Classifications

• • 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
• • 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

Definitions

• the invention relates to so-called dirt-release polymers based on polycarbonates, which, as a component of formulations, contribute to the easier removal of oil and grease soiling, in particular in washing processes and in textile finishing.
• 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 it easier to handle these fibers 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 soil release polymers are polyesters based on terephthalic acid / polyoxyalkylene glycol / monomeric glycols.
• DE 14 69 403 describes a method for the surface-changing treatment of articles derived from polyesters.
• the fiber is coated by heat treatment with the polyester at temperatures of approximately 90 ° C., as a result of which the fabric undergoes a permanent surface treatment which, in addition to acting as a protective layer, also prevents the fabric from being statically charged.
• polyesters which contain the sodium salt of sulfoisophthalic acid as a further polymerization component.
• the polymerized polyethylene glycols (PEG) have molecular weights from 200 to 1,000 and, after their polymerization with ethylene glycol and terephthalic acid, give polyesters with molecular weights of 2,000 to 10,000.
• EP 0 319094 also claims the
• ET / POET copolymers as textile auxiliaries for the treatment of laundry in an automatic clothes dryer.
• Polyester is claimed to introduce branched monomeric glycol building blocks, such as. B. 1,2-propylene, 1,2-butylene, 3-methoxy-l, 2-propylene glycols (EP 0 241 985).
• 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 amide (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).
• EP 0 253 567 and EP 0 357 280 also describe in particular end-capped polyesters (capped polyesters) which, on the one hand, are formed by nonionic groups, such as, for example, B. C ⁇ - to C - alkyl, C ; - to C 4 -hydroxyalkyl and C : - to C 4 -acyl, and also to be closed 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.
• PET polyethylene terephthalate
• POET polyoxyethylene terephthalate
• Alkali metal polyacrylates at 70 to 150 ° C and subsequent pulverization (US 4,571,303, US 4,569,772).
• DE 37 27 727 emphasizes the use of PET obtained from waste bottles in the production of PET / POET copolymers.
• EP 0 456 569 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 40 01 415 claims the representation and use of a polyester as a graying-inhibiting and dirt-removing additive to powdery and liquid detergents.
• the polyesters are condensed by receive at least 2 carboxylic acids containing carboxylic acids with polyhydric alcohols.
• EO ethylene oxide
• PO propylene oxide
• EP 0 523 956 describes a detergent formulation which contains a water-soluble or water-dispersible copolymer which contains a UV-absorbing monomer.
• This dirt-dissolving polymer is produced by polycondensation of DMT (dimethyl terephthalate) with EG (ethylene glycol), PEG (molecular weight 200 to 3,000) and methyl 4-amine topzoate.
• a feature of the soil release polymers currently claimed is their insufficient water solubility or poor dispersibility in water. This means that such substances only partially pass into the wash liquor and thus have poor dirt-dissolving properties. Furthermore, the soil release polymers claimed so far are characterized by their firm consistency. This means that when they are later used in a formulation, they have to be packaged. H. the dirt-dissolving polymer obtained in the reaction process has to be ground, granulated or sprayed onto a carrier (eg sodium sulfate). Some of the soil release polymers are also offered as aqueous dispersions with the disadvantages of a low active content, the separation of solid particles during storage and the introduction of water when used in a detergent formulation.
• the object of the present invention was therefore the development of dirt-dissolving polymers without the described disadvantageous features and their use in particular in detergent formulations and in textile processing.
• polyesters based on polycarbonates do not have the disadvantages described.
• the present invention therefore relates to soil release polymers for fibers containing polyester, characterized in that the soil release polymers have the empirical formula I (CAP) (EG / PG) (T). (I), (CAR). (DEG) _. (En) f (I)
• Alkali in particular sodium, ammonium or substituted ammonium
• R for ethylene or mixtures of ethylene and propylene
• EG / PG for an oxyethyleneoxy or oxypropyleneoxy group or mixtures thereof and y for a number from 0 to 80
• (I) for an internal anionic group e.g. B. is in the form of its alkali, ammonium or substituted ammonium salt, and q is a number from 0 to 30,
• (En) is a poly (oxyalkylene) oxy 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 oxyalkylene groups contain 2 to 6 carbon atoms, and the 01igo / polyester molecular weights from 500 to 100,000.
• the values x, y, z, q, r, s and t can also assume non-integer values within the specified limits.
• Another object of the invention is the use of dirt-dissolving polymers as a component of detergent formulations and as a component of formulations in textile processing.
• the invention relates in particular to dirt-releasing dirt-release polymers with molecular weights of 500 to 20,000, which are flowable at room temperature and are composed of the monomers dimethyl terephthalate, dialkyl carbonate, diethylene glycol and polyethylene glycol.
• the polymers can also be sealed by end groups, in particular sulfobenzoyl groups (in the form, for example, of their alkali metal salt, in particular sodium salt).
• anionic groups primarily the sulfoisophthaloyl and there in particular the 5-sulfoisophthaloyl groups in the polymer structure, also in the form of, for. B. their alkali, especially sodium salt.
• the new polycarbonate-based polyesters or oligoesters which are the subject of this invention exhibit higher lightening rates when lightening oil-contaminated fabrics than comparable products of the prior art.
• the soil release polymers obtained are readily dispersible in water. Due to their flowable consistency, they have to be used e.g. B. not be packaged in a detergent formulation.
• the claimed protective release polymers can be prepared by conventional known polymerization processes.
• dialkyl carbonate e.g. B. dimethyl or diethyl carbonate, or mixtures of different dialkyl carbonates with di-, tri- or polyoxyethylene glycols in a molar ratio of 1.5: 1 to 1: 1.
• the alcohol formed during the transesterification is removed via a fractionation column.
• the temperature control of the reaction depends primarily on the boiling point of the dialkyl used carbonats. It must be ensured here that no large amounts of unreacted dialkyl carbonate over-distillate with the reaction alcohol obtained during the transesterification. Basically temperatures from approx. 80 to 250 ° C and pressures from normal pressure to 10 mbar are set.
• a so-called polycarbonate is obtained from alternating units of carbonate and glycol groups.
• the polycarbonates can be adjusted to different molecular weights. These are usually between 150 and 10,000.
• the polycarbonates are preferably adjusted to molecular weights of 200 to 5,000.
• the polycarbonate is reacted with dimethyl terephthalate and diethylene glycol at temperatures from 150 to 250 ° C. and pressures from normal pressure to 1 mbar.
• the molar feed ratio of DMT: polycarbonate is 100: 1 to 1: 100.
• other monomers can also be used, such as. B. methyl sulfobenzoate, by which the polymer chains are closed, and other glycol units, such as. B. ethylene glycol and / or propylene glycol.
• dimethyl sulfoisophthalate in a mixture with dimethyl terephthalate in this reaction step also proves to be advantageous with regard to the performance of the polymers obtained.
• Another possibility for producing the claimed polymers is the direct implementation of all of the monomer units in one step.
• the prerequisite for this is that no ethylene glycol or propylene glycol is used, since these form cyclic carbonates with the dialkyl carbonates, which do not react any further, provided that no acids (e.g. terephthalic acid) are used in this reaction step.
• the ratio of the terephthaloyl group T to the internal anionic group I is preferably 2: 1 to 8: 1.
• the direct implementation of all monomer units in one step can only be done using the dialkyl terephthalates d.
• the terephthalic acid diester can be carried out in the form of a transesterification, since in the presence of acids (for example terephthalic acid) the dialklycarbonates react with the release of carbon dioxide.
• Catalysts are used, such as. B. titanates, mixtures of antimony trioxide and calcium acetate, stannanes, zinc acetate etc. Titanates are, however, to be preferred in principle, since the reactions with these catalysts run faster and the products obtained have better color quality than when using the other catalysts mentioned.
• Antioxidants are also usually used in the transesterification reactions, which also contribute to better color quality of the products obtained.
• dialkyl carbonates are generally suitable for the production of the polycarbonates, such as, for example, B. dimethyl, diethyi, di-n-propyl, di-iso-propyl, di-n-butyl, di-tert-butyl, di-n-pentyl and di-neo-pentyl carbonate.
• B. dimethyl, diethyi, di-n-propyl, di-iso-propyl, di-n-butyl, di-tert-butyl, di-n-pentyl and di-neo-pentyl carbonate Unsymmetrical carbonic acid dialkyl esters and all conceivable mixtures of different carbonic acid dialkyl esters can also be used.
• the polycarbonate-01igo / polyester formed can be provided with different end groups.
• Preferred end groups are u. a. Sulfoaroyl groups, such as. B. the sulfobenzoyl group, which can be introduced in the form of a transesterification with alkyl sulfobenzoate.
• the 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.
• sulfoaroyl groups ethoxylated or propoxylated hydroxyethane and hydroxypropanesulfonates, as described, for example, in WO 95/02029 and WO 95/02030, can also be used.
• the claimed soil release polymers are particularly suitable as a component of detergent formulations and as a component of formulations in textile processing. Examples
• a total of 260.0 g (2.20 mol) of diethyl carbonate (from Aldrich) were placed in a 2 1 multi-necked flask with a glass stirrer, heating bath (oil), protective gas inlet, distillation attachment, packed column, distillation bridge, vacuum distributor, distillation flask, cold trap and internal thermometer.
• 800.0 g (2.00 mol) polyethylene glycol with a molecular weight of 400 g / mol Lipoxol 400 from Huls AG
• the reaction mixture was slowly heated up to approximately 150 ° C. and the ethanol 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 was removed, vacuum ( ⁇ 1 mbar) was applied and the mixture was heated up to a maximum of 220 ° C.
• the diethylene glycol not reacted in the reaction was collected as a distillate.
• Example 2 Analogously to Example 1, a total of 118.1 g (1.00 mol) of diethyl carbonate (Aldrich), 1,000.0 g (1.00 mol) of polyethylene glycol with a molecular weight of 1,000 g / mol (Lipoxol 1,000 the Hüls AG), 0.70 g of 2,6-di-tert-butyl-p-cresol (lonol from Shell) and 4 ml of tetraisopropyl orthotitanate under protective gas and reacted in the manner described above. After the intermediate product had reached a hydroxyl number of about 30 mg KOH / g, the reaction was stopped.
• the reaction was stopped. According to gel permeation chromatography, the product had a weight-average molecular weight of 4,700 g / mol.
• Example 3 In the apparatus described in Example 1, a total of 21.3 g (0.18 mol) of diethyl carbonate (Aldrich), 480.0 g (0.16 mol) of polyethylene glycol with a molecular weight of 3,000 g / mol (lipoxol 3,000 from Huls AG), 155.4 g (0.80 mol) of dimethyl terephthalate, 212.2 g (2.00 mol) of diethylene glycol, 0.35 g of 2,6-di-tert-butyl-p-cresol (lonol from Shell) and 4 ml of tetraisopropyl orthotitanate under protective gas and reacted in one step.
• Diethyl carbonate Aldrich
• 480.0 g (0.16 mol) of polyethylene glycol with a molecular weight of 3,000 g / mol lipoxol 3,000 from Huls AG
• 155.4 g (0.80 mol) of dimethyl terephthalate 212.2
• the reaction was stopped. According to gel permeation chromatography, the product had a weight average molecular weight of 8,410 g / mol.
• the soil release polymers were used with a concentration of 1% (active substance) in 2 detergent formulations.
• n-alkylbenzenesulfonate powder sodium salt 5 C13-0xoalcohol with 9 moles of ethylene oxide per mole of 4
• TAED tetraacetylethylenediamine
• n-alkylbenzenesulfonate powder sodium salt 25 mixed product of fatty alcohol polyalkylene glycol ether and coconut fatty acid salt 15
• test fabrics polyester fabric or cotton / polyester fabric from the Krefeld laundry research institute, WfK
• WfK Krefeld laundry research institute
• Rl remission of the washed tissue
• R2 remission of the oil-contaminated tissue
• R3 remission of the washed oil-contaminated tissue

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Life Sciences & Earth Sciences (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Detergent Compositions (AREA)
• Polyesters Or Polycarbonates (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)
• Lubricants (AREA)
• Cleaning In General (AREA)

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Cited By (10)

Citations (3)

• 1996
  • 1996-07-16 EP EP96925757A patent/EP0847412A1/de not_active Withdrawn
  • 1996-07-16 HU HU9802563A patent/HUP9802563A3/hu unknown
  • 1996-07-16 PL PL96325281A patent/PL325281A1/xx unknown
  • 1996-07-16 WO PCT/EP1996/003113 patent/WO1997009369A1/de not_active Application Discontinuation
  • 1996-07-16 JP JP9510798A patent/JPH11512136A/ja not_active Ceased
  • 1996-07-16 TR TR1998/00343T patent/TR199800343T1/xx unknown
  • 1996-07-16 SK SK241-98A patent/SK24198A3/sk unknown

Patent Citations (3)

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