CN104356348A - 一种硬质耐水解低发孔性高剥离聚氨酯树脂及其制备方法 - Google Patents

一种硬质耐水解低发孔性高剥离聚氨酯树脂及其制备方法 Download PDF

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CN104356348A
CN104356348A CN201410592130.9A CN201410592130A CN104356348A CN 104356348 A CN104356348 A CN 104356348A CN 201410592130 A CN201410592130 A CN 201410592130A CN 104356348 A CN104356348 A CN 104356348A
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dihydric alcohol
hydrolysis
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polyurethane resin
organic solvent
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张彪
李震
尹凯凯
吴兴保
田海英
李晓飞
杜东旭
武春余
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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Abstract

本发明公开了一种硬质耐水解低发孔性高剥离聚氨酯树脂及其制备方法，其特征在于：按配比向反应釜中加入有机溶剂、大分子二元醇、扩链剂、抗氧剂和部分异氰酸酯，于60-80℃常压下反应1-2小时，再加入有机锡类或有机铋类催化剂，保持温度，将剩余的异氰酸酯分批投入反应釜中，然后根据反应体系的粘度情况分批补加有机溶剂至产物粘度为80-120Pa.s/25℃，最后再加入反应终止剂，得到固含量为35-40％的产物硬质耐水解低发孔性高剥离聚氨酯树脂。本发明制得的树脂应用于合成革生产，制成的革制品具有扎实的手感、优异的耐水解性能和低发孔性能。

Description

一种硬质耐水解低发孔性高剥离聚氨酯树脂及其制备方法
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，具体地说是一种硬质耐水解低发孔性高剥离聚氨酯树脂及其制备方法。
背景技术
随着市场和技术的发展，对聚氨酯合成革的物性要求越来越高，迫切需要一种硬质耐水解低发孔的高剥离聚氨酯湿法树脂。中等模量树脂的剥离强度和耐水解性都能达到要求，但成革品质稳定性不佳，手感偏软。而高模量耐水解高剥离树脂市场上鲜有，且往往只能提高成革手感，但不能保证剥离强度和耐水解性的稳定。本发明研究发现高模量和耐水解大分子二元醇都具有较强的疏水性，遇水迅速凝聚，并强制DMF与水快速置换导致大孔产生，不利于高物性合成革的剥离要求。如果能解决高模量耐水解树脂的发孔性问题，使成革切口孔型均匀，无明显孔型缺陷，可明显提升高物性合成革的品质。
发明内容
本发明通过研究发现，可以通过聚氨酯树脂原料的选择与设计来减缓凝聚的发生。本发明旨在提供一种硬质耐水解低发孔性高剥离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硬度、手感、耐水解和剥离强度稳定性，其技术难点在于控制高模量耐水解树脂的发孔性。
为突破上述技术难点，本发明采用如下技术方案：
本发明硬质耐水解低发孔性高剥离聚氨酯树脂的原料构成为：
异氰酸酯；
大分子二元醇；
扩链剂；
抗氧剂；
有机溶剂；
有机锡类或有机铋类催化剂；
反应终止剂；
所述异氰酸酯中的异氰酸根和羟基的摩尔量之比为0.90-1：1；所述羟基为大分子二元醇及扩链剂中的羟基之和；
所述大分子二元醇和所述扩链剂的质量比为3-4：1；
所述抗氧剂的用量占原料总质量的0.01-0.05％；
所述有机溶剂的用量为原料总质量的60-65％；
所述有机锡类或有机铋类催化剂的用量为大分子二元醇质量的0.001-0.05％；
所述反应终止剂的添加量为原料总质量的0.005-0.015％；
所述大分子二元醇为聚酯二元醇、聚碳酸酯二元醇和聚醚二元醇的混合，且聚碳酸酯二元醇和聚醚二元醇的质量和不低于大分子二元醇总质量的30％，以保证较高的耐水解性能。
所述异氰酸酯为4,4′-二苯基甲烷二异氰酸酯；
所述聚酯二元醇为己二酸系聚酯二元醇和/或含间苯环结构的聚酯二元醇，己二酸系聚酯二元醇的原料小分子二元醇宜选用链较长或含有侧基的二元醇，以提高分子链的运动能力，减弱在湿法凝聚过程中发孔性，含间苯结构的聚酯二元醇分子对称性较弱，分子间作用力较低，也可以减弱在湿法凝聚过程中的发孔性；
所述聚醚二元醇选自聚四氢呋喃二元醇和/或聚氧化丙烯二元醇，优选聚氧化丙烯二元醇，因为聚氧化丙烯二元醇含有侧基，分子规整性较差，可以减弱在湿法凝聚过程中的发孔性；
所述大分子二元醇的数均分子量为500-4000，优选为1000-2000。
所述扩链剂选自小分子二元醇，分子量在60-118，优选乙二醇或1,4-丁二醇。
所述有机溶剂优选N,N-二甲基甲酰胺(DMF)。
所述反应终止剂为甲醇。
本发明硬质耐水解低发孔性高剥离聚氨酯树脂的制备方法是：按配比向反应釜中加入有机溶剂、大分子二元醇、扩链剂、抗氧剂和部分异氰酸酯，于温度60-80℃常压下反应1-2小时，加入有机锡类或有机铋类催化剂，保持温度，将剩余的异氰酸酯分批投入反应釜中，根据反应体系的粘度情况分批补加有机溶剂(加入量根据体系粘度调整)至最终产品粘度80-120Pa.s/25℃，加入反应终止剂，得到固含量为35-40％的产物硬质耐水解低发孔性高剥离聚氨酯树脂。
与已有技术相比，本发明的有益效果体现在：
本发明通过上述配方制得的硬质耐水解低发孔性高剥离聚氨酯树脂应用于合成革生产，制成的革制品具有扎实的手感、优异的耐水解性能和低发孔性能。
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方面的物性，产品经久耐用，产品档次高，具有市场竞争力。
附图说明
图1为使用本发明实施例1所制备的树脂制备的革的照片；
图2为使用本发明实施例2所制备的树脂制备的革的照片；
图3为使用空白对比例SW-5080RH树脂制备的革的照片。
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-1000、SP-2400分别为自制的分子量为1000、2400的聚酯二元醇，其中SP-1000为己二酸与1,4-丁二醇、1,6-己二醇共聚制得(1,4-丁二醇、1,6-己二醇的质量比控制在1：5-6)，而SP-2400为间苯二甲酸与1,4-丁二醇、1,6-己二醇共聚制得(1,4-丁二醇、1,6-己二醇的质量比控制在4-5：1)，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；
PC-2000是聚碳酸酯二元醇，日本旭化成生产，商品名为PCDL-5652；
PPG-1、PPG-2分别为分子量为1000、2000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；
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；
有机铋为反应催化剂，其中有机铋的环保性优于有机锡为行业内共知；
DMF为溶剂N,N-二甲基甲酰胺，甲醇为反应终止剂。
实施例1
本实施例所用原料及其配比如表1所示：
表1.实施例1原料及配比
DMF 4000份
PC-2000 190份
SP-1000 380份
SP-2400 360份
PPG-2 320份
EG 370份
I-1010 3份
MDI 1000份
催化剂 0.2份
补加MDI 688份
补加DMF 1180份
终止剂 0.8份
固含量 39％
本实施例硬质耐水解低发孔性高剥离聚氨酯树脂的制备过程如下：
将大分子二元醇PC-2000、SP-1000、SP-2400、PPG-2、EG和抗氧剂I-1010加入4000份溶剂DMF中，搅拌均匀后加入1000份MDI于70℃左右反应2小时，补入催化剂加速反应，保持温度，将剩余的688份异氰酸酯分批投入反应釜中，根据反应体系的粘度情况分三批补加1180份DMF有机溶剂至产品粘度80-120Pa.s/25℃，最后加入链终止剂得到固含量为39％的最终产品。
实施例2
本实施例所用原料及其配比如表2所示：
表2.实施例2原料及配比
DMF 4100份
PC-2000 200份
SP-1000 400份
SP-2400 300份
PTMG-1 400份
EG 360份
I-1010 3份
MDI 1000份
催化剂 0.3份
补加MDI 708份
补加DMF 1996份
终止剂 1.2份
固含量 36％
本实施例硬质耐水解低发孔性高剥离聚氨酯树脂的制备过程如下：
将大分子二元醇PC-2000、SP-1000、SP-2400、PTMG-1、EG和抗氧剂I-1010加入4100份溶剂DMF中，搅拌均匀后加入1000份MDI于70℃左右反应2小时，补入适量催化剂加速反应，保持温度，将剩余的708份异氰酸酯分批投入反应釜中，根据反应体系的粘度情况分批补加1996份有机溶剂至产品粘度80-120Pa.s/25℃，最后加入链终止剂得到固含量为36％的最终产品。
将本发明实施例1和实施例2制备的聚氨酯树脂与中等模量耐水解树脂SW-5080RH复合(各实施例样品与SW-5080RH质量比为10：90)，按照合成革行业常规方法打样，进行剥离强度和耐水解性能的测试，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。切口孔型用光学放大镜人工观察，手感为对比描述。测试结果见下表1。
表1
*SW-5080RH为合肥安利聚氨酯新材料有限公司生产。
从表1中可以看出，本发明聚氨酯树脂能明显提高和稳定剥离强度，稳定剥离强度，测试效果要优于空白对比样。
将实施例1、实施例2及空白对比例的三个革样做切口，在光学显微镜下观察拍照，分别如图1、图2和图3所示，可见本专利树脂的缩孔效果比较明显，整体孔型变得更加细密，这也是剥离强度高，波动小，手感实在的原因。

Claims (5)

1.一种硬质耐水解低发孔性高剥离聚氨酯树脂，其特征在于：其原料包括
异氰酸酯；
大分子二元醇；
扩链剂；
抗氧剂；
有机溶剂；
有机锡类或有机铋类催化剂；
反应终止剂；
所述异氰酸酯中的异氰酸根和羟基的摩尔量之比为0.90-1：1；所述羟基为大分子二元醇及扩链剂中的羟基之和；
所述大分子二元醇和所述扩链剂的质量比为3-4：1；
所述抗氧剂的用量占原料总质量的0.01-0.05％；
所述有机溶剂的用量为原料总质量的60-65％；
所述有机锡类或有机铋类催化剂的用量为大分子二元醇质量的0.001-0.05％；
所述反应终止剂的添加量为原料总质量的0.005-0.015％；
所述大分子二元醇为聚酯二元醇、聚碳酸酯二元醇和聚醚二元醇的混合，且聚碳酸酯二元醇和聚醚二元醇的质量和不低于大分子二元醇总质量的30％。
2.根据权利要求1所述的聚氨酯树脂，其特征在于：
所述异氰酸酯为4,4′-二苯基甲烷二异氰酸酯；
所述聚酯二元醇为己二酸系聚酯二元醇和/或含间位取代苯环结构的聚酯二元醇，所述聚醚二元醇选自聚四氢呋喃二元醇和/或聚氧化丙烯二元醇；
所述扩链剂选自分子量在60-118的小分子二元醇；
所述有机溶剂为N,N-二甲基甲酰胺；
所述反应终止剂为甲醇。
3.根据权利要求1或2所述的聚氨酯树脂，其特征在于：所述大分子二元醇的数均分子量为500-4000。
4.根据权利要求2所述的聚氨酯树脂，其特征在于：所述扩链剂为乙二醇或1,4-丁二醇。
5.权利要求1所述硬质耐水解低发孔性高剥离聚氨酯树脂的制备方法，其特征在于：按配比向反应釜中加入有机溶剂、大分子二元醇、扩链剂、抗氧剂和部分异氰酸酯，于60-80℃常压下反应1-2小时，再加入有机锡类或有机铋类催化剂，保持温度，将剩余的异氰酸酯分批投入反应釜中，然后根据反应体系的粘度情况分批补加有机溶剂至产物粘度为80-120Pa.s/25℃，最后再加入反应终止剂，得到固含量为35-40％的产物硬质耐水解低发孔性高剥离聚氨酯树脂。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111412A (zh) * 2015-09-29 2015-12-02 合肥安利聚氨酯新材料有限公司 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
CN107739427A (zh) * 2017-11-01 2018-02-27 合肥安利聚氨酯新材料有限公司 一种高聚醚含量压纹型湿法聚氨酯树脂及其制备方法
WO2019082475A1 (ja) * 2017-10-27 2019-05-02 Dic株式会社 ウレタン樹脂組成物、皮膜、及び合成皮革
CN112745473A (zh) * 2021-01-15 2021-05-04 禾瑞（漳州）助剂有限公司 高水压耐水洗的纺织涂层用聚氨酯底胶树脂及其制备方法
CN112876645A (zh) * 2021-02-02 2021-06-01 福建兴宇树脂有限公司 一种高填充高剥离聚氨酯树脂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532462A (zh) * 2011-12-23 2012-07-04 上海汇得化工有限公司 一种易染色脂肪族聚氨酯树脂及其制备方法
CN102875774A (zh) * 2012-10-12 2013-01-16 合肥安利聚氨酯新材料有限公司 一种高剥离强度、耐水解的湿式聚氨酯树脂及其制备方法
CN103450436A (zh) * 2013-08-22 2013-12-18 旭川化学（苏州）有限公司 一种聚氨酯树脂及其制备方法和应用
CN103755910A (zh) * 2013-12-27 2014-04-30 浙江华峰合成树脂有限公司 耐寒耐酒精不黄变革用聚氨酯树脂及其制法
CN104004159A (zh) * 2014-06-16 2014-08-27 旭川化学（苏州）有限公司 一种聚氨酯树脂及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532462A (zh) * 2011-12-23 2012-07-04 上海汇得化工有限公司 一种易染色脂肪族聚氨酯树脂及其制备方法
CN102875774A (zh) * 2012-10-12 2013-01-16 合肥安利聚氨酯新材料有限公司 一种高剥离强度、耐水解的湿式聚氨酯树脂及其制备方法
CN103450436A (zh) * 2013-08-22 2013-12-18 旭川化学（苏州）有限公司 一种聚氨酯树脂及其制备方法和应用
CN103755910A (zh) * 2013-12-27 2014-04-30 浙江华峰合成树脂有限公司 耐寒耐酒精不黄变革用聚氨酯树脂及其制法
CN104004159A (zh) * 2014-06-16 2014-08-27 旭川化学（苏州）有限公司 一种聚氨酯树脂及其制备方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
刘晓燕 等: "聚碳酸酯二元醇及其在聚氨酯材料中的应用", 《聚氨酯工业》 *
管云林 等: "聚碳酸酯改性聚酯型热塑性聚氨酯弹性体的合成与性能", 《应用化学》 *
聚碳酸酯二元醇及其在聚氨酯材料中的应用 ;刘晓燕 等;《聚氨酯工业》;20040228;第19卷(第01期);6-8 *
聚碳酸酯改性聚酯型热塑性聚氨酯弹性体的合成与性能 ;管云林 等;《应用化学》;19941220;第11卷(第06期);65-68 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105111412A (zh) * 2015-09-29 2015-12-02 合肥安利聚氨酯新材料有限公司 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
CN105111412B (zh) * 2015-09-29 2018-01-30 合肥安利聚氨酯新材料有限公司 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
WO2019082475A1 (ja) * 2017-10-27 2019-05-02 Dic株式会社 ウレタン樹脂組成物、皮膜、及び合成皮革
JP6528915B1 (ja) * 2017-10-27 2019-06-12 Dic株式会社 ウレタン樹脂組成物、皮膜、及び合成皮革
CN107739427A (zh) * 2017-11-01 2018-02-27 合肥安利聚氨酯新材料有限公司 一种高聚醚含量压纹型湿法聚氨酯树脂及其制备方法
CN112745473A (zh) * 2021-01-15 2021-05-04 禾瑞（漳州）助剂有限公司 高水压耐水洗的纺织涂层用聚氨酯底胶树脂及其制备方法
CN112876645A (zh) * 2021-02-02 2021-06-01 福建兴宇树脂有限公司 一种高填充高剥离聚氨酯树脂及其制备方法

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