CN1041093C - 膦酰基羧酸和膦基羧酸的氟化羧酸酯其制备方法和用途 - Google Patents
膦酰基羧酸和膦基羧酸的氟化羧酸酯其制备方法和用途 Download PDFInfo
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- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 title claims abstract description 21
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical class OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- -1 hydrocarbyl carboxylic acid esters Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229960005102 foscarnet Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910018828 PO3H2 Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
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- DSRUAYIFDCHEEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n-(2-hydroxyethyl)-n-methylbutane-1-sulfonamide Chemical compound OCCN(C)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DSRUAYIFDCHEEV-UHFFFAOYSA-N 0.000 description 2
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical compound OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- KMDMOMDSEVTJTI-UHFFFAOYSA-N 2-phosphonobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)P(O)(O)=O KMDMOMDSEVTJTI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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Abstract
本发明涉及膦酰基羧酸或膦基羧酸的氟化羧酸酯及其作为表面活性的应用。
Description
本发明涉及膦酰基羧酸或膦基羧酸的氟化羧酸酯及其作为表面活性剂的用途。
由于含全氟烃基的化合物具有高度的表面活性，作为含氟表面活性剂它在工业上有广泛的用途。有代表性的包括作为交联剂、乳化剂、涂膜、涂料或洗碟剂和清洁剂的流动改良剂(参见“Ullmann，Enzyklo-padie der technischen Chemie，4th edition1982，Vol.22，p500”)。表面处理和电镀代表着其新的应用领域，例如它可以解决受潮问题、减少由于夹带和蒸发带来的损失，改善表面抛光的效果(参见，“J.N.MeuBdoerffer and H.Niederprum，Chemikerzeitung 104(1980)，pp.45-52”)。
这种含氟表面活性剂的实例有全氟羧酸或磺酸与聚酯取代的全氟烃化合物的盐类(参见“H.G.Klein，J.N.MeuBdoerffer andH.Niederprum，Metalloberflache 29(1975)，pp 559-567。“J.N.MeuBdoerffer and Niederprum，Chemikerzeitung 104(1980)，pp45-52”描述了合成路线。对于前面提到了含氟表面活性剂，其全氟化的初始物在工业上可通过三条不同的合成路线得到：
a)电化学氟化
b)全氟烯烃的调聚反应，尤指四氟乙烯
c)四氟乙烯的低聚
由于用上述方法制备全氟化初始物使用昂贵的工艺，因此这种含氟化合物的制备非常耗钱。
本目标是制造能用作表面活性物质的适用的含氟有机改性的表面活性剂，而且这种制备比较容易，花费也低廉。
该目标可通过按本发明所述的膦酰基羧酸和膦基羧酸的氟化羧酸酯来实现。
本发明的目的之一是制备式(I)膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯。
其中
R′是羟基、甲基、乙基或苯基。
RF是含有1至18个碳原子的支链成直链的氟代烃基，或者是含有1至18个碳原子的支链或直链的氟化单醚或聚醚。
RH是1至10个碳原子的支链或直链烷基。
Y是
或
基团，
Z代表1至20个碳原子的直链或支链亚烷基；或者是1至20个碳原子的末端为氨基的直链或支链的亚烷基，这些氨基本身又要被1至10个碳的烷基或芳香基所取代；或者是含1至20个碳原子的支链或直链亚烷基，其中含有一个或多个-COR2结构的取代基；或者是含1至20个碳原子的直链或支链亚烷基，其中含有一个或多个-PO2HR′结构的取代基，其中R′的含义与上面是一样的。
m是0或1，
n是0至6的一个整数。
R2代表羟基或是具有下式结构的基团。或
含1至20个碳原子的直链或支链烷氧基，其中n，m，RH，RF和Y的含义与上面是一样的。也可以是它们的盐类。
对于膦酰基羧酸或膦基羧酸的含氟烃羧酸酯，最好其中的RF是3至10个碳原子的支链或直链氟烃基，RH是1至2个碳原子的烷基，n是1或2，m是1。
膦酰基羧酸的含氟烃基羧酸酯最好如同以下结构所示： 
下面所列的是特别优选的基团：对于RF：CF3-(CF2)2-CF3-(CF2)3-CF3-(CF2)5-CF3-(CF2)6-CF3-(CF2)7-CF3-(CF2)11-C6F5-CF3-C6F4-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-
对于 Z-CH2-，-CH(CH3)-，-CH2-CH2-，-CH2-CH(CH3)-，-CH(CH3)-CH2-，-CH2-CH2-CH2-，-CH(COOH)-CH2-，-CH2-CH(CH2-COOH)-，-CH(CH2-CH2-COOH)-CH2-，-CH[-CH(COOH)(PO3H2)]-，-CH(OH)-，-C(CH2-COOH)(CH2-CH2-COOH)-，-C(CH2-COOH)(CH2-CH2-PO3H2)-，-C(CH2-COOH)(-CH(COOH-CH2-COOH)-，-CH(CH2-CH2-COOH)-，-CH(CH2-CH2-PO3H2)-，-C(CH2-CH2-COOH)2-，-C(CH2-CH2-COOH)(CH2)-CH2-PO3H2)-，-C(CH2-CH2-PO3H2)2-，-C(CH2-COOH)(CH2-CH2-CN)-，-CH(CH2-CH2-CN)-，-C(CH2-CH2CN)2，-C(CH2-CH2CN)(CH2)-CH2)-PO3H2)-，-C(OH)(CH3)-CH2-，-C(OH)(CH3)-CH2-，-C(OH)(CH3)-CH(COOH)-CH2-，-CH2-N(CH2-PO3H2)-CH2-，-CH2-N(CH2-COOH)-CH2-，-CH2-NH-(CH2，-CH2-NH-CH(CH3)-，-CH2-N(CH2-PO3H2)(CH(CH3))-，
本发明所述的膦酰基羧酸或膦基羧酸的含氟烃基的羧酸酯可如同实施例中那样通过相应的膦酰基羧酸或膦基羧酸或其盐类与含氟醇进行酯化反应以一步合成的方式制得：
其中
RF，RH，Y，Z，m和n的含义与上文相同；
A是氢阳离子，铵阳离子或是单价或多价的金属阳离子；
X是阳离子A的价数。
本发明的另一个目的是利用膦酰基羧酸或膦基羧酸的含氟烃基的羧酸酯作为表面活性剂。
由于本发明中的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯具有高度的表面活性，它们可作为高效表面活性剂应用于下述领域中：
电解处理(如电镀铬、电镀铜和电镀镍，阳极化和电解脱垢)，本发明所述的化合物可用作雾化抑制剂以防止夹带损失。
非电解槽处理(如化学镀铜和镀镍，化学除垢或除锈，蚀刻或镂蚀，浸液上光，酸浸，镀青铜或钝化，阳极氧化或溶出)中本发明所述的化合物可用作雾化抑制剂和洗涤助剂。
本发明所说的化合物还可加入清洁剂和护理制剂(如玻璃、炉具、汽车、建筑物、建筑物或金属表面的清洁剂、去污剂、香波、用于汽车、家具等上面的抛光剂、自光亮乳液或蜡)中，作为流动改良剂、铺展和交联剂以增强防重染污的性能。
本发明所述的化合物也可加入制剂中或直接用作抗沉积剂或者用来防止起霜(如在玻璃、金属或塑料上)。
本发明所述的化合物也可加入制剂中，或直接用作缓蚀剂或防腐蚀涂饰(如在聚合反应中，用在填充剂、纤维、盐或磁性固体上，在涂料或在血液替换品中)。
由于按本发明所述的化合物易于形成气密隔离层从而防止液体蒸发，因此它也适合用作灭火剂的添加剂。
根据本发明所述的化合物也可用作模具润滑剂。
将本发明所述的化合物加入涂料和油漆中后，改善了它们的流动、交联和粘附性。此外它们防止了由于空气抽空而引起的表面疵点(如形成凹形点或边缘皱缩)的形成。另外它们还改善了色素的分布。特别值得一提的优点是该化合物在配制可用水释稀的涂料时具有无泡沫稳定作用。
由于本发明所述的化合物易形成疏水和亲油的阻挡层，因此它们可制成保护建筑材料的制剂。
本发明所述化合物也可用作流动剂或滑动剂(例如在矿石或矿盐中，在磁性输送机或在建筑材料中)。
本发明所述的化合物适合于用作润滑剂，切削油添加剂或水力油。
本发明所述的化合物也可用于钻井的辅助物质(例如提高钻孔出油量)。
本发明所述的化合物也可用在照像药品或胶片制造(如作为交联剂或抗静电物)中。
本发明所述的化合物也可用在植物保护产品(例如作为交联剂和流动改良剂)中。
将本发明所述的化合物加到织物、皮革或纸张的整理剂中，可以促进整理剂的润湿和渗透，起脱泡和增强整理剂的疏水/亲油作用。
将照本发明所述的化合物可用作防火剂(例如在塑料中)。
本发明所述的化合物可进一步用作液晶。
下面将通过实施例来更详细地介绍本发明。
实施例1
在盛有150ml 4-甲基戊烷-2-酮并带有搅拌装置和水分分离器的三颈烧瓶中加入0.5摩尔(178.5g)N-(2-羟乙基)-N-甲基-全氟丁基磺酰胺，溶解后再加入0.5ml浓硫酸。该溶液在116℃下进行回流，一边回流一边缓慢加入0.5摩尔(77g)3-膦酰基丙酸。将回流温度维持在100℃直至反应混合物中的水分完全蒸馏出去，温度将再次升高至116℃。
然后将溶剂在116℃下蒸去，获得的产品在50℃和50毫巴的条件下进行干燥。所需的3-膦酰基丙酸N-(2-羟乙基)-N-甲基-全氟丁基-磺酰氨基酯的产量是238.6g(相当于理论产量的96.8％)其0.1％水溶液的表面张力是28.1毫牛顿/米，相应的1％溶液的表面张力是20.4毫牛顿/米(用出自Lauda公司的环形表面张力计测定)。
熔点：156℃。
实施例2
在盛有150ml 4-甲基戊烷-2-酮并带有搅拌装置和水分离器的三颈烧瓶中加入0.5摩尔(278.5g)N-(2-羟乙基)-N-甲基-全氟辛基磺酰胺，溶解后加入0.5ml浓硫酸。该溶液在116℃下进行回流，一边回流一边缓慢加入0.5摩尔(77g)3-膦酰基丙酸。将回流温度维持在100℃直至反应混合物中的水分(0.5摩尔)完全蒸馏出去，温度将再次升至116℃。
然后在116℃下将溶剂蒸去，获得的产品在50℃和50毫巴条件下进行干燥。所需的3-膦酰基丙酸N-(2-羟乙基)-N-甲基-全氟辛基磺酰氨基酯的产量是342.2克(相当于理论产量的98.8％)。其0.1％水溶液的表面张力是31毫牛顿/米(通过Lauda环形张力计测定)。
熔点：208℃。
实施例3
将0.4摩尔(222.8g)N-(2-羟乙基)-N-甲基-全氟辛基磺酰胺溶于盛在带有搅拌装置和水分离器的三颈烧瓶中的150ml4-甲基戊烷-2-酮中，加入0.5毫升浓硫酸。将该溶液在116℃下进行回流一边回流一边缓慢加入0.2摩尔(39.6g)膦酰基乙烷-1，2-二羧酸中。将回流温度维持在100℃直至蒸出反应混合物中的所有水分(0.4摩尔)，温度将再次升至116℃。
在116℃下将溶剂蒸干，获得的产品在50℃及50毫巴条件下进行干燥。所需的膦酰基乙烷-1，2-二羧酸N-(2-羟乙基)-N-甲基-全氟辛基磺酰胺基酯的产量是247g(相当于96.8％的理论产量)。其0.1％水溶液的表面张力是34.5毫牛顿/米，相应的1％水溶液的表面张力是28.4毫牛顿/米(通过Lauda环就张力计测量)。
熔点：185℃。
实施例4
将3.0摩尔(1071g)N-(2-羟乙基)-N-甲基-全氟丁基磺酰胺溶解于盛在带有搅拌装置和水分离器的三颈烧瓶中的850ml氯苯中，接着加3ml浓硫酸。将溶液加热至120℃，然后缓慢加入1.0摩尔(54.0g)2-膦羧基丁烷-1，2，4-三羧酸。加完后将温度维持在100℃进行回流直至蒸出所有反应混合物中的水分(0.6摩尔)，温度将再次升至116℃。
然后将溶剂在70℃和70毫巴的条件下蒸干，并使所获的产品得到完全干燥。所需的2-膦羧基丁烷-1，2，4-三羧酸N-(2-羟乙基)-N-甲基-全氟丁基磺酰氨基酯的产量是1281克(相当于99.5％的理论产量)。其0.1％水溶液的表面张力是22.4毫牛顿/米(用Lauda环形张力计测量)。
熔点：71℃。
实施例5
将0.4摩尔(222.8g)N-(2-羟乙基)-N-甲基-全氟辛基磺酰胺溶解于盛在带有搅拌装置和水分离器的三颈烧瓶中的150ml 4-甲基戊烷-2-酮中，接着加入0.5ml浓硫酸。将该溶液在116℃下进行回流，一边回流一边缓慢加入0.2摩尔(54g)2-膦酰基丁烷-1，2，4-三羧酸。将温度维持在100℃下进行回流直至蒸出反应混合物中的所有水分(0.4摩尔)，温度将再次升至116℃。
在116℃下将溶剂蒸干后，获得的产品在50℃及50毫巴条件下进行干燥。所需的2-膦酰基丁烷-1，2，4-三羧酸N-(2-羟乙基)-N-甲基-全氟辛基磺酰氨基酯的产量是268g(相当于99.4％的理论产量)。其0.1％水溶液的表面张力是28.2毫牛顿/米，相应的1％水溶液的表面张力是27.6毫牛顿/米(用Lauda环形张力计测量)。
熔点：180℃。
Claims (8)
1.通式(I)的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯或其盐，式(I)如下：
其中R1是羟基，甲基、乙基或苯基；RF是含有1至10个碳原子的支链或直链的氟代烃基；RH是1至10个碳原子的支链或直链烷基；Y是
Z代表1至10个碳原子的直链或支链亚烷基；或者是含1至10个碳原子的支链或直链亚烷基，其中含有一个或多个-COR2结构的取代基；
m是0或1n是0至6的一个整数R2代表羟基或是具有下式结构的基团或
含1至10个碳原子的直链或支链烷氧基，其中n、m、RH、RF和Y的含义与上面是一样的。
2.按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯，其中RF是3至10个碳原子的支链或直链氟烃基。
3.按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯，其中RH是1至2个碳原子的烷基。
4.按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯，其中n是1或2。
5.按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯，其中m是1。
6.制备按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯的方法，其中相应的式(II)一步合成的膦酰基羧酸或膦基羧酸或们的盐与相应的式(III)含氟醇以一步合成方式进行酯化反应；式(II)如下：
其中A是氢阳离子、铵阳离子或是单价或多价的金属阳离子，X是阳离子A的所带电荷数(价数)，R’和Z的含义与权利要求1中的一样；式(III)如下：
其中n，m，RH，Y和RF的含义与权利要求1的一样。
7.按照权利要求1的膦酰基羧酸或膦基羧酸的含氟烃基羧酸酯的使用方法，其中所述的含氟烃基羧酸酯可加入制剂中或者直接用作表面活性剂。
8.按照权利要求1的含氟烃基羧酸酯，其中所述的酯具有下列结构之一：
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4241478A DE4241478A1 (de) | 1992-12-09 | 1992-12-09 | Fluorierter Carbonsäureester von Phosphono- und Phosphinocarbonsäuren sowie deren Verwendung |
| DEP4241478.4 | 1992-12-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1096030A CN1096030A (zh) | 1994-12-07 |
| CN1041093C true CN1041093C (zh) | 1998-12-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93120454A Expired - Fee Related CN1041093C (zh) | 1992-12-09 | 1993-12-09 | 膦酰基羧酸和膦基羧酸的氟化羧酸酯其制备方法和用途 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5342986A (zh) |
| EP (1) | EP0601418B1 (zh) |
| JP (1) | JP3310434B2 (zh) |
| KR (1) | KR100291397B1 (zh) |
| CN (1) | CN1041093C (zh) |
| CA (1) | CA2110727A1 (zh) |
| DE (2) | DE4241478A1 (zh) |
| ES (1) | ES2114997T3 (zh) |
| TW (1) | TW242143B (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776983B2 (en) * | 2004-12-30 | 2010-08-17 | 3M Innovative Properties Company | Fluorochemical polymeric surfactants |
| US7160850B2 (en) * | 2004-12-30 | 2007-01-09 | 3M Innovative Properties Company | Compositions of monomeric surfactants |
| US7495118B2 (en) * | 2004-12-30 | 2009-02-24 | 3M Innovative Properties Company | Compositions containing C4-swallow tail silanes |
| US7547732B2 (en) * | 2005-08-30 | 2009-06-16 | 3M Innovative Properties Company | Compositions of fluorochemical surfactants |
| US7164041B1 (en) | 2005-11-17 | 2007-01-16 | 3M Innovative Properties Company | Fluorinated Gemini surfactants |
| US7629298B2 (en) * | 2006-02-21 | 2009-12-08 | 3M Innovative Properties Company | Sandstone having a modified wettability and a method for modifying the surface energy of sandstone |
| DE102006025847A1 (de) * | 2006-06-02 | 2007-12-06 | Merck Patent Gmbh | Verwendung von Phosphinsäure in der Galvanotechnik |
| US7569715B2 (en) * | 2006-07-05 | 2009-08-04 | 3M Innovative Properties Company | Compositions containing silanes |
| DE102007029837A1 (de) * | 2007-06-28 | 2009-01-02 | Siemens Ag | Zusatz für ein Reinigungs- und/oder Pflegemittel zur Verwendung in Haushaltsgeräten sowie derartiges Reinigungs- und/oder Pflegemittel |
| CN102959026B (zh) | 2010-06-30 | 2014-12-24 | 3M创新有限公司 | (甲基)丙烯酰压敏泡沫粘合剂 |
| EP2836563B1 (en) | 2012-04-13 | 2016-07-06 | 3M Innovative Properties Company | Pressure sensitive adhesive foams and articles therefrom |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2424243A1 (de) * | 1974-05-18 | 1975-11-27 | Bayer Ag | Perfluoralkansulfonamidoalkanphosphonsaeure- bzw. -phosphinsaeurederivate |
| US4293441A (en) * | 1979-03-12 | 1981-10-06 | Minnesota Mining And Manufacturing Company | Corrosion inhibiting heat transfer liquid |
| US4602092A (en) * | 1983-09-19 | 1986-07-22 | E. R. Squibb & Sons, Inc. | Method for making phosphinic acid intermediates |
| DE3663666D1 (en) * | 1985-03-28 | 1989-07-06 | Hoechst Ag | Functional derivatives of phosphorus containing acetic acids, process for their preparation and herbicidal and plant growth regulator composition containing them |
| US4740608A (en) * | 1985-10-09 | 1988-04-26 | Monsanto Company | (Phosphonomethyl)trifluoromethyl sulfonates |
| DE3605800A1 (de) * | 1986-02-22 | 1987-08-27 | Bayer Ag | 2-phosphonobutan-1,2,4-tricarbonsaeurederivate als emulgatoren |
-
1992
- 1992-12-09 DE DE4241478A patent/DE4241478A1/de not_active Withdrawn
-
1993
- 1993-11-10 TW TW082109406A patent/TW242143B/zh active
- 1993-11-24 US US08/157,820 patent/US5342986A/en not_active Expired - Fee Related
- 1993-11-26 DE DE59308469T patent/DE59308469D1/de not_active Expired - Fee Related
- 1993-11-26 ES ES93119099T patent/ES2114997T3/es not_active Expired - Lifetime
- 1993-11-26 EP EP93119099A patent/EP0601418B1/de not_active Expired - Lifetime
- 1993-12-06 CA CA002110727A patent/CA2110727A1/en not_active Abandoned
- 1993-12-08 JP JP34019993A patent/JP3310434B2/ja not_active Expired - Fee Related
- 1993-12-08 KR KR1019930026817A patent/KR100291397B1/ko not_active IP Right Cessation
- 1993-12-09 CN CN93120454A patent/CN1041093C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06234780A (ja) | 1994-08-23 |
| JP3310434B2 (ja) | 2002-08-05 |
| EP0601418B1 (de) | 1998-04-29 |
| KR940014422A (ko) | 1994-07-18 |
| US5342986A (en) | 1994-08-30 |
| KR100291397B1 (ko) | 2001-11-22 |
| DE59308469D1 (de) | 1998-06-04 |
| CA2110727A1 (en) | 1994-06-10 |
| TW242143B (zh) | 1995-03-01 |
| ES2114997T3 (es) | 1998-06-16 |
| DE4241478A1 (de) | 1994-06-16 |
| EP0601418A1 (de) | 1994-06-15 |
| CN1096030A (zh) | 1994-12-07 |
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