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