CN108623771A - 羟基封端的聚氨酯预聚体及其制备方法 - Google Patents
羟基封端的聚氨酯预聚体及其制备方法 Download PDFInfo
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- CN108623771A CN108623771A CN201710180071.8A CN201710180071A CN108623771A CN 108623771 A CN108623771 A CN 108623771A CN 201710180071 A CN201710180071 A CN 201710180071A CN 108623771 A CN108623771 A CN 108623771A
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- Prior art keywords
- diisocyanate
- polyurethane prepolymer
- acid
- base polyurethane
- polyisocyanates
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- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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Abstract
本发明属于聚氨酯领域,涉及一种羟基封端的聚氨酯预聚体及其用于合成阻燃聚异氰脲酸酯泡沫的用途。所述羟基封端的聚氨酯预聚体为以下原料的反应产物:a)一种或更多种聚合物多元醇,其选自聚醚多元醇和聚酯多元醇;b)一种或更多种磷酸酯;和c)一种或更多种多异氰酸酯。所述羟基封端的预聚体可用于制备聚异氰脲酸酯,所得聚异氰脲酸酯泡沫的保温性能、粘结性能、压缩强度、尺寸稳定性优异,成本低,阻燃效果佳。
Description
技术领域
本发明属于聚氨酯领域。具体地讲,本发明涉及一种羟基封端的聚氨酯预聚体、其制备方法及其用于合成聚异氰脲酸酯泡沫的用途。
背景技术
聚氨酯喷涂泡沫具有良好的保温性能、优异的成型性能以及与基材的良好粘结性。随着国家和社会对节能低碳的要求越来越高,聚氨酯喷涂泡沫材料在建筑保温领域的应用越来越广。国家65#文件《关于进一步明确民用建筑外保温材料消防监督管理有关要求的通知》与46#关于印发《民用建筑外保温系统及外墙装饰防火暂行规定》的通知规定上墙材料最低达到B2级阻燃的要求。因此提高聚氨酯喷涂泡沫的阻燃性能,并控制高阻燃喷涂泡沫的成本,成为聚氨酯喷涂泡沫开发的重点。
专利CN200910186702.2公开了一种高效无卤阻燃聚氨酯硬泡及制备方法,该聚氨酯硬泡通过添加无机阻燃剂红磷以及有机阻燃剂甲基磷酸二甲酯(简称DMMP)来实现泡沫的高阻燃性,这一方法的优点是能够制得阻燃性较好的泡沫,但是添加无机剂颗粒增加了工艺混合难度,并且添加DMMP后系统料的储存稳定性和泡沫的尺寸稳定性都会有一些影响,不利于泡沫的大规模生产使用。
专利CN201210196201.4公开了一种聚氨酯喷涂保温材料,该喷涂聚氨酯采用在阻燃剂DMMP体系下的发泡工艺,该工艺制得的泡沫尺寸稳定性较好,但是阻燃等级较低,只能满足GB8624-2006中E级使用要求。
专利CN 103073986 B公开了一种高阻燃聚氨酯喷涂泡沫材料及其制备方法,该喷涂泡沫通过引入溴磷复合阻燃聚醚多元醇、曼尼烯聚醚多元醇、聚酯多元醇这一复配体系,改善了泡沫收缩、尺寸稳定性差和阻燃能力低的问题,但是所采用的阻燃聚醚及多元醇存在成本昂贵、来源有限的问题。
综合以上的专利,主要都是通过添加大量的各类阻燃剂,或溴磷复合阻燃聚醚多元醇来提高阻燃性能,但是这会造成泡沫的机械性能特别是压缩强度偏低,原料成本过高。
聚氨酯泡沫塑料PUR是多羟基醇与多异氰酸酯反应产生,而聚异氰脲酸酯泡沫塑料PIR则是多异氰酸酯自身的三聚反应产生异氰脲酸酯环,所以从分子结构上来看聚异氰脲酸酯泡沫塑料更加稳定,具有优良耐热性、耐寒性、尺寸稳定性及阻燃性。PIR和PUR相比,由于结构上的差异,聚异氰脲酸酯泡沫塑料具有高效阻燃性,良好的耐热性能及工艺性能。但是聚异氰脲酸酯泡沫的生成需要异氰酸酯相对于羟基大大过量,从而通过异氰酸酯自身的三聚反应产生异氰脲酸酯环。
专利CN 105940032 A公开了一种制备耐火的聚氨酯或氨基甲酸酯改性聚异氰脲酸酯隔热泡沫体,其具有良好的泡沫性质和良好的加工特性,且具有最小量的阻燃剂,在不使用含溴阻燃剂的情况下可通过DIN4102测试(提供B2级通过(<15cm)),但是其多异氰酸酯(B料)与组合聚醚多元醇(A料)的比例要远远大于1∶1,达到约1∶1.6。而当前聚氨酯喷涂行业绝大多数使用的是A、B料比为1∶1的喷涂机,很明显一般的聚异氰脲酸酯泡沫不能采用现有的聚氨酯喷涂机施加。
为了在料比为1∶1而多异氰酸酯NCO含量不变的限制下得到高异氰酸酯指数的聚异氰脲酸酯喷涂泡沫,势必要降低多元醇重量份的羟值。现在通常有两种方法来达成这一目的。其一,使用相对低羟值的聚醚/聚酯多元醇作为原料制成多元醇组分;其二,在多元醇组分中加入大量添加型阻燃剂来达到降低羟值的目的。无论使用哪种方法,都会使得泡沫的物理机械性能受到影响,而且也无法真正得到异氰酸酯指数大于250%、氧指数大于30、物理机械性能较好的聚异氰脲酸酯喷涂泡沫。本文所用的术语“异氰酸酯指数”表示以百分比形式给出的泡沫体配制品中存在的NCO-基团相对于反应性氢原子的摩尔比。
因此,需要开发一种能通过A、B料比为1∶1的喷涂机制备的阻燃聚异氰脲酸酯喷涂泡沫,其具有相对较好的物理机械性能及氧指数。
发明内容
本发明所要解决的技术问题是提供一种能通过A、B料比为1∶1的喷涂机制备的阻燃聚异氰脲酸酯喷涂泡沫,其具有相对较好的物理机械性能及氧指数。
本发明所要解决的技术问题通过以下技术方案得以解决:
根据本发明的一个方面,提供一种羟基封端的聚氨酯预聚体,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其选自聚醚多元醇和聚酯多元醇;
b)一种或更多种磷酸酯;和
c)一种或更多种多异氰酸酯。
根据本发明的另一方面,一种制备上述羟基封端的聚氨酯预聚体的方法,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇、b)一种或更多种磷酸酯和c)一种或更多种多异氰酸酯混合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
根据本发明的一个方面,提供一种羟基封端的聚氨酯预聚体,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其包含卤代聚醚多元醇;和
b)一种或更多种多异氰酸酯。
根据本发明的另一方面,一种制备上述羟基封端的聚氨酯预聚体的方法,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇和b)一种或更多种多异氰酸酯混合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
根据本发明的另一方面,提供一种聚异氰脲酸酯泡沫,其由以下A、B两组分反应得到:
A组分,其包括:
a)上述羟基封端的聚氨酯预聚体;
b)任选的一种或更多种聚合物多元醇;
c)一种或更多种泡沫稳定剂;
d)一种或更多种催化剂;和
e)一种或更多种发泡剂;
B组分,其为一种或更多种多异氰酸酯。
根据本发明的另一方面,提供制备上述聚异氰脲酸酯泡沫的方法,其包括如下步骤:
i)将a)上述羟基封端的聚氨酯预聚体、b)任选的一种或更多种聚合物多元醇、c)一种或更多种泡沫稳定剂、d)一种或更多种催化剂和e)一种或更多种发泡剂混合并搅拌均匀,得到混合物A组分;
ii)将上述B组分一种或更多种多异氰酸酯与A组分混合得到反应混合物;和
iii)使反应混合物反应以得到聚异氰脲酸酯泡沫。
本发明通过在原料中添加卤素和/或磷等阻燃元素来制备具有阻燃元素的聚氨酯预聚体。
本发明的羟基封端的聚氨酯预聚体可用于在A、B料比为1∶1喷涂机上制备的阻燃聚异氰脲酸酯喷涂泡沫。
通过本发明制备的聚异氰脲酸酯泡沫的保温性能、粘结性能、压缩强度、尺寸稳定性优异,成本低,阻燃效果佳,能够实现阻燃、机械性能及成本的平衡。
具体实施方式
以下对实施本发明的具体实施方式进行描述。
根据本发明的一个方面,提供一种羟基封端的聚氨酯预聚体,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其选自聚醚多元醇和聚酯多元醇;
b)一种或更多种磷酸酯;和
c)一种或更多种多异氰酸酯。
所述聚醚多元醇的官能度优选2-8,特别优选2-4,其羟值优选35-800,特别优选35-400。
所述聚醚多元醇选自自糖(山梨糖醇、葡萄糖、蔗糖)、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇和水起始的聚醚多元醇。
所述聚醚多元醇包括卤代聚醚多元醇和非卤代聚醚多元醇。
所述卤代聚醚多元醇为含有卤素的聚醚多元醇,即含有卤素的、自糖(山梨糖醇、葡萄糖、蔗糖)、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇。
所述卤素选自氯和溴。
在所述卤代聚醚多元醇中,优选卤素含量为相对于卤代聚醚多元醇质量的35~60wt%。
所述卤代聚醚多元醇优选还含有磷,即优选为卤磷复合阻燃聚醚多元醇。
优选在所述卤磷复合阻燃聚醚多元醇中,卤素含量为相对于卤磷复合阻聚醚多元醇的15~40wt%,磷含量为卤磷复合阻燃聚醚多元醇质量的1~7wt%,以所述卤磷复合阻燃聚醚多元醇的总重计。
所述卤磷复合阻燃聚醚多元醇的官能度优选2-6,特别优选2-4,其羟值优选200-800,特别优选200-400。
所述非卤代聚醚多元醇为不含卤素的聚醚多元醇,即不含有卤素的、自糖(山梨糖醇、葡萄糖、蔗糖)、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇。
在本申请中,提及“聚醚多元醇”而未明确描述“卤代”或“非卤代”时,包括卤代聚醚多元醇和非卤代聚醚多元醇。
所述聚酯多元醇为酸(酐)和多元醇缩合而成的聚酯多元醇,所述的酸(酐)选自邻苯二甲酸(酐)、间苯二甲酸(酐)、对苯二甲酸(酐)、己二酸(酐)、戊二酸(酐)和丁二酸(酐),所述多元醇选自乙二醇、丙二醇、二甘醇、一缩二丙二醇、丁二醇、甘油、三羟甲基丙烷、季戊四醇和山梨醇。
所述聚酯多元醇优选官能度为2-3、羟值为200-400的聚酯多元醇。
所述聚酯多元醇优选为以对苯二甲酸及乙二醇为原料生产的聚酯多元醇。
在一个实施方案中,所述聚合物多元醇包含卤代聚醚多元醇。
在一个实施方案中,所述聚合物多元醇包含卤磷复合阻燃聚醚多元醇。
在一个实施方案中,所述聚合物多元醇为卤代聚醚多元醇。
在一个实施方案中,所述聚合物多元醇为卤磷复合阻燃聚醚多元醇。
在一个实施方案中,所述聚合物多元醇包含卤磷复合阻燃聚醚多元醇和聚酯多元醇。
在一个实施方案中,所述聚合物多元醇包含卤磷复合阻燃聚醚多元醇、聚酯多元醇和非卤代聚醚多元醇。
所述聚合物多元醇在所述预聚体中的量为1-60重量份,优选5-55重量份,特别优选为10-55重量份。
所述磷酸酯优选选自:三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、三(一缩二丙二醇)亚磷酸酯(俗称P430)、甲基磷酸二甲酯(DMMP)、丙基磷酸二甲酯(DMPP)、乙基磷酸二乙酯(DEEP)、磷酸三乙酯(TEP)、磷酸三甲苯酯(TPP)等。特别优选磷酸三乙酯(TEP)。
所述磷酸酯在所述预聚体中的量为5-60重量份,优选10-50重量份,特别优选15-40重量份,更特别优选30-40重量份。
在本发明中,磷酸酯可以同时起到阻燃和降低粘度的作用。
所述多异氰酸酯选自4,4-亚甲基二(2,6-二乙基苯基异氰酸酯)、四亚甲基1,4-二异氰酸酯、己二异氰酸酯(HDI)、十二烷基1,2-二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷、六氢甲苯-2,4-二异氰酸酯、六氢苯基-1,3-二异氰酸酯、六氢苯基-1,4-二异氰酸酯、全氢化-二苯甲烷2,4-二异氰酸酯、全氢化-二苯甲烷4,4-二异氰酸酯、亚苯基1,3-二异氰酸酯、亚苯基1,4-二异氰酸酯、杜烯1,4-二异氰酸酯、均二苯乙烯1,4-二异氰酸酯、3,3-二甲基4,4-二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯(TDI)、甲苯-2,6-二异氰酸酯(TDI)、二苯甲烷-2,4’-二异氰酸酯(MDI)、二苯甲烷-2,2’-二异氰酸酯(MDI)、二苯甲烷-4,4’-二异氰酸酯(MDI)、亚萘基-1,5-二异氰酸酯(NDI)、它们的异构体及其混合物。
所述多异氰酸酯优选为4,4′-、2,4′和2,2′-二苯基甲烷二异氰酸酯的混合物,更优选2,4′-二苯基甲烷二异氰酸酯含量高于50%,NCO含量为33%的4,4′-、2,4′和2,2′-二苯基甲烷二异氰酸酯混合物。
所述多异氰酸酯在所述聚氨酯预聚体中的量为5-60重量份,优选10-50重量份,特别优选15-40重量份。
本领域技术人员可以根据反应产物的目标羟值和多元醇的羟值、种类以及多元醇的量确定多异氰酸酯的量。
根据本发明的另一方面,一种制备上述羟基封端的聚氨酯预聚体的方法,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇、b)一种或更多种磷酸酯和c)一种或更多种多异氰酸酯混合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
步骤i)中的混合可按照如下进行:将a)一种或更多种聚合物多元醇和b)一种或更多种磷酸酯混合并在110℃~130℃、真空下脱水以去除其中的水分,然后通入氮气保护,使温度降至70-80℃,接着加入c)一种或更多种多异氰酸酯并搅拌。
所述真空压力为0.5mbar~1mbar。
步骤ii)中的反应在70-80℃下进行2-3小时。
根据本发明的一个方面,提供一种羟基封端的聚氨酯预聚体,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其包含卤代聚醚多元醇;和
b)一种或更多种多异氰酸酯。
所述卤代聚醚多元醇如上所定义。
上述卤代聚醚多元醇优选为如上所定义的卤磷复合阻燃聚醚多元醇。
所述多异氰酸酯如上所定义。
一种或更多种聚合物多元醇还任选包含如上所定义的聚酯多元醇和/或非卤代聚醚多元醇。
所述聚合物多元醇在所述预聚体中的量为1-60重量份,优选5-55重量份,特别优选为10-55重量份。
所述多异氰酸酯在所述预聚体中的量为5-60重量份,优选10-50重量份,特别优选15-40重量份,更特别优选30-40重量份。
根据本发明的另一方面,一种制备上述羟基封端的聚氨酯预聚体的方法,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇和b)一种或更多种多异氰酸酯混合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
步骤i)中的混合可按照如下进行:将a)一种或更多种聚合物多元醇在110℃~130℃、真空下脱水以去除其中的水分,然后通入氮气保护,使温度降至70-80℃,接着加入b)一种或更多种多异氰酸酯并搅拌。
所述真空压力为0.5mbar~1mbar。
步骤ii)中的反应在70-80℃下进行2-3小时。
根据本发明的另一方面,提供一种聚异氰脲酸酯泡沫,其由以下A、B两组分反应得到:
A组分,其包括:
a)上述羟基封端的聚氨酯预聚体;
b)任选的一种或更多种聚合物多元醇;
c)一种或更多种泡沫稳定剂;
d)一种或更多种催化剂;和
e)一种或更多种发泡剂;
B组分,其为一种或更多种多异氰酸酯。
所述羟基封端的聚氨酯预聚体在A组分中的量为40-100重量份,优选50-95重量份,特别优选70-95重量份。
用于A组分中的聚合物多元醇选自针对聚氨酯预聚体所述的聚醚多元醇和聚酯多元醇。
所述聚合物多元醇在A组分中的量为0-40重量份,优选5-30重量份,特别优选5-20重量份。
用于A组分中的泡沫稳定剂为在泡沫形成过程中促进形成规整泡孔结构的物质。可提及的实例有:含聚硅氧烷的泡沫稳定剂如硅氧烷-氧化烯共聚物和其它有机聚硅氧烷、脂肪醇、羰基合成醇、脂肪胺、烷基苯酚、二烷基苯酚、烷基甲酚、烷基间苯二酚、荼酚、烷基荼酚、荼胺、苯胺、烷基苯胺、甲苯胺、双酚A、烷基化双酚A、聚乙烯醇的烷氧基化产物以及甲醛和烷基苯酚、甲醛和二烷基苯酚、甲醛和烷基甲酚、甲醛和烷基间苯二酚的缩合产物的烷氧基化产物,以及两种或更多种这些泡沫稳定剂的混合物。
所述泡沫稳定剂在A组分中的量为1-10重量份,优选1-5重量份,特别优选1-3重量份。
用于A组分中的催化剂的非限定性实例有叔胺,如三乙胺、三丁胺、二甲基苄基胺、二环己基甲基胺、二甲基环己基胺、N,N,N’,N’-四甲基二氨基二乙基醚、双(二甲基氨基丙基)脲、N-甲基吗啉或N-乙基吗啉、N-环己基吗啉、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基丁烷二胺、N,N,N’,N’-四甲基己烷-1,6-二胺、五甲基二亚乙基三胺、二甲基哌嗪、N-二甲基氨基乙基哌啶、1,2-二甲基咪唑、1-氮杂双环-[2.2.0]辛烷、1,4-二氮杂双环[2.2.2]辛烷(Dabco),和烷醇胺化合物,如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺、二甲基氨基乙醇、2-(N,N-二甲基氨基乙氧基)乙醇,N,N’,N”-三(二烷基氨基烷基)六氢三嗪,如N,N’,N”-三(二甲基氨基丙基)-六氢三嗪,和三亚乙基二胺。金属盐如氯化铁(II)、氯化锌、辛酸铅也是合适的,并且优选锡盐如二辛酸锡、二乙基己酸锡和二月桂酸二丁基锡,以及特别地叔胺和有机锡盐的混合物。同时,作为可用的三聚反应催化剂,醋酸钾及辛酸钾能够有效提高异氰酸酯三聚反应的转化率,使泡沫较好地后熟化。
所述催化剂在A组分中的量为1-15重量份,优选1-10重量份,特别优选3-9重量份。
用于A组分中的发泡剂可为已知用于制备聚氨酯泡沫的发泡剂,包括化学发泡剂和/或物理发泡剂。
化学发泡剂是指通过与异氰酸酯反应产生气体产物的化合物。这类物质的实例有水或羧酸。
物理发泡剂是指对多异氰酸酯呈惰性并在大气压下具有低于100℃、优选低于50℃的沸点的液体,其在放热加聚反应的条件下蒸发。可使用的物理发泡剂的实例为烷烃,如庚烷、己烷、正戊烷和异戊烷;环烷烃,如环戊烷和环己烷;醚,如呋喃、二甲醚和二乙醚;酮,如丙酮和甲基乙基酮;羧酸烷基酯,如甲酸甲酯、草酸二甲酯和乙酸乙酯;以及卤代烃,如二氯甲烷、二氯一氟甲烷、二氟甲烷、三氟甲烷、二氟乙烷、四氟乙烷、氯二氟乙烷、1,1-二氯-2,2,2-二氟乙烷、2,2-二氯-2-氟乙烷和七氟丙烷。
可以使用一种或更多种化学发泡剂和/或物理发泡剂,也可使用这些发泡剂与其它取代的或未取代的烃的混合物。
优选正戊烷和异戊烷的混合物、正丁烷和异丁烷和丙烷的混合物。
所述发泡剂在A组分中的量为5-40重量份,优选10-35重量份,特别优选15-35重量份。
本发明中用于B组分的合适的多异氰酸酯可为本领域中已知用于制备硬质聚氨酯或氨基甲酸酯改性聚异氰脲酸酯泡沫体的那些,且特别是芳族多异氰酸酯,例如二苯甲烷二异氰酸酯及其低聚物,甲苯二异氰酸酯,1,5-萘二异氰酸酯和1,4-二异氰酸根合苯,例如为其2,4’-、2,2’-和4,4’-异构体及其混合物形式的二苯甲烷二异氰酸酯,二苯甲烷二异氰酸酯(MDI)和其低聚物的混合物(在本领域中已知为“粗产品”)或具有大于2的异氰酸酯官能度的聚合MDI(多亚甲基多亚苯基多异氰酸酯(polymethylene polyphenylene polyisocyanate)),为其2,4-至2,6-异构体及其混合物形式的甲苯二异氰酸酯。可提及的其它有机多异氰酸酯包括脂肪族二异氰酸酯,例如异佛尔酮二异氰酸酯、1,6-二异氰酸根合己烷和4,4’-二异氰酸根合二环己基甲烷。
在聚异氰脲酸酯泡沫制备过程中,由于使用A、B料比为1∶1喷涂机,B组分的多异氰酸酯的体积需与A组分体积相同,因此根据A组分体积确定B组分中多异氰酸酯的量。
根据本发明的另一方面,提供制备上述聚异氰脲酸酯泡沫的方法,其包括如下步骤:
i)将a)上述羟基封端的聚氨酯预聚体、b)任选的一种或更多种聚合物多元醇、c)一种或更多种泡沫稳定剂、d)一种或更多种催化剂和e)一种或更多种发泡剂混合并搅拌均匀,得到混合物A组分;
ii)将上述B组分与A组分混合得到反应混合物;和
iii)使反应混合物反应以得到聚异氰脲酸酯泡沫。
在A组分和B组分混合之前,所述A组分和B组分保持在35~40℃下。
除非另外限定,本文所使用的所有技术和科学术语具有本发明所属领域技术人员通常理解的相同意义。当本说明书中术语的定义与本发明所属领域技术人员通常理解的意义有矛盾时,以本文中所述的定义为准。
以下通过实施例对本发明进行示例性说明,但应理解本发明的范围不受这些实施例的限定。
实施例
本申请实施例中性能参数测试说明:
导热系数:按照DIN-52612进行测定。
泡沫闭孔率:按照ASTMD2856进行测定。
压缩强度:按照DIN-53421进行测定。
泡沫尺寸稳定性:按照GB8811进行测定。
氧指数:按照GB/T 2406.2-2009进行测定。
实施例1:羟基封端的聚氨酯预聚体的制备
向装备有电动搅拌器的三颈烧瓶中加入40克溴磷复合阻燃聚醚多元醇(羟值235,Saytex RB-79,购自美国雅宝公司)、10克聚酯多元醇(羟值255,CF-6245,购自南京康塑德)、4克非卤代聚醚多元醇(丙二醇为起始剂,官能度为2,羟值56,DC210,购自中国上海高桥石化公司)、38克磷酸三乙酯,搅拌混合并在120℃、真空下脱水以去除原料中的水分,然后通入氮气保护,使温度降至70℃,接着滴加入18克4,4′-、2,4′和2,2′-二苯基甲烷二异氰酸酯的混合物(来自Covestro的DESMODUR TP PU0129M)并搅拌以进行反应2.5小时,获得羟基封端的聚氨酯预聚体。
实施例2:羟基封端的聚氨酯预聚体的制备
向装备有电动搅拌器的三颈烧瓶中加入10克溴磷复合阻燃聚醚多元醇(羟值235,Saytex RB-79,购自美国雅宝公司)、30克聚酯多元醇(邻苯二甲酸缩聚而成,羟值400,官能度2.7,PS-4027,购自金陵斯泰潘),5克非卤代聚醚多元醇(丙二醇为起始剂,官能度为2,羟值56,DC210,购自中国上海高桥石化公司)、30克磷酸三乙酯,搅拌混合并在120℃、真空下脱水以去除原料中的水分,然后通入氮气保护,使温度降至70℃,接着滴加入22克4,4′,2,4′和2,2′-二苯基甲烷二异氰酸酯的混合物(来自Covestro的DESMODUR TP PU0129M)并搅拌以进行反应2.5小时,获得羟基封端的聚氨酯预聚体。
实施例3:羟基封端的聚氨酯预聚体的制备
向装备有电动搅拌器的三颈烧瓶中加入34克溴磷复合阻燃聚醚多元醇(羟值235,如Saytex RB-79,购自美国雅宝公司)、10克聚酯多元醇(对苯二甲酸缩聚而成,羟值255,CF-6245,购自南京康塑德)、10克卤代聚醚多元醇(含溴和氯,羟值330,官能度为3,IXOL B-251,购自瑞士苏威公司)、38克磷酸三乙酯,搅拌混合并在120℃、真空下脱水以去除原料中的水分,然后通入氮气保护,使温度降至70℃,接着滴加入22克4,4′-、2,4′和2,2′-二苯基甲烷二异氰酸酯的混合物(来自Covestro的DESMODUR TP PU0129M)并搅拌以进行反应2.5小时,获得羟基封端的聚氨酯预聚体。
实施例4:羟基封端的聚氨酯预聚体的制备
向装备有电动搅拌器的三颈烧瓶中加入40克溴磷复合阻燃聚醚多元醇(羟值235,Saytex RB-79,购自美国雅宝公司),35克磷酸三乙酯,搅拌混合并在120℃、真空下脱水以去除原料中的水分,然后通入氮气保护,使温度降至70℃,接着滴加入25克4,4′-、2,4′和2,2′-二苯基甲烷二异氰酸酯的混合物(来自Covestro的DESMODUR TP PU0129M)并搅拌以进行反应2.5小时,获得羟基封端的聚氨酯预聚体。
表1:实施例1-4中所用原料
实施例5-8:聚异氰脲酸酯泡沫的制备
根据表2使用实施例1-4所获得的羟基封端的聚氨酯预聚体制备聚异氰脲酸酯泡沫。
将羟基封端的聚氨酯预聚体、任选的聚合物多元醇与泡沫稳定剂(硅氧烷-氧化烯共聚物表面活性剂)、发泡剂、催化剂、任选的阻燃剂混合并搅拌均匀,得到混合物A组分,将A组分加入到喷涂发泡机中的A组分料桶中,其中喷涂发泡机包括A组分料桶和B组分料桶、A提料泵和B提料泵、A比例泵和B比例泵、A料管和B料管、装料腔体,其中A提料泵、A比例泵和A料管依次连接,B提料泵、B比例泵和B料管依次连接,且A料管与B料管均与装料腔体连接。
将B组分多异氰酸酯加入到喷涂发泡机中的B组分料桶中。
将A比例泵和B比例泵的比例系数设定为1∶1,通过A提料泵将喷涂发泡机中A组分料桶中的A组分输送到A比例泵中,通过A比例泵增压将A组分通过A料管打入到喷涂发泡机中的装料腔体中;通过B提料泵将喷涂发泡机中B组分料桶中的B组分输送到B比例泵中,通过B比例泵增压将B组分通过B料管打入到喷涂发泡机中的装料腔体中,A组分与B组分在装料腔体中进行混合,其中A比例泵和B比例泵、A料管和B料管的温度均设定为35~40℃;
通过输送到装料腔体中的高压气将混合后的混合物喷出到待喷涂的工件表面,完成制备聚异氰脲酸酯泡沫的喷涂成型。
对照实施例9:聚异氰脲酸酯泡沫的制备
根据表2使用高黑白(A/B)料比配方制备聚异氰脲酸酯泡沫。
参照实施例5-8进行,所不同的是A组分中不存在羟基封端的聚氨酯预聚体。
表2:制备聚异氰脲酸酯泡沫所用原料及所得聚异氰脲酸酯泡沫性能
*根据黑/白料比确定二苯基甲烷二异氰酸酯的量
从实施例5-8和对照实施例9可看出:采用羟基封端的聚氨酯预聚体制备聚异氰脲酸酯泡沫可使黑白(A/B)料比达到1∶1,该聚异氰脲酸酯硬质泡沫性能与常规黑白(A/B)料比非1∶1体系(例如1∶1.36体系)的泡沫物理和阻燃性能相当。采用羟基封端的聚氨酯预聚体在达到同样阻燃性能泡沫时,可采用市场常见料比1∶1设备,大幅减低实际生产过程的复杂性和成本,同时提高产品阻燃性能。
尽管上文针对本发明目的详细说明了本发明,但应理解的是,这种详细说明只是示例性的,除了可以由权利要求书限定的内容外,在不偏离本发明的精神及范围的情况下,本领域技术人员可以进行各种改变。
Claims (19)
1.一种羟基封端的聚氨酯预聚体,其特征在于,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其选自聚醚多元醇和聚酯多元醇;
b)一种或更多种磷酸酯;和
c)一种或更多种多异氰酸酯。
2.根据权利要求1所述的聚氨酯预聚体,其特征在于,所述聚醚多元醇选自自糖、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇。
3.根据权利要求1或2所述的聚氨酯预聚体,其特征在于,所述聚醚多元醇的官能度优选2-8,特别优选2-4,其羟值优选35-800,特别优选35-400。
4.根据权利要求1或2所述的聚氨酯预聚体,其特征在于,所述聚酯多元醇为酸(酐)和多元醇缩合而成的聚酯多元醇,所述酸(酐)选自邻苯二甲酸(酐)、间苯二甲酸(酐)、对苯二甲酸、己二酸(酐)、戊二酸(酐)和丁二酸(酐),所述多元醇选自乙二醇、丙二醇、二甘醇、一缩二丙二醇、丁二醇、甘油、三羟甲基丙烷、季戊四醇和山梨醇。
5.根据权利要求1或2所述的聚氨酯预聚体,其特征在于,所述聚酯多元醇为官能度为2-3、羟值为200-400的聚酯多元醇。
6.根据权利要求1或2所述的聚氨酯预聚体,其特征在于,所述磷酸酯选自三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、三(一缩二丙二醇)亚磷酸酯、甲基磷酸二甲酯(DMMP)、丙基磷酸二甲酯(DMPP)、乙基磷酸二乙酯(DEEP)、磷酸三乙酯、磷酸三甲苯酯(TPP)。
7.根据权利要求1或2所述的聚氨酯预聚体,其特征在于,所述多异氰酸酯选自4,4-亚甲基二(2,6-二乙基苯基异氰酸酯)、四亚甲基1,4-二异氰酸酯、己二异氰酸酯(HDI)、十二烷基1,2-二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷、六氢甲苯-2,4-二异氰酸酯、六氢苯基-1,3-二异氰酸酯、六氢苯基-1,4-二异氰酸酯、全氢化-二苯甲烷2,4-二异氰酸酯、全氢化-二苯甲烷4,4-二异氰酸酯、亚苯基1,3-二异氰酸酯、亚苯基1,4-二异氰酸酯、杜烯1,4-二异氰酸酯、均二苯乙烯均二苯乙烯1,4-二异氰酸酯、3,3-二甲基4,4-二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯(TDI)、甲苯-2,6-二异氰酸酯(TDI)、二苯甲烷-2,4’-二异氰酸酯(MDI)、二苯甲烷-2,2’-二异氰酸酯(MDI)、二苯甲烷-4,4’-二异氰酸酯(MDI)、亚萘基-1,5-二异氰酸酯(NDI)及其异构体。
8.一种制备权利要求1-7中任一项所述的预聚体的方法,其特征在于,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇、b)一种或更多种磷酸酯和c)一种或更多种多异氰酸酯混合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
9.根据权利要求8所述的方法,其特征在于,其中步骤i)中的混合可按照如下进行:将a)一种或更多种聚合物多元醇和b)一种或更多种磷酸酯混合并在110℃~130℃、真空下脱水以去除其中的水分,然后通入氮气保护,使温度降至70-80℃,接着加入c)一种或更多种多异氰酸酯并搅拌。
10.一种羟基封端的聚氨酯预聚体,其特征在于,其为以下原料的反应产物:
a)一种或更多种聚合物多元醇,其包含卤代聚醚多元醇;和
b)一种或更多种多异氰酸酯。
11.根据权利要求10所述的聚氨酯预聚体,其特征在于,所述卤代聚醚多元醇为含有卤素的、自糖、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇。
12.根据权利要求10或11所述的聚氨酯预聚体,其特征在于,所述卤代聚醚多元醇的官能度优选2-8,特别优选2-4,其羟值优选35-800,特别优选35-400。
13.根据权利要求10或11所述的聚氨酯预聚体,其特征在于,所述多异氰酸酯选自4,4-亚甲基二(2,6-二乙基苯基异氰酸酯)、四亚甲基1,4-二异氰酸酯、己二异氰酸酯(HDI)、十二烷基1,2-二异氰酸酯、环丁烷-1,3-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷、六氢甲苯-2,4-二异氰酸酯、六氢苯基-1,3-二异氰酸酯、六氢苯基-1,4-二异氰酸酯、全氢化-二苯甲烷2,4-二异氰酸酯、全氢化-二苯甲烷4,4-二异氰酸酯、亚苯基1,3-二异氰酸酯、亚苯基1,4-二异氰酸酯、杜烯1,4-二异氰酸酯、均二苯乙烯均二苯乙烯1,4-二异氰酸酯、3,3-二甲基4,4-二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯(TDI)、甲苯-2,6-二异氰酸酯(TDI)、二苯甲烷-2,4’-二异氰酸酯(MDI)、二苯甲烷-2,2’-二异氰酸酯(MDI)、二苯甲烷-4,4’-二异氰酸酯(MDI)、亚萘基-1,5-二异氰酸酯(NDI)以及其异构体。
14.一种制备权利要求10-13中任一项所述的羟基封端的聚氨酯预聚体的方法,其包括以下步骤:
i)将a)一种或更多种聚合物多元醇和b)一种或更多种多异氰酸酯合以得到反应混合物,和
ii)使反应混合物反应以得到羟基封端的聚氨酯预聚体。
15.根据权利要求14所述的方法,其特征在于,步骤i)中的混合可按照如下进行:将a)一种或更多种聚合物多元醇在110℃~130℃、真空下脱水以去除其中的水分,然后通入氮气保护,使温度降至70-80℃,接着加入b)一种或更多种多异氰酸酯并搅拌。
16.一种聚异氰脲酸酯泡沫,其特征在于,其由以下A、B两组分反应得到:
A组分,其包括:
a)根据权利要求1-7或10-13中任一项所述的羟基封端的聚氨酯预聚体;
b)任选的一种或多种聚合物多元醇;
c)一种或多种泡沫稳定剂;
d)一种或多种催化剂;和
e)一种或多种发泡剂;
B组分,其为一种或多种多异氰酸酯。
17.根据权利要求16所述的聚异氰脲酸酯泡沫,其特征在于,其中用于A组分中的聚合物多元醇选自:
卤代聚醚多元醇,其为含有卤素的、自糖、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇;
非卤代聚醚多元醇,其为不含有卤素的、自糖(山梨糖醇、葡萄糖、蔗糖)、季戊四醇、山梨糖醇、三羟甲基丙烷、丙三醇、甲苯二胺、乙二胺、乙二醇、丙二醇或水起始的聚醚多元醇;和
聚酯多元醇,其为酸(酐)和多元醇缩合而成的聚酯多元醇,所述酸(酐)选自邻苯二甲酸(酐)、间苯二甲酸(酐)、对苯二甲酸、己二酸(酐)、戊二酸(酐)和丁二酸(酐),所述多元醇选自乙二醇、丙二醇、二甘醇、一缩二丙二醇、丁二醇、甘油、三羟甲基丙烷、季戊四醇和山梨醇。
18.根据权利要求17所述的聚异氰脲酸酯泡沫,其特征在于,所述多异氰酸酯选自芳族多异氰酸酯,例如二苯甲烷二异氰酸酯及其低聚物,甲苯二异氰酸酯,1,5-萘二异氰酸酯和1,4-二异氰酸根合苯,以及脂肪族二异氰酸酯,例如异佛尔酮二异氰酸酯、1,6-二异氰酸根合己烷和4,4’-二异氰酸根合二环己基甲烷。
19.一种制备根据权利要求16-18中任一项所述的聚异氰脲酸酯泡沫的方法,其特征在于,其包括如下步骤:
i)将a)根据权利要求1-7和10-13中任一项所述的羟基封端的聚氨酯预聚体、b)任选的一种或更多种聚合物多元醇、c)一种或更多种泡沫稳定剂、d)一种或更多种催化剂和e)一种或更多种发泡剂混合并搅拌均匀,得到混合物A组分,
ii)将B组分:一种或更多种多异氰酸酯与A组分混合得到反应混合物;和
iii)使反应混合物反应以得到聚异氰脲酸酯泡沫。
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CN112608707B (zh) * | 2020-12-15 | 2022-12-13 | 广东普赛达密封粘胶有限公司 | 一种双组分聚氨酯结构胶及其制备方法 |
CN113637145A (zh) * | 2021-07-13 | 2021-11-12 | 广东图恩新材料有限公司 | 一种高储存稳定性聚氨酯组合料及其制备方法 |
CN113637145B (zh) * | 2021-07-13 | 2022-04-29 | 广东图恩新材料有限公司 | 一种高储存稳定性聚氨酯组合料及其制备方法 |
CN114479006A (zh) * | 2022-01-28 | 2022-05-13 | 万华节能科技(烟台)有限公司 | 适用于冷库滑雪场建筑内保温的结构性阻燃聚氨酯泡沫材料 |
CN114773565A (zh) * | 2022-03-09 | 2022-07-22 | 安丹达工业技术(上海)有限公司 | 阻燃热塑性聚氨酯树脂及其制备方法及其应用和防护服 |
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