CN106167540A - 连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法 - Google Patents

连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法 Download PDF

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CN106167540A
CN106167540A CN201610620577.1A CN201610620577A CN106167540A CN 106167540 A CN106167540 A CN 106167540A CN 201610620577 A CN201610620577 A CN 201610620577A CN 106167540 A CN106167540 A CN 106167540A
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徐业峰
周生鹏
李欣
张佳佳
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于聚氨酯技术领域，具体涉及一种连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法。所述的高阻燃组合聚醚由A组分和B组分组成，A组分和B组分的重量比为1:1.5‑1.8，其中，A组分由以下重量百分比的原料制成：阻燃型聚醚多元醇Ⅰ25‑35﹪；聚醚多元醇Ⅱ2‑5﹪；阻燃型聚酯多元醇20‑35﹪；交联剂2‑5％；泡沫稳定剂1‑1.5﹪；发泡剂13‑25﹪；催化剂2.5‑4.5﹪；阻燃剂Ⅰ15‑25﹪；阻燃剂Ⅱ3‑8％；水0.5‑2.0﹪；B组分为多亚甲基多苯基多异氰酸酯。本发明的高阻燃组合聚醚制得的聚氨酯板材绝热性好，闭孔率高，总体阻燃级别能够达到国家B2级阻燃标准。

Description

连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法
技术领域
本发明属于聚氨酯技术领域，具体涉及一种连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法。
背景技术
聚氨酯作为六大合成材料之一，近年来发展迅速，在不同的领域逐步部分取代其他合成材料。但与此同时，聚氨酯泡沫塑料也是消耗HCFCs系列发泡剂的大户，HCFCs系列发泡剂对大气臭氧层具有极强的破坏作用，导致全球气温回暖、皮肤癌患者增多。为了维护生态环境，国际公约已经对其生产和使用做出了严格的限制和规定。中国2010年就完全淘汰CFC-11，而现在，一度作为CFC-11替代品的HCFC-141b也处在被淘汰的路上。根据蒙特利尔议定书规定的HCFCs淘汰时间表，2015年我国就完成冰箱/冷柜、冷藏集装箱、小家电3个子行业完全淘汰HCFC-141b发泡剂。2020年，聚氨酯泡沫行业将HCFC-141b的消费量控制在不超过基线水平的65％，即至少淘汰约8500吨HCFC-141b。2006-2008年调查表明，发泡板材和建筑喷涂子行业的消耗量约占HCFC-141b总使用量的36％。随着我国淘汰ODS步伐的加快，聚氨酯板材行业对HCFC-141b的替代已经迫在眉睫。
作为零ODP和低GWP值的戊烷系列发泡剂具有相对低廉的价格和相对低的热导率，在聚氨酯硬泡下游的各个领域应用愈来愈广。目前国内各大型冰箱厂家已全部使用环戊烷做为发泡剂，环戊烷作为发泡剂的生产技术已经比较成熟。
在过去的几年里，在发泡剂没有限制的情况下，环戊烷因为易燃易爆，导致以环戊烷为发泡剂的高阻燃产品技术发展缓慢。但受HCFCs系列产品的淘汰时间的推进，聚氨酯发泡剂面临压力也越来越大，为此，部分企业或者科研单位推出HFC-245Fa，HFC-365mf等系列产品，但是这些新型发泡剂的价格在170000左右，而且同属于HCFCS系列，目前HFC-245Fa现在在美国已经开始淘汰，综合考虑，开发使用环戊烷系列作为聚氨酯板材发泡剂已经成为未来聚氨酯板材发展的趋势。
发明内容
本发明的目的是提供一种使用环戊烷与异戊烷作为发泡剂的连续式生产聚氨酯板材用高阻燃组合聚醚，制得的聚氨酯板材绝热性好，闭孔率高，总体阻燃级别能够达到国家B2级阻燃标准；本发明同时提供其科学合理、简单易行的制备方法。
本发明所述的连续式生产聚氨酯板材用高阻燃组合聚醚，由A组分和B组分组成，A组分和B组分的重量比为1:1.5-1.8，其中，
A组分由以下重量百分比的原料制成：
B组分为多亚甲基多苯基多异氰酸酯。
其中：
所述的阻燃型聚醚多元醇Ⅰ为卤代脂肪族聚醚三醇。其主要成分是一种环氧氯丙烷基多元醇与少量磷酸三乙酯的混和物，优选瑞典苏威Ixol B251。
所述的聚醚多元醇Ⅱ为4官能度，数均分子量为500-700的聚醚多元醇，粘度为1400-2400(50℃)，优选山东蓝星东大化工有限责任公司NT-403A。
所述的阻燃型聚酯多元醇为粘度2000-3000mpa.s/25℃，2-3官能度的苯酐聚酯多元醇。优选山东一诺威股份有限公司PE-B175，其酸值较低。
所述的交联剂为数均分子量在100-200的醇氨类物质。优选三异丙醇胺(TIPA)或三乙醇胺(TEA)。
所述的泡沫稳定剂为非水解硅碳类表面活性剂。优选赢创德固赛B8545和迈图Y-16268的混合物，两者质量比3:1。
所述的发泡剂为环戊烷(CP)与异戊烷(IP)的混合物，两者质量比为70:30。异戊烷的沸点为27.8℃，环戊烷沸点为49℃，当以70:30的质量比例混合时，发泡剂与聚醚的互溶性良好，发出的泡沫的低温尺寸稳定性、流动性、闭孔率都满足国标要求。
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；叔胺类催化剂为三乙烯二胺、1,3,5-三(二甲氨基丙基)六氢三嗪中的一种或两种；有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种。
所述的阻燃剂Ⅰ为磷酸三(2-氯丙基)酯(TCPP)或二-(2-卤代乙基)-(3-溴代-2,2-二甲基丙基)磷酸酯中的一种或两种。
所述的阻燃剂Ⅱ为甲基膦酸二甲酯。
所述的连续式生产聚氨酯板材用高阻燃组合聚醚的制备方法，包括以下步骤：
(1)A组分的制备：将阻燃型聚醚多元醇Ⅰ、聚醚多元醇Ⅱ和阻燃型聚酯多元醇加入到反应釜中搅拌，加入交联剂、泡沫稳定剂、发泡剂、催化剂、阻燃剂Ⅰ和水，在常温下搅拌0.5-1.5小时，再加入阻燃剂Ⅱ，混合得到A组分；
(2)B组分的制备：将多亚甲基多苯基多异氰酸酯称量备用。
本发明的有益效果如下：
(1)本发明采用环戊烷和异戊烷为发泡剂，其ODP的效率值为0，无毒，符合“蒙特利尔协议”，是目前为止最为环保的物理发泡剂。与传统聚氨酯产品相比，以环戊烷和异戊烷为发泡剂的聚氨酯产品成本低廉，一般为6600元/吨，而以141b为发泡剂的聚氨酯产品价格为23000元/吨(2016年7月)，而且141b市场普遍短缺。本发明大大降低了成本。
(2)本发明制备的组合聚醚生产的聚氨酯板材泡孔细腻，无开裂，收缩率维持在1.0％以下，且产品质量稳定，密度分布均匀，导热系数低，泡孔细腻，泡沫强度高，泡沫性质稳定，板面平整，符合国标要求。采用本发明组合聚醚生产的聚氨酯板材，可以在常温常压下操作，施工时气味小，生产使用方便。
(3)本发明的制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，成本低，效率高。
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)A组分的制备：
A组分原料组成见表1。
表1 实施例1中A组分原料组成
将称量好的上述原料加入反应釜中，在常温下搅拌0.5小时，充分混合。然后加入12kg甲基膦酸二甲酯DMMP，混合得到A组分。
(2)B组分的制备：称量多亚甲基多苯基多异氰酸酯100kg。
(3)将A组分与B组分按照重量比1:1.6混合均匀，其中自由泡密度36.6kg/m3，发泡速度控制在乳白时间12秒，凝胶时间50秒，制得聚氨酯硬泡材料，质量指标见表4。
实施例2
(1)A组分的制备：
A组分原料组成见表2。
表2 实施例2中A组分原料组成
B251 50kg
NT-403 5kg
PE-B175 40kg
TIPA 5kg
Y-16268 1kg
B8545 3kg
H2O 2kg
三乙烯二胺 0.7kg
1,3,5-三(二甲氨基丙基)六氢三嗪 0.5kg
醋酸钾 3kg
TCPP 20kg
CP/IP 8.4kg/3.6kg
将称量好的上述原料加入反应釜中，在常温下搅拌0.5小时，充分混合。然后加入12kg甲基膦酸二甲酯DMMP，混合得到A组分。
(2)B组分的制备：称量多亚甲基多苯基多异氰酸酯100kg。
(3)将A组分与B组分按照重量比1:1.7通过均匀混合成型，其中自由泡密度39.2kg/m3，发泡速度控制在乳白时间12秒，凝胶时间52秒，制得聚氨酯硬泡材料，质量指标见表4。
实施例3
(1)A组分的制备：
A组分原料组成见表3。
表3 实施例3中A组分原料组成
B251 45kg
NT-403 5kg
PE-B175 45kg
TIPA 5kg
Y-16268 1kg
B8545 3kg
H2O 2.3kg
三乙烯二胺 0.9kg
1,3,5-三(二甲氨基丙基)六氢三嗪 0.5kg
异辛酸钾 3kg
TCPP 20kg
CP/IP 8.4kg/3.6kg
将称量好的上述原料加入反应釜中，在常温下搅拌0.5小时，充分混合，然后加入12kg甲基膦酸二甲酯DMMP，混合得到A组分。
(2)B组分的制备：称量多亚甲基多苯基多异氰酸酯100kg。
(3)将A组分与B组分按照重量比1:1.8均匀混合，泡沫迅速成型熟化，其中自由泡密度42.0kg/m3，发泡速度控制在乳白时间13秒，凝胶时间52秒，制得聚氨酯硬泡材料，制得的产品质量指标见表4。
表4 实施例1-3的泡沫产品质量检测数据GB21558-2008T
由表4可知，组合聚醚产品对臭氧层无破坏，环保性能优；制得的聚氨酯泡沫导热系数低，密闭性好，阻燃性能优、产品稳定性好。

Claims (10)

1.一种连续式生产聚氨酯板材用高阻燃组合聚醚，由A组分和B组分组成，其特征在于：A组分和B组分的重量比为1:1.5-1.8，其中，
A组分由以下重量百分比的原料制成：
B组分为多亚甲基多苯基多异氰酸酯。
2.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的阻燃型聚醚多元醇Ⅰ为卤代脂肪族聚醚三醇。
3.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的聚醚多元醇Ⅱ为4官能度，数均分子量为300的聚醚多元醇。
4.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的阻燃型聚酯多元醇为粘度2000-3000mpa.s/25℃，2-3官能度的苯酐聚酯多元醇。
5.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的交联剂为数均分子量在100-200的醇氨类物质，优选三异丙醇胺或三乙醇胺。
6.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，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，优选B8545和Y-16268的混合物，两者质量比为3:1。
7.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的发泡剂为环戊烷与异戊烷的组合，两者质量比为70:30。
8.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，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；叔胺类催化剂为三乙烯二胺、1,3,5-三(二甲氨基丙基)六氢三嗪中的一种或两种；有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种。
9.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃组合聚醚，其特征在于：所述的阻燃剂Ⅰ为磷酸三(2-氯丙基)酯或二-(2-卤代乙基)-(3-溴代-2,2-二甲基丙基)磷酸酯中的一种或两种；所述的阻燃剂Ⅱ为甲基膦酸二甲酯。
10.一种权利要求1-9任一所述的连续式生产聚氨酯板材用高阻燃组合聚醚的制备方法，其特征在于包括以下步骤：
(1)A组分的制备：将阻燃型聚醚多元醇Ⅰ、聚醚多元醇Ⅱ和阻燃型聚酯多元醇加入到反应釜中搅拌，加入交联剂、泡沫稳定剂、发泡剂、催化剂、阻燃剂Ⅰ和水，在常温下搅拌0.5-1.5小时，再加入阻燃剂Ⅱ，混合得到A组分；
(2)B组分的制备：将多亚甲基多苯基多异氰酸酯称量备用。
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