-二甲基甲酰胺50-60份、乙酯10-15份、抗氧化剂0.1-0.3份、聚酯多元醇4-7份、聚醚多元醇10-15份、异氰酸酯5-8份、离子交换树脂1-3份、醋酸丁酸纤维素0.4-0.8份、扩链剂1.1-1.8份、丙烯腈-苯乙烯共聚物1-2份。
进一步地，所述超纤超软质耐刮耐磨面层树脂由以下重量份的原料组成：
N，N-二甲基甲酰胺57.43份、乙酯11.04份、抗氧化剂0.11份、聚酯多元醇5.74份、聚醚多元醇13.03份、异氰酸酯6.63份、离子交换树脂2.21份、醋酸丁酸纤维素0.5份、扩链剂1.43份、丙烯腈-苯乙烯共聚物1.88份。
通过采用上述技术方案，本申请中，N，N-二甲基甲酰胺为溶剂，能够溶解本申请公开的大部分原料，便于各原料的分子之间接触充分而提高物料之间的反应效率。乙酯对醋酸丁酸纤维素具有良好的溶解性，在本申请中添加适量的乙酯能够增加醋酸丁酸纤维素的溶解量，此外其还具有一定的杀菌杀虫效果，使得其制得的面层树脂具有优异的抗菌抗虫性能。
另一方面，本申请的面层树脂可以看作为一种含软链段和硬链段的嵌段共聚物。其中，软链段是由低聚物多元醇构成，多数为聚醚多元醇，同时配合有聚酯多元醇。在聚醚多元醇的分子结构中含有醚键，易旋转，链的柔顺性比酯键好，因此聚醚型的聚氨酯软化温度低，耐低温性能好，有较好的韧性和延伸性。此外，用不同的低聚物多元醇制得的聚醚型聚氨酯一般比聚酯型多元醇具有较高的耐寒耐水解性和柔软性，而聚酯型多元醇的耐热性和抗氧化性较优。所以，无论是聚酯型还是聚醚型的聚氨酯，其软段的结晶性对聚氨酯的物性最终机械强度和模量有较大的影响，当两者按上述重量份数配合使用时，其制得的面层树脂兼具优异的手感柔软性、耐低温性、耐高温性、抗氧化性以及韧性和延伸性。
硬链段中异氰酸酯的结构对聚氨酯的性能，特别是刚性和强度有很大的影响。然而，由于异氰酸酯中的异氰酸酯基团能直接与苯核上碳原子相联，这样异氰酸酯基团与苯核形成醌型结构易于氧化变黄，抗UV降解性能较差。对此，抗氧化剂的添加能够阻止异氰酸酯基团与苯核的结合，进而提高其面层树脂的光稳定性。
由于两链段的热力学不相溶，产生相分离，在聚合物基体内部形成相区和微相区。聚氨酯中存在的氨酯和脲键产生氢键对硬段相区的形成有较大的贡献，硬段相区起增强作用，而软段基体被硬段相区交联。所以聚氨酯具有柔韧性和宽范围的物性，按照本申请的软硬链段的化学组成或结构来制备，其制得的面层树脂的各种性能可大幅度得到提升，从而满足手感柔软、折纹细致、耐磨耐刮的要求。
离子交换树脂在本申请中可作为催化剂，代替无机酸、碱等，促使反应可控的进行。另外，离子交换树脂可以反复使用，且与产品容易分离，因此能有效减少其对环境的污染，具有节能环保的特点。
醋酸丁酸纤维素作为流平剂，能改善面层树脂的成膜效果。扩链剂则增加面层树脂的分子量，使其制得的面层树脂的粘度满足要求。丙烯腈-苯乙烯共聚物能配合硬链段，进一步提高面层树脂的光泽度、刚性和强度，使得面层树脂折纹细致且耐刮耐磨。
综上，本申请按照上述原料及重量份数配制而成的面层树脂，具有手感柔软、折纹细致、耐磨耐刮、抗菌抗虫、耐候抗氧化的特点。
进一步地，所述聚酯多元醇为PBA-2000。
通过采用上述技术方案，PBA-2000为聚四氢呋喃醚二醇2000，其可作为生产聚氨酯的原料，在丙烯腈-苯乙烯共聚物中耐迁移性显著，由此制得的面层树脂具有优异的刚性和强度。
进一步地，所述聚醚型多元醇为PTMEG-2000。
通过采用上述技术方案，PTMEG-2000为聚四氢呋喃-2000，其可作为生产聚氨酯的原料，当温度超过室温时会变成透明液体，易溶于醇、酯、芳烃中，因此能与本申请的其他原料具有良好的相容性，有效改善面层树脂的加工性能。
进一步地，所述异氰酸酯为MDI。
通过采用上述技术方案，MDI为二苯甲烷二异氰酸酯，其分子结构对称，产生结构规整有序的相区结构，因此MDI比甲苯二异氰酸酯(TDI)制备的聚氨酯具有较高的模量和撕裂强度。芳香族异氰酸酯制备的聚氨酯由于具有刚性的芳环，硬段内聚能增大，其强度比来自脂肪族的异氰酸酯的聚氨酯大，并且抗热氧化性能也好。由此，在本申请中，选用MDI制得的聚氨酯具有更高的机械强度和抗热氧化性能。
进一步地，所述离子交换树脂为MB20树脂。
通过采用上述技术方案，MB20树脂是一种离子平衡的混床树脂，为完全再生的即用型强酸性阳离子交换剂与强碱性Ⅰ型阴离子交换剂的混合物。其不但能够较好的起到催化作用，还能够对反应产生的二氧化碳等杂质加以去除，进而提高面层树脂的生产效率。
进一步地，所述扩链剂为乙二醇和1,4-丁二醇中的一种或两种的混合物。
通过采用上述技术方案，聚醚或聚酯多元醇与异氰酸酯等反应，生成异氰酸酯预聚体，使用时，加热熔融涂覆于材料表面，与环境中的潮气或水分反应生成脲键而部分交联固化，形成了网状结构且不溶、不熔、不可回收或二次利用。
乙二醇、1,4-丁二醇均为小分子二元醇扩链剂，其会与异氰酸酯反应生成链状的高分子化合物氨基甲酸酯，然后再加上其他黏性树脂如丙烯腈-苯乙烯共聚物进行改性，使用时加热至一定温度熔化涂布于基材表面，经冷却而固化，固化过程主要利用组成中的氢键作用而发生物理交联，具有优良的韧性和粘结强度。其一定温度受热后会失去氢键作用而变成粘稠状液体，冷却后有恢复原来的物性，因此实现反复加工-冷却固化的特点，使得面层树脂可以被回收利用。
所以使用乙二醇和/或1,4-丁二醇扩链的聚氨酯具有更高的机械强度、模量、粘附性、耐热性，并且还有较好的低温性能，以此作为优选。
进一步地，所述扩链剂由乙二醇和1,4-丁二醇按重量比为(1-3):(11-15)复配而成。
通过采用上述技术方案，经过实验验证，当扩链剂由乙二醇和1,4-丁二醇按重量比为(1-3):(11-15)复配而成时，对面层树脂的机械耐刮耐磨性能的改善效果明显优于其他配比时的，因此将其作为进一步的优选。
为实现上述第二个目的，本发明提供了如下技术方案：
一种超纤超软质耐刮耐磨面层树脂的制备方法，包括以下步骤：
①、往反应釜中加入适量N，N-二甲基甲酰胺，随后依次加入设定重量份数的乙酯、抗氧化剂、聚酯多元醇、聚醚多元醇、离子交换树脂、醋酸丁酸纤维素、扩链剂和丙烯腈-苯乙烯共聚物，在45-50℃的温度下以300rpm的转速搅拌5min；
②、往步骤①搅拌完成得到的物料中投入异氰酸酯，在70-75℃的温度下继续搅拌反应1h，加入剩余份数的N，N-二甲基甲酰胺，得到粘度为8×104-14×104cps/25℃的树脂料；
③、测定树脂料的异氰酸酯基含量，根据化学计量比确定甲醇的添加量，随后在树脂料中加入甲醇终止反应，降温至40℃以下送检，合格后过200目筛网过滤，得到最终的超纤超软质耐刮耐磨面层树脂，包装后入库。
通过采用上述技术方案，步骤①原料在45-50℃加热搅拌，便于各原料先充分混匀，随后在步骤②中加入异氰酸酯，异氰酸酯与多元醇和扩链剂充分反应，最后再又甲醇终止反应，由此制得的面层树脂具有手感柔软、折纹细致、耐磨耐刮的特点，还能实现回收利用。其制备方法的工序简单、操作方便，便于面层树脂的批量生产。
综上所述，本发明具有以下有益效果：
1、本申请的面层树脂按照特定原料及重量份数配制而成，具有手感柔软、折纹细致、耐磨耐刮、抗菌抗虫、耐候抗氧化的特点；
2、本申请的面层树脂在制备时先对原料混匀，再加入异氰酸酯，以此便于原料之间充分反应，其工序简单、操作方便，便于批量生产。
附图说明
图1为制备超纤超软质耐刮耐磨面层树脂的工艺流程图。
具体实施方式
以下结合附图对本发明作进一步详细说明。
1、原料
N，N-二甲基甲酰胺：购自上海麦克林生化科技有限公司，CAS号为68-12-2，纯度为99％；乙酯：又称甲酸乙酯，购自上海阿拉丁生化科技股份有限公司，CAS号为109-94-4，纯度为99％；
抗氧化剂：本申请以抗氧剂1010和抗氧剂168为例，均购自江苏汉光实业股份有限公司，具体以抗氧化剂a和抗氧化剂b为例，抗氧化剂a由抗氧剂1010和抗氧剂168按重量比为1:0.8混合而成，抗氧化剂b由抗氧剂1010和抗氧剂168按重量比1:1混合而成；
聚酯多元醇：本申请以PBA-1000和PBA-2000为例，均购自长兴化学(天津)有限公司；聚醚多元醇：本申请以PTMEG-1000和PTMEG-2000为例，均购自广州昊毅化工科技有限公司；
异氰酸酯：本申请以甲苯二异氰酸酯(TDI)和二苯基甲烷二异氰酸酯(MDI)为例，均购自北京华美互利生物化工；
离子交换树脂：本申请以争光ZGER-8420抛光树脂和罗门哈斯MB20树脂为例，前者购自苏州润淼环保科技有限公司，后者购自凯茵化工；
醋酸丁酸纤维素：购自江苏维科特瑞化工有限公司，CAS号为9004-36-8，密度为1.15-1.22g/cm3；
扩链剂：本申请以乙二醇、1,4-丁二醇和1,6-己二醇为例，均购自郑州恩铭化工产品有限公司；丙烯腈-苯乙烯共聚物：购自湖北鑫鸣泰化学有限公司，CAS号为9004-54-7，密度为1.08g/mL。
2、实施例
2.1、实施例1
一种超纤超软质耐刮耐磨面层树脂，由以下重量份的原料组成：
N，N-二甲基甲酰胺57.43份、乙酯11.04份、抗氧化剂a 0.11份、PBA-2000 5.74份、PTMEG-2000 13.03份、MDI 6.63份、MB20树脂2.21份、醋酸丁酸纤维素0.5份、由乙二醇和1,4-丁二醇按重量比为2:11复配而成的扩链剂1.43份、丙烯腈-苯乙烯共聚物1.88份。
上述超纤超软质耐刮耐磨面层树脂的制备方法，包括以下步骤：
①、往反应釜中加入适量N，N-二甲基甲酰胺，随后依次加入设定重量份数的乙酯、抗氧化剂a、PBA-2000、PTMEG-2000、MB20树脂、醋酸丁酸纤维素、扩链剂和丙烯腈-苯乙烯共聚物，在50℃的温度下以300rpm的转速搅拌5min；
②、往步骤①搅拌完成得到的物料中投入MDI，在72℃的温度下继续搅拌反应1h，加入剩余份数的N，N-二甲基甲酰胺，得到粘度为11×104cps/25℃的树脂料；
③、测定树脂料的异氰酸酯基含量，根据化学计量比确定甲醇的添加量，随后在树脂料中加入甲醇终止反应，降温至40℃以下送检，合格后过200目筛网过滤，得到最终的超纤超软质耐刮耐磨面层树脂，包装后入库。
2.2、实施例2-10
实施例2-10在实施例1的方法基础上，对面层树脂的原料及其制备参数加以调整，具体调整情况参见下表一，原料的重量单位为kg。
表一实施例1-10的原料及其制备参数比表
Figure BDA0002365228670000071
3、对比例
3.1、对比例1
对比例1在实施例1的方法基础上，未添加PBA-2000。
3.2、对比例2
对比例2在实施例2的方法基础上，未添加PTMEG-2000。
3.3、对比例3
对比例3在实施例3的方法基础上，未添加乙酯。
3.4、对比例4
对比例4在实施例1的方法基础上，未添加丙烯腈-苯乙烯共聚物。
4、性能检测
将上述实施例1-10以及对比例1-4制得的面层树脂进行如下性能测试，检测结果参见下表二。
4.1、固含量(120℃，1.5h)、粘度(25℃)、密度(25℃)和挥发性(40℃，1h)：按QB/T4197-2011的规定进行检测。
4.2、手感：检测员手测。
4.3、折纹程度：将待测皮革180°折叠30次，观察折纹的深浅，1表示基本无折纹，2表示有少量折纹印记，3表示有较明显的折纹印记。
4.4、成革后耐刮耐磨性：按QB/T2726-2005的规定进行检测，其中荷重为1kg、选择H-18磨轮、转数400转，观察产品表面涂层，无磨穿而露出布基即为合格。
4.5、成革后耐水解性：按QB/T4671-2014的规定进行检测，应用其中的B法检测即常温碱液12小时后，革面没有明显破裂即为合格。
4.6、成革后抗菌性：将1mL菌含量为8×105cfu/mL的霉菌涂布于10cm×10cm待测皮革的表面，于36℃的环境下培养2天，观察皮革表面的菌落数。
4.7、成革后抗虫性：将30只健康的螨虫和10cm×10cm的待测皮革置于洁净培养容器中，于36℃的环境下培养7d，观察螨虫的存活数量。
4.8、耐候抗氧化性：按GB/T 16422.2方法B的规定进行检测，辐照度为1.25W，420nm，湿度50％，连续光照，黑标100℃，测定皮革断裂强度的变化率。
表二实施例1-10以及对比例1-4的检测结果
Figure BDA0002365228670000091
参见表二，将实施例1-3的检测结果可以看出，按照本申请特定原料及重量份数配制的面层树脂，其固含量、粘度、密度和挥发性的要求符合标准的规定，其相对于对比例1-4的检测结果，还具有手感柔软、折纹细致、耐磨耐刮、抗菌抗虫、耐候抗氧化的特点。
将实施例1与实施例4的检测结果进行对比，可以得到，采用由抗氧剂1010和抗氧剂168按重量比为1:0.8混合而成的抗氧化剂a能有效提高面层树脂的耐候抗氧化性能，还能在一定程度上减少挥发性物质的产生。
将实施例1与实施例5-7的检测结果进行对比，可以得到，当“聚酯多元醇为PBA-2000、聚醚型多元醇为PTMEG-2000、异氰酸酯为MDI、离子交换树脂为MB20树脂”时，能够使得面层树脂的折纹更加细致。此外，当“异氰酸酯为MDI、离子交换树脂为MB20树脂”时，还能减少挥发性物质的量，增加面层树脂的稳定性。
将实施例1与实施例8-10的检测结果进行对比，可以得到，当“扩链剂为乙二醇和1,4-丁二醇中的一种或两种的混合物”时，其制得的面层树脂折纹更加细致，且具有更为优异的耐刮耐磨性能。其中，当“扩链剂由乙二醇和1,4-丁二醇按重量比为(1-3):(11-15)复配而成”时，其制得的面层树脂耐刮耐磨性能尤为突出。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。

Claims (9)

1.一种超纤超软质耐刮耐磨面层树脂，其特征在于，由以下重量份的原料组成：
N，N-二甲基甲酰胺50-60份、乙酯10-15份、抗氧化剂0.1-0.3份、聚酯多元醇4-7份、聚醚多元醇10-15份、异氰酸酯5-8份、离子交换树脂1-3份、醋酸丁酸纤维素0.4-0.8份、扩链剂1.1-1.8份、丙烯腈-苯乙烯共聚物1-2份。
2.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，由以下重量份的原料组成：
N，N-二甲基甲酰胺57.43份、乙酯11.04份、抗氧化剂0.11份、聚酯多元醇5.74份、聚醚多元醇13.03份、异氰酸酯6.63份、离子交换树脂2.21份、醋酸丁酸纤维素0.5份、扩链剂1.43份、丙烯腈-苯乙烯共聚物1.88份。
3.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述聚酯多元醇为PBA-2000。
4.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述聚醚型多元醇为PTMEG-2000。
5.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述异氰酸酯为MDI。
6.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述离子交换树脂为MB20树脂。
7.根据权利要求1所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述扩链剂为乙二醇和1,4-丁二醇中的一种或两种的混合物。
8.根据权利要求7所述的一种超纤超软质耐刮耐磨面层树脂，其特征在于，所述扩链剂由乙二醇和1,4-丁二醇按重量比为(1-3):(11-15)复配而成。
9.根据权利要求1至8中任意一项所述的一种超纤超软质耐刮耐磨面层树脂的制备方法，其特征在于，包括以下步骤：
①、往反应釜中加入适量N，N-二甲基甲酰胺，随后依次加入设定重量份数的乙酯、抗氧化剂、聚酯多元醇、聚醚多元醇、离子交换树脂、醋酸丁酸纤维素、扩链剂和丙烯腈-苯乙烯共聚物，在45-50℃的温度下以300rpm的转速搅拌5min；
②、往步骤①搅拌完成得到的物料中投入异氰酸酯，在70-75℃的温度下继续搅拌反应1h，加入剩余份数的N，N-二甲基甲酰胺，得到粘度为8×104-14×104cps/25℃的树脂料；
③、测定树脂料的异氰酸酯基含量，根据化学计量比确定甲醇的添加量，随后在树脂料中加入甲醇终止反应，降温至40℃以下送检，合格后过200目筛网过滤，得到最终的超纤超软质耐刮耐磨面层树脂，包装后入库。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289053A (zh) * 2012-03-05 2013-09-11 旭川化学（昆山）有限公司 一种超软质鞋革用人造革浆料及其制备方法
CN107541053A (zh) * 2017-09-04 2018-01-05 瑞安市鸿日塑胶有限公司 改良性tup薄膜
CN107722219A (zh) * 2017-10-25 2018-02-23 合肥安利聚氨酯新材料有限公司 一种服装革湿法聚氨酯树脂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289053A (zh) * 2012-03-05 2013-09-11 旭川化学（昆山）有限公司 一种超软质鞋革用人造革浆料及其制备方法
CN107541053A (zh) * 2017-09-04 2018-01-05 瑞安市鸿日塑胶有限公司 改良性tup薄膜
CN107722219A (zh) * 2017-10-25 2018-02-23 合肥安利聚氨酯新材料有限公司 一种服装革湿法聚氨酯树脂及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
张玉龙: "《泡沫塑料制品配方设计与加工实例》", 31 January 2006, 国防工业出版社 *
施孝: "铸膜溶剂对CAB膜形态和性能的影响", 《功能高分子学报》 *
黄锐: "《塑料工程手册 上》", 30 April 2000, 机械工业出版社 *

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