WO1997030141A1

WO1997030141A1 - Polyetherestercarbonate as dirt dissolving polymers in washing and textile adjuvants

Info

Publication number: WO1997030141A1
Application number: PCT/EP1996/005833
Authority: WO
Inventors: Herbert Koch
Original assignee: HÜLS Aktiengesellschaft
Priority date: 1996-02-17
Filing date: 1996-12-24
Publication date: 1997-08-21
Also published as: DE19606012A1

Abstract

Dirt dissolving polymers for fibers containing polyester are corresponding to the total formula (I): (CAP)x(T)z(I)q(CAR)r(DEG)s(En)t(A)y in which (CAP) represents end groups which close off the polymer at the end, (T) means an arylene dicarbonyl group and z a number from 1 - 50, (I) means an internal anionic group and q a number form 0 - 30, (CAR) means a carbonyl group of a carbonate unit and r a number from 1 - 80, (DEG) means a poly(oxyethylene)oxy group which is composed of from 2 to 100 oxyalkylene groups and where t is a number from 0 - 25 and the alkyl groups contain 2 to 6 C atoms, and (A) means a 1,n alkylene dicarbonyl group which is composed of 2 to 24 C atoms and where y is a number from 0 - 15, and where the oligo/polyesters have molecular weights from 500 to 100 000. The dirt dissolving polymer can be prepared in one stage by reaction of the various monomer components. The dirt dissolving polymers are used as components in detergent formulations in textile treatment and as an additive in after-treatment agents and/or as a viscosity control agent.

Description

POLYETHERESTER CARBONATES AS DIRT SOLVING POLYMERS IN DETERGENTS AND TEXTILES

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) is significantly improved with the hydrophobic fabrics treated with 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. The polyesters produced are composed of ethylene terephthalate units (ET) with ET: POET = 2-6: 1, polyethylene glycols with molecular weights of 1,000-4,000 being used (POET-polyoxyethylene terephthalate). The fiber is coated by heat treatment with the polyester at temperatures of approx. 90 ° C, which gives the fabric a permanent surface treatment, which, in addition to acting as a protective layer, also prevents the fabric from being statically charged. In US-A-4427 557 and EP-A-0066944 anionic modifications of the above-mentioned polyesters are described 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.

US-A-3959230 claims ET / POET polyester with ET: POET = 25: 75-35: 65, low molecular weight polyethylene glycols with molecular weights of 300-700 being used and the resulting polyester having molecular weights of 25,000-55,000.

In addition to its effectiveness as a soil release polymer, 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.

As an inexpensive assembly of the dirt-dissolving polymers, i.e. US Pat. No. 4,740,326 describes a "coating" on a water-insoluble carrier as a method for introducing soil release polymers into an aqueous formulation or into the wash liquor. Various fiber systems, such as Nylon or a so-called Reemay fiber. As a further variation of the above Polyester is claimed to incorporate branched monomeric glycol building blocks, such as 1,2-propylene, 1,2-butylene and 3-methoxy-1,2-propylene glycols (EP-A-0241 985).

The performance of the soil release polymers used (WO 92/06152) 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).

In EP-A-0 253 567 and EP-A-0357 280 in particular also 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.

According to DE-A-34 11 941, 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-33 24 258 describes the dissolving or dispersing of a PET / POET polyester with PET: POET = 2-6: 1 in a liquid, nonionic surfactant and spraying this as a further form of assembling dirt-dissolving polymers Mix on a builder (PET polyethylene terephthalate).

Storage of the dirt-release polymers together with alkaline detergent components causes them to lose activity which can be attributed to hydrolysis of the ester bonds. This can be counteracted by melting PET / POET copolymers with alkali metal polyacrylates at 70-150 ° C. and subsequent pulverization (US Pat. No. 4,571,303, US Pat. No. 4,569,772).

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. In addition, alkoxylated polyvalent Alcohols are used, which are obtained by the addition of 5 - 80 mol ethylene oxide (EO) and / or propylene oxide (PO). The products are characterized by improved effectiveness and better compatibility with liquid and powder detergent formulations.

EP-A-0 523 956 describes a detergent formulation which contains a water-soluble or water-dispersible copolymer which contains a UV-absorbing monomer. This dirt-release polymer is produced by polycondensation of DMT with EG, PEG (molecular weight 200 - 3,000) and methyl 4-aminobenzoate (DMT = dimethyl terephthalate).

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.

The object is achieved according to the invention with amphiphilic carbonate-modified polyesters or oligoesters with a random structure, which can be described by the following empirical empirical formula:

(CAP) (T) (I) (CAR) (DEG) (Enh (A) x z q r s t y

in the

(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

Contains carbon atoms and in which the polyoxyalkylene group consists of 2 to 200 oxyalkylene units, d.) Poly (oxyalkylene) monoalkylphenol ethers in which the alkyl group 6 to

Contains 18 carbon atoms and in which the polyoxyalkylene group

0 to 80 oxyalkylene units, or e.) Mixtures thereof

and x for values greater than 0 to 2,

(T) for an arylene dicarbonyl group and z for a number from 1-50,

(I) for an internal anionic group and q for a number from 0 to 30, (CAR) for a carbonyl group of a carbonate unit and r for a number from 1 to 80,

(DEG) for di (oxyethylene) oxy and s for a number from 1 to 80,

(En) for a poly (oxyalkylene) oxy, in particular poly (oxyethylene) 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 alkyl groups contain 2 to 6 C atoms, and

(A) for an l, n-alkylenedicarbonyl group which is built up from 2 to 24 carbon atoms and y represents a number from 0 to 15

and wherein the oligo- / polyester molecular weights are from 500 to 100,000.

In the empirical empirical formula, the values x, z, q, r, s, t and y can also assume non-integer values within the specified limits.

It has been found to be particularly advantageous if y = 0 and the ratio z: q = 2: 1 to 8: 1.

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. In principle, due to their thickening effect, such 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.

In the empirical empirical formula, the ester unit on which the radical (T) = arylenedicarbonyl group is based is preferably selected from dialkyl terephthalate, isophthalate and dialkyl phthalate, mixtures of these components also being possible, of course.

In principle, aliphatic diesters can also be used as monomer units. The aliphatic diesters on which the group (A) = 1, n-alkylenedicarbonyl group is based are preferably selected from: malonic, succinic, fumaric, maleic, glutaric, adipic, pimelic, suberic, azelaic and Dialkyl esters of sebacic acid.

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. In general, 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 (CAP) 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.

The following are typical representatives of 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.

Further end groups of the soil release polymers according to the invention are poly (oxyalkylene) monoalkylphenol ethers, which are claimed, for example, in DE-A-4001 415.

Surprisingly, it has been found that the new carbonate-modified polyesters or oligoesters which are the subject of this invention show 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.

The claimed soil release polymers can be produced by simple polymerization processes.

To produce the polymers according to the invention, the monomeric building blocks are preferably reacted in a reaction mixture. In principle, 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.

All 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. However, titanates are fundamentally preferred because the reactions with these catalysts run faster and the products obtained have better color quality.

A number of different 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. However, preference is given to using dimethyl carbonate and diethyl carbonate or mixtures of these two carbonic acid diesters because the alcohols (methanol and ethanol) formed in the preparation of the polycarbonate-modified polyesters or oligoesters can be easily removed from the reaction mixture by distillation.

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.

The use of 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.

Depending on the choice of monomers (internal anionic groups (I)), both anionic and nonionic soil release polymers are 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.

If the 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.

In principle, it is also possible to spray a solution or a dispersion of the dirt-releasing active ingredient in nonionic surfactant onto a builder-containing detergent particle.

example 1

A total of 60.25 g (0.51 mol) of diethyl carbonate (Aldrich) were placed in a 4 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. 1,350 g (0.45 mol) of polyethylene glycol with a weight-average molecular weight of 3,000 g / mol (Lipoxol 3,000 from Huls AG), 582.6 g (3.00 mol) of dimethyl terephthalate, 955.0 g (9 , 0 mol) diethylene glycol, 75 g C ₁₂ -C ₁₄ fatty alcohol polyethylene glycol ether (7 E0) (0.15 mol) (Marlipal 24/70 from Huls AG), lg 2,6-di-tert-butyl-p -cresol (Shell's Ionol) and 14.0 ml of tetraisopropyl orthotitanate are introduced under a protective gas.

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.

After most of the theoretically expected amount of methanol / ethanol had been collected, the 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.

After the product had reached a hydroxyl number of about 18-25 mg KOH / g substance, the reaction was stopped.

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.

The reaction mixture was again slowly heated up to temperatures of 150 to 210 ^{° C.} C and catch the formed methanol / ethanol mixture aufge¬. 11

After most of the theoretically expected amount of methanol / ethanol had been collected, the 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.

After the product had reached a hydroxyl number of about 22-27 mg KOH / g substance, the reaction was stopped.

Claims

Claims:

1. soil release polymers for fibers containing polyester, characterized in that the soil release polymers by the empirical empirical formula (I)

(CAP) _χ (T) _z (I) _q (CAR) _r (DEG) _s (En) _t (A) _y (I)

are described in the

(CAP) represents end groups which seal the polymer at the end and which independently of one another a.) Acyl and aroyl groups with 4 to 40 carbon atoms, b.) Hydroxyacyl and hydroxyaroyl groups with 2 to 25 carbon atoms c.) Poly (oxyalkylene) monoalkyl ethers in which the alkyl group contains 7 to 24 carbon atoms and in which the polyoxyalkylene group consists of 2 to 200 oxyalkylene units, d.) poly (oxyalkylene) monoalkylphenol ethers in which the alkyl group contains 6 to 18 carbon atoms and in which the polyoxyalkylene group consists of 0 up to 80 oxyalkylene units, or e.) mixtures thereof

and x for values greater than 0 to 2,

(T) for an arylene dicarbonyl group and z for a number from 1-50,

(I) for an internal anionic group and q for a number from 0 to 30,

(CAR) for a carbonyl group of a carbon unit and r for a number from 1 to 80,

(DEG) for di (oxyethylene) oxy and s for a number from 1 to 80,

(En) for a poly (oxyalkylene) oxy group which is composed of 2 to 100 oxyalkylene lefts, where t is a number from 0-25 and the alkyl groups contain 2 to 6 carbon atoms, and

(A) for an l, n-alkylenedicarbonyl group which is composed of 2 to 24 carbon atoms and y is a number from 0 to 15, and the oligo- / polyester molecular weights of 500 to

Own 100,000.

2. soil release polymers according to claim 1, characterized in that the soil release polymers have molecular weights from 500 to 20,000 zen.

3. soil release polymers according to at least one of claims 1 or 2, characterized in that (en) stands for a poly (oxyethylene) oxy group.

4. soil release polymers according to at least one of claims 1 to 3, characterized in that (T) stands for a terephthaloyl group.

5. soil release polymers according to at least one of claims 1 to 4, characterized in that (I) stands for the sodium salt of the 5-sulfoisophthaloyl group.

6. soil release polymers according to at least one of the preceding claims, characterized in that q and y are 0.

7. dirt-dissolving polymers according to at least one of the preceding claims, characterized in that the poly (oxyethylene) oxy groups are composed of 4 to 50 oxyethylene units.

8. soil release polymers according to at least one of the preceding claims, characterized in that y = 0 and the ratio z: q is 2: 1 to 8: 1.

9. Process for the preparation of the soil release polymers according to one of the preceding forthcoming claims, characterized in that the production takes place by reacting the various Monomerbau¬ blocks in a reaction mixture.

10. Use of the soil release polymers according to at least one of claims 1 to 8 as a component of detergent formulations.

11. Use of the soil release polymers according to at least one of claims 1 to 8 as a component of formulations in textile processing, as an additive for laundry aftertreatment agents and / or as a viscosity regulator.