CN111518259B - 高回弹性的聚氨酯微孔弹性体及其制备方法和应用 - Google Patents

高回弹性的聚氨酯微孔弹性体及其制备方法和应用 Download PDF

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CN111518259B
CN111518259B CN202010371273.2A CN202010371273A CN111518259B CN 111518259 B CN111518259 B CN 111518259B CN 202010371273 A CN202010371273 A CN 202010371273A CN 111518259 B CN111518259 B CN 111518259B
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白堃
卞强
陈凤秋
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Abstract

本发明涉及到一种具有高回弹性的聚氨酯微孔弹性体及其制备方法和应用，主要解决了现有技术中用于玩具、鞋底、减震材料回弹性、抗撕裂性能不能同时达到较高水平的问题。本组分通过采用一种高回弹性的聚氨酯微孔弹性体，由组分A和组分B制备得到，组分A以重量份数计包括含有‑OH基团的多元醇Ⅰ70～90份，醇类扩链剂5～20份，胺类交联剂1～5份，发泡剂0.1～1份，叔胺类催化剂0.2～1份，有机金属化合物类催化剂0.05～0.1份，聚醚改性有机硅类表面活性剂0.3～1.5份，开孔剂0.1～0.5份，抗老化剂0～1份，抗紫外线剂0～1份；组分B为多元醇Ⅱ改性的异氰酸酯组分的技术方案较好的解决了该问题，可用于玩具、鞋底或减震材料中。

Description

高回弹性的聚氨酯微孔弹性体及其制备方法和应用
技术领域
本发明属于聚氨酯微孔弹性体领域，具体涉及一种高回弹性的微孔弹性体及其制备方法和应用。
背景技术
聚氨酯微孔弹性体在工业及民用日常消费品的实际需求量大，可应用于工业生产设备、物流运输设备的防震减震、支撑结构件、填充结构件等；以及民用消费品，如儿童玩具、鞋底、家具、犬类训练器械等。聚氨酯微孔弹性体是一种新型的、适用范围广的聚氨酯材料，其他聚氨酯微孔弹性体大多以阻尼、减震为使用目的，回弹特性主要体现为慢回弹、低回弹。但随着民用消费品的实际使用需求日益丰富，部分场合对于聚氨酯微孔弹性体有较高的弹性要求。同时，在工业领域中的大多数动态负荷下，所吸收的动能以热能形式释放，而聚氨酯材料的导热性低，内生热较为严重，加速了材料的老化损耗。而本发明所制备的聚氨酯微孔弹性体回弹性能优异，动能损耗较低，降低了内生热，可缓解材料老化损耗。同时本发明所制备产品尤其具有较高的撕裂强度，无论是工业用途还是民用消费品都具有较高的实用价值。
中国专利CN1428359A公开了一种聚醚基聚氨酯微孔弹性体的制备方法，是以水作发泡剂，利用双金属氰化物催化剂合成的新型低不饱和度聚醚多元醇以及部分含活性氢的小分子物质首先与异氰酸酯反应，制得异氰酸酯封端的半预聚体。该半预聚体与多元醇混合物组份经充分混合、浇注、发泡、脱模，制得了聚氨酯微孔弹性体。此专利制备得到的聚氨酯微孔弹性体在300Kg/m3密度下的回弹率为42％，拉伸强度最高可达2320KPa，撕裂强度为10.03N/mm。
通常情况下，采用聚氨酯微孔弹性体的测试指标能够满足用于玩具、鞋垫和减震材料的成型条件。
表1微孔弹性体的测试项目及测试标准
Figure BDA0002478388940000011
Figure BDA0002478388940000021
发明内容
现有技术中微孔弹性体力学性能尤其是撕裂强度与回弹性不能同时达到较高的水平。本发明所要解决的技术问题之一是现有技术中撕裂强度和回弹性不能同时达到较高水平的问题，提供了一种高回弹性的聚氨酯微孔弹性体，该弹性体具有高拉伸强度、高撕裂强度且同时具有高回弹性能。在不同的密度下，实现回弹性(落球回弹)在45-60％之间，拉伸强度达到2629～3766KPa，撕裂强度达到30.2～40.2N/mm的优点；本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的制备方法；本发明所要解决的技术问题之三是提供一种与解决技术问题之一相对应的应用。
为解决上述技术问题之一，本发明采用的技术方案如下：一种高回弹性的聚氨酯微孔弹性体，由组分A和组分B反应制备得到，组分A与组分B的重量比为100:70～110，其中：组分A以重量份数计包括含有-OH基团的多元醇Ⅰ70～90份，醇类扩链剂5～20份，胺类交联剂1～5份，发泡剂0.1～1份，叔胺类催化剂0.2～1份，有机金属化合物类催化剂0.05～0.1份，聚醚改性有机硅类表面活性剂0.3～1.5份，开孔剂0.1～0.5份，抗老化剂0～1份，抗紫外线剂0～1份；组分B由以下步骤制备：
a)预聚体制备，在55～110℃、且有对反应呈惰性的气体的保护下，在容器B中将含有-OH基团的多元醇Ⅱ和含有-NCO基团的异氰酸酯Ⅰ进行反应，得到混合物Ⅰ，当混合物Ⅰ中异氰酸根重量百分含量为13～17％时，反应结束；
b)组分B的制备：在容器B中，将混合物Ⅰ与异氰酸酯Ⅱ在干燥且有对反应呈惰性的气体的保护下进行混合，当异氰酸根重量百分含量为19～21％时，反应结束，得到组分B；
其中，含有-NCO基团的异氰酸酯Ⅰ选自二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯中的至少一种；异氰酸酯Ⅱ为含有-NCO基团的多亚甲基多苯基异氰酸酯。
上述技术方案中，优选地组分A中的具有-OH基团的多元醇Ⅰ选自聚酯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇或其他烯烃多元醇中的至少一种，官能度不小于2，分子量为200～13000；组分B中的具有-OH基团的多元醇Ⅱ选自聚酯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇或其他烯烃多元醇中的至少一种，官能度不小于2，分子量为200～13000；对反应呈惰性的气体选自氮气。
上述技术方案中，优选地醇类扩链剂的分子量为80～450，官能度为2～5，选自1,4-丁二醇、一缩二乙二醇、乙二醇、三羟甲基丙烷、季戊四醇或低分子量聚醚多元醇中的至少一种；胺类交联剂的官能度为3～4，选自二乙基甲苯二胺、三乙醇胺、二乙醇胺或乙醇胺中的至少一种；发泡剂为水或二氧化碳；叔胺类催化剂选自三亚乙基二胺、双(二甲氨基乙基)醚、N,N-二甲基环己胺、四甲基丁二胺或二甲基乙醇胺中的至少一种；有机金属化合物类催化剂选自辛酸亚锡、二月桂酸二丁基锡或异辛酸锌中的至少一种。聚醚改性有机硅类表面活性剂选自B8738、LF2、B8629、DC 3042或B8946 PF中的至少一种；开孔剂为聚氧化烯烃-聚硅氧烷共聚物，选自CHK-350D、B8930或FK-8300中的至少一种；抗老化剂选自受阻胺类光稳定剂292、622、770、944或783中的至少一种；抗紫外线剂选自苯并三唑类紫外线吸收剂UV-1、UV-320、UV-327、UV-328、UV-571或UV-1130中的至少一种。
为解决上述技术问题之二，本发明采用的技术方案包括如下步骤：
(1)组分A的配制：在容器A中按照重量份数计，加入多元醇Ⅰ70～90份，醇类扩链剂5～20份，胺类交联剂1～5份，发泡剂0.1～1份，叔胺类催化剂0.2～1份，有机金属化合物类催化剂0.05～0.1份，聚醚改性有机硅类表面活性剂0.3～1.5份，开孔剂0.1～0.5份，抗老化剂0～1份，抗紫外线剂0～1份，搅拌，制备得到组分A；
(2)预聚体的制备：在55～110℃、且有对反应呈惰性的气体的保护下，在容器B中将含有-OH基团的多元醇Ⅱ和含有-NCO基团的异氰酸酯Ⅰ进行反应，得到混合物Ⅰ，当混合物Ⅰ中异氰酸根重量百分含量为13～17％时，反应结束；
(3)组分B的配制：在容器B中，将混合物Ⅰ与异氰酸酯Ⅱ在干燥且有对反应呈惰性的气体的保护下进行混合，当异氰酸根重量百分含量为19～21％时，反应结束，得到组分B；
(4)在模具温度为25～60℃时，将组分A和组分B高速混合后立刻浇注到可密闭的模具内，浇注完成后，控制温度在30～90℃，5～60min后脱模，得到高回弹性的聚氨酯微孔弹性体，其中，组分A与组分B的重量比为100:70～110。
为解决上述技术问题之三，本发明主要在玩具、鞋底或减震材料中应用。
本发明中，依据异氰酸酯基(-NCO)与醇羟基(-OH)合成氨基甲酸酯基团(R-NHCOO-R')，同时调节预聚体中多元醇Ⅱ、异氰酸酯Ⅰ和异氰酸酯Ⅱ这三个变量的共同作用下，提高了硬段在多元醇软段中的相容性，减少了硬段相外延，使微相分离程度得以改善，因而提高了抗张强度、伸长率、撕裂强度及回弹性能。(在不同的密度下，实现回弹性(落球回弹)在45-60％之间，拉伸强度达到2629～3766KPa，撕裂强度达到30.2～40.2N/mm取得了较好的技术效果。
具体实施方式
以下实施例为本发明的部分实施例，仅用以描述本发明技术方案的实现过程。
活性-NCO基团在预聚体中所占质量比用NCO％表示，其定义为：预聚体中未反应的-N＝C＝O基团(包括游离状态异氰酸酯中的-N＝C＝O基团)所占预聚体总质量的百分比。
原料清单
含有-OH基团的多元醇：
Figure BDA0002478388940000042
醇类扩链剂：
原料名称 分子量 官能度 厂家
1,4-丁二醇 90 2 福辰(天津)化学试剂有限公司
一缩二丙二醇 134 2 美国Sheel化学品有限公司
一缩二乙二醇 106 2 美国Huntsman公司
三羟甲基丙烷 134 3 中国石油天然气股份有限公司
胺类交联剂：
Figure BDA0002478388940000041
Figure BDA0002478388940000051
发泡剂：
原料名称 分子量 厂家
纯净水 18 自制蒸馏水
叔胺类催化剂
Figure BDA0002478388940000054
有机金属化合物类催化剂：
原料名称 类别 厂家
Kosmosis 29 辛酸亚锡 德国赢创工业集团公司
Dabco T-12 二月桂酸二丁基锡 美国空气化工产品有限公司
表面活性剂：
原料名称 类别 厂家
B8946PF 聚醚改性有机硅类 德国赢创工业集团公司
DC 3042 聚醚改性有机硅类 美国空气化工公司产品
开孔剂：
Figure BDA0002478388940000052
抗老化剂：
原料名称 类别 厂家
Tinuvin-292 受阻胺类 德国BASF公司
Tinuvin-770 受阻胺类 德国BASF公司
抗紫外线剂：
Figure BDA0002478388940000053
Figure BDA0002478388940000061
含有-NCO基团的异氰酸酯Ⅰ：
Figure BDA0002478388940000062
异氰酸酯Ⅱ：
Figure BDA0002478388940000063
实施例1：
(1)组分A的制备：在容器A中按重量份数计，加入60.10份CHE-220，14.10份CHE-822，10.10份CHE-628，12.10份1,4-丁二醇，1.80份二乙醇胺、0.61份纯净水、0.24份叔胺催化剂Dabco BLV、0.06份辛酸亚锡催化剂Kosmosis 29、0.3份B8946 PF、0.18份开孔剂B8930，0.3份抗老化剂Tinuvin-292，0.2份抗紫外线Tinuvin-326，搅拌，制备得到组分A；
(2)预聚体的制备：在75～85℃、且有氮气保护的条件下，在容器B中将31份CHE-220和34份熔融状态下的4,-4二苯基甲烷二异氰酸酯44M进行反应，当反应90分钟后，得到混合物Ⅰ，测得混合物Ⅰ中异氰酸根重量百分含量为15.63％时，反应结束；
(3)组分B的配制：在容器B中，将65份混合物Ⅰ与35份多亚甲基多异氰酸酯M20S在干燥且有氮气保护的条件下进行混合，当异氰酸根重量百分含量为20.29％时，反应结束，得到组分B；
(4)在模具温度为50～55℃时，控制料温在35～40℃，将组分A和组分B按100:84的重量比高速混合后立刻浇注到可密闭的模具内，浇注完成后12min脱模，得到高回弹性的聚氨酯微孔弹性体，其产品性能检测数据如表3所示。
(5)将制备得到的高回弹性的聚氨酯微孔弹性体，该弹性体直接制成鞋材/玩具/缓冲(减震)结构件。
实施例与对比例
实施例2-5按照实施例1的各个步骤进行，唯一的区别为反应原料种类、原料配比不同。对比例1-2中的B组分为简单(半)预聚体，而实施例1-5中的B组分为预聚体与异氰酸酯Ⅱ组成，为区分对比例中的预聚体故命名为混合物Ⅰ，具体见表2。制备得到高回弹性的聚氨酯微孔弹性体，实施例2-5的聚氨酯微孔弹性体直接制成鞋材/玩具/缓冲(减震)结构件；对比例1的聚氨酯微孔弹性体直接制成鞋材；对比例2的聚氨酯微孔弹性体直接制成玩具；其产品性能检测数据如表3所示。
表2实施例1-5、对比例1-2中各组分的原料重量份数
Figure BDA0002478388940000071
Figure BDA0002478388940000081
Figure BDA0002478388940000091
表3实施例1-5及对比例1-2制备得到的微孔弹性体的性能检测数据
Figure BDA0002478388940000092
从表3中可以看出，实施例1～2相比对比例1在密度近似(300Kg/m3左右)的情况下，落球回弹、拉伸强度与扯断伸长率均有提升，最显著的是撕裂强度提升了175.2％～201.3％。而实施例4～5相比于对比例2密度近似(520Kg/m3左右)，落球回弹提升了45％～50％，虽然扯断伸长率略有降低，但拉伸强度提升40.2％～48.9％，撕裂强度提升了108.6％～109.3％。综合来看，本发明所提供材料具备更好的回弹性和力学性能，同时通过发泡剂含量的改变调整密度以满足不同场合的应用需求。

Claims (3)

1.一种高回弹性的聚氨酯微孔弹性体，由组分A和组分B反应制备得到，组分A与组分B的重量比为100:70~110，其中：组分A以重量份数计由以下组分组成：具有-OH基团的多元醇Ⅰ70～88.3份，醇类扩链剂5~20份，胺类交联剂1~5份，发泡剂0.1~1份，叔胺类催化剂0.2~1份，有机金属化合物类催化剂0.05~0.1份，聚醚改性有机硅类表面活性剂0.3~1.5份，开孔剂0.1~0.5份，抗老化剂0~1份，抗紫外线剂0~1份；组分B由以下步骤制备：
a)预聚体制备，在55~110℃、且有对反应呈惰性的气体的保护下，在容器B中将具有-OH基团的多元醇Ⅱ和具有-NCO基团的异氰酸酯Ⅰ进行反应，得到混合物Ⅰ，当混合物Ⅰ中异氰酸根重量百分含量为13~17%时，反应结束；
b)组分B的制备：在容器B中，将混合物Ⅰ与异氰酸酯Ⅱ在干燥且有对反应呈惰性的气体的保护下进行混合，当异氰酸根重量百分含量为19~21%时，反应结束，得到组分B；
其中，具有-NCO基团的异氰酸酯Ⅰ选自二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯中的至少一种；异氰酸酯Ⅱ为具有-NCO基团的多亚甲基多苯基异氰酸酯；
其中，组分A中的具有-OH基团的多元醇Ⅰ选自聚酯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇或其他烯烃多元醇中的至少一种，官能度不小于2，分子量为200~13000；组分B中的具有-OH基团的多元醇Ⅱ选自聚酯多元醇、聚氧化丙烯多元醇、聚四氢呋喃多元醇或其他烯烃多元醇中的至少一种，官能度不小于2，分子量为200~13000；对反应呈惰性的气体选自氮气；所述的醇类扩链剂选自1,4-丁二醇、一缩二乙二醇、乙二醇、三羟甲基丙烷或季戊四醇中的至少一种；胺类交联剂选自三乙醇胺或二乙醇胺中的至少一种；发泡剂为水或二氧化碳；叔胺类催化剂选自三亚乙基二胺、双(二甲氨基乙基)醚、N,N-二甲基环己胺、四甲基丁二胺或二甲基乙醇胺中的至少一种；有机金属化合物类催化剂选自辛酸亚锡、二月桂酸二丁基锡或异辛酸锌中的至少一种；聚醚改性有机硅类表面活性剂选自B8738、LF2、B8629、DC 3042或B8946 PF中的至少一种；开孔剂选自CHK-350D、B8930或FK-8300中的至少一种；抗老化剂选自受阻胺类光稳定剂292、622、770、944或783中的至少一种；抗紫外线剂选自苯并三唑类紫外线吸收剂UV-320、UV-327、UV-328、UV-571或UV-1130中的至少一种。
2.权利要求1所述的高回弹性的聚氨酯微孔弹性体的制备方法，包括如下步骤：
（1）组分A的配制：在容器A中按照重量份数计，加入多元醇Ⅰ70～88.3份，醇类扩链剂5~20份，胺类交联剂1~5份，发泡剂0.1~1份，叔胺类催化剂0.2~1份，有机金属化合物类催化剂0.05~0.1份，聚醚改性有机硅类表面活性剂0.3~1.5份，开孔剂0.1~0.5份，抗老化剂0~1份，抗紫外线剂0~1份，搅拌，制备得到组分A；
（2）预聚体的制备：在55~110℃、且有对反应呈惰性的气体的保护下，在容器B中将具有-OH基团的多元醇Ⅱ和具有-NCO基团的异氰酸酯Ⅰ进行反应，得到混合物Ⅰ，当混合物Ⅰ中异氰酸根重量百分含量为13~17%时，反应结束；
（3）组分B的配制：在容器B中，将混合物Ⅰ与异氰酸酯Ⅱ在干燥且有对反应呈惰性的气体的保护下进行混合，当异氰酸根重量百分含量为19~21%时，反应结束，得到组分B；
（4）在模具温度为25~60℃时，将组分A和组分B高速混合后立刻浇注到可密闭的模具内，浇注完成后，控制温度在30~90℃，5~60min后脱模，得到高回弹性的聚氨酯微孔弹性体，其中，组分A与组分B的重量比为100:70~110。
3.权利要求1所述的高回弹性的聚氨酯微孔弹性体在玩具、鞋底或减震材料中应用。
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