CN104140516B - 一种合成革用二液型粘结层聚氨酯树脂及其制备方法 - Google Patents

一种合成革用二液型粘结层聚氨酯树脂及其制备方法 Download PDF

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CN104140516B
CN104140516B CN201410157915.3A CN201410157915A CN104140516B CN 104140516 B CN104140516 B CN 104140516B CN 201410157915 A CN201410157915 A CN 201410157915A CN 104140516 B CN104140516 B CN 104140516B
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杨银龙
蒋红梅
唐劲松
蔡善来
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Zhejiang Huafeng Synthetic Resin Co., Ltd.
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Abstract

本发明提供一种合成革用二液型粘结层聚氨酯树脂及其制备方法。本发明的合成革用二液型粘结层聚氨酯树脂，由包含以下组分的原料制成：多元醇、扩链剂、二异氰酸酯和溶剂；扩链剂的总摩尔数与多元醇的总摩尔数之比为0.5：1～3：1；二异氰酸酯的总摩尔数与多元醇的总摩尔数之比为1.5：1～4：1；溶剂为多元醇、扩链剂、二异氰酸酯与溶剂的质量之和的29%～71%；扩链剂包括含羧基扩链剂和不含羧基扩链剂，含羧基扩链剂的摩尔数占扩链剂的总摩尔数的20%～50%。与现有技术相比，本发明的合成革用二液型粘结层聚氨酯树脂在进行粘接时能实现低温快速固化，从而降低了生产能耗，同时提高了离型纸的周转次数和利用效率。

Description

一种合成革用二液型粘结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，特别涉及一种合成革用二液型粘结层聚氨酯树脂及其制备方法。
背景技术
聚氨酯合成革是由聚氨酯和纤维组成的复合材料，多数情况下，聚氨酯合成革由上至下依次为面层聚氨酯树脂膜、粘结层聚氨酯树脂膜、聚氨酯微孔层和基布。由于粘结层聚氨酯树脂主要担任着粘合面层与微孔层的作用，因此粘结层聚氨酯树脂在整个合成革生产过程中至关重要。常用的粘结层聚氨酯树脂有一液型和二液型。由于二液型粘结层聚氨酯树脂克服了一液型粘结层聚氨酯树脂在固含量、粘结强度与弹性等方面的缺陷，已逐渐引起合成革与聚氨酯树脂行业的广泛关注。根据交联剂的种类不同，可将现有的合成革用二液型粘结层聚氨酯树脂分为两类。一类为异氰酸酯交联型二液型粘结层聚氨酯树脂。由于该类聚氨酯树脂与交联剂的反应较为温和，需要在60-80℃暖房里熟化24小时以上才能固化，然后才能将合成革与离型纸分离，这就带来了能耗增大、离型纸的周转次数降低、需要更多的存储场地等问题。另一类为醚化三聚氰胺树脂交联型二液型粘结层聚氨酯树脂。该类聚氨酯树脂需要较高的反应温度，一般在140℃以上才会有较快的反应速度，过高的温度会增加能耗且会损害离型纸，降低离型纸的重复使用次数。
发明内容
本发明目的在于提供一种合成革用二液型粘结层聚氨酯树脂，以解决现有的二液型粘结层聚氨酯树脂存在的上述技术问题。
本发明的另一目的在于提供上述的合成革用二液型粘结层聚氨酯树脂的制备方法，以解决现有的二液型粘结层聚氨酯树脂存在的上述技术问题。
本发明的目的通过以下技术方案实现：
一种合成革用二液型粘结层聚氨酯树脂，由包含以下组分的原料制成：多元醇、扩链剂、二异氰酸酯和溶剂；所述扩链剂的总摩尔数与所述多元醇的总摩尔数之比为0.5：1～3：1；所述二异氰酸酯的总摩尔数与所述多元醇的总摩尔数之比为1.5：1～4：1；所述溶剂为所述多元醇、所述扩链剂、所述二异氰酸酯与所述溶剂的质量之和的29%～71%；所述扩链剂包括含羧基扩链剂和不含羧基扩链剂，所述含羧基扩链剂的摩尔数占所述扩链剂的总摩尔数的20%～50%。
在本发明优选的实施例中，所述多元醇选自聚碳酸酯二醇、聚己内酯二醇、聚四氢呋喃醚二醇、聚环氧丙烷醚二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸己二醇酯二醇、聚己二酸乙二醇丁二醇共聚酯二醇、聚己二酸新戊二醇己二醇共聚酯二醇中的一种或几种，所述多元醇的数均分子量为500～3500。
在本发明优选的实施例中，所述含羧基扩链剂选自2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、甘油单丁二酸酯、甘油单马来酸酯、三羟甲基丙烷单丁二酸酯、三羟甲基丙烷单马来酸酯、二氨基苯甲酸中的一种或几种。
在本发明优选的实施例中，所述不含羧基扩链剂选自乙二醇、1,4-丁二醇、一缩二乙二醇、1,6-己二醇、乙醇胺、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、新戊二醇中的一种或几种。
在本发明优选的实施例中，所述二异氰酸酯选自二苯基甲烷二异氰酸酯、甲苯二异氰酸酯中的一种或两种。
在本发明优选的实施例中，所述溶剂选自二甲基甲酰胺、甲苯、丙酮、丁酮、乙酸乙酯、环己酮中的一种或几种。
上述的合成革用二液型粘结层聚氨酯树脂的制备方法，包括以下步骤：
1）将多元醇、扩链剂和占总溶剂量30%～50%的溶剂投入反应釜，50～60℃搅拌均匀；
2）将二异氰酸酯分批投入反应釜，使反应温度在65～80℃之间，常压反应7～11小时，并根据体系的粘度，用剩余溶剂分次稀释，使最终粘度控制在60～120Pa.S@25℃，即可制得所述合成革用二液型粘结层聚氨酯树脂。
与现有技术相比，本发明有以下有益效果：
本发明的合成革用二液型粘结层聚氨酯树脂采用扩链剂向聚氨酯分子中引入了羧基，在进行粘接时利用能和羧基反应的市售化合物作为交联剂（如多元氮丙啶等），使粘合温度在130℃即可快速固化，较现有的粘合温度（即140℃以上）低，能实现合成革用二液型粘结层聚氨酯树脂的低温快速固化，从而降低了生产能耗，同时提高了离型纸的周转次数和利用效率。
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
原料名称 重量（单位：克）
聚四氢呋喃醚二醇（数均分子量2000） 320
2,2-二羟甲基丙酸 32.16
乙二醇 14.88
二苯基甲烷二异氰酸酯 144
二甲基甲酰胺 125.25
甲苯 83.5
本实施例的合成革用二液型粘结层聚氨酯树脂的制备步骤如下：
1）将104g二甲基甲酰胺、320g聚四氢呋喃醚二醇、32.16g2,2-二羟甲基丙酸和14.88g乙二醇投入反应釜，50～55℃搅拌均匀；
2）将144g二苯基甲烷二异氰酸酯分批投入反应釜，严格控制反应温度在65～70℃之间，常压反应7小时，并根据体系的粘度情况，用剩余二甲基甲酰胺和甲苯分次稀释，最终粘度控制在60～120Pa.S@25℃，即可得合成革用二液型粘结层聚氨酯树脂。
实施例2
本实施例所用原料及重量如表2。
表2
原料名称 重量（单位：克）
聚己二酸丁二醇酯二醇（数均分子量1000） 40
聚己二酸丁二醇酯二醇（数均分子量3000） 120
2,2-二羟甲基丙酸 6.432
乙二醇 11.904
二苯基甲烷二异氰酸酯 80
二甲基甲酰胺 506
丁酮 126.5
本实施例的合成革用二液型粘结层聚氨酯树脂的制备步骤如下：
1）将190g二甲基甲酰胺、40g数均分子量为1000的聚己二酸丁二醇酯二醇、120g数均分子量为3000的聚己二酸丁二醇酯二醇、6.432g2,2-二羟甲基丙酸和11.904g乙二醇投入反应釜，55～60℃搅拌均匀；
2）将80g二苯基甲烷二异氰酸酯分批投入反应釜，严格控制反应温度在70～75℃之间，常压反应11小时，并根据体系的粘度情况，用剩余二甲基甲酰胺和丁酮分次稀释，最终粘度控制在60～120Pa.S@25℃，即可得合成革用二液型粘结层聚氨酯树脂。
实施例3
本实施例所用原料及重量如表3。
表3
本实施例的合成革用二液型粘结层聚氨酯树脂的制备步骤如下：
1）将171g二甲基甲酰胺、320g聚己二酸乙二醇丁二醇共聚酯二醇、5.36g2,2-二羟甲基丙酸、1.8g1,4-丁二醇和1.24g乙二醇投入反应釜，55～60℃搅拌均匀；
2）将60g二苯基甲烷二异氰酸酯分批投入反应釜，严格控制反应温度在75～80℃之间，常压反应9小时，并根据体系的粘度情况，用剩余二甲基甲酰胺和丁酮分次稀释，最终粘度控制在60～120Pa.S@25℃，即可得合成革用二液型粘结层聚氨酯树脂。
实施例4
本实施例所用原料及重量如下表4。
表4
原料名称 重量（单位：克）
聚己二酸丁二醇酯二醇（数均分子量1000） 80
聚四氢呋喃醚二醇（数均分子量1000） 80
2,2-二羟甲基丁酸 14.21
1,4-丁二醇 20.16
二苯基甲烷二异氰酸酯 120
二甲基甲酰胺 471.6
本实施例的合成革用二液型粘结层聚氨酯树脂的制备步骤如下：
1）将157.2g二甲基甲酰胺、80g聚己二酸丁二醇酯二醇、80g聚四氢呋喃醚二醇、14.21g2,2-二羟甲基丁酸、20.16g1,4-丁二醇投入反应釜，50～55℃搅拌均匀；
2）将120g二苯基甲烷二异氰酸酯分批投入反应釜，严格控制反应温度在65～75℃之间，常压反应7小时，并根据体系的粘度情况，用剩余二甲基甲酰胺分次稀释，最终粘度控制在60～120Pa.S@25℃，即可得合成革用二液型粘结层聚氨酯树脂。
一般地，能用做合成革粘结层的二液型聚氨酯树脂需要具有以下特点：1、室温条件下，在8小时之内，配制的工作浆的粘变化小于等于2000CPS；2、在合成革正常贴合温度下（120～150℃），固化时间小于等于10分钟。为验证本发明的合成革用二液型粘结层聚氨酯树脂能够满足以上特点，将上述实施案例制备的聚氨酯树脂、二甲基甲酰胺和三元氮丙啶交联剂按照表5的配制比例来配制工作浆，分别获得工作浆一至四，并考察工作浆在室温下的粘度变化和在130℃条件下的凝胶时间，见表6与表7。
表5各实施列配制工作浆的配料比（重量，单位：克）
表6室温下各实施例所配制的工作浆粘度随时间的变化
表7130℃条件下各实施例所配制的工作浆的凝胶时间
从表6可知，本发明生产的合成革用二液型粘结层聚氨酯树脂所配制的工作浆于室温条件下，在8小时之内，工作浆的粘度变化小于2000CPS。
从表7可知，本发明生产的合成革用二液型粘结层聚氨酯树脂所配制的工作浆在130℃条件下凝胶时间小于等于10分钟，说明了本发明生产的合成革用二液型粘结层聚氨酯树脂的固化时间小于等于10分钟。
为进一步说明本发明生产的合成革用二液型粘结层聚氨酯树脂能够满足合成革的粘结需求，选取合成革行业内周知的高物性的1.2mm厚超细纤维合成革贝斯作为基材，将上述工作浆用做粘结基材的粘合剂，粘合后于130℃下烘10分钟，冷却后将样条裁至2.5cm宽，并测试剥离强度，测试结果见表8。
表8各实施例的剥离强度
实施例一 实施例二 实施例三 实施例四
剥离强度（N） 基材破裂 基材破裂 基材破裂 基材破裂
从表8可知，工作浆一至四粘结超细纤维合成革后，测试剥离强度时基材破裂，说明其剥离强度高于基材的强度，进一步说明了本发明生产的合成革用二液型粘结层聚氨酯树脂完全满足合成革的粘结需求。
本发明的合成革用二液型粘结层聚氨酯树脂在进行粘接时粘合温度在130℃即可快速固化，较现有的粘合温度（即140℃以上）低，能实现低温快速固化，从而降低了生产能耗，同时提高了离型纸的周转次数和利用效率。
在本发明及上述实施例的教导下，本领域技术人员很容易预见到，本发明所列举或例举的各原料或其等同替换物、各加工方法或其等同替换物都能实现本发明，以及各原料和加工方法的参数上下限取值、区间值都能实现本发明，在此不一一列举实施例。

Claims (7)

1.一种合成革用二液型粘结层聚氨酯树脂，其特征在于，由包含以下组分的原料制成：多元醇、扩链剂、二异氰酸酯和溶剂；所述扩链剂的总摩尔数与所述多元醇的总摩尔数之比为0.5：1～3：1；所述二异氰酸酯的总摩尔数与所述多元醇的总摩尔数之比为1.5：1～4：1；所述溶剂为所述多元醇、所述扩链剂、所述二异氰酸酯与所述溶剂的质量之和的29％～71％；所述扩链剂包括含羧基扩链剂和不含羧基扩链剂，所述含羧基扩链剂的摩尔数占所述扩链剂的总摩尔数的20％～50％。
2.如权利要求1所述的合成革用二液型粘结层聚氨酯树脂，其特征在于，所述多元醇选自聚碳酸酯二醇、聚己内酯二醇、聚四氢呋喃醚二醇、聚环氧丙烷醚二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸己二醇酯二醇、聚己二酸乙二醇丁二醇共聚酯二醇、聚己二酸新戊二醇己二醇共聚酯二醇中的一种或几种，所述多元醇的数均分子量为500～3500。
3.如权利要求1所述的合成革用二液型粘结层聚氨酯树脂，其特征在于，所述含羧基扩链剂选自2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、甘油单丁二酸酯、甘油单马来酸酯、三羟甲基丙烷单丁二酸酯、三羟甲基丙烷单马来酸酯、二氨基苯甲酸中的一种或几种。
4.如权利要求1所述的合成革用二液型粘结层聚氨酯树脂，其特征在于，所述不含羧基扩链剂选自乙二醇、1,4-丁二醇、一缩二乙二醇、1,6-己二醇、乙醇胺、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇、新戊二醇中的一种或几种。
5.如权利要求1所述的合成革用二液型粘结层聚氨酯树脂，其特征在于，所述二异氰酸酯选自二苯基甲烷二异氰酸酯、甲苯二异氰酸酯中的一种或两种。
6.如权利要求1所述的合成革用二液型粘结层聚氨酯树脂，其特征在于，所述溶剂选自二甲基甲酰胺、甲苯、丙酮、丁酮、乙酸乙酯、环己酮中的一种或几种。
7.如权利要求1-6中任意一项所述的合成革用二液型粘结层聚氨酯树脂的制备方法，其特征在于，包括以下步骤：
1)将多元醇、扩链剂和占总溶剂量30％～50％的溶剂投入反应釜，50～60℃搅拌均匀；
2)将二异氰酸酯分批投入反应釜，使反应温度在65～80℃之间，常压反应7～11小时，并根据体系的粘度，用剩余溶剂分次稀释，使最终粘度控制在60～120Pa.S@25℃，即可制得所述合成革用二液型粘结层聚氨酯树脂。
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