CN105462236B - 一种预制降噪块的高分子复合材料 - Google Patents
一种预制降噪块的高分子复合材料 Download PDFInfo
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Abstract
本发明公开了一种预制降噪块的高分子复合材料，涉及有轨电车领域一种与橡胶颗粒混合后生产预制降噪块的高分子复合材料。主要由以下原料制备得到，异氰酸酯和丙烯酸酯树脂接枝共聚物，含前述异氰酸酯的聚氨酯预聚体A和固化组分B。本发明是一种预制降噪块时与橡胶颗粒有良好浸润性、附着能力，制成降噪块后具有较高与钢轨粘接能力、拉伸强度及耐环境老化能力的聚氨酯复合材料。
Description
技术领域
本发明涉及有轨电车领域一种与橡胶颗粒混合后生产预制降噪块的高分子复合材料。
背景技术
随着国内城市有轨电车的兴起及减振降噪要求的提高，在钢轨两侧包覆弹性材料已经成为减振降噪的重要手段，如中国专利203420186U、202298383U都有所叙述。目前相关专利中披露的弹性材料需要与钢轨形成良好的粘接，才能充分发挥其防水、防腐、绝缘、减振降噪特性，材料主要有两种类型：其一是采用橡胶硫化成设计结构的弹性体；其二是采用聚氨酯填充一定比例的橡胶颗粒、无机填料等压制而成。
而目前相关专利中披露的两种类型包覆弹性材料，硫化橡胶制成的弹性体与钢轨粘接效果不理想，在钢轨长期高频振动下易于钢轨脱粘，且本身重量较轻，减振效果一般；而聚氨酯填充橡胶颗粒制备的弹性体，由于其采用的橡胶颗粒为废旧回收料，目前市场上的废旧颗粒为回收天然胶、三元乙丙胶、丁苯橡胶及顺丁橡胶等非极性橡胶为主，在与传统聚氨酯结合时两者的粘接效果很差，制品拉伸强度不高、耐热老化等能力差，不利于在振动状态下长期使用。
针对上述不足，有必要开发一种高分子复合材料，提高其预制降噪块时与橡胶颗粒等的附着能力，保证制成降噪块后与钢轨粘接能力、拉伸强度及耐环境老化能力，保证包覆材料对钢轨的防护效果，延长使用寿命。
发明内容
本发明的目的在于：提供一种预制降噪块时与橡胶颗粒有良好浸润性、附着能力，制成降噪块后具有与钢轨较高粘接能力、拉伸强度及耐环境老化能力的聚氨酯复合材料。
本发明目的通过下述技术方案来实现：
一种预制降噪块的高分子复合材料，按质量份计，主要由以下原料制备得到：
异氰酸酯和丙烯酸酯树脂接枝共聚物 5～15份
含前述异氰酸酯的聚氨酯预聚体A 20～50份
固化组分B 10～40份。
作为选择，所述的预制降噪块的高分子复合材料，按质量份计，由以下原料制备得到：
异氰酸酯和丙烯酸酯树脂接枝共聚物 5～10份，更优选5～6份
含前述异氰酸酯的聚氨酯预聚体A 30～40份，更优选30～35份
固化组分B 20～40份，更优选30～40份。
作为进一步选择，异氰酸酯为重均分子量2000以下的低分子量线性嵌段TDI半预聚体，丙烯酸酯树脂为环氧丙烯酸酯树脂。该方案中，经聚氨酯改性的丙烯酸酯保具有良好的浸润性，耐化学性和强度；同时由于引入了聚氨酯链段，提高了共聚物粘接性和柔韧性。作为选择，低分子量线性嵌段TDI半预聚体(TDI全称Toluene-2,4-diisocyanate；2,4-tolylene diisocyanate，是甲苯二异氰酸酯的英文缩写)采用以下方法制得，制备步骤包括：按质量份计，将40-50份(更优选40～45份)的TDI加入到干燥的反应釜中，通入氮气保护后，滴加10-20份(更优选10～14份)的聚醚二醇PPG、1-3份(更优选1份)锡类催化剂，在80-90℃下反应2-3h，反应完成后降温至室温，密封保存待用。异氰酸酯和丙烯酸酯树脂接枝共聚物采用以下方法制得，制备步骤包括：将低分子量线性嵌段TDI半预聚体与环氧丙烯酸酯按质量比1:3-5(更优选1:3-3.5)的比例混合，混合物再与活性稀释剂按质量比为1:0.5-1(更优选1:0.9-1)混合后制成。活性稀释剂是指为降低体系黏度而加入的溶剂，且该溶剂具有反应活性，能参与体系后续反应，优选为甲基丙烯酸甲酯(MMA)或异冰片基丙烯酸醋(IBOA)、甲基丙烯酸异冰片醋(IBOMA)、二缩丙二醇双丙烯酸醋(DPGDA)和1,6己二醇双丙烯酸醋(HDDA)中的一种或至少两种；作为另一进一步选择，聚氨酯为A、B双组分，其中聚氨酯预聚体A为含异氰酸酯的预聚体组分，该组分采用上述低分子量线性嵌段TDI半预聚体的合成方法合成，差别在于持续滴加聚醚二醇PPG，直到体系中-NCO含量降至20％-30％时终止。具体而言，聚氨酯预聚体A采用以下方法制得，制备步骤包括：按质量份计，将40-50份(更优选40份)的TDI加入到干燥的反应釜中，通入氮气保护后，滴加1-3份(更优选1份)锡类催化剂，持续滴加聚醚二醇PPG，直到体系中-NCO含量降至20％-30％(更优选25％-30％)时终止，在80-90℃下反应2-3h，反应完成后降温至室温，密封保存待用。
作为另一进一步选择，固化组分由聚醚多元醇组分、催化剂及填料混合组成。固化组分由100份聚醚多元醇，1-3份(更优选1.5～2.5份)催化剂，5-10份(更优选7～9份)填料组成。作为选择，聚醚多元醇组分为重均分子量均在1000±500的聚醚二醇、聚醚三醇、硬泡聚醚三醇三种聚醚多元醇组成，按质量份计，组成为聚醚二醇30-50份，聚醚三醇5-15份(更优选6份)，硬泡聚醚三醇10-20份(更优选10份)。催化剂为无毒性的有机铋类催化剂，可以是异辛酸铋、环烷酸铋、奎烷酸铋中的一种或几种。低分子量的聚醚多元醇混合物通过处理后体系具有较低的黏度、良好的渗透性，与橡胶颗粒等有良好的粘附性；且和聚氨酯预聚体反应速度快，生产效率高；同时固化后制品强度高，耐候性好。填料优选对聚氨酯补强效果好，抗撕裂能力强的白炭黑等。
前述本发明主方案及其各进一步选择方案可以组合以形成多个方案，均为本发明可采用并要求保护的方案；进一步地，各选择即可和其他选择组合，本领域技术人员在了解本发明方案后根据现有技术和公知常识可明了有多种组合，均为本发明所要保护的技术方案，在此不做穷举。
本发明采用异氰酸酯和丙烯酸酯树脂接枝共聚物作为重要组分，降低体系的黏度，增强体系最终与橡胶颗粒的附着能力。
本发明采用了低分子量的聚醚多元醇、硬泡聚醚多醇互混体系作为固化组分，体系黏度低，黏附能力好，固化后体系强度高，满足高模量需求。
本发明中的异氰酸酯和丙烯酸酯树脂接枝共聚物能在后期三组分混合中参与反应，形成互穿网络，避免了简单物理互混容易分相弊端，有益于增强体系的强度和使用寿命。
本发明的有益效果：预制降噪块时与橡胶颗粒有良好浸润性、附着能力，制成降噪块后具有与钢轨较高粘接能力、拉伸强度及耐环境老化能力。
具体实施方式
下列非限制性实施例用于说明本发明。
实施例1：
异氰酸酯和丙烯酸酯树脂接枝共聚物：将45份的TDI加入到干燥的反应釜中，通入氮气保护后，滴加14份的聚醚二醇PPG、1份二月桂酸二丁基锡，在80-90℃下反应2h，反应完成后降温至室温，搅拌下加入200份的环氧丙烯酸酯，250份甲基丙烯酸甲酯(MMA)，混合均匀后密封待用。
聚氨酯预聚体A：将40份的TDI加入到干燥的反应釜中，通入氮气保护后，持续滴加聚醚二醇PPG、1份二月桂酸二丁基锡，在80-90℃下反应2h，直到体系中-NCO含量为25％-30％反应完成，后降温至室温出料。
固化组分B：将聚醚二醇50份，聚醚三醇6份，升温至75-85℃下搅拌2h，再加入硬泡聚醚三醇10份升温至90-100℃搅拌3h，三原料重均分子量均在1000±500范围，冷却至室温后加入1份异辛酸铋，5份白炭黑，搅拌均匀后出料。
将异氰酸酯和丙烯酸酯树脂接枝共聚物6份，聚氨酯预聚体A 30份，固化组分B 40份均匀混合后，与2-4mm粒径的废旧橡胶颗粒按质量比为1:9快速混合后，填充入模具，在120℃、5MPa下压制可得最终降噪块。
降噪块测试物理性能如下：
实施例2：
异氰酸酯和丙烯酸酯树脂接枝共聚物：将40份的TDI加入到干燥的反应釜中，通入氮气保护后，滴加10份的聚醚二醇PPG、1份二月桂酸二丁基锡，在80-90℃下反应2h，反应完成后降温至室温，搅拌下加入160份的环氧丙烯酸酯，200份甲基丙烯酸甲酯(MMA)，混合均匀后密封待用。
聚氨酯预聚体A：将40份的TDI加入到干燥的反应釜中，通入氮气保护后，持续滴加聚醚二醇PPG、1份二月桂酸二丁基锡，在80-90℃下反应2h，直到体系中-NCO含量为25-30％反应完成，后降温至室温出料。
固化组分B：将聚醚二醇30份，聚醚三醇6份，升温至75-85℃下搅拌2h，再加入硬泡聚醚三醇10份升温至90-100℃搅拌3h，三原料重均分子量均在1000±500范围，冷却至室温后加入1份环烷酸铋，4份白炭黑，搅拌均匀后出料。
将异氰酸酯和丙烯酸酯树脂接枝共聚物5份，聚氨酯预聚体A 35份，固化组分B 30份均匀混合后，与2-4mm粒径的废旧橡胶颗粒按质量比为1:9快速混合，然后填充入模具，在120℃、5MPa下压制可得最终降噪块。
降噪块测试物理性能如下：
Claims (8)
1.一种预制降噪块的高分子复合材料，其特征在于按质量份计，主要由以下原料制备得到：
异氰酸酯和丙烯酸酯树脂接枝共聚物 5～15份
含前述异氰酸酯的聚氨酯预聚体A 20～50份
固化组分B 10～40份；
异氰酸酯为重均分子量2000以下的低分子量线性嵌段TDI半预聚体，丙烯酸酯树脂为环氧丙烯酸酯树脂；固化组分由聚醚多元醇组分、催化剂及填料混合组成。
2.如权利要求1所述的预制降噪块的高分子复合材料，其特征在于按质量份计，由以下原料制备得到：
异氰酸酯和丙烯酸酯树脂接枝共聚物 5～10份
含前述异氰酸酯的聚氨酯预聚体A 30～40份
固化组分B 20～40份。
3.如权利要求1或2所述的预制降噪块的高分子复合材料，其特征在于低分子量线性嵌段TDI半预聚体采用以下方法制得，制备步骤包括：按质量份计，将40-50份的TDI 加入到干燥的反应釜中，通入氮气保护后，滴加10-20份的聚醚二醇PPG 、1-3份锡类催化剂，在80-90℃下反应2-3h，反应完成后降温至室温，密封保存待用。
4.如权利要求1或2所述的预制降噪块的高分子复合材料，其特征在于异氰酸酯和丙烯酸酯树脂接枝共聚物采用以下方法制得，制备步骤包括：将低分子量线性嵌段TDI半预聚体与环氧丙烯酸酯按质量比1:3-5的比例混合，混合物再与活性稀释剂按质量比为1:0.5-1混合后制成。
5.如权利要求4所述的预制降噪块的高分子复合材料，其特征在于：活性稀释剂为甲基丙烯酸甲酯或异冰片基丙烯酸醋、甲基丙烯酸异冰片醋、二缩丙二醇双丙烯酸醋和1,6 己二醇双丙烯酸醋中的一种或至少两种。
6.如权利要求1或2所述的预制降噪块的高分子复合材料，其特征在于聚氨酯预聚体A采用以下方法制得，制备步骤包括：按质量份计，将40-50份的TDI 加入到干燥的反应釜中，通入氮气保护后，滴加1-3份锡类催化剂，持续滴加聚醚二醇PPG，直到体系中-NCO含量降至20%-30%时终止，在80-90℃下反应2-3h，反应完成后降温至室温，密封保存待用。
7.如权利要求1或2所述的预制降噪块的高分子复合材料，其特征在于：聚醚多元醇组分为重均分子量均在1000±500的聚醚二醇、聚醚三醇、硬泡聚醚三醇三种聚醚多元醇组成，按质量份计，组成为聚醚二醇30-50份，聚醚三醇5-15份，硬泡聚醚三醇10-20份。
8.如权利要求1或2所述的预制降噪块的高分子复合材料，其特征在于：催化剂为有机铋类催化剂。
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