CN101563387B - 多亚苯基多亚甲基多异氰酸酯及其在制备聚氨酯泡沫中的用途 - Google Patents
多亚苯基多亚甲基多异氰酸酯及其在制备聚氨酯泡沫中的用途 Download PDFInfo
- Publication number
- CN101563387B CN101563387B CN200780042797XA CN200780042797A CN101563387B CN 101563387 B CN101563387 B CN 101563387B CN 200780042797X A CN200780042797X A CN 200780042797XA CN 200780042797 A CN200780042797 A CN 200780042797A CN 101563387 B CN101563387 B CN 101563387B
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- China
- Prior art keywords
- polymethylene
- polyphenylene
- weight
- polyphenylisocyanate
- polymethylene polyphenylisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及多亚苯基多亚甲基多异氰酸酯(B),其包含(B1)多亚苯基多亚甲基多异氰酸酯的2环产物,(B2)多亚苯基多亚甲基多异氰酸酯的3环产物,(B3)多亚苯基多亚甲基多异氰酸酯的4环产物,(B4)多亚苯基多亚甲基多异氰酸酯的5环产物,其中在(B1)的含量基于(B)的重量为至多55重量%的前提下,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,且组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)。
Description
本发明提供了具有特定组成的多亚苯基多亚甲基多异氰酸酯(MDI)、其制备方法及其在制备聚氨酯,尤其是聚氨酯泡沫中的用途。
很久以来就已知聚氨酯泡沫,并多次对其进行了描述。聚氨酯泡沫可用于许多工业应用。其一般通过使多异氰酸酯与具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物反应制备。
两种常用的聚氨酯泡沫为硬质聚氨酯泡沫和也被称作气溶胶泡沫的单组分泡沫。
硬质聚氨酯泡沫主要在例如制冷设备、运输设备或建筑中用于隔热,也用于制备结构构件,尤其是夹层构件。
用于制备上述聚氨酯的多异氰酸酯一般为芳族多异氰酸酯,具体为MDI及其高级同系物。
来自气溶胶容器的单组分泡沫为安装材料,在建筑业中常用于在建筑物中安装窗户和门,也用作填充材料,用于由建筑所产生的空洞或用于管道安装的穿过墙壁的孔洞。此类气溶胶容器包含预聚物以及发泡剂和添加剂。通过利用发泡剂喷出容器中的内容物形成所需泡沫,进而通过起泡发泡和通过接触大气中的湿气固化。已知基于含NCO的预聚物的单组分泡沫是这种泡沫中的最好一种。存在着产生硬质泡沫至软质泡沫的多种产品,这取决于所述产品的组成。
聚氨酯泡沫必须满足的一个重要要求是尺寸稳定性。尺寸稳定性指泡沫固化后不会改变其体积,尤其是不会收缩。就硬质泡沫而言,收缩可在泡沫中产生孔隙,并导致其从覆盖层脱离。
就用于安装窗户和门的单组分泡沫而言,收缩可导致已安装门窗的稳定性不够。
尺寸稳定性问题,尤其是单组分泡沫的尺寸稳定性问题,在工业上仍未得到彻底解决,因此,就目前已知的等级而言,作为技术上不可避免的收缩值,室温应用中至多5%的收缩以及热带应用中在40℃和90%相对湿度下至多10%的收缩仍是允许的。
就双组分泡沫而言,尤其是就双组分硬质泡沫而言,收缩问题尤其存在于大型模制品中,且不存在该问题解决方案的任何指引。
此外,市场日益需求具有浅色的泡沫。目前所提供的利用常用的多亚苯基多亚甲基多异氰酸酯制备的泡沫一般为褐色。可能认为这不令人满意,尤其是在其中泡沫是可看见的应用中。
因此本发明目的在于提供具有良好加工性能和使用性能,尤其是良好尺寸稳定性的聚氨酯泡沫。此外,浅色泡沫的市场需求应得到解决。所述方法应允许制备用于各种应用的泡沫,尤其是单组分现制泡沫和硬质聚氨酯泡沫。
出人意料的是,可通过在泡沫的制备过程中将二苯基甲烷二异氰酸酯和具有特定组成的多亚苯基多亚甲基多异氰酸酯的混合物用作异氰酸酯组分实现该目的。
相应地,本发明提供了多亚苯基多亚甲基多异氰酸酯(B),其包含:
(B1)多亚苯基多亚甲基多异氰酸酯的2环产物
(B2)多亚苯基多亚甲基多异氰酸酯的3环产物
(B3)多亚苯基多亚甲基多异氰酸酯的4环产物
(B4)多亚苯基多亚甲基多异氰酸酯的5环产物
其中在(B1)的含量基于(B)的重量为至多55重量%的前提下,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,且组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)。
本发明还提供了通过使(A)具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物(下文也称作多元醇组分)与(B)多异氰酸酯反应制备聚氨酯泡沫的方法,其中将本发明多亚苯基多亚甲基多异氰酸酯用作多异氰酸酯(B)。
本发明还提供了制备本发明多亚苯基多亚甲基多异氰酸酯的方法,所述方法包括如下步骤:
a)通过使多亚苯基多亚甲基多胺与光气反应制备多亚苯基多亚甲基多异氰酸酯,
b)去除步骤a)的多亚苯基多亚甲基多异氰酸酯中的副产物。
除组分(B1)-(B4)外,本发明多亚苯基多亚甲基多异氰酸酯还具有其他组分。因此,本发明多亚苯基多亚甲基多异氰酸酯(B)还包含具有6个或更多个环的多亚苯基多亚甲基多异氰酸酯。为此,术语“环”指芳环。下文也可将包含两个以上芳环的化合物称作高级同系物。
本发明多亚苯基多亚甲基多异氰酸酯(B)还可包含具有异氰酸酯基团的其他化合物,例如异氰酸酯相互间的反应产物,具体为二氮杂环丁酮亚胺(uretonimine),和/或具有6个或更多个环的多亚苯基多亚甲基多异氰酸酯。
优选组分(B)的此类其他组分的比例基于组分(B)的重量不多于15重量%。
优选多亚苯基多亚甲基多异氰酸酯(B)在所有情况下基于(B)的重量包含不多于11重量%,特别优选不多于6重量%,具体不多于3重量%二氮杂环丁酮亚胺。其是基于(B)的重量为15重量%其他化合物的一部分。
一般通过气体色谱确定具有不同环数量的多亚苯基多亚甲基多异氰酸酯的含量。通过FT-IR分析基于利用3环二氮杂环丁酮亚胺的校正(测试方法PFO/A 00/22-03)确定多亚苯基多亚甲基多异氰酸酯中二氮杂环丁酮亚胺的含量。
优选本发明多亚苯基多亚甲基多异氰酸酯的游离NCO端基的含量为31.0-33.3重量%。
优选通过萃取所得的本发明多亚苯基多亚甲基多异氰酸酯(B)依据DIN 6162和DIN 6164测得的碘色值小于5碘,L*值大于96,b*值小于15。
本发明多亚苯基多亚甲基多异氰酸酯可通过传统方法制备。这些方法通常是已知的,并包括通过苯胺和甲醛的酸催化反应制备二苯基甲烷二胺(M DA)及其高级同系物、中和和后处理由此所得的胺混合物、使后者与光气反应生成多亚苯基多亚甲基多异氰酸酯、提纯、后处理以及如果合适部分去除2环MDI。出人意料地发现发生了由于形成副产物而引起的对多亚苯基多亚甲基多异氰酸酯的破坏,具体而言,发生了由后处理多亚苯基多亚甲基多异氰酸酯和蒸馏去除2环产物过程中的热应力所引起的对多亚苯基多亚甲基多异氰酸酯的破坏。如果热应力存在的时间非常短,例如当分离较少量2环MDI时,则可避免这些缺点。此外,重要的是不将所述过程中的温度提高至220℃以上。优选由此制备的本发明多亚苯基多亚甲基多异氰酸酯(B)依据DIN 6162和DIN 6164测得的碘色值小于10碘,L*值大于89,b*值小于30。
以如下优选方法制备本发明多亚苯基多亚甲基多异氰酸酯:首先在工艺步骤a)中使多亚苯基多亚甲基多胺与光气以常规和已知方式反应,在随后的工艺步骤b)中使产物与副产物如二氮杂环丁酮亚胺分离。如果它们生成相同产物,则原则上其他工艺路线也可以。
工艺步骤a)一般是已知的,并如上所述包括苯胺与甲醛的酸催化反应、中和和后处理所生成的多胺、使后者与光气反应生成相应的多异氰酸酯以及后处理和提纯所述多异氰酸酯。如上所述,在步骤b)中使本发明多亚苯基多亚甲基多异氰酸酯与次级化合物如二氮杂环丁酮亚胺分离。在制备和后处理中生成这些次级化合物,尤其是多异氰酸酯在热应力作用下。起始多异氰酸酯最多包含25重量%这些来自制备过程中的次级化合物,例如二氮杂环丁二酮(uretdione)、二氮杂环丁酮亚胺和氨基甲酰氯。优选通过使用极性或非极性溶剂的液液萃取去除这些次级化合物。在一个优选实施方案中,优选烃如环己烷为溶剂。例如DE 1,543,258或EP 133 538描述了此类方法。
在步骤b)的一个优选实施方案中,使所使用的多亚苯基多亚甲基多异氰酸酯与环己烷以异氰酸酯∶溶剂=1∶1-1∶15,优选1∶1.5-1∶12,特别优选1∶2.5-1∶10的比率在20-90℃,优选30-80℃的温度下接触1-180分钟,优选5-150分钟。然后在20-40℃,优选室温下静置产物混合物,直至完成相分离。下层相为包含待分离掉的二氮杂环丁酮亚胺以及环更多的MDI同系物的“提余液”。上层相为包含所需二氮杂环丁酮亚胺含量低的多亚苯基多亚甲基多异氰酸酯和溶剂的“萃取物”。分离两相,例如通过真空蒸馏基本完全去除溶剂。优选残留环己烷的含量小于20ppm。
优选通过萃取获得的本发明多亚苯基多亚甲基多异氰酸酯(B)依据DIN 6162和DIN 6164测得的碘色值小于5碘,L*值大于96,b*值小于15。
当在制备过程中使作用在多亚苯基多亚甲基多异氰酸酯上的热应力保持较低且又进行多亚苯基多亚甲基多异氰酸酯的萃取时获得特别好的结果。
也可对不具有本发明组成的多亚苯基多亚甲基多异氰酸酯批料进行萃取。此时,次级化合物的含量可从15重量%以上降低至本发明含量。此外,由此可以环较少的产物为方向改变环分布。也可在部分去除2环MDI后进行多亚苯基多亚甲基多异氰酸酯的萃取,因为去除2环MDI过程中通常会发生次级化合物含量的增加。
优选在多亚苯基多亚甲基多异氰酸酯制备过程中通过上述方法特征所得的本发明多亚苯基多亚甲基多异氰酸酯(B)的2环产物(B1)的含量基于(B)的重量为20-50重量%,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)。
当通过萃取获得本发明多亚苯基多亚甲基多异氰酸酯(B)时,优选2环产物(B1)的含量基于(B)的重量为20-55重量%,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)。
当通过部分去除2环MDI和随后萃取获得本发明多亚苯基多亚甲基多异氰酸酯(B)时,优选2环产物(B1)的含量基于(B)的重量为2-20重量%,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)。
本发明多亚苯基多亚甲基多异氰酸酯可如上所述用于制备聚氨酯泡沫。本发明优选的应用为单组分聚氨酯泡沫和硬质聚氨酯泡沫。为此,使本发明多亚苯基多亚甲基多异氰酸酯(B)与具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物(A)反应。
在单组分聚氨酯泡沫的制备中,在发泡剂存在下在压力容器,优选气溶胶罐中进行异氰酸酯组分(B)与具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物(A)的反应。为此,将上文所述比例的多元醇组分(A)和异氰酸酯组分(B)与发泡剂一起引入压力容器中,从而在压力容器中生成游离异氰酸酯基团含量更低的本发明预聚物。用于制备单组分现制泡沫的常用发泡剂为例如R134a(四氟乙烷)、R152a(1,1-二氟乙烷)、二甲醚、丙烷、正丁烷和异丁烷,优选丙烷、正丁烷和异丁烷的混合物。
优选存在于气溶胶罐中的预聚物的NCO含量为约5-28重量%,优选8-24重量%,特别优选9-18重量%。NCO含量较低的预聚物产生较软的气溶胶泡沫,而NCO含量较高的预聚物则相应地产生较硬的泡沫。
为使用所述单组分聚氨酯泡沫,降低压力容器的压力。此时,喷出的预聚物通过发泡剂的起泡作用发泡,并通过接触大气中的湿气固化。
对单组分聚氨酯泡沫的许多应用而言,需要加入阻燃剂作为添加剂,它们同样具有降低粘度的作用。仅需加入达到成品泡沫燃烧等级所必需量的阻燃剂。
一般将磷酸三烷基酯和磷酸三氯烷基酯用作加入的阻燃剂。优选烷基具有1-4个,特别优选1-3个碳原子。特别优选的化合物为磷酸三甲酯、磷酸三乙酯、磷酸三丙酯、磷酸三氯甲酯、磷酸三氯乙酯和磷酸三氯丙酯。可单独或以相互间的任意混合物使用这些化合物。
阻燃剂的加入量取决于泡沫所需满足的要求。对耐火的单组分聚氨酯泡沫的配方而言,罐中存在的NCO预聚物中加入的阻燃剂总含量基于预聚物的重量必须为约8-18重量%,优选12-16重量%。含量偏低,防火保护可能不足,而加入的阻燃剂含量高,泡沫流动,即其不能应用于竖直表面,或者大量阻燃剂从泡沫中迁移出。
在本发明硬质泡沫的制备中,如通常所知,异氰酸酯组分与具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物(A)在催化剂和发泡剂存在下反应,其中将本发明多亚苯基多亚甲基多异氰酸酯(B)用于本发明方法。
可将与异氰酸酯基团反应消除二氧化碳的水用作发泡剂。也可与水组合使用物理发泡剂,或用物理发泡剂代替水。这些是对起始组分呈惰性,室温一般为液体和在尿烷反应条件下蒸发的化合物。优选这些化合物的沸点低于50℃。物理发泡剂还包括室温为气体且在加压下引入起始组分中或溶解在其中的化合物,例如二氧化碳、低沸点链烷烃和氟代链烷烃。
所述化合物一般选自具有至少4个碳原子的链烷烃和/或环烷烃、二烷基醚、酯、酮、缩醛、具有1-8个碳原子的氟代链烷烃和在烷基链中具有1-3个碳原子的四烷基硅烷,具体为四甲基硅烷。
可提及的实例为丙烷,正丁烷、异丁烷和环丁烷,正戊烷、异戊烷和环戊烷,环己烷,二甲醚,甲基乙基醚,甲基丁基醚,甲酸甲酯,丙酮以及在对流层中降解并因此不会破坏臭氧层的氟代链烷烃,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、二氟乙烷和七氟丙烷。特别优选使用环戊烷和/或正戊烷。可单独或以相互间的任意组合使用所述物理发泡剂。
为制备硬质聚氨酯泡沫,使多元醇组分(A)与多异氰酸酯(B)以使异氰酸酯指数为100-220,优选125-195的量反应。
可借助已知混合装置分批或连续制备硬质聚氨酯泡沫。
一般通过双组分法制备本发明硬质PUR泡沫。在该方法中,使具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物(A)与阻燃剂、发泡剂、催化剂和其他助剂和/或添加剂混合形成多元醇组分,多元醇组分与多异氰酸酯或多异氰酸酯以及如果合适阻燃剂和发泡剂的混合物(也称作异氰酸酯组分)反应。
一般在温度为15-35℃,优选20-30℃下混合起始组分。可利用高压或低压计量机将反应混合物引入封闭的支撑工具中。例如通过该方法分批制备夹层构件。
利用本发明方法制备的泡沫出人意料地具有非常浅的颜色,有时甚至是白色。所述泡沫尺寸稳定,且可非常好地应用。
至于用于制备本发明聚氨酯泡沫的其他多元醇,可提供以下细节:
可用于本发明制备硬质泡沫和制备用于单组分现制泡沫的预聚物方法的具有至少两个对异氰酸酯有反应活性的氢原子的化合物(A)具体为OH值为100-1200mg KOH/g的聚醚醇和/或聚酯醇。
一般通过具有2-12个碳原子,优选2-6个碳原子的多官能醇,优选二元醇与具有2-12碳原子的多官能羧酸(例如丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸和富马酸,优选邻苯二甲酸、间苯二甲酸、对苯二甲酸和异构的萘二甲酸)缩合制备所使用的聚酯醇。
所使用的聚醚醇的官能度一般为2-8,具体为3-8。
具体而言,使用通过已知方法制备的聚醚多元醇,例如通过环氧烷在催化剂(优选碱金属氢氧化物)存在下的阳离子聚合制备的聚醚多元醇。
一般将环氧乙烷和/或环氧丙烷,优选纯1,2-环氧丙烷用作环氧烷。
所使用的起始剂分子具体为分子中具有至少3个,优选4-8个羟基或至少两个伯氨基的化合物。
优选将三羟甲基丙烷、甘油、季戊四醇、糖化合物(例如葡萄糖、山梨醇、甘露糖醇和蔗糖)、多羟基酚、甲阶酚醛树脂(例如苯酚与甲醛的低聚缩合产物)以及酚、甲醛、二链烷醇胺和三聚氰胺的Mannich缩合物用作分子中具有至少3个,优选4-8个羟基的起始剂分子。
优选将芳族二胺和/或多胺(例如苯二胺,2,3-、2,4-、3,4-和2,6-甲苯二胺以及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)用作分子中具有至少两个伯氨基的起始剂分子。
优选聚醚多元醇的官能度为3-8,优选羟值为100-1200mg KOH/g,具体为240-570mg KOH/g。也可使用羟值小于100mg KOH/g和官能度为2-3的多元醇,尤其是聚醚醇。由此可调整泡沫的性质,例如在单组分现制泡沫的情况下以更高挠性为方向。
具有至少两个对异氰酸酯有反应活性的氢原子的化合物(A)还包括可同时使用的增链剂和交联剂。可证明加入双官能增链剂、三官能和更多官能交联剂或如果合适其混合物有利于改变机械性能。优选将链烷醇胺和尤其是分子量小于400,优选为60-300的二元醇和/或三元醇用作增链剂和/或交联剂。
有利的是,增链剂、交联剂或其混合物的用量基于多元醇组分(A)为1-20重量%,优选2-5重量%。
除所述聚酯多元醇和聚醚多元醇、增链剂和交联剂外,还可将一元醇用作其他OH官能化合物,所述OH官能化合物作为定向试剂用于在单组分聚氨酯泡沫领域所需多元醇组分(A)的制备过程中调节分子量,以形成可透性的泡沫面层并最终提高储存稳定性。如果需要,这些分子量为至多1400g/mol(OH值:约40mg KOH/g)的一元醇的用量基于多元醇组分(A)一般为至多10重量%。
所使用的聚醚醇和聚酯醇的其他信息及其制备可见例如Kunststoffhandbuch,第7卷“聚氨酯”,Günter Oertel编,Carl-Hanser-Verlag,Munich,第3版,1993。
在制备单组分聚氨酯泡沫的一个特别优选实施方案中,将如下组分的混合物用作多元醇组分(A):
(A1)分子量不大于600g/mol的聚酯多元醇和
(A2)平均分子量为1000-5000g/mol的聚醚多元醇或聚醚多元醇混合物。
优选将基于邻苯二甲酸酐/二甘醇/聚乙二醇的聚酯多元醇用作聚酯多元醇(A1)。
优选以聚酯多元醇(A1):聚醚多元醇或聚醚多元醇混合物(A2)=1∶6-3∶1的重量比使用多元醇(A1)和(A2)。
所使用的催化剂具体为大大加速异氰酸酯基团与对异氰酸酯基团有反应活性的基团的反应的化合物。此类催化剂为强碱性胺,例如脂族仲胺、咪唑类、脒类以及链烷醇胺。
如果要将异氰脲酸酯基团结合到硬质泡沫中,则需要特定催化剂。一般将金属羧酸盐,具体为乙酸钾及其溶液用作异氰脲酸酯催化剂。在此类泡沫(也称作聚氨酯-聚异氰脲酸酯泡沫)的制备过程中,一般以160-450的指数进行组分(A)与(B)的反应。
通过以下实施例阐述本发明。
实施例1-(单组分泡沫)
1.1多元醇组分的制备:
通过混合300g基于邻苯二甲酸酐/二甘醇/聚乙二醇和分子量为470g/mol的聚酯多元醇、208g基于甘油/环氧丙烷/环氧乙烷和分子量为4000g/mol的聚醚多元醇、30g基于蔗糖/戊二醇/二甘醇和平均分子量为540g/mol的聚醚多元醇、40g分子量为600g/mol的聚乙二醇、59g分子量为500g/mol的单官能甲基化聚乙二醇、25g泡沫稳定剂、330g磷酸三氯丙酯、8g二(吗啉代乙基)醚和0.5g硅油制备多元醇组分。
1.2异氰酸酯制剂的制备:
如下所述利用环己烷以单步萃取法萃取单体MDI含量为37%、NCO含量为31.2%重量、25℃时的粘度为213mPa·s、色值为20碘、L*值为85.6、b*值为70.1和二氮杂环丁酮亚胺含量为8.4%重量的多亚苯基多亚甲基多异氰酸酯(商品名:M20)。
使多亚苯基多亚甲基多异氰酸酯与环己烷以异氰酸酯∶溶剂=1∶3的比率在50℃下接触60分钟。然后室温静置产物混合物直至完成相分离。
上层相为包含所需多亚苯基多亚甲基多异氰酸酯和溶剂的“萃取物”。通过真空蒸馏彻底去除萃取物中的溶剂(残留环己烷的含量小于20ppm)。
由此获得产物,可如下表征所述产物:
粘度:50mPas(25℃)
NCO含量:32.6重量%
单体(B1)含量:49.1重量%
二氮杂环丁酮亚胺含量:1.6重量%
色值:0.8碘
L*值:99.3
b*值:5.1
二苯基甲烷二异氰酸酯的高级同系物的含量和比率:
(B2)多亚苯基多亚甲基多异氰酸酯的3环产物:30.4重量%
(B3)多亚苯基多亚甲基多异氰酸酯的4环产物:11.4重量%
(B4)多亚苯基多亚甲基多异氰酸酯的5环产物:4.2重量%
获得组分(B1)∶(B2)∶(B3)=7.2∶2.7∶1的比率。
以该种形式将如上所述制备的产物用作用于下述单组分现制泡沫制备的异氰酸酯组分。
1.3浅色和尺寸稳定的单组分现制泡沫的制备
将268g实施例1.1的多元醇组分引入1升气溶胶罐中。加入361g实施例1.2的异氰酸酯制剂后,可通过斜阀利用适于气溶胶罐实验室制备的装置封闭气溶胶罐。
接着通过阀引入56g二甲醚、38g由20重量%丙烷和80重量%丁烷组成的丙烷/丁烷混合物以及94g四氟甲烷(R134a),通过振摇匀化内容物。
通过在50℃保温保存由此制备的气溶胶罐实现人工老化,从而可在保存24小时和冷却至室温后对制备的气溶胶罐进行测试。
为此,润湿一张放置在平整基板上的吸水纸,利用旋上的泡沫管打开倾阀以发泡混合物喷出气溶胶罐的内容物。
以条带形式喷出泡沫,用水润湿以层形式喷出的泡沫条带间的泡沫表面。
对固化的泡沫进行测试以测定其性能(见表1.4)。
1.4单组分现制泡沫的性能
实施例1所述泡沫 | 与市售泡沫对比 | |
颜色 | 白色 | 黄/褐色 |
抗拉强度 | 24.1N/cm2 | 8N/cm2 |
断裂伸长 | 21% | 20% |
抗压应力(10%变形) | 5N/cm2 | 5N/cm2 |
尺寸稳定性* | 没有收缩 | -4.2% |
尺寸稳定性*
测量由两片粗纸板和隔离棒以及引入其间并在其中固化的泡沫制成的受试样品的尺寸稳定性。泡沫固化和移除隔离棒后,测定板间空间变化率作为尺寸稳定性的度量。
实施例2-(双组分硬质PUR泡沫)
2.1多元醇组分的制备
由377g Lupranol 3424(基于蔗糖、季戊四醇、二甘醇和环氧丙烷的聚醚多元醇,OH值为403mg KOH/g)、230g Lupranol 3423(基于蔗糖、甘油和环氧丙烷的聚醚多元醇,OH值为490mg KOH/g)、20g甘油、300gLupranol 1100(基于丙二醇和环氧丙烷的聚醚多元醇,OH值为104mgKOH/g)、54g Lupranol VP9319(基于三羟甲基丙烷和环氧丙烷的聚醚多元醇,OH值为160mg KOH/g)、10g稳定剂Tegostab B8443、5g稳定剂NiaxSilicone SR 393和4.5g水制备多元醇混合物。向该混合物加入34g催化剂混合物(23.3%N,N-二甲基环己胺、18.7%1-甲基咪唑,28%四甲基己二胺和30%Lupranol 1200[基于丙二醇和环氧丙烷的聚醚多元醇,OH值为248mg KOH/g])以及50g甘油/二醇的含水混合物(包含9%甘油和31%二丙二醇),并由其制备多元醇组分。
2.2异氰酸酯组分
使用实施例1.2所述异氰酸酯组分。
2.3加工所述组分以制备硬质PUR泡沫
以多元醇组分∶异氰酸酯组分=100∶136的混合比混合实施例2.1和2.2所述组分,发泡和固化后获得白色硬质泡沫。所述泡沫(自由泡沫)具有以下性能:
开始时间:15秒
固化时间:48秒
起发时间:85秒
泡沫密度:37.2kg/m3
抗压强度:28.1N/cm2
2.4尺寸稳定性的对比
*数据来源于Elastopor H 1101/1/0上的技术信息
Claims (17)
1.一种多亚苯基多亚甲基多异氰酸酯(B),其包含:
(B1)多亚苯基多亚甲基多异氰酸酯的2环产物
(B2)多亚苯基多亚甲基多异氰酸酯的3环产物
(B3)多亚苯基多亚甲基多异氰酸酯的4环产物
(B4)多亚苯基多亚甲基多异氰酸酯的5环产物
其中(B1)的含量基于(B)的重量为2-55重量%,组分(B2)、(B3)和(B4)以(B2)∶(B3)∶(B4)=8±4∶3.5±1.8∶1.2±0.9的重量比存在,且组分(B)基于组分(B)的重量包含至少85重量%组分(B1)、(B2)、(B3)和(B4)以及基于组分(B)的重量包含不多于15重量%具有至少6个环的多亚苯基多亚甲基多异氰酸酯和包含异氰酸酯基团的其他化合物,所述包含异氰酸酯基团的其他化合物包括二氮杂环丁酮亚胺。
2.权利要求1的多亚苯基多亚甲基多异氰酸酯,其中包含异氰酸酯基团的其他化合物基于多亚苯基多亚甲基多异氰酸酯(B)的重量包含不多于11重量%二氮杂环丁酮亚胺。
3.权利要求1的多亚苯基多亚甲基多异氰酸酯,其中包含异氰酸酯基团的其他化合物基于多亚苯基多亚甲基多异氰酸酯(B)的重量包含不多于6重量%二氮杂环丁酮亚胺。
4.权利要求1的多亚苯基多亚甲基多异氰酸酯,其中包含异氰酸酯基团的其他化合物基于多亚苯基多亚甲基多异氰酸酯(B)的重量包含不多于3重量%二氮杂环丁酮亚胺。
5.权利要求1的多亚苯基多亚甲基多异氰酸酯,其中多亚苯基多亚甲基多异氰酸酯的游离NCO端基的含量为31.0-33.3重量%。
6.一种通过使(A)具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物与(B)多异氰酸酯反应制备聚氨酯泡沫的方法,其中将权利要求1的多亚苯基多亚甲基多异氰酸酯用作多异氰酸酯(B)。
7.权利要求6的方法,其中反应在发泡剂存在下进行。
8.权利要求6的方法,其中反应在催化剂存在下进行。
9.一种通过混合(A)具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物和(B)多异氰酸酯从而使组分(A)与(B)在发泡剂存在下在压力容器中反应制备单组分聚氨酯泡沫的方法,其中将权利要求1的多亚苯基多亚甲基多异氰酸酯用作多异氰酸酯(B)。
10.权利要求9的方法,其中在组分(A)与(B)的反应中组分(B)的用量为至少三倍化学计算过量。
11.一种通过使(A)具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物与(B)多异氰酸酯在发泡剂存在下反应制备硬质聚氨酯泡沫的方法,其中将权利要求1的多亚苯基多亚甲基多异氰酸酯用作多异氰酸酯(B)。
12.权利要求11的方法,其中使组分(A)与组分(B)以使异氰酸酯指数为100-220的量进行反应。
13.权利要求11的方法,其中利用双组分法进行反应。
14.一种通过使(A)具有至少两个对异氰酸酯基团有反应活性的氢原子的化合物与(B)多异氰酸酯在发泡剂和三聚催化剂存在下反应制备硬质聚氨酯-聚异氰脲酸酯泡沫的方法,其中将权利要求1的多亚苯基多亚甲基多异氰酸酯用作多异氰酸酯(B)。
15.权利要求14的方法,其中使组分(A)与组分(B)以使异氰酸酯指数为160-450的量进行反应。
16.一种通过使多亚苯基多亚甲基多胺与光气反应制备权利要求1的多亚苯基多亚甲基多异氰酸酯的方法,其中制备和后处理多亚苯基多亚甲基多异氰酸酯过程中温度不超过220℃。
17.权利要求1的多亚苯基多亚甲基多异氰酸酯在制备聚氨酯泡沫中的用途。
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EP06124306 | 2006-11-17 | ||
EP06124306.9 | 2006-11-17 | ||
PCT/EP2007/062188 WO2008058920A1 (de) | 2006-11-17 | 2007-11-12 | Polyphenylenpolymethylenpolyisocyanat und seine verwendung zur herstellung von polyurethan-schaumstoffen |
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CN101578314B (zh) * | 2007-01-12 | 2012-01-18 | 巴斯夫欧洲公司 | 硬质聚氨酯泡沫 |
GB201106774D0 (en) * | 2011-04-21 | 2011-06-01 | Occutec Ltd | Polymers for contact lenses |
US10472454B2 (en) | 2012-01-18 | 2019-11-12 | Basf Se | Preparing rigid polyurethane foams |
CN104080827B (zh) * | 2012-01-18 | 2016-04-27 | 巴斯夫欧洲公司 | 制备硬质聚氨酯泡沫的方法 |
TR201905142T4 (tr) * | 2012-04-30 | 2019-05-21 | Covestro Deutschland Ag | Köpürtülmüş kalıplanmış cisimlerin üretilmesi için yöntem. |
US20160304657A1 (en) * | 2013-12-04 | 2016-10-20 | Covestro Deutschland Ag | Reaction system for a low-monomer one-component polyurethane foam |
PL235304B1 (pl) * | 2014-01-14 | 2020-06-29 | Selena Labs Spolka Z Ograniczona Odpowiedzialnoscia | Jednoskładnikowa mieszanina prepolimeru izocyjanianu oraz sposób wytwarzania pianki poliuretanowej w pojemniku dozującym w jednoetapowym procesie |
JP6480775B2 (ja) * | 2015-03-26 | 2019-03-13 | 積水化学工業株式会社 | ウレタン樹脂組成物、建材の耐火補強方法、および建材の耐火補強構造 |
KR20170139022A (ko) * | 2015-04-21 | 2017-12-18 | 코베스트로 도이칠란트 아게 | 단열성 조건 하에 제조된 폴리이소시아누레이트 중합체를 기재로 하는 고형물 |
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EP0114970A2 (en) * | 1983-01-26 | 1984-08-08 | The Dow Chemical Company | Improved process for the preparation of polymethylene polyphenyl polyisocyanates |
EP1518874B1 (de) * | 2003-09-24 | 2006-12-13 | Basf Aktiengesellschaft | Monomerarmes Gemisch, enthaltend polymeres MDI |
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CA2289530A1 (en) * | 1997-06-13 | 1998-12-17 | Huntsman Ici Chemicals Llc | Isocyanate compositions for blown polyurethane foams |
ATE478907T1 (de) * | 2006-04-12 | 2010-09-15 | Basf Se | Verfahren zur herstellung von polyurethanen |
CN101578314B (zh) * | 2007-01-12 | 2012-01-18 | 巴斯夫欧洲公司 | 硬质聚氨酯泡沫 |
US20090105359A1 (en) * | 2007-09-21 | 2009-04-23 | O'connor James | Preparation of Liquid Isocyanurate-Modified Polymethylene Bis(Phenylisocyanate) Compositions of Controlled Viscosities |
US20090082481A1 (en) * | 2007-09-21 | 2009-03-26 | O'connor James | Preparation of liquid isocyanurate-modified polymethylene bis(phenylisocyanate) compositions of controlled viscosities |
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- 2007-11-12 CN CN200780042797XA patent/CN101563387B/zh not_active Expired - Fee Related
- 2007-11-12 WO PCT/EP2007/062188 patent/WO2008058920A1/de active Application Filing
- 2007-11-12 EP EP07822476A patent/EP2091992A1/de not_active Withdrawn
- 2007-11-12 JP JP2009536712A patent/JP2010510339A/ja not_active Withdrawn
- 2007-11-12 KR KR1020097011536A patent/KR20090091739A/ko not_active Application Discontinuation
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EP0114970A2 (en) * | 1983-01-26 | 1984-08-08 | The Dow Chemical Company | Improved process for the preparation of polymethylene polyphenyl polyisocyanates |
EP1518874B1 (de) * | 2003-09-24 | 2006-12-13 | Basf Aktiengesellschaft | Monomerarmes Gemisch, enthaltend polymeres MDI |
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JP2010510339A (ja) | 2010-04-02 |
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US20100076101A1 (en) | 2010-03-25 |
WO2008058920A1 (de) | 2008-05-22 |
EP2091992A1 (de) | 2009-08-26 |
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