CN104903371B - 包含噁唑烷和醛亚胺的液体施加防水膜 - Google Patents
包含噁唑烷和醛亚胺的液体施加防水膜 Download PDFInfo
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- CN104903371B CN104903371B CN201480004120.7A CN201480004120A CN104903371B CN 104903371 B CN104903371 B CN 104903371B CN 201480004120 A CN201480004120 A CN 201480004120A CN 104903371 B CN104903371 B CN 104903371B
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- MEBONNVPKOBPEA-UHFFFAOYSA-N trimethyl cyclohexane Natural products CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 1
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- E04D7/00—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3253—Polyamines being in latent form
- C08G18/3256—Reaction products of polyamines with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- 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
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- E04D11/00—Roof covering, as far as not restricted to features covered by only one of groups E04D1/00 - E04D9/00; Roof covering in ways not provided for by groups E04D1/00 - E04D9/00, e.g. built-up roofs, elevated load-supporting roof coverings
- E04D11/02—Build-up roofs, i.e. consisting of two or more layers bonded together in situ, at least one of the layers being of watertight composition
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
- B32B2419/06—Roofs, roof membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
Abstract
本发明描述了一种单组分湿固化液体施加防水膜,其包含聚氨酯聚合物以及在特定比例范围的醛亚胺和噁唑烷两者作为封闭胺硬化剂。该膜具有低气味、长的保存期稳定性、在低溶剂含量下的低粘度、足够长的开放时间以允许手工施用并且快速固化为固体弹性材料。该液体施加防水膜特别适用于屋顶应用,在室外天气条件下在宽的温度范围内具有高强度、高伸长率和良好的耐久性。
Description
发明领域
本发明涉及一种基于单组分湿固化聚氨酯的液体施加防水膜,特别是用于屋顶应用的。
发明背景
液体施加的防水膜是已知的。在屋面应用中,它们被用来作为预制片膜的替代品,提供更方便的应用,特别是在复杂的屋顶几何形状的情况下和用于翻新的任务,提供了完全粘附到基材的柔韧的无缝屋面涂层。
屋顶上的液体施加防水膜必须满足苛刻的要求。它们需要具有低粘度以作为自流平涂料施加,和足够长的开放时间以适用手工应用,但仍快速固化以很快失去其脆弱性。当完全固化时,屋顶膜需要具有持久的弹性和强度以在广泛的温度范围内和户外天气条件如风力、积水、霜冻、强烈的阳光照射、微生物侵袭和根穿透下,有效地保护建筑物免于进水。
现有技术的液体施加防水膜往往是反应型聚氨酯组合物,其配制为单组分或双组分体系,也分别被称为单部分或双部分体系。双组分体系应用更复杂,需要特殊的混合设备和适当计量两种组分,因为混合质量和/或化学计量中的错误强烈地影响膜的性能。单组分体系很容易应用,但易于发生固化缺陷。现有技术的单组分体系包含封闭胺硬化剂,特别是噁唑烷,以防止当固化时形成二氧化碳导致过度放气。它们通常含有相当量的溶剂,以保证低的粘度和足够的保存期。由收紧的VOC法规驱使来减少这种单组分体系的溶剂含量的尝试通常导致保存期稳定性困难和由于高粘度的坏的加工性,因为组合物的粘度起始于一个较高水平,并且由于在储存过程中预聚物的NCO基团和噁唑烷硬化剂之间的早期交联反应而进一步增加。基于噁唑烷的单组分膜的另外的缺点涉及固化慢和由封端剂、挥发性醛或酮的排放所引起的难闻气味。
WO2008/000831公开了低VOC涂料组合物,优选用于地板目的,其基于醛醇酯聚醛亚胺作为封闭胺硬化剂。虽然这些组合物具有良好的保存期稳定性且固化不会产生不愉快的气味,但由于低官能的硬化剂和醛醇酯封闭剂的增塑效果,它们在强度发展方面受到限制。实施例的涂层要么对于屋顶应用而言太刚性,要么含有大量的溶剂。
发明概述
本发明的任务是提供一种用于屋顶应用的单组分液体施加防水膜,其在低溶剂含量下具有良好的保存期稳定性和良好的加工性,甚至当只含约每升50g或以下的VOC时,以及具有快速和可靠的固化性能。
令人惊奇地发现,根据权利要求1所述的液体施加防水膜满足了这一任务,并具有额外的好处。它包含异氰酸酯官能的聚氨酯聚合物,其提供了良好的拉伸强度和高伸长率,并几乎与温度无关,在寒冷气候条件下仍保持弹性。它还包含在特定比例范围的醛醇酯醛亚胺和噁唑烷。该特定组合令人惊奇地提供了单独基于醛亚胺或噁唑烷的现有技术膜未达到的非常有吸引力的性质组合:甚至在低溶剂含量下良好的保存期稳定性和低的粘度,良好的机械性能,特别是高拉伸强度以及高伸长率,允许手工施用的长的开放时间,但快速和可靠的防止缺陷的固化性能。作为两个单独分子的醛亚胺和噁唑烷的组合,而不是使用同时带有醛亚胺氨基和噁唑基的一个分子,提供了醛亚胺和噁唑烷衍生自不同类型的醛的优点,因为衍生自醛醇酯醛的噁唑烷水解速度不够快,而衍生自醛的醛亚胺增加膜的气味和醛的排放。
结合低溶剂含量与长保存期的可能性为配制者提供了独特的机会,以获得满足最严峻VOC法规的高端产品,其具有最小的收缩和非常低的气味性能。快速固化性能结合长的开放时间允许小心施用,并提供高的早期强度,从而最小化膜呈脆弱的时间并加快在多层结构的情况下的应用。良好的机械性能在宽的温度范围内提供很高的裂缝桥接质量并确保高耐久性。
本发明的另一方面是醛醇酯醛亚胺作为噁唑烷基单组分湿固化液体施加防水膜用非VOC稀释剂的用途,这可提供额外的益处,如未固化材料的良好的保存期稳定性、更快的固化、较少的气味以及固化的膜的高强度和高伸长率。
根据权利要求1所述的液体施加防水膜特别适合于在屋顶上使用,特别是在平坦的或低坡度屋顶上。这对于琐碎的工作和整修目的是特别有利的。
本发明的其它方面披露在其他独立权利要求中。本发明的优选方面披露在从属权利要求中。
发明详述
本发明的主题是一种单组分湿固化液体施加防水膜,其包含
-至少一种异氰酸酯官能的聚氨酯聚合物,
-至少一种式(I)的醛亚胺,
其中
A是分子量在28至5000g/mol范围的任选地含醚或氨基甲酸酯基团的n价烃基部分,
R1和R2是相同或不同的C1至C12直链或支链烷基,或连接在一起形成二价的直链或支链的C4至C12烃基部分,其是5-至8-元碳环的一部分;
R3是氢,或者直链或支链的C1至C12烷基或芳烷基或烷氧基羰基,
R4是任选地含醚基、羰基或酯基的一价C6至C20烃基部分,和
n为2至6;
-至少一种式(II)的噁唑烷,
B是分子量在28至2000g/mol范围的任选地含醚、酯、酰胺、碳酸酯、氨基甲酸酯或脲基团的m价烃基部分,
R5和R6彼此独立地选自氢或C1至C12直链或支链烷基,和
m为2或3;
由此,醛亚氨基的数目与噁唑基的数目之间的比率在80/20至20/80范围内。
在本文中,术语“单组分湿固化”是指一种液体施加膜,其包含在单个不透水分的容器中,具有一定的保存期稳定性并且当暴露于水分时固化。
在本文中,术语“液体施加防水膜”是指以液体形式作为层施加到基材上的材料,并且其固化以形成弹性膜使得基材防水。
在本文中,术语“聚氨酯聚合物”包括由所谓的二异氰酸酯加聚过程制备的所有聚合物。它包括通过使多异氰酸酯和多元醇反应获得的异氰酸酯官能的聚氨酯聚合物,其也可以称为预聚物并且是多异氰酸酯本身。
在本文中,术语“保存期稳定性”是指组合物可以在室温下在排除水分下保存在合适的容器中一定时间间隔的能力,特别是数月,而不发生在应用或最终使用性质方面的显著变化。
在本文中,以“多/聚(poly)”起始的物质名称如多元醇、多异氰酸酯或多胺,是指每分子携带两个或更多个相应的官能基团(例如在多元醇的情况下是OH基团)的物质。
在本文中,当胺或异氰酸酯的氨基或异氰酸酯基团分别直接键合到脂族、环脂族或芳基脂族部分时,其被称为“脂族”。因此,对应的官能团分别被称为脂族氨基或脂族异氰酸酯基。
在本文中,当胺或异氰酸酯的氨基或异氰酸酯基团分别直接键合到芳族部分时,其被称为“芳族”。因此,对应的官能团分别被称为芳族氨基或芳族异氰酸酯基。
在本文中,术语“伯氨基”是指键合到有机部分的NH2-基团,以及术语“仲氨基”是指键合到两个有机部分(它们一起可以是环的一部分)的NH-基团。
在本文中,缩写“VOC”代表“挥发性有机化合物”,其是在293.14K的温度下具有至少0.01kPa蒸汽压的有机物质。
在本文中,术语“溶剂”是指一种液体,其为VOC,其能够溶解本文中描述的异氰酸酯官能的聚氨酯聚合物,并且其不携带任何异氰酸酯-反应性官能团。
在本文中,“室温”是指23℃的温度。
在本文中,术语“分子量”是指分子或分子的一部分(也称为“部分”)的摩尔质量(以克每摩尔给出)。术语“平均分子量”是指分子或部分的低聚或聚合混合物的数均分子量(Mn)。
本发明的液体施加膜包括至少一种异氰酸酯官能的聚氨酯聚合物。
合适的异氰酸酯官能的聚氨酯聚合物可以由至少一种多异氰酸酯与至少一种多元醇的反应获得,由此异氰酸酯基对于羟基为化学计量过量。多异氰酸酯和多元醇是通过已知的方法反应,优选在50至100℃的温度下,任选地通过使用合适的催化剂。优选地,多异氰酸酯以对应于异氰酸酯与羟基的比例在1.3至5、更优选1.5至3范围内的量使用。优选地,聚氨酯聚合物具有1-10wt-%、优选2-8wt-%范围内的游离NCO基团含量。任选地,多元醇和多异氰酸酯可在不含异氰酸酯-反应性基团的溶剂或者增塑剂的存在下反应。
优选地,异氰酸酯官能的聚氨酯聚合物具有在1000至10000g/mol、更优选1000至5000g/mol范围内的平均分子量。
优选地,异氰酸酯官能的聚氨酯聚合物具有在1.7至3、更优选1.8至2.5范围内的平均异氰酸酯官能度。
用于制备异氰酸酯官能的聚氨酯聚合物的合适的多元醇是聚醚多元醇,包括含有分散的苯乙烯-丙烯腈(SAN)、丙烯腈-甲基丙烯酸甲酯或尿素颗粒的那些,还有聚酯多元醇如二醇或三醇与内酯或者二羧酸或它们的酯或酐的缩聚反应的产物,还有聚碳酸酯多元醇,具有至少两个不同的聚醚、聚酯或聚碳酸酯单元的嵌段的嵌段共聚物多元醇,聚丙烯酸酯和聚甲基丙烯酸酯多元醇,多羟基官能的脂肪和油,特别是天然脂肪和油,和聚烃多元醇,如多羟基官能的聚烯烃。
随着上述的多元醇,可以使用少量低分子量的二价或多价醇,如1,2-乙二醇,1,2-丙二醇,新戊二醇,二溴新戊二醇,二乙二醇,三乙二醇,异构的二丙二醇和三丙二醇,异构的丁二醇,戊二醇,己二醇,庚二醇,辛二醇,壬二醇,癸二醇,十一烷二醇,1,3-和1,4-环己烷二甲醇,氢化双酚A,二聚脂肪醇,1,1,1-三羟甲基乙烷,1,1,1-三羟甲基丙烷,甘油,季戊四醇,糖醇如木糖醇、山梨糖醇或甘露糖醇,糖如蔗糖,其它多元醇,上述二价或多价醇的低分子量烷氧基化产物,以及上述醇的混合物。
优选的多元醇是平均分子量在500至6000g/mol、特别是在1000至5000g/mol范围的二醇和三醇。
优选的多元醇是聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇和聚丙烯酸酯多元醇。
特别优选的多元醇是聚醚多元醇,特别是聚氧化亚烷基多元醇。这些多元醇有助于在固化膜中发展良好的低温柔韧性。
聚氧化亚烷基多元醇是环氧乙烷、1,2-环氧丙烷、1,2-或2,3-环氧丁烷、氧杂环丁烷、四氢呋喃或其混合物的聚合产物,任选地使用具有两个或更多个活性氢原子的起始分子如水、氨或具有若干OH-或NH-基团的化合物进行聚合,后者如1,2-乙二醇,1,2-和1,3-丙二醇,新戊二醇,二乙二醇,三乙二醇,异构的二丙二醇和三丙二醇,异构的丁二醇,戊二醇,己二醇,庚二醇,辛二醇,壬二醇,癸烷二醇,十一烷二醇,1,3-和1,4-环己烷二甲醇,双酚A,氢化双酚A,1,1,1-三羟甲基乙烷,1,1,1-三羟甲基丙烷,甘油,苯胺,以及上述化合物的混合物。
优选的是具有低不饱和度(根据ASTM D-2849-69测量,并以每克多元醇的不饱和度的毫当量表示(meq/g))的聚氧化亚烷基多元醇,例如可通过使用所谓的双金属氰化物络合催化剂(DMC催化剂)获得,以及具有较高不饱和度的聚氧化亚烷基多元醇,例如可通过使用阴离子催化剂如NaOH、KOH、CsOH或碱金属醇盐获得。
特别优选的聚氧化亚烷基多元醇是环氧乙烷和/或环氧丙烷的聚合产物。
更优选的是聚氧亚丙基多元醇和所谓的环氧乙烷封端的聚氧亚丙基多元醇。后者是特定的聚氧亚丙基-聚氧亚乙基多元醇,其可通过后乙氧基化纯的聚氧亚丙基多元醇获得,并因此具有伯羟基。这些多元醇在固化的膜中提供良好的低温柔韧性和良好的耐候性。
特别优选的是平均分子量在500至6000g/mol、特别是在1000至4000g/mol范围内的聚氧亚丙基二醇和三醇以及环氧乙烷封端的聚氧亚丙基二醇和三醇。
这些聚醚多元醇在固化的膜中提供低粘度、良好的耐候性和良好的机械性能的组合。
进一步特别优选的多元醇是聚碳酸酯多元醇,特别是碳酸二烷基酯、碳酸二芳基酯或光气与二醇或三醇的缩聚产物,所述二醇或三醇如乙二醇、二乙二醇、丙二醇、二丙二醇、新戊二醇、1,4-丁二醇,1,5-戊二醇、3-甲基-1,5-己二醇、1,6-己二醇、1,8-辛二醇、1,10-癸二醇、1,12-十二烷二醇、1,12-十八烷二醇、1,4-环己烷二甲醇、二聚脂肪酸二醇(二聚二醇)、羟基新戊酸新戊二醇酯、甘油和1,1,1-三羟甲基丙烷。
这样的聚碳酸酯多元醇可以有助于发展膜的良好耐候性能。
优选的低分子量的醇是具有在60至150g/mol范围内的分子量的双官能醇。特别优选的是1,2-乙二醇,1,3-丙二醇,1,4-丁二醇,1,5-戊二醇,1,6-己二醇,1,3-环己烷二甲醇,1,4-环己烷二甲醇和二乙二醇。这些醇特别地改进膜的强度。最优选的是1,4-丁二醇。
进一步优选的低分子量的醇是双官能的溴化醇,如二溴新戊二醇。这些醇特别地改进膜的阻燃性质。
优选地,异氰酸酯官能的聚氨酯聚合物由含至少50wt-%、更优选至少80wt-%和最优选至少90wt-%聚醚多元醇的多元醇混合物制备。
在一个特别优选的实施方式中,异氰酸酯官能的聚氨酯聚合物由至少一种分子量在500至6000g/mol范围的聚醚多元醇和至少一种分子量在60至150g/mol范围的二醇,特别是1,4-丁二醇的组合获得。这样的异氰酸酯官能的聚氨酯聚合物显示低粘度,并提供良好的机械性能,特别是高强度。
合适的获得异氰酸酯官能的聚氨酯聚合物的多异氰酸酯如下:
-脂族多异氰酸酯,特别是1,4-四亚甲基二异氰酸酯,2-甲基五亚甲基-1,5-二异氰酸酯,1,6-己烷二异氰酸酯(HDI),2,2,4-和2,4,4-三甲基-1,6-己烷二异氰酸酯(TMDI),1,10-癸烷二异氰酸酯,1,12-十二烷二异氰酸酯,赖氨酸或赖氨酸酯二异氰酸酯,环己烷-1,3-和-1,4-二异氰酸酯,1-甲基-2,4-和-2,6-二异氰酸基环己烷和这些异构体的任意混合物(HTDI或H6TDI),1-异氰酸根-3,3,5-三甲基-5-异氰酸基甲基-环己烷(异佛尔酮二异氰酸酯或IPDI),全氢-2,4'-和-4,4'-二苯基甲烷二异氰酸酯(HMDI或H12MDI),1,4-二异氰酸根-2,2,6-三甲基环己烷(TMCDI),1,3-和1,4-双(异氰酸基甲基)环己烷,间-和对-亚二甲苯基二异氰酸酯(m-和p-XDI),间-和对-四甲基-1,3和-1,4-亚二甲苯二异氰酸酯(间-和对-TMXDI),双(1-异氰酸基-1-甲基乙基)萘,二聚或三聚脂肪酸异氰酸酯如3,6-双-(9-异氰酸基壬基)-4,5-二-(1-庚烯基)环己烯(二聚二异氰酸酯),和α,α,α',α',α”,α”-六甲基-1,3,5-三甲基苯三异氰酸酯。优选其是HDI、TMDI、IPDI和H12MDI。
-芳族多异氰酸酯,特别是4,4'-二苯基甲烷二异氰酸酯,2,4'-二苯基甲烷二异氰酸酯和/或2,2'-二苯基甲烷二异氰酸酯和这些异构体(MDI)的任何混合物,2,4-和/或2,6-甲苯二异氰酸酯和这些异构体(TDI)的任何混合物,1,3-和1,4-亚苯基二异氰酸酯,2,3,5,6-四甲基-1,4-二异氰酸根合苯,萘-1,5-二异氰酸酯(NDI),3,3'-二甲基-4,4'-二异氰酸基联苯(TODI),联茴香胺二异氰酸酯(DADI),1,3,5-三(异氰酸基甲基)苯,三(4-异氰酸根合苯基)甲烷和三(4-异氰酸根合苯基)硫代磷酸酯。优选其为MDI和TDI。
优选的获得异氰酸酯官能的聚氨酯聚合物的多异氰酸酯为脂族多异氰酸酯。这种聚合物使液体施加膜具有特别好的保存期稳定性和耐光性,即在阳光暴露下耐黄变性,以及良好的耐UV性。
最优选的获得异氰酸酯官能的聚氨酯聚合物的脂族多异氰酸酯是IPDI。这种聚合物提供具有高强度和高伸长率的特别低粘性的膜。
在本发明一个实施方式中,优选的获得异氰酸酯官能的聚氨酯聚合物的多异氰酸酯是芳族多异氰酸酯,特别是MDI。从EHS观点来看MDI是优选的,因为它具有非常低的挥发性。此外,MDI价格低廉并且能提供快速固化性能和高强度的膜。
为了获得异氰酸酯官能的聚氨酯聚合物,可能有利的是使用含一定量它们的低聚物或聚合物或其它衍生物的多异氰酸酯。特别是在MDI的情况下,可能有利的是使用MDI与MDI的低聚物或聚合物或衍生物的混合物,优选所谓的含有碳化二亚胺的改性MDI或者MDI的脲酮亚胺或氨基甲酸酯,其是可例如作为CD、PF、PC(所有来自Bayer)或者M 143(来自Dow),以及所谓的代表MDI与MDI同系物的混合物的聚合的MDI或PMDI,如VL、VL50、VL R10、VL R20、VH 20 N和VKS 20F(所有来自Bayer)、M 309、M 229和M 580(所有来自Dow)或M 10 R(来自BASF)。
单组分湿固化液体施加防水膜进一步包含至少一种式(I)的醛亚胺。
优选n为2或3。这些醛亚胺衍生自二或三胺,并能使膜具有良好的机械性能,特别是高伸长率和高强度的良好组合。
优选R1和R2各为甲基。这些醛亚胺提供具有低粘度以及快速、可靠的固化性能的膜。
优选R3是氢。这些醛亚胺提供具有低粘度以及快速、可靠的固化性能的膜。
优选R4是C11烷基。这些醛亚胺提供在低温下具有低粘度和高柔韧性的无气味的膜。
特别优选的是式(I)的醛亚胺,其中R1和R2是甲基,R3是氢并且R4是十一烷基。这些醛亚胺提供在低温下具有低粘度、快速并可靠的固化性能和高柔韧性的无气味的膜。
优选地,A是分子量在28至2000g/mol、特别是在84至600g/mol范围的任选地含醚基的n价烃基部分。这些醛亚胺提供具有特别良好的机械性能、在低温下特别高的柔韧性和在温暖条件下的高强度。
优选地,A是当除去选自以下组的多胺的伯氨基后剩余的部分:六亚甲基-1,6-二胺,2-甲基戊烷-1,5-二胺,3-氨基甲基-3,5,5-三甲基环己胺(异佛尔酮二胺),2,2,4-和2,4,4-三甲基六亚甲基二胺,1,3-双(氨基甲基)苯,1,3-双(氨基甲基)环己烷,1,4-双(氨基甲基)环己烷,双(4-氨基环己基)甲烷,双(4-氨基-3-甲基环己基)甲烷,2,5(2,6)-双(氨基甲基)双环[2.2.1]庚烷,3(4),8(9)-双(氨甲基)-三环[5.2.1.02,6]癸烷,1,2-二氨基环己烷,1,3-二氨基环己烷,1,4-二氨基环己烷,2,2,6-三甲基环己烷-1,4-二胺,3,6-二氧杂辛烷-1,8-二胺,4,7-二氧杂癸烷-1,10-二胺,4-氨基甲基-1,8-辛二胺,平均分子量为200至5000g/mol、优选200至2000g/mol、更优选200至600g/mol的聚氧化亚丙基二胺和三胺,1,3-苯二胺,1,4-苯二胺,2,4-和2,6-甲代亚苯基二胺和4,4’-、2,4’-和2,2’-二氨基二苯基甲烷。
在本发明一个特别优选的实施方式中,A是当除去六亚甲基-1,6-二胺的伯氨基时剩余的部分。这些醛亚胺提供具有特别低粘度和快速固化性能的膜。
在本发明另一个特别优选的实施方案中,A是当除去异佛尔酮二胺的伯氨基时剩余的部分。这些醛亚胺提供具有特别低的粘度和高强度的膜。
在本发明另一个特别优选的实施方案中,A是当除去平均分子量为200至5000g/mol、优选200至2000g/mol、更优选200至600g/mol的聚氧化亚丙基二胺或三胺的伯胺基的剩余部分。
这些亚胺提供具有特别低的粘度、快速固化性和高伸长率的膜。
在本发明最优选的实施方式中,A是当除去平均分子量在400至5000g/mol、优选400至500g/mol范围的聚氧化亚丙基三胺的伯氨基时剩余的部分,所述三胺特别是来自Huntsman的T-403或者来自BASF或Nitroil的相应级别产品,或者来自Huntsman的T-5000或来自BASF或Nitroil的相应级别产品。这些醛亚胺为膜提供非常快速的固化性能以及高伸长率与强度的良好结合。
优选的式(I)的醛亚胺选自由以下组成的组:N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-六亚甲基-1,6-二胺,N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己胺,平均分子量在700至4600g/mol范围的N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基二胺和平均分子量在1200至5800g/mol范围的N,N’,N”-三(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基三胺。这些醛亚胺提供具有良好的加工性和快速固化性能,以及当固化时高伸长率和良好的强度的无气味的膜。
在本发明的一个特别优选的实施方式中,式(I)的醛亚胺为N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-六亚甲基-1,6-二胺。该醛亚胺提供具有特别低的粘度和快速固化性能的无气味的膜。
在本发明的另一个特别优选的实施方式中,式(I)的醛亚胺为N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己胺。该醛亚胺提供具有特别低的粘度和高强度的无气味的膜。
在本发明的另一个特别优选的实施方式中,式(I)的醛亚胺为N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基二胺或N,N’,N”-三(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基三胺。这些醛亚胺提供具有特别低的粘度、快速固化性能和高伸长率的膜。尤其优选的是三醛亚胺。它们提供非常快的固化性能以及高强度与高伸长率的良好的结合。
在本发明的一个特别优选的实施方式中,液体施加膜包含至少两种不同的式(I)的醛亚胺的结合。使用多于一种式(I)的醛亚胺,给出了以优化的方式平衡性能如粘度、固化速度、拉伸强度和伸长率的可能。
优选地,式(I)的两种不同的醛亚胺之一是二醛亚胺且另一个是三醛亚胺。
所述三醛亚胺优选是平均分子量在1200至5800g/mol、优选1200至1300g/mol范围的N,N’,N”-三(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基三胺。
所述二醛亚胺优选选自N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-六亚甲基-1,6-二胺和N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己胺。
这种膜显示出低粘度、快速固化性能、高强度和高伸长率之间预料不到的良好结合。
式(I)的醛亚胺优选可从至少一种式(III)的胺和至少一种式(IV)的醛的缩合反应获得。
在式(III)和(IV)中,A、n、R1、R2、R3和R4具有前面提到的含义。
对于此缩合反应,式(IV)的醛相对于式(III)的胺的伯氨基以化学计量使用或以过量使用。该反应可以有利地在15至120℃范围的温度下进行,在溶剂的存在下或没有溶剂存在下进行。所释放的水用合适的溶剂共沸除去,或者直接真空除去。
单组分湿固化液体施加防水膜进一步包含至少一种式(II)的噁唑烷。
优选B是分子量为118至500g/mol范围的含碳酸酯或氨基甲酸酯基团的m价烃基部分。
优选R5是氢。
优选R6是C3至C7支链烷基。特别优选是2-丙基和3-庚基。
优选m是2。
这种噁唑烷提供具有高伸长率和高强度的膜。
特别优选的是式(II)的噁唑烷,其中R5是氢和R6是2-丙基或3-庚基。
特别优选的是噁唑烷,其中式(II)对应于式(II a)或(II b)。
在式(II a)或(II b)中R5和R6具有已经提到的含义。
式(II a)和(II b)的噁唑烷是N-(2-羟乙基)-四氢噁唑的衍生物,后者可经由二乙醇胺与醛或酮,特别是与异丁醛或2-乙基己醛的缩合反应获得。
式(II a)的噁唑烷可由N-(2-羟基乙基)-四氢噁唑与有机碳酸酯的反应获得。
式(II b)的噁唑烷可经由N-(2-羟基乙基)-四氢噁唑与1,6-己烷二异氰酸酯(HDI)的反应获得。
这些噁唑烷使膜具有良好的加工性能、良好的伸长率和高强度。
可商购获得的式(II)的噁唑烷的实例为Hardener OZ(来自Bayer)、RD-4(来自Angus Chemical)以及LV、4、HP、NC、CF、EH和K(来自Incorez)。
在液体施加膜中,醛亚氨基的数目与噁唑烷基的数目之间的比例为80/20至20/80。在该范围内,该膜特征在于良好的保存期稳定性、快速和可靠的固化性能以及良好的机械性能。
如果醛亚氨基/噁唑烷基的比例高于80/20,则膜太软并具有低的拉伸强度。
如果醛亚氨基/噁唑烷基的比例低于20/80,则膜具有低的保存期稳定性、不足的固化性能特别是长的结皮时间,并且伸长率有限。
优选地,醛亚胺基/噁唑烷基的比例在75/25至25/75范围内。在该范围内,膜可以快速固化,具有非常好的保存期稳定性,在低溶剂含量下也是如此,并且具有高强度和高伸长率的良好结合。
更优选地,醛亚氨基/噁唑烷基的比例在70/30至30/70范围内。在该范围内,膜可以快速固化,具有非常好的保存期稳定性,以及特别高的强度和伸长率。
优选地,醛亚胺和噁唑烷在液体施加膜中的含量为使得封闭的氨基和羟基的总数与异氰酸酯基团的数目之间的比率是在0.3至1.0的范围内,优选为0.4到1.0,更优选0.6至1.0。
在此范围内,该膜快速地固化为高强度的材料,而不形成气泡或水泡。
优选地,异氰酸酯官能的聚氨酯聚合物在液体施加膜中的含量是在15-70wt-%的范围,更优选为15-60wt-%,特别是15-50wt-%。
除了已经提及的成分,该液体施加膜可以包含其它成分。
优选地,液体施加膜包含至少一种填料。填料有助于开发强度以及耐久性。
优选的填料是无机填料,特别是碳酸钙(白垩)如研磨碳酸钙(GCC)和沉淀碳酸钙(PCC),硫酸钡(重晶石)、板岩、硅酸盐(石英)、镁硅酸盐(滑石)和铝硅酸盐(粘土、高岭土)、白云石、云母、玻璃泡和硅酸特别是来自热解过程的高分散硅酸(热解二氧化硅)。这些填料可以带有或可以不带有表面涂层,例如硬脂酸酯或硅氧烷涂层。
进一步优选的填料是有机填料,特别是炭黑和微球。
优选地,所述液体施加膜还包含至少一种颜料。
颜料定义该膜的颜色,有助于发展强度,并且可以提高耐久性,特别是UV稳定性。
优选的颜料是二氧化钛、氧化铁和碳黑。
优选地,所述液体施加膜还包含至少一种阻燃填料。优选的阻燃填料是氢氧化铝(ATH),氢氧化镁,三氧化锑,五氧化锑,硼酸,硼酸锌,磷酸锌,三聚氰胺硼酸酯,氰尿酸三聚氰胺,乙二胺磷酸盐,多磷酸铵,二-三聚氰胺正磷酸盐,二-三聚氰胺焦磷酸盐,六溴环十二烷,十溴二苯醚和三(溴新戊基)磷酸酯。
优选地,液体施加膜包含至少一种阻燃增塑剂,特别是磷酸酯或膦酸酯,特别是磷酸三苯酯(TPP),二苯基-叔丁基苯基磷酸酯,二苯基甲酚磷酸酯(DPK),磷酸三甲苯酯(TKP),磷酸三乙酯,三(2-乙基己基)磷酸酯,磷酸二苯基-2-乙基己酯(DPO),三(2-乙基己基)磷酸酯(TOF),二苯基异癸基磷酸酯,二甲基丙烷膦酸酯(DMPP),四苯基间苯二酚二磷酸酯,间苯二酚二磷酸酯低聚物(RDP),乙二胺二磷酸酯,以及氯代烷基磷酸酯如三(1-氯-2-丙基)磷酸酯,三(1,3-二氯-2-丙基)磷酸酯和2,2-双(氯甲基)三亚甲基双(二(2-氯乙基)磷酸酯)。
优选地,液体施加膜进一步包含至少一种具有大于两个NCO-官能度的多异氰酸酯交联剂,特别是已经提及的二异氰酸酯的低聚物、聚合物或衍生物。优选的脂族多异氰酸酯交联剂是HDI-缩二脲,如N 100和N 3200(来自Bayer)、HDB和HDB-LV(来自Rhodia)以及24A-100(来自Asahi Kasei);HDI-异氰脲酸酯,如N 3300、N 3600和N 3790 BA(来自Bayer),HDT、HDT-LV和HDT-LV2(来自Rhodia),TPA-100和THA-100(来自Asahi Kasei)以及HX(来自Nippon Polyurethane);HDI-脲二酮,如N 3400(来自Bayer);HDI-亚氨基噁二嗪二酮如3900(来自Bayer);HDI-脲基甲酸酯,如VP LS 2102(来自Bayer)和HA 100、HA 200和HA 300(所有来自BASF);IPDI-异氰脲酸酯,如Z 4470(来自Bayer)和T1890/100(来自Evonik);基于IPDI/HDI的混合异氰脲酸酯,如NZ 1(来自Bayer)。优选的芳族多异氰酸酯交联剂是TDI-低聚物,如IL(来自Bayer);含有碳化二亚胺的改性MDI或MDI的脲酮亚胺,如前面已经提到的那些。也可使用混合的芳族/脂族多异氰酸酯交联剂,特别是基于TDI/HDI的异氰脲酸酯,如Des-HL(来自Bayer)。
在含基于脂族多异氰酸酯的异氰酸酯官能的聚氨酯聚合物的膜中,脂族多异氰酸酯交联剂是特别优选的。
特别优选的是IPDI-异氰脲酸酯和含IPDI的混合的异氰脲酸酯。
液体施加膜优选进一步包含至少一种促进异氰酸酯基团的反应的金属基催化剂。优选的金属基催化剂是二烷基锡络合物,特别是二甲基锡、二丁基锡或二辛基锡羧酸盐、硫醇盐或乙酰丙酮化物,如DMTDL、DBTDL、DBT(acac)2、DOTDL、新癸酸二辛基锡(IV)或DOT(acac)2,铋(III)络合物如辛酸铋(III)或新癸酸铋(III),锌(II)络合物如辛酸锌(II)或新癸酸锌(II),和锆(IV)络合物如辛酸锆(IV)或新癸酸锆(IV)。
液体施加膜优选进一步包含至少一种促进醛亚氨基和噁唑烷基水解的酸催化剂。优选的酸催化剂是羧酸和磺酸,特别是芳族羧酸如苯甲酸或水杨酸。
液体施加膜优选进一步包含至少一种UV稳定剂。优选的UV稳定剂是UV吸收剂,如二苯甲酮、苯并三唑、草酰苯胺(oxalanilides)、苯基三嗪和特别地2-氰基-3,3-二苯基丙烯酸乙酯,和位阻胺光稳定剂(HALS)如双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯和其它含至少一种1,2,2,6,6-五甲基-4-哌啶基部分的化合物。UV稳定剂有助于防止聚合物在光线曝露下降解。
液体施加膜还可以进一步包括以下成分:
-其它多异氰酸酯,如其它异氰酸酯官能的聚氨酯聚合物,特别是基于MDI、TDI、IPDI或HDI的那些;
-不同于式(I)的醛亚胺和式(II)的噁唑烷的封闭胺硬化剂,特别是其它醛亚胺;
-除了磷酸酯和膦酸酯之外的增塑剂,特别是邻苯二甲酸酯、偏苯三酸酯、琥珀酸酯、戊二酸酯、己二酸酯、癸二酸酯、壬二酸酯、柠檬酸酯、苯甲酸酯、乙酰化甘油或单甘油酯、氢化邻苯二甲酸酯、脂肪酸酯、芳基磺酸酯或烃类树脂;
-有机溶剂如烃、酯或醚,特别是乙酰基丙酮,异亚丙基丙酮,环己酮,甲基环己酮,乙酸乙酯,乙酸丙酯,1-甲氧基-2-丙基乙酸酯,乙酸丁酯,丙二酸二乙酯,二异丙醚,二乙醚,二丁醚,乙二醇二乙醚,二乙二醇二乙醚,甲苯,二甲苯,庚烷,辛烷,二异丙基萘和石油馏分如石脑油、白油和石油醚,如SolvessoTM溶剂(来自Exxon),氢化芳族溶剂如氢化石脑油,二氯甲烷,碳酸亚丙酯,丁内酯,N-甲基吡咯烷酮和N-乙基吡咯烷酮;
-添加剂如润湿剂,流动增强剂,流平剂,消泡剂,脱气剂,干燥剂,抗氧化剂,粘附促进剂,流变改性剂,尤其是热解二氧化硅,和杀生物剂。
当使用这样的另外的成分时,有利的是确保它们不会强烈影响未固化的膜的保存期稳定性,即不大量触发导致储存期间聚合物的交联的反应。特别是,这些另外的成分不应含微量以上的水。可能有利的是在使用之前物理或化学干燥所述成分。
优选地,液体施加膜包含:
-至少一种选自无机填料和颜料的成分,
-至少一种选自阻燃增塑剂和阻燃填料的成分,和
-至少一种选自催化剂、增塑剂、溶剂和UV稳定剂的成分。
这些进一步的成分提供具有良好的保存期稳定性、良好的加工性、快的固化性能以及高强度和耐久性的膜,其在火灾情况下具有低的发展火焰和浓烟的趋势。这种膜高度适合在屋顶上应用。
优选地,所述液体施加膜具有在20-80wt-%范围内的填料含量,更优选在30-60wt-%,该填料包括无机、有机和阻燃填料以及颜料。在这个填料含量下,所述膜提供高强度和耐久性。
特别优选的液体施加膜含有:
-15到70wt-%的异氰酸酯官能的聚氨酯聚合物,
-20至80wt-%的填料,包括无机填料、阻燃填料和颜料,
-5至30wt-%、特别优选5至20wt-%的增塑剂,包括阻燃增塑剂,
-和包含至少一种选自催化剂、溶剂和UV稳定剂的其它成分。
优选地,其包含至少一种选自阻燃填料和阻燃增塑剂的阻燃剂成分。这种膜具有良好的保存期稳定性、在低溶剂含量下良好的加工性、良好的机械性能和耐用性以及在火灾情况下低的发展火焰和浓烟的趋势。
优选地,液体施加膜具有低的粘度。这使得当作为自流平涂层施涂时有良好的加工性。特别地,所述膜在20℃下测量具有2000至15000mPa·s的Brookfield粘度,优选在20℃下在2000至10000mPa·s的范围。在该粘度范围,膜足以自流平以允许在平坦或低坡度屋顶表面便利地施用,但不流入基材表面上的小腔中。
优选地,液体施加膜具有低溶剂含量,最优选其每升含有50g或以下的VOC。在这样低溶剂含量下,所述膜满足最严峻的VOC技术指标,例如南海岸空气质量管理区(SouthCoast Air Quality Management District)的那些。
现有技术的基于异氰酸酯官能的聚氨酯聚合物和封闭胺硬化剂的单组分湿固化液体施加防水膜在低溶剂含量下难以配制。特别地,在不使用大量溶剂下难以实现低粘度和足够的保存期稳定性。在本发明中,令人惊奇地发现,在包含异氰酸酯官能的聚氨酯聚合物和噁唑烷的单组分湿固化液体施加防水膜中使用式(I)的醛亚胺是降低膜的粘度和增强保存期稳定性,从而允许降低溶剂含量并为配制高端但低VOC和低气味的防水膜提供可能性的有效方法。此外,令人惊奇地发现,在噁唑烷基膜中使用式(I)的醛亚胺是显著促进固化的有效方法。
本发明的再一个主题是至少一种式(I)的醛亚胺在单组分湿固化液体施加防水膜中作为稀释剂的用途,所述膜包含至少一种异氰酸酯官能的聚氨酯聚合物和至少一种式(II)的噁唑烷。
优选地,式(I)的醛亚胺以这样的量使用,该量对应于醛亚氨基与噁唑烷基的比率在80/20至20/80范围内,优选75/25至35/65,更优选60/40至40/60。
此用途提供具有在低溶剂含量下低的粘度、良好的保存期稳定性、快速固化性能以及在固化之后高强度和高伸长率的膜。
单组分湿固化液体施加防水膜可通过在排除水分下混合所有成分以获得均匀的流体来制备。它可以被存储在合适的不透水分的容器中,特别是桶、鼓、带锁扣盖的小圆桶(hobbock)、袋子、肠状容器(sausage)、筒、罐或瓶中。
将膜在其开放时间内以液体状态施涂,典型地通过将其倾倒到基材上,接着将其散布开,例如用辊或刮板,以获得所需的层厚度,该厚度典型地在0.5至3mm,特别是0.75至1.5mm。
在此“开放时间”是指暴露于湿气和在膜表面上形成结皮之间的时间段,也被称为“不粘时间”或“结皮时间”。
液体施加膜是自流平的,这意味着它的粘度足够低以在通过辊或刷散布之后建立均匀的表面。
当与水分(通常大气中的水分)接触时,膜的固化开始。固化过程通过化学反应进行。醛亚氨基和噁唑烷基都被水分活化,然后与异氰酸酯基团反应。当活化时,各醛亚氨基形成伯氨基,而每个噁唑烷基团形成仲氨基和羟基。此外,异氰酸酯基团也可以直接与水分反应。作为这些反应的结果,该膜固化成固体弹性材料。固化过程也可以称为交联。固化后,得到对大量基材具有非常好的粘附性的弹性材料。
在固化反应过程中,膜中存在的醛亚胺和噁唑烷的封闭剂被释放。在式(I)的醛亚胺的情况下,封闭剂是式(IV)的醛;在式(II)的噁唑烷的情况下,其为脂族醛或酮,优选醛。这些封闭剂,取决于它们的挥发性和其他因素如其在膜中的溶解性,可以在固化期间或在固化之后从膜蒸发,或者可以保留在固化的膜中。后者特别是对于式(IV)的醛的情况,其具有低的挥发性并且具有很小的气味或是无味的。这减小了气味、排放和膜的收缩率。优选的式(I)的醛亚胺释放2,2-二甲基-3-月桂酰氧基丙醛,其是完全无味的并且几乎完全保留在膜中,与交联的聚氨酯聚合物相容并起到增塑剂的作用。
该膜可以被施加到各种基材上,在基材上形成弹性涂层。它可特别用于防水屋顶、屋顶平台或屋顶花园,以及花盆、阳台、露台、广场或地基。它也可以在室内用于防水,特别是在陶瓷砖、如在浴室中、餐饮厨房或植物室,保护它们免受水侵入。液体施加膜特别适合于翻修目的。
最优选的是在屋顶上使用,特别是平的或低坡度屋顶上。它可用于新的屋顶的防水以及翻修目的,并且对于琐碎工作特别有用。
液体施加膜优选用作防水系统的一部分,该系统由以下组成:
-任选地,底漆和/或底涂层,
-一层或多层所述膜,优选与纤维增强网组合,和
-任选地,顶涂层。
液体施加膜优选通过以下施用:将其倾倒到基材上,在其开放时间内通过辊、刷、扩散刀或刮刀均匀地散布至所希望的层厚度,该厚度通常在0.5至3mm的范围内,特别是在0.75至1.5mm的范围内。
优选地,纤维增强网在所述膜的第一层之后施加,通过将其放置在新施加的膜的顶部,然后在膜的开放时间内将其辊压或处理完全透入到膜中,特别是通过辊或刷。然后在任选的下一层膜施涂之前,将掺入纤维增强网的膜至少固化至其适合行走的程度。
可能有利的是向膜的顶层施加顶涂层,如覆盖漆等。特别是对于基于芳族异氰酸酯的膜,有利的是向固化的膜上应用抗紫外线的顶涂层。
本发明的另一个主题是使屋顶结构防水的方法,包括:
-以0.5至3mm、特别是0.75至1.5mm范围的层厚度将液体状态的膜施涂到所述屋顶结构的基材上,
-在所述膜的开放时间内使所述膜与纤维增强网接触,
-将所述膜暴露于水分,由此部分或完全固化所述膜以获得弹性涂层,
-任选地以0.5至3mm、特别是0.75至1.5mm范围的厚度施涂第二层膜,并通过暴露于水分将其固化。
纤维增强材料网优选是无纺聚酯纤维网,更优选非织造玻璃纤维网。
纤维增强材料网起到膜的增强作用,提供增加的强度和耐久性。在优选的非织造纤维网中无规取向的纤维赋予膜多方向的强度,同时使其保持高度弹性。它改进了强度、抗撕裂性和抗穿刺性。无纺玻璃纤维网显示出特别容易处理,因为它不是刚性的,但很容易适应于给定的表面形貌。
在其上可以施涂膜的基材特别为:
-混凝土,轻质混凝土,砂浆,砖,土坯,瓦,石板,石膏和天然石材,如花岗岩或大理石;
-金属和合金,如铝、铜、铁、钢、有色金属,包括表面精加工的金属和合金,如镀锌金属和镀铬金属;
-沥青;
-沥青毡;
-塑料,如PVC、ABS、PC、PA、聚酯、PMMA、SAN、环氧树脂、酚醛树脂、PUR、POM、PO、PE、PP、EPM、EPDM,其为未处理形式或用等离子体、电晕或火焰进行表面处理的;尤其是PVC、PO(FPO、TPO)或EPDM膜;
-涂覆的基材,如上漆瓷砖、涂覆混凝土和涂覆的金属。
可以是有利的是在施涂膜之前预处理基材,例如通过洗涤、压力清洗、擦拭、吹净、研磨和/或施加底漆和/或底涂层。
通过这种方法,获得包含具有掺入纤维增强网的固化的膜的防水屋顶结构。
屋顶结构优选建筑物的屋顶的部分,特别是结构和土木工程的建筑物,优选房子、工业建筑、飞机库、购物中心、运动体育场等。
本文所述的单组分湿固化液体施加防水膜具有一系列优点。它具有低气味、在低溶剂含量下长的保存期稳定性和低粘度,甚至当每升仅含约50g或以下的VOC时。作为单组分体系,不需要混合步骤,这有利于应用。它具有足够长的开放时间以允许手工施用,使得没有必要使用特殊设备如喷涂机。它的开放时间可以在宽范围内调节,特别是通过选择催化剂以及催化剂的量。当与水分接触时,其令人吃惊地快地固化为适合行走的固体材料。完全固化后,膜是具有高强度、伸长率和耐久性的弹性材料。优选地,它具有至少3.5MPa的拉伸强度,更优选至少4MPa,且最优选至少5MPa。优选地,它具有至少为200%的伸长率,更优选至少300%,并且最优选至少350%。
具有这些性质,所述膜能够在宽的温度范围内保护建筑物的屋顶免于进水。
实施例:
“标准气候”是指23±1℃的温度和50±5%的相对空气湿度。
所制备的醛亚胺的胺含量(游离胺和封闭胺即醛亚氨基的总含量)是通过滴定法测定(用冰醋酸中的0.1N HClO4,以结晶紫为指示剂),并以mmol N/g给出。
1.使用的物质
聚合物-1通过使906.1g平均分子量约1000g/mol的聚氧化亚丙基二醇(1010L,来自Dow)、28.1g 1,4-丁二醇和514.4g异佛尔酮二异氰酸酯(IPDI,来自Evonik)在1.4g二月桂酸二丁基锡(DBTDL)的存在下根据已知方法在80℃下反应制备,获得NCO含量为6.34wt-%的异氰酸酯官能的聚氨酯聚合物。
聚合物-2通过使290.4g平均分子量约2000g/mol的聚氧化亚丙基二醇(2000L,来自Dow)、838.8g平均分子量为4000g/mol的聚氧化亚丙基二醇(4200,来自Bayer)、9.8g 1,4-丁二醇和361.0g MDI(VL 50,来自Bayer)根据已知方法在90℃下反应制备,获得NCO含量为5.2wt-%的异氰酸酯官能的聚氨酯聚合物。
醛亚胺-1:N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己胺
在氮气气氛下将598g(2.1mol)2,2-二甲基-3-月桂酰氧基-丙醛置于圆底烧瓶中。然后在良好的搅拌下加入170.3g(1mol)3-氨基甲基-3,5,5-三甲基环己胺(IPD,来自Evonik),然后在80℃和10mbar真空下除去挥发性含量。产率为732g几乎无色的液体,胺含量为2.73mmol N/g,对应于约367g/Eq计算的醛亚胺当量重。
醛亚胺-2:N,N’,N”-双(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基三胺
在对醛亚胺-1所给出的相同的条件下,使875g(3.08mol)2,2-二甲基-3-月桂酰氧基-丙醛和440g(约2.8mol N)平均分子量约440g/mol的聚氧化亚丙基三胺(T-403来自Huntsman,胺含量6.40mmol N/g)反应。产率为1264g几乎无色的液体,胺含量为2.23mmol N/g,相应于约449g/Eq计算的醛亚胺当量重。
醛亚胺-3:N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-六亚甲基-1,6-二胺
在对醛亚胺-1所给出的相同的条件下,使622g(2.2mol)2,2-二甲基-3-月桂酰氧基-丙醛和166.0g(1mol)六亚甲基-1,6-二胺溶液(70wt-%在水中)反应。产率为702g几乎无色的液体,胺含量为2.85mmol N/g,相应于约351g/Eq计算的醛亚胺当量重。
2.未填充的单组分湿固化液体施加防水膜
对于每个膜,在排除水分下通过离心混合器(SpeedMixerTM DAC150,FlackTekInc.)将表1中给出的成分在密封的聚丙烯烧杯中混合,直至得到均匀流体。
在环境温度下将膜储存在紧紧密封的防潮罐中24小时,然后进行如下试验:
为了测定机械性能,对于每个膜制备两层固化的膜。为了制备膜,用引流棒施涂800μm厚的第一层,并在标准气候条件(NC)下静置固化24小时;然后以90°在其上施涂400μm厚的第二层,并再次在NC下静置固化24小时;然后将两层膜置于烘箱中在60℃下24小时。在NC下另外24小时后,从所述膜冲压出长度为75mm、横梁长度为30mm和横梁宽度为4mm的哑铃体,并根据DIN EN 53504以200mm/min的十字头速度测定拉伸强度和断裂伸长率。
各个膜的固化的自由薄膜是清晰、无气泡和无粘性的。
结果列在表1中。
液体施加膜Ex-1至Ex-3是根据本发明的实施例,液体施加膜Ref-1和Ref-2是比较例。
表1显示不同的醛亚胺和噁唑烷组合对固化的未填充膜的机械性能的影响。
Ref-1 | Ex-1 | Ex-2 | Ex-3 | Ref-2 | |
聚合物-1 | 465.3 | 465.3 | 465.3 | 465.3 | 465.3 |
溶剂<sup>1</sup> | 176.5 | 176.5 | 176.5 | 176.5 | 176.5 |
IPDI三聚体 | 65.2 | 65.2 | 65.2 | 65.2 | 65.2 |
噁唑烷 | 110.0 | 88.0 | 54.8 | 38.3 | – |
醛亚胺-1 | – | 12.9 | 15.4 | 23.3 | 45.0 |
醛亚胺-2 | – | 75.1 | 85.0 | 128.3 | 243.0 |
DBTDL | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
水杨酸 | 0.70 | 0.8 | 0.8 | 0.8 | 0.8 |
醛亚胺/噁唑烷比例<sup>2</sup> | 0/100 | 37/63 | 51/49 | 70/30 | 100/0 |
拉伸强度[MPa] | 12.76 | 11.5 | 10.23 | 9.67 | 2.27 |
断裂伸长率[%] | 369 | 531 | 548 | 610 | 526 |
表1:膜Ex-1至Ex-3和膜Ref-1至Ref-2的组分(重量份)和测试结果
11-甲氧基-2-丙基醋酸酯
2醛亚氨基和噁唑烷之间的比例
3.填充的脂族单组分湿固化液体施加防水膜
对于每个膜,在排除水分下通过离心混合器(SpeedMixerTMDAC150,FlackTekInc.)将以下成分在密封的聚丙烯烧杯中混合,直至得到均匀流体:
554.7重量份聚合物1,
58.6重量份1-甲氧基-2-丙基醋酸酯,
71.5重量份IPDI三聚体,
278.9重量份二氧化钛,
545.3重量份ATH,
213.1重量份重晶石,
18.4重量份的热解二氧化硅,
26.9重量份炭黑,
10.0重量份HALS,
0.2重量份DBTDL,
0.8重量份水杨酸和
在表2中给出的成分。
在环境温度下将膜储存在紧紧密封的防潮罐中24小时,然后进行如下试验:
在20℃的温度下用Brookfield DV-E纺锤型粘度计测量粘度,锭子n°5,30rpm。“初始”是指在成分混合24小时后测得的粘度。“28d 40℃”是指在40℃下另外存储28天后测量的粘度。“42d 40℃”是指在40℃下另外存储42天后测量的粘度。
固化速度(“BK干燥时间”)根据ASTM D5895在20℃/45%相对湿度下使用Beck-Koller干燥时间记录器测定。第2阶段的结果大致表明膜的结皮时间。
按照对表1中未填充的膜所述测量拉伸强度和断裂伸长率。
各个膜的固化的自由薄膜是无气泡和无粘性的。
结果列在表2中。
液体施加膜Ex-4至Ex-6是根据本发明的实施例,液体施加膜Ref-3和Ref-4是比较例。
表2显示基于从脂族多异氰酸酯获得的聚氨酯聚合物的填充的低VOC膜。
表2:膜Ex-4至Ex-6和膜Ref-3至Ref-4的组成(重量份)和测试结果
2醛亚氨基和噁唑烷基之间的比例
4.填充的芳族单组分湿固化液体施加防水膜
对于每个膜,在排除水分下通过离心混合器(SpeedMixerTM DAC150,FlackTekInc.)将以下成分在密封的聚丙烯烧杯中混合,直至得到均匀流体。
652.1重量份聚合物-2
569.5重量份二甲苯,
160.8重量份二氧化钛,
221.1重量份重晶石,
881.9重量份白垩,
40.4重量份热解二氧化硅,
202.0重量份邻苯二甲酸二异癸酯和
在表3中给出的成分。
在环境温度下将膜储存在紧紧密封的防潮罐中24小时,然后按照与表2的填充的脂族膜相同的方式进行试验。
测试结果在表3中给出。
膜Ex-7和Ex-8是根据本发明的实施例,液体施加膜Ref-5和Ref-6是比较例。
表3显示基于由芳族多异氰酸酯获得的聚氨酯聚合物的填充的膜。
Ref-5 | Ex-7 | Ex-8 | Ref-6 | |
上述给出的成分 | 2‘727.8 | 2‘727.8 | 2‘727.8 | 2‘727.8 |
噁唑烷 | 91.3 | 45.7 | 45.7 | 68.5 |
醛亚胺-1 | - | 45.7 | - | - |
醛亚胺-3 | - | - | 45.7 | 22.8 |
醛亚胺/噁唑烷比例<sup>1</sup> | 0/100 | 41/59 | 42/58 | 19/81 |
粘度[mPa·s],最初 | 9’500 | 8’500 | 9’000 | 10’000 |
粘度[mPa·s],42d 40℃ | 26’000 | 18’000 | 19’000 | 25’000 |
拉伸强度[MPa] | 4.1 | 3.9 | 3.6 | 4.0 |
断裂伸长率[%] | 178 | 223 | 242 | 204 |
表3:实施例Ex-7、Ex-8、Ref-5和Ref-6的组成(重量份)和测试结果
1醛亚氨基和噁唑烷基之间的比例。
Claims (17)
1.一种单组分湿固化液体施加防水膜,其包含
-至少一种异氰酸酯官能的聚氨酯聚合物,其中所述异氰酸酯官能的聚氨酯聚合物基于脂族多异氰酸酯,
-至少一种式(I)的醛亚胺,
其中
A是分子量在28至5000g/mol范围的任选地含醚或氨基甲酸酯基团的n价烃基部分,
R1和R2各自是甲基;
R3是氢,或者直链或支链的C1至C12烷基或芳烷基或烷氧基羰基,
R4是任选地含醚基、羰基或酯基的一价C6至C20烃基部分,和
n为2至6;
-至少一种式(II)的噁唑烷,
其中
B是分子量在28至2000g/mol范围的任选地含醚、酯、酰胺或脲基团的m价烃基部分,
R5是氢和R6独立地选自氢或C1至C12直链或支链的烷基,和
m为2或3;
由此,醛亚氨基的数目与噁唑烷基的数目之间的比率在75/25至25/75范围内。
2.根据权利要求1所述的膜,其中B是分子量在28至2000g/mol范围的任选地含碳酸酯或氨基甲酸酯基团的m价烃基部分。
3.根据权利要求1或2所述的膜,其中所述式(I)的醛亚胺选自由以下组成的组:N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-六亚甲基-1,6-二胺,N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-3-氨基甲基-3,5,5-三甲基环己胺,平均分子量为700至4600g/mol的N,N’-双(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基二胺和平均分子量在1200至5800g/mol范围的N,N’,N”-三(2,2-二甲基-3-月桂酰氧基亚丙基)-聚氧化亚丙基三胺。
4.根据权利要求1或2所述的膜,其包含至少两种不同的式(I)的醛亚胺的组合。
5.根据权利要求1或2所述的膜,其中R6是2-丙基或3-庚基。
6.根据权利要求1或2所述的膜,其中所述式(II)对应于式(II a)或(II b)
7.根据权利要求1或2所述的膜,其进一步包含
-至少一种选自无机填料和颜料的成分,
-至少一种选自阻燃增塑剂和阻燃填料的成分,和
-至少一种选自催化剂、增塑剂、溶剂和UV稳定剂的成分。
8.根据利要求1或2所述的膜,其包含
-15到70wt%的异氰酸酯官能的聚氨酯聚合物,
-20至80wt%的填料,包括无机填料、阻燃填料和颜料,
-5至30wt%的增塑剂,包括阻燃增塑剂,
-和包含至少一种选自催化剂、溶剂和UV稳定剂的其它成分。
9.根据权利要求1或2所述的膜,其在20℃下具有在2000至15000mPa·s范围的Brookfield粘度。
10.根据权利要求1或2所述的膜,其含有每升50g或更少的VOC,其中VOC表示在293.14K的温度下具有至少0.01kPa蒸气压的有机物质。
11.根据权利要求1至10任一项所述的膜在屋顶上的用途。
12.防水系统,其由以下组成:
-任选地底漆和/或底涂层,
-一层或多层根据权利要求1至10任一项所述的膜,和
-任选地顶涂层。
13.根据权利要求12所述的防水系统,其中所述的膜与纤维增强网组合。
14.使屋顶结构防水的方法,包括
-以0.5至3mm范围的层厚度将根据权利要求1至10任一项所述的膜以液体状态施加到屋顶结构的基材上,
-在所述膜的开放时间内使所述膜与纤维增强网接触,
-将所述膜暴露于水分,由此使得所述膜部分或完全固化以获得弹性涂层,
-任选地以0.5至3mm范围的层厚度施加第二层膜,并通过暴露于水分将其固化。
15.防水屋顶结构,其根据权利要求14的方法获得。
16.至少一种式(I)的醛亚胺在单组分湿固化液体施加防水膜中作为稀释剂的用途,
其中
A是分子量在28至5000g/mol范围的任选地含醚或氨基甲酸酯基团的n价烃基部分,
R1和R2各自是甲基;
R3是氢,或者直链或支链的C1至C12烷基或芳烷基或烷氧基羰基,
R4是任选地含醚基、羰基或酯基的一价C6至C20烃基部分,和
n为2至6;
所述膜包含至少一种异氰酸酯官能的聚氨酯聚合物和至少一种式(II)的噁唑烷,
其中
B是分子量在28至2000g/mol范围的任选地含醚、酯、酰胺或脲基团的m价烃基部分,
R5是氢和R6独立地选自氢或C1至C12直链或支链的烷基,和
m为2或3;
其中醛亚氨基的数目与噁唑烷基的数目之间的比率在75/25至25/75范围内。
17.根据权利要求16所述的用途,其中B是分子量在28至2000g/mol范围的任选地含碳酸酯或氨基甲酸酯基团的m价烃基部分。
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CN101312942A (zh) * | 2005-09-30 | 2008-11-26 | Sika技术股份公司 | 带有具有活性氢的反应性基团的醛亚胺及其用途 |
CN101484491A (zh) * | 2006-06-30 | 2009-07-15 | Sika技术股份公司 | 无voc或低voc含量的聚氨酯涂层 |
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KR102243167B1 (ko) | 2021-04-22 |
EP2948485B1 (en) | 2019-09-11 |
US10415250B2 (en) | 2019-09-17 |
JP6348913B2 (ja) | 2018-06-27 |
JP2016510354A (ja) | 2016-04-07 |
WO2014114640A1 (en) | 2014-07-31 |
US20160024318A1 (en) | 2016-01-28 |
CN104903371A (zh) | 2015-09-09 |
KR20150108359A (ko) | 2015-09-25 |
EP2948485A1 (en) | 2015-12-02 |
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