CN104321357B - 含碳二亚胺的组合物用于控制适用期的用途 - Google Patents
含碳二亚胺的组合物用于控制适用期的用途 Download PDFInfo
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Abstract
本发明涉及含碳二亚胺的组合物用于在制造聚氨酯(PU)基体系、优选PU弹性体、PU粘合剂、PU铸塑树脂或PU泡沫中控制适用期的用途。
Description
本发明涉及含碳二亚胺的组合物用于在生产聚氨酯(PU)基体系、优选PU弹性体、PU粘合剂、PU铸塑树脂或PU泡沫中控制适用期(pot life)的用途。
聚氨酯通过聚异氰酸酯与多羟基醇(多元醇)的以一种实际上定量的方式的聚加成反应或缩聚反应形成。键联通过一个分子的异氰酸酯基(–N=C=O)与另一个分子的羟基(-OH)的反应以形成一个尿烷基团(-NH-CO-O-)发生。
二异氰酸酯与多元醇之间的反应过程取决于这些组分的摩尔比。可以相当可能地获得具有所希望的平均分子量和所希望的端基的中间体。然后,可以使这些中间体与一种二醇或二胺在后面的连接点(later juncture)反应(链延长),在这情况下,形成所希望的聚氨酯或聚氨酯-聚脲混合物。这些中间体通常被称为预聚合物。
用于生产预聚合物的合适的多元醇不但是二元醇而且还是聚亚烷基乙二醇醚、具有末端羟基的聚醚酯或聚酯(聚酯多元醇)。
为了制备机械或动态持久的聚氨酯,优选使用聚酯多元醇。
通过简单的二元醇与羧酸的缩聚制备的、具有末端羟基的聚醚酯或聚酯仍然包含游离的羧酸。这些催化存在于该预聚合物中的游离异氰酸酯基与链延长所需要的二胺之间的反应,这导致短的适用期并且使该反应不可控。此外,这些经常具有低的水解稳定性。
市场上目前可得到的碳二亚胺,如在EP-A 0799843中描述的,对于在制备预聚合物允许的时间内的快速酸降解是太慢反应的,或由于过低的溶解度是不可用的和不经济的。
因此,本发明的一个目的是提供适用于生产聚氨酯(PU)基体系、尤其适用于生产PU弹性体、PU粘合剂或PU铸塑树脂或PU泡沫的组合物,它们是以水解稳定的形式并且以一种经济上可行的方式可生产的,并且它们具有可接受的适用期而不需要昂贵并且难以制备的材料。
出人意料地,这个目的通过使用特别的含碳二亚胺的组合物得以实现。
因此,本发明提供了组合物用于控制适用期的用途,这些组合物包括
至少一种多元醇以及
至少一种具有式(I)的碳二亚胺
R1-(O)-OC-HN-(R-N=C=N-)m-R-NH-CO-(O)-R1(I),
其中m=1至40,
R是C6-C18-亚烷基或C6-C18-亚环烷基,优选
R1是C1-C4-烷基或一个-(CH2)h-O-[(CH2)k-O]g-R2基团,
其中h=1-3,k=1-3,g=5-20,并且R2是H或C1-C4-烷基、优选CH3。
在本发明的另一个优选的实施例中,所使用的碳二亚胺是具有式(I)的一种化合物,其中
m=10-30,
R是C6-C18-亚烷基或C6-C18-亚环烷基,优选
R1是C1-C4-烷基或者一个-(CH2)h-O-[(CH2)k-O]g-R2基团,
其中h=1-3,k=1-3,g=10-12,并且R2=H或C1-C4-烷基,优选CH3。
在本发明的另一个特别优选的实施例中,该具有式(I)的碳二亚胺是以下的一种化合物,在这种化合物中
m=20,
R定义为C6-C18-亚烷基或C6-C18-亚环烷基,优选
R1是一个-(CH2)h-O-[(CH2)k-O]g-R2基团,
其中h=2、k=2、g=10-12,并且R2是CH3。
优选地,R具有在具有式(I)的碳二亚胺范围内的相同的定义。
具有式(I)的化合物是例如从莱茵化学莱脑有限公司(Rhein Chemie RheinauGmbH)、例如在商品名下可获得的商用化学品。
同样给予优选的是多种具有式(I)的碳二亚胺的混合物。在一种混合物的情况下,对于m的平均值的确定还可能产生分数。
在本发明的背景下,这些多元醇是优选地具有以(g/mol)表示的高达2000、优选地在从500至2000的范围中的并且更优选地在从500至1000的范围中的分子量的化合物。
术语“多元醇”在本发明的背景下涵盖每分子具有两个或三个羟基的化合物以及每分子具有多于三个羟基的化合物两者。
优选的多元醇是聚酯多元醇和/或聚醚酯多元醇,更优选聚酯多元醇。
当该多元醇具有高达200、优选地在20与150之间并且更优选地在50与115之间的OH数量时是有利的。
尤其合适的是多种二元醇与芳香族或脂肪族二羧酸和/或内酯的聚合物的反应产物的聚酯多元醇。
在此,给予优选的是芳香族二羧酸,它们可以用于形成适合的聚酯多元醇。在此,给予特别优选的是对苯二甲酸、间苯二甲酸、邻苯二甲酸、邻苯二甲酸酐、以及取代的具有一个苯环的二羧酸化合物。
优选的脂肪族二羧酸是可以用于形成合适的聚酯多元醇的那些,更优选癸二酸、己二酸和戊二酸。
优选的内酯聚合物是可以用于形成合适的聚酯多元醇的那些,更优选聚己酸内酯。
这些二羧酸和内酯聚合物都是商用化学品。
还给予特别优选的是可以用于形成适合的聚酯多元醇的那些二元醇,更优选乙二醇、丁二醇、新戊二醇、己二醇、丙二醇、二丙二醇、二乙二醇以及环己烷二甲醇。
为此目的,给予优选的是多种上述多元醇与芳香族或脂肪族二羧酸和/或内酯的聚合物(例如聚己酸内酯)的反应产物。
在本发明的背景下所使用的多元醇是从拜耳材料科技股份有限公司(BayerMaterialScience AG)在商品名下可获得的商用化学品。
在本发明的另一个实施例中,该组合物附加地包括至少一种二异氰酸酯。
优选的二异氰酸酯是芳香族和脂肪族二异氰酸酯。给予特别优选的是甲苯2,4-二异氰酸酯、甲苯2,6-二异氰酸酯、亚苯基二异氰酸酯、4,4-二苯甲烷二异氰酸酯、亚甲基双(4-苯基异氰酸酯)、萘1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯和/或六亚甲基1,6-二异氰酸酯,非常特别优选的是甲苯2,4-二异氰酸酯和甲苯2,6-二异氰酸酯。
在本发明的背景下所使用的二异氰酸酯是从拜耳材料科技股份有限公司在商品名下可获得的商用化学品。
在本发明的另一个实施例中,该组合物附加地包括至少一种二胺。
用于链延长的优选的二胺是2-甲基丙基3,5-二氨基-4-氯代苯甲酸、双(4,4′-氨基-3-氯苯基)甲烷、3,5-二甲硫基-2,4-甲苯二胺(tolylenediamine)、3,5-二甲硫基-2,4-甲苯二胺、3,5-二乙基-2,4-甲苯二胺、3,5-二乙基-2,6-甲苯二胺、4,4′-亚甲基双(3-氯-2,6-二乙基苯胺)和1,3-丙二醇双(4-氨基苯甲酸酯)。
在本发明的背景下用于链延长的二胺是从莱茵化学莱脑有限公司在商品名下可获得的商用化学品。
碳二亚胺与多元醇的比例优选为每100重量份多元醇0.1-5重量份,更优选1-3重量份。
二异氰酸酯与多元醇的比例优选为20至50:100重量份,更优选30:100重量份。
在其中该组合物不但包括该多元醇和该碳二亚胺以及该二异氰酸酯,而且附加地包括至少一种二胺的情况下,该二胺的量基于该组合物是按重量计5%-30%。
本发明附加地提供了本发明组合物的生产,其中将该多元醇最初地进料并且搅拌进具有式(I)的碳二亚胺或具有式(I)的碳二亚胺的一种混合物。
在其中本发明的混合物附加地包括二异氰酸酯的情况下,在80℃与130℃之间的温度下将该二异氰酸酯搅拌进由多元醇和至少一种具有式(I)的碳二亚胺组成的组合物中。
在其中本发明的混合物不但包括该二异氰酸酯,而且附加地包括一种二胺的情况下,在从40℃至130℃范围内的温度下将该二胺搅拌进由多元醇和至少一种具有式(I)的碳二亚胺和二异氰酸酯组成的组合物中。
上述组合物优选地在PU弹性体、粘合剂或铸塑树脂中用于控制适用期和/或用作抵御水解降解的防护。
本发明的范围包括以上和以下提及的所有的一般基团定义、指标、参数和解释,以及在彼此优选的范围内,即,还有在对应范围与优选范围之间的任何组合内提及的那些。
以下实例用于说明本发明,但是不具有限制性作用。
工作实例
在以下实例中,使用以下物质:
2000MM,具有56mg KOH/g的OH数量和0.83mg KOH/g酸值的、来自拜耳材料科技股份有限公司的一种直链聚酯多元醇。
一种具有式(I)的碳二亚胺,该式(I)具有20的平均m,R1=-(CH2)h-O-[(CH2)k-O]g-R2其中R2=甲基、h=2、k=2并且g=10-12。
P200,一种基于四甲基二甲苯二异氰酸酯的聚合的芳香族碳二亚胺,来自莱茵化学莱脑有限公司。
I,一种基于2,6-二异丙基苯基异氰酸酯的单体碳二亚胺,来自莱茵化学莱脑有限公司。
T100,一种来自拜耳材料科学公司(Bayer Material Science)的甲代亚苯基2,4-二异氰酸酯。
1604,一种来自莱茵化学莱脑有限公司的2-甲基丙基3,5-二氨基-4-氯代苯甲酸作为二胺组分。
HMV-8CA:一种来自日清纺工业株式会社(Nisshinbo Industries,INC)的聚合的脂肪族碳二亚胺。
如下制备以下混合物:
混合物A(对比):在100℃下熔化100g的2000MZ。
混合物B(本发明的):在100℃下熔化100g的2000MZ并且将其与0.6g的具有式(I)的碳二亚胺混合,该式(I)具有20的平均m,R1=-(CH2)l-O-[(CH2)k-O]g-R2其中R2=甲基,
h=2、k=2并且g=10-12。
混合物C(对比):在100℃下熔化100g的2000MM并且将其与0.6g的基于2,6-二异丙基苯基异氰酸酯的单体碳二亚胺混合。
混合物D(对比):
将100g的2000MM与0.6g的HMV-8CA混合并且将其在30℃下储存24h。这两种物质是不互混的。因此,这种混合物对于进一步的试验是不可用的。
所有数字都是以重量份表示的,除非另行说明。
表1:
C=对比实例,inv.=本发明的
使混合物A至C在80℃的温度下与表2中指定的量的T100反应一直到异氰酸酯含量为5%,并且然后以表2中指定的量与1604扩链剂反应。确定了以下混合物的适用期,该混合物仍然是液体,在几分钟之后胶凝并且反应以产生一种固体弹性体。该适用期是在混合一种多组分物质与可加工性结束之间的时间。确定的值在表3中示出。
表2:
混合物 | 以秒表示的适用期 |
I | 240 |
II | 420 |
III | 340 |
试验结果的解释:
从混合物II的值明显可以看出,包括本发明的具有式(I)的碳二亚胺的混合物导致适用期的明显延长并且因此导致加工性的改进,该式(I)具有20的平均m,R1=-(CH2)l-O-[(CH2)k-O]g-R2,其中R2=甲基、I=2、k=2并且g=10-12。
Claims (17)
1.包括以下各项的组合物用于在生产聚氨酯基体系中控制适用期的用途:
-至少一种多元醇以及
-至少一种具有式(I)的碳二亚胺
R1-(O)-OC-HN-(R-N=C=N-)m-R-NH-CO-(O)-R1(I),
其中m=1至40,
其中R是:
并且R1是-(CH2)h-O-[(CH2)k-O]g-R2,其中
h=1-3,k=1-3,g=5-20,并且其中R2是H或C1-C4烷基。
2.如权利要求1所述的用途,其特征在于,在该具有式(I)的碳二亚胺中,其中m=10-30并且g=10-12。
3.如权利要求1所述的用途,其特征在于,在该具有式(I)的碳二亚胺中,其中m=20,h=2,k=2,g=10-12,并且R2是CH3。
4.如权利要求1至3中任一项所述的用途,其特征在于,这些碳二亚胺是多种具有该式(I)的碳二亚胺的混合物。
5.如权利要求1所述的用途,其特征在于,
h=2,k=2,并且g=10-12,并且R2是CH3。
6.如权利要求1至3中任一项所述的用途,其特征在于,该多元醇包括聚酯类多元醇和/或聚醚酯类多元醇。
7.如权利要求6所述的用途,其特征在于,该多元醇具有20至150之间的OH数量。
8.如权利要求6所述的用途,其特征在于,该多元醇具有50至115之间的OH数量。
9.如权利要求1至3中任一项所述的用途,其特征在于,这些组合物附加地包括至少一种二异氰酸酯。
10.如权利要求9所述的用途,其特征在于,该二异氰酸酯是甲苯2,4-二异氰酸酯、甲苯2,6-二异氰酸酯、亚苯基二异氰酸酯、4,4’-二苯甲烷二异氰酸酯、亚甲基双(4-苯基异氰酸酯)、萘1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯和/或六亚甲基1,6-二异氰酸酯。
11.如权利要求9所述的用途,其特征在于,该二异氰酸酯是甲苯2,4-二异氰酸酯和甲苯2,6-二异氰酸酯。
12.如权利要求1至3中任一项所述的用途,其特征在于,这些组合物包括至少一种催化剂。
13.如权利要求1至3中任一项所述的用途,其特征在于,这些组合物附加地包括至少一种二胺。
14.如权利要求13所述的用途,其特征在于,用于链延长的该二胺是2-甲基丙基3,5-二氨基-4-氯代苯甲酸、双(4,4′-氨基-3-氯苯基)甲烷、3,5-二甲硫基-2,4-甲苯二胺、3,5-二甲硫基-2,4-甲苯二胺、3,5-二乙基-2,4-甲苯二胺、3,5-二乙基-2,6-甲苯二胺、4,4′-亚甲基双(3-氯-2,6-二乙基苯胺)和1,3-丙二醇双(4-氨基苯甲酸酯)。
15.如权利要求1至3中任一项所述的用途,其特征在于,碳二亚胺与多元醇的比例为0.1-5重量份碳二亚胺每100重量份多元醇。
16.如权利要求9所述的用途,其特征在于,二异氰酸酯与多元醇的比例为20至50:100重量份。
17.如权利要求13所述的用途,其特征在于,该组合物附加地包括至少一种二胺,该二胺的量基于该组合物是按重量计5%-30%。
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CN1805984A (zh) * | 2003-07-03 | 2006-07-19 | 斯塔尔国际有限公司 | 不含有机溶剂而且可作为交联剂的稳定的聚碳二亚胺水分散体的制备方法 |
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DE2020330A1 (de) * | 1970-04-25 | 1971-11-11 | Glanzstoff Ag | Verfahren zur Verbesserung der Stabilitaet von Polyestern |
EP0647701B1 (en) * | 1993-03-25 | 1999-10-06 | Asahi Denka Kogyo Kabushiki Kaisha | Refrigerator lubricant and refrigerant composition containing the same |
JP3629041B2 (ja) * | 1994-06-10 | 2005-03-16 | 日清紡績株式会社 | 水性テトラメチルキシリレンカルボジイミド |
JPH09235516A (ja) * | 1996-02-29 | 1997-09-09 | Nisshinbo Ind Inc | プレコートメタル用塗料 |
JPH09255752A (ja) * | 1996-03-22 | 1997-09-30 | Nisshinbo Ind Inc | ウレタン樹脂の製造方法 |
JP3422642B2 (ja) * | 1996-12-24 | 2003-06-30 | 日清紡績株式会社 | エステル基を有する樹脂の微生物による劣化に対する耐性を向上する薬剤及び同方法 |
JP3936813B2 (ja) | 1998-10-29 | 2007-06-27 | 三洋化成工業株式会社 | 摺動性ウレタンエラストマー成形体 |
JP4278265B2 (ja) | 1999-04-30 | 2009-06-10 | 日本ペイント株式会社 | 熱硬化性水性塗料組成物およびこれを用いた塗膜形成方法、ならびに、複層塗膜形成方法 |
JP2006016556A (ja) | 2004-07-05 | 2006-01-19 | Nisshinbo Ind Inc | 硬化塗膜の製造方法 |
WO2007090735A1 (de) * | 2006-02-03 | 2007-08-16 | Basf Se | Verfahren zum behandeln von substraten |
JP4916007B2 (ja) * | 2007-03-01 | 2012-04-11 | 三洋化成工業株式会社 | スラッシュ成形用樹脂粉末組成物及び成形品 |
JP5408888B2 (ja) * | 2008-03-13 | 2014-02-05 | 日本ペイント株式会社 | 水分散型樹脂、二液型熱硬化性樹脂組成物及びこれらの製造方法 |
JP5539623B2 (ja) * | 2008-03-27 | 2014-07-02 | 日清紡ホールディングス株式会社 | カルボジイミド化合物、カルボジイミド組成物及び水性塗料組成物 |
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US6153718A (en) * | 1996-04-02 | 2000-11-28 | Nisshinbo Industries, Inc. | Polyurethane resins |
CN1805984A (zh) * | 2003-07-03 | 2006-07-19 | 斯塔尔国际有限公司 | 不含有机溶剂而且可作为交联剂的稳定的聚碳二亚胺水分散体的制备方法 |
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EP2660258A1 (de) | 2013-11-06 |
PT2844682T (pt) | 2018-03-01 |
US20150133624A1 (en) | 2015-05-14 |
KR101993499B1 (ko) | 2019-06-26 |
CA2871802A1 (en) | 2013-11-07 |
WO2013164136A1 (de) | 2013-11-07 |
EP2844682B1 (de) | 2017-12-13 |
MX2014013361A (es) | 2015-02-10 |
ES2660759T3 (es) | 2018-03-26 |
EP2844682A1 (de) | 2015-03-11 |
RU2014148482A (ru) | 2016-06-27 |
JP2015516004A (ja) | 2015-06-04 |
US9540480B2 (en) | 2017-01-10 |
CN104321357A (zh) | 2015-01-28 |
PL2844682T3 (pl) | 2018-05-30 |
BR112014027443A2 (pt) | 2017-06-27 |
MX364233B (es) | 2019-04-16 |
KR20150003390A (ko) | 2015-01-08 |
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