CN104114514B - 用于涂料的疏水剂 - Google Patents
用于涂料的疏水剂 Download PDFInfo
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- CN104114514B CN104114514B CN201380009659.7A CN201380009659A CN104114514B CN 104114514 B CN104114514 B CN 104114514B CN 201380009659 A CN201380009659 A CN 201380009659A CN 104114514 B CN104114514 B CN 104114514B
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- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229940104261 taurate Drugs 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- NIDHFQDUBOVBKZ-NSCUHMNNSA-N trans-hex-4-enoic acid Chemical compound C\C=C\CCC(O)=O NIDHFQDUBOVBKZ-NSCUHMNNSA-N 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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Classifications
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
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Abstract
本发明涉及通式(I)MmDnToQp(I)的有机硅氧烷与通式(II)(A-B)qC(II)的环氧化物的混合物,其中M代表通式(Ia)R1R2R3SiO1/2(Ia)的端基,D代表通式(Ib)R4R5SiO2/2(Ib)的双官能基团,T代表通式(Ic)R6SiO3/2(Ic)的三官能基团,并且Q代表通式为SiO4/2的单元,其中至少一个烃基R6含有至少一个胺官能团并且所有基团中最多75%为羟基或烷氧基,条件是通式(II)的化合物含有至少一个环氧官能团,其中R1、R2、R3、R4、R5、R6、A、B、C、m、n、o、p和q具有在权利要求1中所规定的含义。本发明还涉及通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物作为用于耐候性油漆和涂料的疏水化添加剂的用途;以及涉及含有通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物的耐候性油漆和涂料。
Description
技术领域
本发明涉及包括环氧基官能团的化合物和包括氨基官能团的有机硅氧烷的混合物,及其在耐候性油漆和涂料中的用途,以及包括该混合物的耐候性油漆和涂料。
背景技术
对工业建造的建筑物的保护,尤其是由吸水无机建筑材料例如混凝土和由砖块或石灰砂盐构成的砌体而制成的建筑物的正面的保护,抵抗潮湿和水分是建筑学保护的主要任务之一。
水渗透具有多种有害作用:其浸湿建筑物,溶解油漆中使用的无机盐以及助剂和添加剂,并在蒸发时将它们传送至表面,在那里它们可通过所述油漆成分以及通过微生物例如真菌、藻类和藓类的感染进而导致风化和盐诱导的剥落和脱落、斑点。还可能由于降低的热绝缘对内部气候具有不利影响并且增加了能耗。
近年来,已研制出有效的既疏水又“透气的”建筑油漆,意指外部雨水以小珠子形式流掉,但是在建筑材料中位于油漆下方的水分能够以水蒸汽形式通过油漆。该油漆一般是基于含水聚合物的分散体,所述分散体作为粘合剂可包括既可交联的又可不可交联类型的任何有机树脂,但是主要是乙酸乙烯酯共聚物和苯乙烯丙烯酸酯共聚物,以及直链聚丙烯酸酯,并且包括防水性有机硅氧烷添加剂的含水乳液作为给予油漆其主要特征的成分。
用于涂料或浸渍的防水效果的标准是EN1062-3透水率。
DE 10328636全面阐释了如何在实践中仅在相当长一段时间后才实现常规油漆体系的水分保护。为了克服该缺点,其提出在配制物中添加0.01-10重量%的用氧化烯醚基团改性的环氧聚硅氧烷。环氧官能聚硅氧烷在涂料组合物(聚合物分散体)中作为疏水化添加剂的有效性在DE 69922682中早已被描述:其中采用仅携带环氧基官能团的聚硅氧烷乳液。DE 60108984要求保护用于防水浸渍多孔和无孔建筑材料的相同产品的用途。其中环氧基官能团对于基本底物的高反应性被认为是造成特定效果的原因。
然而,在该两种情况中,环氧官能聚硅氧烷仅通过氢化硅烷化反应可获得,所述反应由于使用不可回收的铂催化剂是昂贵的,此外,该反应需要不饱和的环氧化物原料,所述原料在一些情况下具有高毒性,并且在工业规模生产中处理起来需要高成本和复杂的安全操作。为了防止在终端产物中夹带有毒的、未反应的起始原料,并因此进入环境,需要相应的高代价和不方便的后处理程序。
DE 3713126要求保护氨基官能的聚二有机硅氧烷与硅树脂的组合,用于含水乳液油漆的疏水处理,但是不确定有利的效果是来自于高比例的昂贵硅树脂或来自氨基官能的聚硅氧烷,还是来自二者添加剂的组合。
发明内容
本发明提供通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物:
MmDnToQp (I)
(A-B)qC (II),
其中
M为通式(Ia)的端基
R1R2R3SiO1/2 (Ia),
D为通式(Ib)的双官能基团
R4R5SiO2/2 (Ib),
T为通式(Ic)的三官能基团
R6SiO3/2 (Ic),
Q为通式SiO4/2的单元,
其中R1、R2、R3、R4、R5和R6彼此独立地代表具有1-20个碳原子的烃基,其可含有杂原子,或者代表羟基或具有1-10个碳原子的烷氧基,其中至少一个烃基R6含有至少一个胺官能团,并且在这些所有的基团中不超过75%为羟基或烷氧基,
m为0-20的整数,
n为0-1000的整数,
o为1-30的整数,
p为0-20的整数,并且
m+n+o+p为至少是2的整数,
其中
A在每次出现时独立地为具有1-30个碳原子的直链或支链一价烃基,其可被杂原子取代,其中可插入杂原子,并且其可含有一个或多个环氧官能团,
B在每次出现时独立地为二价的醚、碳酸酯、或脲官能团,或者为酸、酯、氨基甲酸酯、酸酐,或者羧酸、硫代羧酸、硫酸、膦酸或磷酸的酰胺官能团,
q为1-8的数值,
c为具有1-30个碳原子的q价的直链或支链烃基,其可含有杂原子,并且可含有一个或多个环氧官能团,
条件是通式(II)的化合物包括至少一个环氧官能团。
本发明同样提供通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物作为用于耐候性油漆和涂料的疏水化添加剂的用途。
本发明同样提供包括通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物的耐候性油漆和涂料。
出人意料地,已发现可商购获得的携带环氧基团的通式(II)的脂肪酸酯与通式(I)的氨基官能有机硅氧烷的简单混合物赋予常规的耐候性油漆和涂料,尤其是乳液油漆,强烈的防水效果。在其使用期间,没有释放出讨厌的或有毒的消除产物或排放物例如溶剂蒸气。在完全固化的油漆薄膜上也没有发生任何颜色改变的效果例如风化。该混合物的另一个优点是这两个组分都是普通的可商购获得的,并且廉价。此外,通式(II)的环氧脂肪酸酯是可以由可再生原料例如植物油环境友好地生产的并且不具有任何毒性或对环境有害的性能的产品。
乳液油漆一般基于含水聚合物分散体,其作为粘合剂可包括既可交联的又可不可交联类型的任何有机树脂。在本上下文中使用的聚合物优选为选自以下的单体的聚合物或共聚物:乙烯酯例如乙酸乙烯酯、月桂酸乙烯酯、叔碳酸乙烯酯(vinyl versatate),丙烯酸酯例如丙烯酸正丁酯,甲基丙烯酸酯例如甲基丙烯酸甲酯,苯乙烯,异丁烯,1-丁烯,1,3-丁二烯,乙烯,1-己烯,氯乙烯,四氟乙烯等,但是尤其是乙酸乙烯酯与乙烯和/或氯乙烯的共聚物,苯乙烯丙烯酸酯共聚物,以及直链聚丙烯酸酯。此外还通常存在的是颜料,尤其是金红石类二氧化钛,填料例如方解石,天然碳酸,沉淀碳酸钙,硅酸铝和云母,以及石英。此外还使用常规助剂和添加剂例如纤维素衍生物、膨润土、PU增稠剂和/或用于调节流变学行为的缔合增稠剂、中和剂,润湿和分散添加剂例如尤其是聚羧酸,防腐剂,基于矿物油、硅油或聚醚硅氧烷的消泡剂。此外还可存在的是硅酸盐例如硅酸钠和/或硅树脂和/或氟烷基聚合物分散体。
通式(I)的有机硅氧烷优选为可商购获得的氨基(聚)硅氧烷。这里的胺官能团位于键合在通式(Ic)的三级Si单元上的基团R6中。通式(I)的化合物例如可通过OH封端的聚二有机硅氧烷与氨基官能的三烷氧基硅烷的消去乙醇的反应而获得,或者可通过氨基官能的聚硅氧烷与其他(聚)硅氧烷的碱催化平衡而获得。
R1、R2、R3、R4、R5和R6优选代表直链、支链、环状、芳族、饱和或不饱和的一价烃基,以及代表羟基或具有1-10个碳原子的烷氧基,所述烷氧基可以是直链、支链或环状,在这些所有的基团中优选不超过50%,更优选不超过25%,尤其是不超过3%是羟基或烷氧基。
通式(I)中的R1、R2、R3、R4和R5优选代表具有1-20个碳原子的一价烃基,其是未取代的,或者被卤原子或烷氧基、铵基或甲硅烷基取代,或者代表羟基,以及代表具有1-10个碳原子的烷氧基。尤其优选为未取代的烷基、环烷基、烷基芳基、芳基烷基以及苯基。烃基R1、R2、R3、R4和R5优选具有1-8个碳原子。尤其优选为甲基、乙基、正丙基、2-丙基(=异丙基)、3,3,3-三氟丙基、乙烯基、1-正丁基、2-甲基丙基(=异丁基)、2-丁基、叔丁基、正戊基、环戊基、环己基、正壬基、正癸基、正十一基、10-十一碳烯基、正十二烷基、异十三烷基、正十四烷基、正十六烷基、烯丙基、苯基、苄基、对-氯苯基、邻-(苯基)苯基、间-(苯基)苯基、对(苯基)苯基、1-萘基、2-萘基、2-苯乙基、1-苯乙基、3-苯丙基、1-正己基、1-正庚基、1-正辛基、2,4,4-三甲基-1-戊基、2-乙基-1-己基、2-甲基-1-戊基、以及由共同术语异己基和异辛基包括的基团,尤其是甲基、乙基、丙基、异丁基、1-正己基、1-正辛基、异己基、异辛基和苯基。
取代的基团R1、R2、R3、R4和R5的实例如下:3-氯丙基、氯甲基、甲氧基甲基、乙氧基甲基、2-三甲基甲硅烷基乙基、2-三甲基甲硅烷氧基乙基、2-三甲氧基甲硅烷基乙基、2-二甲基甲氧基甲硅烷基乙基、2-二甲氧基甲基甲硅烷基、3-三甲基铵基丙基和3-二甲基苄基铵基丙基。
取代的基团R1、R2、R3、R4和R5的其他实例为被通式(III)的基团取代的C1-C12烃基
-(CR7R8)rO)s-R9 (III)
其中r代表1-6的数值,s可为1-100的数值,并且R7、R8和R9具有除了羟基和烷氧基以外的R1、R2、R3、R4和R5的定义,或者代表氢,其中具有通式(III)的不同单元的基团可优选以嵌段形式存在,例如
-CH2CH2CH2-O-(CH2CH2O)6-CH3、-CH2CH2CH2-O-(CH2CH(CH3)O)8-H、
-CH2CH2CH2-O-(CH2CH2CH2CH2O)10-CH2CH2CH2CH3、
-CH2CH2CH2-O-(CH2CH2O)10-(CH2CH(CH3)O)8-CH2CH2CH2CH3。
尤其是在乙烯氧基或季铵基的存在下,通式(I)的化合物和/或通式(I)和(II)的两个化合物的混合物可具有自乳化性质,通式(I)的化合物中优选不超过60%、更优选不超过30%、尤其是不超过10%的基团代表乙烯氧基和/或季铵基。
R1、R2、R3、R4和R5尤其优选为甲基、乙基、丙基、3,3,3-三氟丙基、乙烯基和苯基。尤其是甲基。
如果R1、R2、R3、R4和R5为具有1-10个碳原子的烷氧基,该烷氧基的烃基优选具有1-4个碳原子。特别优选该烷氧基的烃基为甲基、乙基、正丙基、2-丙基(=异丙基)、乙烯基、1-正丁基、2-甲基丙基(=异丁基)、2-丁基和叔丁基。
R6具有如基团R1、R2、R3、R4和R5相同的定义。此外,R6代表C1-C20的烃基,优选C1-C10的烃基,其具有至少一个胺官能团,优选-NR10R11,其中R10和R11具有除了羟基和烷氧基之外R1、R2、R3、R4和R5的定义,或者代表氢。基团R6的实例如下:氨基甲基、2-氨基乙基、3-氨基丙基、4-氨基丁基、3-(2-氨基乙基)氨基丙基、(2-氨基乙基)氨基甲基、N-甲基氨基甲基、N-乙基氨基甲基、N,N-二乙基氨基甲基、N,N-二丁基氨基甲基、N-丁基氨基甲基、N-戊基氨基甲基、N-环己基氨基甲基、N-己基氨基甲基、N-辛基氨基甲基、N-(2-乙基己基)氨基甲基、N-十二烷基氨基甲基、N-十六烷基氨基甲基、2-N-甲基氨基乙基、3-N-甲基氨基丙基、4-N-甲基氨基丁基、N-苯基氨基甲基、N-苯基-N-甲基氨基甲基、N-苯基氨基丙基、N-吗啉基甲基、N-吡咯烷基甲基、3-(N-环己基)氨基丙基、1-N-咪唑啉基丙基。
R6的其他实例为被-(CH2CH2NH)tH取代的C1-C12烃基,其中t表示1-10的数值,尤其是1、2、3。
在通式(I)的化合物中胺浓度为0.01-10mol/kg,优选不超过5mol/kg,更优选不超过1mol/kg,尤其不超过0.5mol/kg,并且还优选为至少0.02mol/kg,更优选为至少0.05mol/kg,尤其为至少0.1mol/kg。
通式(II)的环氧化合物优选为环氧化的醚、酸、酯、氨基甲酸酯、酸酐或酰胺,其优选是可商购获得或可通过简单反应获得。环氧官能团优选位于烃基A中。
一价基团A优选含有至少一个碳原子并且优选不超过26个碳原子,更优选不超过12个碳原子,并且为直链或支链结构,并且任选被杂原子或官能团取代。除了优选的脂族单元之外,其还可包括芳族单元以及桥接杂原子,优选氧。携带环氧官能团的基团更优选为包括至少一个环氧官能团的直链烃基。尤其是,环氧官能团的两个碳原子优选每个都携带氢原子。基团A优选含有6个或更多,尤其是12个或更多个碳原子。基团A优选含有22个或更少碳原子并且平均不超过2个C=C双键。在小的程度上,基团A还可包括醇OH基,例如作为环氧官能团的水解产物。
单元B优选为酸、酯、氨基甲酸酯、酸酐、或羧酸的酰胺官能团,更优选为酸或酯官能团,尤其是羧酸的酯官能团。
q优选代表1、2或3,更优选3。在q>1的情况下,单元A和B可相同或不同。
C代表任选取代的、一价、二价、三价、四价、五价、六价、七价或八价的直链或支链烃基,其任选包括杂原子并且具有不超过30个碳原子,或者代表氢原子。C优选源自官能化合物F,所述化合物形式上能够与酸、更优选羧酸反应形成酯、酰胺、氨基甲酸酯、或酸酐基团。因而该官能化合物F包括具有至少一个羟基官能团或至少一个伯胺或仲胺官能团的化合物,实例为醇例如甲醇或乙醇、2-丁氧基乙醇、二乙二醇单乙醚、单侧甲基封端的聚乙二醇,二醇例如1,2-乙二醇或1,2-丙二醇、二乙二醇、三乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇,三醇例如丙三醇、三羟甲基乙烷或三羟甲基丙烷,四醇例如季戊四醇或双三羟甲基丙烷,酚类例如苯酚,羧酸例如甲酸、苯甲酸、乙酸、油酸、硬脂酸、棕榈酸、亚麻油酸、月桂酸,二羧酸例如草酸、己二酸,三羧酸例如柠檬酸,羟基羧酸例如乳酸、水杨酸或酒石酸,氨基羧酸例如甘氨酸或丙氨酸,和胺类例如正丁胺或二乙胺,和二胺例如1,2-二氨基乙烷(=乙二胺)、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷,三胺例如二亚乙基三胺、三聚氰胺和糖类,尤其是己糖例如葡萄糖或二糖类例如蔗糖。根据官能化合物F的一个还是多个官能团经由单元B与基团A链接,基团C为一价或多价基团。因此基团C不同于官能化合物F的结构在于链接至基团B的官能团已被化学键代替。一价烃基C优选包括具有至少两个,尤其是至少一个碳原子的脂族直链、环状或支链、任选取代的基团;该烃基优选含有不超过22个碳原子并且优选具有除了羟基和烷氧基之外与基团R1、R2、R3、R4和R5相同的定义和优选的定义;此外其优选包括用羟基、用2-羟基乙基、2-羟基丙基,特别优选2,3-二羟基丙基取代的烃基。
多价烃基C优选为具有至少两个,尤其是至少一个碳原子的脂族、环状、或直链或支链、任选取代的基团,该烃基优选含有不超过22个碳原子。
烃基C的实例如下:
甲基、乙基、2-丙基、1-丙基、2-乙基己基、环己基、苯基、2-羟乙基、2,3-二羟丙基、1,3-二羟基-2-丙基、2-羟基-3-丙基、3-羟基-2-丙基、3-羟基-1-丙基、2-丁氧基乙基、2-氨基乙基、1,2-乙二基(ethanediyl)、1,2-丙二基、1,3-丙二基、1,2-丁二基、1,4-丁二基、1,5-戊二基、1,6-己二基、1,8-辛二基、1,3-(2-羟基)丙二基、1,2-(3-羟基)丙二基、1,2-环己二基、1,4-环己二基、1,4-亚苯基、1,2,3-丙三基、2-乙氧基羰基乙基。
通式(II)的化合物包括携带一个或多个环氧基的脂族链作为烃基A,其可通过不饱和脂族化合物的环氧化而获得。合适的不饱和脂族化合物的实例为烯键式不饱和酸、烯键式不饱和酯和烯键式不饱和酰胺。一般烯键式不饱和键不位于不饱和脂族化合物的杂原子的α、β位置。如果杂原子通过双键与碳原子键接时,还优选环氧基不位于杂原子的β、γ位置。如果脂族链具有多个不饱和键,还优选烯键式不饱和键彼此不共轭。一般有超过两个,优选三个饱和碳原子位于杂原子和不饱和键之间。合适的烯键式不饱和脂族化合物的实例为4-戊烯酸、10-十一碳烯酸甲酯和N,N-二丁基-6-十二碳烯酰胺。此外,不饱和的酸、酯、氨基甲酸酯以及脂肪酸的酰胺也是合适的。代表性的不饱和脂肪酸包括月桂烯酸、肉豆蔻油酸、棕榈油酸、油酸、亚麻油酸、亚麻酸、蓖麻油酸、二十碳-9-烯酸(gadoleic acid)和芥酸,以及来自鲱鱼油或沙丁鱼油的不饱和脂肪酸(具有多不饱和键的C20和C22)。环氧基优选不是端基。在通式(II)的化合物中的环氧基主要包括内部环氧基,如通式(IIa)所示:
尽管没必要,通式(II)的化合物通常包括超过一个脂肪链作为烃基A,并且可包括多个携带至少一个环氧基的链。还可以使用聚环氧化的多元不饱和脂肪酸,例如以烷基酯的形式,其中所述烷基例如为甲基、乙基、丙基、环己基或2-乙基己基。
通式(II)的化合物的平均官能度优选为至少1,更优选为至少1.7,尤其是至少2.1。平均官能度优选低于8。
通式(II)的化合物的实例为植物或动物产生的部分或完全环氧化的不饱和油,或者为相应的环氧化不饱和脂肪酸,其已与多元醇完全或部分酯化。通式(II)的化合物可包括例如环氧化油和/或含有环氧基的天然油。在天然产生的脂肪链中,烯键式不饱和键一般为远离羰基的七个CH2基团。任选部分环氧化的脂肪酸的剩余双键可保留或可除去,例如通过氢化作用和/或通过进一步环氧化。“脂肪链”表示当量的脂肪酸、脂肪醇或脂肪胺的脂族链。通式(II)的合适的化合物的实例为环氧化油,该油为亚麻籽油、大豆油、红花油、奥蒂树油、香菜油、油菜籽油、蓖麻油、无水蓖麻油、棉仔油、桐油、斑鸠菊油(天然的环氧官能油)、妥尔油、葵花油、花生油、橄榄油、大豆叶油、玉米油、鱼油例如鲱鱼油或沙丁鱼油,以及非环状萜油。该环氧化油优选为环氧化大豆油和/或环氧化亚麻籽油。通式(II)的环氧化合物包括多元醇的二酯、三酯以及低聚酯,所述多元醇例如丙三醇、1,2-丙二醇、1,2-乙二醇、1,3-丙二醇、1,4-丁二醇、聚乙二醇(例如PEG63、PEG125、PEG250、PEG400)、三羟甲基丙烷、季戊四醇、二季戊四醇和不饱和脂肪酸。妥尔油脂肪酸以及上述不饱和油的脂肪酸可用作脂肪酸。如果通式(II)的化合物需要具有相对低的官能度,使用由这些油的脂肪酸与一元醇组成构成的酯交换的脂肪酸可能是有利的。典型的一元醇为乙醇、叔丁醇、1-己醇和2-乙基己醇,或单侧封端的聚乙二醇。使用由这些油的脂肪酸与二醇、三醇或多元醇构成的酯交换的脂肪酸也可以是有利的,其中还可以使用部分酯,在部分酯中并不是多元醇的所有OH基团都与脂肪酸酯化。通式(II)的化合物还可以例如由携带环氧基并且已与包含一个或多个羧基的羧酸酯化的醇组成。该化合物的实例为偏苯三甲酸和3,4-环氧己醇的三酯,或者是环氧化不饱和脂肪醇的三酯。作为不饱和脂肪醇,可使用与脂肪酸当量的醇。通式(II)的其他化合物可通过不饱和脂肪醇与磷酸的酯化来制备。这可通过将脂肪醇与P2O5反应来完成。另一种方法包括脂肪醇与三甲基磷酸酯的酯交换反应。具有磷酸酯和/或膦酸酯官能团的通式(II)的脂族化合物例如可通过磷酸和/或膦酸与脂肪醇的反应获得。在脂肪链中的不饱和键可以已知方式随后被环氧化。通式(II)的另外其他合适的化合物可通过常规方式制备,例如通过脂肪酸或脂肪胺与聚缩水甘油化合物例如异氰尿酸三缩水甘油酯或对苯二甲酸二缩水甘油酯的反应,并随后进行烯键式不饱和键的环氧化反应来制备。通式(II)的其他化合物可通过脂肪醇与碳酸二甲酯的酯交换反应获得,或者通过碳酰氯与脂肪醇的反应产生脂肪碳酸酯,随后被常规环氧化。此外,通式(II)合适的化合物可以通过环氧化脂肪与CO2和不饱和脂肪酸的连续反应,随后环氧化反应而获得。在这种情况下在第一步中获得的环状碳酸酯在第二步中被酯交换。通式(II)合适的化合物还包括例如环氧化脂肪酸和聚硫醇的硫酯。通式(II)化合物的其他实例包括脂肪酰胺、脂肪氨基甲酸酯,或含有环氧基的脂肪脲衍生物。酰胺化合物是有利的,因为它们例如可增加涂料混合物以及由其生产的涂料的储存稳定性。脂肪酰胺可通过不饱和脂肪酸与二胺、三胺或多胺的反应简单制备。合适胺类的实例包括1,2-二氨基乙烷、1,6-二氨基己烷、1,4-环己烷-二甲基胺、异佛尔酮二胺、1,4-二氨基丁烷,和1,5-二氨基-2-乙基氨基戊烷。然后不饱和脂肪酰胺可常规环氧化。制备合适的脂肪酰胺的另一种方法包括脂肪胺与多元酸例如对苯二甲酸、间苯二甲酸、偏苯三甲酸、或1,4-环己烷二羧酸的反应。然后不饱和脂肪酰胺被常规环氧化。脂肪氨基甲酸酯可通过不饱和脂肪醇与二异氰酸酯、三异氰酸酯或聚异氰酸酯的反应以及随后不饱和脂肪链的环氧化反应来制备。脂肪脲化合物可通过不饱和脂肪胺与二异氰酸酯、三异氰酸酯或聚异氰酸酯的反应以及随后脂肪链的环氧化反应来制备。可使用一系列聚异氰酸酯。其中相当合适的为六亚甲基二异氰酸酯(HMDI)或其三聚体、异佛尔酮二异氰酸酯(IPDI)或其三聚体、二苯基甲烷二异氰酸酯(MDI)、二环己烷甲烷二异氰酸酯、甲苯2,4-二异氰酸酯(TDI)以及四甲基二甲苯二异氰酸酯(TMXDI)。同样可使用改性的环氧化油或环氧化醇酸树脂。油可例如用单官能的和/或多官能的环氧活性化合物改性。该环氧活性化合物的实例为含有羧酸基团的化合物、含有酸酐基团的化合物、含有胺基团的化合物、或双酚。该环氧活性化合物的实例为邻苯二甲酸、间苯二甲酸、对-叔丁基苯甲酸、对苯二甲酸、苯甲酸和己二酸、邻苯二甲酸酸酐、六氢化邻苯二甲酸酐、四氢化邻苯二甲酸酐、琥珀酸酐,这些酸酐的组合,1,4-二氨基丁烷和1,6-二氨基己烷以及双酚A。另一种合适的改性包括含有例如一个羟基的油例如蓖麻油与单异氰酸酯和二异氰酸酯的氨基甲酸酯化(urethanization),随后该低聚油-氨基甲酸酯被常规环氧化。通式(II)的其他合适的改性化合物为例如环氧化的氨基甲酸酯化油(epoxidized urethanized oil)。合适的产物优选通过环氧化油与多元醇和二元羧酸或多羧酸的二烷基酯或多烷基酯的混合物的一级或二级酯交换。例如可首先环氧化4-己烯酸的甲基酯,然后将得到的环氧化油与等摩尔量的三羟甲基丙烷进行酯交换,蒸馏除去甲醇。随后4,5-环氧己酸的三羟甲基丙烷酯可进一步与二甲基对苯二甲酸酯化,蒸馏除去甲醇。结果为环氧化的醇酸树脂。以类似方式,例如可将环氧化油与季戊四醇酯交换并同时或随后与己二酸二甲酯进行酯交换。还可使用本文描述的通式(II)的化合物的混合物并可以预选比例组合。所述预选比例将取决于所需要的应用。
此外,可采用2,3-环氧-3-苯基丙酸乙酯(苯基缩水甘油酸乙酯,EPG)。
通式(II)的化合物的环氧基的氧含量一般大于1重量%,优选大于2重量%。一般环氧基的氧含量将小于20重量%,实践中小于15重量%。
通式(II)的化合物中的环氧官能团和通式(I)的化合物中的胺官能团的摩尔当量比优选为1-50。该数值优选不超过40,更优选不超过30,尤其不超过25,并且优选至少为1.5,更优选至少为3,尤其是至少为5。
通式(I)的化合物中的胺官能团的这些边界条件和浓度和通式(II)的化合物中环氧官能团的浓度产生用于油漆的该两个组分的优选质量比。源自通式(II)的化合物的环氧官能团的浓度,在耐候性油漆和涂料中优选为10-0.05mmol/100g。该数值优选不超过5mmol/100g,更优选不超过2mmol/100g,尤其不超过1.5mmol/100g,并且优选至少为0.1mmol/100g,更优选至少为0.2mmol/100g,尤其是至少为0.3mmol/100g。
由该边界条件测定通式(I)和(II)的两个化合物添加至耐候性油漆和涂料的量,根据商购获得的通式(I)和(II)的化合物,这两个组分都通常为0.1-5重量份每100份重量油漆。
通式(I)和(II)的两个组分可分别加入或作为混合物加入耐候性油漆和涂料中。它们优选直接使用,作为在溶剂中的溶液使用,或以含水乳液的形式使用。
合适的溶剂包括所有常用的不与通式(I)和(II)的化合物发生任何不需要的反应的有机和无机溶剂或它们的混合物,例如芳族或脂族的、任选卤代烃、醇、酯、醚、酰胺、砜类、烷氧基硅烷和硅氧烷,实例为烷烃,例如戊烷、己烷、庚烷、异己烷、异辛烷或烷烃混合物,苯、甲苯、二甲苯、氯苯、二氯甲烷、甲醇、乙醇、异丙醇、1-丁醇、乙酸乙酯、脂肪酸酯或其基于例如植物油的酯交换产物,丁内酯、四氢呋喃、二丁基醚、甲基叔丁基醚、N,N-二甲基乙酰胺、环丁砜、二甲基亚砜、四乙氧基硅烷、甲基三乙氧基硅烷、六甲基二硅氧烷、八甲基环四硅氧烷。当采用溶液或乳液时,活性成分含量,即通式(I)和(II)的两个纯化合物的含量,在每种情况下基于100重量份的溶液或乳液,优选至少为1重量%,更优选至少为10重量%,尤其至少为30重量%,并且优选不超过95重量%,更优选不超过70重量%,尤其不超过55重量%。
在通式(I)和(II)的添加剂自身缺乏足够的自乳化性时,可添加乳化剂或保护胶体以产生乳液。它们优选是本身已知的乳化剂。特别合适的阴离子型乳化剂包括:
1.烷基硫酸盐,尤其是具有8-18个碳原子链长的那些,在疏水基上具有8-18个碳原子并且具有1-40个环氧乙烷(EO)和/或环氧丙烷单元的烷基硫酸盐和烷基醚硫酸盐。
2.磺酸盐,尤其是具有8-18个碳原子的烷基磺酸盐,具有8-18个碳原子的烷基芳基磺酸盐,氨基乙磺酸盐(tauride),磺基琥珀酸与具有4-15个碳原子的一元醇或烷基酚的酯和单酯;这些醇或烷基酚还可以任选用1-40个EO单元乙氧基化。
3.在烷基、芳基、烷基芳基或芳基烷基上具有8-20个碳原子的羧酸的碱金属盐和铵盐。
4.磷酸偏酯及其碱金属盐和铵盐,尤其是在有机基团中具有8-20个碳原子的烷基磷酸酯和烷基芳基磷酸酯,在烷基或烷基芳基中具有8-20个碳原子并且具有1-40个EO单元的烷基醚磷酸酯和烷基芳基醚磷酸酯。
特别合适的非离子型乳化剂包括:
5.聚乙烯醇,其还具有5-50%、优选8-20%的乙酸乙烯酯单元,具有500-3000的聚合度。
6.烷基聚乙二醇醚,优选具有8-40个EO单元且具有8-20个碳原子的烷基的那些。
7.烷基芳基聚乙二醇醚,优选具有8-40个EO单元并且在烷基和芳基上具有8-20个碳原子的那些。
8.环氧乙烷/环氧丙烷(EO/PO)嵌段共聚物,优选具有8-40个EO和/或PO单元的那些。
9.具有8-22个碳原子的烷基的烷基胺与环氧乙烷或环氧丙烷的加合物。
10.具有6-24个碳原子的脂肪酸。
11.通式R*-O-Zu的烷基多糖苷,其中R*为平均具有8-24个碳原子的直链或支链、饱和或不饱和的烷基,并且Zu为平均具有u=1-10个己糖或戊糖单元或其混合物的低聚糖苷基团。
12.天然物质及其衍生物,例如卵磷脂、羊毛脂、皂苷、纤维素;纤维素烷基醚和羧基烷基纤维素,其烷基在每种情况下具有至多4个碳原子。
13.含有极性基团的线型有机(聚)硅氧烷,尤其是具有至多24个碳原子的烷氧基和/或至多40个EO和/或PO基团的那些。
特别合适的阳离子型乳化剂包括:
14.具有8-24个碳原子的伯、仲、叔脂肪胺与乙酸、硫酸、盐酸和磷酸的盐。
15.季烷基苯铵盐和烷基苯铵盐,尤其是其烷基具有6-24个碳原子的那些,尤其是卤化物、硫酸盐、磷酸盐和乙酸盐。
16.烷基吡啶鎓盐、烷基咪唑啉鎓盐和烷基噁唑啉嗡盐,尤其是其烷基链至多具有18个碳原子的那些,尤其是卤化物、硫酸盐、磷酸盐和乙酸盐。
特别合适的两性乳化剂包括:
17.用长链取代的氨基酸,例如N-烷基-二(氨乙基)甘氨酸或N-烷基-2-氨基丙酸盐。
18.甜菜碱,例如具有C8-C18酰基的N-(3-酰氨基丙基)-N,N-二甲基-铵盐,和烷基咪唑啉嗡甜菜碱。
优选作为乳化剂的是非离子型乳化剂,尤其是以上第6项所列出的烷基聚乙二醇醚,第9项所列出的烷基胺与环氧乙烷或环氧丙烷的加合物,第11项所列出的烷基聚糖苷,和第5项所列出的聚乙烯醇。
尤其优选聚乙烯醇还含有5-20%,尤其10-15%的乙酸乙烯酯单元,并且优选具有500-3000,尤其是1200-2000的聚合度。
在通式(I)和(II)的化合物的乳液中乳化剂的含量优选为0.1-5重量%,尤其是0.2-2重量%,尤其是0.3-1重量%。由于其不是疏水活性成分,因此需要低含量的乳化剂是有利的。
与配制物的模式无关,还可使用通式(I)的不同化合物的混合物和/或通式(II)的化合物的混合物。
两种组分(I)和(II)具有优异的兼容性,因此在用于油漆之前可作为混合物存储。还可使用通式(I)的不同化合物的混合物与通式(II)的化合物,或者通式(II)的不同化合物的混合物与通式(I)的化合物,或者通式(I)的化合物的混合物与通式(II)的化合物的混合物。是否预混合一种或两种成分或混合物并与一种或多种耐候性油漆和涂料组分储存在本发明中不重要,如果其具有优势。可以想象,例如其是与乳化剂、生物杀灭剂、聚合物分散体、流变学添加剂或填料的混合物。如果本发明的混合物以其含水乳液形式储存,明智的做法是添加生物杀灭剂以提高储存稳定性。另外,可向乳液中添加其他添加剂,例如除臭剂、腐蚀抑制剂、缓冲物质和消泡剂。助剂的优选量优选不超过3重量%,更优选不超过1重量%,尤其不超过0.5重量%。
在以上通式中的全部以上符号在每种情况下有其彼此独立的定义。在全部通式中硅原子为四价。
具体实施方式
在以下实施例中,除非在每种情况下另有说明,全部数量和百分数均是基于重量,全部压力都是0.10MPa(绝对压力),并且全部温度均为20℃。全部粘度均是在25℃和0.10MPa下测量。
乳液油漆A743的制备
将以下物质在商用高速搅拌机中以所述顺序混合,以生产含水建筑涂料。
表1:乳液油漆A743的制备
将具有表1组成的乳液油漆A743与在表2中所显示的量的乳液通过搅拌混合。
采用以下产品作为通式(I)的化合物:
(WACKER Chemie AG)=氨基官能硅油,其由二甲基甲硅烷氧基单元和N-(2-氨基乙基)氨基丙基甲硅烷氧基单元(T单元)组成,并且具有约0.13重量%残余甲氧基含量,胺数=0.15meq/g,粘度~700mm2/s。
BS1306(WACKER Chemie AG)=50%的含水乳液(含有5重量%乳化剂)。
采用以下产品作为通式(II)的化合物:
ELSO=B316(BASF)=环氧化亚麻籽油(6.51mol/kg环氧基的氧)
ESBO=D81(BASF/Emery Oleochemicals)=环氧化大豆油(4.58mol/kg环氧基的氧)
EPG=3-苯基缩水甘油酸乙酯(Aldrich)(5.2mol/kg环氧基的氧)
EOD=4050(Arkema)=32重量%甲基酯和68重量%的具有约18个碳原子的环氧化脂肪酸酯的2-乙基己酯的混合物(3.8mol/kg环氧基的氧)。
采用以下产品作为用于对比实验的非本发明的化合物:
PDMS=OH封端的聚二甲基硅氧烷(链长约45),购自WACKERChemie AG
WR1100(WACKER Chemie AG)=氨基官能硅油,其由二甲基甲硅烷氧基单元和N-(2-氨基乙基)氨基丙基甲基甲硅烷氧基单元(D单元)组成,并且具有约0.14重量%的残余甲氧基含量,胺数=0.15meq/g,粘度~3000mm2/s
亚麻籽油=商用亚麻籽油
由通式(I)和(II)的化合物制备乳液
将以下物质在商用高速搅拌机中按所述顺序混合,生产含水乳液。
乳液 | |
25.00重量份 | 乳化剂(Arlypon IT5和Arlypon IT10/80,购自Clariant) |
17.50重量份 | 水 |
248.80重量份 | 活性成分混合物 |
207.50重量份 | 水 |
1.20重量份 | 防腐剂(Konservierer MIT10和Konservierer BIT10,购自Thor |
总计: | |
500重量份 |
首先通过将1/10的水与乳化剂混合制备含水乳液。然后按比例添加环氧化油和氨基官能的聚二甲基硅氧烷的混合物。随后非常缓慢的将水通过搅拌加入该混合物的粘稠相中,直到乳液又高度流动。将防腐剂在最后一部分水中加入混合物中。
参数测定:
在每种情况下确定四个灰砂砖(根据DIN106)的透水率(w24,以kg/m2h0.5表示,根据DIN EN1062-3)。为了验证颜色稳定性(黄色试验),使用BYK Gardener的光谱指导,根据DIN6174在紫外光照射之前和之后进行固化油漆的颜色测量。在每种情况下参数显示为b值的不同(Δb)。
表2:结果
1)乳液在室温下存储6个月之后
*不是本发明
说明:
实施例2、3、4、7、8、10、11、13、16和17作为对照,以说明只有通过本发明的环氧化物油和氨基硅氧烷的组合才出现w24值的降低。用无胺的PDMS(10)替换L652,用PDMS(8)替换环氧化物,并且用类似的不含环氧化物的亚麻籽油(7)替换ELSO,比相应的本发明的活性成分混合物显示出明显高得多的W24值(10->9;8->5、9、12、14;7->6)。使用纯单个物质相比两个组分的组合也较无效(2、3、4、11、13)。相对于类似的在D单元(双官能甲硅烷氧基单元)上携带胺官能团的胺油WR1100,ELSO与L652的组合明显更有效(17->6),虽然两种纯胺油显示出较小的差别(16->2)。与未添加添加剂的油漆相比,在任何情况下均没有观察到变黄。QUV-B处理后,出现明显的滴液流出效果。
Claims (15)
1.通式(I)的有机硅氧烷与通式(II)的环氧化物的混合物:
MmDnToQp (I),
(A-B)qC (II),
其中
M为通式(Ia)的端基
R1R2R3SiO1/2 (Ia),
D为通式(Ib)的双官能基团
R4R5SiO2/2 (Ib),
T为通式(Ic)的三官能基团
R6SiO3/2 (Ic),
Q为通式为SiO4/2的单元,
其中R1、R2、R3、R4、R5和R6彼此独立地代表具有1-20个碳原子的烃基,其可含有杂原子;或者代表羟基或具有1-10个碳原子的烷氧基,其中至少一个烃基R6含有至少一个胺官能团,并且在这些所有的基团中不超过25%为羟基或烷氧基,
m为0-20的整数,
n为0-1000的整数,
o为1-30的整数,
p为0-20的整数,并且
m+n+o+p是至少为2的整数,
其中
A在每次出现时独立地为具有1-30个碳原子的直链或支链一价烃基,其可被杂原子取代,其中可插入杂原子,并且其可含有一个或多个环氧官能团,
B在每次出现时独立地为二价的醚、碳酸酯、或者脲官能团,或者为酸、酯、氨基甲酸酯、酸酐官能团,或者羧酸、硫代羧酸、磺酸、膦酸或磷酸的酰胺官能团,
q为1-8的数值,
C为具有1-30个碳原子的q价的直链或支链烃基,其可含有杂原子,并且其可含有一个或多个环氧官能团,
条件是通式(II)的化合物包含至少一个环氧官能团。
2.权利要求1的混合物,其中R1、R2、R3、R4和R5选自甲基、乙基、丙基、3,3,3-三氟丙基、乙烯基、苯基、羟基、甲氧基和乙氧基。
3.权利要求1或2的混合物,其中在R6上的胺官能团具有式-NR10R11,其中R10和R11具有除了羟基和烷氧基之外如在权利要求1或2中所述的R1、R2、R3、R4和R5的定义,或者代表氢。
4.权利要求1或2的混合物,其中R6具有式-CH2-CH2-CH2-NH-CH2-CH2-NH2。
5.权利要求1或2的混合物,其中在通式(I)的化合物中的胺浓度为0.01-10mol/kg。
6.权利要求1或2的混合物,其中环氧官能团位于烃基A中。
7.权利要求1或2的混合物,其中单元B为酸、酯、氨基甲酸酯、酸酐、或羧酸的酰胺官能团。
8.权利要求1或2的混合物,其中C源自官能化合物F,所述官能化合物形式上能够与酸反应形成酯、酰胺、氨基甲酸酯或酸酐基团。
9.权利要求1或2的混合物,其中通式(II)的化合物选自植物或动物产生的环氧化不饱和油,或者选自植物或动物产生的已完全或部分与多元醇酯化的环氧化不饱和脂肪酸。
10.权利要求1或2的混合物,其中通式(II)的化合物的环氧基的氧含量大于1重量%并且小于20重量%。
11.权利要求1或2的混合物,其中在通式(II)的化合物中的环氧官能团和通式(I)的化合物中的胺官能团之间的摩尔当量比为1-50。
12.权利要求1-11之一的混合物作为用于耐候性涂料的疏水化添加剂的用途。
13.权利要求12的用途,其中所述涂料包括油漆。
14.耐候性涂料,其包含权利要求1-11之一所述的混合物。
15.权利要求14的耐候性涂料,其中所述涂料包括油漆。
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JP3783453B2 (ja) * | 1999-03-18 | 2006-06-07 | 荒川化学工業株式会社 | エポキシ樹脂−ケイ素系ハイブリッド材料用組成物、コーティング剤およびプラスチックの表面コーティング方法 |
JP2001002757A (ja) * | 1999-06-18 | 2001-01-09 | Asahi Chem Ind Co Ltd | 液状感光性樹脂組成物 |
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