CN1129626C - 用于制备水发泡硬质聚氨酯泡沫材料的多元醇 - Google Patents
用于制备水发泡硬质聚氨酯泡沫材料的多元醇 Download PDFInfo
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Abstract
通过苯酚、链烷醇胺、甲醛以1∶1∶1-1∶2.2∶2.2的摩尔比相混合而形成一种中间体,再与环氧乙烷和环氧丙烷的混合物进行烷氧基化就可制得标称官能度为3-5.4的、25℃粘度为300-3500厘泊(0.3-3.5帕·秒)的Mannich多元醇。
Description
本发明涉及用于制备水发泡聚氨酯泡沫材料的多元醇。本发明尤其涉及用于制备水发泡的聚氨酯泡沫材料的Mannich多元醇。
早已知道,通过多异氰酸酯与端羟基聚酯或羟值为350-900的聚(氧化烯)醚的反应来制备硬质聚氨酯泡沫材料的方法。用于制备这类泡沫材料的一组多元醇包括公开在美国专利3297597、4137265和4383102(’102)中的含氮多元醇。由苯酚、链烷醇胺与甲醛的反应产物经烷氧基化作用而制得的含氮多元醇(如公开在上述’102中的那些含氮多元醇)在下文中被称为Mannich多元醇。据文献报导,由这些多元醇制得的聚氨酯泡沫材料的特征在于当使用外加阻燃剂时,具有较高的固有阻燃性和良好的耐变形力。
这类多元醇的一个应用领域是用于顶盖和管道绝热的喷发泡沫材料体系。喷发聚氨酯泡沫材料工业通常采用的设备是能供给正确组分比的连续物流的“双作用”正排量泵。这种计量体系的一个主要缺点是只有在B组分的室温粘度低于1000厘泊时才能可靠地发挥作用。在粘度较高时,在B组分会产生空洞,从而导致组分比改变而影响泡沫塑料产品质量。
一般来说,在过去,用于制备喷发体系的配方都含卤烃发泡剂。近来,许多传统的发泡剂因会破坏能限制紫外辐射进入大气层数量的臭氧层而不再继续使用或中止使用。这就需要研发其它发泡剂如水。
虽然水可用作许多类型聚氨酯泡沫材料的发泡剂,但它不是具有它所替代的卤烃发泡剂的所有性能。例如,水作为多元醇配方(包括Mannich多元醇)发泡剂的一个缺点是水不会象卤烃发泡剂那样能有效降低Mannich多元醇的粘度。如上所述,以很高粘度的配方来制造泡沫材料时,某些类型的泡沫材料制造设备会发生问题。因此,理想的是利用粘度足够低的超低粘度Mannich多元醇,由包含Mannich多元醇的配方来制造水发泡聚氨酯泡沫材料以避免在加工时产生问题例如泡沫材料成形设备所引起的空洞问题。
本发明的一方面是制备25℃时粘度为300-3500厘泊(0.3-3.5帕·秒)的Mannich多元醇的方法,该方法包括下列步骤:将苯酚、链烷醇胺与甲醛相混合制成Mannich碱,然后使Mannich碱与环氧乙烷和环氧丙烷在满足制备Mannich多元醇的反应条件下进行烷氧基化反应。
本发明的另一方面是25℃时粘度为300-3500厘泊(0.3-3.5帕·秒)的曼尼希(Mannich)多元醇。
本发明的另一方面是包含多异氰酸酯A组分与包括25℃时粘度为300-3500厘泊(0.3-3.5帕·秒)的Mannich多元醇的B组分的聚氨酯泡沫材料配方。
本发明的再一方面是包括以包含多异氰酸酯A组分与包括25℃时粘度为300-3500厘泊(0.3-3.5帕·秒)的Mannich多元醇的B组分的聚氨酯泡沫塑料配方制成的聚氨酯泡沫材料在内的聚氨酯泡沫材料。
本发明的一个实施方案是25℃时粘度为300-3500厘泊(0.3-3.5帕·秒)的超低粘度Mannich多元醇。本发明的Mannich多元醇是通过苯酚、链烷醇胺、甲醛以一定的摩尔比混合而形成一种中间体,再经烷氧基化而制成的,其中制得的Mannich多元醇的标称官能度为3-5.5。对于本发明目的来说,本发明多元醇的标称官能度等于中间体的理论官能度。例如,如果采用摩尔比为1∶3∶3的未取代酚和二乙醇胺与甲醛来制备本发明的Mannich中间体的话,则所得多元醇的标称官能度为7,因为苯酚上有三个能与甲醛相键合的位置,而该三个位置又与本身为二羟基官能度的二乙醇胺相键合。因此,这种多元醇为7官能度,这是因为每个二乙醇胺有2个羟基基团,三个二乙醇胺共6个羟基基团,再加上苯酚的羟基总共有7个羟基基团。
本发明的Mannich中间体是经环氧乙烷和环氧丙烷的混合物烷氧基化的。以环氧乙烷和环氧丙烷的混合物使这些中间体烷氧基化,可制得粘度很低的Mannich多元醇(下文称为超低粘度Mannich多元醇)。本发明超低粘度Mannich多元醇的粘度优选为300-1500厘泊(0.3-1.5帕·秒),更优选为300-1000厘泊(0.3-1.0帕·秒)。
当制备本发明Mannich多元醇中间体时,要使苯酚、链烷醇胺、甲醛有适当的摩尔比以达到所要求的标称官能度。用于制备本发明Mannich多元醇的苯酚与甲醛的优选摩尔比为1∶1-1∶2.2,更优选的苯酚与甲醛的摩尔比为1∶1.5-1∶2。
用于本发明方法的甲醛与链烷醇胺的优选摩尔比为1∶1。在制备本发明中间体时,可采用附加量的链烷醇胺,但并不是必需的,通常也不是理想的。附加链烷醇胺的采用可促进链烷醇胺的烷氧基化作用而形成多元醇。例如,当其中链烷醇胺是二乙醇胺,并且用量超过上述摩尔比、在烷氧基化前不除去时,链烷醇胺会经烷氧基化而形成三元醇。这类能引发生成多元醇的胺的存在能形成较低粘度的多元醇混合物,但也会降低平均官能度,这一结果有时是不希望的。链烷醇胺与甲醛的摩尔比低于1∶1也会产生具有较高标称官能度的Mannich多元醇中间体。制备本发明Mannich多元醇中间体的苯酚、链烷醇胺、甲醛的优选摩尔比为1∶1∶1-1∶2.2∶2.2,更优选为1∶1.5∶1.5-1∶2∶2,而最优选为1∶2∶2。
可用于制备本发明多元醇的苯酚包括邻位、间位或对位甲酚、乙基酚、壬基酚、对苯基酚、2,3-双(4-羟基酚)丙烷、β-萘酚、β-羟基蒽、对氯酚、邻溴酚、2,6-二氯酚、对硝基酚、4-硝基-6-苯基酚、2-硝基-4-甲酚、3,5-二甲基酚、对异丙基酚、2-溴-4-环己基酚、4-叔丁基酚、2-甲基-4-溴酚、2-(2-羟丙基)酚、2-(4-羟基酚)乙醇、2-乙酯基酚、4-氯-甲基酚以及它们的混合物。特别优选用于制备本发明Mannich多元醇的苯酚是未取代苯酚或有单个亲水取代基的苯酚。最优选的苯酚是未取代苯酚。
按照本发明与苯酚化合物和甲醛反应的链烷醇胺是选自单和二链烷醇胺和氨的链烷醇胺。适用的链烷醇胺实例是单乙醇胺、二乙醇胺、异丙醇胺、二异丙醇胺、双(2-羟丙基)胺、羟乙基甲基胺、N-羟基-乙基哌嗪、N-羟基丁基胺、N-羟乙基-2,5-二甲基哌嗪以及它们的混合物。二乙醇胺是特别优选的。可以预期,氨(NH3)也能用来替代链烷醇胺,因而也属本发明范围。链烷醇胺混合物也可用来制备本发明的超低粘度多元醇。
本发明的Mannich多元醇是在满足制备含活性氢物质(称为Mannich中间体或Mannich碱)的反应条件下,使胺、苯酚与甲醛混合,然后使Mannich中间体经烷氧基化而制备的。任何满足制备中间体的反应条件以及普通技术熟练人员熟知的关于制备芳族胺多元醇的反应条件都可采用。例如,美国专利’102中的通用方法可用于本发明中,该方法包括:(1)首先,使苯酚与胺,接着再与甲醛混合;(2)然后从50℃加热至150℃,加热时间要足以使甲醛浓度降低至低于1(重量)%;(3)除去所得溶液中水以及(4)使除去水的中间体在30℃-200℃进行烷氧基化。
在本发明的优选实施方案中,要在中间体进行烷氧基化前先除去Mannich中间体中的水。优选的是,在进行烷氧基化前,除去中间体中水直至Mannich碱中的水含量达到0.5-1.5(重量)%。象过量的链烷醇胺一样,水也能与烯化氧反应生成多元醇,但生成的多元醇是二元醇。本发明的多元醇中存在过多的二元醇会降低平均官能度,这种结果有时是不希望出现的。
本发明的Mannich多元醇是通过Mannich中间体的烷氧基化而制成的。较少量的任何烯化氧都可用来制备本发明的Mannich多元醇,但至少50(重量)%的烯化氧是环氧乙烷和环氧丙烷。用来制备本发明Mannich多元醇的环氧乙烷和环氧丙烷的混合物中环氧乙烷占5-55(重量)%,环氧乙烷既可以混合供料形态或在其它烷氧基化反应完成后作为嵌段添加剂的形态添加。优选的是,在用来制备本发明Mannich多元醇的环氧乙烷与环氧丙烷的混合物中,烯化氧的10-45(重量)%、更优选15-30%、而最优选约20%是环氧乙烷。
除了上述加成方法外,本发明的超低粘度Mannich多元醇也可通过采用技术熟练人员熟知的任何一种制备多元醇的方法来制备。然而,使用上述第一种方法是优选的。这种优选的方法是先使苯酚与链烷醇相混合,然后在添加烯化氧前添加甲醛。应该小心,不要使苯酚与甲醛在会形成不希望有的副产物条件下相混合,除非这种结果是希望得到的。
对于制备本发明的Mannich多元醇来说,烯化氧的最低用量相应于Mannich碱中每一羟基为约0.3摩尔。烯化氧的最高需用量是每一羟基基团为约3.5摩尔。一般来说,酚羟基基团会形成不稳定的氨基甲酸酯键,因而应加以避免。因为酚羟基是有反应性的,它会与烯化氧反应,因此当采用化学计量量的烯化氧时,就能保证酚羟基基团的反应。
本发明的超低粘度Mannich多元醇的OH值(也称为羟值)为250-300。已知当量的多元醇的羟值可由56100除以多元醇的当量而算得。不采用催化剂来补充Mannich碱的自催化性能,可能难以制得本发明羟值低于约350的Mannich多元醇。本发明羟值为250-350的多元醇可通过采用辅助催化剂(如三甲胺、氢氧化钾)来制备。当采用这类辅助催化剂时,如果该多元醇的预期用途中不需要这种催化剂存在时,则应小心地除去或中和该辅助催化剂。本发明的超低粘度多元醇优选的羟值为280-450。最优选的羟值为300-400。
常规Mannich多元醇的25℃粘度高于3500厘泊(3.5帕·秒)。例如,VORANOL 470X*的粘度为7000-约13000厘泊(7-13帕·秒)(25℃),(*VORANOL 470X是Dow Chemical Company的商品名)。在水发泡体系中使用常规Mannich多元醇会引起设备故障和发生其它工艺上的障碍。此外,采用常规Mannich多元醇和水作为发泡剂制备的泡沫材料会呈粗泡孔结构并会发生脱层。本发明Mannich多元醇的超低粘度可使之用于水发泡体系配方中,这种配方在工艺上极少会出现障碍。
虽然以水作为唯一发泡剂的聚氨酯泡沫材料配方是本发明优选的实施方案,但可认为,本发明也包括混合发泡剂的配方。例如,水和一种或多种下列物质也可用作本发明配方的发泡剂:烃类、氯代烃类、氟代烃类。优选与水一起用于本发明配方中的发泡剂为HCFC-141b、HCFC-22、HFC-134a、正戊烷、异戊烷、环戊烷、HCFC-124以及HFC-245。
水是本发明配方中的优选发泡剂。在用于制备本发明聚氨酯泡沫材料的配方中,水的用量浓度是每100份多元醇为0.5-25份。优选水用量浓度是每100份多元醇为3-20份,更优选为4-10份。
本发明的聚氨酯泡沫材料是通过多异氰酸酯“A”组分与包括本发明Mannich多元醇的“B”组分的混合而制成的。本发明配方中的多异氰酸酯组分可选自有机多异氰酸酯、改性多异氰酸酯、异氰酸酯基预聚物以及它们的混合物。其中包括脂族和脂环族异氰酸酯,但芳族尤其是多官能芳族异氰酸酯是优选的,而多苯基多亚甲基多异氰酸酯(PMDI)是最优选的。
其它适用于本发明的多异氰酸酯包括2,4-和2,6-甲苯二异氰酸酯以及相应的异构体混合物;4,4’,2,4-’和2,2’-二苯甲烷二异氰酸酯以及相应的异构体混合物;4,4’,2,4’-和2,2’-二苯甲烷二异氰酸酯与多苯基多亚甲基多异氰酸酯PMDI的混合物;以及PMDI与甲苯二异氰酸酯的混合物。脂族及脂环族异氰酸酯化合物如1,6-六亚甲基二异氰酸酯,1-异氰酸根-3,5,5-三甲基-1,3-异氰酸根合甲基-环己烷,2,4-和2,6-六氢甲苯二异氰酸酯以及相应的异构体混合物;4,4’-,2,2’-和2,4’-二环己基甲烷二异氰酸酯以及相应的异构体混合物也适用于制备本发明的聚氨酯。1,3-四亚甲基二甲苯二异氰酸酯也可用于本发明中。
所谓改性的多官能异氰酸酯,即通过上述二异氰酸酯和/或多异氰酸酯的化学反应而制得的产物,也适用作本发明配方中的多异氰酸酯组分。例证性实例是含酯、脲、缩二脲、脲基甲酸酯,优选碳二亚胺和/或uretonimine的多异氰酸酯;含异氰脲酸酯和/或氨基甲酸酯基团的二异氰酸酯或多异氰酸酯。也可采用含碳二亚胺基团、uretonimine基团和/或异氰脲酸酯环的液态多异氰酸酯,其中异氰酸酯基团(NCO)含量为10-40(重量)%,更优选为20-35(重量)%。它们包括例如:基于4,4’,2,4’-和/或2,2’-二苯甲烷二异氰酸酯及相应的异构体混合物;2,4-和/或2,6-甲苯二异氰酸酯及相应的异构体混合物;二苯甲烷二异氰酸酯与PMDI的混合物以及甲苯二异氰酸酯与PMDI和/或二苯甲烷二异氰酸酯的混合物。
适用作本发明配方中多异氰酸酯组分的预聚物是含有2-40(重量)%,更优选含4-30(重量)%NCO的预聚物。这些预聚物可通过二和/或多异氰酸酯与包括较低分子量的二元醇、三元醇在内的物质相反应而制得,但也可通过与多价的活性氢化合物(如二和三胺及二和三硫醇)相反应而制得。个别的实例是含氨基甲酸酯基团的芳族多异氰酸酯,其中优选的NCO含量为5-40(重量)%,更优选为20-35(重量)%,它是由二异氰酸酯和/或多异氰酸酯与例如较低分子量的二元醇、三元醇、氧化烯二醇、二氧化烯二醇或分子量达约800的聚氧化烯二醇相反应而制得。这些多元醇可单独使用或以二和/或聚氧化烯二醇的混合物形态使用。例如可采用二甘醇、一缩二丙二醇、聚氧乙烯二醇、乙二醇、丙二醇、丁二醇、聚氧丙烯二醇以及聚氧丙烯聚氧乙烯二醇。也可采用聚酯多元醇以及烷基二元醇如丁二醇。其它适用的二元醇包括双羟乙基或双羟丙基双酚A,环己烷二甲醇以及双羟乙基氢醌。
用作本发明预聚合物配方的多异氰酸酯组分是:(i)含碳二亚胺基团和/或含由4,4’-二苯甲烷二异氰酸酯或4,4’-和2,4’-二苯甲烷二异氰酸酯混合物形成的氨基甲酸酯基团的、NCO含量为8-40(重量)%的多异氰酸酯(ii)NCO含量为2-35(重量)%(以预聚物重量计)的含NCO基团的预聚物,该预聚物是由官能度优选为1.75-4、分子量为800-15000的多元醇与4,4’-二苯甲烷二异氰酸酯反应或与4,4’-和2,4’-二苯甲烷二异氰酸酯混合物反应制备的,及(i)与(ii)的混合物;以及(iii)2,4-和2,6-甲苯二异氰酸酯和相应的异构体混合物。
任何形态的PMDI是用于本发明的最优选的多异氰酸酯。它的当量优选为125-300,更优选为130-175,平均官能度大于约1.5,更优选的平均官能度为1.75-3.5。多异氰酸酯组分的粘度优选为25-5000厘泊(0.025-约5帕·秒),但为了易于加工处理,25℃粘度为100-1000厘泊(0.1-1帕·秒)是优选的。当选用另外一些多异氰酸酯组分时,具有相同的粘度是优选的。优选的是,本发明配方的多异氰酸酯组分选自MDI、PMDI、MDI预聚物、PMDI预聚物、改性MDI以及它们的混合物。
除了本发明的超低粘度多元醇外,较少量的其它多元醇和含其它活性氢物质都可包含在配方中,供制造本发明的泡沫材料使用。用在聚氨酯生产中最普通的含活性氢化合物是那些含有至少二个羟基基团的化合物。这些化合物在本文中称为多元醇。适用的代表性多元醇通常是已知的,并在一些出版物中如“高聚物(High Polymer)”,Vol.XVI,“聚氨酯化学和技术(Polyurethane,Chemistry andTechnology)”(Saunders and Frisch,Interscience Publishers,New York,vol.I,pp.32-42,44-54(1962)和Vol.II,pp 5-6,198-199(1964));“有机聚合物化学(Organic PolymerChemistry)”(K.J.Saunders,Chapman and Hall,London,pp.323-325(1973));以及“聚氨酯开发(Developments inPolyurethane)”(vol.I,J.M.Burst,ed.,Applied SciencePublishers,pp.1-76(1978))有过介绍。
然而,任何含活性氢化合物都可用于本发明中。这种含活性氢化合物的实例包括选自下列组分,单独的或以混合物:(a)多羟基烷烃的烯化氧加合物;(b)非还原糖和糖衍生物的烯化氧加合物;(c)磷酸和多磷酸的烯化氧加合物,以及(d)多酚的烯化氧加合物。这些类型的多元醇在本文中称为“基础多元醇”。用在本文中的多羟基烷烃的烯化氧加合物的实例是乙二醇、丙二醇、1,3-二羟基丙烷、1,4-二羟基丁烷和1,6-二羟基己烷、丙三醇、1,2,4-三羟基丁烷、1,2,6-三羟基己烷、1,1,1-三羟甲基乙烷、1,1,1-三羟甲基丙烷、季戊四醇、聚己酸内酯、木糖醇、阿糖醇、山梨醇、甘露糖醇的烯化氧加合物。本文中优选的多羟基烷烃的烯化氧加合物是二和三羟基烷烃的环氧乙烷和环氧丙烷加合物。其它适用的加合物包括乙二胺、甘油、氨、1,2,3,4-四羟基丁烷、果糖以及蔗糖的加合物。
多胺、胺端基的多元醇、聚硫醇以及其它异氰酸酯反应性化合物也是适用于本发明的。含多异氰酸酯加聚的活性氢化合物(PIPA)也可用于本发明中。PIPA化合物通常是TDI与三乙醇胺的反应产物。制备PIPA化合物的方法可在例如美国专利4374209(授予Rowlands)中查到。
能以较少量用于本发明中的其它类型多元醇是“共聚物多元醇”,它们是包含基础多元醇的稳定分散的聚合物如丙烯腈-苯乙烯共聚物。这些共聚物多元醇可由包括各种其它物质例如催化剂(如偶氮二异丁腈),共聚物多元醇稳定剂及链转移剂(如异丙醇)的反应混合物而制得。
也可采用聚酯多元醇,优选以较少量用于本发明中。例如,可采用由回收的聚对苯二甲酸乙二醇酯衍生的聚酯多元醇。也可采用常规聚酯多元醇。就最广泛的范围来说,聚酯多元醇组分,可以是任何一种聚酯多元醇。优选的聚酯多元醇的分子量为400-10000,羟基官能度为2-6。最优选的分子量应在1000-6000范围内,羟基官能度为2-4。
常用的聚酯多元醇包括,例如多元(优选二元)醇,任选添加三元醇,与多元羧酸的反应产物。当然,可用相应的多羧酸酐或相应的低级醇多羧酸酯或它们的混合物来代替游离多羧酸制备聚酯。多元羧酸可以是脂族、脂环族、芳族和/或杂环羧酸,它们可以是被取代的例如被卤原子取代的和/或未被取代的。例证性化合物包括丁二酸、己二酸、癸二酸、邻苯二甲酸、间苯二甲酸、偏苯三酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、四氯邻苯二甲酸酐、戊二酸酐、马来酸、马来酸酐、二聚和三聚脂肪酸如油酸。例证性多元醇包括乙二醇、丁二醇、己二醇、辛二醇、新戊二醇、环己烷二甲醇、2-甲基-1,3-丙二醇、丙三醇、三羟甲基丙烷、己三醇、丁三醇、三羟甲基乙烷、季戊四醇、甘露糖醇、山梨醇、甲基葡糖苷、二甘醇、三甘醇、一缩二丙二醇、聚丙二醇、一缩二丁二醇、聚丁二醇。内酯的聚酯也是可采用的。
本发明的聚氨酯泡沫材料是通过采用添加剂如表面活性剂、催化剂、阻燃剂、填料制成的。例如,胺催化剂可用于本发明的配方中。任何含至少一个叔氮原子的、能催化羟基/异氰酸酯反应的有机化物都可用于本发明的共混物中。常用的胺包括N-烷基吗啉、N-烷基烷醇胺、N,N-二烷基环己胺及烷基胺,其中烷基基团是甲基、乙基、丙基、丁基和它们的异构体;以及杂环胺。常用的胺(但不受此限制)是三亚乙基二胺、四甲基亚乙基二胺、双(2-二甲氨基乙基)醚、三乙胺、三丙胺、三丁胺、三戊胺、吡啶、喹啉、二甲基哌嗪、哌嗪、N,N-二甲基环己胺、N-乙基吗啉、2-甲基哌嗪、N,N-二甲基乙醇胺、四甲基丙二胺、甲基三亚乙基二胺、2,4,6-三(二甲基氨基甲基)酚、N,N’,N″-三个(二甲基氨基丙基)-均六氢三嗪以及它们的混合物。优选的叔胺基团包括双(2-二甲基氨基乙基)醚、二甲基环己胺、N,N-二甲基乙醇胺、三亚乙基二胺、三乙胺、2,4,6-三(二甲基氨基甲基)酚、N,N’,N″-三(二甲基氨基丙基)-均六氢三嗪、N-乙基吗啉以及它们的混合物。
非胺催化剂也可用于本发明中。这类催化剂通常是铋、铅、锡、钛、铁、锑、铀、镉、钴、钍、铝、汞、锌、镍、铈、钼、钒、铜、锰、锆的有机金属化合物。这些化合物的说明性实施例是硝酸铋、2-乙基己酸铅、苯甲酸铅、氯化铁、三氯化锑、乙醇酸锑;优选的有机锡类包括羧酸的亚锡盐如乙酸亚锡、辛酸亚锡、2-乙基己酸亚锡、月桂酸亚锡,以及羧酸的二烷基锡盐如二乙酸二丁基锡、二月桂酸二丁基锡、二马来酸二丁基锡、二乙酸二辛基锡。
一种或多种三聚催化剂可用于本发明中,所采用的三聚催化剂可以是技术熟练人员已知的任何能催化有机异氰酸酯化合物三聚合形成异氰脲酸酯部分的催化剂。对于常用的异氰酸酯三聚催化剂,可参见“微孔塑料杂志(The Journal of Cellular P1astics)”,November/December 1975,p.329,以及美国专利3745133,3896052,3899443,3903018,3954684和4101465,这些专利的公开内容已列入本文供参考。常用的三聚催化剂包括甘氨酸盐、叔胺三聚催化剂和碱金属羧酸盐以及各类催化剂的混合物。这些催化剂中优选的是N-(2-羟基-5-壬基苯基)甲基-N-甲基甘氨酸钠和N,N-二甲基环己胺以及它们的混合物。优选的催化剂组分也包括公开在美国专利3745133中的环氧化物。
用于本发明的其它添加剂可包括一种或多种阻燃剂如三(2-氯乙基)磷酸酯、三(2-氯丙基)磷酸酯、三(2,3-二溴丙基)磷酸酯、三(1,3-二氯丙基)磷酸酯、磷酸氢二铵,各种卤化的芳族化合物,氧化锑、三水氧化铝、聚氯乙烯以及它们的混合物。分散剂、泡孔稳定剂以及表面活性剂也可配入本发明的配方中。表面活性剂例如有机表面活性剂和硅油可作为泡孔稳定剂添加。它们的某些代表性产品是以品名为SF-1109、L-520、L-521和DC-193销售的,它们通常是聚硅氧烷聚氧化烯嵌段共聚物,例如,已公开在美国专利2834748、2917480和2846458中的那些化合物。也可添加其它添加剂如碳黑、着色剂。填料如硫酸钡也可添加在本发明的泡沫材料中。
下面的实施例是为了说明本发明。这些实施例不是用来限制本发明的范围,也不应该解释为是对本发明范围的限制。除非另有说明,所有数量都以重量份或重量百分数表示。
实施例
实施例1
在20加仑反应器中制备多元醇I,并按照下列步骤进行操作:
1)在室温下,将10.18磅(4.62千克)90%苯酚的水溶液加到反应器中;
2)在室温下,将24.08磅(10.92千克)85%二乙醇胺水溶液加到苯酚溶液中,并加热至90℃;
3)在90℃下,使11.85磅(5.38千克)37%甲醛水溶液(福尔马林37)以约0.37磅/分钟(0.17千克/分钟)的添加速率加到反应器中;
4)使反应混合物在90℃保温2小时;
5)在100℃、以流速为8scfh(0.227scmh)的氮气流脱除反应器混合物中的水直至水含量达到0.75-1.00(重量)%(按照卡尔、费歇尔法测定(ASTM D4672-95));
6)在90℃下,使42.0磅(19.05千克)混合的氧化物物料(80(重量)%环氧丙烷/20(重量)%环氧乙烷)以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
7)在95℃,将0.5磅(0.23千克)二甲基乙醇胺加到反应器中;
8)在95℃,使另外的28.22磅(12.80千克)混合的氧化物物料以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
9)使反应物料在95℃下保温至羟基达到9.70(重量)%(以邻苯二甲酸酐湿法测定);以及
10)在100℃、以流速为8scfh(0.227scmh)的氮气流脱除反应混合物中残留的未反应的环氧丙烷和环氧乙烷,直至氧化物浓度低于500ppm(气相色谱法测定)。
得到的多元醇的羟值为320,25℃的粘度为802厘泊(0.8帕·秒),称为多元醇I。
实施例2
在20加仑反应器中制备多元醇II,并按照下列步骤进行操作:
1)在室温下,将9.55磅(4.33千克)90%苯酚的水溶液加到反应器中;
2)在室温下,将22.59磅(10.25千克)85%二乙醇胺水溶液加到苯酚溶液中,并加热至90℃;
3)在90℃下,使11.12磅(5.04千克)福尔马林37以约0.37磅/分钟(0.17千克/分钟)的添加速率加到反应器中;
4)使反应混合物在90℃保温2小时;
5)在100℃、以流速为8scfh(0.23scmh)的氮气流脱除反应器混合物中的水,直至水含量测定为0.75-1.00(重量)%;
6)在90℃下,使43.0磅(19.5千克)混合的氧化物物料(80(重量)%环氧丙烷/20(重量)%环氧乙烷)以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
7)在95℃下,将0.5磅(0.23千克)二甲基乙醇胺加到反应器中;
8)在95℃,使另外的29.0磅(13.15千克)混合的氧化物物料以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
9)使反应物料在95℃下保温至羟基达到9.09(重量)%(以邻苯二甲酸酐湿法测定);以及
10)在100℃,以流速为8scfh(0.227scmh)的氮气流脱除反应混合物中残留的未反应的环氧丙烷和环氧乙烷,直至氧化物浓度低于500ppm(气相色谱法测定)。
得到的多元醇的羟值为300,25℃的粘度为570厘泊(0.57帕·秒),称为多元醇II。
实施例3
在20加仑反应器中制备多元醇III,并按照下列步骤进行操作:
1)在室温下,将10.30磅(4.67千克)90%苯酚的水溶液加到反应器;
2)在室温下,将24.37磅(11.05千克)85%二乙醇胺水溶液加到苯酚溶液中,并加热至90℃;
3)在90℃下,使15.99磅(7.25千克)福尔马林37以约0.37磅/分钟(0.17千克/分钟)的添加速率加到反应器中;
4)使反应混合物在90℃保温2小时;
5)在100℃、以流速为8scfh(0.23scmh)的氮气流脱除反应器混合物中的水,直至水含量测定为0.75-1.00(重量)%;
6)在90℃下,使41.2磅(18.7千克)混合的氧化物物料(80(重量)%环氧丙烷/20(重量)%环氧乙烷)以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
7)在95℃下,将0.50磅(0.23千克)二甲基乙醇胺加到反应器中;
8)在95℃,使另外27.4磅(12.4千克)混合的氧化物物料以0.3磅/分钟(0.14千克/分钟)的添加速率加到反应器中;
9)使反应物料在95℃下保温至羟基达到9.17(重量)%(以邻苯二甲酸酐湿法测定);以及
10)在100℃下、以流速为8scfh(0.227scmh)的氮气流脱除反应混合物中残留的未反应的环氧丙烷和环氧乙烷,直至氧化物浓度低于500ppm(气相色谱法测定)。
得到的多元醇的羟值为303,25℃的粘度为1240厘泊(1.24帕·秒),称为多元醇III。
实施例4
将含Mannich多元醇的多元醇混合物与聚合的MDI相混合,采用装置有Gusmer GX-7*喷枪的Gusmer H-2000*喷射泡沫材料机喷射发泡(*Gusmer H-2000和Gusmer GX-7是Gusmer Machinery Group,Inc.的产品名)。操作压力通常为1000-1200磅/平方英寸,生产能力为7-15磅/分钟(3.2-6.8千克/分钟)。泡沫材料的配方列在表1中。泡沫材料的物理性能列在表2中。
表1:配方
成分 | 配方A | 配方B | 配方C |
多元醇I | 42.30 | ||
多元醇II | 42.02 | ||
多元醇III | 42.16 | ||
VORANOL1 800(胺引发的聚醚多元醇) | 7.05 | 7.00 | 7.03 |
TERATE 2541L2(芳族聚酯多元醇) | 19.03 | 18.91 | 18.97 |
甘油 | 2.11 | 2.10 | 2.11 |
SAYTEX RB-793(四溴邻苯二甲酸酯) | 14.10 | 14.01 | 14.05 |
FYROL PCF4(三(2-氯丙基)磷酸酯) | 7.05 | 7.00 | 7.03 |
POLYCAT 55(五甲基-二亚乙基三胺) | 0.70 | 0.70 | 0.70 |
POLYCAT 85(N,N-二甲基环己胺) | 0.35 | 0.70 | 0.35 |
NIAX A-336(33%三亚乙基二胺的一缩二丙二醇溶液) | 0.35 | 0.70 | 0.35 |
HEXCEM 9777(2-乙基己酸钾) | 1.06 | 1.05 | |
DABCO K-158(70%辛酸钾的二甘醇溶液) | 0.70 | ||
(24%辛酸铅水溶液) | 0.07 | 0.07 | 0.07 |
Dabco LK-4438(硅氧烷表面活性剂) | 1.41 | 1.72 | 1.73 |
水 | 4.41 | 4.38 | 4.40 |
PAPI1 27 Index(聚合的MDI) | 1.54 | 1.50 | 1.50 |
1Dow Chemical Company的商标和/或品名
2KOSA的商标和/或品名
3Albermarle的商标和/或品名
4Akzo Chemical的商标和/或品名
5Air Products的商标和/或品名
6OSi-Witco的商标和/或品名
7OMG Americas的商标和/或品名
8Air Products的商标和/或品名
表2:泡沫材料的物理性能
配方A | 配方B | 配方C | |
密度 | |||
lb./ft3 | 2.86 | 2.24 | 2.82 |
Kg/m3 | 45.81 | 35.88 | 45.11 |
压缩强度ASTM-1621 | |||
垂直(psi) | 35.60 | 22.57 | 41.65 |
(kPa) | 245.55 | 155.61 | 287.09 |
平行(psi) | 41.89 | 36.36 | 53.75 |
(kPa) | 288.81 | 252.54 | 370.40 |
闭孔量(%),ASTM D-2856 | |||
92.56 | 93.82 | 95.88 | |
尺寸稳定性:14天后体积变化%;ASTM-2126 | |||
100%R.H.,158°F(70℃) | -0.19 | -2.31 | -2.21 |
干热200°F(93℃) | - | - | -3.02 |
冷冻-22°F(-30℃) | - | - | -0.48 |
隧道炉耐燃试验;ASTM E84-98 | |||
火焰蔓延 | 40 | - | 35 |
烟气 | 790 | - | 790 |
UL-790耐燃试验,ASTM E108-98 | |||
间歇火焰B级 | - | - | 合格 |
燃烧火印B级 | - | - | 合格 |
Claims (9)
1.一种制备25℃粘度为300-3500厘泊的曼尼希多元醇的方法,该方法包括下列步骤:使苯酚、链烷醇胺、甲醛以1∶1∶1-1∶2.2∶2.2的摩尔比相混合,将混合物从50℃加热到150℃,加热时间足以使甲醛含量降至低于1%,使反应产物脱水,然后以其中环氧乙烷与环氧丙烷混合物中环氧乙烷的含量为5-55(重量)%的环氧乙烷与环氧丙烷的混合物使曼尼希碱烷氧基化而制成曼尼希多元醇,其中所述曼尼希多元醇的羟值为250-350。
2.权利要求1的方法,其中苯酚、链烷醇胺、甲醛的摩尔比为1∶1.5∶1.5-1∶2.2∶2.2。
3.权利要求2的方法,其中链烷醇胺是二乙醇胺。
4.权利要求1的方法,还包括在烷氧基化前从曼尼希碱中脱水的附加步骤。
5.权利要求3的方法,其中环氧乙烷和环氧丙烷的混合物中环氧乙烷占5-55(重量)%。
6.权利要求5的方法,其中环氧乙烷和环氧丙烷的混合物中环氧乙烷占10-45(重量)%。
7.权利要求6的方法,其中环氧乙烷和环氧丙烷的混合物中环氧乙烷占20(重量)%。
8.权利要求1的方法,其中烯化氧的最低用量相应于曼尼希碱中每一羟基基团为0.3摩尔。
9.权利要求1的方法,其中烯化氧的最高用量相应于曼尼希碱中每一羟基基团为3.5摩尔。
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- 1999-09-03 CN CN99812015A patent/CN1129626C/zh not_active Expired - Lifetime
- 1999-09-03 WO PCT/US1999/020359 patent/WO2000015690A1/en active IP Right Grant
- 1999-09-03 CZ CZ20010876A patent/CZ301020B6/cs not_active IP Right Cessation
- 1999-09-03 EP EP99946753A patent/EP1123341B1/en not_active Expired - Lifetime
- 1999-09-03 PT PT99946753T patent/PT1123341E/pt unknown
- 1999-09-03 PL PL346558A patent/PL204573B1/pl not_active IP Right Cessation
- 1999-09-03 AT AT99946753T patent/ATE294207T1/de active
- 1999-09-03 DE DE69925011T patent/DE69925011T2/de not_active Expired - Lifetime
- 1999-09-03 KR KR1020017003036A patent/KR20010079777A/ko not_active Application Discontinuation
- 1999-09-03 AU AU59090/99A patent/AU5909099A/en not_active Abandoned
- 1999-09-03 JP JP2000570224A patent/JP2002524630A/ja active Pending
- 1999-09-03 MX MXPA01002537A patent/MXPA01002537A/es not_active IP Right Cessation
- 1999-09-03 ES ES99946753T patent/ES2237939T3/es not_active Expired - Lifetime
- 1999-09-03 BR BRPI9913873-5A patent/BR9913873B1/pt not_active IP Right Cessation
- 1999-09-03 ZA ZA200101996A patent/ZA200101996B/en unknown
- 1999-09-03 CA CA002343443A patent/CA2343443C/en not_active Expired - Fee Related
- 1999-09-03 US US09/389,699 patent/US6281393B1/en not_active Expired - Lifetime
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108276570A (zh) * | 2017-12-20 | 2018-07-13 | 中国石油天然气股份有限公司 | 一种耐油稠化剂的制备方法以及用于油田含油采出水配液的压裂液 |
CN108276570B (zh) * | 2017-12-20 | 2020-06-09 | 中国石油天然气股份有限公司 | 一种耐油稠化剂的制备方法以及用于油田含油采出水配液的压裂液 |
Also Published As
Publication number | Publication date |
---|---|
KR20010079777A (ko) | 2001-08-22 |
PL204573B1 (pl) | 2010-01-29 |
ES2237939T3 (es) | 2005-08-01 |
PT1123341E (pt) | 2005-08-31 |
JP2002524630A (ja) | 2002-08-06 |
DE69925011T2 (de) | 2005-09-29 |
CZ2001876A3 (cs) | 2001-07-11 |
AU5909099A (en) | 2000-04-03 |
US6281393B1 (en) | 2001-08-28 |
WO2000015690A1 (en) | 2000-03-23 |
NO20011208L (no) | 2001-05-04 |
CN1323327A (zh) | 2001-11-21 |
PL346558A1 (en) | 2002-02-11 |
CZ301020B6 (cs) | 2009-10-14 |
ZA200101996B (en) | 2002-03-11 |
MXPA01002537A (es) | 2003-03-12 |
CA2343443C (en) | 2008-12-02 |
CA2343443A1 (en) | 2000-03-23 |
EP1123341B1 (en) | 2005-04-27 |
BR9913873A (pt) | 2001-06-05 |
EP1123341A1 (en) | 2001-08-16 |
BR9913873B1 (pt) | 2009-05-05 |
ATE294207T1 (de) | 2005-05-15 |
NO20011208D0 (no) | 2001-03-09 |
DE69925011D1 (de) | 2005-06-02 |
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