CN104311786A - 一种交联型抗疲劳耐磨聚氨酯橡胶 - Google Patents

一种交联型抗疲劳耐磨聚氨酯橡胶 Download PDF

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CN104311786A
CN104311786A CN201410533254.XA CN201410533254A CN104311786A CN 104311786 A CN104311786 A CN 104311786A CN 201410533254 A CN201410533254 A CN 201410533254A CN 104311786 A CN104311786 A CN 104311786A
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张凯杰
张刚
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Jiangsu Ding Guan Pipe Technology Co., Ltd.
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JIANGSU JESCI NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种交联型抗疲劳耐磨聚氨酯橡胶的制备方法，所述交联型抗疲劳耐磨聚氨酯橡胶按质量比包括：聚四氢呋喃二醇65%~70%、环聚环氧丙烷醚三元醇6%~10%、甲苯二异氰酸酯14%~20%、1，5—萘二异氰酸酯5%~8%、二邻氯二苯胺甲烷1%~3%、三羟甲基丙烷0.5%~1.5%、炭黑0%~0.5%、二硫化钼1%~2%。本发明具有高耐磨性、回弹性好、耐低温性能好、抗张强度高、耐水解性突出、与金属粘接好、耐振动、抗疲劳性能较好优点。

Description

一种交联型抗疲劳耐磨聚氨酯橡胶
技术领域
本发明产品涉及一种橡胶，特别是一种交联型抗疲劳耐磨聚氨酯橡胶。 
背景技术
丁苯胶、丁基胶、丁腈胶、三元乙丙胶、氯丁胶、硅橡胶、氟橡胶等等，海洋柔性接头用的柔性橡胶虽然品种繁多但是由于其特性比较单一往往导致其使用寿命短。其主要表现在橡胶的耐候性差、橡胶层不耐磨以及耐疲劳破环性差等，因此针对改善橡胶的耐候及耐磨性是十分必要的。此外传统的海洋柔性接头是内胶层、增强层有多层刮胶锦纶帘子布、外胶层复合的橡胶管组成，在制备过程中内部缺陷及其结构很难控制。内部缺陷的存在也很大程度上影响了柔性接头的使用寿命，因此对传统海洋柔性接头的制备工艺的改善也是非常需要的。 
发明内容
本发明的目的是为了克服以上的不足，提供一种高耐磨性、回弹性好、耐低温性能好、抗张强度高、耐水解性突出、与金属粘接好、耐振动、抗疲劳性能较好的海洋柔性接头用交联型抗疲劳耐磨聚氨酯橡胶。 
本发明的目的通过以下技术方案来实现：一种交联型抗疲劳耐磨聚氨酯橡胶的制备方法，其特征在于：所述交联型抗疲劳耐磨聚氨酯橡胶按质量比包括：聚四氢呋喃二醇65%~70%、环聚环氧丙烷醚三元醇6%~10%、甲苯二异氰酸酯14%~20%、1，5—萘二异氰酸酯5%~8%、二邻氯二苯胺甲烷1%~3%、三羟甲基丙烷0.5%~1.5%、炭黑0%~0.5%、二硫化钼1%~2%，制备方法包括以下步骤： 
A：在化学反应釜中，先加入聚四氢呋喃二醇、环聚环氧丙烷醚三元醇、炭黑及二硫化钼，开动搅拌器，转速为60转/分，同时把反应釜内的温度升至100℃，开始抽真空到负压为0.1MPa保持30分钟，后让反应釜内温度将到45℃左右；
B：保持温度在45℃左右，继续搅拌，然后缓慢向反应釜内加入甲苯二异氰酸酯和1，5—萘二异氰酸酯混合物，停止加热，由于该反应是放热反应，在反应过程中保持反应温度在90℃以下，直至温度降至50℃以下停止搅拌；
C：室温下保持反应釜密闭，将料静置24小时以上，后加热至反应釜内温度到90℃，开始抽真空到负压为0.1MPa保持2小时；
D：将二邻氯二苯胺甲烷加热融化后和三羟甲基丙烷按质量比3:1混合后，与从反应釜内放出的预聚体按质量比10:1同时放入搅料桶内搅拌至均匀，将搅拌好的料迅速倒入模具中；
E：温度控制在80℃初步硫化1小时，然后将制品放入硫化仓中100℃硫化8小时制得聚氨酯橡胶。
本发明与现有技术相比具有的优点： 
1、采用聚四氢呋喃二醇其呋喃环与聚氨酯硬段中苯环的共同存在有效提高了聚氨酯橡胶的耐热性及耐磨性。
2、由于醚键的水解稳定性好，所以采用聚四氢呋喃二醇聚合的聚氨酯橡胶耐水解性及耐霉菌性很好，在海洋的碱性环境中其使用寿命明显比其它橡胶有所提升。 
3、采用NDI/TDI复配的混合二异氰酸酯能够大大提高聚氨酯橡胶的耐蠕变性能，从而提高了聚氨酯柔性接头的抗疲劳性能。 
4、通过对投料比严格控制预聚体中游离的—NCO含量，同时通过采用3官能度的聚醚提高了聚氨酯橡胶合成及硫化的交联密度，提高了其机械性能。 
5、扩链剂采用三羟甲基丙烷（TMP）和二邻氯二苯胺甲烷（MOCA）并用有效的提高了橡胶的交联度，调节了制品的硬度，改善了聚氨酯橡胶的性能。 
6、本发明的配制方法、合成工艺控制简单、设备投入较低，运行成本低，便于工业化生产。 
具体实施方式：
为了加深对本发明的理解，下面将结合实施例对本发明作进一步详述，该实施例仅用于解释本发明，并不构成对本发明保护范围的限定。
实施例1 
称取聚氨酯橡胶预聚体的起始剂聚四氢呋喃二醇400KG、环聚环氧丙烷醚三元醇45KG、二硫化钼3KG混合后通过真空泵抽入反应釜中加热到100℃并搅拌在负压0.1MPa下抽真空脱水30min后降温至45℃，然后加入甲苯二异氰酸酯90KG和1，5—萘二异氰酸酯40KG，搅拌并开始反应同时控制反应温度在90℃以下，待反应温度降至室温后停止搅拌，并保持反应釜密封静置24h后重新加热升温至90℃搅拌并在负压0.1MPa下抽真空脱水2h后保持聚氨酯预聚体料温在80℃，然后按照质量比100：0.5：10称取炭黑和扩链剂二邻氯二苯胺甲烷加热融化后在搅料桶内搅拌至均匀。将搅拌好的料倒入模具中在80℃下离心浇铸1h后放入硫化仓经100℃硫化8h制得成品。
实施例2 
称取聚氨酯橡胶预聚体的起始剂聚四氢呋喃二醇400KG、环聚环氧丙烷醚三元醇45KG、二硫化钼3KG混合后通过真空泵抽入反应釜中加热到100℃并搅拌在负压0.1MPa下抽真空脱水30min后降温至45℃，然后加入甲苯二异氰酸酯90KG和1，5—萘二异氰酸酯45KG，搅拌并开始反应同时控制反应温度在90℃以下，待反应温度降至室温后停止搅拌，并保持反应釜密封静置24h后重新加热升温至90℃搅拌并在负压0.1MPa 下抽真空脱水2h后保持聚氨酯预聚体料温在80℃，然后按照质量比100：4：8称取扩链剂三羟甲基丙烷和二邻氯二苯胺甲烷加热融化后在搅料桶内搅拌至均匀。将搅拌好的料倒入模具中在80℃下离心浇铸1h后放入硫化仓经100℃硫化8h制得成品。

Claims (1)

1.一种交联型抗疲劳耐磨聚氨酯橡胶的制备方法，其特征在于：所述交联型抗疲劳耐磨聚氨酯橡胶按质量比包括：聚四氢呋喃二醇65%~70%、环聚环氧丙烷醚三元醇6%~10%、甲苯二异氰酸酯14%~20%、1，5—萘二异氰酸酯5%~8%、二邻氯二苯胺甲烷1%~3%、三羟甲基丙烷0.5%~1.5%、炭黑0%~0.5%、二硫化钼1%~2%，制备方法包括以下步骤：
A：在化学反应釜中，先加入聚四氢呋喃二醇、环聚环氧丙烷醚三元醇、炭黑及二硫化钼，开动搅拌器，转速为60转/分，同时把反应釜内的温度升至100℃，开始抽真空到负压为0.1MPa保持30分钟，后让反应釜内温度将到45℃左右；
B：保持温度在45℃左右，继续搅拌，然后缓慢向反应釜内加入甲苯二异氰酸酯和1，5—萘二异氰酸酯混合物，停止加热，由于该反应是放热反应，在反应过程中保持反应温度在90℃以下，直至温度降至50℃以下停止搅拌；
C：室温下保持反应釜密闭，将料静置24小时以上，后加热至反应釜内温度到90℃，开始抽真空到负压为0.1MPa保持2小时；
D：将二邻氯二苯胺甲烷加热融化后和三羟甲基丙烷按质量比3:1混合后，与从反应釜内放出的预聚体按质量比10:1同时放入搅料桶内搅拌至均匀，将搅拌好的料迅速倒入模具中；
E：温度控制在80℃初步硫化1小时，然后将制品放入硫化仓中100℃硫化8小时制得聚氨酯橡胶。
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CN106632945A (zh) * 2016-12-23 2017-05-10 苏州市运泰利自动化设备有限公司 用于清洁测试夹具探针的聚氨酯及其清洁方法
CN110028778A (zh) * 2019-03-29 2019-07-19 安徽都邦电器有限公司 一种汽车用高稳定性不易吸水老化橡胶管及其制备工艺
CN111954691A (zh) * 2018-04-10 2020-11-17 株式会社德山 使用聚轮烷的氨基甲酸酯树脂以及抛光垫
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CN106632945B (zh) * 2016-12-23 2019-05-31 苏州市运泰利自动化设备有限公司 用于清洁测试夹具探针的聚氨酯及其清洁方法
CN111954691A (zh) * 2018-04-10 2020-11-17 株式会社德山 使用聚轮烷的氨基甲酸酯树脂以及抛光垫
CN111954691B (zh) * 2018-04-10 2022-04-22 株式会社德山 使用聚轮烷的氨基甲酸酯树脂以及抛光垫
CN110028778A (zh) * 2019-03-29 2019-07-19 安徽都邦电器有限公司 一种汽车用高稳定性不易吸水老化橡胶管及其制备工艺
CN112375205A (zh) * 2020-11-20 2021-02-19 南京艾德恒信科技有限公司 一种高强度聚氨酯弹性体的制备方法及其应用

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