EP0000137B1 - Esters polyglycoliques; procédé de préparation et utilisation comme agents tensioactifs - Google Patents

Esters polyglycoliques; procédé de préparation et utilisation comme agents tensioactifs Download PDF

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Publication number
EP0000137B1
EP0000137B1 EP78100138A EP78100138A EP0000137B1 EP 0000137 B1 EP0000137 B1 EP 0000137B1 EP 78100138 A EP78100138 A EP 78100138A EP 78100138 A EP78100138 A EP 78100138A EP 0000137 B1 EP0000137 B1 EP 0000137B1
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Prior art keywords
compounds according
parts
radical
water
printing
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Expired
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EP78100138A
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German (de)
English (en)
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EP0000137A1 (fr
Inventor
Sienling Dr. Ong
Ulrich Dr. Cuntze
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Hoechst AG
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Hoechst AG
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Priority claimed from DE2728767A external-priority patent/DE2728767C3/de
Priority claimed from DE19772759204 external-priority patent/DE2759204A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06—Protein or carboxylic compound containing

Definitions

  • the invention relates to polyglycol esters of the formula I. in which R is an open-chain aliphatic radical having 9 to 19, preferably 11 to 17 C atoms, Z is hydrogen and methyl, the ratio H: CH 3 being 2: 1 to 4: 1, preferably 2.5: 1 to 3.5: 1, a is zero or 1, b is 1 to 1.5 and (4-a) n is 150 to 300, preferably 200 to 250.
  • polyglycol esters in which the radical R-CO is oleyl, the ratio of H: CH 3 in the radical Z 3: 1 is random, a is zero, b is 1.1 and (4-a) n is about 210.
  • the invention further relates to a process for the preparation of said polyglycol esters, which is characterized in that a compound of the formula in which a is zero or 1, with 150-300 times, preferably 200-250 times, in particular about 210 times molar amount of a mixture of ethylene oxide and propylene oxide in a molar ratio of 2: 1 to 4: 1 and the oxalkylate with a
  • a compound of the formula in which a is zero or 1, with 150-300 times, preferably 200-250 times, in particular about 210 times molar amount of a mixture of ethylene oxide and propylene oxide in a molar ratio of 2: 1 to 4: 1 and the oxalkylate with a
  • the rest of the R-CO-introducing acylating agent is partially esterified.
  • Such acylating agents are natural or synthetic fatty acids such as, for example, stearic acid, palmitic acid, oleic acid, linolenic acid, tallow fatty acid, tall oil fatty acid, isostearic acid, coconut fatty acid or mixtures of such acids, and the corresponding acid chlorides.
  • the invention further relates to the use of the new polyglycol esters as surface-active agents.
  • the new polyglycol esters are particularly suitable for increasing or stabilizing the viscosity of aqueous systems, in particular as an additive to printing pastes or padding liquors.
  • the polyglycol esters are added in amounts of about 0.1 to about 10%, based on the weight of the finished preparation, that is to say about 1 to 100 g, preferably 2 to 30 g, of polyglycol ester per kg of printing paste.
  • Aqueous preparations of the polyglycol esters according to the invention can already be used as thickeners without further additives.
  • the new polyglycol esters are particularly advantageous as additives to other known thickeners, and not only can they increase the viscosity of aqueous systems, but above all they can also stabilize them.
  • the thickening agent furthermore offers the possibility of accommodating different reactants in a printing ink, which in its absence would react with one another prematurely, ie already in the printing ink and not only on the fiber.
  • the thickening agent acts as a "spacer" and prevents the premature interaction of reactive components.
  • tannin can be accommodated in a printing ink of a cationic dye without the formation of the tannin varnish, which should only take place when the fibers are steamed.
  • the thickener also has the task of dissolving such substances in high to keep mogeneous dispersion and to ensure that the pigment does not get stuck in the engraving of the rollers, but reaches the goods homogeneously with the printing ink.
  • the selection of a thickener is directed by a variety of factors. Among other things, by the type of printing process, by the composition of the printing ink, by the depth of the roller engraving and the required depth of color of the print by the quality of the goods, especially if there is a requirement for a print run, and also by the type of pattern, i.e. Whether small or large patterns (register or decker) should be printed determines.
  • the polyglycol esters according to the invention are particularly suitable as an addition to purely synthetic thickeners, in particular those which contain carboxyl groups.
  • copolymers of maleic anhydride and a vinyl alkyl ether or other copolymerizable monomers which can be crosslinked with polybasic amines, polyhydric alcohols or amino alcohols, are furthermore polymers of acrylic acid, maleic acid or their anhydrides, such as those with divinylbenzene or unsaturated diesters, such as Dialkylmaleinester or _ ⁇ th_ylenglykoldimethacrylestern can be cross-linked.
  • polyglycol ethers according to the invention are suitable as additives for oil-in-water and water-in-oil emulsions and their mixtures with native thickeners.
  • the polyglycol esters according to the invention can not only increase or stabilize the viscosity, but also allow the viscosity to be restored to a system which has been damaged, for example, by the influence of electrolytes.
  • the compounds of the formula I can also be used as emulsifiers.
  • the compounds of the formula I are preferably used for the preparation of dye emulsions which are used for dyeing and printing textiles. These emulsions show an extraordinarily good penetration into the textiles, so that uniform, deep dyeings with good fastness properties result.
  • the emulsion thickenings customary hitherto have a number of disadvantages: due to the relatively low emulsifying action of the conventional emulsifiers, quite large amounts of these surface-active agents were required, which often led to excessive foaming when the emulsions were prepared.
  • Common defoamers such as those used in the textile industry, can change the stability and effectiveness of the printing pastes. In particular, there is a risk that the addition of defoaming components can cause the emulsion to split, i.e. the already finished emulsions are broken again. This effect is often only a question of the quantity ratio, i.e.
  • the emulsifiers according to the invention show significant advantages compared to the commercially available products: the customary water-swellable thickeners, namely alginates, corn meal ether, starch ether or carboxymethyl cellulose, contain more or less significant amounts of alkali ions that can break down as electrolytes emulsions.
  • An emulsion thickening obtained in accordance with the present invention contains, based on the weight of the finished emulsion thickening, 0.1 to 2, preferably 0.2 to 1% of compounds of the formula I, 50 to 70% of the water-immiscible solvents and 28 to 49, 9% water.
  • Solvents which are immiscible with water are mainly hydrocarbons such as hexanes, heptanes, nonanes, cyclohexylbenzene, toluene, xylene, tetrahydronaphthalene and gasolines or mixtures of such solvents.
  • the printing pastes produced with such emulsion thickenings also contain colorants, in particular pigments, and binders. If necessary, these printing pastes can also contain acid donors such as diammonium hydrogen phosphate.
  • the printing pastes prepared with the emulsions according to the invention result in very level and brilliant prints with very good stability.
  • These printing pastes are particularly suitable for pigment printing on cotton, rayon and other natural and also synthetic fibers and their mixtures, in particular on mixtures of natural and synthetic fibers.
  • the emulsion thickeners according to the invention are also suitable in a mixture with water-swellable thickeners such as alginates, core meal ethers, starch ethers or carboxymethyl celluloses for printing pastes with dyes, for example disperse dyes, reactive dyes and acid dyes.
  • the emulsions according to the invention can be prepared by stirring the oily and aqueous phases together with the emulsifier or by other customary processes known from the literature (P. Becker, Emulsions: Theory and Practice, Reinhold Publishing Corp., New York, 1957, p. 209, Houben-Weyl, Vol. I 2, p. 97). It proves to be advantageous here that the compounds of formula 1 are water-soluble so that they can be used as aqueous solutions for the preparation of the emulsions.
  • a particular advantage of the compounds of the formula I is that generally only simple stirrers have to be used in the preparation of the emulsions. This also results in considerable process simplifications compared to other emulsifiers.
  • the emulsions according to the invention have excellent stability. Should creaming nevertheless occur after prolonged storage under unfavorable conditions, these are reversible and can generally be converted back into the original emulsion by gentle stirring.
  • emulsions can be produced with the emulsifiers according to the invention.
  • block copolymers of ethylene oxide and propylene oxide which are derived from glycerol, pentaerythritol and trimethylolpropane and are - if appropriate partially - esterified. These compounds are suitable as foam preventers.
  • DE-OS 1 619053 discloses water-insoluble reaction products of polyols with ethylene oxide and propylene oxide, which are completely esterified. These compounds substantively attach to the polyester fiber and prevent the escaping of ester oligomers from the fiber material.
  • polyglycols which are obtained by polymerizing mixtures of ethylene oxide and propylene oxide. These compounds are suitable as emulsifiers and as metal lubricants.
  • the rheogram shows that the viscosity of printing paste A with the dash-dot flow curve decreases sharply due to the addition of an electrolyte (printing paste B with the continuous flow curve).
  • Printing paste C with the dash-dash flow curve shows the viscosity-improving effect of the product of the invention.
  • polyglycol ester This product is referred to briefly as "polyglycol ester" in the following examples. These examples described the use of the polyglycol ester as an emulsifier.
  • a cotton poplar fabric is printed with this printing paste, dried and fixed at 150 ° C for 7 minutes. You get brilliant red prints with very good rub fastness.
  • This low-foam, easy-to-process printing paste is used to print a fabric made of cellulose, dry it, fix it in saturated steam for 5 minutes and wash it. After a short rinsing and washing process, the fabric no longer contains any thickener residues. After drying, the high brilliance of the yellow prints becomes clearer.
  • a polymer emulsion is obtained which is practically free of coarse and fine coagulate.
  • the conversion of the monomers is 95%.
  • a polymer emulsion is obtained which is free of coarse or fine deposits, the monomer conversion is 100%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Coloring (AREA)
  • Polyethers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Claims (10)

1. Les composés de formule
Figure imgb0007
dans laquelle R est un radical aliphatique à chaîne ouverte en Cg à C19; Z représente l'hydrogène et un méthyle, le rapport H : CH3 étant compris entre 2 et 4;
a = 0 ou 1,
b est un nombre de 1 à 1,5, et
le produit (4-a) n est compris entre 150 et 300.
2. Composés selon la revendication 1, dans lesquels le radical R-CO- est le radical acyle d'un acide gras en C11 à C17 dans le reste R.
3. Composés selon la revendication 1 ou 2, dans lesquels le rapport H : CH3 (radical Z) est compris entre 2,5 et 3,5.
4. Composés selon l'une quelconque des revendications 1 à 3, dans lesquels le produit (4-a) n est compris entre 200 et 250.
5. Composés selon la revendication 1, dans lesquels le radical R-CO- est le radical oléyle; le rapport H : CH3 (radical Z) est égal à 3 (en répartition statistique), a = 0, le produit n (4-a) est d'environ 210 et b = 1.1.
6. Procédé de préparation des composés selon la revendication 1, caractérisé en ce que l'on soumet à une oxalkylation un composé de formule
Figure imgb0008
dans laquelle a = 0 ou 1, avec un mélange d'oxyde d'éthylène et d'oxyde de propylène dans un rapport molaire compris entre 2 et 4, puis on estérifie partiellement le produit de l'oxalkylation formé avec urf agent acylant qui fixe le radical R-CO-.
7. Utilisation des composés selon la revendication 1, comme agents surfactifs (agents tensioactifs).
8. Utilisation selon la revendication 7, pour élever et stabiliser la viscosité de systèmes et milieux aqueux.
9. Utilisation selon la revendication 7, les composés étant employés comme émulsionnants.
10. Utilisation selon la revendication 7, les composés étant come additifs à des pâtes d'impression ou à des bains de foulardage.
EP78100138A 1977-06-25 1978-06-12 Esters polyglycoliques; procédé de préparation et utilisation comme agents tensioactifs Expired EP0000137B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2728767A DE2728767C3 (de) 1977-06-25 1977-06-25 Polyglykolester, Verfahren zu ihrer Herstellung und ihre Verwendung zur Erhöhung der Viskosität wäßriger Systeme
DE2728767 1977-06-25
DE2759204 1977-12-31
DE19772759204 DE2759204A1 (de) 1977-12-31 1977-12-31 Verwendung von polyglykolestern als emulgatoren

Publications (2)

Publication Number Publication Date
EP0000137A1 EP0000137A1 (fr) 1979-01-10
EP0000137B1 true EP0000137B1 (fr) 1982-03-24

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US (1) US4209333A (fr)
EP (1) EP0000137B1 (fr)
JP (1) JPS5411200A (fr)
DE (1) DE2861683D1 (fr)
IT (1) IT1097277B (fr)

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DE2912497C3 (de) * 1979-03-29 1982-04-15 Hoechst Ag, 6000 Frankfurt Verfahren und Mittel zum Colorieren von Textilien aus Polyesterfasern
DE2915643A1 (de) * 1979-04-18 1980-11-06 Licentia Gmbh Elastische abdeckung aus einem elastomeren material
DE2943902A1 (de) * 1979-10-31 1981-05-14 Hoechst Ag, 6000 Frankfurt Verwendung von veresterten oxalkylaten als praeparationsmittel fuer farbstoffe und entsprechende farbstoffzubereitungen
US4382013A (en) * 1980-02-19 1983-05-03 Basf Wyandotte Corporation Anionic surfactant compositions effective in aqueous solutions of strongly ionizable salts
JPS5836276A (ja) * 1981-08-25 1983-03-03 三洋化成工業株式会社 捺染用助剤および捺染方法
US4426485A (en) 1982-06-14 1984-01-17 Union Carbide Corporation Polymers with hydrophobe bunches
US4496708A (en) * 1983-12-14 1985-01-29 Union Carbide Corporation Water-soluble polyurethane comb polymer production
DE3526790A1 (de) * 1985-07-26 1987-01-29 Bayer Ag Ether- und ethergruppen aufweisende polyhydroxylverbindungen und ihre verwendung als aufbaukomponente bei der herstellung von polyurethankunststoffen, insbesondere als polyolkomponente in polyurethan-beschichtungsmitteln oder -vergussmassen
DE3636086A1 (de) * 1986-10-23 1988-04-28 Henkel Kgaa Fettsaeureester von polyglycerinpolyglykolethern, ihre herstellung und ihre verwendung
US5192462A (en) * 1989-03-21 1993-03-09 Croda Inc. Thickening agents for topical preparations
DE4122439A1 (de) * 1991-07-06 1993-01-07 Standard Elektrik Lorenz Ag Optisches zeitmultiplexen
US5290418A (en) * 1992-09-24 1994-03-01 Applied Biosystems, Inc. Viscous electrophoresis polymer medium and method
US5759369A (en) * 1992-09-24 1998-06-02 The Perkin-Elmer Corporation Viscous electrophoresis polymer medium and method
EP2301645A1 (fr) * 2009-09-28 2011-03-30 Cytec Surface Specialties Austria GmbH Antimoussant pour la pulvérisation sans air
EP2875521B1 (fr) * 2012-07-20 2020-03-11 FUJIFILM Corporation Procédé de gravure, procédé de production d'un substrat semi-conducteur et dispositif à semi-conducteur l'utilisant
GB201408823D0 (en) * 2014-05-19 2014-07-02 Croda Int Plc Demulsifiers

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Publication number Priority date Publication date Assignee Title
US2457139A (en) * 1946-02-26 1948-12-28 Carbide & Carbon Chem Corp Esters of polyoxyalkylene diols
NL128245C (fr) * 1951-05-31
US2911434A (en) * 1956-04-24 1959-11-03 Visco Products Co Surface active dicarboxylic acid esters of polyalkylene oxides
US2987490A (en) * 1956-09-17 1961-06-06 Visco Products Co Surface-active esters of polymerized polyethenoid fatty acids
US2969388A (en) * 1957-01-24 1961-01-24 Rohm & Haas Surface-active monoesters
US2950313A (en) * 1957-07-02 1960-08-23 Visco Products Co Surface active polyoxypropylene esters
US2950299A (en) * 1958-01-06 1960-08-23 Visco Products Co Surface active substances of ether ester class
DE1595369C3 (de) * 1966-12-15 1973-10-04 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Derivate von Blockcopolymerisaten des Äthylenoxids und des 1,2-Propylends und Verfahren zu deren Herstellung
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SE367766B (fr) * 1971-10-04 1974-06-10 Mo Och Domsjoe Ab
JPS5344551B2 (fr) * 1974-03-12 1978-11-29

Also Published As

Publication number Publication date
JPS5411200A (en) 1979-01-27
US4209333A (en) 1980-06-24
DE2861683D1 (en) 1982-04-29
IT7824934A0 (it) 1978-06-23
EP0000137A1 (fr) 1979-01-10
IT1097277B (it) 1985-08-31

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