CN109679051A - 含键合功能的热塑性聚氨酯弹性体及其制备方法 - Google Patents

含键合功能的热塑性聚氨酯弹性体及其制备方法 Download PDF

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CN109679051A
CN109679051A CN201811600268.3A CN201811600268A CN109679051A CN 109679051 A CN109679051 A CN 109679051A CN 201811600268 A CN201811600268 A CN 201811600268A CN 109679051 A CN109679051 A CN 109679051A
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thermoplastic polyurethane
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陈淑海
王真
张宁
范文庆
肖培栋
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Abstract

本发明涉及一种含键合功能的热塑性聚氨酯弹性体及其制备方法，属于聚氨酯弹性体技术领域。本发明所述的弹性体包括以下原料：聚酯型二元醇45％‑59％，二异氰酸酯30％‑44％，键合剂10％‑15％，抗氧化剂0.05‑0.2％，光稳定剂0.05‑0.2％，催化剂0.005‑0.02％；所述键合剂为1,4‑丁二醇和物质A的混合物，物质A为乙醇胺、二乙醇胺、氰甲基二乙醇胺、氰乙基二乙醇胺、氰乙基二丁醇胺、二羟甲基丙二酸二乙酯、二羟甲基丙二酸二丁酯或二羟乙基丙二酸二丁酯中的一种或多种。本发明所述的弹性体机械强度增强，存放时间较长后助剂析出或者迁移现象不明显；本发明同时提供了简单易行的制备方法。

Description

含键合功能的热塑性聚氨酯弹性体及其制备方法
技术领域
本发明涉及一种含键合功能的热塑性聚氨酯弹性体及其制备方法，属于聚氨酯弹性体技术领域。
背景技术
热塑性聚氨酯弹性体(TPU)分子呈线性，分子间很少有交联，玻璃化温度低，具有高模量、高强度、高伸长和高弹性，优良的耐磨、耐油、耐老化以及耐低温特性，因此TPU具有多用途的特性。
不同品种原料固化剂、多元醇和键合剂可合成出品种多样、性能各异、加工多种、用途广泛的TPU制品。不同种类TPU通常通过添加不同种类的助剂来弥补TPU自身性能的不足或者突出自身的特点，如可以抑制TPU水解的水解剂，提高TPU脱模效果的脱模剂，抑制TPU氧化分解的抗氧化剂、光稳定剂等。而TPU的大部分助剂都是在生产过程中通过机械混合法加入，这种方法成本较低、工艺较为简单。但是需要考虑助剂与TPU基体的相容性、助剂在TPU中分散性及助剂与TPU之间界面性等方面，这些方面可能导致大多数添加型助剂在TPU中可能挥发、迁移等问题，将严重影响TPU产品的外观和性能。
发明内容
本发明的目的是提供一种含键合功能的热塑性聚氨酯弹性体，其机械强度增强，存放时间较长后助剂析出或者迁移现象不明显；本发明同时提供了简单易行的制备方法。
本发明所述的含键合功能的热塑性聚氨酯弹性体，包括以下重量百分含量的原料：
所述键合剂为1,4-丁二醇和物质A的混合物，所述物质A为乙醇胺、二乙醇胺、氰甲基二乙醇胺、氰乙基二乙醇胺、氰乙基二丁醇胺、二羟甲基丙二酸二乙酯、二羟乙基丙二酸二乙酯、二羟甲基丙二酸二丁酯或二羟乙基丙二酸二丁酯中的一种或多种。
所述聚酯型二元醇的数均分子量为1000-3000。
所述聚酯型二元醇由二元酸组分和二元醇组分制成，所述二元酸为对苯二甲酸、丁二酸、己二酸或壬二酸中的一种或多种；所述二元醇为1,4-丁二醇、乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇或1,6-己二醇中的一种或多种。
所述二异氰酸酯为二苯基甲烷二异氰酸酯(MDI-100)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)中的一种或多种。
所述催化剂为有机铋、有机锡或钛酸酯类催化剂，优选为有机锡类T9。
所述抗氧剂优选为1010。
所述光稳定剂优选为Tinuvin 770。
所述的含键合功能的热塑性聚氨酯弹性体的制备方法，是将抗氧剂、光稳定剂、催化剂添加到聚酯型二元醇中混合，在80-110℃下真空脱水0.5-5h，然后将脱水后的混合物与二异氰酸酯在80-120℃下搅拌反应1-20h，然后加入键合剂搅拌反应10-120min，浇出，浇出料放入80-120℃烘箱熟化1-48h，经过破碎、造粒，即得到所述含键合功能的热塑性聚氨酯弹性体。
本发明在TPU硬段中引入极性侧基基团，提高了TPU自身分子链之间的相互作用，可有效抑制助剂的迁移或者析出，改善材料的表面性能。
本发明具有以下有益效果：
(1)本发明在TPU硬段中引入极性侧基基团，提高了TPU自身分子链之间的相互作用，可有效抑制助剂的迁移或者析出，改善了材料的表面性能，同时机械强度增强；
(2)本发明所述的含键合功能的热塑性聚氨酯弹性体的制备方法，简单易行，利于工业化生产。
具体实施方式
下面结合实施例对本发明作进一步的说明，但其并不限制本发明的实施。
以下所提到的百分数均为质量百分含量。
实施例1
精确称量聚酯型二元醇、抗氧化剂、光稳定剂及有机锡催化剂，依次加入到反应容器中，混合搅拌均匀，110℃抽真空脱水得到混合料；然后加入计量的MDI-100，于120℃下搅拌反应2h，加入计量的键合剂(1,4-丁二醇和氰乙基二乙醇胺质量比为4:1)，快速搅拌反应20min后浇入模具中，于100℃下熟化24h，粉碎，得到所述的含键合功能的热塑性聚氨酯弹性体颗粒。
实施例2
选用键合剂为1,4-丁二醇和氰乙基二乙醇胺按质量比2:1，按照实施例1的方法合成所述的含键合功能的热塑性聚氨酯弹性体。
实施例3
选用键合剂为1,4-丁二醇和氰乙基二乙醇胺按质量比1:1，按照实施例1的方法合成所述的含键合功能的热塑性聚氨酯弹性体。
实施例4
选用聚己二酸乙二醇酯二醇，键合剂为1,4-丁二醇和氰乙基二丁醇胺按质量比3:1，按照实施例1的方法在110℃搅拌反应3h的条件合成所述的含键合功能的热塑性聚氨酯弹性体。
实施例5
选用聚己二酸丙二醇酯二醇，键合剂为1,4-丁二醇和二羟甲基丙二酸二乙酯按质量比3:1，按照实施例1的方法在90℃搅拌反应6h的条件合成所述的含键合功能的热塑性聚氨酯弹性体。
对比例1
选用键合剂为1,4-丁二醇，按照实施例1的方法在120℃条件合成所述的热塑性聚氨酯弹性体。
对比例2
选用聚己二酸乙二醇酯二醇，键合剂为乙二醇，按照实施例4的方法合成所述的热塑性聚氨酯弹性体。
对比例3
选用聚己二酸丙二醇酯二醇，键合剂为丙二醇，按照实施例5的方法合成所述的热塑性聚氨酯弹性体。
表1各实施例和对比例所制得聚氨酯弹性体制品的性能测试结果
项目 拉伸强度/MPa 断裂伸长率/％ 撕裂强度/KN/m
实施例1 42.4 522 141.1
实施例2 44.5 545 143.6
实施例3 47.7 598 169.4
实施例4 54.2 474 178.1
实施例5 50.7 498 167.4
对比例1 33.9 503 138.1
对比例2 43.7 457 165.3
对比例3 38.3 476 151.4
从表中数据可以看出，本发明所制备的弹性体的机械强度有了进一步提升。
对比例1-3中合成的含键合功能的热塑性聚氨酯弹性体在85℃、湿度85％的环境中，存放5天出粉现象明显，相同条件下含键合功能的热塑性聚氨酯弹性体没有出粉现象。

Claims (10)

1.一种含键合功能的热塑性聚氨酯弹性体，其特征在于：包括以下重量百分含量的原料：
所述键合剂为1,4-丁二醇和物质A的混合物，所述物质A为乙醇胺、二乙醇胺、氰甲基二乙醇胺、氰乙基二乙醇胺、氰乙基二丁醇胺、二羟甲基丙二酸二乙酯、二羟乙基丙二酸二乙酯、二羟甲基丙二酸二丁酯或二羟乙基丙二酸二丁酯中的一种或多种。
2.根据权利要求1所述的含键合功能的热塑性聚氨酯弹性体，其特征在于：聚酯型二元醇的数均分子量为1000-3000。
3.根据权利要求1所述的含键合功能的热塑性聚氨酯弹性体，其特征在于：聚酯型二元醇由二元酸组分和二元醇组分制成，所述二元酸为对苯二甲酸、丁二酸、己二酸或壬二酸中的一种或多种；所述二元醇为1,4-丁二醇、乙二醇、1,2-丙二醇、1,3-丙二醇、2-甲基-1,3-丙二醇或1,6-己二醇中的一种或多种。
4.根据权利要求1所述的含键合功能的热塑性聚氨酯弹性体，其特征在于：二异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种。
5.根据权利要求1所述的含键合功能的热塑性聚氨酯弹性体，其特征在于：催化剂为有机铋、有机锡或钛酸酯类催化剂。
6.一种权利要求1-5任一所述的含键合功能的热塑性聚氨酯弹性体的制备方法，其特征在于：将抗氧剂、光稳定剂、催化剂添加到聚酯型二元醇中混合，真空脱水，然后将脱水后的混合物与二异氰酸酯搅拌反应，然后加入键合剂搅拌反应，浇出，浇出料放入烘箱熟化，经过破碎、造粒，即得到所述含键合功能的热塑性聚氨酯弹性体。
7.根据权利要求6所述的含键合功能的热塑性聚氨酯弹性体的制备方法，其特征在于：真空脱水时的温度为80-110℃，时间为0.5-5h。
8.根据权利要求6所述的含键合功能的热塑性聚氨酯弹性体的制备方法，其特征在于：混合物与二异氰酸酯在80-120℃下搅拌反应1-20h。
9.根据权利要求6所述的含键合功能的热塑性聚氨酯弹性体的制备方法，其特征在于：加入键合剂搅拌反应10-120min。
10.根据权利要求6所述的含键合功能的热塑性聚氨酯弹性体的制备方法，其特征在于：熟化时间为1-48h。
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