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CN111217981A - 具有低残余单体含量的低粘度含nco预聚物的制备方法 - Google Patents

具有低残余单体含量的低粘度含nco预聚物的制备方法 Download PDF

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CN111217981A
CN111217981A CN201911142002.3A CN201911142002A CN111217981A CN 111217981 A CN111217981 A CN 111217981A CN 201911142002 A CN201911142002 A CN 201911142002A CN 111217981 A CN111217981 A CN 111217981A
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diisocyanate
process according
nco
bis
isocyanatomethyl
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E.斯皮劳
H.勒施
S.克赖舍尔
A.迪斯韦尔德
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Evonik Operations GmbH
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Abstract

本发明涉及具有低残余单体含量的低粘度含NCO预聚物的制备方法。具体地，本发明涉及一种制备含NCO预聚物的方法，涉及由该方法制备的预聚物和该预聚物的用途。

Description

具有低残余单体含量的低粘度含NCO预聚物的制备方法
技术领域
聚氨酯和聚脲是漆料(Lack)、粘合剂、密封剂和塑料工业的有价值的原料。一种获得这些物质的途径经历了含NCO预聚物。这些含NCO预聚物可以通过多元醇与二异氰酸酯的反应获得，例如在EP0669353A1、EP0669354A1、DE3030572A1、EP0639598A1和EP0803524A1中公开的含脲二酮基团的二异氰酸酯。
背景技术
WO2009/059848A1公开了由二环己基甲烷二异氰酸酯(H12MDI)、IPDI和至少一种聚醚多元醇得到的含NCO预聚物。然而，其中公开的含NCO预聚物的缺点是，正如众所周知的，其所基于的聚醚具有氧化降解的倾向，因此尤其不是UV稳定的。它们在阳光照射下分解并变色。
在含NCO预聚物的制备中，异氰酸酯通常以化学计量过量使用。然而，缺点是未反应的二异氰酸酯的份额(残余单体含量)，这可能导致毒理学问题。在此特别关键的是未反应的易挥发二异氰酸酯。不乏降低它们的份额以使毒理学问题最小化的尝试。一种可能性是保持二异氰酸酯的化学计量过量尽可能低。但是，这导致较高的粘度，这使得这类产品的应用变得困难。另一种可能性在于随后的蒸馏以通过蒸馏除去该残余单体含量。然而，这需要另外的方法步骤和额外的能量，并且产物经受不可忽略的热负荷。
US3,904,796A公开了由脂族或脂环族异氰酸酯和多羟基化合物得到的含NCO预聚物。在实施例中尤其公开了由IPDI或IPDI和双(异氰酸根合甲基环己基)甲烷的混合物以及羟基官能聚酯得到的预聚物。所述预聚物通过将异氰酸酯加入到预先置入的聚酯中而合成。
EP0452775A2公开了由羟基官能聚酯和IPDI与双(异氰酸根合甲基环己基)甲烷的混合物得到的含NCO预聚物。这里，也将异氰酸酯加入到预先置入的羟基官能聚酯中。
发明内容
本发明的目的是提供具有低粘度和低的易挥发（leicht flüchtigen）二异氰酸酯残余单体含量的含NCO预聚物。
令人惊奇地发现，当合成预聚物时，各组分的顺序具有决定性影响：如果预先置入异氰酸酯(而不是聚酯多元醇)并向其中加入聚酯多元醇(而不是异氰酸酯)，则得到具有更低粘度和更低的更易挥发（leichter flüchtigen）的二异氰酸酯残余单体含量的含NCO预聚物。
因此，本发明的主题在于一种制备含NCO预聚物的方法，其中
a.预先置入双(异氰酸根合甲基环己基)甲烷，和
b.至少一种更易挥发的二异氰酸酯，和
c.向其中加入至少一种聚酯多元醇，
d.和任选的其它助剂。
为了获得特别好的结果，向其中分批加入（portionsweise）所述至少一种聚酯多元醇。
作为组分a)双(异氰酸根合甲基环己基)甲烷(H12MDI)原则上可以使用所有异构体，特别是二环己基甲烷-2,2'-、-2,4'-和/或-4,4'-二异氰酸酯。优选地，双(异氰酸根合甲基环己基)甲烷(H12MDI)包含至少80重量%，优选85-95重量%的4,4'-异构体，和5-20重量%，优选7-15重量%的2,4'-异构体。此外，双(异氰酸根合甲基环己基)甲烷(H12MDI)优选含有低于5重量%，优选低于1重量%的低份额的2,2'-H12MDI。4,4'-H12MDI的反式,反式含量优选小于30%，更优选为5% -25%。
除了H12MDI外，在预聚物的制备过程中还使用至少一种比H12MDI更易挥发的二异氰酸酯。
适合作为更易挥发的二异氰酸酯是沸点低于H12MDI（沸点：在标准压力—1013毫巴—下413℃，任选地使用Advanced Chem. Develop. Software V11.02 2016版(https://www.sigmaaldrich.com/chemistry/solvents/learning-center/nomograph.html)根据Siefken，Werner的文献数据；Annalen der Chemie，Justus Liebigs 1949，V562，P75-136换算；H12MDI的沸点：在0.1托下156-158℃）的所有脂族和脂环族和芳脂族二异氰酸酯。
优选环己烷二异氰酸酯、甲基环己烷二异氰酸酯、乙基环己烷二异氰酸酯、丙基环己烷二异氰酸酯、甲基二乙基环己烷二异氰酸酯、丙烷二异氰酸酯、丁烷二异氰酸酯、戊烷二异氰酸酯(优选五亚甲基二异氰酸酯)、己烷二异氰酸酯(优选六亚甲基二异氰酸酯(HDI)和1,5-二异氰酸根合-2-甲基戊烷(MPDI))、庚烷二异氰酸酯、辛烷二异氰酸酯、壬烷二异氰酸酯(优选1,6-二异氰酸根合-2,4,4-三甲基己烷和1,6-二异氰酸根合-2,2,4-三甲基己烷(TMDI)的混合物)、壬烷三异氰酸酯(优选4-异氰酸根合甲基-1,8-辛烷二异氰酸酯(TIN))、癸烷-二异氰酸酯和-三异氰酸酯、十一烷-二异氰酸酯和-三异氰酸酯、十二烷-二异氰酸酯和-三异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、异氰酸根合甲基甲基环己基异氰酸酯、2,5(2,6)-双(异氰酸根合甲基)双环[2.2.1]庚烷(NBDI)、1,3-双(异氰酸根合甲基)环己烷(1,3-H6-XDI)和1,4-双(异氰酸根合甲基)环己烷(1,4-H6-XDI)、四甲基亚二甲苯基二异氰酸酯(TMXDI)和赖氨酸二异氰酸酯烷基酯。
进一步优选异佛尔酮二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯和三甲基六亚甲基二异氰酸酯，后者优选1,6-二异氰酸根合-2,4,4-三甲基己烷和1,6-二异氰酸根合-2,2,4-三甲基己烷的混合物。作为组分b)更优选使用所提及的四种二异氰酸酯中的至少两种的混合物。
异氰酸酯b)与H12MDI相比更易挥发。原则上，这些异氰酸酯可以通过不同的方法制备。在工业中特别经证实有用的方法是通过有机多胺的光气化反应制备相应的聚氨基甲酰氯，并将其热裂解为有机多异氰酸酯和氯化氢。或者，有机多异氰酸酯也可以不使用光气制备，即通过不使用光气的方法制备。脂(环)族二异氰酸酯如1-异氰酸根合-3-异氰酸根合甲基-3,5,5-三甲基环己烷(异佛尔酮二异氰酸酯或IPDI)可以通过使所基于的脂(环)族二胺与脲和醇反应得到脂(环)族双氨基甲酸酯并将其热裂解为相应的二异氰酸酯和醇而制得。
H12MDI与所述（一种或多种）更易挥发的二异氰酸酯组分的质量比优选为90:10至10:90，基于两种组分a)和b)的重量份额。优选使用过量的H12MDI，即该比例大于55:45，更优选大于65:35，还更优选大于75:25。
作为组分c)使用至少一种至少双官能的含羟基的聚酯多元醇。聚酯多元醇的OH值优选为10-2000 (单位为mg KOH/g)。特别优选OH值为20-150和数均分子量为500-6000g/mol的含羟基聚酯。
优选的助剂d)尤其是非质子溶剂和聚氨酯化学中已知的用于NCO-OH反应的催化剂(尤其是有机金属化合物如二月桂酸二丁基锡= DBTL或叔胺如二氮杂双环辛烷和三乙胺)。
该反应可以在有或没有溶剂的情况下进行。优选不使用溶剂。此外，反应优选在40-80℃和在催化剂存在下进行。
合适的反应设备包括所有常规的装置、釜、静态混合器、挤出机等，优选具有混合或搅拌功能的设备。
NCO/OH比优选为10:1-1.2:1，更优选5:1-1.6:1，特别优选3:1-1.8:1。
本发明方法优选如此进行：以使反应产物中更易挥发的二异氰酸酯组分的残余单体含量优选最多为6.2%，更优选＜2.5%，并特别优选＜0.5%，这通过GC测定。此外，残余单体H12MDI的份额优选小于33%，更优选＜6.6%。粘度可以通过所用的多元醇和NCO:OH比进行控制。该方法优选如此进行：以使所得产物的粘度低于在相同NCO比下使用纯H12MDI时的粘度。
本发明的主题还在于可通过本发明方法获得的含NCO预聚物。如上所述，该含NCO预聚物与现有技术中已知的预聚物在粘度和残余单体含量方面不同。
本发明的主题还在于本发明预聚物和/或可通过本发明方法制备的产物作为漆料、粘合剂、密封剂或塑料配制剂的成分的用途。
具体实施方式
实施例：
实施例1，根据本发明：
将80g VESTANAT H12MDI (沸点：在1013毫巴下413℃，如上所述计算，EvonikIndustries AG)和20g VESTANAT IPDI (沸点：303.7℃，Evonik Industries AG)的混合物在搅拌的三颈烧瓶中加热至40℃，并与0.05g催化剂(二月桂酸二丁基锡，DBTL)混合。向其中滴加207g的Oxyester T1136 (聚酯多元醇，OH值107 mg KOH/g，Evonik Industries)(NCO:OH = 2:1)。在加入后，温度仍保持在40℃达4小时。产物的NCO值为5.3%，IPDI的残余单体含量为0.17%，H12MDI的残余单体含量为3.9%，粘度(23℃)为760 Pas。
实施例2，非本发明：
将100g VESTANAT H12MDI (沸点：在1013 毫巴下413℃，如上所述计算，EvonikIndustries AG)在搅拌的三颈烧瓶中加热到40℃，并与0.05g催化剂(二月桂酸二丁基锡，DBTL)混合。向其中滴加200g的Oxyester T1136 (聚酯多元醇，OH值107 mg KOH/g，EvonikIndustries) (NCO:OH = 2:1)。在加入后，温度仍保持在40℃达4小时。产物的NCO值为5.1%，H12MDI的残余单体含量为4.0%，粘度(23℃)为3000 Pas。
实施例3，非本发明：
将100g VESTANAT IPDI (熔点：303.7℃，Evonik Industries AG)在搅拌的三颈烧瓶中加热到40℃，并与0.05g催化剂(二月桂酸二丁基锡，DBTL)混合。向其中滴加236gOxyester T1136 (聚酯多元醇，OH值107 mg KOH/g，Evonik Industries) (NCO:OH = 2:1)。在加入后，温度仍保持在40℃达4小时。产物的NCO值为5.1%，IPDI的残余单体含量为1.33%，粘度(23℃)为820 Pas。
实施例4，非本发明：
将207g的Oxyester T1136 (聚酯多元醇，OH值107 mg KOH/g，Evonik Industries)在搅拌的三颈烧瓶中加热到40℃并与0.05g的催化剂(二月桂酸二丁基锡，DBTL)混合。向其中滴加80g VESTANAT H12MDI (沸点：在1013 毫巴下413℃，如上所述计算，EvonikIndustries AG)和20g VESTANAT IPDI (沸点：303.7℃，Evonik Industries AG) (NCO:OH= 2:1)的混合物。在加入后，温度仍保持在40℃达4小时。产物的NCO值为5.1%，IPDI的残余单体含量为1.1%，H12MDI的残余单体含量为5.2%，粘度(23℃)为870 Pas。
实施例5，非本发明：
在三颈烧瓶中混合207g的Oxyester T1136 (聚酯多元醇，OH值107 mg KOH/g，EvonikIndustries)以及80g的VESTANAT H12MDI (沸点：在1013 毫巴下413℃，如上所述计算，Evonik Industries AG)和20g的VESTANAT IPDI (沸点：303.7℃，Evonik Industries AG)(NCO:OH = 2:1)的混合物和0.05g的催化剂(二月桂酸二丁基锡，DBTL)，并加热到40℃。保持该温度在40℃达4小时。产物的NCO值为5.0%，IPDI的残余单体含量为0.5%，H12MDI的残余单体含量为5.5%，粘度(23℃)为790 Pas。
Figure DEST_PATH_IMAGE002
。
*非根据本发明的。
仅根据本发明的实施例既具有低的IPDI残余单体含量又具有低粘度。

Claims (12)

1.制备含NCO预聚物的方法，其特征在于
a.预先置入双(异氰酸根合甲基环己基)甲烷，和
b.至少一种更易挥发的二异氰酸酯，和
c.向其中加入至少一种聚酯多元醇，
d.和任选的其它助剂。
2.根据权利要求1所述的方法，其特征在于，向其中分批加入所述至少一种聚酯多元醇。
3.根据权利要求1或2所述的方法，其特征在于，双(异氰酸根合甲基环己基)甲烷包含至少80重量%的4,4'-异构体和5-20重量%的2,4'-异构体。
4.根据权利要求1-3中任一项所述的方法，其特征在于，所述二异氰酸酯选自环己烷二异氰酸酯、甲基环己烷二异氰酸酯、乙基环己烷二异氰酸酯、丙基环己烷二异氰酸酯、甲基二乙基环己烷二异氰酸酯、丙烷二异氰酸酯、丁烷二异氰酸酯、戊烷二异氰酸酯、己烷二异氰酸酯、庚烷二异氰酸酯、辛烷二异氰酸酯、壬烷二异氰酸酯、壬烷三异氰酸酯、癸烷-二异氰酸酯和-三异氰酸酯、十一烷-二异氰酸酯和-三异氰酸酯、十二烷-二异氰酸酯和-三异氰酸酯、异佛尔酮二异氰酸酯、异氰酸根合甲基甲基环己基异氰酸酯、2,5(2,6)-双(异氰酸根合甲基)双环[2.2.1]庚烷、1,3-双(异氰酸根合甲基)环己烷以及1,4-双(异氰酸根合甲基)环己烷、四甲基亚二甲苯基二异氰酸酯和赖氨酸二异氰酸酯烷基酯。
5.根据前述权利要求中任一项所述的方法，其特征在于，所述二异氰酸酯是异佛尔酮二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯和/或三甲基六亚甲基二异氰酸酯。
6.根据前述权利要求中任一项所述的方法，其特征在于，双(异氰酸根合甲基环己基)甲烷与所述一种或多种更易挥发的二异氰酸酯组分之间的质量比为90:10至10:90。
7.根据前述权利要求中任一项所述的方法，其特征在于，所述至少一种聚酯多元醇具有20至150的OH值和500至6000g/mol的数均分子量。
8.根据前述权利要求中任一项所述的方法，其特征在于，所述方法在无溶剂的情况下进行。
9.根据前述权利要求中任一项所述的方法，其特征在于，所述方法在40℃至80℃的温度并且在催化剂的存在下进行。
10.根据前述权利要求中任一项所述的方法，其特征在于，NCO/OH比是10:1至1.2:1。
11.可通过根据前述权利要求中任一项的方法获得的含NCO预聚物。
12.根据权利要求11的预聚物作为漆料、粘合剂、密封剂或塑料配制剂的成分的用途。
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