EP0074057A2 - Esters perfluoro-alkyliques, procédé de préparation et utilisation comme produits repoussant la saleté - Google Patents

Esters perfluoro-alkyliques, procédé de préparation et utilisation comme produits repoussant la saleté Download PDF

Info

Publication number
EP0074057A2
EP0074057A2 EP82107984A EP82107984A EP0074057A2 EP 0074057 A2 EP0074057 A2 EP 0074057A2 EP 82107984 A EP82107984 A EP 82107984A EP 82107984 A EP82107984 A EP 82107984A EP 0074057 A2 EP0074057 A2 EP 0074057A2
Authority
EP
European Patent Office
Prior art keywords
formula
group
alkyl
substituted
perfluoroalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP82107984A
Other languages
German (de)
English (en)
Other versions
EP0074057A3 (fr
Inventor
Erich Dr. Schinzel
Emmerich Dr. Paszthory
Rolf Dr. Kleber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19813135012 external-priority patent/DE3135012A1/de
Priority claimed from DE19823204378 external-priority patent/DE3204378A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0074057A2 publication Critical patent/EP0074057A2/fr
Publication of EP0074057A3 publication Critical patent/EP0074057A3/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof

Definitions

  • the invention relates to perfluoroalkyl esters which are suitable for the dirt-repellent finishing of fibers or fabrics made of synthetic or semi-synthetic materials, preferably of polyethylene terephthalate or polyamides.
  • perfluoroalkyl or “perfluoroalkoxy” encompasses both those groups with terminal -CF 3 and with terminal -CF 2 H groups.
  • lower includes those groups which contain 1 to 4 carbon atoms 10.
  • the perfluoroalkyl esters according to the invention are dirt-repellent compounds which have a high repellency to water and oil and which remain on the fiber even after repeated washing and dry cleaning.
  • Another advantage of the compounds according to the invention is that they can be applied to the synthetic fiber materials in solution or as a dispersion or can be incorporated by mixing with pellets of the thermoplastic and subsequent shaping into fibers or threads.
  • a special advantage of the new dirt-repellent agents is also that they allow the fibers or threads in which these agents are incorporated to be properly dyed.
  • the new dirt-repellent agents can also be applied with a dye from a bath with satisfactory results.
  • the compounds (1) according to the invention are prepared by reacting a maleic anhydride with 1 mol of a perfluorinated alcohol or alkoxy alcohol of the formula R 1 - (CH 2 ) m OH, optionally in the presence of an inert organic solvent, such as dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, Tetramethyl urea, toluene, chlorobenzene or dichlorobenzene at temperatures from 30 to 130 ° C, preferably at 40 to 70 ° C.
  • This reaction can be carried out by adding a tert.
  • Amines like Triethylamine, N, N-dimethylaniline, pyridine, methylpyridines can be accelerated catalytically.
  • the maleic acid and / or fumaric acid perfluoroalkyl half esters formed can be converted in a customary manner by reaction with phosphorus chlorides, phosgene or thionyl chloride into the corresponding maleic and / or fumaric acid perfluoroalkyl half esters chloride, which, with suitable alcohols, have the formula appropriate in the presence of proton scavengers such as ter. Amines, to react to the compounds of formula (1).
  • the maleic acid and / or fumaric acid-perfluoroalkyl half-esters can, however, also be reacted with epoxides, for example with ethylene oxide, propylene oxide or epichlorohydrin, the ⁇ -hydroxyalkyl esters being formed by opening the oxygen-containing three ring.
  • epoxides for example with ethylene oxide, propylene oxide or epichlorohydrin
  • This reaction is advantageously carried out with excess epoxide in the presence of an inert organic solvent at temperatures from 30 to 130 ° C., preferably at 40 to 70 ° C.
  • the basic esters obtained with amino alcohols such as dimethylaminoethanol, diethylaminoethanol or morpholinoethanol can be reacted further in inert organic solvents with alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides to give ammonium alkyl esters.
  • alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides to give ammonium alkyl esters.
  • alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides
  • alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides
  • Amines such as triethylamine.
  • the compounds of formula (1) according to the invention are suitable for the simultaneous hydrophobization and oleophobicization of synthetic and natural fibers and fabrics, in particular for polyester, polyamide and polyacrylonitrile. These compounds are applied to the textile material by known methods by impregnation with a solution of the compounds of the formula (1) in a suitable organic solvent, preferably in acetone or dimethylformamide. However, the compounds of the formula (1) can also be used in the form of aqueous dispersions. The textile material is squeezed off after impregnation, dried and heat set. The simultaneous use of the compounds of the formula (1) in a conventional fiber preparation agent is particularly preferred.
  • the amount of the compounds (1) on the textile material is generally 0.05 to 1, preferably 0.1 to 0.4% by weight of fluorine, calculated from the fluorine content of the compounds of the formula (1) and based on the fiber weight.
  • thermoplastics are imparted by the present compounds of formula (1) because of their function of reducing the surface energy of the thermoplastics.
  • This effect can be improved by tempering at temperatures above the glass transition temperature of the thermoplastics and below the decomposition temperature of both the thermoplastics and the dirt-repellent. Suitable times for such annealing are in the range of about 5 to 240 minutes. The tempering temperatures are typically around 100 to 220 ° C.
  • a further improvement in the effect of the present soil repellants which contain a hydroxyl group in the esterified residue is obtained by using a difunctional or trifunctional epoxide or isocyanate in the liquid medium containing the soil repellent and in which the fiber or other thermoplastic article is incorporated is immersed or sprayed or otherwise treated with a catalyst such as an amine to promote reaction of the hydroxyl group with an epoxy group or isocyanate group upon subsequent annealing.
  • the mixture is heated to 50 to 60 ° with stirring and held at this temperature for 7 1/2 hours. According to gas chromatographic determination, after this reaction time the telomer alcohol is used up to a remainder of approx. 2%.
  • (102) consists of 90% maleic acid and 10% fumaric acid bis-ester.
  • NMR spectroscopy (103) consists of 62% maleic acid and 38% fumaric acid bis-ester.
  • the hydrogenation iodine numbers of 40 and 41 g / 100 g correspond to a molecular weight of 627, while a molecular weight of 642.5 is calculated taking into account the composition of the telomer alcohol.
  • the cis content is less than 1%.
  • the acetone solution of the acid chloride from Example 18 was mixed with the same amount of water and the calculated amount of pyridine and stirred for 4 hours at room temperature. After acidification with hydrochloric acid (1: 1), a beige precipitate was obtained, which was stirred, suction filtered, washed free of Cl ions and dried at 60 ° in vacuo. The titration provides good values for the expected equivalent weight.
  • the alcohol was (if miscible with water, possibly in a 100% excess) in acetone with the calculated
  • the amount of pyridine is initially charged and an acetone solution of the acid chloride from Example 18 is added dropwise.
  • the reaction mixture was refluxed for 3 hours, the solvent was distilled off, the remaining, mostly resinous residue was stirred several times with water (from 50 °) until no more Cl ions were detectable and dried at 50 ° in vacuo. If separation from the aqueous phase proved difficult, the resinous reaction product was taken up in ethyl acetate, washed with water free of ions, dried and evaporated.
  • the half ester from Example 16 was dissolved in dimethylformamide, the equimolar amount of glycidyl-trimethyl-ammonium chloride was added at 54 ° and the mixture was stirred at this temperature for 24 hours. After cooling to 20 °, the product was filtered off with suction, the filter cake was washed with dimethylformamide and the reaction product was precipitated in the filtrate with toluene. The mixture was stirred at 50 °, decanted, washed with toluene and dried at 50 ° in vacuo.
  • a polyamide fabric was impregnated under the same conditions as indicated above with a liquor consisting of a solution of 5 g of compound (104) from Example 4 in 1 liter of acetone.
  • the heat setting was carried out here at 190 ° C. for 5 minutes.
  • the value 5 was measured here for the oil repellency effect according to AATCC No. 118-1966. After washing five times at 40 ° C, the value was still 4.
  • the compounds listed below were applied to a fabric made of polyamide 6 filaments and polyester using a padding machine with a liquor absorption of 40-50%.
  • the amount of product was chosen so that about 0.125% circulation There is fluorine on the fabrics after drying.
  • the work was carried out from acetone solutions which contained approximately 1.2 g of substance in 250 ml of acetone.
  • the following compounds according to the invention were used:
  • the fabrics were air dried once, once condensed at 160 ° C for 1 minute and once at 160 ° G for 30 minutes.
  • the oil repellency values according to AATCC were checked directly (AN) and after 3 x washing at cooking temperature (3 x kW) in a washing machine.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Epoxy Compounds (AREA)
EP82107984A 1981-09-04 1982-08-31 Esters perfluoro-alkyliques, procédé de préparation et utilisation comme produits repoussant la saleté Withdrawn EP0074057A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19813135012 DE3135012A1 (de) 1981-09-04 1981-09-04 Perfluoralkylester, verfahren zu deren herstellung und ihre verwendung als schmutzabweisendes mittel
DE3135012 1981-09-04
DE3204378 1982-02-09
DE19823204378 DE3204378A1 (de) 1982-02-09 1982-02-09 Perfluoralkyl-malein- und -fumarsaeureester, verfahren zu deren herstellung und ihre verwendung als schmutzabweisendes mittel

Publications (2)

Publication Number Publication Date
EP0074057A2 true EP0074057A2 (fr) 1983-03-16
EP0074057A3 EP0074057A3 (fr) 1983-06-29

Family

ID=25795775

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82107984A Withdrawn EP0074057A3 (fr) 1981-09-04 1982-08-31 Esters perfluoro-alkyliques, procédé de préparation et utilisation comme produits repoussant la saleté

Country Status (5)

Country Link
US (1) US4473371A (fr)
EP (1) EP0074057A3 (fr)
AU (1) AU8797882A (fr)
BR (1) BR8205212A (fr)
ES (1) ES515453A0 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0302331A3 (en) * 1987-08-05 1989-10-18 Hoechst Aktiengesellschaft Esters of arylbisperfluoralkylcarbinols, method for the preparation of the same and of the arylbisperfluoralkylcarbinols in question
EP0301444A3 (en) * 1987-07-29 1989-10-25 Hoechst Aktiengesellschaft Method for the production of arylperfluor alkyl ketones
US5188747A (en) * 1990-09-04 1993-02-23 Matsushita Electric Industrial Co., Ltd. Fluorine-containing lubricant compounds
US5266724A (en) * 1990-09-04 1993-11-30 Matsushita Electric Industrial Co., Ltd. Fluorine-containing compounds
WO2022038365A3 (fr) * 2020-08-21 2022-04-14 Sitryx Therapeutics Limited Nouveaux composés

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3307420A1 (de) * 1983-03-03 1984-09-13 Bayer Ag, 5090 Leverkusen Textilausruestungsmittel
US4668726A (en) * 1984-03-30 1987-05-26 Minnesota Mining And Manufacturing Company Cationic and non-ionic fluorochemicals and fibrous substrates treated therewith
US4606737A (en) * 1984-06-26 1986-08-19 Minnesota Mining And Manufacturing Company Fluorochemical allophanate compositions and fibrous substrates treated therewith
GB2254476A (en) * 1991-03-20 1992-10-07 Plant J W & Co Ltd Flurocarbon treatment of flags
JPH05209954A (ja) * 1992-01-31 1993-08-20 Nec Corp 安全高度限界表示機能付精測レーダー表示装置
US5578387A (en) * 1992-03-31 1996-11-26 Matsushita Electric Industrial Co., Ltd. Fluorine-containing alkylsuccinic acid diester, process for preparing the same and use thereof
TW265452B (fr) * 1994-04-11 1995-12-11 Hitachi Seisakusyo Kk
US6413918B1 (en) 1998-04-27 2002-07-02 E. I. Du Pont De Nemours And Company Non-symmetric, partially fluorinated lubricant additives
CN1649955A (zh) * 2002-03-07 2005-08-03 彼德罗弗姆公司 防尘合成物
KR20080059111A (ko) * 2005-04-12 2008-06-26 인비스타 테크놀러지스 에스.에이.알.엘 내구성 오염 방지 및 오염 제거 피니쉬로 처리된 직물 및피니쉬의 내구성을 유지하기 위한 산업용 세탁 방법
US7385077B1 (en) 2007-03-27 2008-06-10 E. I. Du Pont De Nemours And Company Fluoroalkyl surfactants
US7692035B2 (en) * 2008-07-01 2010-04-06 E. I. Du Pont De Nemours And Company Fluorinated esters
US8263800B2 (en) 2008-07-01 2012-09-11 E. I. Du Pont De Nemours And Company Partially fluorinated sulfonated surfactants
CN102295560A (zh) * 2011-07-15 2011-12-28 苏州大学 一种顺丁烯二酸双氟烷基酯及其制备方法
WO2019124585A1 (fr) * 2017-12-21 2019-06-27 니카코리아(주) Composition d'agent d'apprêtage antisalissure et produit textile utilisant celle-ci
CN116354907B (zh) * 2023-04-12 2026-01-09 智仑新材料科技（西安）有限公司 一种含氟环氧树脂及其制备方法、应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094723A (en) * 1965-02-05 1967-12-13 Monsanto Chemicals Flame-retardant resin materials and new halogen-containing flame-retardant esters
DE1958012C3 (de) * 1968-11-18 1981-02-26 Daikin Kogyo Co., Ltd., Osaka (Japan) 2-Hydroxypropylperfluoralkyldicarbonsäureester und ihre Verwendung
DE2209538A1 (de) * 1971-03-08 1973-02-01 Ciba Geigy Ag Fluorierte polymerisate
BE791514A (fr) * 1971-11-17 1973-05-17 Ciba Geigy Di- et triesters alpha, beta-insatures contenant le groupe perfluoroalkyle et polymeres obtenus a partir de ces composes
US3965148A (en) * 1972-08-16 1976-06-22 Ciba-Geigy Corporation Perfluoroalkyl alcohols
US4346235A (en) * 1979-06-15 1982-08-24 Okamura Oil Mill Limited Fluorine-containing compounds
US4316986A (en) * 1980-09-23 1982-02-23 E. I. Dupont De Nemours & Company Preparation of difluoromalonyl fluoride

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301444A3 (en) * 1987-07-29 1989-10-25 Hoechst Aktiengesellschaft Method for the production of arylperfluor alkyl ketones
EP0302331A3 (en) * 1987-08-05 1989-10-18 Hoechst Aktiengesellschaft Esters of arylbisperfluoralkylcarbinols, method for the preparation of the same and of the arylbisperfluoralkylcarbinols in question
US5188747A (en) * 1990-09-04 1993-02-23 Matsushita Electric Industrial Co., Ltd. Fluorine-containing lubricant compounds
US5266724A (en) * 1990-09-04 1993-11-30 Matsushita Electric Industrial Co., Ltd. Fluorine-containing compounds
WO2022038365A3 (fr) * 2020-08-21 2022-04-14 Sitryx Therapeutics Limited Nouveaux composés

Also Published As

Publication number Publication date
EP0074057A3 (fr) 1983-06-29
ES8306091A1 (es) 1983-05-01
US4473371A (en) 1984-09-25
BR8205212A (pt) 1983-08-16
ES515453A0 (es) 1983-05-01
AU8797882A (en) 1983-03-10

Similar Documents

Publication Publication Date Title
EP0074057A2 (fr) Esters perfluoro-alkyliques, procédé de préparation et utilisation comme produits repoussant la saleté
DE3002369C2 (fr)
CH642052A5 (de) Verfahren zur herstellung von neuen quaternaeren ammoniumsalzen und diese enthaltende mittel.
EP0429983B1 (fr) Composition hydro- et oléophobante
EP0022562A2 (fr) Composés d'ammonium quaternaire, leur préparation et leur utilisation comme adoucissant de textile
EP0036076B1 (fr) Procédé de préparation d'apprêts exempts de formaldéhyde pour matières textiles cellulosiques et leurs applications
EP0073364A2 (fr) Procédé pour la préparation de produits de condensation contenant des substituants perfluoroalcoyles, les produits de condensation ainsi préparés et leur utilisation
DE2430140B2 (de) Kationaktive Bis-(2-Acyloxypropyl)-Ammonium-Salze, Verfahren zu deren Herstellung und Mittel auf deren Basis
DE2256234C2 (de) Kationische Verbindungen enthaltende Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung für die Behandlung von Textilmaterialien
EP0103274A2 (fr) Perfluoroalkyl-maléique amides et perfluoroalkyl-fumarique amides, procédé de leur préparation, et leur usage comme agents repoussants les souillures
DE1205097B (de) Verfahren zur Herstellung neuer Phosphorverbindungen
DE2120090A1 (de) Neue Hilfsstoffe zur Ausrüstung von Keratinfasern enthaltenden Textilien
DE1795262A1 (de) Waschfeste oelabweisende Ausruestung von Textilien
EP0140062B1 (fr) Esters perfluoroalcoyliques de l'acide anthranilique, procédés pour leur préparation et leur utilisation comme agents antisalissants
CH354878A (de) Verfahren zur Verbesserung modifizierter Glycerinphthalatharze
DE2114610A1 (de) Derivate mehrwertiger Alkohole
DE3318451A1 (de) Farbstoffmischungen
DE69112248T2 (de) Polyzyklische Farbstoffe.
DE2334346A1 (de) Fluorierte urethan-n-sulfonsaeureester
DE3204378A1 (de) Perfluoralkyl-malein- und -fumarsaeureester, verfahren zu deren herstellung und ihre verwendung als schmutzabweisendes mittel
DE2104731A1 (de) Perfluoralkylalkylmonocarbonsaure ester, Verfahren zur Herstellung dieser Verbindungen und ihre Verwendung
CH632783A5 (de) Verfahren zur herstellung von loesungen von salzen wasserloeslicher carbonsaeuren kationischer farbstoffe bzw. optischer aufheller.
DE3228711C2 (de) Verfahren zur Herstellung von Präparationen von Kobaltphthalocyanin-polyamin-Komplexen und deren Verwendung
AT207977B (de) Verfahren zur Herstellung neuer Phthalocyaninfarbstoffe
AT222100B (de) Verfahren zur Herstellung neuer saurer Ester

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19831025

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19841018

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KLEBER, ROLF, DR.

Inventor name: SCHINZEL, ERICH, DR.

Inventor name: PASZTHORY, EMMERICH, DR.