• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to acid derivatives, in particular the preparation of N, N-dialkyl- or N, N, N- -trialkyl-N-2- (tJ-liftropyl-cyclo-l--carbonnl) -ethyl-l-mono derivatives of the general formula, —C (0) —CH. — CH, —NR, where n is 6-12; R, - And or methyl; H and R, - C, -Cb-alkyl; X - C1, HSG, (0) 0, with R, - H, or X - CHjOSO, with R, - CH, which can be used as emulsifiers. The goal is to create new useful substances of the specified class. Their synthesis is carried out from acrylic ester and the corresponding amine, -CHi-CH., -0-C (0) -CH.-CH -l-NHRjR, followed by alkylation with R, X (in which R, Rj, R ,, JC, n are listed above). New ammonium salts | have good oil and water repellency. 1 tab. 1SO with
    公开号:SU1395137A3
    申请号:SU853846604
    申请日:1985-02-04
    公开日:1988-05-07
    发明作者:Рамлох Херберт；Зайдель Манфред；Лаузе Йоахим；Вальдманн Карл
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    co
    with

    s
    The invention relates to a process for the preparation of new fluoroalkyl groups containing salts of the p-alkyl-amino esters of propionic acid, derived from the derivatives of K, dialkyl or H, H, I-trialkyl-H-2- (polyfluoroalkoxy-1 -CARBONIL) -ethyl-ammonium with the general formula
    CnFin.j-CHj-CHrO-C-CHj-CHj-K-RzX®
    About AJ
    where n 6-12;
    R is hydrogen or methyl; R. and Bj is C, -CY-alkyl; X - С1, HS04, СН, СОО- with R, or X - СН, ОЗОЗ with R, - СН.
    These compounds can be used as an emulsifier for the preparation of aqueous polymer dispersions from fluorine-containing acrylic acid sugars. Such half-tepOB dispersions of fluorinated esters of acrylic acid serve to form oil-repellent and water-repellent coatings on textile materials.
    The aim of the invention is a method of obtaining a new compound - an emulsifier with improved properties.
    Example 1. Obtaining esters and-dialkylaminopropionic acid and ethylperfluoroalkyl.
    42 g (0.1 mol) of ethyl perfluoroalkyl acrylic ester are loaded and 12.9 g (0.1 mol) of dialkylamine are added with stirring. After the release of the thermal effect is complete, the reaction ends. The resulting products are colorless oily liquids with a boiling point of () 205-2 ° C (with decomposition). When using acrylic acid esters (for example ethyl acrylic acid), which are solid at room temperature, they are taken in dissolved form and after the end of the reaction the organic solvent is distilled off. At the same time, isopropanol is convenient as an organic solvent.
    When used as adducts of a complex ethyl perfluorohydrohex-turn
    with
    0
    five
    0
    5 Q

    ." with
    0
    five
    th ether n & after gas chromatography composition,% (a):
    CgF ,, j-0-CO-CH CH.j 99.5
    CgF, 7-CH, j-CH-0-CO-CH CH2 0.5 and complex. Ethyl perfluorooctyl ester of acrylic acid after gas chromatography composition,% (b):
     -CH - CHN-0 CO-CH CH2 99.1
    SbH, - CH2-CH2-0-CO-CH.N.g as reaction products with dialkylamines: dibutylamine, diethylamine, dipropylamine and dihexylamine (with exit data determined by gas chromatography and analysis of the content of the main N, determined by titration with perchloric acid) is obtained:
    Transformation Products (a) and:
    dibutylamine: 99.5% ester; 0.5% amine residue; found: 2.56% N; calculated: 2.53% N;
    diethylamine: 99.5% ester; 0.5% amine residue; found: 2.85% N; calculated: 2.80% N;
    dipropylamine: 99.5% ester; 0.5% amine residue; found: 2.69% H; calculated: 2.65% N;
    dihexylamine: 99.5% ester; 0.5% amine residue; found: 2.32% N; calculated: 2.26% N;
    conversion products (b) and:
    dibutylamine: 99.1% ester; 0.9% amine residue; found: 2.17% N; calculated: 2.10% N;
    diethylamine: 99.1% ester; 0.9% amine residue; found: 2.37% N; calculated: 2.30% N;
    diproplamine: 99.1% ester; 0.9% amine residue; found: 2.17% N; calculated: 2.21% N;
    dihexylamine: 99.0% ester; 1.0% amine residue; Found: 1.99% .N; calculated: 1.95% N.
    The reaction with the corresponding ethyl perfluorobutyl, ethyl perfluorodecyl or ethyl perfluorododecyl esters of acrylic acid and the indicated amines proceeds in the same way as described; under these conditions, the product is obtained in almost 100% (i.e., after gas chromatographic analysis and 98%) yield. The spectroscopic and analytical data of which also confirm the structure of the obtained compound.
    Example 2. Preparation of ethyl perfluoroalkyl ester salt
     13951
    - dialkyl ammonium propionic acid, H in the general formula.
    By adding gaseous HC1 to a solution of ethyl perfluoroalkyl esters of dialkylaminopropionic acid obtained in Example 1 in isopropanol and subsequent distillation of the organic solvent, one can obtain the corresponding hydrochlorides (ammonium salts), which confirm the indicated spectroscopic and analytical data.
    For further use of ammonium salts as an emulsifier for aqueous dispersions, the esters obtained in Example 1 are distributed in water by means of placement and hydrochloric acid, diluted sulfuric acid, acetic acid 20 or glycolic acid (X C1, HSO, CHjCOO - or glycol t). Aqueous solutions of salts are directly applicable as emulsifier solutions.
    Example 3. Obtaining the salt 25 of ethyl perfluoroalkyl ester of p-dialkyl monomethylammonium propionic acid (R, CH, and X CHjOSO in the general formula).
    54.7 g (0.1 mol) of ethyl p-dibutyl-aminopropionic acid perfluorohexyl ester was dissolved in 100 ml of ethyl acetate and treated with 12.6 g (0.1 mol) of dimethyl sulfate. After g of the discoloration, the organic solvent is distilled off from heating. A crystalline quaternary ammonium salt remains in the precipitate. The corresponding quaternary ammonium salts are also obtained from other esters prepared in Example 1 ...
    For further use of the ammonium salts as an emulsifier for aqueous dispersions, the esters prepared in Example 1 are distributed in water by stirring and dimethyl sulfate is added. By the end of the year, the Scientific Research Institute for Investing the Thermal Effect of a Reaction, solutions of quaternary salts are directly applicable as an emulsifier solution.
    Example 4. Preparation of aqueous 55 containing polymer (perfluoroalkyl group of dispersions).
    Example 4.1. 25 ma.ch. ethyl perfluoroalkyl ester mixtures37
    ditch of acrylic acid containing approximately%:
    CE CE OCOCR CE 2.5
     SN. OCOSN CH g
    61.5
    C F CE CE QCOCK SY. 27
    C ,, CH OSOSN SNg 7.5
    С, РгчСНгСНгОСОСН СН1. | 5. 1 ma.ch. lauryl acrylate, 0.3 mAh, acrylamide and 1.5 mae. a stearylalkyl condensed from 15 moles of ethylene oxide is loaded and 75 wt.h is poured. the solution obtained by stirring 5 mach. Fl-dibutylaminopropionic kieloty ester and ethyl perfluorohekeyl in hydrochloric acid water to pH 2.5, and then water is added. After heating prior to stirring, an emulsion is obtained, which is stirred for approximately 30 minutes at a nitrogen nitrogen atmosphere. Then initiate the polymerization by adding 0.1 mash. azodiisobutyramidine, 2 HC1 and heating to 65 ° C. After 3 hours, with Strong agitation and 65 temperature, you finish the polymerization. After cooling to room temperature, a transparent polymer is obtained, as well as water, and the dispersion of the polymer.
    Example 4.2. 25 ma.ch. Ethyl perfluoroalkyl ether and acrylic acid composition of the composition is analogous to Example 4.1: 1 wt.h. lauryl acrylate; 0.3 ma.ch. acrylamide; 1.5 ma.ch. nonylphenol condensed with 8 moles of ethylene oxide was charged and 75 wt.h. a rotetower, out of 3 ma.ch. B-dibutylaminopropionic acid ester and ethyl perfthegekeyl, which are distributed in water with stirring and by the addition of 0.7 wt.h. dimethyl sulfate is converted to a quaternary salt and after cooling from the heat of reaction (about 45 minutes), water is added to the desired concentration. After heating to 50 ° C with stirring, an emulsion is obtained which is stirred for about 30 minutes under a nitrogen atmosphere. Then the polymerization is initiated by adding 0.1 mas. azodiisobutyr amide 2 HC1; 0.03 math. akorbiyi kieloty and heating with strong stirring to 65 ° C.
    513
    After cooling to room temperature, a transparent, almost like water, polymer dispersion is obtained.
    Example 5. (comparative). Polymer dispersion.
    May 25, h mixtures of ester of ethyl perfluoroalkyl and acrylic acid according to example 4.1: 1 wt.h. lauryl acrylate; 0.3 ma.ch. acrylamide; 2.5 ma.ch. the sodium salt of tetrahydroperfluorooctyloxcarbonamidoethylthio. gray acid ;,
    (,,, ООШШН2 СН., 320зКа) as an emulsifier; 12.5 ma.ch. isopropanol and 95 May, h. water under nitrogen with stirring is heated to 50 ° C. After 30 minutes while stirring, the polymerization is initiated by the addition of 0.1 mash of ammonium peroxydisulfate (NII) S20g and 0.03 May, h, ascorbic acid. At 50-55 ° C, stir A h, then cool to room temperature.
    A comparative check of the fluorine-containing aqueous dispersion of the polymer in examples 4.1 and 5 is given in the table.
    As can be seen from the table, obtained using a new emulsifier, fluorine-containing aqueous dispersions of polymers impart high oil-repellent and water-repellent characteristics to the treated or textile fabrics, as claimed.
    The method of obtaining derivatives NjN-dialkyl-. M, K, W-trialkyl-M-2 Water repellency: sprinkling (AATCC 22)
    To circle
    Poelle three washes at 60 ° C
    After three dry cleaners According to Bundesmann (DI N53888)
    Getting wet at the beginning,%
    Poelle three washes at 60 ° C
    After three dry cleaners
    376
    - (polyfluoroalkoxy-1-carbonyl) -ethyl | ammonia of the general formula
    Rj
    A1L
    Spga. CH, -0-C-CHg-CH t-V-R, X, LR,
    where n 6-12;
    R, is hydrogen or methyl;
    R, and RJ - C-C-alkyl;
    X - 01, HSO, СН, СОО- with R, Н
    or X -, shsh R, - CH characterized in that the ester of acrylic acid of the formula
    CrGyy + 1-SNg-CH, -0-C-CH-CH1,
    ABOUT
    where n has the indicated meanings, is reacted with the secondary.
    an amine of formula NH
    x
    R,
    and received
    the product is alkylated with a compound of the formula R - X, where R, and X have the indicated meanings.
    Properties
    Transmission, start, micron After three washes at 60 ° С After three dry cleaners
    Oil repellency, ZM test At the beginning
    After three washes with After three dry cleaners
    Verification by AATSS 118 First
    After three washes with After three dry cleaners
    13951378
    Table continuation
    Indicators for Example A.II 5
    I
    2032
    1342
    2828
    权利要求:
    Claims (1)
    [1]
    SUMMARY OF THE INVENTION A method for producing derivatives of Ν, Ν-dialkyl or Ы, M, I-trialkyl-I-2 where η has the indicated meanings, is reacted with a secondary 30. -.z R i with an amine of the formula NH and the resulting R r product is alkylated with a compound of the formula R ^ - X, where R and X have the indicated meanings.
    I
    Properties
    Metrics for example
    Water repellent: splashing (AATSS 22)
    Circle
    100
    After three washes at 60 ° C 80 fifty After three dry cleaners 100 70 According to the Bundesmann (DI N 53 888)Wet at the beginning, 7 <, 12.1 19,4 After three washes at 60 ° C 32,2 32.6 After three dry cleaners 26.8 27.1
    Ί
    Table continuation
    Properties Metrics for example - t 5 Transmission, start, mk 20 32 After three washes at 60 ° C thirteen 42 After three dry cleaners 28 28 Oil repellent, ZM testinitially 100 80 After three washes at 60 ° C 90 60 After three dry cleaners 90 70 AATCC Verification 118initially 5 3 After three washes at 60 ° C 4 1 After three dry cleaners 4 2
    类似技术:
    公开号 | 公开日 | 专利标题
    CA1238319A|1988-06-21|Synthesis of 7-halo-7-deoxylincomycins
    SU1395137A3|1988-05-07|Method of producing derivatives of n,n-dialkyl- or n,n,n-trialkyl-n-2[|-ethyl] of ammonium
    HU230546B1|2016-11-28|In situ process for preparing quaternary ammonium bicarbonates and quaternary ammonium carbonates
    JP2966114B2|1999-10-25|Polyfluoro nitrogen-containing organic compounds
    JP3310439B2|2002-08-05|Fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids containing hydroxyl and / or mercapto groups, methods for their preparation and use
    US5157159A|1992-10-20|Process for hydroxyalkylation of fluorinated alcohols
    US3535381A|1970-10-20|Unsaturated fluoroalkyl amines and process for the preparation thereof
    DE69916314T2|2005-03-17|PROCESS FOR CONVERTING AN ALCOHOL IN THE CORRESPONDING FLUORIDE
    US4883612A|1989-11-28|Preparation of para-acyloxybenzene sulfonates
    US5144069A|1992-09-01|Process for the preparation of fluoroaliphatic aminocarboxylate surfactants
    KR0142384B1|1998-07-01|Process for the preparation of halogenated esters of carboxylic or dicarboxylic acids
    US4977264A|1990-12-11|Process for the production of 4,5-dichloro-6-ethylpyrimidine
    US4001309A|1977-01-04|Method of preparing polyfluoroalkyl group containing compounds
    US3663604A|1972-05-16|Polyfluorocarbamates
    US4127731A|1978-11-28|Process for producing fluorinated acyl fluoride having an ester group
    JPH06104646B2|1994-12-21|Method for producing optical isomer of 2-chloropropionic acid ester
    US3285975A|1966-11-15|omega-perfluoroalkyl alkenols
    SU1728236A1|1992-04-23|Symmetric or non-symmetric fluoro-containing diesters of sulfosuccinic acid as wetters for film-and-photomaterials
    US4259263A|1981-03-31|Halogenated hydrocarbons and a method for their preparation
    KR100315053B1|2001-11-24|Tetraalkylfluoroformamidinium trifluoroacetate and preparation process of same
    CZ302796A3|1997-05-14|Process for preparing alkylimidazolodone|acrylates
    JP2013515067A|2013-05-02|Fluorinated arylene-containing compounds, methods, and polymers prepared therefrom
    CN112159322A|2021-01-01|Auxiliary monomer for modified polyacrylate and modified polyacrylate
    US3725464A|1973-04-03|Process for methoxyethyl carbamate
    EP0128489B1|1989-11-29|Process for the preparation of dialkyl esters of succinylsuccinic acid
    同族专利:
    公开号 | 公开日
    AU3828485A|1985-08-08|
    JPS60188354A|1985-09-25|
    EP0152784B1|1987-10-28|
    DE3403880A1|1985-08-08|
    EP0152784A1|1985-08-28|
    ES540074A0|1985-12-01|
    US4658052A|1987-04-14|
    AU569605B2|1988-02-11|
    DE3560828D1|1987-12-03|
    DD251146A5|1987-11-04|
    US4780244A|1988-10-25|
    ES8602609A1|1985-12-01|
    AT30414T|1987-11-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2562974C2|2011-12-15|2015-09-10|Налко Компани|Composition and method of reducing agglomeration of hydrates|US3557214A|1966-03-31|1971-01-19|Basf Ag|Production of monoquaternary ammonium halides|
    DE1643568B2|1967-10-03|1976-06-16|Wacker-Chemie GmbH, 8000 München|PROCESS FOR THE PREPARATION OF BETA-DIALKYLAMINOPROPIONIC ACID DIALKYLAMIDES|
    GB1200987A|1968-05-29|1970-08-05|Bp Chem Int Ltd|Quaternary compounds of dialkylamino acetic acid esters|
    US3563999A|1968-11-01|1971-02-16|Allied Chem|Certain perfluoroalkylene oxyalkylene esters of pyridinium carboxylates|
    US3689530A|1969-06-24|1972-09-05|Bristol Myers Co|2,2,2 trihaloethyl glycinate|
    GB1382594A|1971-06-04|1975-02-05|Unilever Ltd|Quaternary ammonium compounds for use in bleaching systems|
    US3776857A|1971-09-24|1973-12-04|Witco Chemical Corp|Water-in-oil emulsions|
    US3925349A|1972-09-18|1975-12-09|Desoto Inc|Radiation curable non-gelled michael addition reaction products|
    IT1042172B|1974-09-12|1980-01-30|Du Pont|IMPROVED POLYMER REPEL LENS AND WATER REPELLENT OIL|
    DE2854540A1|1978-12-16|1980-06-26|Bayer Ag|FUELS|
    DE3004611A1|1980-02-08|1981-08-13|Hoechst Ag, 6000 Frankfurt|HIGHLY CONCENTRATED FUEL SLURRIES|
    US4379869A|1981-01-15|1983-04-12|W. R. Grace & Co.|Cationic latices and their electrodeposition|FR2641781B1|1988-12-27|1991-04-19|Atochem|SUBSTITUTED POLYFLUOROALKYL ACETATES, THIOACETATES AND ACETAMIDES, PROCESSES FOR THEIR PREPARATION AND THEIR APPLICATION|
    DE4011171A1|1990-04-06|1991-10-10|Degussa|PRODUCTION OF-AMINO ACID-2,2,2, -TRIFLUORETHYLESTER|
    US5252400A|1990-11-13|1993-10-12|Matsushita Electric Industrial Co., Ltd.|Fluorine-containing compounds|
    US5266076A|1992-01-24|1993-11-30|E. I. Du Pont De Nemours And Company|Fluorinated finishes for aramids|
    AT211728T|1995-11-02|2002-01-15|Procter & Gamble|AMINOESTERS OF PERFUME ALCOHOLS AND THEIR USE IN CLEANING AND DETERGENT COMPOSITIONS|
    EP0996523B1|1997-07-15|2002-06-12|Seimi Chemical Co., Ltd.|Composition for preventing creeping of a flux for soldering|
    US7385077B1|2007-03-27|2008-06-10|E. I. Du Pont De Nemours And Company|Fluoroalkyl surfactants|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19843403880|DE3403880A1|1984-02-04|1984-02-04|SALTS OF SS-ALKYLAMINOPROPIONIC ACID ESTERS CONTAINING FLUORALKYL GROUPS, METHOD FOR THEIR SYNTHESIS AND THE USE THEREOF FOR THE PREPARATION OF AQUEOUS POLYACRYLATE DISPERSIONS CONTAINING FLUORINE KYLL|
    [返回顶部]