CN102336887A - 包含作为脱水剂的甲硅烷基衍生物的组合物 - Google Patents
包含作为脱水剂的甲硅烷基衍生物的组合物 Download PDFInfo
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Abstract
本发明公开了一种组合物，包含具有最多5％二异氰酸酯单体的异氰酸酯亚组合物，选自带有连接到硫族的准金属上或氮族的原子上的二烃基甲硅烷基基团的化合物的脱水剂。本发明可应用于涂料工业，特别是油漆和粘合剂。
Description
本分案申请是基于申请号为200580047562.0，申请日为2005年12月20日，发明名称为“具有良好混合性能的异氰酸酯组合物和甲硅烷基化衍生物作为异氰酸酯组合物的辅助剂特别是混合辅助剂的用途”的中国专利申请的分案申请。
技术领域
本发明涉及具有良好混合性能的异氰酸酯组合物，更特别地涉及甲硅烷基化衍生物作为脱水剂的用途，以改进异氰酸酯组合物与在例如涂料和粘合剂的交联领域中所用的各种溶剂的相容性。
背景技术
多异氰酸酯组合物通常由二、三或四异氰酸酯的低聚缩合生成的衍生物构成并且在本领域中是公知的。异氰酸酯官能团与具有可提取氢的共反应物的交联通常在溶剂中进行，尽管由于溶剂方面越来越严格的规章，溶剂的量近年来被显著降低。
共反应物以及其它附加组分如溶剂可能包含损害多异氰酸酯反应的杂质。在这些杂质中，具有含可提取氢的官能团的那些往往是有害的。难应付的杂质之一是附加组分和溶剂中存在的水。这对于极性溶剂来说是特别相关的(参见Vogel的Textbook of Production Organic第5版Amedis 5，第1442页)。能够在环境条件下溶解至少0.5重量％水的溶剂特别受该问题困扰。当附加组分尤其是溶剂中溶解了水时，水解反应特别有害。此外，异氰酸酯官能团的含量降低。这种水解反应由于两点是难应付的：首先，释放出二氧化碳气体，其次，存在形成脲的风险。因此需要找到可以防止水解反应的技术。
二氧化碳气体的释放是储存中的另一缺点，包含异氰酸酯组合物的容器存在过压，甚至爆炸的风险。使用传统脱水剂是不够的，因为异氰酸酯官能团本身极其渴望水并且通常被用作吸水剂。
发明内容
因此本发明的目标之一是找到能够防止由于例如差脱水组分中存在湿气而生成二氧化碳气体和不溶脲的脱水剂。本发明的另一目标是提供可用于具有脂族性质的异氰酸酯官能团并因此可用于脂族单体、它们的混合物甚至可用于脂族和芳族单体的混合物的技术。本发明的另一目标是提供可以促进异氰酸酯组合物与通常不推荐与异氰酸酯一起使用且没有预先脱水的标准级别溶剂的混合而不损害所述异氰酸酯组合物(特别是在与具有吸湿性质的溶剂混合之后或过程中获得的那些组合物)的可储存性的技术。本发明的另一目标是提供具有良好耐湿性并可以无损地承受容纳所述异氰酸酯组合物的容器的频繁开关而不用采取限制性的预防措施的异氰酸酯组合物。这些目标和随后变得显而易见的其它目标通过下述组合物实现，该组合物包含至少一种具有最多5％，例如最多2％，或者最多1％的二异氰酸酯单体的异氰酸酯亚组合物，至少一种下式的脱水剂：
其中Z是烃基，硅氧烷基(silanoxanyl)或者硅氮烷基，Hc和Hc’独立地是具有至多15个碳原子的烃基，v代表0或1，并且Y是：
i)氨基，任选地具有选自如下的取代基：含氧酸在去除羟基之后的残基，烃基，三烃基甲硅烷基，和下式的基团；
其中Hc°、Hc°’和Z’分别具有前述针对Hc、Hc’和Z的定义，或者
ii)带有取代基的硒、硫或氧原子，该取代基是含氧酸如羧酸、烃基硫酸、磺酸、亚磺酸、磷酸、膦酸或次膦酸在去除羟基之后的残基，
以及至少一种不可烷基化的有机或无机碱，其用量为以硅原子当量表示的二烃基亚甲硅烷基的量的至少0.1倍，优选至少2倍。
在本发明的优选实施方案中，所述脱水剂具有至少0.1‰并且至多3％的二烃基亚甲硅烷基基团的含量，以基于所产生的单体单元的量计算的硅原子的重量表示。
本发明的组合物合适地另外包含至少一种具有可提取氢的多官能亚组合物，至少一种表面活性剂和/或至少一种溶剂如具有极性官能团的吸湿溶剂。当然，尽管不是优选的，所述亚组合物可以与在本领域中传统已知的脱水剂一起使用。
特别有利的表面活性剂包括通过向异氰酸酯上接枝具有聚环氧烷基团如聚环氧乙烷基团的分子而获得的那些表面活性剂。这可以通过异氰酸酯官能团与聚环氧烷之间的缩合进行，该聚环氧烷的两个末端中的至少一个带有具有可提取氢的官能团，特别是醇或胺官能团。表面活性剂还可以选自其它离子化合物，例如烷基硫酸盐或磷酸盐、烷基膦酸盐、烷基亚膦酸盐、烷基磺酸盐、脂肪酸盐和/或两性离子盐，以及选自非离子化合物。
所述烃基合适地并且优选地选自芳基和烷基如甲基、乙基、丙基和丁基。术语烷基，包括芳烷基，取自已经去除了羟基的烷基醇。
有利地，二烃基甲硅烷基具有至多8个，优选至多7个，更优选至多4个碳原子。希望二烃基甲硅烷基具有至多8个，优选至多7个，更优选至多4个碳原子，并且三烃基甲硅烷基具有至多10个，优选至多9个，更优选至多6个碳原子。所述二烃基甲硅烷基还可以是环成员。
所述不可烷基化的有机或无机碱优选是相对较弱的碱，这些碱不与异氰酸酯官能团反应。优选的碱包括叔胺和叔膦，其是至少部分芳族的，也就是单、二或三芳族的(单、二或三芳基)。
在本发明的特别优选的实施方案中，所述脱水剂选自双三甲基甲硅烷基乙酰胺，双三甲基甲硅烷基脲，六甲基二硅氮烷和三甲基甲硅烷基磷酸酯。
当使用吸湿溶剂和/或对水具有高亲合力的溶剂如能够溶解至少5重量％如至少10重量％水或者与至少5重量％如至少10重量％水混溶的溶剂时，本发明特别有利。
当然，尽管并不是优选的，所述亚组合物可与传统脱水剂一起使用。
具体实施方式
下列非限制性实施例例证了本发明。
在此研究中所用的组合物如下：
乙酸甲氧基丙酯(MPA)：55重量％，最后时刻添加，并导致500ppm水存在；
亲水多异氰酸酯组合物：
-4.66％被包含13个碳原子和6个环氧乙烷单元的聚乙氧基化醇酯化的磷酸酯；单/二比率70/30
-4.66％被包含8个环氧乙烷单元的聚乙氧基化醇酯化的磷酸酯；单/二比率70/304.66％；4％非离子型
-2.22％二甲基环己胺(DMCHA)
适量，对于基于具有低粘度且三聚物与总重量的比率为0.6(数学舍入)的HDI的100％异氰酸酯组合物：
-NCO 23％
-粘度(23℃)600mPa.s
-当量重量183
-100％固含量
-官能度3.25
水的检测(通过Karl-Fischer)表明，该固化剂组合物平均包含0.5重量‰的水。
所研究的被评价的脱水剂是：
-对比：
唑啉(来自Industrial Copolymer的Incozol 2)
-实施方案甲硅烷基化的结构：双三甲基甲硅烷基乙酰胺(BSA)
双三甲基甲硅烷基脲(BSU)
六甲基二硅氮烷(HMDZ)
三甲基甲硅烷基磷酸酯(TMSP)
所有甲硅烷基化产品由Aldrich提供。
组成
所评价的制剂的组成在下表I中给出。混合物3至10在添加脱水剂的情况下配制，同时计入在进一步添加水之前在最初加入混合物1的乙酸酯的添加过程中加入的500ppm。在所有情况下，最后(即，在加入脱水剂之后)加入外加的水以避免与NCO官能团的任何反应。
混合物8和11在超声浴中花费30分钟以确保BSU和TMSP溶解。
气体释放的监测
使用有刻度的注射器测量在使用隔膜密闭的烧瓶中27克溶液生成的气体量，由此监测存在和不存在根据本发明的实施方案的脱水剂时的气体释放。异氰酸酯组合物保持在40℃。每天进行测量。在用注射器穿孔以量化释放出的气体体积之后，将该隔膜换成新隔膜。
结果
混合物3、4、5和6在40℃21天的稳定性试验期间保持不变且没有任何显著的气体释放。包含超过5000ppm水的混合物2在40℃仅数小时后就变化，在密闭烧瓶中观察到轻微混浊的化学凝胶。气体释放的测量表明在40℃24小时后剧烈释放出24毫升。这种变化符合NCO官能团与水的预期反应，其导致CO2的生成。通过用包含根据本发明实施方案的脱水剂的混合物获得的结果，清楚证明受试脱水剂的影响。包含Incozol 2的混合物7在40℃数小时后脱气。此外，通过Karl-Fischer法随时间监测制剂13和14中的水量，由此量化水从制剂中的消除。
详细的结果在下表II中给出。
表II
动态监控混合物13和14的水与NCO官能团的消耗
Claims (12)
1.组合物，包含至少一种具有最多5重量％的二异氰酸酯单体的异氰酸酯亚组合物，至少一种下式的脱水剂：
其中Z是烃基，硅氧烷基或者硅氮烷基，Hc和Hc’独立地是具有至多15个碳原子的烃基，v是0或1，并且Y是：
i)氨基，任选地具有选自如下的取代基：含氧酸在去除羟基之后的残基，烃基，三烃基甲硅烷基，以及下式的基团；
其中Hc°、Hc°’和Z’分别具有前述针对Hc、Hc’和Z的定义，或者
ii)带有取代基的硒、硫或氧原子，该取代基是含氧酸在去除羟基之后的残基，
以及
至少一种不可烷基化的有机或无机碱，其用量为以硅原子当量表示的二烃基亚甲硅烷基的量的至少0.1倍。
2.权利要求1的组合物，所述亚组合物包含最多2重量％的二异氰酸酯单体。
3.权利要求1的组合物，所述亚组合物包含最多1重量％的二异氰酸酯单体。
4.权利要求1的组合物，所述脱水剂具有至少0.1‰并且至多3％的二烃基亚甲硅烷基基团的含量，以基于所产生的单体单元的量计算的硅原子的重量表示。
5.权利要求1的组合物，所述含氧酸是羧酸、烃基硫酸、磺酸、亚磺酸、磷酸、膦酸或次膦酸。
6.权利要求1的组合物，所述碱存在的量为以硅原子当量表示的二烃基亚甲硅烷基的量的至少2倍。
7.权利要求1的组合物，所述组合物另外包含具有可提取氢的多官能亚组合物。
8.权利要求1的组合物，所述组合物另外包含至少一种表面活性剂。
9.权利要求1的组合物，所述组合物另外包含溶剂。
10.权利要求1的组合物，所述溶剂是具有极性官能团的吸湿溶剂。
11.权利要求1的组合物，所述脱水剂选自双-三甲基甲硅烷基乙酰胺，双-三甲基甲硅烷基脲，六甲基二硅氮烷和三甲基甲硅烷基磷酸酯。
12.权利要求1的组合物，所述不可烷基化的有机或无机碱是叔胺或叔膦，其是至少部分芳族的。
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| FR0413847A FR2880021B1 (fr) | 2004-12-23 | 2004-12-23 | Compositions isocyanates presentant de bonnes proprietes de melange et utilisation de derives silyles comme adjuvants de compositions isocyanates, notamment de melange |
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| US9617402B2 (en) | 2011-10-28 | 2017-04-11 | Basf Se | Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates |
| EP2773612B1 (de) | 2011-10-28 | 2018-12-12 | Basf Se | Verfahren zur herstellung von in lösungsmitteln flockulationsstabilen polyisocyanaten von (cyclo)aliphatischen diisocyanaten |
| EP3517559B1 (en) * | 2016-09-23 | 2021-02-24 | Asahi Kasei Kabushiki Kaisha | Polyisocyanate composition, block polyisocyanate composition, coating composition, aqueous coating composition, and coating base material |
| EP3305863A1 (de) | 2016-10-07 | 2018-04-11 | Basf Se | Verfahren zur herstellung von in lösungsmitteln flockulationsstabilen polyisocyanaten von (cyclo)aliphatischen diisocyanaten |
| EP3336118A1 (de) * | 2017-09-20 | 2018-06-20 | Basf Se | Farbstabile härterzusammensetzungen enthaltend polyisocyanate (cyclo)aliphatischer diisocyanate |
| EP3336117A1 (de) * | 2017-09-20 | 2018-06-20 | Basf Se | Verfahren zur herstellung von in lösungsmitteln flockulationsstabilen polyisocyanaten von (cyclo)aliphatischen diisocyanaten |
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| EP0765893A1 (en) * | 1995-09-29 | 1997-04-02 | Bayer Corporation | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
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| JPS5813557A (ja) * | 1981-07-15 | 1983-01-26 | Nippon Polyurethan Kogyo Kk | イソシアネ−ト組成物 |
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| US5223174A (en) * | 1991-08-15 | 1993-06-29 | Angus Chemical Company | Moisture-scavenging iminoalcohol-oxazolidine mixtures |
| JPH05345871A (ja) * | 1992-06-16 | 1993-12-27 | Kansai Paint Co Ltd | 硬化剤組成物 |
| CN1126476A (zh) * | 1993-07-10 | 1996-07-10 | 纽恩希里茨化工厂有限公司 | 制备有机硅氧烷或聚有机硅氧烷用的催化剂 |
| JPH0841353A (ja) * | 1994-08-01 | 1996-02-13 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
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| JP4201582B2 (ja) * | 2002-11-26 | 2008-12-24 | 旭化成ケミカルズ株式会社 | イソシアヌレート基を含有するポリイソシアネート組成物 |
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| US3598852A (en) * | 1967-09-20 | 1971-08-10 | Gen Electric | Method of preparing isocyanurate containing organosilicon materials |
| US4412073A (en) * | 1981-02-03 | 1983-10-25 | Rhone-Poulenc Specialites Chimiques | Isocyanurate preparation by catalytic, aminosilyl initiated cyclotrimerization of isocyanates |
| US4762879A (en) * | 1986-04-28 | 1988-08-09 | Rhone-Poulenc Chimie | Single-component, storage-stable diorganopolysiloxane CVE compositions |
| EP0765893A1 (en) * | 1995-09-29 | 1997-04-02 | Bayer Corporation | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
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| Publication number | Publication date |
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| EP1833785B1 (fr) | 2013-10-23 |
| WO2006070100A1 (fr) | 2006-07-06 |
| KR100939942B1 (ko) | 2010-02-04 |
| JP2008529973A (ja) | 2008-08-07 |
| CN102336887B (zh) | 2013-12-11 |
| EP1833785A1 (fr) | 2007-09-19 |
| JP5039562B2 (ja) | 2012-10-03 |
| FR2880021B1 (fr) | 2007-02-09 |
| PL1833785T3 (pl) | 2014-02-28 |
| CN101111474A (zh) | 2008-01-23 |
| FR2880021A1 (fr) | 2006-06-30 |
| KR20070087685A (ko) | 2007-08-28 |
| ES2440691T3 (es) | 2014-01-30 |
| US20080257214A1 (en) | 2008-10-23 |
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