CN1042635C - 含丙烯酸酯和/或甲基丙烯酸酯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
含丙烯酸酯和/或甲基丙烯酸酯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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Abstract
本发明涉及含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基羧酸的氟化羧酸酯及其盐类以及其制备方法和其作为防水剂或抗油剂的用途。
Description
本发明涉及含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-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H,Niederprum,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丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-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)的含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-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是如下结构的丙烯酸酯基团：
或者是如下结构的甲基丙烯酸酯基团：
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，
o是0至6的整数，
R2代表羟基，或如下结构的基团：
或结构为O-(CH2)o-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、o、RH、RF、R和Y的定义同上。
含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-或膦基羧酸的氟化羧酸酯中较好的是其中RH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合有丙烯酸酯和/或甲基丙烯酸酯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的那些含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-或膦基羧酸的氟化羧酸酯是特别优选的。
其中o是1或2的那些含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-或膦基羧酸的氟化羧酸酯是特别优选的。
其中m等于1的那些含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-或膦基羧酸的氟化羧酸酯是特别优选的。
例如，特别优选的含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-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-C6F5-CF3C6F4-H-(CF2)6-H-(CF2)2-O-CF3-CHF-CF2-O-CF3-CF2-CF2-O-CF(CF3)-CF3-CF2-[CF2-O-CF(CF3)]2-CF3-CF2-[CF2-O-CF(CF3)]3-Z的例子：
按照本发明的含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基-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和有羟基官能的丙烯酸或甲基丙烯酸衍生物的酯化反应通过多级合成制备：其中
R1、R、RF、RH、Y、Z、m、n和o的定义同上，
A是氢阳离子、铵阳离子或一价或多价金属阳离子，
X是对应于阳离子A电荷的一个整数。
本发明也涉及按照本发明的含有丙烯酸酯和/或甲基丙烯酸酯的膦酰基-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(如包装材种或羊毛状物)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-全氟辛基氨磺酰(0.4摩尔/223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54克水中的2-膦酰基丁烷-1,2,4-三羧酸(0.2摩尔/54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(61 2毫升)蒸出为止。
然后缓慢加入丙烯酸羟乙基酯(0.2摩尔/23.2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-全氟辛基氨磺酰和1个当量的丙烯酸羟乙基酯的三酯化产物，产量277克(95.8％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(0.2摩尔/71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54克水中的2-膦酰基丁烷-1,2,4-三羧酸(0.2摩尔/54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(57.6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(0.2摩尔/54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。
然后缓慢加入甲基丙烯酸羟乙基酯(0.2摩尔/26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-1,2,4-三羧酸与各为1当量的N-(2-羟乙基)-N-甲基-全氟丁基氨磺酰、十八(碳)醇和甲基丙烯酸羟乙基酯的三酯化产物，产量180克(92.5％理论产率)。
Claims (8)
1．通式(Ⅰ)所示的含有丙烯酸酯和/或甲基丙烯酸酯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是如下结构的丙烯酸酯基团：或者是如下结构的甲基丙烯酸酯基团：
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至6的整数，
o是0至6的整数，和
R2代表羟基，或如下结构的基团：
或结构为O-(CH2)o-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、o、RH RF和Y的定义同上。
2．按照权利要求1的化合物，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的化合物，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的化合物，其中n是1或2。
5．按照权利要求1的化合物，其中o是1或2。
6．按照权利要求1的化合物，其中m是1。
7．用多级合成法制备按照权利要求1的含有丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基羧酸的氟化羧酸酯的方法，包括第一步使式(Ⅱ)的膦酰基羧酸或其盐与式(Ⅲ)的含有氟基团的一种醇进行酯化反应，
式中A是氢阳离子、铵阳离子或一个一价或多价金属阳离子，X是对应于该阳离子A电荷的一个整数，R1和Z如权利要求1所定义，式中n、m、RH、Y和RF的定义如权利要求1所述，和第二步与式(Ⅳ)的含羟基官能团的丙烯酸或甲基丙烯酸衍生物反应，
HO(CH2)o-R (Ⅳ)式中R和o的定义如权利要求1所述。
8．含有如权利要求1所述的含丙烯酸酯和/或甲基丙烯酸酯基团的膦酰基羧酸的羧酸酯的防水剂或抗油剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4300799A DE4300799C2 (de) | 1993-01-14 | 1993-01-14 | Acrylat- und/oder methacrylatgruppenhaltige fluorierte Carbonsäureester von Phosphono- und Phosphinocarbonsäuren, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
| DEP4300799.6 | 1993-01-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1097762A CN1097762A (zh) | 1995-01-25 |
| CN1042635C true CN1042635C (zh) | 1999-03-24 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100612A Expired - Fee Related CN1042635C (zh) | 1993-01-14 | 1994-01-14 | 含丙烯酸酯和/或甲基丙烯酸酯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) | US5414102A (zh) |
| EP (1) | EP0606833B1 (zh) |
| JP (1) | JP3310438B2 (zh) |
| KR (1) | KR940018391A (zh) |
| CN (1) | CN1042635C (zh) |
| CA (1) | CA2113238A1 (zh) |
| DE (2) | DE4300799C2 (zh) |
| ES (1) | ES2110123T3 (zh) |
| TW (1) | TW280830B (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6646088B2 (en) | 2000-08-16 | 2003-11-11 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
| US6803109B2 (en) | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
| US6753380B2 (en) | 2001-03-09 | 2004-06-22 | 3M Innovative Properties Company | Water-and oil-repellency imparting ester 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 |
| US9120888B2 (en) * | 2006-06-15 | 2015-09-01 | Dow Global Technologies Llc | Functionalized olefin interpolymers, compositions and articles prepared therefrom and methods for making the same |
| WO2008147796A1 (en) * | 2007-05-23 | 2008-12-04 | 3M Innovative Properties Company | Aqueous compositions of fluorinated surfactants and methods of using the same |
| CN101679569A (zh) * | 2007-06-06 | 2010-03-24 | 3M创新有限公司 | 氟化醚组合物以及使用该组合物的方法 |
| WO2008154279A1 (en) | 2007-06-06 | 2008-12-18 | 3M Innovative Properties Company | Fluorinated compositions and surface treatments made therefrom |
| CN101679705B (zh) | 2007-06-08 | 2013-12-11 | 3M创新有限公司 | 含氟烷基的酯低聚物与聚碳二亚胺的共混物 |
| WO2008154414A2 (en) * | 2007-06-08 | 2008-12-18 | 3M Innovative Properties Company | Water- and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties |
| EA201100053A1 (ru) * | 2008-07-18 | 2011-08-30 | 3М Инновейтив Пропертиз Компани | Фторированные эфирные соединения и способы их применения |
| JP2012509937A (ja) * | 2008-11-25 | 2012-04-26 | スリーエム イノベイティブ プロパティズ カンパニー | フッ素化エーテルウレタン及びその使用方法 |
| MX2011006673A (es) | 2008-12-18 | 2011-07-20 | 3M Innovative Properties Co | Metodo para poner en contacto formaciones que contienen hidrocarburos con posiciones de fosfatos y fosfonatos fluorados. |
| 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 |
| CN102311455A (zh) * | 2011-05-19 | 2012-01-11 | 张春华 | 可辐射固化的含膦酸基的多官能（甲基）丙烯酸酯的组合物及其制备方法 |
| US8859098B2 (en) * | 2012-05-18 | 2014-10-14 | Lord Corporation | Acrylic adhesion promoters |
| CN103695578B (zh) * | 2013-12-30 | 2017-01-11 | 青昊环保科技（上海）有限公司 | 一种皮革防水养护剂及其制备方法 |
| WO2016099952A1 (en) | 2014-12-18 | 2016-06-23 | 3M Innovative Properties Company | Fluorinated polymers comprising phosphonic moieties |
| CN105986344B (zh) * | 2015-02-02 | 2019-02-15 | 福建省泉州海丝船舶评估咨询有限公司 | 一种防水透气棕丝面料的生产方法 |
| CN116063207A (zh) * | 2022-12-22 | 2023-05-05 | 浙江大学 | 含n-氧化三级胺基团的双亲性脂质、脂质体递药系统及应用 |
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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 |
|---|---|---|---|---|
| US4602092A (en) * | 1983-09-19 | 1986-07-22 | E. R. Squibb & Sons, Inc. | Method for making phosphinic acid intermediates |
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1993
- 1993-01-14 DE DE4300799A patent/DE4300799C2/de not_active Expired - Fee Related
- 1993-12-17 TW TW082110694A patent/TW280830B/zh active
- 1993-12-27 US US08/172,751 patent/US5414102A/en not_active Expired - Fee Related
-
1994
- 1994-01-03 ES ES94100005T patent/ES2110123T3/es not_active Expired - Lifetime
- 1994-01-03 EP EP94100005A patent/EP0606833B1/de not_active Expired - Lifetime
- 1994-01-03 DE DE59404795T patent/DE59404795D1/de not_active Expired - Fee Related
- 1994-01-10 JP JP01205494A patent/JP3310438B2/ja not_active Expired - Fee Related
- 1994-01-11 CA CA002113238A patent/CA2113238A1/en not_active Abandoned
- 1994-01-13 KR KR1019940000457A patent/KR940018391A/ko not_active IP Right Cessation
- 1994-01-14 CN CN94100612A patent/CN1042635C/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 |
|---|---|
| JPH06279468A (ja) | 1994-10-04 |
| US5414102A (en) | 1995-05-09 |
| CN1097762A (zh) | 1995-01-25 |
| CA2113238A1 (en) | 1994-07-15 |
| DE59404795D1 (de) | 1998-01-29 |
| EP0606833A1 (de) | 1994-07-20 |
| DE4300799C2 (de) | 1996-09-19 |
| EP0606833B1 (de) | 1997-12-17 |
| TW280830B (zh) | 1996-07-11 |
| JP3310438B2 (ja) | 2002-08-05 |
| KR940018391A (ko) | 1994-08-16 |
| ES2110123T3 (es) | 1998-02-01 |
| DE4300799A1 (de) | 1994-07-21 |
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