EP0131865B1 - Composés d'ammonium quaternaire oxalkylés estérifiés, procédé pour leur fabrication et leur utilisation comme agent de traitement pour fibres - Google Patents

Composés d'ammonium quaternaire oxalkylés estérifiés, procédé pour leur fabrication et leur utilisation comme agent de traitement pour fibres Download PDF

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Publication number
EP0131865B1
EP0131865B1 EP84107892A EP84107892A EP0131865B1 EP 0131865 B1 EP0131865 B1 EP 0131865B1 EP 84107892 A EP84107892 A EP 84107892A EP 84107892 A EP84107892 A EP 84107892A EP 0131865 B1 EP0131865 B1 EP 0131865B1
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Prior art keywords
acid
anion
quaternary ammonium
ammonium compounds
formula
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EP84107892A
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German (de)
English (en)
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EP0131865A1 (fr
Inventor
Manfred Dr. Hofinger
Rolf Dr. Kleber
Lothar Jaeckel
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Hoechst AG
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Hoechst AG
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    • 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
    • D06M13/322—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 nitrogen
    • D06M13/372—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 nitrogen containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight

Definitions

  • the invention relates to novel quaternary ammonium compounds, a process for their preparation and their use as fiber preparation agents.
  • Quaternary ammonium compounds with only one long-chain alkyl radical as described, for example, in DE-OS 23 35 675 and recommended as fiber preparation agents, can indeed be converted into aqueous dispersions with an active substance content of up to 50% and have a good antistatic activity, but have such an effect Compounds have a significantly reduced softening and softening effect.
  • EP-A-69948 describes quaternary N-alkyl-N, N ', N'-polyoxyalkyl-a-w-diaminoalkylene fatty acid esters. From GB-A 1 567 947 diesters of quaternized amino alcohols are known. Both classes of compounds are described as fabric softeners. None is said about its use as a fiber preparation agent.
  • the compounds of the formula are prepared from the compounds of the formula II. These are obtained by known processes by oxyalkylating primary fatty amines or fatty alkylalkylenediamines, such as, for example, tallow fat propylene diamine. An overview of methods for the preparation of this well-known class of compounds is given in Schönfeldt, "Surface Active Ethylene Oxide Adducts", Erasmusliche Verlagsgesellschaft, Stuttgart, 1976, pages 70 to 73. The esterification of these compounds is carried out according to known methods with a fatty acid in higher-boiling inert solvents such as Toluene or xylene or preferably without solvent in the melt and covered with a protective gas.
  • a fatty acid in higher-boiling inert solvents such as Toluene or xylene or preferably without solvent in the melt and covered with a protective gas.
  • the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically.
  • the water of reaction is distilled off directly from the reaction mixture.
  • the reaction temperatures here are 140 to 220 ° C, preferably 150 to 180 ° C.
  • an acid catalyst such as p-toluenesulfonic acid or hypophosphorous acid, is advantageously used.
  • the completeness of the reaction is checked by determining the acid number.
  • the molar ratio of fatty acid to compounds of formula II is constant 1, so that practically exclusively the monoester results.
  • the corresponding aminoxalkylate fatty acid ester is reacted with an equivalent amount (corresponding to the number of N atoms) of one of those carboxylic acids on which the anions A defined above are based.
  • carboxylic acids forming the anion which have already been mentioned as preferred above, the following may also be mentioned: capric, lauric, myristic, palmitic, stearic acid, glycolic acid, oxalic, succinic, adipic, sebacic and malic acid.
  • the equivalent amount is to be measured accordingly.
  • the reaction is optionally carried out in a lower alkanol, such as ethanol or isopropanol, or in water.
  • the quaternization reaction is advantageously carried out with ethylene oxide or propylene oxide or mixtures thereof at a temperature of 80 to 95 ° C. in a suitable stirred autoclave, the reaction pressure generally being up to 3 bar. Ethylene oxide is preferably used. Typical reaction times are in the range of 5 to 10 hours, with degrees of quaternization of up to 85% being achieved. The degrees of quaternization are determined by two-phase titration of the quaternary product of the formula with sodium dodecyl sulfate at pH 1 to 2 or pH 10.
  • Particularly preferred amines which can be alkoxylated to give starting compounds of the formulas Ila and Ilb are the industrially available products stearyl arachidyl / behenyl amine and stearyl, arachidyl / behenyl propylene diamine.
  • the diamines are prepared in a known manner by adding acrylonitrile to primary fatty amines and then catalytically hydrogenating the propionitriles.
  • Fatty acids suitable for esterification are products on a natural or synthetic basis, which can be individual chemical individuals; however, mixtures with appropriate chain distribution are often used.
  • Such fatty acids or fatty acid mixtures are, for example, tallow fatty acid, palm oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, rapeseed oil fatty acid (hardened or not hardened), stearic acid, erucic acid, behenic acid, oleic acid, ricinoleic acid, or branched-chain compounds from oxo synthesis, such as, for example, isostearic acid.
  • the mixtures according to the invention of the esterified, oxyalkylated quaternary ammonium compounds of the formula and the corresponding amine salts are highly thermostable, highly plasticizing and antistatically effective, liquor and substance-stable preparation agents for native and synthetic fibers which, in liquid to soft-pasty state, are dispersible in water and are easily miscible with this high active ingredient content. They can be used for filament ( «endless») preparation as well as for the preparation of staple fibers and especially tear cables. These mixtures according to the invention do not cause any corrosion on the thread-carrying organs of the textile machines. They create an ideal friction behavior of the fibers thus prepared and give them a soft, voluminous, pleasant grip.
  • the fibers and threads to be prepared are primarily those made from cotton, wool, viscose, polyacrylonitrile, polyester, polyamide-6 and -6.6 and from polyolefins.
  • the mixtures according to the invention do not contain any inorganic salts. They do not have a yellowing effect on the fiber even under thermal stress. They are generally used in amounts of 0.2 to 4, preferably 0.5 to 2% by weight, based on the weight of the fiber or thread.
  • polyacrylonitrile fibers When preparing polyacrylonitrile fibers, they give the fiber softness, antistatic properties and smoothness, reduce the static fiber-fiber static friction, whereby the dynamic thread-metal sliding friction is regulated and the resolving power of the acrylonitrile fiber structure is increased so that a This results in trouble-free tearing on the tearing machine and leads to perfect running properties during the subsequent spinning.
  • the mixtures according to the invention can also be applied to the dyed fibers, especially those made from polyacrylonitrile, after dyeing in the last rinsing bath or added already in the dyebath. It is advantageous that these compounds according to the invention can also be stored down to pH 4 in acid dye baths and up to pH 9 in alkaline dye baths and fully develop their softening effect.
  • the use of an additional antistatic can be dispensed with here, since the compounds of the formula according to the invention also have a sufficiently antistatic effect in such baths.
  • the mixtures according to the invention can also be applied to the fiber as a finishing agent in front of the crimping chamber, in order to provide the cut flake with good dissolving power or good willingness to open, which is particularly important in the case of acrylic wool types for carpet manufacture.
  • the preparation pad is 0.05 to 1.5, preferably 0.15 to 0.5% by weight, based on the fiber weight.
  • such preparation and finishing agents can also contain customary additives, such as nonionic or other cationic agents, mineral or ester oils, emulsifiers, such as, for example, fatty alcohol oxalkylates.
  • customary additives such as nonionic or other cationic agents, mineral or ester oils, emulsifiers, such as, for example, fatty alcohol oxalkylates.
  • 360 g (0.6 mol) of monostearic acid ester prepared according to a) is neutralized in the presence of 43 g (2.4 mol) of water and 60 g of isopropanol with 75 g (0.6 mol) of lactic acid and with 132 g (3, 0 mol) quaternized ethylene oxide.
  • the reaction is complete in 6 hours at a temperature of 85 ° C and a maximum pressure of 3 bar.
  • the degree of quaternization of the product is determined from the ratio of the acidic or alkaline two-phase titration with sodium lauryl sulfate and is 80%.
  • PA 6 filament, dtex 220f40, as well as experimentally spun PAC filament, dtex 300f100, are treated with aqueous solutions of the following products in the immersion roller process by means of godets, a preparation layer of 0.7% active substance, based on the fiber weight, being set.
  • the prepared threads are measured analogously to DE-OS 23 35 675 for their dynamic friction and analogously to DE-PS 2518124 for their static friction (as a measure of the tape adhesion and the resolving power).
  • PA 6 flake, 1.2 dtex / 40 mm, PAC flake, 3 dtex / 60 mm and PES flake, 1.4 dtex / 40 mm, are treated according to Comparative Example A with aqueous solutions of the following products (edition 0.2 %).
  • conductivity values are determined for the dried and air-conditioned fibers using a textometer from Mahlo GmbH, Saal / Donau, measured in divisions (high values indicate high antistatic effect):
  • a PAC tear cable colored, total titer 800,000 dtex, is treated with an aqueous solution of the following products, the preparation being applied on a Lisseux by padding and adjusted to 0.5% active substance.
  • the cables are torn on a Seydel tearing machine, after which the following tearing effects are observed:
  • the cable equipped with the pasty comparison product b) does show good running behavior, but the stack diagram created from the torn fibers is uneven due to column tears and long fibers present . In some cases, pimples and nits can also be found on the fibers.
  • the cable equipped with the liquid preparation of Example 13 according to the invention shows no pimples.
  • the stack diagram is uniform. There are no column cracks. The fibers are bulky and separate well from one another.

Claims (7)

1. Mélanges constitués 57 à 85 % en moles de composés d'ammoniums quaternaires oxalkylés estérifiés qui répondent à la formule :
Figure imgb0017
et de 43 à 15 % en moles de sels d'amines répondant à la formule :
Figure imgb0018
formules dans lesquelles :
R' représente un radical alkyle ou un radical alcényle contenant de 8 à 23 atomes de carbone,
R2 représente l'hydrogène ou un radical CH3 avec la condition que R2 puissent aussi avoir, dans l'ensemble de la molécule, les deux significations.
R3 représente un radical alkyle ou le radical alkyle d'un acide gras naturel contenant de 8 à 45 atomes de carbone, ce dernier pouvant éventuellement contenir aussi de 1 à 3 liaisons multiples et porter de 1 à 3 radicaux -OH,
A- représente l'anion d'un acide alcane-carboxylique ou d'un acide monohydroxy-alcane-carboxylique à alkyle en C1-C23, l'anion d'un acide. dicarboxylique contenant de 0 à 8 radicaux méthylènes, ces radicaux méthylènes pouvant porter 1 ou 2 substituants -OH, l'anion de l'acide fumarique, de l'acide maléique ou de l'acide citrique, l'anion de l'acide benzoïque ou l'anion d'un acide benzoïque porteur d'un hydroxy ou d'un méthyle, le nombre des fonctions acides x de ces acides carboxyliques pouvant donc être égal à 1, à 2 ou à 3,
a, b et c représentent chacun un nombre entier ou fractionnaire de 1 à 3,
d et e représentent chacun un nombre entier ou fractionnaire de 1 à 3,
m est égal à 2 ou à 3 et
n est égal à 0 ou à 1.
2. Mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon la revendication 1, mélanges caractérisés en ce que R' représente un radical alkyle ou alcényle contenant de 12 à 23 atomes de carbone.
3. Mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon l'une des revendications 1 et 2, mélanges caractérisés en ce que R2 représente l'hydrogène.
4. Mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon l'une quelconque des revendications 1 à 3, mélanges caractérisés en ce que m est égal à 3.
5. Mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon l'une quelconque des revendications de 1 à 4, mélanges caractérisés en ce que A- représentent l'anion d'un acide alcane-monocarboxylique ou d'un acide monohydroxy-alcane-monocarboxylique contenant de 1 à 6 atomes de carbone, l'anion d'un acide dicarboxylique contenant de 0 à 4 radicaux méthylènes, ces radicaux méthylènes pouvant porter 1 ou 2 substituants -OH, ou l'anion de l'acide fumarique, de l'acide maléique, de l'acide citrique, de l'acide benzoïque ou de l'acide salicylique.
6. Procédé pour préparer des mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon la revendication 1, procédé caractérisé en ce qu'on estérifie des amines oxalkylées répondant à la formule Il :
Figure imgb0019
dans laquelle RI, R2, a, b, c, m et n ont les significations données à propos de la formule I, avec un acide carboxylique R3COOH dans lequel R3 a la signification indiquée à propos de la formule I, on forme un sel en faisant réagir avec un acide carboxylique apte à former l'anion A― défini à propos de la formule I, puis on quaternise avec au moins un oxyde d'alkylène pris dans l'ensemble constitué par l'oxyde d'éthylène et l'oxyde de propylène.
7. Application des mélanges de composés d'ammoniums quaternaires oxalkylés estérifiés et de sels d'amines selon l'une quelconque des revendications 1 à 5 comme agents de traitement pour fibres.
EP84107892A 1983-07-13 1984-07-06 Composés d'ammonium quaternaire oxalkylés estérifiés, procédé pour leur fabrication et leur utilisation comme agent de traitement pour fibres Expired EP0131865B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3325228 1983-07-13
DE19833325228 DE3325228A1 (de) 1983-07-13 1983-07-13 Veresterte, oxalkylierte quaternaere ammoniumverbindungen, verfahren zu deren herstellung und deren verwendung als faserpraeparationsmittel

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EP0131865A1 EP0131865A1 (fr) 1985-01-23
EP0131865B1 true EP0131865B1 (fr) 1988-09-07

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EP (1) EP0131865B1 (fr)
JP (1) JPS6038349A (fr)
DE (2) DE3325228A1 (fr)
ES (1) ES534194A0 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3717454A1 (de) * 1987-05-23 1988-12-01 Bayer Ag Praeparationsmittel fuer synthesefasern
DE4018750A1 (de) * 1990-06-12 1991-12-19 Rewo Chemische Werke Gmbh Poly(oxyalkylen)aminoalkanolester, deren ammoniumverbindungen, verfahren zu ihrer herstellung und ihre verwendung in emulgatoren, reinigungsmitteln, desinfektionsmitteln und konservierungsmitteln
EP0525271B1 (fr) * 1991-07-29 1996-09-04 Kao Corporation, S.A. Procédé pour la préparation de composés quaternaires
FR2688419B1 (fr) * 1992-03-12 1994-07-08 Stepan Europe Base tensioactive comprenant un compose cationique d'ammonium quaternaire et un compose a titre de solvant et composition assouplissante comprenant une telle base.
ES2094893T3 (es) * 1991-12-31 1997-02-01 Stepan Europe Tensioactivos a base de compuestos de amonio cuaternario, procedimientos de preparacion, bases, y composiciones suavizantes derivadas.
FR2685649B1 (fr) * 1991-12-31 1994-09-23 Stepan Europe Tensioactifs a base de composes d'ammonium quaternaire, procede de preparation, bases et compositions assouplissantes derivees.
DE4243547C2 (de) * 1992-12-22 1994-10-20 Henkel Kgaa Quaternierte Fettsäure-triethanolaminester-Salze
ES2097476T3 (es) * 1993-09-17 1997-04-01 Stepan Europe Base tensioactiva que comprende un compuesto cationico de amonio cuaternario y un compuesto a titulo de disolvente y composicion suavizante que comprende dicha base.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1567947A (en) * 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
DE2642517A1 (de) * 1976-09-22 1978-03-23 Hoechst Ag Salze sekundaerer aetheramine und deren verwendung als praeparationsmittel fuer synthesefasern
DE3127239A1 (de) * 1981-07-10 1983-01-20 Hoechst Ag, 6000 Frankfurt Quartaere n-alkyl-n,n',n'-polyoxyalkyl-(alpha),(omega)-diaminoalkylenfettsaeureester, verfahren zu deren herstellung und deren verwendung

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ES8504105A1 (es) 1985-04-01
EP0131865A1 (fr) 1985-01-23
ES534194A0 (es) 1985-04-01
DE3473873D1 (en) 1988-10-13
DE3325228A1 (de) 1985-01-24
JPS6038349A (ja) 1985-02-27

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