CN112552479A - 一种水解速度可控的无溶剂聚氨酯弹性体组合物 - Google Patents

一种水解速度可控的无溶剂聚氨酯弹性体组合物 Download PDF

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CN112552479A
CN112552479A CN201910853418.XA CN201910853418A CN112552479A CN 112552479 A CN112552479 A CN 112552479A CN 201910853418 A CN201910853418 A CN 201910853418A CN 112552479 A CN112552479 A CN 112552479A
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CN112552479B (zh
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段友智
艾爽
刘欢乐
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China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering
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Abstract

本发明提供了一种水解速度可控的无溶剂聚氨酯弹性体组合物，包括单独分开且使用时才混合的组分A和组分B，组分A为多异氰酸酯和聚酯多元醇的反应得到的异氰酸根含量为5wt％‑20wt％的预聚物；组分B包括以下组分或由以下组分组成：70wt％‑80wt％的聚酯多元醇、6wt％‑23.5wt％的聚乙二醇、5wt％‑10wt％的扩链剂、0.5wt％‑2wt％的催化剂和任选地0‑2wt％的高分子吸水树脂。本发明提供的聚氨酯弹性体水解速度较快且速度可控。

Description

一种水解速度可控的无溶剂聚氨酯弹性体组合物
技术领域
本发明涉及一种水解速度可控的无溶剂聚氨酯弹性体组合物及其制备方法和应用。
背景技术
聚氨酯弹性体强韧、附着力强、耐腐蚀性，近年来应用日益增多。但是，由于聚氨酯最大的缺陷在于其容易水解，在潮湿环境中使用时容易降解而缩短使用寿命，造成材料浪费与巨大的经济损失。
目前，针对聚氨酯材料容易水解这一性质，更多的研究是侧重于耐水解性聚氨酯材料的研究，尚无对水解可控无溶剂聚氨酯弹性体的研究。
发明内容
本发明的目的在于提供一种水解速度可控的无溶剂聚氨酯弹性体及其制备方法。
根据本发明的第一方面，提供了一种水解速度可控的无溶剂聚氨酯弹性体组合物，包括单独分开且使用时才混合的组分A和组分B，组分A为多异氰酸酯和聚酯多元醇的反应得到的异氰酸根含量为5wt％-20wt％的预聚物；
组分B包括以下组分或由以下组分组成：70wt％-80wt％的聚酯多元醇、6wt％-23.5wt％的聚乙二醇、5wt％-10wt％的扩链剂、0.5wt％-2wt％的催化剂和任选地0wt％-2wt％的高分子吸水树脂。
根据本发明的优选实施方式，组分A是由20wt％-65wt％多异氰酸酯与35wt％-80wt％的聚酯多元醇反应得到的。
组分A中异氰酸根含量可以为5wt％、6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％以及它们之间的任意值。
组分B中聚酯多元醇的含量可以为70wt％、72wt％、74wt％、76wt％、78wt％、80wt％以及它们之间的任意值；聚乙二醇的含量可以为6wt％、7wt％、8wt％、9wt％、10wt％、11wt％、12wt％、13wt％、14wt％、15wt％、16wt％、17wt％、18wt％、19wt％、20wt％、21wt％、22wt％、23wt％、23.5wt％以及它们之间的任意值；扩链剂的含量可以为5wt％、6wt％、7wt％、8wt％、9wt％、10wt％以及它们之间的任意值；催化剂的含量可以为0.5wt％、0.6wt％、0.7wt％、0.8wt％、0.9wt％、1.0wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.0wt％以及它们之间的任意值。高分子吸水树脂的含量为0、0.5wt％、1.0wt％、1.1wt％、1.2wt％、1.3wt％、1.4wt％、1.5wt％、1.6wt％、1.7wt％、1.8wt％、1.9wt％、2.0wt％以及它们之间的任意值，优选为1wt％-2wt％。
根据本发明的优选实施方式，所述组分A和组分B的质量比为(30-90):100，例如可以为30:100、40:100、50:100、60:100、70:100、80:100、90:100以及它们之间的任意值。
根据本发明的优选实施方式，所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯(包括MDI和液化改性MDI)和多苯基甲烷多异氰酸酯(PAPI)中的一种或多种。甲苯二异氰酸酯(TDI)有2，4-甲苯二异氰酸酯和2，6-甲苯二异氰酸酯两种异构体。按两种异构体含量的不同，工业上有三种规格的产品：(1)TDI-65/35，其含2，4-TDI 65％，2，6-TDI35％；(2)TDI-80/20，其含2，4-TDI80％，2，6-TDI 20％；(3)TDI-100其含2，4-TDI 100％。
根据本发明的优选实施方式，所述聚酯多元醇选自己二酸系聚酯多元醇和/或蓖麻油聚酯多元醇。
根据本发明的优选实施方式，所述己二酸系聚酯多元醇为己二酸与C2-C5二元醇中的一种或多种醇的反应产物，C2-C5二元醇优选选自乙二醇、丙二醇、丁二醇、新戊二醇、甲基丙二醇和二甘醇中的一种或多种。通过控制聚酯多元醇的分子量以及多元醇侧基的种类及含量来控制聚酯多元醇的水解速度。
根据本发明的优选实施方式，所述聚酯多元醇的数均分子量为1000-4000。
根据本发明的优选实施方式，所述扩链剂选自3,3’-二氯-4,4’-二氨基二苯基甲烷(MOCA)、二氨基二甲硫基甲苯(DMTDA)、乙二醇、1,4-丁二醇(BDO)、二甘醇(DEG)、三羟甲基丙烷(TMP)、三乙醇胺(TGA)和二乙醇胺(DEOA)中的一种或多种。
根据本发明的优选实施方式，所述催化剂选自叔胺类催化剂和/或有机金属催化剂；优选地，所述叔胺类催化剂选自三亚乙基二胺、四甲基乙二胺和二甲基环己胺中的一种或多种；所述有机金属催化剂选自二月桂酸二丁基锡、辛酸亚锡、异辛酸钾、乙酸钾、油酸钾、乙酸苯汞和异辛酸锌中的一种或多种。
根据本发明的另一方面，提供了一种水解速度可控的无溶剂聚氨酯弹性体的制备方法，包括上述水解速度可控的无溶剂聚氨酯弹性体组合物中的组分A和组分B混合，使用半预聚物法聚合反应而成。
根据本发明的优选实施方式，所述混合在30-60℃条件下进行；
聚合反应的条件包括：在20-35℃条件下固化10-30min，然后在60-100℃条件下反应1-3h。
根据本发明的优选实施方式，所述聚氨酯弹性体的拉伸强度为5～30MPa，硬度shoreA为40～90。
上述水解速度可控的无溶剂聚氨酯弹性体组合物可以用于温敏型高分子复合材料井下石油过滤筛管的喷涂束缚与保护、药物以及肥料的缓释。
聚乙二醇具有良好的亲水性，在组B分中加入少量的聚乙二醇与组分A反应可增大材料的亲水程度，加速水解速率；高分子吸水树脂(SAP)作为一种不参与反应的高吸水树脂，也可起到增大材料亲水程度的作用，来调节材料的水解速率。
本申请的发明人经过研究发现，聚氨酯弹性体的聚酯多元醇的主链上酯基含量以及侧基含量会影响聚氨酯材料的水解速率，聚酯多元醇分子主链上酯基含量越多，侧基含量越低，其水解速率越快，可通过调节二元醇的分子量和结构来调节聚酯多元醇分子主链的酯基含量以及侧基密度进而调节水解速率。
本发明提供的聚氨酯弹性体组合物由预聚物组分(组分A)和多元醇组分(组分B)组成，聚氨酯弹性体的制备方法简单，喷涂得到的聚氨酯弹性涂层具有较高的力学性能以及可控的水解速度，安全环保，具有很大的经济意义。
本发明喷涂制成的试样，由于配方不同，初始拉伸强度可在5-30MPa，优选为15-30MPa之间调节，可通过调节聚酯多元醇的分子结构、聚乙二醇以及SAP的加入量来调节水解的速度，将试样分别置于常温水(25℃)、60℃、90℃等几种典型温度中进行水解速率测试，测试表明常温水浴水解3天后拉伸强度极限下降百分比为20％，60℃水浴水解3天后拉伸强度极限下降百分比为40％，90℃水浴水解3天后拉伸强度极限下降百分比为80％。水解速度较快且速度可控。
具体实施方式
以下结合实施例对本发明进行详细说明，但本发明并不受下述实施例限定。
在本发明实施例中，所用的材料，如无特征说明，各百分数均为质量百分数。
PEA2000聚己二酸乙二醇酯二醇数均分子量2000(实验室自制)
PEA4000聚己二酸乙二醇酯二醇数均分子量4000(实验室自制)
PBA2000聚己二酸丁二醇酯二醇数均分子量2000(实验室自制)
PBA4000聚己二酸丁二醇酯二醇数均分子量4000(实验室自制)
PNA4000聚己二酸新戊二醇酯二醇数均分子量4000(实验室自制)
PEBA4000聚己二酸乙二醇丁二醇酯二醇数均分子量4000(实验室自制)
PENA4000聚己二酸乙二醇新戊二醇酯二醇数均分子量4000(实验室自制)
PEG600聚乙二醇数均分子量600美国陶氏公司
PEG4000聚乙二醇数均分子量4000美国陶氏公司
MDI-100 4，4′-二苯基甲烷二异氰酸酯(万华化学集团股份有限公司)
TDI-100甲苯二异氰酸酯(万华化学集团股份有限公司)
BDO 1,4-丁二醇(BASF公司)
HDO 1,6-己二醇(BASF公司)
DEOA二乙醇胺(BASF公司)
DMTDA二甲硫基甲苯二胺(美国Albemarle公司)
SAP河北燕兴化工有限公司
辛酸亚锡(美国气体化学公司)
实施例1
A组分(异氰酸酯组分)：按照如下制备方法得到：以重量百分数计，2官能度、分子量2000的聚己二酸乙二醇酯二醇(PEA-2000)49.2％，二苯基甲烷二异氰酸酯(MDI-100)50.8％，在80℃反应2～3小时得到异氰酸根含量为15％的预聚物。
B组分(多元醇组分)：按照如下制备方法得到：以重量份计，分子量2000的聚己二酸乙二醇酯二醇(PEA-2000)20份，分子量为4000的聚己二酸乙二醇酯多元醇(PEA-4000)70份，聚乙二醇(PEG4000)10.0份，扩链剂BDO 5.0份，催化剂辛酸亚锡0.5份，用高速搅拌机搅拌均匀。
异氰酸酯组分与多元醇组分以0.95的扩链系数进行混合反应，混合温度50℃、喷涂成2mm厚度薄片，2min凝胶，5min固化成型后即得到水解速度可控无溶剂聚氨酯弹性涂层。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
实施例2：
A组分(异氰酸酯组分)：按照如下制备方法得到：以重量百分数计，2官能度、分子量2000的聚己二酸丁二醇酯二醇(PBA-2000)49.2％，二苯基甲烷二异氰酸酯(MDI-100)50.8％，在80℃反应2～3小时得到异氰酸根含量为15％的预聚物。
B组分(多元醇组分)：按照如下制备方法得到：以重量份计，分子量2000的聚己二酸丁二醇酯二醇(PBA-2000)30份，分子量为4000的聚己二酸乙二醇酯多元醇(PEA-4000)60份，分子量为600的聚乙二醇(PEG600)10份，扩链剂HDO 5.0份，扩链剂DEOA5.0份，催化剂辛酸亚锡0.5份，用高速搅拌机搅拌均匀。
异氰酸酯组分与多元醇组分以0.95的扩链系数进行混合反应，混合温度50℃、喷涂成2mm厚度薄片，2min凝胶，5min固化成型后即得到水解速度可控无溶剂聚氨酯弹性涂层。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
实施例3：
A组分(异氰酸酯组分)：按照如下制备方法得到：以重量百分数计，2官能度、分子量4000的聚己二酸新戊二醇酯二醇(PNA-4000)60.5％，二苯基甲烷二异氰酸酯(MDI-100)39.5％，在80℃反应2～3小时得到异氰酸根含量为12％的预聚物。
B组分(多元醇组分)：按照如下制备方法得到：以重量份计，分子量4000的聚己二酸新戊二醇酯二醇(PNA-4000)80份，分子量4000的聚己二酸乙二醇新戊二醇酯二醇(PENA4000)20份，SAP2.0份，扩链剂BDO 5.0份，催化剂辛酸亚锡0.5份，用高速搅拌机搅拌均匀。
异氰酸酯组分与多元醇组分以0.95的扩链系数进行混合反应，混合温度50℃、喷涂成2mm厚度薄片，2min凝胶，5min固化成型后即得到水解速度可控无溶剂聚氨酯弹性涂层。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
实施例4：
A组分(异氰酸酯组分)：按照如下制备方法得到：以重量百分数计，2官能度、分子量2000的聚己二酸丁二醇酯二醇(PBA-2000)49.2％，二苯基甲烷二异氰酸酯(MDI-100)50.8％，在80℃反应2～3小时得到异氰酸根含量为15％的预聚物。
B组分(多元醇组分)：按照如下制备方法得到：以重量份计，分子量2000的聚己二酸丁二醇酯二醇(PBA-2000)30份，分子量为2000的聚己二酸乙二醇酯多元醇(PEA-2000)50份，分子量为600的聚乙二醇(PEG600)20份，SAP2.0份，扩链剂BDO 5.0份，催化剂辛酸亚锡0.5份，用高速搅拌机搅拌均匀。
异氰酸酯组分与多元醇组分以0.95的扩链系数进行混合反应，混合温度50℃、喷涂成2mm厚度薄片，2min凝胶，5min固化成型后即得到水解速度可控无溶剂聚氨酯弹性涂层。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
实施例5：
A组分(异氰酸酯组分)：按照如下制备方法得到：以重量百分数计，2官能度、分子量2000的聚己二酸乙二醇丁二醇酯二醇(PEBA-4000)68％，甲苯二异氰酸酯(TDI-100)32％，在80℃反应2～3小时得到异氰酸根含量为14％的预聚物。
B组分(多元醇组分)：按照如下制备方法得到：以重量份计，分子量2000的聚己二酸丁二醇酯二醇(PBA-2000)30份，分子量为2000的聚己二酸乙二醇酯多元醇(PEA-2000)60份，分子量为4000的聚乙二醇(PEG4000)10份，SAP2.0份，扩链剂DMTDA 4.0份，催化剂辛酸亚锡0.5份，用高速搅拌机搅拌均匀。
异氰酸酯组分与多元醇组分以0.95的扩链系数进行混合反应，混合温度50℃、喷涂成2mm厚度薄片，2min凝胶，5min固化成型后即得到水解速度可控无溶剂聚氨酯弹性涂层。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
对比例1
与实施例1的区别仅在于，组分B中不含有聚乙二醇。
将制得的聚氨酯弹性涂层分别置于常温水(25℃)、60℃、90℃温度中进行水解速率测试，测试结果如表1所示。
表1
Figure BDA0002197582590000071
Figure BDA0002197582590000081
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (10)

1.一种水解速度可控的无溶剂聚氨酯弹性体组合物，包括单独分开且使用时才混合的组分A和组分B，组分A为多异氰酸酯和聚酯多元醇的反应得到的异氰酸根质量含量为5％-20％的预聚物；
组分B包括以下组分或由以下组分组成：70wt％-80wt％的聚酯多元醇、6wt％-23.5wt％的聚乙二醇、5wt％-10wt％的扩链剂、0.5wt％-2wt％的催化剂和任选地0wt％-2wt％的高分子吸水树脂。
2.根据权利要求1所述的组合物，其特征在于，所述组分A和组分B的质量比为(30-90):100。
3.根据权利要求1或2所述的组合物，其特征在于，所述多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯中的一种或多种。
4.根据权利要求1-3中任一项所述的组合物，其特征在于，所述聚酯多元醇选自己二酸系聚酯多元醇和/或蓖麻油聚酯多元醇。
5.根据权利要求1-4中任一项所述的组合物，其特征在于，所述扩链剂选自3,3’-二氯-4,4’-二氨基二苯基甲烷、二氨基二甲硫基甲苯、乙二醇、1,4-丁二醇、二甘醇、三羟甲基丙烷、三乙醇胺和二乙醇胺中的一种或多种。
6.根据权利要求1-5中任一项所述的组合物，其特征在于，所述催化剂选自叔胺类催化剂和/或有机金属催化剂；优选地，所述叔胺类催化剂选自三亚乙基二胺、四甲基乙二胺和二甲基环己胺中的一种或多种；所述有机金属催化剂选自二月桂酸二丁基锡、辛酸亚锡、异辛酸钾、乙酸钾、油酸钾、乙酸苯汞和异辛酸锌中的一种或多种。
7.根据权利要求4-6中任一项所述的组合物，其特征在于，所述己二酸系聚酯多元醇为己二酸与C2-C5二元醇中的一种或多种醇的反应产物，C2-C5二元醇优选选自乙二醇、丙二醇、丁二醇、新戊二醇、甲基丙二醇和二甘醇中的一种或多种。
8.一种水解速度可控的无溶剂聚氨酯弹性体的制备方法，包括将权利要求1-7中任一项所述的组合物中的组分A和组分B混合，使用半预聚物法聚合反应而成。
9.根据权利要求8所述的制备方法，其特征在于，所述混合在30-60℃条件下进行；
聚合反应的条件包括：在20-35℃条件下固化10-30min，然后在60-100℃条件下反应1-3h。
10.权利要求1-7中任一项所述的组合物在温敏型高分子复合材料井下石油过滤筛管的喷涂束缚与保护、药物以及肥料的缓释中的应用。
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