CN106146798A - 管道与釜体保温用耐老化喷涂型组合聚醚及其制备方法和应用 - Google Patents
管道与釜体保温用耐老化喷涂型组合聚醚及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于聚氨酯技术领域,具体涉及一种管道与釜体保温用耐老化喷涂型组合聚醚及其制备方法和应用。所述组合聚醚由A组分和B组分组成,其中A组份为,以质量百分数计:聚醚多元醇A 18~30%;聚醚多元醇B 5~40%;聚醚多元醇C 11~19%;聚醚多元醇D 7~15%;交联剂1~5%;抗氧剂1~4%;泡沫稳定剂1~2%;化学发泡剂0.02~0.2%;催化剂3.4~6%;物理发泡剂12~16%。B组份为多亚甲基多苯基多异氰酸酯。本发明组合聚醚制得的泡沫塑料的保温性能、粘结性能、压缩强度、尺寸稳定性优异,耐高温性能,耐蠕变性能突出,其制备方法简单易行,易于实现。
Description
技术领域
本发明属于聚氨酯技术领域,具体涉及一种管道与釜体保温用耐老化喷涂型组合聚醚及其制备方法和应用。
背景技术
聚氨酯泡沫塑料是目前所有隔热保温材料中的佼佼者,广泛用于供热管道、石油化工管道、交通运输、冰箱冰柜、建筑保温、航空军用等诸多方面。在我国,随着国家西部大开发政策的实施、城市集中供热的普及以及旧城改造,保温管道行业在最近几年发展迅速,但传统的两步法浇筑工艺,由于其密度分布差异大,夹克皮膨胀率较大,易开裂等缺点限制了其在大管径保温管生产中的应用与推广。聚氨酯喷涂施工工艺,由于其现场成型,施工速度快,与基材粘结力较好,泡孔细腻导热系数低等特点,近年来在建筑保温领域应用越加广泛,但传统的喷涂型组合聚醚受配方影响,其泡沫熟化时间长,耐高温老化性能较差,较难在一些高温器材的保温中获得应用。因此,如何解决喷涂型组合聚醚的耐高温性能,匹配管道与釜体保温需要的质量标准与施工要求,成为喷涂型组合聚醚在石化及热力输送行业推广的制约因素。
目前市场上使用的耐高温型聚氨酯组合聚醚,主要使用水作为化学发泡剂,通过提高异氰酸酯指数来提高泡沫中的脲健含量以提高耐高温性能,同时通过两步法浇筑施工,整体密度较高且分布不均匀。市场上常见的喷涂型组合聚醚,由于熟化速度较慢,很难匹配管道生产的流水化作业,同时由于配方设计因素,耐高温性能较差,一些需求耐高温性能的反应釜体与管道,只能使用岩棉等无机材料进行保温,导热系数较高,经济性较差。由于聚氨酯喷涂施工的工艺特殊性,其得到的泡沫具有粘结力好,泡孔细腻导热系数低的优点,同时聚氨酯材料可在施工面快速成型,具有较高的形状可塑性。如果能提高其耐高温性能,并改善泡沫的韧性与压缩强度等物理指标,同时保证材料可在短时间内熟化,匹配管道保温的流水化作业,则可将该技术广泛应用于有耐高温需求的管道与釜体保温行业,对于降低能耗,控制施工成本具有显著意义。
综上,为适应市场需求,亟需开发一种耐高温性能良好的管道与釜体保温用耐老化喷涂型组合聚醚。
发明内容
本发明的目的是提供一种适应管道与釜体施工特点,且制得的泡沫在保温、粘结力、压缩强度、高低温尺寸稳定性方面性能优异的耐高温的管道与釜体保温用耐老化喷涂型组合聚醚;本发明同时提供其制备方法和应用。
本发明所述的管道与釜体保温用耐老化喷涂型组合聚醚,由A组分和B组分组成,A组份与B组分质量比为100:100~150,其中:
A组份为,以质量百分数计:
B组份为:
多亚甲基多苯基多异氰酸酯。
其中:
所述聚醚多元醇A为官能度4~5,分子量500~650的聚醚多元醇。优选山东一诺威新材料有限公司YNW-6001A;山东隆华化工科技有限公司4110。
所述聚醚多元醇B为官能度5.5~6,分子量600~800的聚醚多元醇。优选山东一诺威新材料有限公司YNW-6207;山东蓝星东大化工有限责任公司SA460。
所述聚醚多元醇C为官能度4,分子量290~310的聚醚多元醇。优选山东一诺威新材料有限公司NT403。
所述聚醚多元醇D为官能度3,分子量为500~1000的聚醚多元醇。优选山东一诺威新材料有限公司YNW-305,优选山东一诺威新材料有限公司YNW-310。
所述交联剂为小分子醇类,优选三异丙醇胺或乙二醇。
所述的抗氧剂为酚类抗氧剂,优选台湾双键化工股份有限公司1135。
所述泡沫稳定剂是为非水解硅碳类表面活性剂,优选迈图硅油L6868。
所述化学发泡剂为水。
所述催化剂为胺类催化剂与有机金属类催化剂的混合物,优选五甲基二乙烯三胺(PC-5)、33%的三乙烯二胺溶液(A33)、二月桂酸二丁基锡(T-12)、四甲基乙二胺(TMR-2)、1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41)五者的混合物。五甲基二乙烯三胺、33%的三乙烯二胺溶液、二月桂酸二丁基锡、四甲基乙二胺、1,3,5-三(二甲氨基丙基)六氢三嗪分别占A组份总质量的0.5~2%、1.5~2.5%、0.2~0.5%、0.4~0.7%、0.4~0.8%。
所述物理发泡剂为1,1,1,3,3-五氟丁烷(HFC-365mfc)和反式-1-氯-3,3,3-三氯丙烯(LBA)的混合物HFC-365mfc/LBA,其中1,1,1,3,3-五氟丁烷的质量含量为70%,反式-1-氯-3,3,3-三氯丙烯的质量含量为30%。
所述的管道与釜体保温用耐老化喷涂型组合聚醚的制备方法如下:
制备A组份料:将称量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C、聚醚多元醇D、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂,依次加入反应釜中,在常温下搅拌0.5~1小时即可装桶。
制备B组分料:将多亚甲基多苯基多异氰酸酯,直接装桶。
将A组份与B组分按照重量比100:100~150,经喷涂机进行混合施工,即可得到管道与釜体保温用耐老化喷涂型组合聚醚制备的耐老化喷涂型泡沫塑料。
与现有技术相比,本发明的有益效果如下:
对传统的喷涂型组合聚醚进行体系重建与配方优化,结合交联剂的使用,加快了泡沫熟化速度,并提高了泡沫的抗压强度,使泡沫在较短的时间内即可获得最大的抗压强度,从而使泡沫可以承担大管径钢管自重,满足喷涂管道的连续化生产。另外通过对料比的调节,提高泡沫体系中杂环类结构含量,同时搭配抗氧剂的使用,提高泡沫的耐老化及耐蠕变性能,使最终制得的泡沫具有一定的抗老化耐蠕变性能,满足管道与釜体保温需要的较高温度的工作环境。
提高喷涂型泡沫耐老化性能以适应管道与釜体保温的需要,解决传统的喷涂型组合聚醚泡沫熟化慢,泡沫压缩强度低不足以支持大管径钢管连续生产的问题,最终得到的聚氨酯泡沫具有密度分布均匀,泡孔细腻导热系数低,压缩强度高等特点,该组合聚醚的研制成功,对于国内热力输送行业的发展起到了重大的推进作用,具有较好的经济效益和社会效益。。
本发明A组分料生产方便,使用A、B组分,利用喷涂机对管道与釜体直接进行喷涂施工,泡沫与基材粘合充分,泡沫性能优良,可在5min内完成初步固化,5min抗压强度250kPa以上,同时泡沫CCOT温度提升至120℃以上,室温条件下,径向蠕变量23℃±2℃,50%±5%RH(1000h)由原来的6mm减少到5mm以内,泡沫塑料各项性能满足GBT29047-2012中对于聚氨酯泡沫塑料的要求。
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
在1吨反应容器内制备A组份料,分别称量:聚醚多元醇A(山东一诺威新材料有限公司YNW-6001A):40份;聚醚多元醇B(山东蓝星东大化工有限责任公司SA460):10份;聚醚多元醇C(山东一诺威新材料有限公司NT403):25份;聚醚多元醇D(山东一诺威新材料有限公司YNW-305):20份;交联剂(中国石油化工集团公司乙二醇):6份,抗氧剂(台湾双键1135):5份;硅油L6868(迈图):2.5份;化学发泡剂H2O:0.25份;五甲基二乙烯三胺(PC-5)2.7份;33%的三乙烯二胺溶液(A33):3份;二月桂酸二丁基锡(T-12):0.3份;四甲基乙二胺(TMR-2):0.9份;1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41):0.8份;1,1,1,3,3-五氟丁烷和反式-1-氯-3,3,3-三氯丙烯的混合物(HFC-365mfc:LBA质量比为7:3)HFC-365mfc/LBA:21份。将称量好的聚醚多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂,依次加入反应釜中,在常温下搅拌0.5小时,取出进行检验,满足工艺参数,发出泡沫,即得A组份合格产品,从反应釜中取出装桶入库。B组份为多亚甲基多苯基多异氰酸酯。
将A、B组份料按A:B=100:130重量配比经喷涂机高压混合喷涂施工,即可制成管道与釜体保温用耐老化喷涂型泡沫塑料,测试产品质量指标。
实施例1的管道与釜体保温用耐老化喷涂型组合聚醚制得的泡沫塑料达到以下指标,见表1。
表1实施例1泡沫塑料性能参数表
项目 | 指标 |
密度Kg/m3≥ | 70 |
导热系数w/(/m·K)≥ | 0.030 |
平均孔径mm≤ | 0.3 |
5min径向抗压强度kPa≥ | 280 |
径向抗压强度kPa≥ | 400 |
闭孔率%≥ | 90 |
吸水率%≤ | 10 |
CCOT℃≥ | 130 |
径向蠕变量23℃±2℃,50%±5%RH(1000h)mm≤ | 4 |
径向蠕变量23℃±2℃,50%±5%RH(100h)mm≤ | 2 |
实施例2
在1吨反应容器内制备A组份料,分别称量:聚醚多元醇A(山东隆华化工科技有限公司4110):25份;聚醚多元醇B(山东一诺威新材料有限公司YNW-6207):50份;聚醚多元醇C(山东一诺威新材料有限公司NT403):15份;聚醚多元醇D(山东一诺威新材料有限公司YNW-310):10份;交联剂(抚顺佳化化学三异丙醇胺):2份,抗氧剂(台湾双键1135):2份;硅油L6868(迈图):2份;化学发泡剂H2O:0.05份;五甲基二乙烯三胺(PC-5):1份;33%的三乙烯二胺溶液(A33):2份;二月桂酸二丁基锡(T-12):0.6份;四甲基乙二胺(TMR-2):0.6份;1,3,5-三(二甲氨基丙基)六氢三嗪(PC-41):0.7份;1,1,1,3,3-五氟丁烷和反式-1-氯-3,3,3-三氯丙烯的混合物(HFC-365mfc:LBA质量比为7:3)HFC-365mfc/LBA:17份。将称量好的聚醚多元醇、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂,依次加入反应釜中,在常温下搅拌0.5小时,取出进行检验,满足工艺参数,发出泡沫,即得A组份合格产品,从反应釜中取出装桶入库。B组份为多亚甲基多苯基多异氰酸酯。
将A、B组份料按A:B=100:100重量配比经喷涂机高压混合喷涂施工,即可制成管道与釜体保温用耐老化喷涂型泡沫塑料,测试产品质量指标。
实施例2的管道与釜体保温用耐老化喷涂型组合聚醚制得的泡沫塑料达到以下指标,见表2。
表2实施例2泡沫塑料性能参数表
项目 | 指标 |
密度Kg/m3≥ | 60 |
导热系数w/(/m·K)≤ | 0.030 |
平均孔径mm≤ | 0.3 |
5min径向抗压强度kpa≥ | 180 |
径向抗压强度kpa≥ | 300 |
闭孔率%≥ | 90 |
吸水率%≤ | 10 |
CCOT℃≥ | 120 |
径向蠕变量23℃±2℃,50%±5%RH(1000h)mm≤ | 5 |
径向蠕变量23℃±2℃,50%±5%RH(100h)mm≤ | 3 |
常规品种的聚氨酯硬泡在100℃以下的环境中,尺寸不会明显变化,但超过100度,尺寸变化率较难保证。而本发明中的CCOT温度提升至120℃以上。
本发明管道与釜体保温用耐老化喷涂型组合聚醚制得的泡沫塑料的密度在60Kg/m3以上较好,径向抗压强度在300~450kPa之间较好,闭孔率在90~95%之间较好。
Claims (10)
1.一种管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于由A组分和B组分组成,A组份与B组分质量比为100:100~150,其中:
A组份为,以质量百分数计:
B组份为:
多亚甲基多苯基多异氰酸酯。
2.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述聚醚多元醇A为官能度4~5,分子量500~650的聚醚多元醇;所述聚醚多元醇B为官能度5.5~6,分子量600~800的聚醚多元醇;所述聚醚多元醇C为官能度4,分子量290~310的聚醚多元醇;所述聚醚多元醇D为官能度3,分子量为500~1000的聚醚多元醇。
3.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述交联剂为小分子醇类。
4.根据权利要求3所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述交联剂为三异丙醇胺或乙二醇。
5.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述抗氧剂为酚类抗氧剂。
6.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述泡沫稳定剂为非水解硅碳类表面活性剂;所述化学发泡剂为水。
7.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述催化剂为胺类催化剂与有机金属类催化剂的混合物;所述催化剂为五甲基二乙烯三胺、33%的三乙烯二胺溶液、二月桂酸二丁基锡、四甲基乙二胺、1,3,5-三(二甲氨基丙基)六氢三嗪的混合物;五甲基二乙烯三胺、33%的三乙烯二胺溶液、二月桂酸二丁基锡、四甲基乙二胺、1,3,5-三(二甲氨基丙基)六氢三嗪分别占A组份总质量的0.5~2%、1.5~2.5%、0.2~0.5%、0.4~0.7%、0.4~0.8%。
8.根据权利要求1所述的管道与釜体保温用耐老化喷涂型组合聚醚,其特征在于:所述物理发泡剂为1,1,1,3,3-五氟丁烷和反式-1-氯-3,3,3-三氯丙烯的混合物,其中1,1,1,3,3-五氟丁烷的质量含量为70%,反式-1-氯-3,3,3-三氯丙烯的质量含量为30%。
9.一种权利要求1~8任一所述的管道与釜体保温用耐老化喷涂型组合聚醚的制备方法,其特征在于:
制备A组份料:将称量好的聚醚多元醇A、聚醚多元醇B、聚醚多元醇C、聚醚多元醇D、交联剂、抗氧剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂,依次加入反应釜中,在常温下搅拌0.5~1小时即可。
10.一种权利要求1~8任一所述的管道与釜体保温用耐老化喷涂型组合聚醚的应用,其特征在于:
将A组份与B组分按照重量比100:100~150,经喷涂机进行混合施工,即可得到管道与釜体保温用耐老化喷涂型组合聚醚制备的耐老化喷涂型泡沫塑料。
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