CN107254244A - 用于密封表面的涂料组合物 - Google Patents
用于密封表面的涂料组合物 Download PDFInfo
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- CN107254244A CN107254244A CN201710348947.5A CN201710348947A CN107254244A CN 107254244 A CN107254244 A CN 107254244A CN 201710348947 A CN201710348947 A CN 201710348947A CN 107254244 A CN107254244 A CN 107254244A
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- 238000004132 cross linking Methods 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
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- QRANWKHEGLJBQC-UHFFFAOYSA-N n-(trimethoxysilylmethyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CNC1CCCCC1 QRANWKHEGLJBQC-UHFFFAOYSA-N 0.000 description 1
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- 230000001473 noxious effect Effects 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical class [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical class CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- UOTGHAMTHYCXIM-UHFFFAOYSA-N trimethoxysilylmethylurea Chemical compound CO[Si](OC)(OC)CNC(N)=O UOTGHAMTHYCXIM-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Abstract
本发明涉及用于密封表面的涂料组合物,具体为湿固化涂料组合物(C),包含:A)100重量份具有通式(I)‑A‑Si(OR1)xR2 3‑x的端基的硅烷封端的聚合物(P),B)7至200重量份通式(II)R3‑Si(OR4)yR5 3‑y的反应性增塑剂(RW),C)0至400重量份填料(F)和D)0.1至20重量份固化催化剂(K),其中A为具有1至10个碳原子的直链或支链的亚烷基,R1和R4各自为直链或支链的、未取代的或卤代的具有1至10个碳原子的烷基,R2和R5各自为直链或支链的、未取代的或卤代的具有1至5个碳原子的烷基,R3为具有6至40个碳原子的芳基或者直链、支链的或环状的烷基或烯基,并且x和y各自为1、2或3,以及还有一种密封表面的方法。
Description
本申请是申请日为2011年4月11日、发明名称为“用于密封表面的涂料组合物”的中国专利申请号201180020051.5的分案申请。
技术领域
本发明涉及一种包含硅烷封端的聚合物的湿固化涂料组合物(moisture-curingcoating composition)和一种用于密封表面的方法。
背景技术
在建筑物或屋顶上内部地和外部地密封有机和无机建筑材料,例如木材或混泥土,防止水渗透,以便防止随着时间的推移材料的破坏是极其重要的。
在具有冗长细节复杂的屋顶上,过去经常使用许多密封材料,例如油毛毡,由于密封角和边难度很大,几乎完全消失。随后通过使用熔融沥青解决了此问题,但代价是对操作员来说的其它危害,经过有毒蒸汽和用非常热的液体操作。VOC限制和毒理学考虑已看到了其它之前使用的解决方法,例如溶剂沥青体系,被不同的技术取代。
当今,主要使用水基涂覆材料,例如丙烯酸酯改性或聚合物改性的沥青乳液,虽然单组份或双组份(two-component)聚氨酯体系也继续发挥重要作用,例如,在屋顶密封中。
水乳液的主要缺点是材料的物理干燥,特别地当低于温度15℃时变得非常缓慢。相反地,高于25℃时表面干燥相对较快,可能与水内容物相关,接着,形成气泡。在这种方式中,在涂层中形成了薄弱点,并可能导致泄漏。
单组份(one-component)、基于聚氨酯的密封体系通常包括大量的溶剂以使粘度降低至用于涂刷或辊施于屋顶区域可接受的水平。相比之下,双组份聚氨酯体系是非常昂贵的并需要复杂的施加技术。所有聚氨酯密封体系包括剧毒异氰酸酯化合物,在几乎所有家庭应用中,并且在许多专业应用中,其使用被认为是危险的。
RTV-1硅酮涂料制剂,例如醋酸酯体系或肟体系在固化过程中释放出具有较差气味或甚至对健康有害的消除反应产物,例如乙酸或肟。这些材料的其它缺点是对大量的建筑材料的粘附性差、再涂性差,并且气候稳定性不足。
单组份、湿固化涂覆材料基于MS聚合物(由特定过程制备的硅烷封端的聚酯)以应用于建筑领域的密封材料的形式是已知的,来自EP 1695989A,WO 2007/093382,和WO2008/077510。
此外,EP 2135852描述了基于硅烷封端的聚合物的制剂,通过多元醇和异氰酸酯基官能化聚合物反应制备,另外也包括氨烷基烷氧基硅烷和相对小的量,即,优选地按重量计1%至5%的烷基烷氧基硅烷无需额外的反应性有机官能团。
然而,所有已知的产品都具有缺点,在某些情况下,这些缺点是大量的。例如,基于传统硅烷交联预聚物的所有制剂的共同特性是它们反应相对缓慢—换句话说,对于合理的结皮时间和可通过的固化体积,通常需要锡催化剂。而且,基于MS聚合物的制剂具有缺点,具有大量残余粘度。这导致快速弄脏并且是不希望的结果,尤其是在屋顶区域应用中。此外,为了实现可接受的机械性能,基于MS聚合物的制剂需含有按重量计超过25%的MS聚合物,作为一个比较昂贵的制剂成分,如从WO 2007/093382中已知的。
然而,所有已知体系的主要缺点在于使用的硅烷交联预聚物的高粘度。为了获得可喷涂的、可辊涂的或可抹涂的制剂,因此,一般需要添加有机溶剂和/或大量的具有稀释效果的增塑剂。溶剂,作为挥发性有机成分,由于环境原因是不希望的。增塑剂,用于其部分,可以随时间的推移从产品中“渗出”,这同样是很严重的问题。
发明内容
本发明的目的是提供一种单组份(one-component)、湿固化、无异氰酸酯和无沥青的组合物,该组合物适用于密封表面,特别是外部和内部建筑表面、屋顶和类似物,并且其不再具有上述缺点。
本发明提供了一种湿固化涂料组合物(C),包括
A)100重量份具有通式(I)的端基的硅烷封端的聚合物(P),
-A-Si(OR1)xR2 3-x (I),
B)7至200重量份的通式(II)的反应性增塑剂(RW),
R3-Si(OR4)yR5 3-y (II),
C)0至400重量份填料(F),和
D)0.01至20重量份固化催化剂(K),其中
A是具有1至10个碳原子的直链或支链的亚烷基,
R1和R4各自为具有1至10个碳原子的直链或支链的、未取代的或卤代的烷基,
R2和R5各自为具有1至5个碳原子的直链或支链的、未取代的或卤代的烷基,
R3为具有6至40个碳原子的芳基或直链、支链的或环状的烷基或烯基,其中单个氢原子可以被有机基团取代,并且,如果R3为或直链、支链的或环状的烷基或烯基,碳链可以被氧原子中断,和
x和y为1、2或3。
湿固化涂料组合物(C)尤其适用于密封表面防止水或水蒸汽的渗透。只需要很少量,或完全没有有机增塑剂,并不包含挥发性溶剂。通过刷涂、辊涂或喷涂仍然粘度足够低能够施加,没有任何问题。此外,不需要含金属的催化剂,例如含锡催化剂,并且需要相对少量的可交联聚合物。其固化形成无粘性涂料。
首先本发明基于令人惊讶的发现,增塑剂(RW)可以添加至湿固化涂料组合物(C)中,即使在浓度按重量计高于5%情况下,此添加不损害产品的重要性能。因此,传统烷氧基硅烷的相对大量的加入——即,通式(II)的非发明的烷氧基硅烷,其中R3是具有小于6个碳原子的烷基或有机官能团烷基(例如,氨丙基)——在密封剂固化上,通常导致脆化情况和形成不光滑和均匀的表面。此外,这种涂料在固化状态下表现出降低的断裂伸长率,同时,特别是在有机官能化硅烷的情况下,表现出相对差的疏水性以及拒水性能。
其次,本发明基于发现:通过添加反应性增塑剂(RW)可以实现多个积极的产品性能的组合。例如,首先反应性增塑剂(RW)大大降低了涂料组合物(C)的粘度。然而,由于它们化学地结合到在涂料组合物(C)固化过程中形成的网络,反应性增塑剂既不易挥发,也不能从固化的密封剂中渗出。同时,它们增加了固化的涂料组合物的疏水性以及从而拒水性。
涂料组合物(C)优选地具有在20℃粘度不超过20000mPa.s,优选的粘度不超过10000mPa.s并且特别优选的粘度不超过5000mPa.s。
聚合物(P)优选地包含通式(IV)的端基
~O-C(=O)-NH-A-Si(OR1)xR2 3-x (IV),
其中,所有的变量具有通式(I)说明的定义。
A优选地为亚丙基或亚甲基。亚甲基是特别优选的,由于其高湿反应性。制剂包括具有通式(IV)的端基的聚合物(P),其中A为亚甲基,其优势在于可以其被固化优选无金属催化剂和更特别地无含锡催化剂。
当然,也可以使用具有通式(I)和/或(IV)的端基的两种或多种聚合物(P)的混合物,其中A、R1、R2和x具有不同的定义,实例为聚合物(P)其中R1代表部分为甲基基团和部分为乙基基团,和/或A代表部分为亚丙基和亚甲基。
湿固化涂料组合物(C)优选地包括具有通式(I)的端基的聚合物(P)或——更优选地——通式(IV)的端基,浓度按重量计为至少5%,更优选地按重量计为至少8%,更特别地按重量计为至少10%,并且优选地按重量计不超过50%,更优选地按重量计不超过40%,更特别地按重量计不超过25%。
反应性增塑剂(RW)优选地符合通式(V)
R6-Si(OR1)xR2 3-x (V),
其中
R6为具有8至40个碳原子的取代的或未取代的、直链或支链的烷基,其中碳链可以被氧原子中断,
并且所有其它变量具有为本发明的通式(I)说明的定义。
优选地R6为具有8至20个碳原子的纯支链或无支链的烃基。尤其优选的基团R6为异辛基、辛基、癸基、十二烷基、十四烷基,和更特别地十六烷基。
湿固化涂料组合物(C)优选包括具有通式(II)的端基的反应性增塑剂(RW)或——更优选地——通式(V)的端基,浓度按重量计不超过为40%,更优选地按重量计不超过30%,和优选地按重量计为至少10%,更优选地按重量计为至少15%。
湿固化涂料组合物(C)优选地包括至少15重量份的通式(II)的反应性增塑剂(RW),更优选地至少30重量份,更特别地至少50重量份,并且优选地不超过150重量份,更优选地不超过100重量份。
烷基R1、R2、R4和R5的实例为甲基、乙基、正丙基、异丙基、正丁基、异丁基或叔丁基基团。
R1和R4优选地为甲基或乙基基团。
R2和R5优选地为甲基基团。
x和y优选地为2或3。
包括通式(I)的端基的聚合物(P)的实例优选聚酯、聚醚、聚烯烃(polyalkylene)或聚丙烯酸酯。尤其优选的为直链聚醚,例如聚环氧丙烷。聚合物(P)的平均分子量Mn优选地为至少2000g/mol,更优选地至少4000g/mol,更特别地至少10000g/mol,并且优选地不超过25000g/mol,更优选地不超过20000g/mol,更特别地不超过19000g/mol。聚合物(P)的粘度优选地在20℃为至少0.2Pa.s,更优选地在20℃至少1Pa.s,非常优选地在20℃至少5Pa.s,并且优选地在20℃不超过100Pa.s,更优选地在20℃不超过40Pa.s。聚合物(P)优选地通过WO 2006/136261、EP 1 535 940 A1或WO 2007/131986中描述的工艺种类制备。
作为本发明的涂料组合物(C)的基础优选硅烷封端的聚醚,更特别地硅烷封端的聚丙二醇,具有分子式(IV)的二甲氧基甲基甲硅烷基、三甲氧基甲硅烷基、二乙氧基甲基甲硅烷基或三乙氧基甲硅烷基端基,具有不同粘度。
值得注意的是,基于具有通式(IV)端基的硅烷封端的聚合物(P)的本发明的涂料制剂(C)固化为完全无粘性涂层,并因此显著不同于基于所谓的MS聚合物的硅烷交联密封体系,如在现在技术中描述的。
此外,令人惊奇地发现,本发明的基于具有通式(IV)端基的硅烷封端的聚合物(P)的涂料制剂(C),用相对低水平的聚合物(P)经历有效的体积固化(volume curing),并且固化的涂料拥有足够的机械性能。
当使用含具有通式(IV)端基的硅烷封端的聚合物(P)的涂料组合物(C)时,进一步的优势在于它们需要非常小的量,或没有,为了达到足够的固化速率含金属催化剂,更特别地含锡催化剂。如已描述的,由于端基拥有特别高的反应性,当聚合物(P)具有至少40mol%——优选至少50mol%——的具有通式(IV)(其中A为亚甲基)端基的聚合物分子时,该优势尤其明显。因此,特别优选要求保护的为基于具有相应组成的聚合物(P)的涂料组合物(C)。
反应性增塑剂(RW)的实例是所有具有至少6个,优选地至少8个,碳原子的烷基R5的硅烷。由于其易于获得,此处优选具有带偶数个碳原子的烷基R5的通式(V)硅烷。实例包括异辛基三甲氧基硅烷、异辛基三乙氧基硅烷、N-辛基三甲氧基硅烷、N-辛基三乙氧基硅烷、癸基三甲氧基硅烷、癸基三乙氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷、十四烷基三甲氧基硅烷、十四烷基三乙氧基硅烷、十六基三甲氧基硅烷、十六基三乙氧基硅烷,以及带更长烷基的硅烷。
填料(F)的实例为氢氧化铝、碳酸钙、硫酸钡、滑石、云母、高岭土、二氧化硅、石英、重晶石和炭黑。
一种优选的填料(F)是碳酸钙。优选的碳酸钙类型是重质或沉淀的并且可选地用脂肪酸表面处理的,例如硬脂酸或其盐类。组合物(C)优选地按重量计包括至少10%,更优选地按重量计至少为20%,并优选地按重量计不超过75%,更优选地按重量计不超过70%,非常优选地按重量计不超过65%的碳酸钙。
湿固化涂料组合物(C)优选地包括至少20重量份,更优选地至少30重量份,更特别地至少60重量份,更特别优选至少100重量份,并且优选不超过300重量份,更优选不超过200重量份的填料(F)。
特别优选的填料(F)为滑石和氢氧化铝。这两种类型的填料与其它填料相比具有更少强度地增加所产生的涂料组合物(C)的粘性的优势。组合物(C)优选包含按重量计至少10%,更优选地按重量计至少20%,并且优选地按重量计不超过75%,更优选地按重量计不超过70%,并且非常优选地按重量计不超过65%的滑石和/或氢氧化铝。
另一种特别优选的填料(F)为二氧化硅,更特别地气相法二氧化硅。非常特别优选组合物(C)不仅包括二氧化硅,更特别地气相法二氧化硅,而且包括其它填料(F),优选碳酸钙。在这种情况下,组合物(C)包括二氧化硅,更特别地气相法二氧化硅,优选地用量按重量计为至少0.1%,更优选地按重量计至少0.4%,并且优选地按重量计不超过10%,更优选地按重量计不超过5%,以上述指定的量的氢氧化铝。替代氢氧化铝也可以使用滑石、碳酸钙或氢氧化铝、滑石和/或碳酸钙的混合物。所有填料(F)一起的用量按重量计不超过80%。
进一步优选的组合物(C)是透明的并且只包括二氧化硅,更特别地气相法二氧化硅,作为填料(F),优选用量为按重量计为5%至50%。
含金属固化催化剂(K)的实例包括有机钛和锡化合物,实例为钛酸酯,例如钛酸四丁酯、钛酸四丙酯、钛酸四异丙酯,和四乙酰丙酮钛;锡化合物,例如二月桂酸二丁基锡、马来酸二丁基锡、二乙酸二丁基锡、二辛酸二丁基锡、乙酰丙酮二丁基锡、二丁基锡氧化物,和相应的二辛基锡化合物。
无金属固化催化剂(K)的实例为碱性化合物,例如氨基硅烷,实例有3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-氨丙基甲基二甲氧基硅烷、3-氨丙基甲基二乙氧基硅烷、N-(2-氨乙基)-3-氨基-丙基三甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基甲基二甲氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷、环己基氨甲基三乙氧基硅烷、环己基氨甲基甲基二乙氧基硅烷、环己基氨甲基三甲氧基硅烷、环己基氨甲基甲基二甲氧基硅烷、3-环己基氨丙基三甲氧基硅烷和3-环己基氨丙基三甲氧基硅烷,或其它有机胺,如三乙胺、三丁胺、1,4-二氮杂双环-[2.2.2]辛烷、1,5-二氮杂双环[4.3.0]壬-5-烯、1,8-二氮杂双环[5.4.0]十一-7-烯、N,N-双(N,N-二甲基-2-氨乙基)甲胺、N,N-二甲基环己胺、N,N-二甲基苯胺、和N-乙基吗啉;酸性化合物,如磷酸及其酯类、甲苯磺酸、硫酸、硝酸或有机羧酸,实例有乙酸、苯甲酸。
固化催化剂(K)即可以纯形式又可以混合物形式使用。
不同的固化催化剂(K)的一个优选的组合物由同时使用氨基硅烷和二烷基锡化合物来表示。在这种情况下,涂料组合物(C)可以包括一种或多种含锡固化催化剂(K),用量按重量计优选地不超过0.5%,更优选地按重量计不超过0.2%,非常优选地按重量计不超过0.1%。
然而,特别优选,本发明的涂料组合物(C)是完全无锡的。在这种情况下,作为催化剂(K)优选地为氨基硅烷、不同氨基硅烷的混合物,或氨基硅烷与其它无金属化合物的混合物。
涂料组合物(C)优选地包括一种或多种固化催化剂(K),优选地无金属固化催化剂,总量按重量计优选地为至少0.01%,更优选地按重量计至少0.05%,并且优选地按重量计不超过4%,更优选地按重量计不超过2%。
湿固化涂料组合物(C)优选包括不超过10重量份,更优选地不超过5重量份,更特别地不超过1重量份的固化催化剂(K)。
优选地通过使用具有通式(IV)(其中A为亚甲基)端基的聚合物(P)获得涂料组合物(C)的无锡组合物。使用基于这些聚合物的无锡涂料组合物(C)因此组成了本发明的一个特别优选的实施方式。
涂料组合物(C)优选地可以包括至多20重量份,更特别地为至多10重量份一种或多种水清除剂(W)。水清除剂(W)的实例为硅烷,如乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基甲基二甲氧基硅烷、O-甲基氨基甲酸酯基甲基甲基二甲氧基硅烷、O-甲基氨基甲酸酯基甲基三甲氧基硅烷、O-乙基氨基甲酸酯基甲基甲基二乙氧基硅烷、O-乙基氨基甲酸酯基甲基三乙氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、甲基丙烯酰氧甲基甲基二甲氧基硅烷、甲基丙烯酰氧甲基三乙氧基硅烷、甲基丙烯酰氧甲基甲基二乙氧基硅烷、3-丙烯酰氧丙基三甲氧基硅烷、丙烯酰氧甲基三甲氧基硅烷、丙烯酰氧甲基甲基二甲氧基硅烷、丙烯酰氧甲基三乙氧基硅烷、丙烯酰氧甲基甲基二乙氧基硅烷、氨基硅烷,此外,可以使用已经描述的作为催化剂(K)的相同的氨基硅烷;和原酯,例如1,1,1-三甲氧基乙烷、1,1,1-三乙氧基乙烷、三甲氧基甲烷、三乙氧基甲烷,和相关化合物。
涂料组合物(C)优选地包括按重量计至少0.1%,更优选地按重量计至少0.5%,并且优选地按重量计不超过5%,更优选地按重量计不超过2%的一种或多种水清除剂(W)。
涂料组合物(C)优选地可以包括至多20重量份,更特别地为至多10重量份的一种或多种粘合促进剂(H)。粘合促进剂(H)的实例是氨基硅烷,此外,可以使用已描述的作为催化剂(K)的相同的氨基硅烷。环氧硅烷,例如缩水甘油氧丙基甲基二甲氧基硅烷、缩水甘油氧丙基三乙氧基硅烷或缩水甘油氧丙基甲基二乙氧基硅烷,以及其它具有有机官能团的硅烷,例如,像2-(3-三乙氧基甲硅烷基丙基)马来酸酐、N-(3-三甲氧基甲硅烷基丙基)脲、N-(3-三乙氧基甲硅烷基丙基)脲、N-(三甲氧基甲硅烷基甲基)脲、N-(甲基二甲氧基甲硅烷基甲基)脲、N-(3-三乙氧基甲硅烷基甲基)脲、N-(3-甲基二乙氧基甲硅烷基甲基)脲、O-甲基氨基甲酸酯基甲基甲基二甲氧基硅烷、O-甲基氨基甲酸酯基甲基三甲氧基硅烷、O-乙基氨基甲酸酯基甲基甲基二乙氧基硅烷、O-乙基氨基甲酸酯基甲基三乙氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、甲基丙烯酰氧甲基三甲氧基硅烷、甲基丙烯酰氧甲基甲基二甲氧基硅烷、甲基丙烯酰氧甲基三乙氧基硅烷、甲基丙烯酰氧甲基甲基二乙氧基硅烷、3-丙烯酰氧丙基三甲氧基硅烷、丙烯酰氧基甲基三甲氧基硅烷、丙烯酰氧甲基甲基二甲氧基硅烷、丙烯酰氧甲基三乙氧基硅烷,和丙烯酰氧甲基甲基二乙氧基硅烷,可以用作粘合促进剂。
涂料组合物(C)包括一种或多种粘合促进剂(H),用量按重量计优选地为至少0.01%,更优选地按重量计至少0.5%,并且优选地按重量计不超过5%,更优选地按重量计不超过2%。
氨基硅烷用作固化催化剂(K)时,它们优选地同时也作为水清除剂(W)和/或粘合促进剂(H)。氨基硅烷在本发明的涂料组合物中的用量优选地按重量计至少为0.01,更优选地按重量计为至少0.5%,并且优选地按重量计不超过5%,更优选地按重量计不超过3%。
湿固化涂料组合物(C)优选地包括至多100重量份,更特别地为至多50重量份一种或多种通式(III)的四烷氧基硅烷(TS)
Si(OR6)4 (III),
其中,R6为具有1至10个碳原子的直链或支链的、可选卤化的烷基,
和/或四烷氧基硅烷(TS)的部分缩合物。
在涂料组合物(C)中,优选使用四乙氧基硅烷并且更优选地使用具有1.5-15平均缩合度的四乙氧基硅烷的部分缩合物,更优选具有3至8的平均缩合度。通式(III)的四烷氧基硅烷(TS)和/或这些四烷氧基硅烷的部分缩合物在涂料组合物(C)的量优选地按重量计为至少0.01%,更优选地按重量计至少0.5%,并且优选地按重量计不高于20%,更优选地按重量计不高于10%。
涂料组合物(C)可以进一步包括常用于湿固化涂料组合物的物质。这些物质包括非反应性增塑剂、流变添加剂、稳定剂如抗氧化剂和UV稳定剂、杀真菌剂、颜料、阻燃剂,和溶剂。
涂料组合物(C)优选地可以包括至多50重量份,更特别地至多10重量份一种或多种增塑剂,优选地非反应性增塑剂如邻苯二甲酸酯(如,邻苯二甲酸二辛酯、邻苯二甲酸二异辛酯、邻苯二甲酸十一烷酯,等)、全氢化邻苯二甲酸酯(如,1,2-环己烷二甲酸二异壬酯、1,2-环己烷二甲酸二辛酯,等)、己二酸酯(如,己二酸二辛酯,等)、苯甲酸酯、二醇酯、饱和烷二醇酯(如,2,2,4-三甲基-1,3-戊二醇单异丁酸酯、2,2,4-三甲基-1,3-戊二醇二异丁酸酯)、磷酸酯、磺酸酯、聚酯、聚醚(如聚乙二醇、聚丙二醇,等)、聚苯乙烯、聚丁二烯、聚异丁烯、链烷烃,以及高分子量的支链烃。存在于组合物(C)中的所有增塑剂的总量优选地按重量计为不超过30%,更优选地按重量计不超过20%,并且非常优选地按重量计不超过10%。
本发明的涂料制剂(C)可以包括一种或多种流变添加剂,例如,亲水性气相法二氧化硅、涂覆的疏水性气相法二氧化硅、沉淀二氧化硅、聚酰胺蜡、氢化蓖麻油、硬脂酸盐,和沉淀碳酸钙,优选地按重量计以至少0.1%的量使用,更优选地按重量计至少0.5%,并且优选地按重量计不超过10%,更优选地按重量计不超过5%。
本发明的涂料制剂(C)可以进一步包括稳定剂,例如光稳定剂(如,HALS化合物)、杀真菌剂、阻燃剂、颜料、溶剂,或典型的单组份、硅烷交联体系的其它添加剂。
优选下面涂料组合物(C):
按重量计13%至35%的硅烷封端的聚合物(P)
按重量计6%至30%的反应性增塑剂(RW)
按重量计10%至70%的氢氧化铝、滑石、云母或碳酸钙
按重量计0.5%至4%的水清除剂(W)
按重量计0.05%至3%的固化催化剂(K),更特别地无锡固化催化剂
按重量计0.1%至5%的粘合促进剂(A)
按重量计0.1至10%的四烷氧基硅烷(TS)
按重量计0%至20%的增塑剂
按重量计0%至5%的流变添加剂
按重量计0%至5%的稳定剂和颜料
按重量计0%至30%的阻燃剂
按重量计0%至10%的溶剂
加入总量至按重量计100%。
反应性增塑剂(RW)在该优选的涂料组合物(C)中的量优选地按重量计高于10%,更优选地按重量计至少为15%。
在一个优选的实施方式中本发明的涂料组合物(C)是无溶剂的。在特别优选的实施方式中,本发明的涂料组合物(C)是无溶剂和无增塑剂的。
涂料组合物(C)可以由用于生产湿固化涂料组合物的常规技术和混合方法制备。
同样本发明提供一种密封表面的方法,其中本发明的涂料组合物(C)施加至要密封的表面。在这种情况下,施加优选地通过刷、辊、刮刀或商购喷涂设备,如无气设备,来进行。
本发明的涂料组合物(C)优选以0.1至5mm的膜厚度施加。
本发明的涂料组合物(C)和本发明的方法适合于密封表面防止水渗透。它们适合于密封外部建筑表面,内部建筑区域(例如,在潮湿房间,在这种情况下,涂覆的表面后也可以镶瓷砖或其它装饰材料),屋顶及其类似物的表面。此外,本发明的涂料组合物(C)也可以用作减振和隔音材料。
本发明的涂料组合物(C)施加的表面的实例为矿物建筑材料、金属、屋顶油毡、塑料、机织织物、玻璃或陶瓷。本发明的涂料组合物表现出触变行为并且即可以用于水平区域又可用于垂直区域。
本发明的涂料组合物(C)优选地施加于要涂层的表面,并使其固化。固化优选在温度0至50℃进行,更优选地10至40℃,在周围大气压力下(约1020hPa)。然而,固化也可以发生在更高或更低压力下。
固化后获得的涂层具有显著的弹性、高气候稳定性,和良好的重涂性。
以上分子式中的所有上述符号在每种情况下彼此独立地具有其定义。在所有分子式中硅原子为四价。
除非另有说明,下面实施例中所有量和百分比是按重量计的,所有压力为0.10MPa(绝对压力),并且所有温度为20℃。表达“按重量计%”总是,无例外地,涉及整个涂料组合物(C)。
具体实施方式
实施例1:
将20.0g STP-E10(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚甲基、R1=甲基、R2=甲基,和x=2,商购自Wacker Chemie AG),10.0g的 STP-E15(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚丙基、R1=甲基,和x=3,商购自Wacker Chemie AG),23.5g十六基三甲氧基硅烷,2.0g乙烯基三甲氧基硅烷,1.0g疏水性二氧化硅( H2000;商购自Wacker Chemie AG),21.0g氢氧化铝(ATH),21.5g滑石,和1.0g的3-氨丙基三甲氧基硅烷混合在合适的混合装置中。
制得米色密封剂具有15000m Pas粘度(Brookfield,转子6,5.0min-1)或4800mPas(Brookfield,转子6,50min-1)。从该混合物,铸造尺寸为255×130×2nm的样品,并且测定了机械值如表I所示:
实施例2:
将20.0g STP-E10(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚甲基、R1=甲基、R2=甲基,和x=2,商购自Wacker Chemie AG),10.0g STP-E15(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚丙基、R1=甲基,和x=3,商购自Wacker Chemie AG),23.5g苯基三乙氧基硅烷,2.0g乙烯基三甲氧基硅烷,1.0g疏水性二氧化硅( H2000;商购自Wacker Chemie AG),21.0g氢氧化铝(ATH),21.5g滑石,和1.0g 3-氨丙基三甲氧基硅烷在合适的混合装置中混合。制得米色密封剂具有10600mPas粘度(Brookfield,转子6,5.0min-1)或4500mPas(Brookfield,转子6,50min-1)。从该混合物,铸造尺寸为255×130×2nm的样品,并且测定了机械值如表II所示:
实施例3:
将20.0g STP-E10(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚甲基、R1=甲基、R2=甲基,和x=2,商购自Wacker Chemie AG),10.0g STP-E15(硅烷封端的聚合物P;具有通式(IV)端基的聚丙二醇,其中A=亚丙基、R1=甲基,和x=3,商购自Wacker Chemie AG),23.5g异辛基三甲氧基硅烷,2.0g乙烯基三甲氧基硅烷,1.5g水解的硅酸四乙酯( SILIKAT TES 40WN;商购自Wacker Chemie AG),0.5g疏水性二氧化硅( H2000;商购自Wacker Chemie AG),20.0g氢氧化铝(ATH),22.4g滑石,和0.1g(N-环己基氨甲基)三乙氧基硅烷混合在合适的混合装置中。制得米色密封剂具有15600mPas粘度(Brookfield,转子6,5.0min-1)或4800mPas(Brookfield,转子6,50min-1)。由该混合物,铸造尺寸为255×130×2nm样品,并且测定了机械值如表III所示:
实施例4(未发明):
将20.0g STP-E10(硅烷封端的聚合物P;具有通式(IV)的端基的聚丙二醇,其中A=亚甲基、R1=甲基、R2=甲基,和x=2,商购自Wacker Chemie AG),10.0g STP-E15(硅烷封端的聚合物P;具有通式(IV)的端基的聚丙二醇,其中A=亚丙基、R1=甲基,和x=3,商购自Wacker Chemie AG),23.5g硅树脂( SY 231;商购自Wacker Chemie AG),2.0g乙烯基三甲氧基硅烷,1.0g疏水性二氧化硅(H2000;商购自Wacker Chemie AG),20.5g氢氧化铝(ATH),21.0g滑石,和2.0g的3-氨丙基三甲氧基硅烷在合适的混合装置中混合。制得米色密封剂具有28400mPas粘度(Brookfield,转子6,5.0min-1)或14.3200mPas(Brookfield,转子6,50min-1)。从该混合物,铸造尺寸为255×130×2nm的样品,并且测定了机械值如表IIV所示:
Claims (10)
1.一种湿固化涂料组合物(C),包括
A)100重量份具有通式(I)端基的硅烷封端的聚合物(P)
-A-Si(OR1)xR2 3-x (I),
B)30至200重量份的通式(II)的反应性增塑剂(RW),
R3-Si(OR4)yR5 3-y (II),
C)0至400重量份填料(F),和
D)0.01至20重量份固化催化剂(K),
其中
A为具有1至10个碳原子的直链或支链的亚烷基,
R1和R4各自为具有1至10个碳原子的直链或支链的、未取代的或卤代的烷基,
R2和R5各自为具有1至5个碳原子的直链或支链的、未取代的或卤代的烷基,
R3为具有6至40个碳原子的芳基或者直链、支链的或环状的烷基或烯基,和
x和y为1、2或3;并且
其中,所述聚合物(P)选自聚酯、聚醚、聚烯烃、和聚丙烯酸酯。
2.一种湿固化涂料组合物(C),包括
A)100重量份具有通式(I)端基的硅烷封端的聚合物(P)
-A-Si(OR1)xR2 3-x (I),
B)7至200重量份的通式(V)的反应性增塑剂(RW),
R6-Si(OR1)xR2 3-x (V),
C)0至400重量份填料(F),和
D)0.01至20重量份固化催化剂(K),
其中
A为具有1至10个碳原子的直链或支链的亚烷基,
R1为具有1至10个碳原子的直链或支链的、未取代的或卤代的烷基,
R2为具有1至5个碳原子的直链或支链的、未取代的或卤代的烷基,
R6选自癸基、十二烷基、十四烷基和十六烷基,和
x为1、2或3;并且
其中,所述聚合物(P)选自聚酯、聚醚、聚烯烃、和聚丙烯酸酯。
3.一种湿固化涂料组合物(C),包括
A)100重量份具有通式(I)端基的硅烷封端的聚合物(P)
-A-Si(OR1)xR2 3-x (I),
B)7至200重量份的通式(II)的反应性增塑剂(RW),
R3-Si(OR4)yR5 3-y (II),
C)0至400重量份填料(F),和
D)0.01至20重量份固化催化剂(K),
其中
A为具有1至10个碳原子的直链或支链的亚烷基,
R1和R4各自为具有1至10个碳原子的直链或支链的、未取代的或卤代的烷基,
R2和R5各自为具有1至5个碳原子的直链或支链的、未取代的或卤代的烷基,
R3为具有6至40个碳原子的芳基或者直链、支链的或环状的烷基或烯基,和
x和y为1、2或3,
条件为所述反应性增塑剂(RW)选自癸基三甲氧基硅烷、癸基三乙氧基硅烷、十二烷基三甲氧基硅烷、十二烷基三乙氧基硅烷、十四烷基三甲氧基硅烷、十四烷基三乙氧基硅烷、十六基三甲氧基硅烷、十六基三乙氧基硅烷,以及带更长烷基的硅烷;并且
其中,所述聚合物(P)选自聚酯、聚醚、聚烯烃、和聚丙烯酸酯。
4.根据权利要求1至3任一项所述的湿固化涂料组合物(C),其中所述聚合物(P)包括通式(IV)的端基
~O-C(=O)-NH-A-Si(OR1)xR2 3-x (IV),
其中,所有变量具有为权利要求1中的所述通式(I)说明的定义。
5.根据权利要求1至3任一项所述的湿固化涂料组合物(C),其中A为亚丙基或亚甲基。
6.根据权利要求1至3任一项所述的湿固化涂料组合物(C),其中包括至少20重量份的填料(F)。
7.根据权利要求1至3任一项所述的湿固化涂料组合物(C),其中所述填料(F)选自氢氧化铝、碳酸钙、硫酸钡、滑石、云母、高岭土、二氧化硅、石英、重晶石、和炭黑。
8.根据权利要求1至3任一项所述的湿固化涂料组合物(C),其中所述固化催化剂(K)选自有机钛和锡化合物、氨基硅烷、有机胺、和酸性化合物。
9.一种密封表面的方法,其中权利要求1至8任一项所述的涂料组合物(C)施加至要密封的表面。
10.根据权利要求9所述的方法,施加至要密封的表面的所述涂料组合物(C)在温度0至50℃固化。
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