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CN105111412A - 一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法 - Google Patents

一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法 Download PDF

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CN105111412A
CN105111412A CN201510634214.9A CN201510634214A CN105111412A CN 105111412 A CN105111412 A CN 105111412A CN 201510634214 A CN201510634214 A CN 201510634214A CN 105111412 A CN105111412 A CN 105111412A
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张彪
武春余
姚克俭
李震
尹凯凯
李晓飞
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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Abstract

本发明公开了一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法，该聚氨酯树脂的原料优选了碳化二亚胺改性的异氰酸酯、高活性的聚氧化丙烯二元醇、低结晶性的聚碳酸酯二元醇，通过预聚法合成工艺制成。本发明聚氨酯树脂较大提高了树脂的剥离强度和耐水解性能，用其制成的合成革经久耐用。

Description

一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法
一、技术领域
本发明涉及一种功能性聚氨酯树脂及其制备方法，具体地说是一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法。
二、背景技术
合成革用耐水解湿法树脂使用到大量的聚醚和聚碳材料，其中聚醚多以PTMG为主，也有使用PPG的报导，但PPG反应活性较低，应用受到限制，近年来改性PPG技术发展迅速，产品反应活性高，品质稳定，逐渐受到合成革行业的重视，本发明中使用了改性的PPG，国内生产厂家很多，如天津石化、蓝星东大、德信联邦等，货源充足；聚碳的价格高，结晶性强，内聚能大，应用较少，但近年来聚碳技术发展，出现了很多低结晶性的聚碳酸酯二元醇，适量加入能明显提高成品加工性能和耐用性。
聚氨酯树脂合成用的扩链剂多来源于石油，由杜邦公司开发的1，3-丙二醇由生物质提取，属可再生能源，现已工业化生产，可稳定供货，应用于聚氨酯树脂的合成，可减小对石油的依赖，环境友好。
合成革用异氰酸酯以MDI为主，现碳化二亚胺改性的MDI，刚性更强，适合制成高强度的聚氨酯树脂以提高革制品的力学性能。
三、发明内容
本发明旨在提供一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂及其制备方法，所要解决的技术问题是提高聚氨酯合成革的剥离强度和耐水解性能。
本发明软质耐水解复合聚醚型高剥离湿法聚氨酯树脂，其原料及配比为：
所述异氰酸酯为4,4′-二苯基甲烷二异氰酸酯(MDI)和碳化二亚胺改性的4,4′-二苯基甲烷二异氰酸酯CD-MDI100L(烟台万华生产，牌号为CD-MDI100L)。
所述多元醇化合物由聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇构成，其质量比为4-5:4-5:0.5-1.5；所述多元醇化合物的数均分子量为1000-4000。
所述二元醇扩链剂为乙二醇和1,3-丙二醇。
所述聚酯多元醇为己二酸系聚酯二元醇。
所述聚醚多元醇为聚四氢呋喃多元醇和改性的聚氧化丙烯多元醇，聚四氢呋喃多元醇和改性的聚氧化丙烯多元醇质量比为0.5-2:1；其中改性的聚氧化丙烯多元醇为市购得到，选自山东德信联邦的DDL-2000D、DDL-3000D、DDL-4000D等。
所述改性的聚氧化丙烯多元醇为高反应活性的聚醚多元醇，分子量优选3000-4000。
所述聚碳酸酯多元醇为低结晶性的聚碳，常温下具有流动性，分子量优选1000-2000。
所述抗氧剂优选为抗氧剂I-1010。
所述有机铋类催化剂优选为8106，美国领先化学品公司生产。
本发明软质耐水解复合聚醚型高剥离湿法聚氨酯树脂的制备方法，包括如下步骤：
1)将聚酯多元醇、聚醚多元醇和抗氧剂加入有机溶剂中，控制固含量在35-45％，搅拌均匀后加入12-16％的MDI于75-85℃反应1小时；再向体系中加入聚碳酸酯多元醇和20-25％的二元醇扩链剂，搅拌均匀后分批补加MDI增粘(欠量法补加，溶剂法合成行业共知)，于75-85℃反应1-3小时，制得预聚物；
2)向步骤1)制备的预聚物中加入余量的二元醇扩链剂和CD-MDI100L于75-85℃继续反应1h后分批加入余量的MDI，在反应的过程中随着体系粘度的增加不断补充有机溶剂使得最终固含量为25％、粘度为30-80Pa.S/25℃，反应完成后加入反应终止剂甲醇，搅拌均匀后即可下料包装。
步骤1)中预聚物的固含量控制在45-50％，粘度控制在60-80Pa.S/75℃；
步骤2)中CD-MDI100L与余量的MDI的质量比为0.5-1.5:10。
所述有机溶剂优选N,N′-二甲基甲酰胺(DMF)。
通过上述配方制得的湿式聚氨酯树脂应用于合成革生产，制成的革制品具有优异的剥离强度和耐水解性能。
本发明聚氨酯树脂较大改善和提高了树脂的剥离强度和耐水解性能，产品质量好档次高，具有市场竞争力。
四、具体实施方式
下面结合具体实施例对本发明作进一步解释说明。
SP-2、SP-3分别为自制的分子量为2000、3000的聚酯多元醇，所用原料及配方为己二酸8000kg、乙二醇1600kg、1,4-丁二醇3360kg，制备方法参见：聚氨酯树脂及其应用，化学工业出版社(2011.11)，刘益军，P62聚酯多元醇的生产方法和物料计算；
EG为乙二醇；
1,3-PG为1,3-丙二醇；
PPG-3、PPG-4分别为分子量为3000、4000的改性的聚氧化丙烯二元醇；
PTMG-1、PTMG-2分别为分子量为1000、2000的聚四氢呋喃二元醇；
PCDL-1、PCDL-2分别为分子量为1000、2000的聚碳酸酯二元醇；
I-1010为市售抗氧剂，全名为四[β-(3,5-二叔丁基-4羟基苯基)丙酸]季戊四醇酯；
MDI为4,4′-二苯基甲烷二异氰酸酯；
CD-MDI100L为碳化二亚胺改性的MDI，烟台万华生产，异氰酸酯基的质量分数为29％；
有机铋类催化剂(8106，美国领先化学品公司生产)；
DMF为溶剂N,N′-二甲基甲酰胺，甲醇为反应终止剂。
实施例1：
1、原料及配比：
表格中的单位均为kg
2、制备方法：
1)将多元醇化合物SP-3、SP-2、PTMG-2、PPG-3和抗氧剂I-1010加入溶剂DMF中，搅拌均匀后加入15％的MDI于75-85℃反应1小时，再向体系中加入PCDL-2和EG，搅拌均匀后补加MDI增粘，于75-85℃反应1-3小时，反应过程中加入有机铋类催化剂，制得固含量47％，粘度60-80Pa.S/75℃的预聚物；
2)向步骤1)制备的预聚物中加入二元醇扩链剂EG、1，3-PG和CD-MDI100L，于75-85℃继续反应1h后加入余量的MDI，反应2-4小时，在反应的过程中随着体系粘度的增加不断补充有机溶剂使得最终粘度控制在30-80Pa.S/25℃，反应完成后加入反应终止剂甲醇0.5-2kg即可，搅拌均匀后即可下料包装。
实施例2：
1、原料及配比：
表格中的单位均为kg
2、制备方法：
1)将多元醇化合物SP-3、SP-2、PTMG-2、PPG-2和抗氧剂I-1010加入溶剂DMF中，搅拌均匀后加入13％的MDI于75-85℃反应1小时，再向体系中加入PCDL-1和EG，搅拌均匀后补加MDI增粘，于75-85℃反应1-3小时，反应中途加入有机铋类催化剂，制得固含量47％，粘度60-80Pa.S/75℃的预聚物；
2)向步骤1)制备的预聚物中加入二元醇扩链剂EG、1，3-PG和CD-MDI100L，于75-85℃继续反应1h后加入余量的MDI，反应2-4小时，在反应的过程中随着体系粘度的增加不断补充有机溶剂使得最终粘度控制在30-80Pa.S/25℃，反应完成后加入反应终止剂甲醇0.5-2kg即可，搅拌均匀后即可下料包装。
将根本发明实施例1和实施例2制备的聚氨酯树脂以及普通树脂按照合成革行业常规方法打样，进行剥离强度和耐水解性的测试，测试方法详见合成革工艺学，曲建波等编著，化学工业出版社(2010.3)，P127-158成革加工工艺，P368剥离强度测试方法、P369耐水解检测方法，采用快速耐碱测剥离。常规方法检测厚度和单位面积重量。测试结果见下表1。
表1
*软质耐水解树脂SW-6030H为合肥安利聚氨酯新材料有限公司生产，原料中不含聚碳酸酯二元醇。
从表1中可以看出，专利树脂透明澄清，表现出聚碳型聚氨酯树脂的清澈状态，专利树脂在剥离强度和耐水解性方面均大大超过了普通软质耐水解树脂。其中实施例2合成的树脂强度要高于实施例1，湿法发孔略小。表中专利树脂成革厚度厚但单位面积重量轻。同等厚度下单位面积样品质量重的物耗高，可见专利树脂的物耗低，节约物料成本。

Claims (7)

1.一种软质耐水解复合聚醚型高剥离湿法聚氨酯树脂，其特征在于其原料及配比为：
2.根据权利要求1所述的软质耐水解复合聚醚型高剥离湿法聚氨酯树脂，其特征在于：
所述异氰酸酯为4,4′-二苯基甲烷二异氰酸酯和碳化二亚胺改性的4,4′-二苯基甲烷二异氰酸酯CD-MDI100L；
所述多元醇化合物由聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇构成，所述多元醇化合物的数均分子量为1000-4000；
所述二元醇扩链剂为乙二醇和1,3-丙二醇；
所述聚酯多元醇为己二酸系聚酯二元醇；
所述聚醚多元醇为聚四氢呋喃多元醇和改性的聚氧化丙烯多元醇。
3.根据权利要求2所述的软质耐水解复合聚醚型高剥离湿法聚氨酯树脂，其特征在于：
多元醇化合物中聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇的质量比为4-5:4-5:0.5-1.5；
聚醚多元醇中聚四氢呋喃多元醇和改性的聚氧化丙烯多元醇的质量比为0.5-2:1；其中改性的聚氧化丙烯多元醇为DDL-2000D、DDL-3000D或DDL-4000D；
所述改性的聚氧化丙烯多元醇数均分子量为3000-4000；
所述聚碳酸酯多元醇为低结晶性的聚碳，常温下具有流动性，数均分子量为1000-2000。
4.根据权利要求1所述的软质耐水解复合聚醚型高剥离湿法聚氨酯树脂，其特征在于：
所述抗氧剂为抗氧剂I-1010；
所述有机铋类催化剂为
5.一种权利要求1所述的软质耐水解复合聚醚型高剥离湿法聚氨酯树脂的制备方法，其特征在于包括如下步骤：
1)将聚酯多元醇、聚醚多元醇和抗氧剂加入有机溶剂中，控制固含量在35-45％，搅拌均匀后加入12-16％的MDI于75-85℃反应1小时；再向体系中加入聚碳酸酯多元醇和20-25％的二元醇扩链剂，搅拌均匀后分批补加MDI增粘，于75-85℃反应1-3小时，制得预聚物；
2)向步骤1)制备的预聚物中加入余量的二元醇扩链剂和CD-MDI100L于75-85℃继续反应1h后分批加入余量的MDI，在反应的过程中随着体系粘度的增加不断补充有机溶剂使得最终固含量为25％、粘度为30-80Pa.S/25℃，反应完成后加入反应终止剂甲醇，搅拌均匀后即可下料包装。
6.根据权利要求5所述的制备方法，其特征在于：
步骤1)中预聚物的固含量控制在45-50％，粘度控制在60-80Pa.S/75℃；
步骤2)中CD-MDI100L与余量的MDI的质量比为0.5-1.5:10。
7.根据权利要求5所述的制备方法，其特征在于：
所述有机溶剂为N,N′-二甲基甲酰胺。
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