CN115427474B - 用于防污和防刮擦涂料的氟化烷氧基甲硅烷基官能聚合物 - Google Patents
用于防污和防刮擦涂料的氟化烷氧基甲硅烷基官能聚合物 Download PDFInfo
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- CN115427474B CN115427474B CN202180022950.2A CN202180022950A CN115427474B CN 115427474 B CN115427474 B CN 115427474B CN 202180022950 A CN202180022950 A CN 202180022950A CN 115427474 B CN115427474 B CN 115427474B
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- alkoxysilyl
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Abstract
本发明涉及一种氟化烷氧基甲硅烷基官能聚合物,其可通过包括以下步骤的方法获得:a)使OH官能(全)氟聚醚(PFPE)与多异氰酸酯A在氨基甲酸酯形成反应条件下反应,以获得异氰酸酯官能中间体B,b)使中间体B与仲烷氧基甲硅烷基官能单胺C反应,以获得烷氧基甲硅烷基官能聚合物。所述聚合物可用作制备具有易清洁、防污和抗刮擦性能的涂料的添加剂,其可有利地用于涂覆消费电子或汽车应用中的各种基材,例如玻璃、金属、金属合金、阳极化基材、塑料、复合材料等。
Description
发明领域
本发明涉及一种氟化烷氧基甲硅烷基官能聚合物,其可用于制备用于防污和防刮擦涂层的涂料组合物。所述涂料在消费电子或汽车涂料领域特别有用。
背景
在消费电子设备领域,例如手机、平板电脑、笔记本电脑和汽车内饰,使用各种基材,例如玻璃、金属、塑料、复合材料等。通常需要用易清洁、耐污和耐刮擦的涂层覆盖这些基材。易清洁意味着表面防水、防油和/或防尘。易清洁的涂层减少或消除了清洁表面的需要。
本领域已知的是,氟化聚合物,特别是(全)氟聚醚(PFPE),具有不粘和润滑性能,并且可用于产生易清洁和防污的涂层。然而,该类树脂仅可溶于氟化溶剂,因此在不使用特殊溶剂的情况下难以用于涂料配制剂中。PFPE基聚合物的另一个问题是它们通常不具有良好的耐污性和耐刮擦性。
需要提供也耐用且同时耐刮擦的防污涂料组合物。还希望涂层能很好地粘附在消费电子和汽车工业中使用的各种基材上,例如玻璃、金属、金属合金、阳极化基材、塑料、复合材料等。
发明概述
为了解决上述期望,本发明在第一方面提供了一种氟化烷氧基甲硅烷基官能聚合物,其可通过包括以下步骤的方法获得:
a)使OH官能(全)氟聚醚(PFPE)与多异氰酸酯A在氨基甲酸酯形成反应条件下反应以获得异氰酸酯官能中间体B,
b)使中间体B与仲烷氧基甲硅烷基官能单胺C反应,以获得烷氧基甲硅烷基官能聚合物。
在另一方面中,本发明提供了一种涂料组合物,其包含根据权利要求1-5中任一项所述的氟化烷氧基甲硅烷基官能聚合物和/或通过水解该聚合物获得的氟化聚硅氧烷树脂,此外还有无氟聚硅氧烷树脂。
本发明还提供了一种涂覆基材的方法,包括将本发明的涂料组合物施加到基材上并固化该涂料组合物。
在另一方面中,本发明提供了根据本发明获得的涂覆基材。
附图简述
图1(a)显示了未涂覆的玻璃基材(顶部)和具有本发明涂层的涂覆玻璃基材(底部)。
图1(b)所示的与图1(a)所示的相同,但在用布擦拭之后。
发明详述
本发明提供了一种氟化烷氧基甲硅烷基官能聚合物。所述聚合物基于(全)氟聚醚(PFPE),并在聚合物链末端含有烷氧基甲硅烷基。
本发明的氟化烷氧基甲硅烷基官能聚合物可通过包括以下步骤的方法获得:
a)使OH官能(全)氟聚醚(PFPE)与多异氰酸酯A在氨基甲酸酯形成反应条件下反应以获得异氰酸酯官能中间体B,
b)使中间体B与仲烷氧基甲硅烷基官能单胺C反应,以获得烷氧基甲硅烷基官能聚合物。
步骤(a)
在步骤(a)中,使OH官能(全)氟聚醚与摩尔过量的多异氰酸酯A反应以获得异氰酸酯官能中间体B。
(全)氟聚醚(PFPE)是包含直链或支化的完全或部分氟化的聚氧亚烷基链的氟化聚合物,其包含具有至少一个链醚键和至少一个氟碳结构部分的重复单元。PFPE可分为非官能的和官能的;前者包括其末端具有(全)卤代烷基的PFPE链,而后者包括具有至少两个末端的PFPE链,其中至少一个末端包含官能团。官能PFPE,特别是单官能和双官能PFPE,包含具有两个末端的PFPE链,其中一个或两个末端具有官能团。在一些实施方案中,可优选使用双官能PFPE。在其他实施方案中,使用单官能PFPE。也可将单官能和双官能PFPE的混合物用于合成步骤(a)中。
本发明中使用的PFPE是OH官能的,这意味着聚合物链的至少一端带有羟基(羟基封端)。末端基团也可为-CH2OH。OH官能PFPE优选是单羟基封端(PFPE单醇)或二羟基封端的(PFPE二醇)。在单羟基官能团的情况下,另一端优选具有全氟化基团,例如-CF3。
OH官能(全)氟聚醚优选具有400-4000的数均分子量。Mn可通过凝胶渗透色谱法(GPC)使用聚苯乙烯标样以四氢呋喃作为流动相测定。
二羟基官能(全)氟聚醚可具有HO-(CF2-CF2-O)n-OH或HO-(CF2-CF2-O)n-(CF2-O)m-OH的一般结构。其还可包含具有氧化乙烯单元的嵌段,并且具有一般结构:
HO-(CH2CH2O)p-CH2-CF2-Rf-CF2-CH2-(OCH2CH2)q-OH
其中p和q是独立地选自0-50,优选1-50的整数,其中Rf表示具有(全)氟聚醚结构(CF2CF2O)n、(CF2O)m或(CF2-CF2-O)n-(CF2-O)m的双官能基团,并且其中n和m是独立地选自1-100的整数。当p和q不同时为零时,所得聚合物在水中具有更好的分散性。优选地,p为1-5,q为1-4。也可使用-CH2OH基团代替-OH基团。
羟基封端的(全)氟聚醚可由Solvay以PFPE或/>PFPE商购获得,例如/>5174X、/>E10H、/>PEG45。市售单羟基封端PFPE(PFPE单醇)的实例包括获自Tianjin Changlu Flrorochemicals的PFPE1600和PFPE3200,以及获自Chemours的PFPE AL-2和PFPE AL-4。
多异氰酸酯A是具有反应性异氰酸酯基的化合物,并且具有至少2的异氰酸酯官能度。优选使用二异氰酸酯。也可使用多异氰酸酯的混合物。多异氰酸酯可为脂族、脂环族或芳族的。合适的多异氰酸酯的实例包括六亚甲基二异氰酸酯(HDI)、2,2,4-和/或2,4,4-三甲基六亚甲基异氰酸酯、对-和间-四甲基二甲苯二异氰酸酯、亚甲基双(4-环己基异氰酸酯)(氢化MDI)、4,4-亚甲基二苯基异氰酸酯(MDI)、对-和间-亚苯基二异氰酸酯、2,4-和/或2,6-甲苯二异氰酸钠(TDI)及其加合物,以及异佛尔酮二异氰酸酯(IPDI)。优选的多异氰酸酯包括脂族二异氰酸酯,例如IPDI和HDI。更优选使用脂环族二异氰酸酯,例如IPDI。
步骤(a)中的反应在氨基甲酸酯形成反应条件下进行。形成氨基甲酸酯化合物的反应条件是本领域技术人员所公知的。反应温度可为40-160℃,优选为50-100℃。可使用常规催化剂,例如二月桂酸二丁基锡(DBTDL)、辛酸亚锡、二氮杂双环(2.2.2)辛烷(DABCO)、ZnACAC、辛酸锡。催化剂的量优选为0.005-1重量份/每100重量份氨基甲酸酯形成单体。
反应(a)优选在有机溶剂或溶剂混合物中进行。可使用对反应物不具反应性的任何合适的溶剂。实例包括酯(例如乙酸乙酯、乙酸丙酯)、芳族溶剂(例如甲苯)、酮溶剂(例如丙酮、甲基乙基酮、甲基异丁基酮、环己酮、双丙酮醇);脂族烃;醚(例如***、四氢呋喃)及其混合物。优选的有机溶剂包括乙酸正丁酯、N-甲基吡咯烷酮、甲苯、甲基异丁基酮(MIBK)、甲基乙基酮(MEK)、乙酸甲氧基丙酯(PMA)或其混合物。
步骤(a)中的反应优选在多异氰酸酯A的摩尔过量下进行。因此,在该反应中形成的异氰酸酯官能中间体化合物B是异氰酸酯官能的,并且可参与随后的反应步骤。PFPE与多异氰酸酯A的摩尔比优选为1:1至3:1。
中间体化合物B的数均分子量优选为400-4,000,更优选为500-3,000。Mn可通过凝胶渗透色谱法(GPC)使用聚苯乙烯标样以四氢呋喃作为流动相测定。中间体B优选不具有羧基官能团。中间体B也优选不具有OH官能团。
步骤(b)
在步骤(b)中,使异氰酸酯官能中间体化合物B与仲烷氧基甲硅烷基官能单胺C反应,从而获得本发明的烷氧基甲硅烷基官能聚合物。
烷氧基甲硅烷基官能单胺C是具有一个氮原子的仲氨基硅烷,其中氮原子被两个相同或不同的基团取代,其中至少一个基团带有烷氧基甲硅烷基官能团。发明人认为,在制备最终聚合物时,使用仲氨基硅烷比伯氨基硅烷更有助于提高包含所述聚合物的涂层的防污和防刮擦性能。
在一些实施方案中,优选与氨基硅烷C的氮原子结合的两个基团都带有烷氧基甲硅烷基官能团。该化合物也可称为(双甲硅烷基)胺。在其他实施方案中,两个取代基中只有一个具有烷氧基甲硅烷基官能团。
合适的(双甲硅烷基)胺可具有以下通式:
HN-(Y-Si-(OR1)x(R2)3-x)2 (I)
其中Y为共价键或双官能的饱和C1-C10亚烷基,R1和R2彼此独立地为C1-C3烷基,x为选自0-3的整数。Y优选为C1-C4亚烷基,更优选为亚乙基或亚丙基。R1和R2优选为C1-C3烷基,更优选为甲基或乙基。
具有两个烷氧基硅烷官能团的氨基硅烷的实例包括双-(2-三甲氧基甲硅烷基乙基)胺、双-(2-三乙氧基甲硅烷基乙基)胺、双(3-三乙氧基甲硅烷基丙基)胺(可以以商品名1122由Degussa获得)、双(3-三甲氧基甲硅烷基丙基)胺(可以以商品名1124由Degussa获得),双(4-三乙氧基甲硅烷基丁基)胺。优选地,(双甲硅烷基)胺C为双[3-(三烷氧基甲硅烷基)丙基]胺,更优选为双[3-(三甲氧基甲硅烷基)丙基]胺。
具有一个烷氧基硅烷官能团的氨基硅烷的实例包括N-正丁基-3-氨基丙基三甲氧基硅烷(可以以商品名1189由Degussa获得)、N-正丁基-3-氨基丙基三乙氧基硅烷、N-环己基-3-氨基丙基三甲氧基硅烷(可以以商品名/>GF 92由WackerChemie获得)、N-环己基-3-氨基丙基三乙氧基硅烷、N-环己基氨基甲基甲基二乙氧基硅烷(可以以商品名/>XL 924由Wacker Chemie获得)、N-环己基氨基甲基三乙氧基硅烷(可以以商品名/>XL 926由Wacker Chemie获得)、N-苯基氨基甲基三甲氧基硅烷(可以以商品名/>XL 973由Wacker Chemie获得)。这些也适用于本发明,尽管可能不那么优选。
步骤(b)中的反应优选在有机溶剂或溶剂混合物中进行。合适的溶剂与上文对步骤(a)中的反应所提及的那些相同。优选地,在合成期间不存在二胺和二元醇,因为使用它们会导致聚合物的分子量不希望地增加。
步骤(b)中反应的进展可通过分析NCO含量随时间的变化来监测。当不再检测得到NCO含量时,反应停止。
所得的烷氧基甲硅烷基官能聚合物含有氨基甲酸酯连接键。所述聚合物具有优选为2,000-20,000,更优选为4,000-15,000的重均分子量Mw。所述聚合物具有优选为1,000-8,000,更优选为2,000-6,000的数均分子量Mn。该分子量使得所述烷氧基甲硅烷基官能聚合物可以作为溶剂型体系中的(可溶性)添加剂使用。
所得聚合物优选不含羧基和羟基。因此,酸值优选低于5mg KOH/g,更优选0mgKOH/g。酸值可通过电位滴定法测量,例如根据DIN EN ISO3682。优选地,所得聚合物不具有OH官能团。羟值优选<5mg KOH/g,更优选0mg KOH/g。羟值可通过使用TSI方法的电位滴定法测量,例如根据ASTM E1899-08。
所得聚合物的烷氧基甲硅烷基官能团可在水或醇溶剂中水解,任选地在硅烷醇缩合催化剂存在下水解。
所得聚合物或在其水解期间获得的含氟聚硅氧烷树脂可有利地用于制备涂料组合物,特别是作为无氟聚硅氧烷树脂的添加剂。
涂料组合物
在另一方面中,本发明提供了一种涂料组合物,其包含上述氟化烷氧基甲硅烷基官能聚合物和/或其水解产物(氟化聚硅氧烷树脂)以及无氟聚硅氧烷树脂。
所述涂料组合物优选包含可通过水解上述氟化烷氧基甲硅烷基官能聚合物而获得的氟化聚硅氧烷树脂,以及无氟聚硅氧烷树脂。
氟化硅氧烷树脂可通过在水和/或醇溶剂中水解上述聚合物的烷氧基甲硅烷基官能团而获得。优选使用醇或醇的混合物。合适的醇包括例如甲醇和乙醇。也可使用水与醇的混合物(或醇的混合物)。
任选地,水解在硅烷醇缩合催化剂的存在下进行。该催化剂是本领域技术人员所已知的。
合适的催化剂例如为金属盐(例如硝酸锆、氯化铝),金属有机化合物,特别是有机锡化合物(例如二月桂酸二丁基锡、乙酰乙酸二丁基锡)、酸和碱如叔胺(例如三乙基胺、三亚乙基胺或2,2'-二氮杂双环[2.2.2]辛烷(DABCO))。酸意指布朗斯台德酸和路易斯酸二者。酸性催化剂的实例包括磺酸及其衍生物,例如甲烷磺酸、1-丙烷磺酸、1-戊烷磺酸、十二烷基苯磺酸、对甲苯磺酸。在一些实施方案中,可优选使用酸性催化剂,特别是磺酸或其衍生物,更特别是对甲苯磺酸。
无氟聚硅氧烷树脂可通过水解无氟硅烷D制备。有利地,水解可在制备涂料组合物期间原位进行。
无氟硅烷D优选为烷氧基官能的硅烷。任选地,其可进一步包含其他官能团,例如胺基或环氧基。在一些实施方案中,烷氧基官能硅烷不含胺官能团。该类硅烷的实例包括甲基三甲氧基硅烷(MTMS)、甲基三乙氧基硅烷、苯基三甲氧基硅烷(PTMS)、苯基三乙氧基硅烷(PTES)、双[三甲氧基甲硅烷基丙基]乙烷(BTES)、甲基丙烯酰氧基丙基三甲氧硅烷(MAPTS)、巯基丙基三甲氧基硅烷(MPTES),、原硅酸四乙酯(TEOS)、原硅酸四甲酯(TMOS)、3-缩水甘油氧基丙基三甲氧基硅烷(GPTMS)。
在一些实施方案中,无氟硅烷D是烷氧基官能的氨基硅烷,例如伯或仲氨基硅烷。伯烷氧基官能的氨基硅烷可具有以下通式:
NH2-X3-Si(R3)y(OR4)3-y (II)
其中X3为共价键或双官能饱和C1-C10亚烷基,R3和R4彼此独立地为C1-C3烷基,y为选自0-3的整数。X3优选为双官能C1-C4烷基,更优选为亚丙基或亚丁基。R3和R4优选同时为乙基。烷氧基官能氨基硅烷可例如为N-(单烷氧基甲硅烷基烷基)胺、N-(二烷氧基甲硅烷基烷基)氨或N-(三烷氧基甲硅烷基烷基)胺。作为烷氧基,优选甲氧基和乙氧基,特别优选乙氧基。在优选实施方案中,烷氧基官能氨基硅烷为N-(三乙氧基甲硅烷基丙基)胺,也称为(3-氨基丙基)-三乙氧基硅烷(APTES)。
仲氨基硅烷可与上文对仲烷氧基甲硅烷基官能单胺C所述的那些相同。
在一些实施方案中,可优选使用氨基硅烷和非氨基硅烷的混合物。
硅烷D的水解可在水和/或醇溶剂的存在下进行,例如上文对氟化烷氧基甲硅烷基官能聚合物水解所述的那些。任选地,可使用硅烷醇缩合催化剂,例如上文所述的那些。
在一些实施方案中,可优选在制备涂料组合物期间原位进行氟化烷氧基甲硅烷基官能聚合物和无氟硅烷D的水解。在其他实施方案中,可有利的是分开进行水解,然后将所得的氟化和非氟化聚硅氧烷树脂混合。
因此,所述涂料组合物可通过在水和/或醇溶剂,优选醇或醇混合物存在下混合上述氟化烷氧基甲硅烷基官能聚合物和硅烷D而制备。或者,所述涂料组合物可通过将已分别制备的氟化和非氟化硅氧烷树脂混合而制备。
所述涂料组合物优选包含0.1-50重量%的氟化聚硅氧烷树脂,基于涂料组合物的总重量。
所述涂料组合物优选包含50-99.9重量%的无氟聚硅氧烷树脂,基于涂料组合物的总重量。
不希望受特定理论的约束,发明人相信在相同组合物中使用非氟化聚硅氧烷树脂在固化后提供了更高的交联密度,这有助于更致密的涂层。因此,固化涂层具有更好的耐磨性和耐污性。此外,在相同的组合物中使用氟化和非氟化聚硅氧烷树脂被认为会导致固化过程中的分层以及树脂在不同层或区域中的分离。这将导致涂料组合物与各种基材(例如玻璃、无机、金属和陶瓷基材)更好的相容性。
除上述树脂外,所述涂料组合物中还可存在其他基料树脂,例如聚氨酯、聚醚、聚酯、聚丙烯酸酯。
所述涂料组合物优选是溶剂型的。溶剂型涂料组合物包含有机溶剂或有机溶剂混合物作为制备和/或施加涂料组合物时的主要液相。“主要液相”意指有机溶剂占液相的至少50重量%,优选至少80重量%,更优选至少90重量%,在一些实施方案中甚至100重量%。与水性涂料组合物相比,溶剂型组合物被认为在某些性能方面具有更好的性能,例如耐刮擦性。
所述涂料组合物优选包含10-70重量%,更优选20-60重量%的有机溶剂,基于涂料组合物的总重量。
合适的有机溶剂的实例包括醇(例如乙醇、异丙醇、正丁醇、正丙醇)、酯(例如乙酸乙酯、乙酸丙酯)、芳族溶剂(例如甲苯)、酮溶剂(例如丙酮、甲基乙基酮、甲基异丁基酮、环己酮、双丙酮醇);脂族烃;氯化烃(例如CH2Cl2);醚(例如***、四氢呋喃、丙二醇单甲醚)及其混合物。优选的有机溶剂包括乙酸丁酯、N-甲基吡咯烷酮、甲苯、甲基异丁基酮(MIBK)、甲基乙基酮(MEK)、丙二醇单甲醚和乙酸甲氧基丙酯(PMA)或其混合物。
本发明的涂料组合物的固含量可为1-90重量%,优选为5-65重量%,更优选为10-50重量%。
所述涂料组合物可进一步包含常规添加剂,例如填料、抗氧化剂、消光剂、颜料、耐磨颗粒、流动调节剂、表面活性剂、增塑剂、增粘剂、触变剂、光稳定剂等。
本发明进一步提供了一种涂覆基材的方法,包括将本发明的涂料组合物施加到基材上并固化该涂料组合物。
所述涂料组合物可通过常规技术(包括喷涂、辊涂、刮涂、倾注、刷涂或浸涂)施加到宽范围的基材上。
所述涂料组合物优选是可热固化的。固化优选在升高的温度下进行,例如在40-190℃,更优选50-150℃下。固化温度可根据基材选择。本领域技术人员知晓合适的固化温度。可使用常规加热方法,例如放置在烘箱中。
本发明的涂料组合物可施加到宽范围的基材上,包括金属和非金属基材,例如玻璃、金属、金属合金、阳极化基材、塑料、复合材料等。合适的基材包括聚碳酸酯-丙烯腈-丁二烯-苯乙烯(PC/ABS)、聚碳酸酯、聚丙烯酸酯、聚烯烃、聚酰胺、聚苯乙烯、聚酰胺、玻璃、木材、石材、铝、阳极化铝、铝合金、镁铝合金、铜、碳纤维增强聚合物/塑料(CFRP)。优选地,基材为玻璃或铝。
本发明的涂料组合物可以用作直接施加到基材上的单层,或用于多层体系,例如用作底漆、底色漆或透明漆。
本发明的涂料组合物可用于各种涂料行业,例如消费电子、汽车、包装、木地板和家具、家用电器、玻璃和窗户、运动设备。
本发明进一步提供了一种涂覆有由本发明涂料组合物获得的涂层的基材。本发明的涂层具有特别好的总体性能,包括附着力和耐刮擦性。此外,所述涂层还具有优异的易清洁和防污性能,可使用永久标记笔和化学品进行测试。
实施例
本发明将参照以下实施例进行证实。除非另有说明,否则所有份数和百分比均为重量。
E10-H—获自Solvay的双醇封端乙氧基化全氟聚醚,平均分子量(NMR):1700amu,20℃下的运动粘度:115cSt。
1124—获自Evonik的双(三甲氧基甲硅烷基丙基)胺
IPDI—异佛尔酮二异氰酸酯
DBTDL—二月桂酸二丁基锡
MIBK—甲基异丁基酮
BAC—乙酸丁酯
PMA—乙酸甲氧基丙酯
实施例1:含氟添加剂的合成
首先,在60℃下经约1小时将60gE10-H滴入含有0.05g DBTDL的15g IPDI中。在一半异氰酸酯反应后,经约30分钟将25g/>1124和50g BAC滴入反应混合物中。然后反应继续进行,直至检测不到游离NCO。
实施例2:防指纹涂层
首先,将80g1124在80g BAC中用3.6g水和70g乙醇在室温下水解约3小时。然后,将1g实施例1中制备的含氟添加剂和另外250g BAC添加到反应体系中。反应进行约2小时,用25μm滤纸收集过滤后的产物。
实施例3:涂层的性能
通过等离子体处理玻璃基材。将实施例2中制备的防指纹涂料组合物喷涂到玻璃和Al基材上,干膜厚度为2-4μm。将样品在150℃下固化30分钟,然后置于室温下连续固化5天。
测量涂层的静态接触角、铅笔硬度和附着力。静态接触角分别在固化涂层的顶部用20静滴法测量。液滴设定为3μl/液滴,测量温度为约20℃。接触角使用带有软件SCA 20的DataPhysics仪器测量。铅笔硬度根据使用铅笔(9B至9H级)的标准测试测量。附着力根据ASTM D3359-02,通过胶带测试测量。附着力测试结果可从0B—最差结果(胶带移除大于65%的十字格面积)到5B—最佳结果(移除0%的十字格面积)。
结果如表1所示。
表1.表面性能
易清洁性能
易清洁性能通过在涂覆基材上用黑色墨水用ZEBRA永久性标记笔书写“污渍”来测试。
图1(a)显示了上半部分为未涂覆的玻璃基材,下半部分为涂覆有实施例2中制备的涂层的基材。
图1(b)显示了与图1(a)相同的基材,但在用布擦拭墨水之后。
可以看出,黑色墨水在未涂覆的玻璃基材上不收缩(图1(a),上半部分)。相反,黑色墨水在本发明涂层表面上收缩成珠粒(图1(a),下半部分)。这意味着本发明的涂覆表面具有拒墨性。
在擦拭后(图1(b),下半部分),本发明的涂覆表面是干净的,没有显示出任何墨水残留。无法从未涂覆的玻璃上擦掉墨水(图1(b),上半部分)。这证明了本发明涂层的易清洁性能。
钢木摩擦
使用的5750Linear Abraser测试耐磨性。测试使用置于涂覆板上的#0000钢丝棉并在其上放置0.5或1kg的重物来进行(1cm×1cm摩擦表面积)。摩擦速率设定为60循环/分钟,距离60mm。在测试后,再次测量水接触角(WCA)。结果如表2所示。
表2
测试前的WCA | 测试后的WCA | |
1000T/500g | 108-111° | 105-107° |
2000T/500g | 108-111° | 100-105° |
3000T/500g | 108-111° | 95-101° |
1000T/1kg | 108-111° | 95-105° |
从表2看出,在测试后,水接触角没有显著降低。这意味着涂层在很大程度上保持了防污和易清洁的性能。
Claims (12)
1.一种氟化烷氧基甲硅烷基官能聚合物,其可通过包括以下步骤的方法获得:
a)使OH官能全氟聚醚(PFPE)与多异氰酸酯A在氨基甲酸酯形成反应条件下反应以获得异氰酸酯官能中间体B,
b)使中间体B与通式(I)的仲烷氧基甲硅烷基官能单胺C反应,以获得烷氧基甲硅烷基官能聚合物,
HN-(Y-Si-(OR1)x(R2)3-x)2(I)
其中Y为共价键或双官能的饱和C1-C10亚烷基,R1和R2彼此独立地为C1-C3烷基,x为选自0-3的整数,
其中多异氰酸酯A为二异氰酸酯。
2.根据权利要求1所述的聚合物,其中所述OH官能全氟聚醚是二羟基封端的PFPE或单羟基封端的PFPE。
3.根据权利要求2所述的聚合物,其中二羟基封端的全氟聚醚具有如下一般结构:
HO-(CH2CH2O)p-CH2-CF2-Rf-CF2-CH2-(OCH2CH2)q-OH其中p和q是独立地选自0-50的整数,Rf表示具有全氟聚醚结构O(CF2CF2O)n、O(CF2O)m或O(CF2-CF2-O)n-(CF2-O)m的双官能基团,并且其中n和m是独立地选自1-100的整数。
4.根据权利要求1-3中任一项所述的聚合物,其中多异氰酸酯A为脂环族二异氰酸酯。
5.根据权利要求1-4中任一项所述的聚合物,其中仲烷氧基甲硅烷基官能单胺C为双[3-(三烷氧基甲硅烷基)丙基]胺。
6.一种溶剂型涂料组合物,其包含根据权利要求1-5中任一项所述的氟化烷氧基甲硅烷基官能聚合物和/或通过水解该相同聚合物获得的氟化聚硅氧烷树脂,此外还有无氟聚硅氧烷树脂。
7.根据权利要求6所述的涂料组合物,其中所述无氟聚硅氧烷树脂通过水解无氟硅烷D获得。
8.根据权利要求7所述的涂料组合物,其中无氟硅烷D选自烷氧基硅烷、烷氧基官能氨基硅烷及其混合物。
9.涂覆基材的方法,包括将根据权利要求6-8中任一项所述的涂料组合物施加到基材上并固化所述涂料组合物。
10.涂覆基材,其根据权利要求9所述的方法获得。
11.根据权利要求10所述的基材,其中所述基材选自玻璃、金属、金属合金、阳极化基材、塑料和复合材料。
12.根据权利要求11所述的基材,其中所述基材为玻璃或铝。
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