CN101535361A - 生产硬聚氨酯泡沫材料的方法 - Google Patents
生产硬聚氨酯泡沫材料的方法 Download PDFInfo
- Publication number
- CN101535361A CN101535361A CNA200780042067XA CN200780042067A CN101535361A CN 101535361 A CN101535361 A CN 101535361A CN A200780042067X A CNA200780042067X A CN A200780042067XA CN 200780042067 A CN200780042067 A CN 200780042067A CN 101535361 A CN101535361 A CN 101535361A
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- China
- Prior art keywords
- aethoxy sklerol
- propylene oxide
- processing step
- oxyethane
- mixture
- Prior art date
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Abstract
本发明涉及一种生产硬聚氨酯泡沫材料的方法,其中在c)发泡剂的存在下使a)多异氰酸酯与b)具有至少两个对异氰酸酯基有反应性的氢原子的化合物反应。本发明的特征在于具有至少两个对异氰酸酯基有反应性的氢原子的化合物含有至少一种聚醚醇bi),所述聚醚醇bi)可以通过芳族胺与环氧乙烷和环氧丙烷反应来制备,其中在第一个工艺步骤中先加成环氧丙烷、随后加成环氧乙烷或环氧乙烷和环氧丙烷的混合物,并且在第二个工艺步骤中加成剩余量的环氧丙烷。
Description
本发明涉及一种通过使多异氰酸酯与具有至少两个对异氰酸酯基有反应性的氢原子的化合物反应生产硬聚氨酯泡沫材料的方法。
硬聚氨酯泡沫材料长久以来是已知的,并且主要用于热和冷的隔绝,例如用于制冷器具、热水贮存、局部加热管道或建筑和建造,例如夹层构件。硬聚氨酯泡沫材料的生产和应用的简要综述可以例如参见Kunststoff-Handbuch,第7卷,聚氨酯,1966年由Dr.R.Vieweg和Dr.A.编著的第一版,1983年由Dr.Günter Oertel编著的第二版,和1993年由Dr.Günter Oertel编著的第三版,Carl Hanser,Munich,Vienna。
在硬聚氨酯泡沫材料的使用中,重要的是达到对于相关应用而言最佳的性能。
在硬聚氨酯泡沫材料的生产和应用中,最经常使用具有至少两个对异氰酸酯基有反应性的氢原子的化合物。
特别对于制冷应用,通过将环氧烷加成到芳族胺上获得的聚醚醇通常用作具有至少两个对异氰酸酯基有反应性的氢原子的化合物。在芳族胺中,甲苯二胺(TDA)的异构体是特别重要的。这些产品导致在泡沫材料的生产中最佳的流动性能以及泡沫材料的低热导率。
基于TDA的聚醚醇和这些产物的制备方法也是公知的。因此,EP 747411描述了基于邻-TDA的聚醚醇,称为邻位TDA。在这些聚醚醇的制备中,在第一个工艺步骤中在不使用催化剂的情况下加成纯环氧乙烷,并且在第二个工艺步骤中使用碱性催化剂加成纯环氧丙烷。
以此方式制得的聚醚醇具有较低的官能度,并导致聚氨酯体系的晚固化。所以可能存在甚至复杂的中空空间,特别在要完全填充的制冷应用中出现。在聚醚醇中的高含量环氧乙烷导致与多异氰酸酯之间的相容性差,从而导致更差的固化和泡沫材料的更大脱模厚度。
WO 05/044889也描述了使用基于TDA的聚醚醇制备的硬聚氨酯泡沫材料。其中,在第一个反应步骤中加成环氧乙烷和环氧丙烷的混合物,并在第二步中加成纯环氧丙烷。基于聚醚醇计,环氧乙烷的比例是2-25重量%。
在硬质泡沫材料的许多应用中,尤其在制冷装置的绝热中,一个重要的因素是所用体系的固化行为,这对装置生产中的循环时间有关键影响。
本发明的目的是提供一种生产硬聚氨酯泡沫材料的方法,此方法导致优良的热导率,并显示发泡剂在体系中的高溶解度,以及最佳的流动时间和固化时间。另外,所用的多元醇应当彼此相容。
此目的惊奇地通过使用一种能通过芳族胺与环氧乙烷和环氧丙烷反应制备的多元醇来实现,其中在第一个工艺步骤中先加成环氧丙烷和随后加成环氧乙烷,并且在第二个工艺步骤中加成环氧丙烷。
据此,本发明提供一种生产硬聚氨酯泡沫材料的方法,其中在c)发泡剂的存在下使
a)多异氰酸酯,与
b)具有至少两个对异氰酸酯基有反应性的氢原子的化合物反应,
其中具有至少两个对异氰酸酯基有反应性的氢原子的化合物含有至少一种聚醚醇bi),所述聚醚醇bi)可以通过芳族胺、优选甲苯二胺与环氧乙烷和环氧丙烷反应来制备,其中在第一个工艺步骤中先加成环氧丙烷、随后加成环氧乙烷或环氧乙烷和环氧丙烷的混合物,并且在第二个工艺步骤中加成剩余量的环氧丙烷。
本发明还提供聚醚醇bi),以及通过将环氧乙烷和环氧丙烷加成到芳族胺上制备聚醚醇bi)的方法,其中在第一个工艺步骤中先加成环氧丙烷、随后加成环氧乙烷或环氧乙烷和环氧丙烷的混合物,并且在第二个工艺步骤中使用碱性催化剂加成剩余量的环氧丙烷。
甲苯二胺的氨基先与环氧丙烷进行反应是特别有利的。这形成仲羟基。随后环氧乙烷的进一步加成反应优先在剩余的氨基上进行,并主要与这些氨基键合。这导致游离氨基的进一步减少,从而进一步降低聚醚醇的固有反应性。在已经加入环氧丙烷之后,如上所述优选加入纯环氧乙烷。也可以加入环氧乙烷和环氧丙烷的混合物,在这种情况下在此混合物中的环氧丙烷含量应当不超过20重量%,基于此混合物计。
聚醚醇bi)的羟值优选是140-480mg KOH/g,特别是140-470mgKOH/g。在本发明特别优选的实施方案中,羟值可以根据按照本发明方法制备的聚醚醇的优选应用领域而在140-180mg KOH/g的范围内或在370-420mg KOH/g的范围内。
作为用于制备聚醚醇bi)的芳族胺,可以单独使用二苯基甲烷二胺(MDA),或使用它与更高级同系物或甲苯二胺(TDA)的混合物。优选使用TDA,其中TDA特别优选具有至少95重量%的邻位TDA比例。
在制备聚醚醇bi)中的第一个工艺步骤优选在不存在催化剂的情况下进行。
此外,在制备聚醚醇bi)中的第二个工艺步骤优选在碱性催化剂的存在下进行。作为碱性催化剂,优选使用碱性化合物和/或胺,特别优选碱金属和/或碱土金属的氧化物和氢氧化物,尤其是氢氧化钾。
优选在第一个工艺步骤中使用2.5-4摩尔环氧烷/摩尔芳族胺。特别优选在第一个工艺步骤中使用1.5-2摩尔环氧乙烷和1-2摩尔环氧丙烷/摩尔芳族胺。
在第一阶段中的环氧乙烷的量是35-80重量%,基于在第一阶段中环氧烷的总重量计。聚醚醇中的环氧乙烷含量优选是4-20重量%,基于聚醚醇的重量计。
在第二个工艺步骤中,代替纯环氧丙烷,可以使用环氧丙烷和从>0到20重量%、优选从>0到5重量%的环氧乙烷的混合物,在每种情况下基于混合物的重量计。
在制备聚醚醇bi)的一个优选实施方案中,第二个工艺步骤在水或至少一种其它具有至少两个反应性氢原子的化合物的存在下进行。水可以原样加入或作为用于碱性催化剂的溶剂加入。
聚醚醇bi)的制备通过常规方法进行,例如描述在EP 747 411中。其中,环氧烷的加成反应优选在100-135℃的温度和0.1-8巴的压力下进行。引入环氧烷之后通常是环氧烷的后反应阶段,从而完全反应。以此方式获得的粗聚醚醇通过蒸馏而脱除未反应的环氧烷和挥发性化合物,优选在减压下蒸馏,脱水,并且通过酸中和和除去所形成的盐进行后处理。
在使用叔胺催化的情况下,粗产物用氮气和/或在减压下汽提,随后在合适时过滤。
如上所述,硬聚氨酯泡沫材料的生产通过多元醇与多异氰酸酯的反应进行,通常在催化剂、发泡剂和助剂和/或添加剂的存在下进行。
聚醚醇bi)在这里可以单独使用,但是优选在其它具有至少两个对异氰酸酯基有反应性的氢原子的化合物的存在下使用。
关于在本发明方法中使用的其它原材料,可以如下所述。
作为有机多异氰酸酯a),优选使用芳族的多官能异氰酸酯。
具体例子是:甲苯2,4-和2,6-二异氰酸酯(TDI)以及相应的异构体混合物,二苯基甲烷4,4’-、2,4’-和2,2’-二异氰酸酯(MDI)以及相应的异构体混合物,二苯基甲烷4,4’-和2,4’-二异氰酸酯的混合物,聚苯基聚亚甲基多异氰酸酯,二苯基甲烷4,4’-、2,4’-和2,2’-二异氰酸酯和聚苯基聚亚甲基多异氰酸酯的混合物(粗MDI),以及粗MDI和甲苯二异氰酸酯的混合物。有机二异氰酸酯和多异氰酸酯可以单独使用或以混合物的形式使用。
通常也使用改性的多官能异氰酸酯,即通过有机二异氰酸酯和/或多异氰酸酯的化学反应获得的产物。可以提到的例子是含有异氰脲酸酯基和氨基甲酸酯基的二异氰酸酯和/或多异氰酸酯。改性的多异氰酸酯可以任选地彼此混合,或与未改性的多异氰酸酯例如二苯基甲烷2,4’-和4,4’-二异氰酸酯、粗MDI、甲苯2,4-和/或2,6-二异氰酸酯混合。
也可以使用多官能异氰酸酯与多官能多元醇的反应产物,或它们与其它二异氰酸酯和多异氰酸酯的混合物。
发现特别有用的是使用NCO含量为29-33重量%且25℃下的粘度为150-1000mPa.s的粗MDI作为有机多异氰酸酯。
作为可以与本发明聚醚醇bi)一起使用的具有至少两个对异氰酸酯基有反应性的氢原子的化合物b),特别使用羟值为100-1200mg KOH/g的聚醚醇或聚酯醇。
与本发明聚醚醇bi)一起使用的聚酯醇通常通过使具有2-12个碳原子、优选2-6个碳原子的多官能醇(优选二醇)与具有2-12个碳原子的多官能羧酸缩合制备,所述多官能羧酸是例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸以及优选邻苯二甲酸、间苯二甲酸、对苯二甲酸和同分异构的萘二羧酸。
与本发明使用的聚醚醇bi)一起使用的聚醚醇通常具有2-8、特别是3-8的官能度。
特别地,使用由已知方法制得的聚醚醇,例如通过在催化剂、优选碱金属氢氧化物存在下环氧烷的阴离子聚合制得的聚醚醇。
所用的环氧烷通常是环氧乙烷和/或环氧丙烷,优选纯1,2-环氧丙烷。
作为起始分子,尤其使用在分子中具有至少3个、优选4-8个羟基或至少两个伯氨基的化合物。
作为在分子中具有至少3个、优选4-8个羟基的起始分子,优选使用三羟甲基丙烷,甘油,季戊四醇,糖化合物例如葡萄糖、山梨醇、甘露醇和蔗糖,多元酚,甲阶酚醛树脂,例如苯酚和甲醛的低聚缩合产物,以及苯酚、甲醛和二烷醇胺以及三聚氰胺的曼尼奇缩合物。
作为在分子中具有至少两个伯氨基的起始分子,优选使用芳族二胺和/或多胺,例如亚苯基二胺,2,3-、2,4-、3,4-和2,6-甲苯二胺,和4,4’-、2,4’-和2,2’-二氨基二苯基甲烷;以及脂族二胺和多胺,例如乙二胺。
聚醚醇的官能度优选为3-8,羟值优选为100-1200mg KOH/g,特别为120-570mg KOH/g。
在多元醇组分中使用分子量为500-1500的双官能多元醇,例如聚乙二醇和/或聚丙二醇,能调节多元醇组分的粘度。
具有至少两个对异氰酸酯基有反应性的氢原子的化合物b)还包括可以伴随使用的任何扩链剂和交联剂。可以在伴随使用或不伴随使用扩链剂和交联剂的情况下生产硬PUR泡沫材料。可以证明双官能扩链剂、三官能和更高官能的交联剂或者任选它们的混合物的加入对改进机械性能是有利的。作为扩链剂和/或交联剂,优选使用链烷醇胺,特别是分子量小于400、优选为60-300的二醇和/或三醇。
扩链剂、交联剂或其混合物的用量有利地是1-20重量%、优选2-5重量%,基于多元醇组分b)计。
关于使用的聚醚醇和聚酯醇及其制备的详细资料可以例如参见Günter Oertel编著的Kunststoffhandbuch,第7卷,“聚氨酯”,Carl-Hanser-Verlag Munich,1993年第3版。
在本发明方法的一个特别优选的实施方案中,组分b)包含能通过H-官能糖与环氧烷反应制备的聚醚醇bii)。
用于制备聚醚醇bii)的糖优选是蔗糖和/或山梨醇。聚醚醇bii)优选具有350-800mg KOH/g的羟值。
所用的催化剂尤其是能强烈促进异氰酸酯基与能与异氰酸酯基反应的基团之间的反应的化合物。这些催化剂是强碱性胺,例如脂族仲胺、咪唑、脒和链烷醇胺;或有机金属化合物,特别是有机锡化合物。
如果异氰脲酸酯基也要被引入硬聚氨酯泡沫材料中,则为此需要特殊的催化剂。作为异氰脲酸酯催化剂,通常使用金属羧酸盐,特别是乙酸钾和其溶液。
催化剂可以根据需要单独使用或以彼此的混合物形式使用。
作为发泡剂c),优选使用能与异氰酸酯基反应的水来代替二氧化碳。也可以使用物理发泡剂代替水或与水结合使用。这些发泡剂是对起始组分呈惰性、在室温下通常为液体并且在氨基甲酸酯反应条件下蒸发的化合物。这些化合物的沸点优选低于50℃。物理发泡剂也包括在室温为气态且在压力下被引入起始组分中或溶于起始组分中的化合物,例如二氧化碳、低沸点烷烃和氟代烷烃。
物理发泡剂通常选自:具有至少4个碳原子的烷烃和环烷烃,二烷基醚,酯,酮,缩醛,具有1-8个碳原子的氟代烷,以及在烷基链中具有1-3个碳原子的四烷基硅烷,特别是四甲基硅烷。
可以提及的实例为丙烷、正丁烷、异丁烷、环丁烷、正戊烷、异戊烷、环戊烷、环己烷、二甲醚、甲乙醚、甲基丁基醚、甲酸甲酯、丙酮和在对流层中分解并且因此不破坏臭氧层的氟代烷,例如三氟甲烷、二氟甲烷、1,1,1,3,3-五氟丁烷、1,1,1,3,3-五氟丙烷、1,1,1,2-四氟乙烷、二氟乙烷和1,1,1,2,3,3,3-七氟丙烷,以及全氟链烷烃,例如C3F8、C4F10、C5F12、C6F14和C7F17。特别优选戊烷,尤其是环戊烷。所述物理发泡剂可以单独使用或以彼此任何组合物的形式使用。
本发明方法可以任选地在阻燃剂和常规助剂和/或添加剂的存在下进行。
作为阻燃剂,可以使用有机磷酸酯和/或膦酸酯。优选使用不能与异氰酸酯基反应的化合物。优选的化合物也包括含氯的磷酸酯。
此类阻燃剂的典型代表是磷酸三乙酯、磷酸二苯基甲酚酯、磷酸三(氯丙基)酯和乙烷膦酸二乙基酯。
也可以使用含溴的阻燃剂。作为含溴的阻燃剂,优选使用具有对异氰酸酯基有反应性的基团的化合物。这些化合物是四溴邻苯二甲酸与脂族二醇形成的酯,以及二溴丁烯二醇的烷氧基化产物。也可以使用从一系列溴化的含羟基的新戊基化合物衍生的化合物。
使用的助剂和/或添加剂是对于本目的本身已知的材料,例如表面活性物质、泡沫稳定剂、泡孔调节剂、填料、颜料、染料、水解抑制剂、抗静电剂、抑霉剂和抑菌物质。
关于实施本发明方法所使用的原材料、发泡剂、催化剂和助剂和/或添加剂的其它资料可以例如参见Kunststoffhandbuch,第7卷,“聚氨酯”,Carl-Hanser-Verlag Munich,1966年第1版、1983年第2版和1993年第3版。
为了生产硬聚氨酯泡沫材料,多异氰酸酯a)和具有至少两个对异氰酸酯基有反应性的氢原子的化合物b)以这样的量反应,使得异氰酸酯指数在100-220的范围内,优选在115-195的范围内。硬聚氨酯泡沫材料可以在公知的混合装置的帮助下间歇或连续地生产。
聚异氰脲酸酯泡沫材料的生产也可以在更高的指数下进行,优选最高350。
本发明的硬聚氨酯泡沫材料通常通过双组分工艺生产。在此工艺中,将具有至少两个对异氰酸酯基有反应性的氢原子的化合物b)与阻燃剂、催化剂、发泡剂和其它助剂和/或添加剂混合形成多元醇组分,并且使其与多异氰酸酯或多异氰酸酯和任选发泡剂的混合物(亦称为异氰酸酯组分)反应。
起始组分通常在15-35℃、优选20-30℃的温度下混合。可以通过高压或低压计量机器将反应混合物引入到闭合的支撑工具中。例如,通过此技术不连续地生产夹心元件。
如上所述,通过本发明方法生产的聚醚醇可以与多异氰酸酯反应形成硬聚氨酯泡沫材料。它们非常容易与多元醇组分的其它成分混溶,并且能与优选用作用于生产硬聚氨酯泡沫材料的发泡剂的烃相容。所述泡沫材料具有低的热导率、优良的流动性、优良的固化性能和优良的脱模性。
本发明通过下面的实施例来说明。
实施例1(本发明):
将43.6kg的邻位甲苯二胺放入带有拉杆搅拌器(250rpm)、反应器加热和冷却装置、用于固体和液体物质以及环氧烷的计量添加装置、以及用于氮气保护和真空体系的装置的250L压力釜中,并加热到90℃。随后计量加入22.0kg的环氧丙烷,并在130℃反应。在计量添加结束后10分钟时,用2.5巴氮气填充反应器,并且在130℃计量加入28.7kg的环氧乙烷。在3小时的后反应时间后,向反应混合物加入0.705kg的48%氢氧化钾溶液,并混合。随后计量加入100.2kg的环氧丙烷,同时确保压力不超过6.5巴。在反应期间,反应温度升高到135℃,并在整个反应时间期间保持此温度。然后在135℃进行后反应3小时。
粗聚醚醇用水水解,用磷酸中和,过滤并且真空汽提。
最终产物具有以下数值:
羟值:391mg KOH/g
胺值:105mg KOH/g
水含量:0.044重量%
在25℃下的粘度:11,144mPa.s
实施例2(本发明):
将43.6kg的邻位甲苯二胺放入带有拉杆搅拌器(250rpm)、反应器加热和冷却装置、用于固体和液体物质以及环氧烷的计量添加装置、以及用于氮气保护和真空体系的装置的250L压力釜中,并加热到90℃。随后计量加入22.0kg的环氧丙烷,并在110℃反应。在计量添加结束后10分钟时,用2.5巴氮气填充反应器,并且在110℃计量加入28.7kg的环氧乙烷。在3小时的后反应时间后,向反应混合物加入1.945kg的二甲基乙醇胺,并混合。随后计量加入100.2kg的环氧丙烷,同时确保压力不超过6.5巴。在反应期间,反应温度升高到112℃,并在整个反应时间期间保持此温度。然后在120℃进行后反应3小时。
得到的粗聚醚醇进行真空汽提和过滤。
最终产物具有以下数值:
羟值:395mg KOH/g
胺值:111mg KOH/g
水含量:0.032重量%
在25℃下的粘度:25,620mPa.s
实施例3(本发明):
将17.3kg的邻位甲苯二胺放入带有拉杆搅拌器(250rpm)、反应器加热和冷却装置、用于固体和液体物质以及环氧烷的计量添加装置、以及用于氮气保护和真空体系的装置的250L压力釜中,并加热到90℃。随后计量加入8.75kg的环氧丙烷,并在130℃反应。在计量添加结束后10分钟时,用2.5巴氮气填充反应器,并且在130℃计量加入11.4kg的环氧乙烷。在3小时的后反应时间后,向反应混合物加入0.80kg的48%氢氧化钾溶液,并混合。随后计量加入160kg的环氧丙烷,同时确保压力不超过6.5巴。在反应期间,反应温度升高到135℃,并在整个反应时间期间保持此温度。然后在135℃进行后反应3小时。
粗聚醚醇用水水解,用磷酸中和,过滤并且真空汽提。
最终产物具有以下数值:
羟值:161mg KOH/g
pH值:8.5
水含量:0.07重量%
在25℃下的粘度:834mPa.s
实施例4
生产硬聚氨酯泡沫材料
以下组分混合形成多元醇组分:
58.75份的蔗糖/甘油引发的PO聚醚醇,其羟值为450mg KOH/g,
10.00份的来自实施例2的聚醚醇,
25.00份的TDA引发的PO/EO/PO聚醚醇,其羟值为160mg KOH/g,
2.50份的Tegostab B8462,
0.50份的PMDETA,
0.50份的DMCHA,
0.40份的1,3,5-三(3-二甲基氨基丙基)六氢-s-三嗪,
2.35份的水。
测得以下值:
乳化时间:7秒
纤维化时间:39秒
在15%过度填充时的脱模厚度(90mm模具):
4分钟:93.1mm
5分钟:92.0mm
热导率:19.2mW/mK,平均温度23℃
压缩强度:0.13N/mm2
Claims (17)
1.一种生产硬聚氨酯泡沫材料的方法,其中在c)发泡剂的存在下使
a)多异氰酸酯,与
b)具有至少两个对异氰酸酯基有反应性的氢原子的化合物反应,
其中具有至少两个对异氰酸酯基有反应性的氢原子的化合物含有至少一种聚醚醇bi),所述聚醚醇bi)通过芳族胺与环氧乙烷和环氧丙烷反应来制备,其中在第一个工艺步骤中先加成环氧丙烷、随后加成环氧乙烷或环氧乙烷和环氧丙烷的混合物,并且在第二个工艺步骤中加成剩余量的环氧丙烷。
2.权利要求1的方法,其中在制备聚醚醇bi)中的第一个工艺步骤在不存在催化剂的情况下进行。
3.权利要求1的方法,其中在制备聚醚醇bi)中的第二个工艺步骤在碱性催化剂的存在下进行。
4.权利要求1的方法,其中在第一个工艺步骤中按照35-80重量%的环氧乙烷比例先加入环氧丙烷并随后加入环氧乙烷,基于在第一个工艺步骤中环氧烷的总重量计。
5.权利要求1的方法,其中在第二个工艺步骤中的混合物中的环氧乙烷含量是从>0到5重量%,基于在第二个工艺步骤中环氧乙烷和环氧丙烷的混合物的重量计。
6.权利要求1的方法,其中在第一个工艺步骤中使用2.5-4摩尔环氧烷/摩尔芳族胺。
7.权利要求1的方法,其中在第一个工艺步骤中使用1.5-2摩尔环氧乙烷和1-2摩尔环氧丙烷/摩尔芳族胺。
8.权利要求1的方法,其中第二个工艺步骤在水或至少一种其它具有至少两个反应性氢原子的化合物的存在下进行。
9.权利要求1的方法,其中聚醚醇中的环氧乙烷总含量是4-20重量%,基于聚醚醇的重量计。
10.权利要求1的方法,其中聚醚醇bi)的羟值是140-480mg KOH/g,
11.权利要求1的方法,其中聚醚醇bi)的羟值是140-420mg KOH/g。
12.权利要求1的方法,其中甲苯二胺用作用于制备聚醚醇bi)的芳族胺。
13.权利要求9的方法,其中使用邻位甲苯二胺比例为至少95重量%的甲苯二胺作为用于制备聚醚醇bi)的芳族胺。
14.权利要求1的方法,其中组分b)包含能通过H-官能糖与环氧烷反应制备的聚醚醇bii)。
15.权利要求13的方法,其中用于制备聚醚醇bii)的糖是蔗糖和/或山梨醇。
16.一种通过将环氧乙烷和环氧丙烷加成到芳族胺上制备聚醚醇的方法,其中在第一个工艺步骤中先加成环氧丙烷、随后加成环氧乙烷或环氧乙烷和环氧丙烷的混合物,并且在第二个工艺步骤中使用碱性催化剂加成剩余量的环氧丙烷。
17.一种能通过权利要求16的方法制备的聚醚醇。
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CN102858832A (zh) * | 2010-04-26 | 2013-01-02 | 巴斯夫欧洲公司 | 生产硬质聚氨酯泡沫的方法 |
CN103373929A (zh) * | 2012-04-20 | 2013-10-30 | 罗门哈斯公司 | 二苄基胺疏水物 |
CN103415544A (zh) * | 2011-03-08 | 2013-11-27 | 巴斯夫欧洲公司 | 聚氨酯硬质泡沫的制备方法 |
CN104045847A (zh) * | 2013-12-17 | 2014-09-17 | 中集集团集装箱控股有限公司 | 发泡剂组合物、发泡体组合物及发泡体的制备方法 |
CN105940032A (zh) * | 2014-01-22 | 2016-09-14 | 亨茨曼国际有限公司 | 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方法 |
CN110582522A (zh) * | 2017-03-24 | 2019-12-17 | 亨茨曼国际有限公司 | 制造硬质的聚氨酯改性的聚异氰脲酸酯泡沫的方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20120022179A1 (en) * | 2009-01-20 | 2012-01-26 | Basf Se | Process for producing rigid polyurethane foams |
US20110218259A1 (en) * | 2010-03-02 | 2011-09-08 | Basf Se | Preparing polyurethanes |
BR112013019599A2 (pt) | 2011-04-07 | 2017-01-31 | Basf Se | processo para a produção de espumas rígidas de poliuretano, espuma rígida de poliuretano, e, uso da mesma. |
CA2833077A1 (en) * | 2011-04-15 | 2012-10-18 | Basf Se | Process for producing rigid polyurethane foams |
KR101306144B1 (ko) | 2011-06-13 | 2013-09-17 | (주)동성화인텍 | 육상 lng탱크의 보냉재용 수발포 폴리우레탄 조성물 및 그 제조 방법 |
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JPS5217875B2 (zh) * | 1973-12-27 | 1977-05-18 | ||
JPS57158219A (en) * | 1981-03-25 | 1982-09-30 | Toshiba Corp | Production of rigid urethane foam |
JPS58134108A (ja) * | 1982-02-02 | 1983-08-10 | Asahi Oorin Kk | 硬質ポリウレタンフオ−ムの製造法 |
DE3829290A1 (de) * | 1988-08-30 | 1990-03-15 | Bayer Ag | Polyetherpolyole auf basis aromatischer di- und/oder polyamine, verfahren zu ihrer herstellung und verwendung fuer polyurethan- und polyisocyanurat-kunststoffe |
DE4232970B4 (de) * | 1992-10-01 | 2005-07-07 | Basf Schwarzheide Gmbh | Polyetheralkohole, sowie ihre Verwendung zur Herstellung von Polyurethanen |
JPH07206966A (ja) * | 1994-01-20 | 1995-08-08 | Sanyo Chem Ind Ltd | 硬質ポリウレタンフォームの製造法 |
DE19521058A1 (de) * | 1995-06-09 | 1996-12-12 | Basf Ag | Verfahren zur Herstellung von Aromaten enthaltenden Polyetherpolyolen |
JPH10139847A (ja) * | 1996-11-01 | 1998-05-26 | Sanyo Chem Ind Ltd | 硬質ポリウレタンフォームの製造法 |
US5786405A (en) * | 1996-11-01 | 1998-07-28 | Bayer Corporation | Amine-initiated polyether polyols and a process for their production |
CN100523041C (zh) * | 2003-11-03 | 2009-08-05 | 陶氏环球技术公司 | 以甲苯二胺-引发的多元醇为基础的硬质聚氨酯泡沫体 |
-
2007
- 2007-11-05 JP JP2009536700A patent/JP5351762B2/ja active Active
- 2007-11-05 US US12/513,446 patent/US20090306238A1/en not_active Abandoned
- 2007-11-05 CN CNA200780042067XA patent/CN101535361A/zh active Pending
- 2007-11-05 WO PCT/EP2007/061862 patent/WO2008058863A1/de active Application Filing
- 2007-11-05 KR KR1020097010340A patent/KR101475959B1/ko active Active
- 2007-11-05 EP EP07822191.8A patent/EP2094757B1/de active Active
Cited By (12)
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CN102858832A (zh) * | 2010-04-26 | 2013-01-02 | 巴斯夫欧洲公司 | 生产硬质聚氨酯泡沫的方法 |
CN102858832B (zh) * | 2010-04-26 | 2015-08-05 | 巴斯夫欧洲公司 | 生产硬质聚氨酯泡沫的方法 |
CN103415544A (zh) * | 2011-03-08 | 2013-11-27 | 巴斯夫欧洲公司 | 聚氨酯硬质泡沫的制备方法 |
CN103415544B (zh) * | 2011-03-08 | 2015-12-09 | 巴斯夫欧洲公司 | 聚氨酯硬质泡沫的制备方法 |
CN102432859A (zh) * | 2011-08-24 | 2012-05-02 | 山东蓝星东大化工有限责任公司 | 软泡阻燃聚醚多元醇的合成方法 |
CN103373929A (zh) * | 2012-04-20 | 2013-10-30 | 罗门哈斯公司 | 二苄基胺疏水物 |
CN103373929B (zh) * | 2012-04-20 | 2015-07-22 | 罗门哈斯公司 | 二苄基胺疏水物 |
CN104045847A (zh) * | 2013-12-17 | 2014-09-17 | 中集集团集装箱控股有限公司 | 发泡剂组合物、发泡体组合物及发泡体的制备方法 |
CN105940032A (zh) * | 2014-01-22 | 2016-09-14 | 亨茨曼国际有限公司 | 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方法 |
CN105940032B (zh) * | 2014-01-22 | 2019-09-13 | 亨茨曼国际有限公司 | 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方法 |
CN110582522A (zh) * | 2017-03-24 | 2019-12-17 | 亨茨曼国际有限公司 | 制造硬质的聚氨酯改性的聚异氰脲酸酯泡沫的方法 |
CN110582522B (zh) * | 2017-03-24 | 2022-02-01 | 亨茨曼国际有限公司 | 制造硬质的聚氨酯改性的聚异氰脲酸酯泡沫的方法 |
Also Published As
Publication number | Publication date |
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JP5351762B2 (ja) | 2013-11-27 |
EP2094757B1 (de) | 2021-01-13 |
KR20090089333A (ko) | 2009-08-21 |
KR101475959B1 (ko) | 2014-12-23 |
JP2010509477A (ja) | 2010-03-25 |
WO2008058863A1 (de) | 2008-05-22 |
EP2094757A1 (de) | 2009-09-02 |
US20090306238A1 (en) | 2009-12-10 |
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