CN1299384A - 一种物质体系 - Google Patents

一种物质体系 Download PDF

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CN1299384A
CN1299384A CN99805666A CN99805666A CN1299384A CN 1299384 A CN1299384 A CN 1299384A CN 99805666 A CN99805666 A CN 99805666A CN 99805666 A CN99805666 A CN 99805666A CN 1299384 A CN1299384 A CN 1299384A
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component dispersion
dispersion according
component
isocyanate
dispersion
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C·特尔弗洛斯
D·古瑟
T·希波尔德
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
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Abstract

一种低温(低于70℃)便可交联的含钝化异氰酸酯类的单组分分散体。

Description

一种物质体系
本发明涉及权利要求1的单组分分散体。
当前，高性能粘合剂粘合是按照本领域采用反应性粘合剂实现的。已知一系列用于此目的不同粘合剂体系。由于具有高反应性，多异氰酸酯广泛被用在这一领域中的许多用途。
例如，有一类异氰酸酯端基聚合物，在加湿以后发生交联。此类体系的缺点是需要长时间才能固化，因为交联反应取决于水的扩散速率。再有，当各层非常粘稠时，交联反应可能仍然进行得不完全。
双组分粘合剂是在二者临施涂之前彼此混合的，这意味着使用者需要完成附加的步骤。再者，在调配双组分体系期间，可能出现配比或混合方面的误差。
此外，单组分体系也是已知的，它可通过以单官能反应物封堵异氰酸酯来配制。所述封堵是热可逆的，因此在提高温度时，封堵剂便分离出去，于是，被释放的异氰酸酯便与反应性聚合物基团通过交联反应形成热稳定的结合。
此类体系的缺点是，如果所述封堵剂在施涂温度下能够挥发，则它将蒸发并从而构成对环境的负担或者，如果所述封堵剂依然留在粘合剂中，它将导致所述粘合剂品质的恶化或降解。
EP 0 204 970公开了一种通过以稳定剂处理所述多异氰酸酯制备一种由细粉末多并氰酸酯在液体中组成的稳定分散体的方法。为制备多异氰酸酯的，特别是固态多异氰酸酯的贮存-稳定分散体，以及为防止与分散介质发生过早的、不希望的反应，使该分散的异氰酸酯的表面钝化。于是，它们便具有一种所谓受阻滞的反应性。
EP 0 204 970还公开了按照所述文献方法制备的所述细粉末多异氰酸酯的稳定分散体作为交联剂的应用。该多异氰酸酯的稳定化是通过施加聚合物外壳实现的。用于形成此种聚合物外壳的化合物被称作稳定剂。钝化的多异氰酸酯，包括所述聚合物外壳在内，被称作稳定化多异氰酸酯。此种体系的缺点在于该聚脲胶囊易于爆裂或破碎，并由此导致在70～180℃温度发生交联。
综上所述，本发明的目的是提供一种低温交联的单组分分散体。
所述问题可用权利要求1的包含钝化异氰酸酯类作为交联组分的单组分分散体予以解决。本申请人惊奇地发现，本身已知的囊封或钝化异氰酸酯类用作水分散体的交联剂，能导致贮存-稳定体系在低于70℃的温度便发生交联。
据认为，聚合物膜成形期间产生的自粘力能够机械地破坏该异氰酸酯类的聚合物外壳，从而导致交联反应的发生，这可根据薄膜内聚力的增加或薄膜弹性的降低分别来证明。
本发明单组分分散体的优点在于，它能在较低温度，特别是室温下交联，从而克服了稳定的先有技术单组分体系的缺点。与先有技术双组分粘合剂相比，本发明单组分分散体提供的优点在于，它们排除了使用者在施涂期间出现误差，例如配比或混合误差的可能。
按照本发明的一种实施方案，钝化异氰酸酯类在本发明单组分分散体中的含量介于0.1wt％～最高20wt％，尤其是1wt％～最高10wt％。
本发明单组分分散体可用于多种多样用途，例如作为油漆或清漆(lacquer)，作为涂料，作为密封材料，作为铸造材料和/或作为粘合剂。
当作为粘合剂时，合适的本发明分散体粘合剂可包含，例如Dispercoll_KA 8758。按照本发明，合适的异氰酸酯类例如是MDI或TDI，例如TDI-氨酯二酮(urethdione)或TDI-脲。该异氰酸酯类按本身已知的方法钝化，然后，生成的钝化异氰酸酯在搅拌下加入到适当聚合物，例如分散体粘合剂中。当钝化异氰酸酯均匀并细腻地结合进去时，该本发明单组分分散体便可供使用了。
本发明单组分分散体可有利地用于，例如粘合三维家具正面。当今，这类家具正面当前是这样生产的：塑料膜或箔在加热的同时，通过压力压在表面起伏的中密度纤维板载体上，使得该薄膜或箔采取中密度纤维板表面的形状或起伏。为在这2种基材之间获得摩擦型粘合，需要预先在该载体上施涂粘合剂。已知，为实现具有良好热稳定性的高性能粘合，采用双组分聚氨酯分散体系，其中该水分散体在临使用前与水-可乳化多异氰酸酯进行混合。由于配比误差以及均化不充分，无法达到最佳热稳定性。再有，此种双组分体系的适用期被限制在仅仅数小时之内。
上述缺点可采用本发明单组分分散体粘合剂予以有利地克服。
下面，描述实施例。
实例1：钝化异氰酸酯的合成
实例1.1：
100mL环己烷加入到烧杯中，然后20g TDI-氨酯二酮(Desmodur_TT，拜耳公司)在剧烈搅拌下悬浮于其中。随后，加入0.06g甲基五亚甲基二胺(Dytek_A，杜邦公司)在50mL环己烷中的溶液。搅拌2h后，从获得的溶液中赶出溶剂，从而获得精细白色粉末。
实例1.2：
合成方法类似于实例1.1的，不同的是，采用TDI-脲(Desmodur_LS 2116，拜耳公司)代替所述TDI-氨酯二酮。
实例2：单组分分散体粘合剂的制备及交联
来自实例1.1和1.2的钝化异氰酸酯在搅拌下加入到Dispercoll_KA 8758中。继续搅拌，直至异氰酸酯均匀并细腻地结合于其中。
下面的实例，清楚地展示该贮存稳定的单组分分散体粘合剂在室温下的交联。
对比例：
热塑性单组分分散体：100g Dispercoll_KA 8758。
实例2.1：
可交联单组分分散体：100g Dispercoll_KA 8758与4g实例1.1的钝化异氰酸酯。
实例2.2
可交联单组分分散体：100g Dispercoll_KA 8758与4g实例1.2的钝化异氰酸酯。
利用薄膜刮涂棒获得1000μm厚度的刮涂膜，干燥(20℃/65％相对湿度)并贮存。采用拉伸试验机测定这些薄膜的抗张强度。获得的结果载于下表1中。表1：室温下交联后，单组分分散体粘合剂的抗张强度
天数* 抗张强度,N/mm2
对比例 实例2.1 实例2.2
4 7.2 10.5 13.4
7 7.3 13.1 14.6
14 7.1 13.8 13.3
28 6.5 11.2 15.2
*薄膜贮存在室温下。
从表1可以看出，薄膜在室温下贮存4-、7-、14-或28-天之后，对比例的抗张强度分别在6.5～7.3N/mm2范围内。实例2.1和实例2.2薄膜的抗张强度则显著高于对比例薄膜的抗张强度：实例2.1薄膜在规定贮存时间显示出介于10.5～13.8N/mm2的抗张强度，而实例2.2薄膜则显示出介于13.3～15.2N/mm2的抗张强度。
实例2.1和实例2.2制备的单组分分散体粘合剂的粘度，在室温下贮存3个月时间以后仍维持不变。

Claims (13)

1．一种单组分分散体，其特征在于，它包含钝化异氰酸酯类并可在低于70℃的温度交联。
2．权利要求1的单组分分散体，其特征在于，交联温度介于5℃～40℃，尤其是室温。
3．权利要求1或2的单组分分散体，其特征在于，所述钝化异氰酸酯的含量介于0.1wt％～最高20wt％，尤其是1wt％～最高10wt％。
4．权利要求1～3中任何一项的单组分分散体作为清漆或油漆的应用。
5．权利要求1～3中任何一项的单组分分散体作为涂料的应用。
6．权利要求1～3中任何一项的单组分分散体作为密封材料的应用。
7．权利要求1～3中任何一项的单组分分散体作为铸造材料的应用。
8．权利要求1～3中任何一项的单组分分散体作为粘合剂的应用。
9．权利要求8的单组分分散体，其特征在于，它是Dispercoll_KA 8758。
10．权利要求1～9中任何一项的单组分分散体，其特征在于，所述异氰酸酯是表面钝化的异氰酸酯。
11．权利要求1～10中任何一项的单组分分散体，其特征在于，所述异氰酸酯是甲苯二异氰酸酯。
12．权利要求11的单组分分散体，其特征在于，所述甲苯二异氰酸酯是TDI-氨酯二酮或TDI-脲。
13．权利要求1～10中任何一项的单组分分散体，其特征在于，所述异氰酸酯是4,4’-亚甲基-二(苯基异氰酸酯)。
CNB998056669A 1998-05-07 1999-01-29 一种物质体系 Expired - Fee Related CN1142958C (zh)

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DE59906875D1 (de) 2003-10-09
HK1038030A1 (zh) 2002-03-01
KR20010024983A (ko) 2001-03-26
CZ20004045A3 (cs) 2001-04-11
US6686415B1 (en) 2004-02-03
CZ292951B6 (cs) 2004-01-14
ES2207183T3 (es) 2004-05-16
WO1999058590A1 (de) 1999-11-18
CN1142958C (zh) 2004-03-24
ATE248874T1 (de) 2003-09-15
CA2327615C (en) 2006-12-05
PL343841A1 (en) 2001-09-10
EP1082373B1 (de) 2003-09-03
AU2825099A (en) 1999-11-29
EP1082373A1 (de) 2001-03-14
JP2002514668A (ja) 2002-05-21
MY137567A (en) 2009-02-27
CA2327615A1 (en) 1999-11-18
BR9910202A (pt) 2001-01-30
DE29923700U1 (de) 2001-02-22
DE19980843B4 (de) 2006-01-05
AU749308B2 (en) 2002-06-20
DE19980843D2 (de) 2001-05-10
DK1082373T3 (da) 2004-01-12
PL196942B1 (pl) 2008-02-29
BR9910202B1 (pt) 2009-01-13
RU2204570C2 (ru) 2003-05-20

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