CN106188495A - 用于连续板材的环保型组合聚醚及其制备方法 - Google Patents

用于连续板材的环保型组合聚醚及其制备方法 Download PDF

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CN106188495A
CN106188495A CN201610628543.7A CN201610628543A CN106188495A CN 106188495 A CN106188495 A CN 106188495A CN 201610628543 A CN201610628543 A CN 201610628543A CN 106188495 A CN106188495 A CN 106188495A
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sheet material
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polyether
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徐业峰
李欣
张佳佳
周生鹏
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于高分子材料技术领域，具体涉及一种用于连续板材的环保型组合聚醚及其制备方法。用于连续板材的环保型组合聚醚由A组分和B组分组成，A组分：聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂、阻燃剂；B组分为聚合二苯基甲烷二异氰酸酯。本发明采用HCFO‑1233zd三氟丙烯为发泡剂，无毒，ODP接近于0，GWP小于5，不可燃且属于非挥发性有机物，环保性能优异；制备方法工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。

Description

用于连续板材的环保型组合聚醚及其制备方法
技术领域
本发明属于高分子材料技术领域，具体涉及一种用于连续板材的环保型组合聚醚及其制备方法。
背景技术
第一代氯氟烃类发泡剂，以CFC-11(CCl3F)为代表，由于其破坏臭氧层及产生温室效应，此类发泡剂已经被禁止使用。目前作为CFC-11替代品的第二代发泡剂HCFC-141b仍具有一定的臭氧破坏作用和温室效应，也处在被淘汰的边缘，必然会被环保型发泡剂所替代。目前国内连续板材行业主要使用第三代戊烷类发泡剂进行替代。但戊烷类发泡剂的气相热导率较高，制备的聚氨酯泡沫隔热保温性能较差。另戊烷类发泡剂易燃易爆，在操作使用及储存运输中要十分注意安全。同时要对生产线发泡装置安装防爆装置，生产区内要有防静电设备和戊烷检测报警装置。HCFO-1233zd三氟丙烯(LBA)无毒，ODP接近于0，GWP小于5，不可燃且属于非挥发性有机物。气相热导率(25℃)10.2，沸点19℃。
发明内容
本发明的目的是提供一种用于连续板材的环保型组合聚醚，在达到环保目的的同时，所生产的聚氨酯泡沫，具有导热系数低，压缩强度高，尺寸稳定性好的优点，各项指标均达到国标的要求；本发明同时提供了用于连续板材的环保型组合聚醚的制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。
本发明所述的用于连续板材的环保型组合聚醚，由A组分和B组分组成，其中，
以重量份数计，A组分：
B组分为聚合二苯基甲烷二异氰酸酯；
所述的聚酯多元醇A为官能度2.0、分子量500-600的聚酯多元醇，优选PS-2002(南京金陵斯泰潘化学有限公司市售产品)；
所述的聚醚多元醇B为官能度4.7、分子量550-650的聚醚多元醇，优选YNW-6001A(山东一诺威新材料有限公司市售产品)；
所述的聚醚多元醇C为官能度4.7、分子量500-600的聚醚多元醇，优选YNW-8345(山东一诺威新材料有限公司市售产品)
所述的泡沫稳定剂为非水解硅碳类表面活性剂，优先选用B8545(赢创集团公司市售产品)。
所述的化学发泡剂为去离子水。
所述的催化剂为叔胺类催化剂和有机金属催化剂的混合物。
所述的叔胺类催化剂为五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺或三(二甲氨基甲基)-2,4,6-苯酚中的一种或几种，优选五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺和三(二甲氨基甲基)-2,4,6-苯酚的混合物。
所述的有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种，优选为异辛酸钾和醋酸钾的混合物。
所述的物理发泡剂为HCFO-1233zd三氟丙烯(LBA)。
所述的阻燃剂为三(2-氯丙基)磷酸酯(TCPP)。
本发明所述的用于连续板材的环保型组合聚醚的制备方法，步骤如下：
(1)A组分的制备：将聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂依次混合，常温搅拌1-2小时，得到A组分；
(2)B组分为聚合二苯基甲烷二异氰酸酯；
(3)将A组分和B组分按A组分：B组分＝100：150-160的重量比混合，制备得到产品。
采用本发明制备得到的组合聚醚与异氰酸酯反应，连续式生产制得聚氨酯阻燃型泡沫。在达到B2级阻燃的前提下，无开裂现象，泡沫收缩率在1.5％以下，并且密度分布均匀、导热系数低、强度高、性能稳定，在节能降耗方面将会起到积极的促进作用；同时生产效率高、耗能低，大大降低了综合生产成本。
本发明所要解决的是针对目前连续板材中发泡剂不环保，不宜长期使用的现状；利用第四代发泡剂HCFO-1233zd三氟丙烯(LBA)研发了一种绝热性能优，不燃，无毒的组合聚醚，适合连续板的生产。
本发明与现有技术相比，具有如下有益效果：
(1)本发明采用HCFO-1233zd三氟丙烯(LBA)为发泡剂，无毒，ODP接近于0，GWP小于5，不可燃且属于非挥发性有机物，环保性能优异。
(2)本发明应用在连续板生产时，无需进行设备防爆等改造，降低了生产成本，提高了生产安全性。
(3)A组分料是在常温下进行，既节约能源又减少供能设备和繁琐的操作。
(4)采用本发明制备的组合聚醚生产的板材泡孔细腻，收缩率低，且产品质量稳定，密度分布均匀，导热系数低，泡沫强度高，板面平整。
(5)本发明提供的制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。
(6)本发明制备得到的连续板材产品(B2级阻燃)各项指标可达到国标的要求：
性能完全达到了GB/T 21558-2008建筑绝热用硬质聚氨酯泡沫塑料的标准、GB/T8624-2012建筑材料及制品燃烧性能B2级中的D级要求。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)制备A组分，分别称量：阻燃聚酯多元醇PS2002(2.0官能度，分子量为560)18.3公斤，聚醚多元醇YNW-6001A(4.7官能度，分子量为610)27.8公斤，聚醚多元醇YNW-8345(4.7官能度，分子量为585)9.4公斤，B8545 1.1公斤(赢创市售)，催化剂五甲基二亚乙烯三胺0.05公斤，N,N二甲基环己胺1.0公斤，N,N二甲基苄胺1.1公斤，三(二甲氨基甲基)-2,4,6-苯酚0.6公斤，异辛酸钾0.6公斤，醋酸钾0.35公斤，去离子水0.8公斤，HCFO-1233zd三氟丙烯(LBA)16.9公斤，三(2-氯丙基)磷酸酯22公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发泡，即得A组分合格产品，从反应釜中取出装桶入库。
(2)B组分为聚合二苯基甲烷二异氰酸酯，市购；
(3)将A、B组分按A组分：B组分＝100：150的重量配比混合，制备得到100mm厚连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：
实施例2
(1)制备A组分，分别称量：阻燃聚酯多元醇PS2002(2.0官能度，分子量为560)22.7公斤，聚醚多元醇YNW-6001A(4.7官能度，分子量为610)23.0公斤，聚醚多元醇YNW-8345(4.7官能度，分子量为585)9.8公斤，B8545 1.4公斤(赢创市售)，催化剂五甲基二亚乙烯三胺0.1公斤，N,N二甲基环己胺1.2公斤，N,N二甲基苄胺1.0公斤，三(二甲氨基甲基)-2,4,6-苯酚1.0公斤，异辛酸钾0.5公斤，醋酸钾0.5公斤，去离子水1.0公斤，HCFO-1233zd三氟丙烯(LBA)17.6公斤，三(2-氯丙基)磷酸酯20.2公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发泡，即得A组分合格产品，从反应釜中取出装桶入库。
(2)B组分为聚合二苯基甲烷二异氰酸酯，市购；
(3)将A、B组分按A组分：B组分＝100：160的重量配比混合，制备得到100mm厚连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：
实施例3
(1)制备A组分，分别称量：阻燃聚酯多元醇PS2002(2.0官能度，分子量为560)30.0公斤，聚醚多元醇YNW-6001A(4.7官能度，分子量为610)12.8公斤，聚醚多元醇YNW-8345(4.7官能度，分子量为585)12.8公斤，B8545 1.5公斤(赢创市售)，催化剂五甲基二亚乙烯三胺0.05公斤，N,N二甲基环己胺0.8公斤，N,N二甲基苄胺0.9公斤，三(二甲氨基甲基)-2,4,6-苯酚0.8公斤，异辛酸钾0.4公斤，醋酸钾0.65公斤，去离子水0.7公斤，HCFO-1233zd三氟丙烯(LBA)19.6公斤，三(2-氯丙基)磷酸酯19公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发泡，即得A组分合格产品，从反应釜中取出装桶入库。
(2)B组分为聚合二苯基甲烷二异氰酸酯，市购；
(3)将A、B组分按A组分：B组分＝100：155的重量配比混合，制备得到100mm厚连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：

Claims (9)

1.一种用于连续板材的环保型组合聚醚，其特征在于由A组分和B组分组成，其中，
以重量份数计，A组分：
B组分为聚合二苯基甲烷二异氰酸酯；
所述的聚酯多元醇A为官能度2.0、分子量500-600的聚酯多元醇；
所述的聚醚多元醇B为官能度4.7、分子量550-650的聚醚多元醇；
所述的聚醚多元醇C为官能度4.7、分子量500-600的聚醚多元醇。
2.根据权利要求1所述的用于连续板材的环保型组合聚醚，其特征在于所述的泡沫稳定剂为非水解硅碳类表面活性剂。
3.根据权利要求1所述的用于连续板材的环保型组合聚醚，其特征在于所述的化学发泡剂为去离子水。
4.根据权利要求1所述的用于连续板材的环保型组合聚醚，其特征在于所述的催化剂为叔胺类催化剂和有机金属催化剂的混合物。
5.根据权利要求4所述的用于连续板材的环保型组合聚醚，其特征在于所述的叔胺类催化剂为五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺或三(二甲氨基甲基)-2,4,6-苯酚中的一种或几种。
6.根据权利要求4所述的用于连续板材的环保型组合聚醚，其特征在于所述的有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种。
7.根据权利要求1所述的用于连续板材的环保型组合聚醚，其特征在于所述的物理发泡剂为HCFO-1233zd三氟丙烯。
8.根据权利要求1所述的用于连续板材的环保型组合聚醚，其特征在于所述的阻燃剂为三(2-氯丙基)磷酸酯。
9.一种权利要求1-8任一所述的用于连续板材的环保型组合聚醚的制备方法，其特征在于步骤如下：
(1)A组分的制备：将聚酯多元醇A、聚醚多元醇B、聚醚多元醇C、泡沫稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂依次混合，常温搅拌1-2小时，得到A组分；
(2)B组分为聚合二苯基甲烷二异氰酸酯；
(3)将A组分和B组分按A组分：B组分＝100：150-160的重量比混合，制备得到产品。
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CN102924685A (zh) * 2012-11-14 2013-02-13 山东东大一诺威新材料有限公司 用于生产聚氨酯泡沫保温板的组合料及其制备方法
CN103570903A (zh) * 2012-07-25 2014-02-12 上海东大聚氨酯有限公司 环保型板材用组合聚醚、聚氨酯原料组合物、硬质聚氨酯泡沫及其制备方法和用途
CN104448230A (zh) * 2014-12-29 2015-03-25 上海东大化学有限公司 一种组合聚醚及由其制得的聚氨酯夹芯板

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CA2272812A1 (en) * 1998-05-26 1999-11-26 Basf Aktiengesellschaft Preparation of prepolymers containing isocyanate groups
CN102558481A (zh) * 2011-12-23 2012-07-11 山东东大一诺威新材料有限公司 用于板材保温的环保型组合料及其制备方法
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