CN105153390A - 环保型聚氨酯发泡轮胎组合料及其制备方法 - Google Patents

环保型聚氨酯发泡轮胎组合料及其制备方法 Download PDF

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CN105153390A
CN105153390A CN201510369183.9A CN201510369183A CN105153390A CN 105153390 A CN105153390 A CN 105153390A CN 201510369183 A CN201510369183 A CN 201510369183A CN 105153390 A CN105153390 A CN 105153390A
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孙清峰
甘经虎
王翠
王会
栾森
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Abstract

本发明属于聚氨酯技术领域，具体涉及一种环保型聚氨酯发泡轮胎组合料及其制备方法。由A组分与B组分按质量比为100:85-105混合制成：A组分由聚醚多元醇、聚合物多元醇、扩链剂、交联剂、泡孔稳定剂、发泡剂和催化剂制成；B组分是一种聚酯多元醇改性的异氰酸酯组分，由聚酯多元醇、异氰酸酯和储存稳定剂制成。本发明与现有技术的原料相比，发泡剂为水，环保的同时，省去物理发泡剂费用，成本大幅度降低。本发明制备的环保型聚氨酯发泡轮胎在满足硬度的同时，也具有良好的结皮性和光亮的表面。能够用于正常发泡轮胎的生产，是轮胎生产的理想替代材料。本发明还提供其制备方法，工艺合理。

Description

环保型聚氨酯发泡轮胎组合料及其制备方法
技术领域
本发明属于聚氨酯技术领域，具体涉及一种环保型聚氨酯发泡轮胎组合料及其制备方法。
背景技术
聚氨酯发泡轮胎以其良好的耐磨性、优良的耐酸碱性及耐针扎，越来越被大家接受。目前被广泛应用于货物推车、童车、慢速电动车等领域。
专利CN102250313A报道了一种用于聚氨酯发泡轮胎的自结皮微孔弹性体组合物，此发明制备的聚氨酯发泡轮胎具有优异的力学性能、良好的回弹性以及优异的耐水解性和耐霉菌性。但是，其用的发泡剂为物理发泡剂—HCFC-141b，141b中含有氯原子，对臭氧层有破坏作用。发达国家已于2010年全面禁止使用141b。戊烷、HFC-365mfc、HFC-245fa等试剂作为141b的替代品，虽然都是零DOP，但是不同试剂在应用过程中存在不同问题。例如：戊烷虽然成本低廉、发泡率与141b相近，但是其易燃易爆的特点，使得运输、生产操作过程中要求极其严格，不利于正常生产使用。因此以上提到的试剂只是过渡品，水发泡才是最终替代品。
专利CN10331985A报道了一种自结皮聚氨酯泡沫塑料及制备方法。此发明用水发泡，具体应用于汽车方向盘、扶手、仪表板等静态自结皮聚氨酯。采用水发泡优点为成本低、与异氰酸酯生成二氧化碳对大气无害、生产现场气味低，无易燃性。但是与正常物理发泡剂(141b)相比，水发泡的制品也存在很明显的缺点：表皮薄，性能差。
发明内容
针对现有技术的不足，本发明的目的是提供一种环保型聚氨酯发泡轮胎组合料，用于制备聚氨酯发泡轮胎，在满足硬度的同时，也具有良好的结皮性和光亮的表面；本发明还提供其制备方法。
本发明所述的环保型聚氨酯发泡轮胎组合料，由A组分与B组分按质量比为100:85-105混合制成：
A组分由以下质量份数的原料制成：
B组分由以下质量分数的原料制成：
聚酯多元醇：15-30％
异氰酸酯：70-85％
储存稳定剂：10ppm。
其中：
B组分是由聚酯多元醇改性的异氰酸酯组分。B组分的-NCO的质量含量在22-27％之间。
A组分中的聚醚多元醇平均官能度为2-4，优选2-3，数均分子量为1000-8000，优选2000-6000，伯羟基质量含量≥75％，不饱和度≤0.008meq/g；优选EP-330NG(市售，山东蓝星东大化工有限责任公司)、FA-703(市售，可利亚聚醚多元醇南京有限公司)或EP-3600(市售，山东蓝星东大化工有限责任公司)中的一种或几种。
A组分中的聚合物多元醇为以乙烯基聚醚三醇为基础聚醚，用苯乙烯或丙烯腈接枝共聚，固含量≥30％的聚合物多元醇。优选POP93/28(市售，山东蓝星东大化工有限责任公司)、POP36/28(市售，山东蓝星东大化工有限责任公司)或POP40(市售，山东蓝星东大化工有限责任公司)中的一种或几种。
A组分中的扩链剂为乙二醇、丙二醇、1,4-丁二醇或一缩二丙二醇中的一种或几种的混合物。
A组分中的交联剂为甘油、二乙醇胺、三乙醇胺或三羟甲基丙烷中的一种或几种的混合物。
A组分中的发泡剂为水。
A组分中的泡沫稳定剂为聚硅氧烷-氧化烯烃嵌段共聚物，优选DC6070(市售，美国空气化工产品有限公司)、AK-7703(市售，南京德美世创化工有限公司)和DC3043(市售，美国空气化工产品有限公司)中的一种或几种。
A组分中的催化剂为叔胺类催化剂或有机锡类催化剂中的一种或几种；叔胺类催化剂优选A-33(市售)、A-1(市售)或C-225(市售，美国，GE公司)，有机锡类催化剂优选CS-12(市售)。
B组分中的异氰酸酯为纯MDI、碳化二亚胺改性MDI或MDI-50中的一种或几种的混合物。
B组分中的聚酯多元醇优选PE-2420或CMA-244中的一种或两种混合物；PE-2420为山东一诺威聚氨酯股份有限公司市售产品，CMA-244为华大化学集团有限公司市售产品。
B组分中的储存稳定剂为磷酸。
本发明所述的环保型聚氨酯发泡轮胎组合料的制备方法，包括以下步骤：
A组分：先将聚醚多元醇和聚合物多元醇投入反应釜中搅拌，然后依次加入扩链剂、交联剂、催化剂、泡沫稳定剂和发泡剂，在室温条件下，搅拌1-2小时后密封保存；
B组分：将聚酯多元醇常温下投入反应釜中，搅拌升温至90-100℃，真空条件下脱水脱气2-3小时，然后降温至40℃，加入异氰酸酯，在80-85℃反应2-3小时，-NCO的质量含量达到22-27％之间，降温至40-50℃，密封保存。
使用时，将A、B料置于低压浇注机对应罐中，按A组分与B组分按质量比为100:85-105的比例浇注到动态轮胎模具中，三分钟左右开模，修剪、排气。静置1小时左右，制备得到环保型聚氨酯发泡轮胎，硬度在邵A85-95。
综上所述，本发明具有以下优点：
(1)本发明与现有技术的原料相比，发泡剂为水，环保的同时，省去物理发泡剂费用，成本有大幅度降低。
(2)现有技术使用141b，由于141b极易挥发，使用过程中不可避免被现场工人吸入、甚至接触，一旦在体内分解，将严重影响身体健康，且对臭氧层有破坏作用。而本发明采用水发泡避免了这一问题，水与异氰酸酯生成二氧化碳对大气无害。
(3)本发明制备的环保型聚氨酯发泡轮胎在满足硬度的同时，也具有良好的结皮性和光亮的表面。能够用于正常发泡轮胎的生产，是轮胎生产的理想替代材料。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
A组分：分别称取EP-330NG90Kg和POP36/2810Kg投入反应釜中搅拌，然后依次加入1,4-丁二醇7Kg，乙二醇13Kg，甘油1.0kg，A-331.5Kg，AK-77030.2Kg，DC-1930.2Kg，水0.5Kg。在30℃下搅拌1小时，充分混合均匀，密封保存，备用。
B组分：称取PE-242010Kg置于釜中，搅拌升温至100℃，真空条件下脱水脱气2小时。然后降温至40℃，开搅拌加入4,4’-二苯基甲烷二异氰酸酯30Kg，碳化二亚胺改性MDI3Kg，缓慢升温至85℃，保温反应1.5小时。搅拌20分钟，取样检测，合格后冲N2放料，备用。
使用时，A、B料温维持在35-40℃，按A组分与B组分按质量比为100:94的比例浇注到动态轮胎模具中，模具温度50-55℃，3分钟开模，修边、排气后。自然熟化，1小时左右制备得到聚氨酯发泡轮胎。
实施例2
A组分：分别称取EP360090Kg和POP36/2810Kg投入反应釜中搅拌，然后依次加入丙二醇14Kg，乙二醇6Kg，二乙醇胺0.5kg，A-10.5kg，A-33:0.8Kg，CS-120.05kg，AK-77030.2Kg，DC60700.2Kg，水0.6Kg。在30℃下搅拌2小时，充分混合均匀，密封保存，备用。
B组分：称取CMA-24415Kg置于釜中，搅拌升温至90℃，真空条件下脱水脱气3小时。然后降温至40℃，开搅拌加入4,4’-二苯基甲烷二异氰酸酯30Kg，碳化二亚胺改性MDI10Kg，缓慢升温至85℃，保温反应1.5小时。搅拌20分钟，取样检测，合格后冲N2放料，备用。
使用时，A、B料温维持在35-40℃，按A组分与B组分按质量比为100:92的比例浇注到动态轮胎模具中，模具温度50-55℃，3分钟开模，修边、排气后。自然熟化，1小时左右制备得到聚氨酯发泡轮胎。
实施例3
A组分：分别称取EP-330NG80Kg和POP93/2820Kg投入反应釜中搅拌，然后依次加入1,4-丁二醇7Kg，乙二醇6Kg，三乙醇胺1.5kg，A-331.5Kg，AK-77030.3Kg，DC60700.3Kg，水0.5Kg。在30℃下搅拌1小时，充分混合均匀，密封保存，备用。
B组分：称取PE-242010Kg置于釜中，搅拌升温至95℃，真空条件下脱水脱气2.5小时。然后降温至40℃，开搅拌加入4,4’-二苯基甲烷二异氰酸酯30Kg，碳化二亚胺改性MDI10Kg，缓慢升温至82℃，保温反应1.5小时。搅拌20分钟，取样检测，合格后冲N2放料，备用。
使用时，A、B料温维持在35-40℃，按A组分与B组分按质量比为100:93的比例浇注到动态轮胎模具中，模具温度50-55℃，3分钟开模，修边、排气后。自然熟化，1小时左右制备得到聚氨酯发泡轮胎。
对比例
采用与实施例1相同的制备方法，唯一的不同是发泡剂采用141b体系配方。
将实施例1-3和对比例制备得到的聚氨酯发泡轮胎进行性能测试，测试结果见表1。
表1实施例1-3和对比例制备得到的聚氨酯发泡轮胎的性能测试结果
由表1可以看出，本发明制备的环保型聚氨酯发泡轮胎在满足硬度的同时，也具有良好的结皮性和光亮的表面。能够用于正常发泡轮胎的生产，是轮胎生产的理想替代材料。

Claims (10)

1.一种环保型聚氨酯发泡轮胎组合料，其特征在于：由A组分与B组分按质量比为100:85-105混合制成：
A组分由以下质量份数的原料制成：
B组分由以下质量分数的原料制成：
聚酯多元醇：15-30％
异氰酸酯：70-85％
储存稳定剂：10ppm。
2.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：A组分中的聚醚多元醇平均官能度为2-4，数均分子量为1000-8000，伯羟基质量含量≥75％，不饱和度≤0.008meq/g。
3.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：A组分中的聚合物多元醇为以乙烯基聚醚三醇为基础聚醚，用苯乙烯或丙烯腈接枝共聚，固含量≥30％的聚合物多元醇。
4.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：扩链剂为乙二醇、丙二醇、1,4-丁二醇或一缩二丙二醇中的一种或几种的混合物；A组分中的交联剂为甘油、二乙醇胺、三乙醇胺或三羟甲基丙烷中的一种或几种的混合物。
5.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：A组分中的发泡剂为水。
6.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：A组分中的泡沫稳定剂为聚硅氧烷-氧化烯烃嵌段共聚物；A组分中的催化剂为叔胺类催化剂或有机锡类催化剂中的一种或几种。
7.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：B组分中的异氰酸酯为纯MDI、碳化二亚胺改性MDI或MDI-50中的一种或几种的混合物。
8.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：B组分中的聚酯多元醇优选PE-2420或CMA-244中的一种或两种混合物。
9.根据权利要求1所述的环保型聚氨酯发泡轮胎组合料，其特征在于：B组分中的储存稳定剂为磷酸。
10.一种权利要求1-9任一所述的环保型聚氨酯发泡轮胎组合料的制备方法，其特征在于：包括以下步骤：
A组分：先将聚醚多元醇和聚合物多元醇投入反应釜中搅拌，然后依次加入扩链剂、交联剂、催化剂、泡沫稳定剂和发泡剂，在室温条件下，搅拌1-2小时后密封保存；
B组分：将聚酯多元醇常温下投入反应釜中，搅拌升温至90-100℃，真空条件下脱水脱气2-3小时，然后降温至40℃，加入异氰酸酯，在80-85℃反应2-3小时，-NCO的质量含量达到22-27％之间，降温至40-50℃，密封保存。
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