WO1997030141A1 - Carbonates d'ester de polyether servant de polymeres eliminant les salissures dans des adjuvants detersifs et textiles - Google Patents

Carbonates d'ester de polyether servant de polymeres eliminant les salissures dans des adjuvants detersifs et textiles Download PDF

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Publication number
WO1997030141A1
WO1997030141A1 PCT/EP1996/005833 EP9605833W WO9730141A1 WO 1997030141 A1 WO1997030141 A1 WO 1997030141A1 EP 9605833 W EP9605833 W EP 9605833W WO 9730141 A1 WO9730141 A1 WO 9730141A1
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WO
WIPO (PCT)
Prior art keywords
soil release
group
release polymers
polymers according
oxyalkylene
Prior art date
Application number
PCT/EP1996/005833
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German (de)
English (en)
Inventor
Herbert Koch
Original Assignee
HÜLS Aktiengesellschaft
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
Application filed by HÜLS Aktiengesellschaft filed Critical HÜLS Aktiengesellschaft
Publication of WO1997030141A1 publication Critical patent/WO1997030141A1/fr

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Classifications

    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D06M15/513—Polycarbonates

Definitions

  • the invention relates to polymers capable of removing dirt, to a process for their preparation and to their use as an additive to detergents, as laundry aftertreatment agents and as textile auxiliaries.
  • Dirt release polymers based on hydrophilic polyester have been marketed for several years.
  • the main sales products include ZELCON (Du Pont), MILEASE T (ICI), ALKARIL QCF / QCJ (Alkaril Inc.) and REPEL-0-TEX (Rhone-Poulenc).
  • the mode of action of soil release polymers is based on a modification of the fiber surface of polyester or cotton / polyester blended fabrics with the aid of the hydrophilic polymer.
  • Moisture transport water absorption and absorbency
  • the soil release polymer such as polyester or polyester / cotton blended fabrics. They also give the fabrics antistatic and gliding properties, which makes handling these fibers easier when cutting and sewing (textile processing).
  • the treatment of the fabric with the soil release polymer is to be understood as a kind of impregnation, i.e. the soil release polymer remains on the fiber for several wash cycles.
  • the majority of the soil release polymers are polyesters based on terephthalic acid / polyalkylene glycol / monomeric glycols.
  • DE-A-1469403 describes a method for the surface-changing treatment of articles derived from polyesters.
  • ET ethylene terephthalate units
  • POET polyethylene glycols with molecular weights of 1,000-4,000 being used
  • POET-polyoxyethylene terephthalate polyoxyethylene terephthalate
  • polyesters which contain the sodium salt of sulfoisophthalic acid as a further polymerization component.
  • the polymerized polyethylene glycols (PEG) have molar masses of 200-1000 and, after their polymerization with ethylene glycol (EG) and terephthalic acid, give polyesters with molecular weights of 2000 - 10000.
  • EP-A-0 319 094 also claims the use of ET / POET copolymers as textile auxiliaries for treating laundry in an automatic clothes dryer.
  • the advantages of the antistatic properties of the laundry treated with soil release polymer are particularly emphasized here.
  • the performance of the soil release polymers used can be increased in anionic or nonionic surfactant formulations, in particular by adding surfactants based on polyhydroxy fatty acid amides (glucamides).
  • a further modification of the polyesters includes the incorporation of cationic components based on quaternary nitrogen compounds, which are said to be even more effective than nonionic polyesters (US Pat. No. 4,956,447).
  • End-capped polyesters (capped polyesters) are described, on the one hand by nonionic groups such as. B. Cl - C4-alkyl, Cl - C4-hydroxyalkyl, Cl-C4-acyl and sealed by ionic succinate groups.
  • the activity of a soil release polymer in a liquid detergent formulation and the storage stability of the formulation can be improved by adding small amounts of salt.
  • DE-A-37 27 727 emphasizes the use of PET in the manufacture of PET / POET copolymers, which was obtained from waste flakes.
  • EP-A-0456 569 describes a special fabric softener formulation which contains a soil release polymer.
  • Conventional formulations with PET / POET soil release polymer, anionic or non-ionic surfactant and cationic fabric softener become unstable over time and tend to flocculate. This can be counteracted by using a water-soluble fraction of a PET / POET copolymer.
  • DE-A-4001 415 claims the representation and use of a polyester as a graying-inhibiting and dirt-removing additive to powdery and liquid detergents.
  • the polyesters are obtained by condensation of at least two carboxylic acids containing carboxyl groups with polyhydric alcohols.
  • alkoxylated polyvalent Alcohols are used, which are obtained by the addition of 5 - 80 mol ethylene oxide (EO) and / or propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • EP-A-0 523 956 describes a detergent formulation which contains a water-soluble or water-dispersible copolymer which contains a UV-absorbing monomer.
  • the present invention was therefore based on the object of developing new dirt-releasing polymers which are more effective in the case of greasy soiling.
  • amphiphilic carbonate-modified polyesters or oligoesters with a random structure, which can be described by the following empirical empirical formula:
  • CAP represents end groups which seal the polymer at the end and a.) Acyl or aroyl groups with 4 to 40 carbon atoms, b.) Hydroxyacyl or hydroxyaroyl groups with 2 to 25 carbon atoms, c.) Poly (oxyalkylene) monoalkyl ethers, in which the alkyl group 7 to 24
  • Group which is composed of 2 to 100, preferably 4 to 50, oxyalkylene groups, where t is a number from 0 to 25 and the alkyl groups contain 2 to 6 C atoms, and
  • oligo- / polyester molecular weights are from 500 to 100,000.
  • the values x, z, q, r, s, t and y can also assume non-integer values within the specified limits.
  • the invention further relates to a process for the preparation of these soil release polymers and the use of carbonate-modified polyesters or oligoesters of this type which enable soil release, as a constituent of washing formulations, laundry aftertreatment agents and as a constituent of formulations in textile processing.
  • these compounds can also be used as viscosity regulators.
  • the invention relates in particular to dirt-releasing polymers with molecular weights of 500 to 20,000 and partial end group closure, which are composed of the monomers dimethyl terephthalate, dialkyl carbonate and diethylene glycol.
  • the compounds according to the invention are preferably prepared in the form of a direct reaction of all monomer units in one Step so that statistically distributed polymers (so-called random structures) are obtained.
  • aliphatic diesters can also be used as monomer units.
  • the internal anionic groups listed under the designation (I) in the empirical formula are preferably selected from sulfophthaloyl, sulfoisophthaloyl, in particular 5-sulfoisophthaloyl and sulfoterephthaloyl groups, in the form of their salts, in particular as alkali, in particular Sodium or ammonium salts can be used.
  • aliphatic, anionic monomers derived from sulfonated aliphatic diesters such as e.g. Derive maleic acid, adipic acid, sebacic acid diesters etc.
  • the end groups bonded via ester groups can be based on acyl and aroyl groups with 4 to 40 carbon atoms, as well as hydroxyacyl and hydroxyaroyl groups.
  • End groups of this type are e.g. B. claimed in DE-A-44 17 686.
  • the following are typical representatives: valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, benzoic acid, the 1 to 5 substituents with a total of up to 30 C atoms, in particular 1 to 12 C atoms wear, all end groups are introduced into the polymer in the form of their alkyl esters.
  • hydroxyacyl and hydroxyaroyl end groups lactic acid, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymo nocarboxylic acids can be linked to one another via their free hydroxyl group and / or their carboxyl group.
  • Poly (oxyalkylene) monoalkyl ethers are listed as further end groups. Ethoxylated alcohols with 7 to 24 carbon atoms in the alkyl radical and 2 to 200 oxyethylene units are preferably used here.
  • the claimed soil release polymers can be produced by simple polymerization processes.
  • the monomeric building blocks are preferably reacted in a reaction mixture.
  • this type of reaction can only be carried out using the corresponding ester compounds in the form of a transesterification, since in the presence of acids (e.g. terephthalic acid) the dialkycarbonates react to release carbon dioxide.
  • the alcohol formed during the transesterification is removed via a fractionation column and / or a dephlegmator.
  • the temperature control of the reaction depends primarily on the boiling point of the dialkyl carbonate used. It must be ensured here that no large amounts of unreacted dialkyl carbonate distill over with the reaction alcohol obtained during the transesterification. Basically temperatures from approx. 80 to 250 ° C and pressures from normal pressure to ⁇ 1 mbar are set.
  • the polymers obtained can be adjusted to different molecular weights. These are preferably between 500 and 20,000.
  • catalysts known for transesterification reactions can be used as catalysts, such as, for example, titanates, mixtures of antimony trioxide and calcium acetate, stannanes, zinc acetate, etc.
  • titanates are fundamentally preferred because the reactions with these catalysts run faster and the products obtained have better color quality.
  • dialkyl carbonates are generally suitable for the production of the carbonate-modified polyesters or oligoesters, e.g. Dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-tert-butyl, di-n-pentyl, di-neo-pentyl carbonate, etc.
  • Unsymmetrical dialkyl carbonates and all mixtures of different dialkyl carbonsates can also be used.
  • the formed carbonate-modified poly / 01igoester are partially provided with different end groups.
  • Partially in this context means that the use of these end groups does not have to be stoichiometric, so that in the polymer mixture (distribution) obtained only a part of the polymer molecules is provided with end groups. x can therefore also take non-integer values as the mean.
  • the partial incorporation of end groups on the one hand has a regulating effect on the molecular weight, on the other hand it leads to the stabilization of the polymers obtained.
  • Viscous (flowable at room temperature), wax-like and solid polymers at room temperature can be produced via the choice and the ratio of the starting materials.
  • the claimed soil release polymers are particularly suitable as a component of detergent formulations and as a component of formulations in textile processing. Furthermore, they can also be used in laundry post-treatment agents, e.g. B. fabric softeners and because of their thickening effect can be used as a viscosity regulator.
  • the soil release polymers to be used are particularly effective if the fabric has already been washed or impregnated with them before they are soiled.
  • the carbonate-modified polyesters or oligoesters can be contained as an additive both in powdered and in liquid detergent formulations.
  • the amounts of soil release polymer used are, for example, 0.05 to 25% by weight, based on the particular formulation.
  • the amphiphilic polyesters or oligoesters are preferably used in phosphate-free and in phosphate-reduced detergents or in laundry aftertreatment agents, such as. B. fabric softener used.
  • the soil release polymers according to the invention are soluble in water or can be dispersed therein. They can be used in various forms in the manufacture of detergents, e.g. in the form of an aqueous solution, as a dispersion or as a powder.
  • soil release polymers according to the invention are obtained as solids, it is advantageous to incorporate them into the washing formulation in the form of pourable and free-flowing granules.
  • the reaction mixture was slowly heated to temperatures of 150 to 210 ° C and the methanol / ethanol mixture formed was collected.
  • the temperature was controlled in such a way that the amount of distilled, unreacted diethyl carbonate was kept as low as possible.
  • reaction mixture was cooled, the column removed, vacuum ( ⁇ 1 mbar) applied and the mixture heated up to a maximum of 210 ° C.
  • the diethylene glycol not reacted in the reaction was collected as a distillate.
  • Example 2 Analogously to Example 1, a total of 108.1 g (0.92 mol) of diethyl carbonate (from Aldrich), 1 290.0 g (0.83 mol) of polyethylene glycol with a weight-average molecular weight of 1,550 g / mol were used (Lipoxol 1550 from Huls AG), 582.6 g (3.0 mol) of dimethyl terephthalate, 636.7 g (6.0 mol) of diethylene glycol, 66 g of nonylphenol polyethylene glycol ether (5 E0) (0.15 mol) (Marlophen NP5 the Hüls AG), lg of 2,6-di-tert-butyl-p-cresol (Ionol from Shell) and 13 ml of tetraisopropyl orthotitanate under protective gas.
  • Diethyl carbonate from Aldrich
  • 290.0 g polyethylene glycol with a weight-average molecular weight of 1,550 g /
  • reaction mixture was again slowly heated up to temperatures of 150 to 210 ° C. C and catch the formed methanol / ethanol mixture practic ⁇ . 11
  • reaction mixture was cooled, the column removed, vacuum ( ⁇ 1 mbar) applied and the mixture heated up to a maximum of 210 ° C.
  • the diethylene glycol not reacted in the reaction was collected as a distillate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des polymères éliminant les salissures et destinés à des fibres contenant du polyester, correspondant à la formule brute (I): (CAP)x(T)z(I)q(CAR)r(DEG)s(En)t(A)y dans laquelle (CAP) represente des groupes terminaux qui ferment le polymère à l'extrémité; (T) représente un groupe arylènedicarbonyle et z est un nombre compris entre 1 et 50; (I) représente un groupe anionique interne et q un nombre compris entre 0 et 30; (CAR) représente un groupe carbonyle d'un motif carbonate et r est un nombre compris entre 1 et 80; (DEG) représente di(oxyéthlyèn)oxy et s est un nombre compris entre 1 et 80; (En) représente un groupe poly(oxyalkylèn)oxy constitué de 2 à 100 groupes oxyalkylène, t étant un nombre compris entre 0 et 25 et les groupes alkyle comportant 2 à 6 atomes de carbone; et (A) représente un groupe 1,n-alkylènedicarbonyle constitué de 2 à 24 atomes de carbone et y est un nombre compris entre 0 et 15, les oligo/polyester présentant un poids moléculaire de 500 à 100 000. Ces polymères éliminant les salissures peuvent être produits par réaction des différents composants monomères, en une seule étape. Ils sont utilisés en tant que constituants de formulations détersives, dans le traitement des textiles, en tant qu'additifs pour agents de traitement ultérieur et/ou en tant qu'agent de régulation de la viscosité.
PCT/EP1996/005833 1996-02-17 1996-12-24 Carbonates d'ester de polyether servant de polymeres eliminant les salissures dans des adjuvants detersifs et textiles WO1997030141A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996106012 DE19606012A1 (de) 1996-02-17 1996-02-17 Schmutzlösepolymere auf Basis von carbonat-modifizierten Poly- bzw. Oligoestern als Bestandteil von Formulierungen zur leichteren Ablösung von Öl- und Fettschmutz
DE19606012.5 1996-02-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021233987A1 (fr) 2020-05-20 2021-11-25 Clariant International Ltd Polyester anti-salissures, à utiliser dans des compositions de détergent

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267120A (en) * 1979-12-14 1981-05-12 Texaco Development Corp. Polyester polycarbonates
EP0066944A1 (fr) * 1981-05-14 1982-12-15 Ici Americas Inc. Composition anionique pour le traitement de matières textiles
EP0338396A2 (fr) * 1988-04-21 1989-10-25 BASF Corporation Agents tensio-actifs à base de polyalkylène carbonates
US5332860A (en) * 1993-06-29 1994-07-26 The Dow Chemical Company Polyols useful for preparing polyurethane foams having improved retention of insulative properties, polyurethane foams prepared therewith and methods for the preparation thereof
WO1995002029A1 (fr) * 1993-07-08 1995-01-19 The Procter & Gamble Company Compositions detersives a agents antisalissure
DE4417686A1 (de) * 1994-05-20 1995-11-23 Henkel Kgaa Endgruppenmodifizierte schmutzablösevermögende Polyester
JPH0859809A (ja) * 1994-08-18 1996-03-05 Mitsubishi Chem Corp 高重合度ポリエステルの製造方法
WO1997009369A1 (fr) * 1995-09-01 1997-03-13 HÜLS Aktiengesellschaft Polymeres antisalissures, a base de polycarbonates et utilises comme constituant de formulations destinees a enlever les huiles et graisses

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267120A (en) * 1979-12-14 1981-05-12 Texaco Development Corp. Polyester polycarbonates
EP0066944A1 (fr) * 1981-05-14 1982-12-15 Ici Americas Inc. Composition anionique pour le traitement de matières textiles
EP0338396A2 (fr) * 1988-04-21 1989-10-25 BASF Corporation Agents tensio-actifs à base de polyalkylène carbonates
US5332860A (en) * 1993-06-29 1994-07-26 The Dow Chemical Company Polyols useful for preparing polyurethane foams having improved retention of insulative properties, polyurethane foams prepared therewith and methods for the preparation thereof
WO1995002029A1 (fr) * 1993-07-08 1995-01-19 The Procter & Gamble Company Compositions detersives a agents antisalissure
DE4417686A1 (de) * 1994-05-20 1995-11-23 Henkel Kgaa Endgruppenmodifizierte schmutzablösevermögende Polyester
JPH0859809A (ja) * 1994-08-18 1996-03-05 Mitsubishi Chem Corp 高重合度ポリエステルの製造方法
WO1997009369A1 (fr) * 1995-09-01 1997-03-13 HÜLS Aktiengesellschaft Polymeres antisalissures, a base de polycarbonates et utilises comme constituant de formulations destinees a enlever les huiles et graisses

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ACS-REGISTRY-Nr. 25052-78-2 *
CHEMICAL ABSTRACTS, vol. 125, no. 2, 8 July 1996, Columbus, Ohio, US; abstract no. 11791, XP002029742 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021233987A1 (fr) 2020-05-20 2021-11-25 Clariant International Ltd Polyester anti-salissures, à utiliser dans des compositions de détergent

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DE19606012A1 (de) 1997-08-21

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