CN106432663A - 不含脲的聚氨酯分散体 - Google Patents
不含脲的聚氨酯分散体 Download PDFInfo
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- CN106432663A CN106432663A CN201610466119.7A CN201610466119A CN106432663A CN 106432663 A CN106432663 A CN 106432663A CN 201610466119 A CN201610466119 A CN 201610466119A CN 106432663 A CN106432663 A CN 106432663A
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- aqueous
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- polyurethane
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Classifications
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了不含脲的聚氨酯分散体。本发明涉及水性聚氨酯分散体、用于生产水性聚氨酯分散体的方法、其用于生产漆层、涂层、胶粘剂或密封剂的用途、水性单组分或双组分涂料组合物以及漆层、涂层、密封剂和胶粘剂。本发明的聚氨酯基本不含脲基团并具有小于0.25重量%的OH含量。
Description
技术领域
本发明涉及水性聚氨酯分散体、用于生产水性聚氨酯分散体的方法、其用于生产漆层（paint）、涂层、胶粘剂或密封剂的用途、水性单组分或双组分涂料组合物以及漆层、涂层、胶粘剂和密封剂。
背景技术
水性聚氨酯分散体如今经常以两阶段法生产，其中多元醇组分通常首先与摩尔过量的多异氰酸酯组分反应以产生NCO官能预聚物。此后将该NCO官能预聚物任选溶于溶剂中，或任选甚至在生产过程中，通过添加具有至少两个对异氰酸酯基团具有反应性的基团的化合物（也经常称为扩链剂）来扩链。这意味着，原始预聚物的摩尔质量通过其NCO基团与扩链剂的NCO反应性基团的反应而增大。随后，将由此获得的较高分子量聚氨酯分散到水中并任选蒸馏去除溶剂。分散所需的亲水性基团通常通过将具有离子基团、潜在离子基团或非离子基团的多元醇引入所述预聚物中或通过使用具有相应基团的扩链剂来引入。
用于所述扩链剂中的NCO反应性基团通常是氨基，因为伯胺和仲胺对NCO基团均具有非常高的反应性。标准扩链剂是例如乙-1,2-二胺、1,2-和1,3-二氨基丙烷、1,4-二氨基丁烷、1,6-二氨基己烷、异佛尔酮二胺、2,2,4-和2,4,4-三甲基六亚甲基二胺的异构体混合物、2-甲基五亚甲基二胺、二亚乙基三胺、4,4-二氨基二环己基甲烷、水合肼和/或二甲基乙二胺、二乙醇胺、3-氨基-1-甲基氨基丙烷、3-氨基-1-乙基氨基丙烷、3-氨基-1-环己基氨基丙烷、3-氨基-1-甲基氨基丁烷、链烷醇胺例如N-氨基乙基乙醇胺、乙醇胺、3-氨基丙醇、新戊醇胺、己二酰肼、乙二酰肼、碳酰肼、丁二酰肼或更长链的氨基官能化合物例如聚醚胺（“Jeffamins”）。异氰酸酯基团与胺的反应总是必然产生脲基团，这是为何被称为“聚氨酯”的大多数化合物事实上是“聚氨酯脲”的原因。
因为脲基团相比于氨基甲酸酯基团赋予聚合物更大的硬度，通过用胺来扩链产生的此类脲基团的存在也影响聚氨酯的性能。然而，聚氨酯脲的相应硬度并非对于所有应用均合意。脲基团的强氢键也是聚氨酯脲通常具有比相应的纯聚氨酯更差的溶解度这一事实的原因。也由于该原因，在聚合物链中减少脲基团对于某些应用而言是合意的。
氨基相比于异氰酸酯基团的高反应性的另一影响是，其本身的反应极快地发生，但这使得在某些情况下更加难以控制反应。根据工艺方案，这一影响甚至可能是，对反应物处理的要求非常高，以防止反应物例如在通往实际反应器的进料管线中的过早反应。从更简单处理的角度来看，还有利的是在某些情况下可降低制备聚氨酯的复杂度，例如通过减少所涉及的反应物数量。
原则上，存在用于制备不具有脲基团的聚氨酯的已知方法。
例如，EP 0 669 352 A1描述了可不含脲基团的水性聚酯-聚氨酯分散体。EP 0669 352 A1的聚酯-聚氨酯通过使不同的多元醇与多异氰酸酯组分反应来制备，但不发生扩链，此类产物被研发用作2-组分体系。因此，其中所述的聚氨酯具有低摩尔质量，这从0.25重量%至6.5重量%的理论OH含量显而易见。然而，特别是对于1-组分组合物而言，这样的摩尔质量通常不足以实现经固化组合物的所需机械性能。类似的聚酯-聚氨酯分散体还公开在EP 0 578 940 A1中。在此同样地，不实施扩链的方法步骤，因此所得摩尔质量也低且特别适用于2-组分体系。尽管EP 0 578 940 A1概括地公开了可获得高摩尔质量，但事实上这些在使用其中所指定的起始组分和比率的实践中无法实现（特别是也不进行扩链），并且这是不合意的，因为该文件涉及2-组分体系。
类似地，在EP 2 239 286 A1中，制备了具有700至3000 g/mol的数均摩尔质量和因此2.5重量%的OH含量的聚酯-聚氨酯。EP 0 751 197 A1的聚酯-聚氨酯的OH含量为0.6重量%至1.8重量%。WO 2010/091898 A1的聚酯-聚氨酯同样具有1.4重量%的OH含量。
EP 1 790 674 A1描述了含氨基甲酸酯基团的羟基官能聚酯分散体，其同样不具有任何脲基团。该聚合物通过使多元醇与多异氰酸酯反应而不经扩链步骤，或经由形成NCO官能预聚物并随后用聚酯多元醇扩链来制备。在此所述的方法的缺点在于以下事实：用官能度> 3的支化聚酯多元醇来扩链穿过这两种共反应物的等当量点。这意味着，在扩链中的一个特定时刻，[NCO]和[OH]浓度是等高的，并因此提高了不可逆胶凝的风险。
从该现有技术出发，由本发明所解决的问题是提供补救现有技术的至少一个和优选所有上述缺点的水性聚氨酯分散体。更具体地，由本发明所解决的问题是提供不含脲基团但具有足够高的摩尔质量的水性聚氨酯分散体。更具体地，该摩尔质量应足以能够产生同样来自该聚氨酯分散体的1-组分涂料体系、所得的经固化组合物具有足够高水平的机械性能。此外，特别地，该生产过程中不可逆胶凝的风险应降至最低。因此，所得聚氨酯应优选具有在水中的良好可分散性以适合用于水基涂料体系。
这些问题通过提供如下文详细描述的本发明的水性聚氨酯分散体、本发明的用于生产水性聚氨酯分散体的方法、其根据本发明用于生产漆层、涂层、胶粘剂和密封剂的用途、本发明的水性1-或2-组分涂料组合物和本发明的漆层、涂层、胶粘剂和密封剂来解决。
发明内容
本发明提供了包含聚氨酯(P)的水性聚氨酯分散体，其中聚氨酯(P)通过将至少一种羟基官能预聚物(A)用至少一种多异氰酸酯(B)扩链来制备，其中羟基官能预聚物(A)包含至少下列构成组分：
(A1) 至少一种官能度> 1的多元醇，
(A2) 任选至少一种不同于(A1)的二醇，
(A3) 任选至少一种亲水性构成组分，其具有至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4) 至少一种多异氰酸酯化合物，
且所述聚氨酯(P)基本不含脲基团，其特征在于，所述聚氨酯(P)具有小于0.25重量%的理论羟基含量，基于所述聚氨酯在经干燥状态下的总重量计。
在另一方面，本发明提供了用于生产水性聚氨酯分散体的方法，其包括以所指定次序的下列步骤：
(i) 由至少下列构成组分制备羟基官能预聚物(A)：
(A1)至少一种官能度> 1的多元醇，
(A2) 任选至少一种不同于(A1)的二醇，
(A3)任选至少一种亲水性构成组分，其具有至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4)至少一种多异氰酸酯化合物，
(ii)将获自步骤(i)的羟基官能预聚物用至少一种多异氰酸酯(B)扩链至所得聚氨酯(P)的理论羟基含量小于0.25重量%的程度，基于所述聚氨酯在经干燥状态下的总重量计，所得聚氨酯(P)基本不含脲基团，
(iii)在步骤(ii)之前或之后，任选中和在任选的构成组分(A3)中的潜在离子基团，并且
(iv)将获自步骤(ii)或(iii)的聚氨酯(P)分散到水中。
已发现，通过OH官能预聚物(A)的制备和随后用多异氰酸酯(B)的扩链，可以获得基本不含脲基团并同时具有高摩尔质量（表现为羟基基团含量小于0.25重量%）的聚氨酯(P)。已特别发现，首先，凭借该程序，处理简单，因为总体来说需要比现有技术方法中少一种的反应物物质类别。这意味着，在本程序中，可以仅仅使用多元醇和多异氰酸酯并因此更特别地无需使用胺。还已发现，该程序经由形成羟基官能预聚物(A)总体来说允许灵活和同时受控地生产聚氨酯分散体。原则上，可分离和储存预聚物(A)而无需任何特殊测量。这样一个过程的做法用NCO官能预聚物是不可行的，因为相对反应性的异氰酸酯基团例如甚至与痕量的水或其它杂质反应并且还可能参与其它不想要的副反应，例如二聚或三聚。然而，该程序经由OH官能聚合物的影响在于，扩链可借助多异氰酸酯(B)实现且完全脱离预聚物(A)的制备。依据时间可看出这一点。这意味着，扩链可在不同于合成预聚物(A)的时间点进行，其作用是从要生产的所需量、储存的经济可行性等的角度来看，各个反应的批量规格可分别考虑。其次，同时，这还导致更加受控地生产聚氨酯分散体。例如，用这种方法可以以简单得多且精确得多的方式混合不同的预聚物(A)，且可特别地定制所得的聚氨酯。
此外，通过其中使用NCO官能预聚物的方法而不可避免地出现的缺点得以避免。此类NCO官能预聚物包含越来越大量的游离低分子量异氰酸酯。因此，在该程序中经常需要进一步的薄膜蒸馏步骤以提纯该预聚物。除了在能源和时间方面无需该提纯的这一方面之外，本发明的OH官能预聚物明确具有低毒性。此外，本发明的工艺路径带来在低分子量预聚物的制备过程中经过等当量点的优点，这明确地将与可能的不可逆胶凝相关的风险降至最低。
更特别地，已发现，可通过本发明的程序将脂族或脂环族的多异氰酸酯(B)用于扩链。因为脂族多异氰酸酯相比于芳族多异氰酸酯对羟基基团的反应性较低，根据本发明令人惊奇的是，尽管如此仍在扩链的方法步骤中获得短的反应时间。本领域技术人员会预期在脂族多异氰酸酯的情况下需要如此长的反应时间以致不可经济利用（例如参见尤其描述在P. Król, J. Appl. Polym. Sci., 57,6, 第739页及以下各页的各个反应的速率常数）。这一偏见被令人惊奇地驳倒。
因此，在一个实施方案中，优选使用脂族多异氰酸酯(B)。在另一实施方案中，也优选使用芳族多异氰酸酯(B)。
根据本发明，提及“包含”、“含有”等优选是指“基本由…组成”和最优选“由…组成”。
本发明上下文中的术语“分散体”包括水性分散体和水溶液两者。分散体和溶液之间的区别尤其取决于离子基团的含量和聚合物的分子量，且在某些情况下无法在此划清界限，这是为何根据本发明包括这两种配置的原因。然而，特别优选的是分散体。
具体实施方式
下面详细地并在优选配置中描述了本发明的聚氨酯分散体和本发明的方法。所有特征涉及分散体和和方法两者，除非另有明确说明。因此，特别优选的是本发明的聚氨酯分散体由本发明的方法可获得或获得。
根据本发明使用的羟基官能预聚物(A)包含至少下列构成组分：
(A1) 至少一种官能度> 1的多元醇，
(A2) 任选至少一种不同于(A1)的二醇，
(A3) 任选至少一种亲水性构成组分，其具有至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4) 至少一种多异氰酸酯化合物。
所述至少一种多元醇组分(A1)优选是选自聚酯多元醇、聚醚多元醇、聚酯醚多元醇和聚碳酸酯多元醇的多元醇。优选地，多元醇组分(A1)的羟基官能度为1.2至4，更优选1.4至3，最优选1.5至2。
如果组分(A1)是聚酯，优选的是这一组分的由计算确定的理论分子量为500至6000 g/mol，更优选750至5000 g/mol和最优选1000至3000 g/mol。
所述聚酯的理论分子量由下式确定：混合物的质量[g] / (COOH的摩尔数 + OH的摩尔数)- COOH的当量。
优选的是，聚酯的羟基官能度为1.2至4，更优选1.4至3，最优选1.5至2。还可以使用不同聚酯的混合物以及具有不同官能度的聚酯的混合物。官能度总是对应于混合物的平均官能度。
优选使用的聚酯(A1)是下列物质的反应产物：
A1i) 30重量%至77重量%，优选40重量%至60重量%的至少一种至少二官能的羧酸或其酸酐，
A1ii) 23重量%至70重量%，优选40重量%至60重量%的至少一种二醇，
A1iii) 0重量%至10重量%的至少一种具有多于2个羟基的醇，
A1iv) 0重量%至10重量%的其它羟基-和/或羧基-官能化合物和/或己内酯。
合适的聚酯原料A1i)是例如邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、己二酸、癸二酸、辛二酸、琥珀酸、马来酸酐、富马酸、二聚脂肪酸、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、环己烷二甲酸和/或偏苯三酸酐或者它们的混合物。优选的组分A1i)选自己二酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、间苯二甲酸和戊二酸，更优选己二酸、六氢邻苯二甲酸和邻苯二甲酸及其酸酐。
合适的聚酯原料A1ii)是例如1,2-乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2-丙二醇、二丙二醇、三丙二醇、丙-1,3-二醇、丁-1,3-二醇、丁-1,4-二醇、己-1,6-二醇、新戊二醇、环己烷-1,4-二甲醇、环己烷-1,4-二醇、丁烯二醇、丁炔二醇、氢化双酚类、三甲基戊二醇、辛-1,8-二醇和/或三环癸烷二甲醇和它们的混合物。优选的组分A1ii)选自丁-1,4-二醇、新戊二醇、1,2-丙二醇、乙二醇、二乙二醇和己-1,6-二醇。特别优选的组分A1ii)选自新戊二醇、丁二醇、乙二醇、二乙二醇和己二醇。
合适的任选聚酯原料A1iii)是例如三羟甲基丙烷、乙氧基化三羟甲基丙烷、丙氧基化三羟甲基丙烷、丙氧基化丙三醇、乙氧基化丙三醇、丙三醇、季戊四醇、蓖麻油和它们的混合物。优选的组分A1iii)是三羟甲基丙烷。
任选使用的合适的聚酯原料A1iv)是例如C8-C22脂肪酸，例如2-乙基己酸、硬脂酸、氢化脂肪酸、苯甲酸；单官能醇，例如乙二醇丁醚、二乙二醇丁醚、环己醇；其它单官能醇，例如聚氧乙烯、聚氧丙烯、聚氧乙烯/氧丙烯共混物共聚物或嵌段共聚物和它们的混合物。
所述聚酯可通过本身已知的方法在100至260℃的温度下通过消除水，任选通过额外使用常规酯化催化剂，优选通过熔融缩合或恒组分缩合（azeotropic condensation）的原理制备。聚酯的优选制备方法是在减压下或使用惰性气体的熔融缩合。此外，合适的聚酯多元醇还有可以通过可再生原料的聚合所获得的那些。在此，举例来说可以提及的是使用琥珀酸，其通过例如描述在DE 10 2008 051727 A1或DE 10 2007 019184 A1中的发酵工艺来获得。
如果组分(A1)是聚碳酸酯，其优选为线性的羟基官能聚碳酸酯。合适的聚碳酸酯是例如通过使碳酸衍生物例如碳酸二苯酯、碳酸二甲酯或光气与多元醇（优选二醇）反应可获得的那些。有用的这类二醇包括例如乙二醇、丙-1,2-二醇和丙-1,3-二醇、丁-1,3-二醇和丁-1,4-二醇、己-1,6-二醇、辛-1,8-二醇、新戊二醇、1,4-双羟甲基环己烷、2-甲基丙-1,3-二醇、2,2,4-三甲基戊-1,3-二醇、二丙二醇、聚丙二醇、二丁二醇、聚丁二醇、双酚A、四溴双酚A，而且还有内酯改性二醇。优选地，所述二醇组分含有40重量%至100重量%的己二醇，优选己-1,6-二醇和/或己二醇衍生物，优选不仅具有末端OH基团还具有醚或酯基团的那些，例如通过使1摩尔己二醇与至少1摩尔，优选1至2摩尔的己内酯反应或通过将己二醇与其自身醚化以产生二-或三己二醇所获得的产物。也可以使用聚醚聚碳酸酯二醇。该羟基聚碳酸酯应当为基本线性的。然而，它们可任选通过并入多官能组分，特别是低分子量多元醇而轻微支化。用于该目的合适实例是丙三醇、三羟甲基丙烷、己-1,2,6-三醇、丁-1,2,4-三醇、三羟甲基丙烷、季戊四醇、甲壳素、甘露醇、山梨醇、甲基糖苷或1,3,4,6-二脱水己糖醇。所述聚碳酸酯多元醇优选通过描述在EP-A 1 404 740（第6-8页，实施例1-6）和EP-A 1 477508（第5页，实施例3）中的制备方法来制备。
特别优选的聚碳酸酯多元醇是含有至少25重量%的丁-1,4-二醇作为构成组分且平均羟基官能度为1.6至4，优选1.8至3和更优选1.9至2.3且数均分子量为240至8000 g/mol，优选500至3000 g/mol，更优选750至2500 g/mol的那些。优选地，所述二醇组分含有45重量%至100重量%的丁-1,4-二醇和1重量%至55重量%的己-1,6-二醇，更优选60重量%至100重量%的丁-1,4-二醇和1重量%至40重量%的己-1,6-二醇。
如果组分(A1)是聚醚多元醇，则它们优选是氧化苯乙烯、环氧乙烷、环氧丙烷、四氢呋喃、环氧丁烷、表氯醇的加聚产物及其混合的加成和接枝产物，以及通过多元醇或其混合物的缩合获得的聚醚多元醇和通过多元醇、胺和氨基醇的烷氧基化获得的那些。
合适的羟基官能聚醚优选具有1.2至4，更优选1.4至3，最优选1.5至2的OH官能度。同样优选地，它们具有50至700 mg，优选100至600 mg KOH/g固体的OH值。优选的分子量Mn为106至4000 g/mol，更优选200至3500和最优选500至3000 g/mol。
特别优选的是羟基官能起始剂分子例如乙二醇、丙二醇、丁二醇、己二醇、三羟甲基丙烷、丙三醇、季戊四醇、山梨醇或这些的混合物以及其它羟基官能化合物与环氧丙烷或环氧丁烷的烷氧基化产物。特别优选为聚环氧丙烷多元醇和聚四氢呋喃（polytetramethylene oxide）多元醇，及其混合物。
组分(A1)还可包含上述多元醇（包括在聚合物链中）的任何所需混合物。
任选的组分(A2)优选为至少一种不同于(A1)且摩尔质量为62至450 g/mol的二醇。更优选为1,2-乙二醇、二乙二醇、三乙二醇、四乙二醇、1,2-丙二醇、二丙二醇、三丙二醇、丙-1,3-二醇、丁-1,3-二醇、丁-1,4-二醇、己-1,6-二醇、新戊二醇、环己烷-1,4-二甲醇、环己烷-1,4-二醇、丁烯二醇、丁炔二醇、氢化双酚类、三甲基戊二醇、辛-1,8-二醇和/或三环癸烷二甲醇和它们的混合物。最优选地，任选的组分(A2)是丁-1,4-二醇、己-1,6-二醇或新戊二醇。
任选的组分(A3)包含至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团。
在本发明的上下文中，潜在离子基团被理解为是指可通过化学反应，尤其通过中和而转化为离子基团的那些基团。优选地，“潜在离子”基团被理解为是指游离酸基团。同样优选地，通过用中和剂中和获得的盐类基团，例如羧酸根或磺酸根基团是“离子”基团。优选地，术语“非离子”被理解为是指不含任何离子基团的化合物。此类离子基团可为磺酸根、羧酸根、磷酸根和膦酸根基团。组分(A3)有助于所述聚氨酯在水中的可分散性。
更优选地，组分(A3)包含至少一种亲水性构成组分，其具有至少一个选自酸基团、聚氧化烯醚基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团。合适的酸基团是例如羧基和磺基。
更优选地，存在组分(A3)作为聚氨酯(P)的构成组分。
非常特别优选使用二羟甲基丙酸、二羟甲基丁酸和/或羟基新戊酸，非常特别优选使用二羟甲基丙酸作为组分(A3)。同样合适的酸是例如其它的2,2-双(羟甲基)烷羧酸，例如二羟甲基乙酸或2,2-二羟甲基戊酸、二羟基琥珀酸、丙烯酸与胺例如异佛尔酮二胺或六亚甲基二胺的迈克尔加成产物，或此类酸和/或二羟甲基丙酸和/或羟基新戊酸的混合物。也可以使用US-A 4 108 814中所述种类的任选具有醚基团的磺酸二醇。
同样优选地，组分(A3)包含含聚乙二醇的单官能组分，其中聚乙二醇的比例为至少50重量%，且其摩尔质量 Mn为1200 g/mol至3000 g/mol。这些聚醚优选含有50重量%至100重量%，优选70重量%至100重量%和更优选80重量%至100重量%比例的衍生自环氧乙烷的单元，其如可以以本身已知的方式通过在(A2)下所述的起始剂分子的烷氧基化获得。适合于该烷氧基化反应的环氧烷特别是环氧乙烷和环氧丙烷，其可在烷氧基化反应中以任何次序或另外以混合物形式使用。该含聚乙二醇的单官能组分(A3)的摩尔质量 Mn优选为300g/mol至6000 g/mol，优选1500 g/mol至3000 g/mol和更优选2000 g/mol至3000 g/mol。
合适的这类非离子亲水化单官能化合物是例如单官能烷氧基聚乙二醇，例如甲氧基聚乙二醇（MPEG Carbowax® 2000或甲氧基 PEG-40，摩尔质量范围1800至2200，The DowChemical Company）和单官能聚醚单烷基醚，例如由丁醇和环氧乙烷和环氧丙烷形成的LB25，其平均摩尔质量 Mn为2250 g/mol，来自Bayer Material Science。
优选地，组分(A3)包含具有至少一个离子基团或潜在离子基团和至少一个羟基的化合物，优选上述化合物，以及具有至少一个非离子基团和至少一个羟基的化合物，优选上述化合物。特别优选的是，亲水性构成组分(A3)包含至少下列化合物：
(A3-1) 至少一种离子化合物或潜在离子化合物，其具有至少一个酸基团和至少一个羟基，和
(A3-2) 至少一种含聚乙二醇的化合物，其中聚乙二醇的比例为至少50重量%，其摩尔质量Mn为1200 g/mol至3000 g/mol并具有羟基。
在此优选的是，组分(A3-1)相对于组分(A3-2)而言过量地使用。更优选地，组分(A3-1)相对于组分(A3-2)以2至5倍重量过量地使用。
组分(A4)是至少一种多异氰酸酯化合物。优选的是所述至少一种多异氰酸酯化合物选自NCO官能度≥ 2的芳族、芳脂族、脂族和脂环族的多异氰酸酯化合物，其可任选具有亚氨代噁二嗪二酮（iminooxadiazinedione）、异氰脲酸酯、脲二酮、氨基甲酸酯、脲基甲酸酯、缩二脲、脲、噁二嗪三酮、噁唑烷酮、酰基脲和/或碳二亚胺结构。此类多异氰酸酯化合物对于本领域技术人员是本身已知的。它们可以单独使用和以任何所需的相互混合的形式使用。
合适的多异氰酸酯(A4)是亚丁基二异氰酸酯、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、2,2,4-和/或2,4,4-三甲基六亚甲基二异氰酸酯、五亚甲基二异氰酸酯（PDI）、异构的双(4,4'-异氰酸根合环己基)甲烷或者其具有任何异构体含量的混合物、异氰酸根合甲基辛烷-1,8-二异氰酸酯、环己烷-1,4-二异氰酸酯、苯-1,4-二异氰酸酯、甲苯-2,4-和/或2,6-二异氰酸酯、1,3-和1,4-双(2-异氰酸根合-丙-2-基)苯（TMXDI）、1,3-双(异氰酸根合甲基)苯（XDI）、萘-1,5-二异氰酸酯、二苯基甲烷-2,4'-或4,4'-二异氰酸酯、三苯基甲烷-4,4',4''-三异氰酸酯或基于上述二异氰酸酯，具有脲二酮、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、缩二脲、亚氨代噁二嗪二酮和/或噁二嗪三酮结构，具有多于2个NCO基团的衍生物。具有每分子多于2个NCO基团的未改性多异氰酸酯的一个实例是4-异氰酸根合甲基辛烷-1,8-二异氰酸酯（壬烷三异氰酸酯）。优选的是仅具有脂族和/或脂环族键合的异氰酸酯基团的上述类型的多异氰酸酯或多异氰酸酯混合物。特别优选的是六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、异构的双(4,4'-异氰酸根合环己基)甲烷、甲苯二异氰酸酯的异构体、二苯基甲烷二异氰酸酯和它们的混合物。
在一个优选的实施方案中，预聚物(A)包含至少下列构成组分：
(A1) 至少一种官能度> 1的多元醇，其选自聚酯多元醇、聚醚多元醇、聚酯醚多元醇和聚碳酸酯多元醇，
(A2) 任选至少一种不同于(A1)且摩尔质量为62至450 g/mol的二醇，
(A3) 任选至少一种亲水性构成组分，其具有至少一个选自酸基团、聚氧化烯醚基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4) 至少一种多异氰酸酯化合物，其选自NCO官能度≥ 2的芳族、芳脂族、脂族和脂环族的多异氰酸酯化合物，其可任选具有亚氨代噁二嗪二酮、异氰脲酸酯、脲二酮、氨基甲酸酯、脲基甲酸酯、缩二脲、脲、噁二嗪三酮、噁唑烷酮、酰基脲和/或碳二亚胺结构。
优选地，所述羟基官能预聚物(A)至少包含
50重量%至87重量%的(A1)，更优选55重量%至85重量%的(A1)，
3重量%至11重量%的(A2)，更优选4重量%至10重量%的(A2)，
0重量%至24重量%的(A3)，更优选0重量%至20重量%的(A3)，最优选1重量%至20重量%的(A3)和3重量%至20重量%的(A4)，更优选4重量%至18重量%的(A4)，
其中构成组分(A1)至(A4)的总和总计达100重量%（这优选不意味着聚氨酯不能包含更进一步的附加构成组分；所述重量%仅仅定义(A1)至(A4)相对于彼此的重量%的比率）。
除上述组分(A1)至(A4)之外，本发明的分散体的聚氨酯还可以包含聚氨酯化学中标准的其它构成组分。
在本发明的方法步骤(i)中的预聚物(A)的制备以本领域技术人员已知的方式实现。优选地，最初装载所有OH官能起始组分，即(A1)和任选的(A2)和(A3)，并使其达到所需温度。该温度优选为40至150℃，甚至更优选50至130℃和特别优选60至120℃。此后，优选添加组分(A4)。优选的是，在羟基官能预聚物(A)的制备中（与本发明的分散体和本发明的方法均有关），所存在的异氰酸酯基团与异氰酸酯反应性基团的摩尔比为0.25至0.95，甚至更优选0.3至0.7和特别优选0.4至0.6（这一比率也被本领域技术人员称为指数）。这意味着，所述OH官能组分相对于所述NCO官能组分而言过量使用。实现产生预聚物(A)的转化直至基本所有NCO基团都已消耗（即，不再能检测到NCO基团）。本领域技术人员熟悉检测NCO基团的方法。优选地，借助FT-IR分析不再能检测到NCO基团。
在一个实施方案中，可以分离和任选储存由此获得的预聚物。本领域技术人员熟悉为此目的方法。例如，所述预聚物可溶解在溶剂，优选丙酮中。此后，可适当储存。
根据本发明，预聚物(A)是经扩链的（还参见本发明的方法步骤(ii)）。根据本发明，扩链被理解为是指增大预聚物(A)的摩尔质量。“扩链”还可以是指“使至少一种羟基官能预聚物(A)与至少一种多异氰酸酯(B)反应”。这优选被理解为是指预聚物(A)的摩尔质量的至少加倍。扩链本身受至少一种预聚物(A)与至少一种多异氰酸酯化合物(B)的反应和接着的后续反应的影响。根据本发明，实施扩链至所得聚氨酯(P)的理论羟基含量小于0.25重量%的程度，基于所述聚氨酯在经干燥状态下的总重量计。
根据本发明，当用作扩链剂的多异氰酸酯(B)中的所有NCO基团已与预聚物(A)的OH基团反应时，理论羟基含量被理解为是指以重量%单位的留在聚氨酯(P)中的OH基团的理论计算含量。理论OH含量由下式计算：
理论OH含量 = (([所用OH基团摩尔量]-[所用NCO基团摩尔量]*17)/所用预聚物的质量) *100
优选地，所得聚氨酯(P)的理论羟基含量小于0.24重量%，特别优选小于0.22重量%，进一步优选小于0.20重量%，进一步优选小于0.18重量%，更优选0.00%至0.22重量%和最优选0重量%，基于所述聚氨酯在经干燥状态下的总重量计。
根据本发明，所得聚氨酯(P)另外基本不含脲基团。在本发明的上下文中的脲基团优选被理解为是指R1R2N-(C=O)N-R3R4基团，其中R1至R4基团各自独立地为氢或有机基团。脲基团也被理解为是指取代的脲基团和它们的衍生物。
根据本发明，“基本不含脲基团”优选是指在扩链中完全不使用具有氨基的化合物。将领会到的是，所用的反应物可含有可能也包含低浓度的氨基的杂质。此类杂质会导致形成脲基团，但它们仍涵盖于本发明中。然而，优选地，这些反应物通常不具有任何含氨基的杂质或任何杂质。更特别地，表述“基本不含脲基团”是指用于制备聚氨酯(P)的反应物具有0.1重量%或更少的氨基，相对于所用反应物的总和计。更优选地，在这一点上，“基本不含脲基团”是指经由标准测试方法（特别优选13C NMR或IR）不能检测到脲基团。在此，特别优选的是所得聚氨酯(P)具有小于0.1重量%的脲基团（基于=N-(C=O)-N=）。
优选地，聚氨酯(P)具有至少一种预聚物(A)和至少一种多异氰酸酯(B)的构成组分，这两种构成组分仅仅经由氨基甲酸酯基团相互连接。
多异氰酸酯(B)优选是芳族多异氰酸酯。在另一实施方案中，其优选为脂族或脂环族多异氰酸酯。如上文已阐明的那样，已令人惊奇地发现，根据本发明，即使用脂族或脂环族多异氰酸酯组分(B)，也可以在经济可行的时间段内实现扩链。
优选地，所述至少一种多异氰酸酯(B)选自NCO官能度≥ 2的芳族、芳脂族、脂族和脂环族的多异氰酸酯化合物，其可任选具有亚氨代噁二嗪二酮、异氰脲酸酯、脲二酮、氨基甲酸酯、脲基甲酸酯、缩二脲、脲、噁二嗪三酮、噁唑烷酮、酰基脲和/或碳二亚胺结构。此类多异氰酸酯化合物对于本领域技术人员是本身已知的。它们可以单独使用和以任何所需的相互混合的形式使用。
合适的多异氰酸酯(B)的实例是亚丁基二异氰酸酯、六亚甲基二异氰酸酯（HDI）、异佛尔酮二异氰酸酯（IPDI）、2,2,4-和/或2,4,4-三甲基六亚甲基二异氰酸酯、五亚甲基二异氰酸酯（PDI）、异构的双(4,4'-异氰酸根合环己基)甲烷或者其具有任何异构体含量的混合物、异氰酸根合甲基辛烷-1,8-二异氰酸酯、环己烷-1,4-二异氰酸酯、苯-1,4-二异氰酸酯、甲苯-2,4-和/或2,6-二异氰酸酯、1,3-和1,4-双(2-异氰酸根合-丙-2-基)苯（TMXDI）、1,3-双(异氰酸根合甲基)苯（XDI）、萘-1,5-二异氰酸酯、二苯基甲烷-2,4'-或4,4'-二异氰酸酯、三苯基甲烷-4,4',4''-三异氰酸酯或基于上述二异氰酸酯，具有脲二酮、异氰脲酸酯、氨基甲酸酯、脲基甲酸酯、缩二脲、亚氨代噁二嗪二酮和/或噁二嗪三酮结构，具有多于2个NCO基团的衍生物。具有每分子多于2个NCO基团的未改性多异氰酸酯的一个实例是4-异氰酸根合甲基辛烷1,8-二异氰酸酯（壬烷三异氰酸酯）。优选地，(B)包含仅具有脂族和/或脂环族键合的异氰酸酯基团的上述类型的多异氰酸酯或多异氰酸酯混合物。特别优选的是六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、异构的双(4,4'-异氰酸根合环己基)甲烷、甲苯二异氰酸酯的异构体、二苯基甲烷二异氰酸酯和它们的混合物。
更优选地，在所述至少一种多异氰酸酯化合物 (A4)中的所有化合物不同于在所述至少一种多异氰酸酯(B)中的所有多异氰酸酯。这意味着，当(A4)包含若干种不同的多异氰酸酯化合物时，所有这些都不同于用作多异氰酸酯(B)的化合物。当(A4)包含仅一种多异氰酸酯化合物时，也是如此。
扩链步骤（还参见方法步骤(ii)）是本领域技术人员已知的。更优选地，这一步骤在惰性有机溶剂，优选酮官能脂族溶剂中实现，其优选选自丙酮和丁酮，其不仅可以在制备开始时添加，也可以任选在后期阶段分份添加。优选地，为此，将预聚物(A)首先溶解在该溶剂中。同样优选地，可以加热该溶剂。在这种情况下，优选加热到25至100℃，更优选到40至60℃。此后，添加所述至少一种多异氰酸酯(B)。
在扩链中，任选也可以使用用于氨基甲酸酯化（urethanization）反应的催化剂。这些催化剂对于本领域技术人员是本身已知的。优选的是有机金属化合物，例如二月桂酸二丁基锡，或不含锡的金属配合物，例如来自OMG Borchers, Langenfeld的Borchi® Kat24。
实施所述扩链至所需OH含量。这优选是指实施该反应直至基本所有NCO基团已消耗（即，不再能检测到NCO基团）。本领域技术人员熟悉检测NCO基团的方法。优选地，借助FT-IR分析不再能检测到NCO基团。优选地，为此，需要的反应时间为20至750 min，更优选60至500 min。
优选地，在所述扩链中，达到80%至100%，更优选90%至100%，最优选95%至100%的扩链度。扩链度由在至少一种多异氰酸酯(B)中所用的NCO基团与在预聚物(A)中所用的OH基团的摩尔比乘以100来计算（扩链度 = ([以摩尔计的所用NCO基团]/[以摩尔计的所用OH基团])*100)。
如果预聚物(A)在任选的构成组分(A3)中含有潜在离子基团，则它们应任选在分散到水中之前被中和。该中和可在预聚物阶段(A)，即在本发明的方法步骤(ii)之前实现，或在聚氨酯(P)本身中，即在本发明的方法步骤(ii)之后实现。因此，本发明的方法步骤(iii)任选包括在方法步骤(ii)之前或之后将任选的构成组分(A3)中的潜在离子基团中和。
合适的中和剂是本领域技术人员已知的。它们可选自例如三乙胺、N-甲基吗啉、二甲基异丙基胺、乙基二异丙基胺、二甲基环己基胺、三乙醇胺、二甲基乙醇胺、氨、氢氧化钾、氢氧化钠和它们的任何所需混合物。
这优选达到至少60%，更优选至少75%，最优选100%的中和度。
将由此获得的聚氨酯(P)随后分散到水中，以获得本发明的水性聚氨酯分散体。本发明的方法步骤(iv)因此提供获自步骤(ii)或(iii)的聚氨酯(P)在水中的分散体。当在方法步骤(iii)中不实施中和时，或在方法步骤(ii)之前实施方法步骤(iii)时，实现获自步骤(ii)的聚氨酯的分散。当在方法步骤(ii)之后的方法步骤(iii)中实施中和时，实现获自步骤(iii)的聚氨酯的分散。
为了执行所述分散步骤，可将水添加到聚氨酯(P)中或可将聚氨酯(P)添加到水中。在这种情况下，可以分别使用无溶剂的聚氨酯(P)或其在惰性溶剂（优选丙酮）中的溶液。该分散步骤通常在20至100℃，优选40至100℃的温度下进行。聚氨酯(P)的可分散性可以任选通过在分散中额外使用外部乳化剂来改进。该分散优选使用剧烈剪切来实现。
在分散步骤后仍存在于分散体中的溶剂通常随后通过蒸馏除去。甚至也可以在分散过程中除去。任何蒸馏除去过量溶剂的实施可在分散到蒸馏水中/用蒸馏水分散期间或之后例如在20至80℃下例如在减压下进行。
根据本发明，所述分散体是水性的。这优选意味着，其基本不再含有任何有机溶剂。有机溶剂的残余含量优选为低于所述聚氨酯分散体总重量的5重量%，更优选低于3重量%和最优选低于1重量%。
在已经制备它们之后，可以将有机溶剂，特别是醇类溶剂（例如乙醇、正丁醇、正辛醇、二乙二醇丁醚、二乙二醇乙醚、二乙二醇甲醚或甲氧基丙醇）添加到本发明的分散体中，以实现特定性能。
本发明的聚氨酯分散体的固含量为优选22重量%至55重量%和更优选30重量%至50重量%。
本发明的聚氨酯分散体还优选具有5.0至8.0，更优选5.5至7.9的pH。
本发明的聚氨酯分散体优选具有例如通过光子相关谱测得的50至500 nm，优选60至300 nm的平均粒径。这通过使用水作为溶剂完成，且该测量在25℃下进行。在每种情况中，中值粒度是Z平均的D50。
更优选地，在所述分散体中的聚氨酯(P)的重均分子量为10 000至500 000 g/mol，更优选15 000至400 000 g/mol和最优选20 000至300 000 g/mol。在本申请的上下文中，重均分子量优选通过凝胶渗透色谱法（GPC）在N,N-二甲基乙酰胺中在40℃下测得。该程序是根据DIN 55672-2 (2008-06)：“凝胶渗透色谱法 (GPC) – 第2部分：N,N-二甲基乙酰胺作为洗脱溶剂”（来自PSS Polymer Service的SECurity GPC System，流速0.6 ml/min；柱：GRAM 3000, HEMA 300, 2x HEMA 40；UV和RI检测器）。已知摩尔质量的聚苯乙烯试样用于校准。使用软件支持来计算数均分子量。基准点和评估极限根据DIN 55672第2部分（2008-06）确定。
已发现，根据本发明，所述聚氨酯分散体具有与标准聚氨酯脲分散体可比拟的指数，例如固含量、pH和/或平均粒径。这意味着，本发明的聚氨酯分散体可以与已知分散体完全相同的方式使用，但同时提供了改进的工艺方案和对所得产品的更好的控制。
通常，本发明的水性聚氨酯分散体可用于生产漆层、涂层、胶粘剂或密封剂。
在本发明的另一方面中，提供了水性1-组分涂料组合物，其包含
(Ia) 至少一种在所有描述的优选实施方案中的本发明的水性聚氨酯分散体，任选以与其它分散体的混合物的形式，
(IIa) 任选至少一种封闭型多异氰酸酯，和
(IIIa) 至少一种辅助剂和/或添加剂。
此类1-组分涂料组合物是例如在120至230℃的温度下固化的烤漆和涂料。特别优选的用途是底漆-二道底漆烘烤涂层（baking primer-surfacer coats）、单涂层漆、抗碎石底漆（anti-stonechip primers）和着色面漆。
组分(Ia)的任何其它分散体也可为聚氨酯或本领域技术人员熟悉的其它分散体。
合适的封闭型多异氰酸酯(IIa)是例如，二官能异氰酸酯如异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、2,4-或2,6-二异氰酸根合甲苯、二苯基甲烷 4,4'-二异氰酸酯和/或其更高分子量三聚体、缩二脲、氨基甲酸酯、亚氨代噁二嗪二酮和/或脲基甲酸酯与封闭剂如甲醇、乙醇、丁醇、己醇、苄醇、丙酮肟、丁酮肟、己内酰胺、苯酚、丙二酸二乙酯、丙二酸二甲酯、二甲基吡唑、三唑、二甲基三唑、乙酰乙酸乙酯、二异丙基胺、二丁基胺、叔丁基苄胺、环戊酮羧乙基酯（cyclopentanone carboxyethyl ester）、二环己基胺和/或叔丁基异丙基胺的反应产物。
所述封闭型多异氰酸酯还可通过并入亲水性基团，例如羧酸根、磺酸根和/或聚氧乙烯结构转化为可水分散形式，并由此与本发明的分散体组合使用。所述封闭型多异氰酸酯还可通过额外使用羟基-或氨基-官能组分，包括更高分子量的组分，例如二醇、三醇、氨基醇、聚酯、聚醚、聚碳酸酯和所述原料和/或其它的混合物。
封闭型多异氰酸酯(IIa)优选具有2.0至5.0，优选2.3至4.5的（平均）NCO官能度，5.0重量%至27.0重量%，优选14.0重量%至24.0重量%的（未封闭和封闭的）异氰酸酯基团含量和小于1重量%，优选小于0.5重量%的单体二异氰酸酯含量。所述可水分散或水溶性的封闭型多异氰酸酯中的多异氰酸酯的异氰酸酯基团以到至少50%的程度，优选到至少60%的程度和更优选到至少70%的程度呈封闭形式。所述可水分散的封闭型多异氰酸酯IIa可通过已知现有技术方法（例如在DE-A 2 456 469，第7-8栏，实施例1-5中和DE-A 2 853 937第21-26页，实施例1-9中）制备。
适合于配制1-组分涂料组合物的辅助剂或添加剂(IIIa)是本领域技术人员已知的。它们是例如表面活性物质、乳化剂、稳定剂、防沉剂、UV稳定剂、用于交联反应的催化剂、消泡剂、抗氧化剂、防结皮剂、均化剂、增稠剂和/或杀菌剂。
在本发明的另一方面中，提供了水性2-组分涂料组合物，其包含
(Ib) 至少一种在所有描述的优选实施方案中的本发明的水性聚氨酯分散体，任选以与其它分散体的混合物的形式，
(IIb) 至少一种多异氰酸酯(C)，和
(IIIb) 至少一种辅助剂和/或添加剂。
组分(Ib)的任何其它分散体也可为聚氨酯或本领域技术人员熟悉的其它分散体。
适合于配制2-组分涂料组合物的辅助剂或添加剂(IIIb)是本领域技术人员已知的。它们是例如表面活性物质、乳化剂、稳定剂、防沉剂、UV稳定剂、用于交联反应的催化剂、消泡剂、抗氧化剂、防结皮剂、均化剂、增稠剂和/或杀菌剂。
在本发明的一个方面中，还提供了通过将在所有描述的优选实施方案中的本发明的水性聚氨酯分散体在基底的至少一部分上固化所获得的漆层、涂层、胶粘剂或密封剂。根据本发明，该固化可优选通过干燥和任选额外的化学交联来实现。
接下来通过下列实施例详细说明本发明。
实施例
原料：
Desmophen 1652 (DE 1652)：由己二酸、丁-1,4-二醇、乙二醇、二乙二醇形成的聚酯多元醇，其摩尔质量为2000 g/mol (BAYER AG, Leverkusen)
聚醚磺酸盐 (PETS)：具有磺酸钠基团的聚氧丙烯二醇，其摩尔质量为435 g/mol(BAYER AG, Leverkusen)
PTHF2K：聚四亚甲基醚二醇，其摩尔质量为2000 g/mol (ALDRICH, 德国).
C2200：聚碳酸六亚甲基酯二醇，其摩尔质量为2000 g/mol (BAYER AG, Leverkusen)
丁-1,4-二醇 (BDO)：(ALDRICH, DE)
LB 25：由环氧乙烷和环氧丙烷形成的单羟基官能聚醚，其具有84重量%的环氧乙烷比例和2250 g/mol的摩尔质量 (BAYER AG, Leverkusen)
Desmodur I (IPDI)：异佛尔酮二异氰酸酯 (BAYER AG, Leverkusen)
Desmodur H (HDI)：六亚甲基二异氰酸酯 (BAYER AG, Leverkusen)
Desmodur T 80 (T80)：甲苯二异氰酸酯 (80%甲苯2,4-二异氰酸酯和20%甲苯2,6-二异氰酸酯，BAYER AG, Leverkusen)
Desmodur T 100 (T100)：甲苯二异氰酸酯 (100%甲苯2,4-二异氰酸酯，BAYER AGLeverkusen)
Desmodur 2460 M (MDI)：二苯基甲烷二异氰酸酯 (二苯基甲烷 2,4'-和4,4'-二异氰酸酯的异构体混合物，BAYER AG Leverkusen)
DMPS：二羟甲基丙酸 (DMPA，ALDRICH, 德国)
TEA：三乙胺 (ALDRICH, 德国)
Borchikat 24：不含锡的氨基甲酸酯化催化剂 (OMG Borchers, Langenfeld, 德国)。
方法：
使用Haake粘度计在室温（23℃）下以45 s-1的剪切速率测定粘度。
根据DIN EN ISO 3251测定固含量（SC）。
借助光子相关谱仪（Malvern Instruments，型号：Zetasizer 1000）测定中值粒度（MPS）。
分散体的制备：
用于生产本发明的分散体的一般方法
最初将适当量的OH官能原料装入反应容器中并加热至70℃的温度。在达到目标温度时，加入所示量的多异氰酸酯1，将该混合物加热至100℃并搅拌直至借助IR测量不再显示出游离的异氰酸酯。将该预聚物冷却至50℃并随后溶解在丙酮中（50%溶液）。加入多异氰酸酯2和200 ppm的氨基甲酸酯化催化剂Borchikat 24。在回流下在所示反应时间（t CE）内实现扩链，并借助IR每间隔一段时间检验转化率，直至反应混合物不再具有任何游离的异氰酸酯。此后，将该混合物冷却至50℃并将软化水加入分散体中（计算该量以使得不含丙酮的PUD具有35.0重量%的理论固含量）。此后，在45℃下在减压（125 mbar）下蒸馏去除丙酮以获得不含脲基团和溶剂的高分子量聚氨酯分散体。
* 将预聚物溶解在丙酮中并随后用三乙胺中和；中和水平相当于100%。
可以看出，本发明的聚氨酯分散体具有可与标准聚氨酯脲分散体相比拟的指数。在此可生产阴离子或非离子粒子或组合的阴离子-非离子粒子。该阴离子基团呈磺酸根或羧酸根基团的形式。
Claims (15)
1.包含聚氨酯(P)的水性聚氨酯分散体，所述聚氨酯(P)通过将至少一种羟基官能预聚物(A)用至少一种多异氰酸酯(B)扩链来制备，所述羟基官能预聚物(A)包含至少下列构成组分：
(A1)至少一种官能度>1的多元醇，
(A2)任选至少一种不同于(A1)的二醇，
(A3)任选至少一种亲水性构成组分，其具有至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4)至少一种多异氰酸酯化合物，
且所述聚氨酯(P)基本不含脲基团，其特征在于，所述聚氨酯(P)具有小于0.25重量%的理论羟基含量，基于所述聚氨酯在经干燥状态下的总重量计。
2.用于制备水性聚氨酯分散体的方法，其包括以所指定次序的下列步骤：
(i) 由至少下列构成组分制备羟基官能预聚物(A)：
(A1)至少一种官能度> 1的多元醇，
(A2)任选至少一种不同于(A1)的二醇，
(A3)任选至少一种亲水性构成组分，其具有至少一个选自离子基团、潜在离子基团、非离子基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4)至少一种多异氰酸酯化合物，
(ii)将获自步骤(i)的羟基官能预聚物用至少一种多异氰酸酯(B)扩链至所得聚氨酯(P)的理论羟基含量小于0.25重量%的程度，基于所述聚氨酯在经干燥状态下的总重量计，所得聚氨酯(P)基本不含脲基团，
(iii)在步骤(ii)之前或之后，任选中和在任选的构成组分(A3)中的潜在离子基团，并且
(iv)将获自步骤(ii)或(iii)的聚氨酯(P)分散到水中。
3.根据权利要求1的水性聚氨酯分散体或根据权利要求2的方法，其中所述聚氨酯(P)的理论羟基含量不大于0.24重量%，基于所述聚氨酯在经干燥状态下的总重量计。
4.根据权利要求1和3之一的水性聚氨酯分散体或根据权利要求2和3之一的方法，其中所述多异氰酸酯(B)是芳族多异氰酸酯。
5.根据权利要求1、3和4任一项的水性聚氨酯分散体或根据权利要求2至4任一项的方法，其中在所述至少一种多异氰酸酯化合物(A4)中的所有化合物不同于在所述至少一种多异氰酸酯(B)中的所有多异氰酸酯。
6.根据权利要求1和3至5任一项的水性聚氨酯分散体或根据权利要求2至5任一项的方法，其中在所述羟基官能预聚物(A)的制备中异氰酸酯基团与异氰酸酯反应性基团的摩尔比为0.25至0.95。
7.根据权利要求1和3至6任一项的水性聚氨酯分散体或根据权利要求2至6任一项的方法，其中所述扩链达到80%至100%的扩链度。
8.根据权利要求1和3至7任一项的水性聚氨酯分散体或根据权利要求2至7任一项的方法，其中所述羟基官能预聚物(A)包含至少下列构成组分：
(A1)至少一种官能度> 1的选自聚酯多元醇、聚醚多元醇、聚酯醚多元醇和聚碳酸酯多元醇的多元醇，
(A2)任选至少一种不同于(A1)且摩尔质量为62至450 g/mol的二醇，
(A3)任选至少一种亲水性构成组分，其具有至少一个选自酸基团、聚氧化烯醚基团和它们的任何所需混合物的亲水性基团，以及至少一个羟基基团，和
(A4)至少一种多异氰酸酯化合物，其选自NCO官能度≥ 2的芳族、芳脂族、脂族和脂环族的多异氰酸酯化合物，其可任选具有亚氨代噁二嗪二酮、异氰脲酸酯、脲二酮、氨基甲酸酯、脲基甲酸酯、缩二脲、脲、噁二嗪三酮、噁唑烷酮、酰基脲和/或碳二亚胺结构。
9.根据权利要求1和3至8任一项的水性聚氨酯分散体或根据权利要求2至8任一项的方法，其中所述亲水性构成组分(A3)包含至少下列化合物：
(A3-1)至少一种离子化合物或潜在离子化合物，其具有至少一个酸基团和至少一个羟基基团，和
(A3-2)至少一种摩尔质量Mn为1200 g/mol至3000 g/mol并具有羟基的含聚乙二醇的化合物，其中聚乙二醇的比例为至少50重量%。
10.根据权利要求1和3至9任一项的水性聚氨酯分散体或根据权利要求2至9任一项的方法，其中羟基官能预聚物(A)至少包含
50重量%至87重量%的(A1)，
3重量%至11重量%的(A2)，
0重量%至24重量%的(A3)，和
3重量%至20重量%的(A4)，
其中构成组分(A1)至(A4)的总和总计达100重量%。
11.根据权利要求1和3至10任一项的水性聚氨酯分散体或根据权利要求2至10任一项的方法，其中所述水性聚氨酯分散体的固含量为20重量%至55重量%。
12.水性单组分涂料组合物，其包含
(Ia)至少一种根据权利要求1和3至11任一项的水性聚氨酯分散体，其任选以与其它分散体的混合物的形式，
(IIa)任选至少一种封闭型多异氰酸酯，和
(IIIa) 至少一种辅助剂和/或添加剂。
13.水性双组分涂料组合物，其包含
(Ib) 至少一种根据权利要求1和3至11任一项的水性聚氨酯分散体，其任选以与其它分散体的混合物的形式，
(IIb)至少一种多异氰酸酯(C)，和
(IIIb)至少一种辅助剂和/或添加剂。
14.根据权利要求1和3至11任一项的水性聚氨酯分散体用于生产漆层、涂层、胶粘剂或密封剂的用途。
15.通过将根据权利要求1和3至11任一项的水性聚氨酯分散体在基底的至少一部分上固化所获得的漆层、涂层、胶粘剂或密封剂。
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| Country | Link |
|---|---|
| US (1) | US20160376438A1 (zh) |
| EP (1) | EP3109269B1 (zh) |
| CN (1) | CN106432663A (zh) |
| ES (1) | ES2708202T3 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666464A (zh) * | 2017-03-29 | 2018-10-16 | 孚能科技（赣州）有限公司 | 灌封胶和电池组 |
| TWI774915B (zh) * | 2019-01-28 | 2022-08-21 | 張娟娟 | 環保型水性聚氨酯分散液及其製備方法與應用 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11498999B2 (en) * | 2017-05-11 | 2022-11-15 | Dow Global Technologies Llc | Aqueous polyurethane dispersion adhesive compositions |
| CN113825800A (zh) * | 2019-02-25 | 2021-12-21 | Dic株式会社 | 氨基甲酸酯树脂水分散体、皮革片及皮革片的制造方法 |
| WO2022011580A1 (en) * | 2020-07-15 | 2022-01-20 | Dow Global Technologies Llc | Polyester polyol-polyether polyol blend having higher stability and comparibility, and polyurethane material prepared therefrom |
| CN117136206A (zh) | 2021-04-16 | 2023-11-28 | 巴斯夫欧洲公司 | 水性聚氨酯和聚氨酯/聚(甲基)丙烯酸酯混合分散体 |
| WO2024232282A1 (ja) * | 2023-05-11 | 2024-11-14 | Dic株式会社 | 合成皮革及び合成皮革の製造方法 |
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| CN102161743A (zh) * | 2009-12-14 | 2011-08-24 | 气体产品与化学公司 | 无溶剂水性聚氨酯分散体及其制备和使用方法 |
| US20110275728A1 (en) * | 2009-01-24 | 2011-11-10 | Bayer Materialscience Ag | Dispersed two-component polyurethane foams |
| CN102317338A (zh) * | 2009-03-27 | 2012-01-11 | 卡尔·弗罗伊登伯格公司 | 制备反应性聚氨酯乳液的方法 |
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| US4108814A (en) | 1974-09-28 | 1978-08-22 | Bayer Aktiengesellschaft | Aqueous polyurethane dispersions from solvent-free prepolymers using sulfonate diols |
| DE2456469C2 (de) | 1974-11-29 | 1983-01-13 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von in Wasser löslichen bzw. dispergierbaren blockierten Polyisocyanaten und ihre Verwendung als Beschichtungsmittel |
| DE2853937A1 (de) | 1978-12-14 | 1980-07-03 | Bayer Ag | Verfahren zur herstellung von wasserdispergierbaren oder -loeslichen blockierten polyisocyanaten, die nach dem verfahren erhaeltlichen blockierten polyisocyanate, sowie diese blockierte polyisocyanate als isocyanatkomponente enthaltende lackbindemittel |
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| DE4216536A1 (de) | 1992-05-19 | 1993-11-25 | Bayer Ag | Wasserverdünnbare Polyesterpolyole und ihre Verwendung |
| CA2127761C (en) * | 1993-07-16 | 2005-10-18 | Armin Gobel | An aqueous dispersion of polyurethane resins, a method of manufacturing them, coating agents containing them and use thereof |
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- 2015-06-25 ES ES15173729T patent/ES2708202T3/es active Active
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2016
- 2016-06-22 US US15/189,271 patent/US20160376438A1/en not_active Abandoned
- 2016-06-24 CN CN201610466119.7A patent/CN106432663A/zh active Pending
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| US20110275728A1 (en) * | 2009-01-24 | 2011-11-10 | Bayer Materialscience Ag | Dispersed two-component polyurethane foams |
| CN102317338A (zh) * | 2009-03-27 | 2012-01-11 | 卡尔·弗罗伊登伯格公司 | 制备反应性聚氨酯乳液的方法 |
| CN102161743A (zh) * | 2009-12-14 | 2011-08-24 | 气体产品与化学公司 | 无溶剂水性聚氨酯分散体及其制备和使用方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108666464A (zh) * | 2017-03-29 | 2018-10-16 | 孚能科技（赣州）有限公司 | 灌封胶和电池组 |
| TWI774915B (zh) * | 2019-01-28 | 2022-08-21 | 張娟娟 | 環保型水性聚氨酯分散液及其製備方法與應用 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3109269A1 (de) | 2016-12-28 |
| ES2708202T3 (es) | 2019-04-09 |
| US20160376438A1 (en) | 2016-12-29 |
| EP3109269B1 (de) | 2018-10-31 |
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