CN104497256B - 用于低模温工艺的聚氨酯组合料及其制备方法 - Google Patents

用于低模温工艺的聚氨酯组合料及其制备方法 Download PDF

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CN104497256B
CN104497256B CN201410781636.4A CN201410781636A CN104497256B CN 104497256 B CN104497256 B CN 104497256B CN 201410781636 A CN201410781636 A CN 201410781636A CN 104497256 B CN104497256 B CN 104497256B
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孙清峰
牛富刚
殷玉鹏
郭永生
代金辉
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Shandong Inov Polyurethane Co Ltd
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Abstract

发明属于聚氨酯合成领域，具体涉及一种用于低模温工艺的聚氨酯组合料及其制备方法。所述的聚氨酯组合料由A组分和与B组分组成，其中，A组分由聚醚胺、聚醚多元醇、聚合物多元醇、扩链剂、交联剂、水、物理发泡剂、泡沫稳定剂、催化剂制成；B组分为异氰酸酯；A组分与B组分的质量比为100：40‑70。所述的聚氨酯组合料有效解决了表面熟化问题，可在模温20℃条件下使用，起到降低能耗和模具制造费用的目的；本发明的制备方法工艺合理、易于实现。

Description

用于低模温工艺的聚氨酯组合料及其制备方法
技术领域
本发明属于聚氨酯合成领域，具体涉及一种用于低模温工艺的聚氨酯组合料及其制备方法。
背景技术
随着经济的发展，聚氨酯高回弹发泡产品的应用也越来越广泛，对聚氨酯。传统的高回弹模塑发泡工艺，一般要求模具温度在50-70℃，才能保证较好的外观表皮和整体弹性，否则会出现脱皮、外观粗糙、开模时间延长等问题。所以制作发泡模具时，材质一般为导热较好的铝或钢，并且需要设计循环水浴电加热系统，模具制造费用和能耗都比较高。其中专利文件CN200910194469涉及利用改性MDI作为B料来达到降低模温的目的，但是利用该方法有两个局限性，一是降低模温程度有限，需求温度在40-50℃；二是限定B料为全MDI体系，不能在TDI体系中应用。
发明内容
针对现有技术的不足，本发明的目的是提供一种用于低模温工艺的聚氨酯组合料，解决表面熟化问题，可在模温20℃条件下使用；本发明同时提供其制备方法，工艺合理，易于实现。
本发明所述的用于低模温工艺的聚氨酯组合料，由A组分和与B组分以质量比为A:B＝100:40-70组成，其中，
A组分由以下重量百分数的原料制成：
B组分为异氰酸酯。
其中：
A组分优选由以下重量百分数的原料制成：
B组分为异氰酸酯。
其中：
聚醚胺是官能度为2，数均分子量为500-900，主链为聚醚结构，末端活性官能团为胺基的聚合物；优选JEFFAMINE ED-600(美国亨斯曼公司)或JEFFAMINE ED-900(美国亨斯曼公司)中的一种或两种。
聚醚多元醇是以甘油为起始剂，伯羟基含量≥65％，数均分子量为4500-7000，用氧化乙烯封端的聚氧化丙烯三元醇，优选FA-703(可利亚聚醚多元醇南京有限公司)或EP-3600Y(山东蓝星东大化工有限责任公司)。
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≥20％的高活性聚合物多元醇，优选POP3630(可利亚聚醚多元醇南京有限公司)或POP40(山东蓝星东大化工有限责任公司)。
异氰酸酯为甲苯二异氰酸酯、纯MDI、碳化二亚胺改性MDI、MDI-50、聚合MDII或NCO封端的改性MDI中的一种或多种的混合物。NCO封端的改性MDI，是MDI与聚醚多元醇预聚反应得到的，NCO的质量含量为17％-30％，NCO封端的改性MDI优选WANNATE8001(万华化学公司)或WANNATE 8019(万华化学公司)。
催化剂为低模温催化剂和叔胺类催化剂的混合物，叔胺类催化剂与低模温催化剂的质量比为0.3-1.5:0.3-0.8。低模温催化剂优选为美国空气化工公司的DC3040；叔胺类催化剂为发泡型催化剂、凝胶型催化剂、反应性催化剂或延迟性催化剂的一种或几种，优选市售的A-1、A-33、DMEA、MP601、MP602或C-225中的一种或几种。
扩链剂为乙二醇(EG)、一缩二乙二醇(DEG)、1,4-丁二醇(1,4-BG)、1,3-丙二醇(1,3-PDO)或一缩二丙二醇(DPG)中的一种或几种；交联剂为三乙醇胺(TEA)、二乙醇胺(DEOA)或甘油中的一种或几种；物理发泡剂为常压下沸点低于70℃的氟氯烃的一种或多种；泡沫稳定剂为聚硅氧烷-氧化烯烃嵌段共聚物，优选L-3150(美国GE Toshiba Silicones公司)。
所述的用于低模温工艺的聚氨酯组合料的制备方法，包括如下步骤：
A组分料：首先将聚醚多元醇、聚合物多元醇、聚醚胺投入中搅拌，然后依次加入计量好的泡沫稳定剂、交联剂、扩链剂、催化剂、水，在室温条件下，转速为30-80r/min，搅拌1-2h，即得A组分合格产品。
B组分料：将基于配方量的甲苯二异氰酸酯、纯MDI、碳化二亚胺改性MDI、MDI-50、聚合MDI、NCO封端的改性MDI依次加入到搅拌釜中，在室温条件下，转速为30-80r/min，搅拌0.5-1h即得B组分合格产品。
使用时，室温条件下将A、B组分料按A：B＝100：40-70的质量比混合均匀，控制不同模温，机械或手工注入模具中，合模密封，4-8min开模，即可得到合格泡沫塑料制品。
与现有技术相比，本发明具有以下有益效果：
(1)本发明组合料在模温20℃条件下使用时可以得到具有较好外观和整体弹性的泡沫塑料制品，所以模具材质也可选用价格较低不耐高温的树脂，而且不用设计循环水浴电加热系统，在频繁更换模具或者供电不足的场所，能大大降低成本和能耗；
(2)经检测，该用于低模温工艺的聚氨酯组合料产品质量指标可以达到：
(3)本发明还提供其制备方法，工艺简单，易于实现。
具体实施方式
下面结合实施例对本发明做进一步说明。实施例中用到的所有原料除特殊说明外，均为市购。
实施例1
A组分为(以重量百分数计)：
B组分为(以重量百分数计)：
TDI80/20： 40
粗MDI： 60
A组分：将称量好的FA-703、POP3630、JEFFAMINE ED600依次投入混拌釜中，开启搅拌，然后分别依次加入称量好的L-3150、DEOA、DEG、MP601、MP602、DC3040、H2O，室温条件下，转速为30r/min，搅拌混合1h后，取样进行检验，满足工艺参数，发出满意泡沫，即得A组分合格产品。
B组分：将称量好的TDI80/20和粗MDI室温下加入混拌釜中，室温条件下，转速为30r/min，搅拌0.5h，取样进行检测，异氰酸基含量达到(37.6±0.5)％，即得B组分合格产品。
使用时，将A、B组分料按A：B＝100：40的重量配比混合注入模具即可得聚氨酯泡沫塑料。
实施例2
A组分为(以重量百分数计)：
B组分为(以重量百分数计)：
A组分：将称量好的FA-703、POP3630、JEFFAMINE ED600、JEFFAMINE DE900依次投入混拌釜中搅拌，然后分别依次加入称量好的L-3150、DEOA、C-225、DC3040、H2O，室温条件下，转速为50r/min，搅拌混合1.5h后，取样进行检验，满足工艺参数，发出满意泡沫，即得A组分合格产品。
B组分：将称量好的TDI80/20、粗MDI、纯MDI和MDI-50室温下加入反应釜中，室温条件下，转速为50r/min，搅拌1h，取样进行检测，异氰酸基含量达到(35.5±0.5)％，即得B组分合格产品。
使用时，将A、B组分料按A：B＝100：55的重量配比混合注入模具即可得聚氨酯泡沫塑料。
实施例3
A组分为(以重量百分数计)：
B组分为(以重量百分数计)：
WANNATE 8001 100
A组分：将称量好的EP-3600Y、JEFFAMINE ED900依次投入混釜中搅拌，然后分别依次加入称量好的L-3150、DEOA、A-1、A-33、DC3040、H2O，室温条件下，转速为80r/min，搅拌混合2h后，取样进行检验，满足工艺参数，发出满意泡沫，即得A组分合格产品。
B组分：选取万华化学股份公司生产的改性MDI，牌号为WANNATE 8001。
使用时，将A、B组分料按A：B＝100：70的重量配比混合注入模具即可得聚氨酯泡沫塑料。
表1是实施例1-3所得制品的性能指标。
表1 实施例1-3所得制品的性能指标
项目 实施例1 实施例2 实施例3
密度(kg/m3) 55 55 55
25％压陷硬度(N) 227 209 189
落球回弹率(％) 63 59 56
抗拉强度(kPa) 0.21 0.35 0.29
直角撕裂强度(kN/m) 0.32 0.49 0.44
伸长率(％) 98 109 95
外观表面 没有起皮，较平整 没有起皮，平整 没有起皮，平整

Claims (5)

1.一种用于低模温工艺的聚氨酯组合料，其特征在于：由A组分和与B组分以质量比为A:B=100:40-70组成，其中，
A组分由以下重量百分数的原料制成：
聚醚胺 10-30%；
聚醚多元醇 35-70%；
聚合物多元醇 5-35%；
扩链剂 0.1-4%；
交联剂 0.1-4%；
水 1.0-5.0%；
泡沫稳定剂 0.2-2.0%；
催化剂 0.6-2.3%；
B组分为异氰酸酯；
聚醚胺是官能度为2，数均分子量为500-900，主链为聚醚结构，末端活性官能团为胺基的聚合物；
聚醚多元醇是以甘油为起始剂，伯羟基含量≥65%，数均分子量为4500-7000，用氧化乙烯封端的聚氧化丙烯三元醇；
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≥20%的聚合物多元醇；
催化剂为低模温催化剂和叔胺类催化剂的混合物，叔胺类催化剂与低模温催化剂的质量比为0.3-1.5:0.3-0.8；
低模温催化剂为DC3040。
2.根据权利要求1所述的用于低模温工艺的聚氨酯组合料，其特征在于：异氰酸酯为甲苯二异氰酸酯、纯MDI、碳化二亚胺改性MDI、MDI-50、聚合MDI或NCO封端的改性MDI中的一种或多种的混合物。
3.根据权利要求2所述的用于低模温工艺的聚氨酯组合料，其特征在于： NCO封端的改性MDI，是MDI与聚醚多元醇预聚反应得到的，NCO的质量含量为17%-30%。
4.根据权利要求1所述的用于低模温工艺的聚氨酯组合料，其特征在于：叔胺类催化剂为A-1、A-33、DMEA、MP601、MP602或C-225中的一种或几种。
5.根据权利要求1所述的用于低模温工艺的聚氨酯组合料，其特征在于：扩链剂为乙二醇、一缩二乙二醇、1,4-丁二醇、1,3-丙二醇或一缩二丙二醇中的一种或几种；交联剂为三乙醇胺、二乙醇胺或甘油中的一种或几种；泡沫稳定剂为聚硅氧烷-氧化烯烃嵌段共聚物。
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