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CN1310995C - 用二异丙胺封闭的水性和/或水可稀释性聚异氰酸酯交联剂及其应用 - Google Patents

用二异丙胺封闭的水性和/或水可稀释性聚异氰酸酯交联剂及其应用 Download PDF

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CN1310995C
CN1310995C CNB028179633A CN02817963A CN1310995C CN 1310995 C CN1310995 C CN 1310995C CN B028179633 A CNB028179633 A CN B028179633A CN 02817963 A CN02817963 A CN 02817963A CN 1310995 C CN1310995 C CN 1310995C
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E·柯尼
J·马扎内克
H·米勒
J·佩措尔德特
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Abstract

本发明涉及用二异丙胺封闭的水性和/或水可稀释性聚异氰酸酯交联剂，其制备方法以及其在单组分烤漆，例如作为汽车涂漆中填料的应用。

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用二异丙胺封闭的水性和/或水可稀释性 聚异氰酸酯交联剂及其应用
本发明涉及用二异丙胺封闭的水性和/或水可稀释性聚异氰酸酯交联剂，其制备方法以及其在单组分烤漆，例如作为汽车涂漆中填料的应用。
封闭型聚异氰酸酯交联剂和任选的蜜胺-甲醛树脂与例如含羟基基团的聚丙烯酸酯配制形成所谓的“单组分”烤漆属于现有技术。如果所考虑的漆为水性漆，则所述各组分必须能分散在水中并且在水相中可稳定储存至少6个月。
仅存在几种能满足这些要求的异氰酸酯封闭剂。丁酮肟是一种这类封闭剂，但它要求至少30分钟/140℃的烘烤条件以确保以此封闭的聚异氰酸酯进行交联。3，5-二甲基吡唑也是一种适宜的封闭剂并且可在仅30分钟/130℃的烘烤条件下使以此封闭的聚异氰酸酯进行交联，如专利申请WO 97/12924和EP-A 0942 023中所讨论的。3，5-二甲基吡唑的缺点在于其制备方法较复杂。可通过乙酰基丙酮与肼水合物的缩合在工业规模上获得3，5-二甲基吡唑，由于例如肼水合物的性质而使该缩合反应复杂。
二异丙胺是一种易于获得的异氰酸酯封闭剂。从专利文献中可知，它用于粉末涂料和卷材涂料漆中，见EP-A 0096210和EP-A900814。
令人惊讶地发现用二异丙胺封闭的聚异氰酸酯在水相中储存时很稳定并且例如不连续放出CO2，例如，就用丙二酸二乙酯或1，2，4-三唑封闭的聚异氰酸酯来说，通常就是这样。
本发明的目的是提供储存稳定且易于获得的水性或水可稀释性封闭型聚异氰酸酯交联剂，其比用丁酮肟封闭的聚异氰酸酯交联剂具有更低的交联或烘烤温度。
该目的是由根据本发明的封闭型水性/水可稀释性聚异氰酸酯交联剂实现的。
本发明提供的水性和/或水可稀释性封闭型聚异氰酸酯交联剂包含如下组分：
a)100当量％聚异氰酸酯组分，
b)50-85当量％二异丙胺，
c)15-40当量％作为亲水试剂的单羟基-和/或二羟基-羧酸，和任选的
d)0-15当量％带有OH和/或NH2基团的双官能团扩链组分，
以及任选的添加剂和辅助物质，
其中反应物的相对比例选择为使组分a)的NCO基团与组分b)，c)和d)的异氰酸酯反应性基团的当量比为1∶0.8-1∶1.2。
本发明还提供了一种制备封闭型水性和/或水可稀释性聚异氰酸酯交联剂的方法，该方法的特征在于将聚异氰酸酯组分a)和任选的占交货形式的封闭型聚异氰酸酯交联剂30wt％的容性水混容性溶剂放入容器中，在第一反应步骤中于约80℃与用来提供亲水性的单羟基羧酸反应，然后将混合物冷却至约50℃，通过加入二异丙胺来封闭残留的NCO基团。
根据本发明的封闭型水性/水可稀释性聚异氰酸酯交联剂的制备可分步进行，例如按如下步骤进行：将聚异氰酸酯组分a)和任选的占交货形式交联剂30wt％的水混容性溶剂，例如N-甲基吡咯烷酮放入容器中，在第一反应步骤中于约80℃与用来提供亲水性的单羟基羧酸反应。然后将混合物冷却至约50℃，残留的约80％的NCO基团与二异丙胺完全地进行反应。
如果亲水作用通过使用二羟基羧酸或二-和单羟基羧酸的混合物来实现，则可以反过来首先在约40-70℃下进行与二异丙胺的封闭反应；随后进行亲水组分与残留NCO基团的反应。以这种方式可以避免生成交联的凝胶颗粒。
当加入用于中和的叔胺，例如二甲基乙醇胺后，羧酸基团被转化为亲水的羧酸根阴离子。随后可以例如通过加入另外水混容性溶剂来制备固含量约为65％、粘度(23℃)约为10,000mPa.s的水可稀释性封闭型聚异氰酸酯交联剂，或者通过加入水来制备固含量约为30％、粘度(23℃)约为400mPa.s的水分散性封闭型交联剂。
本发明还涉及根据本发明的水性和/或水可稀释性封闭型聚异氰酸酯交联剂与水溶性和/或分散性多羟基化合物相结合在制备任选包含涂料技术中的常规辅助物质和添加剂的水性烤漆中的应用。它们优选用于汽车涂漆。
根据本发明的封闭型聚异氰酸酯之基础聚异氰酸酯a)是本身已知的漆料聚异氰酸酯，带有脂族和/或环脂族键接的异氰酸酯基团并且异氰酸酯的含量为7-30wt％，优选为12-25wt％。这里特别考虑本身已知的漆料聚异氰酸酯，它们是基于1，6-二异氰酸根合己烷(HDI)、1-异氰酸根合-3，3，5-三甲基-5-异氰酸根合甲基环己烷(IPDI)和/或二(4-异氰酸根合己基)-甲烷(H12MDI)的并且含有缩二脲、异氰脲酸酯、
氨基二嗪二酮(对称的三聚物)、氨基甲酸酯和/或脲二酮基团。也可以使用任何希望的这些聚异氰酸酯与各种多元醇的预聚物，如聚酯、聚醚、聚丙烯酸酯或其混合物。
也可以使用基于芳族二异氰酸酯，如二异氰酸根合甲苯(TDI)或4，4-二异氰酸根合二苯基甲烷(MDI)的聚异氰酸酯或短链NCO预聚物。
但是，作为组分a)，基于HDI或H12MDI并且含有异氰脲酸酯基团的聚异氰酸酯是特别优选的。
根据本发明二异丙胺是仲胺组中适于作为封闭剂的。在工业上要求的130℃/30分钟的烘烤条件下它被取代或去封闭，并且像丁酮肟或3，5-二甲基吡唑一样，在水性漆料中以稳定的方式封闭异氰酸酯基团，水解后不放出CO2。
考虑作为亲水组分c)优选在α-位带有一个或两个甲基基团的单羟基-和二羟基-羧酸。特别优选羟基新戊酸(羟甲基二甲基乙酸)以及羟基新戊酸与二羟甲基丙酸的混合物。
考虑作为双官能团扩链组分d)为分子量是32-300的二胺、二醇以及羟基胺。实例为肼、乙二胺、异佛尔酮二胺、异佛尔酮二胺和甲基异丁基酮的双酮亚胺、1，4-二羟基丁烷、乙醇胺、N-甲基乙醇胺、羟乙基乙二胺、2mol碳酸异丙烯酯和1mol通式(I)的肼的加成产物：
Figure C0281796300051
适宜的中和试剂为例如二甲基乙醇胺、甲基二乙醇胺、三乙胺、N-甲基吗啉或2-氨基-2-甲基丙醇。
为了防止热黄化，可以向根据本发明的交联剂中加入作为辅助物质的稳定剂，例如肼和Tinuvin770DF型HALS胺(位阻胺光稳定剂)。也可以加入添加剂和其他辅助物质。
根据本发明的交联剂可以以最多80％的浓度分散在水可稀释性溶剂中或以最多50％的浓度占主要地位地分散在水中的形式进入循环。考虑作为水可稀释性溶剂为例如丁基二甘醇乙酸酯、丁基二甘醇、N-甲基吡咯烷酮或要求的其任意混合物。
根据本发明的聚异氰酸酯交联剂具有下列优点：
-交联剂及由其配制的水性烤漆可以稳定储存至少3个月。
-二异丙胺封闭剂是一种便宜的可大规模生产的化学品。
-水性漆料的烘烤温度为30分钟/130℃，因此比用丁酮肟封闭的交联剂低10℃。
通过下面的实施例证明了其组成的简单性和良好的抗腐蚀作用(盐雾试验)。
实施例
实施例1(根据本发明)
在此描述水可稀释性封闭型聚异氰酸酯交联剂的制备方法。
a)起始材料
196g(1.0克当量)市售基于1，6-二异氰酸根合己烷(HDI)的含异氰脲酸酯的漆料聚异氰酸酯，NCO含量为21.4wt％，23℃时的粘度为约3000mPa.s，官能度为约3.5
80.8g(0.8mol)       二异丙胺
23.6g(0.2mol)       羟基新戊酸
16.0g(0.18mol)      二甲基乙醇胺
146.0g              N-甲基吡咯烷酮
462.4g(0.8克当量)   封闭的NCO基团
                    固含量：                65wt％(计算)
                    23℃粘度：              约9000mPa.s
                    封闭的NCO含量：       7.3wt％(计算)
                    1克当量封闭的NCO基团：575g
b)实施过程
在不时进行的搅拌下将聚异氰酸酯、N-甲基吡咯烷酮和羟基新戊酸加热到80℃。在此温度继续搅拌约2小时，直到NCO含量降至约9.1％。然后让混合物冷却至约40℃，并滴加二异丙胺，温度保持在约60℃。当加完二异丙胺时，在60℃搅拌15分钟。其后通过IR光谱不能再检测到NCO基团。加入二甲基乙醇胺，让混合物冷却，得到具有开始时提到的特征的水混容性封闭聚异氰酸酯的即用型浅黄色溶液。
实施例2(根据本发明)
在此描述分散于水中的封闭型聚异氰酸酯交联剂的制备方法。
a)起始材料
196g(1.0克当量)        实施例1中已经描述的HDI三聚物
80.0g(0.8mol)          二异丙胺
17.7g(0.15mol)         羟基新戊酸，M118
3.35g(0.05克当量)      二羟甲基丙酸，M134
15.55g(0.175mol)       二甲基乙醇胺
35.6g                  N-甲基吡咯烷酮
693.0g                 水
1042.0g(0.8克当量)     封闭的NCO基团
                       固含量：                30wt％(计算)
                       23℃粘度：              约400mPa.s
                       封闭的NCO含量：       3.2wt％(计算)
                       1克当量封闭的NCO基团：1303g
b)实施过程
将聚异氰酸酯放到容器中并搅拌。从室温开始，向其中小心滴加二异丙胺。反应是放热进行的，温度保持在70℃。约1小时后，加完二异丙胺。加入羟基新戊酸、二羟甲基丙酸和N-甲基吡咯烷酮；并将混合物加热到80℃，在此温度搅拌约2小时，直到通过IR光谱不能再检测到NCO基团。随后停止供热，加入二甲基乙醇胺，搅拌10分钟，在水中于50℃搅拌。形成分散体，在约50℃搅拌3小时。然后搅拌下让分散体冷却至室温，并再搅拌3小时。分散的封闭型聚异氰酸酯交联剂具有上述特征。
实施例3(对比例)
用丁酮肟封闭的该交联剂具有与实施例2所述相似的组成。其具有下列特征：
固含量：             41wt％
23℃粘度：              约5700mPa.s
封闭的NCO含量：       3.9wt％
1克当量封闭的NCO基团：1077g
实施例4(应用)
a)透明漆料配方
  透明漆料   1   2   3
  BayhydrolVP LS 2290，Bayer AG，45％Lff.，羟基聚丙烯酸酯聚酯分散体，1克当量OH＝850g   30.1   30.5   30.3
  BayhydrolPT 241，Bayer AG，42％Lff.，羟基聚酯分散体，1克当量OH＝1889g   11.0   11.2   11.1
  根据实施例1的交联剂，1克当量NCO＝575g   24.1   -   -
  根据实施例2的交联剂，1克当量NCO＝1303g   -   55.4   -
  根据实施例3(对比例)的交联剂，1克当量NCO＝1077g   -   -   45.4
  Cymel328，85％蜜胺树脂，Dyno CytecGmbH，41460 Neuss   1.7   1.7   1.8
  AdditolXW 395，Vianova树脂，流动剂   0.6   0.6   0.6
  Surfinol104E，AirProduct/Biesterfeld，Benetzungsmittel   0.6   0.6   0.6
  蒸馏水   31.9   -   10.2
  重量份   100.0   100.0   100.0
借助于搅拌器均匀混合上述漆料组分。OH组分和封闭的交联剂以当量比1∶1加入。加入三聚氰胺树脂的作用是改善平滑表面质量。
b)储存稳定性试验
  透明漆料   1   2   3
  固含量[％]   35.2   36.3   37.7
  流出时间，ISO烧杯，5mm/23℃   40s   22s   41s
  40℃储存7天后流出时间   36s   23s   28s
上述漆料在储存期间既没有观察到粘度的显著增加也没有观察到沉淀。
c)漆料性能
通过带有喷嘴(直径1.5mm)且雾化压力为5bar的流动烧杯喷枪将上述三种漆料施涂在下列基材上得到的干燥薄膜厚度为25-35μm。湿润的漆膜于23℃暴露在空气中5分钟，然后在循环热风炉中烘烤。在摆杆硬度和溶解性试验的情况下基材为玻璃板，而在附着力试验/划格法附着力试验、埃氏冲盂试验和盐雾试验的情况下为去油钢片。
  漆料实施例   1   2   3(对比例)
  烘烤条件：30分钟/130℃
  摆杆硬度1)   203s   212s   172s
  耐溶剂性2)
  甲苯   0   0   1
  乙酸甲氧基丙酯   0   0   1
  乙酸乙酯   4   4   4
  丙酮   4   4   4
  埃氏冲盂法3)   ＞10mm   ＞10mm   ＞10mm
  划格法附着力(0-5)4)   0   0   0
  盐雾试验，144小时5)   Wd 5mm   Wd 5mm   Wd 10mm
1)摆杆硬度：根据Knig DIN 53 157的振动疲劳试验
2)耐溶剂性：无遮盖暴露于化学品中1分钟(指标0-5，0＝不溶解，5＝完全溶解)
3)根据DIN EN ISO 1520的埃氏冲盂法
4)根据DIN EN ISO 2409的划格法附着力试验
5)根据DIN 53 167的盐雾试验，Wd＝从DIN切口迁移的mm数
从上述试验可见，含有根据本发明的交联剂的漆料1和2比含有用丁酮肟封闭的聚异氰酸酯交联剂的漆料3的反应性更强。基于二异丙胺封闭剂的更高的反应性可从更大的漆料硬度、更好的耐溶剂性和改进的耐腐蚀性(在漆料下方盐溶液较小的迁移)中看出。

Claims (4)

1.水性和/或水可稀释性封闭型聚异氰酸酯交联剂，包含如下组分：
a)100当量％聚异氰酸酯成分，
b)50-85当量％二异丙胺，
c)15-40当量％作为亲水试剂的单羟基-和/或二羟基-羧酸，和任选的
d)0-15当量％含有OH-和/或NH2-基团的双官能团扩链组分，选自分子量为32-300的二胺、二醇和羟基胺，
以及添加剂和辅助物质，
其中反应物的相对比例选择为使组分a)的NCO基团与组分b)，c)和d)的异氰酸酯反应性基团的当量比为1∶0.8-1∶1.2。
2.制备根据权利要求1的封闭型水性和/或水可稀释性聚异氰酸酯交联剂的方法，该方法的特征在于，将聚异氰酸酯组分a)和任选的占完成形式的封闭型聚异氰酸酯交联剂30wt％的水混容性溶剂放入容器中，在第一反应步骤中于约80℃与用来提供亲水性的单羟基羧酸反应，然后将混合物冷却至约50℃，通过加入二异丙胺来封闭残留的NCO基团。
3.根据权利要求1的水性和/或水可稀释性封闭型聚异氰酸酯交联剂与水溶性和/或分散性多羟基化合物相结合在制备任选包含涂料技术中的常规辅助物质和添加剂的水性烤漆中的应用。
4.根据权利要求3的应用，其中所述水性烤漆用于汽车涂漆。
CNB028179633A 2001-07-13 2002-07-01 用二异丙胺封闭的水性和/或水可稀释性聚异氰酸酯交联剂及其应用 Expired - Fee Related CN1310995C (zh)

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DE10322911A1 (de) * 2003-05-21 2004-12-16 Bayer Materialscience Ag Verfestigungsstabile blockierte Polyisocyanate
DE10328994A1 (de) * 2003-06-27 2005-01-13 Bayer Materialscience Ag Blockierte Polyisocyanate
DE10328993A1 (de) * 2003-06-27 2005-01-20 Bayer Materialscience Ag Blockierte Polyisocyanate
DE102005057336A1 (de) * 2005-12-01 2007-06-14 Bayer Materialscience Ag Herstellung einer Vernetzer-Dispersion mit blockierten Isocyanatgruppen
CN102816294B (zh) * 2012-08-17 2014-06-18 浙江传化股份有限公司 一种水溶性封闭异氰酸酯交联剂的制备方法
CA3026456A1 (en) * 2016-06-03 2017-12-07 Huntsman International Llc A blocked isocyanate composition
CN109206592B (zh) * 2017-07-06 2021-05-28 盐城圣康新材料科技有限公司 一种水性封闭型聚异氰酸酯交联剂及其制备方法
CN107955126B (zh) * 2017-12-01 2020-08-28 万华化学（宁波）有限公司 一种聚氨酯-聚脲多元醇的水分散体及其制备方法
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