CN1042634C - 含羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯类及其制备方法和用途 - Google Patents
含羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯类及其制备方法和用途 Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- C—CHEMISTRY; METALLURGY
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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Abstract
本发明涉及含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯及其作为防水剂和/或抗油剂的用途和制备方法。
Description
本发明涉及含有羟基和/或巯基基团的膦酰基-和膦基羧酸的氟化羧酸酯类及其作为防水剂和/或抗油剂的用途和制备方法。
含有全氟烷基基团的化合物因具有防水和抗油的性能在工业上广泛地用于浸渍剂中(参见Ullmann,Enzyklopadie der technischenChemie，第4版，1976,11卷，644页；及上文第五版，1988,A11卷，373-374页)。典型的应用包括用作浸渍剂，用于使纺织品(参见Ullmann,Enzyklopadie der techmishen Chmie，第4版，1983,23卷，87页)、皮革(参见Ullmann,Enzyklopadie der technischen chemie，第4版，1978,16卷，卷168页)和纸张(参见J.N.MeuBdoerffer和HNiederprum,Chemikerzeitung 104(1980)45-52)防水并使这些材料抗油。
防护剂的实例如包括醇类和含有全氟基团的丙烯酸酯类，或其聚合物分散体(参见J.N.MeBdoerffer和H.Niederprum,Chemikerzeitung 104(1980)45-52；和Ullmann,Enzyklopadie，第4版，1983,23卷，87页)。其合成路线可参见J.N.MeuBdoerffer和H.Niederprum,Chemikerzeitung 104(1980)45-52。
用作上述氟化表面活性剂起始原料的全氟化化合物在工业上用三种不同路线生产：
a)电化学氟化；
b)全氟烯烃，尤其是四氟乙烯的调聚反应；
c)四氟乙烯的低聚反应。
制备全氟化原料的上述方法在工业规模上是很昂贵的，这就使得所希望的含全氟基团的化合物的造价高。
本发明的目的是提供具有防水和/或抗油性能，且生产方法简单造价低的含氟基团的改性有机化合物。
借助于按照本发明的含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯达到了这一目的。
本发明涉及通式(Ⅰ)的含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯及其盐类
式中
R1是羟基、甲基、乙基或苯基，
RF是含有1-18个碳原子的直链或支链的氟化烷基，或含有1-18个碳原子的氟化的支链或直链的单体醚或聚醚，
RH是含有1-10个碳原子的直链或支链烷基，
R是羟基或巯基基团：
X代表含有1-20个碳原子的直链或支链的亚烷基或含有1-20个碳原子且带有一个或多个R取代基的直链或支链的亚烷基，其中R的定义同上，
Y代表如下基团：
Z代表含有1-20个碳原子的直链或支链的链烷三价基团(三价烃基)，或是由氨基基团断开的含有1-20个碳原子的直链或支链链烷三价基团，而氨基基团本身可含有C1-C10的烷基基团或芳基基团作为取代基，或是含有1-20个碳原子并带有一个或多个结构为-COR2的取代基的直链或支链链烷三价基团，或是含有1-20个碳原子并带有一个或多个结构为-PO2HR1的取代基的直链或支链链烷三价基团，式中R1的定义同上，
m可为0或1，
n是0或6的整数，
R2代表羟基，或如下结构的基团：或结构为O-X-R的基团，或含有1-30个碳原子的直链或支链的烷氧基，其中n、m、RH、RF、R、X和Y的定义同上。
含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯中较好的是其中RF是含有3-10个碳原子直链或支链的氟烷基的那些化合物。
其中RH代表含有1个或2个碳原子的烷基的那些含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯是比较好的。
其中n是1或2的那些含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯是特别优选的。
其中m等于1的那些含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯是特别优选的。
例如，特别优选的含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯具有如下结构： 
下面所列出的基团是特别优选的：RF的例子：CF3-(CF2)2-CF3-(CF2)3-CF3-(CF2)5-CF3-(CF2)6-CF3-(CF2)7-CF3-(CF2)11-C5F5-CF3-C5F4-H-(CF2)5-H-(CF2)2-O-CF3-CHF-CF2-O-CF2-CF2-CF2-O-CF(CF3)-CF3-CF2-[CF2-O-CF(CF3)]2-CF3-CF2-[CF2-O-CF(CF3)]3-Z的例子：
按照本发明的含有羟基和/或巯基基团的膦酰基-或膦基羧酸的氟化羧酸酯可利用相应的膦酰基-或膦基羧酸或它们的盐类与含有氟基团的醇类和多元醇或有羟基官能的硫醇的酯化反应通过多级合成制备： 
其中
R1、R、RF、RH、X、Y、Z、m和n的定义同上，
K是氢阳离子、铵阳离子或一价或多价金属阳离子，
a是对应于阳离子K电荷的一个整数。
本发明也涉及按照本发明的含有羟基和/或巯基的膦酰基-或膦基羧酸的氟化羧酸酯作为防水剂和/或抗油剂的用途。
由于按照本发明的化合物具有防水性和抗油性，所以这些化合物在各种应用领域中可用作浸渍剂，从而本发明的这些化合物本身可以施用或例如以聚合物分散体的形式施用。
例如，按照本发明的化合物可以用在天然纤维和合成纤维(如用于纺织品、地毯或遮蓬)上，用来防水、防脂、防油和/或防尘。
按照本发明的化合物也可用在纸张和卡片纸板(如包装材料或羊毛状物)上，用来防水、防脂、防油和/或防尘。
此外，按照本发明的化合物可以用在皮革(如用于室内装饰、鞋或衣服)上，用来防水、防脂、防油和/或防尘。
按照本发明的化合物也可用在陶瓷(如砖瓦)、天然或人造石块(如砂石)、木材(如表面的木制包层)和塑料(如聚酯)等材料上，作为防水、防脂、防油、防尘、防藻类生长和/或耐气候的浸渍层。
本发明将用下列实例加以更详细的说明。
实施例1
在装有搅拌器和聚水器的三颈烧瓶中将N-(2-羟乙基)-N-甲基-全氟丁基氨磺酰(1.0摩尔/235克)溶于150毫升4-甲基-戊-2-酮中，并加入0.5毫升浓硫酸。将该溶液加热到约116℃。然后缓慢加入溶于135克水中的2-膦酰基丁烷-1,2,4-三羧酸(0.5摩尔/135克)。添加完毕之后，使反应混合物在搅拌下回流直至全部水量(153毫升)蒸出为止。
然后缓慢加入乙二醇(0.5摩尔/31克)，接着在搅拌下回流直至全部水量(9毫升)从反应混合物中蒸出为止。
反应完毕后，在70℃和70毫巴条件下将溶剂蒸出，并将所得产品彻底干燥。产品为2-膦酰基-丁烷-1,2,4-三羧酸与2个当量的N-(2-羟乙基)-N-甲基-全氟丁基氨磺酰和1个当量的乙二醇的三酯化产物，产量491克(98.9％理论产率)。
实施例2
在装有搅拌器和聚水器的三颈烧瓶中将N-(2-羟乙基)-N-甲基-全氟丁基氨磺酰(0.6摩尔/214克)溶于150毫升4-甲基-戊-2-酮中，并加入0.5毫升浓硫酸。将该溶液加热至116℃。然后缓慢加入溶于81克水中的2-膦酰基-丁烷-1,2,4-三羧酸(0.3摩尔/81克)。添加完毕之后，使反应混合物在搅拌下回流直至全部水量(91.8毫升)蒸出为止。
然后缓慢加入丙三醇(0.3摩尔/28克)，接着在搅拌下回流直至全部水量(3.6毫升)从反应混合物中蒸出为止。
反应完毕后，在70℃和70毫巴条件下将溶剂蒸出，并将所得产品彻底干燥。产品为2-膦酰基-丁烷-1,2,4-三羧酸与2个当量的N-(2-羟乙基)-N-甲基-全氟丁基氨磺酰和1个当量的丙三醇的三酯化产物，产量305克(99.5％理论产率)。
实施例3
在装有搅拌器和聚水器的三颈烧瓶中将N-(2-羟乙基)-N-甲基-全氟辛基氨磺酰(0.1摩尔/56克)溶于150毫升4-甲基-戊-2-酮中，并加入0.5毫升浓硫酸。将该溶液加热至116℃。然后缓慢加入溶于27克水中的2-膦酰基-丁烷-1,2,4-三羧酸(0.1摩尔/27克)。添加完毕之后，使反应混合物在搅拌下回流直至全部水量(28.8毫升)蒸出为止。
然后缓慢加入溶于50毫升4-甲基-戊-2-酮的十八(碳)醇(0.1摩尔/28克)，接着在搅拌下回流直至全部水量(1.8毫升)从反应混合物中蒸出为止。
然后缓慢加入乙二醇(0.1摩尔/6克)，接着在搅拌下回流直至全部水量(1.8毫升)从反应混合物中蒸出为止。
反应完毕后，在70℃和70毫巴条件下将溶剂蒸出，并将所得产品彻底干燥。产品为2-膦酰基-丁烷-1,2,4-三羧酸与各为1当量的N-(2羟乙基)-N-甲基-全氟辛基氨磺酰、十八(碳)醇和乙二醇的三酯化产物，产量109克(98.8％理论产率)。
Claims (12)
1．通式(Ⅰ)所示的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯及其盐类：
式中
R1是羟基，
RF是含有1-18个碳原子的直链或支链的氟化烷基，或含有1-18个碳原子的氟化的支链或直链的单体醚或聚醚，
RH是含有1-10个碳原子的直链或支链烷基，
R是羟基或巯基基团，
X代表含有1-20个碳原子的直链或支链的亚烷基或含有1-20个碳原子且带有一个或多个R取代基的直链或支链的亚烷基，其中R的定义同上，
Y代表如下基团：
Z代表含有1-20个碳原子的直链或支链的链烷三价基团，或是由氨基基团断开的含有1-20个碳原子的直链或支链的链烷三价基团，而氨基基团本身可含有C1-C10的烷基基团或芳基基团作为取代基，或是含有1-20个碳原子并带有一个或多个结构为-COR2的取代基的直链或支链链烷三价基团，或是含有1-20个碳原子并带有一个或多个结构为-PO2HR1的取代基的直链或支链的链烷三价基团，式中R1的定义同上，
m可为0或1，
n是0或6的整数，和
R2代表羟基，或如下结构的基团：或结构为O-X-R的基团，或含有1-30个碳原子的直链或支链的烷氧基，其中n、m、RH、RF、R、X和Y的定义同上。
2．按照权利要求1的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯，其中RF是含有3-10个碳原子的直链或支链的氟烷基。
3．按照权利要求1的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯，其中RH代表含有1个或2个碳原子的烷基。
4．按照权利要求1的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯，其中n是1或2。
5．按照权利要求1的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯，其中m是1。
6．制备按照权利要求1的含有羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯的方法，其中所述方法包括一种多级合成法，在该方法中，第一步使式(Ⅱ)的适当的膦酰基羧酸或其盐与式(Ⅲ)的含有氟基团的适当的醇类进行酯化反应，
式中K是氢阳离子、铵阳离子或一个一价或多价金属阳离子，a是对应于该阳离子K电荷的一个整数，R1和Z的定义如权利要求1所述，
式中n、m、RH、Y和RF的定义如权利要求1所述，第二步使在第一步骤中所形成的酯与式(Ⅳ)的适当的多元醇或含羟基官能团的硫醇进行酯化反应，
HO-X-R (Ⅳ)式中X和R的定义如权利要求1所述。
7．使用按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯或其盐的方法，其中把所述的酯或盐涂敷在下列至少一种材料上作为防水剂和/或抗油剂，这些材料是：天然纤维、合成纤维、纸张、卡片纸板、皮革、陶瓷、石块、木材和塑料。
8．按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯，其中所述的酯的化学式如下：
9．按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯，其中所述的酯的化学式如下：
10．按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯，其中所述的酯的化学式如下：
11．按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯，其中RF是选自下列基团的基团：
CF3-(CF2)2-
CF3-(CF2)3-
CF3-(CF2)5-
CF3-(CF2)6-
CF3-(CF2)7-
CF3-(CF2)11-
C5F5-
CF3C6F4-
H-(CF2)6-
H-(CF2)2-O-
CF3-CHF-CF2-O-
CF2-CF2-CF2-O-CF(CF3)-
CF3-CF2-[CF2-O-CF(CF3)]2-
CF3-CF2-[CF2-O-CF(CF3)]3-.和
12．按照权利要求1的含有羟基和/或巯基的膦酰基羧酸的氟化羧酸酯，其中Z是选自下列基团的基团：
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4300800A DE4300800C2 (de) | 1993-01-14 | 1993-01-14 | Hydroxy- und/oder mercaptogruppenhaltige fluorierte Carbonsäureester von Phosphono- und Phosphinocarbonsäuren, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
| DEP4300800.3 | 1993-01-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1096788A CN1096788A (zh) | 1994-12-28 |
| CN1042634C true CN1042634C (zh) | 1999-03-24 |
Family
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| Application Number | Title | Priority Date | Filing Date |
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| CN94100611A Expired - Fee Related CN1042634C (zh) | 1993-01-14 | 1994-01-14 | 含羟基和/或巯基基团的膦酰基羧酸的氟化羧酸酯类及其制备方法和用途 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5424474A (zh) |
| EP (1) | EP0606831B1 (zh) |
| JP (1) | JP3310439B2 (zh) |
| KR (1) | KR940018390A (zh) |
| CN (1) | CN1042634C (zh) |
| CA (1) | CA2113239A1 (zh) |
| DE (2) | DE4300800C2 (zh) |
| ES (1) | ES2133422T3 (zh) |
| TW (1) | TW271447B (zh) |
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| US6646088B2 (en) | 2000-08-16 | 2003-11-11 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
| DE10101190A1 (de) * | 2001-01-12 | 2002-08-01 | Clariant Gmbh | Verwendung einer Pulver-Zusammensetzung zur Hydrophobierung von Baustoffmassen |
| US6753380B2 (en) | 2001-03-09 | 2004-06-22 | 3M Innovative Properties Company | Water-and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties |
| US6803109B2 (en) | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
| US6890360B2 (en) | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| US20040147188A1 (en) * | 2003-01-28 | 2004-07-29 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| US20070014927A1 (en) * | 2005-07-15 | 2007-01-18 | Buckanin Richard S | Fluorochemical urethane composition for treatment of fibrous substrates |
| US7459186B2 (en) | 2005-08-05 | 2008-12-02 | Wacker Chemical Corporation | Masonry sealing compositions comprising semi-crystalline ethylene-vinyl acetate polymer emulsions |
| WO2008147796A1 (en) * | 2007-05-23 | 2008-12-04 | 3M Innovative Properties Company | Aqueous compositions of fluorinated surfactants and methods of using the same |
| EP2444428B1 (en) * | 2007-06-06 | 2013-07-24 | 3M Innovative Properties Company | Fluorinated compositions and surface treatments made therefrom |
| JP5453250B2 (ja) * | 2007-06-06 | 2014-03-26 | スリーエム イノベイティブ プロパティズ カンパニー | フッ素化エーテル組成物及びフッ素化エーテル組成物の使用方法 |
| JP2010530445A (ja) * | 2007-06-08 | 2010-09-09 | スリーエム イノベイティブ プロパティズ カンパニー | フルオロアルキル含有エステルオリゴマーとポリジカルボジイミド（類）とのブレンド |
| CN101679229A (zh) * | 2007-06-08 | 2010-03-24 | 3M创新有限公司 | 赋予抗水和抗油性的含有全氟烷基部分的酯低聚物 |
| EA201100053A1 (ru) * | 2008-07-18 | 2011-08-30 | 3М Инновейтив Пропертиз Компани | Фторированные эфирные соединения и способы их применения |
| WO2010062843A1 (en) * | 2008-11-25 | 2010-06-03 | 3M Innovative Properties Company | Fluorinated ether urethanes and methods of using the same |
| CN102317403A (zh) | 2008-12-18 | 2012-01-11 | 3M创新有限公司 | 使含烃地层与氟化醚组合物接触的方法 |
| WO2010080353A2 (en) | 2008-12-18 | 2010-07-15 | 3M Innovative Properties Company | Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions |
| CN117004122A (zh) * | 2023-09-04 | 2023-11-07 | 吴江市拓研电子材料有限公司 | 一种耐高温耐油铁氟龙扎带及其制备方法 |
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| DE2424243A1 (de) * | 1974-05-18 | 1975-11-27 | Bayer Ag | Perfluoralkansulfonamidoalkanphosphonsaeure- bzw. -phosphinsaeurederivate |
| DE2439281A1 (de) * | 1974-08-16 | 1976-02-26 | Henkel & Cie Gmbh | Beta-trifluormethyl-beta-phosphonobuttersaeure und derivate |
| US4824886A (en) * | 1986-02-22 | 1989-04-25 | Bayer Aktiengesellschaft | 2-phosphono-butane-1,2,4,-tricarboxylic acid emulsifier derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4602092A (en) * | 1983-09-19 | 1986-07-22 | E. R. Squibb & Sons, Inc. | Method for making phosphinic acid intermediates |
-
1993
- 1993-01-14 DE DE4300800A patent/DE4300800C2/de not_active Expired - Fee Related
- 1993-12-17 TW TW082110701A patent/TW271447B/zh active
- 1993-12-23 US US08/172,274 patent/US5424474A/en not_active Expired - Fee Related
-
1994
- 1994-01-03 ES ES94100003T patent/ES2133422T3/es not_active Expired - Lifetime
- 1994-01-03 EP EP94100003A patent/EP0606831B1/de not_active Expired - Lifetime
- 1994-01-03 DE DE59408219T patent/DE59408219D1/de not_active Expired - Fee Related
- 1994-01-10 JP JP01205594A patent/JP3310439B2/ja not_active Expired - Fee Related
- 1994-01-11 CA CA002113239A patent/CA2113239A1/en not_active Abandoned
- 1994-01-13 KR KR1019940000456A patent/KR940018390A/ko not_active IP Right Cessation
- 1994-01-14 CN CN94100611A patent/CN1042634C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2424243A1 (de) * | 1974-05-18 | 1975-11-27 | Bayer Ag | Perfluoralkansulfonamidoalkanphosphonsaeure- bzw. -phosphinsaeurederivate |
| DE2439281A1 (de) * | 1974-08-16 | 1976-02-26 | Henkel & Cie Gmbh | Beta-trifluormethyl-beta-phosphonobuttersaeure und derivate |
| US4824886A (en) * | 1986-02-22 | 1989-04-25 | Bayer Aktiengesellschaft | 2-phosphono-butane-1,2,4,-tricarboxylic acid emulsifier derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| KR940018390A (ko) | 1994-08-16 |
| US5424474A (en) | 1995-06-13 |
| TW271447B (zh) | 1996-03-01 |
| DE4300800A1 (de) | 1994-07-21 |
| CN1096788A (zh) | 1994-12-28 |
| EP0606831A1 (de) | 1994-07-20 |
| JPH06279469A (ja) | 1994-10-04 |
| ES2133422T3 (es) | 1999-09-16 |
| CA2113239A1 (en) | 1994-07-15 |
| DE4300800C2 (de) | 1996-09-19 |
| DE59408219D1 (de) | 1999-06-17 |
| EP0606831B1 (de) | 1999-05-12 |
| JP3310439B2 (ja) | 2002-08-05 |
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