WO1997009369A1

WO1997009369A1 - Soil-releasing polymers made from polycarbonates and used as a component of formulations for removing oil and grease

Info

Publication number: WO1997009369A1
Application number: PCT/EP1996/003113
Authority: WO
Inventors: Herbert Koch; Wulf Ruback
Original assignee: HÜLS Aktiengesellschaft
Priority date: 1995-09-01
Filing date: 1996-07-16
Publication date: 1997-03-13
Also published as: HUP9802563A2; JPH11512136A; TR199800343T1; HUP9802563A3; SK24198A3; PL325281A1; EP0847412A1

Abstract

The invention concerns dirt-releasing polymers with molecular weights from 500 to 20,000 which are free-flowing at room temperature and made up essentially of dimethyl terephthalate, dialkyl, carbonate, dialkylene glycol and polyalkylene glycol monomers. The polymer chains can be closed off by terminal groups, in particular by sulphobenzoyl groups.

Description

Soil release polymers based on polycarbonates as part of formulations to remove oil and grease dirt

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) is significantly improved in 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 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 polyesters produced are composed of ET and POET units (ET = ethylene terephthalate, POET = polyoxyethylene terephthalate) with ET: POET = 2 to 6: 1, polyethylene glycols with molecular weights of 1,000 to 4,000 being used. 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. In US 4427 557 and EP 0066944 anionic modifications of the above polyesters are described 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.

US 3 959 230 claims ET / POET polyester with ET: POET = 25: 75 to 35: 65, low molecular weight polyethylene glycols with molecular weights of 300 to 700 being used and the polyesters obtained having molecular weights of 25,000 to 55,000.

In addition to the effect as a soil release polymer, EP 0 319094 also claims the

Use of ET / POET copolymers as textile auxiliaries for the treatment of laundry in an automatic clothes dryer. In particular, the

Advantages of the antistatic properties of the laundry treated with soil release polymers have been highlighted.

As an inexpensive assembly of the soil release polymers, d. H. 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 washing liquor. Various fiber systems, such as Nylon or a so-called Reemay fiber.

As a further variation of the above. 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 (WO 92/06152) 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.

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

Through the storage of the soil release polymers together with alkaline detergent components, the soil release polymers experience activity losses which can be attributed to hydrolysis of the polyester bonds. This can be counteracted by melting PET / POET copolymers together

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

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.

It has now surprisingly been found that 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)

are described in the

(CAP) for end groups which close the polymer at the end and a.) Sulfoaroyl groups,

b.) Groups with the formula M0 _J -S- (0) _j - (CH_) _r - (R0) -, in which M for a -

Alkali, in particular sodium, ammonium or substituted ammonium, R for ethylene or mixtures of ethylene and propylene, u for

0 or 1, p represents 0 or 1 and v represents a number from 1 to 100, c.) Poly (oxyethylene) monoalkyl ether groups in which the alkyl group 1 to

Contains 6 carbon atoms and the polyoxyethylene group consists of 2 to 200 oxyethylene units, or d.) Mixtures thereof

and x for a number from 0 to 2,

(EG / PG) for an oxyethyleneoxy or oxypropyleneoxy group or mixtures thereof and y for a number from 0 to 80,

(T) for a terephthaloyl group and z for a number from 1 to 50,

(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,

(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, and

(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.

In the empirical empirical formula, 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). Also advantageous is the incorporation of 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.

Surprisingly, it was found that 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.

It has been shown to be advantageous in the first part of the reaction to 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. In this reaction, 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.

In the second part of the reaction, 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. In this step, 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. 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.

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.

In principle, the direct implementation of all monomer units in one step can only be done using the dialkyl terephthalates d. H. 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.

All known for transesterification reactions can be used as catalysts 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.

A number of different 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. Unsymmetrical carbonic acid dialkyl esters and all conceivable mixtures of different carbonic acid dialkyl esters 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 during the production of the polycarbonates by transesterification can be easily removed from the reaction mixture by distillation.

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. In addition to sulfoaroyl groups, ethoxylated or propoxylated hydroxyethane and hydroxypropanesulfonates, as described, for example, in WO 95/02029 and WO 95/02030, can also be used.

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

The claimed soil release polymers are particularly suitable as a component of detergent formulations and as a component of formulations in textile processing. Examples

Example 1;

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), 0.35 g 2,6-di-tert-butyl-p-cresol (lonol from Shell ) and 2 ml of tetraisopropyl orthotitanate under protective gas.

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.

At the end of the reaction, a vacuum of about 30 mbar was applied for about 30-40 minutes.

After the intermediate product had reached a hydroxyl number of about 50 mg KOH / g, the reaction was stopped.

In the second step, 450.0 g of the intermediate described above, 194.2 g (1.00 mol) of dimethyl terephthalate, 212.2 g (2.00 mol) of diethylene glycol, 0.35 g of 2,6-di-tert Weighed.-butyl-p-cresol (lonol from Shell) and 2 ml of tetraisopropyl orthotitanate in the apparatus described under protective gas. The reaction mixture was slowly brought to max. Heated 210 ° C and collected the methanol formed.

After the majority of the theoretically expected amount of methanol had been collected, the 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.

After the product had reached a hydroxyl number of about 30 mg KOH / g, the reaction was stopped. After gel permeation chromatography, the product had a weight average molecular weight of 6,390 g / mol. 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.

In the second step, 450.0 g of the intermediate product described above, 194.2 g (1.00 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 2 ml of tetraisopropyl orthotitanate in the apparatus described.

After the product reached a hydroxyl number of 39 mg KOH / g, 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.

After the product reached a hydroxyl number of 22 mg KOH / g, the reaction was stopped. According to gel permeation chromatography, the product had a weight average molecular weight of 8,410 g / mol.

Washing attempts with the addition of polymer on oil-soiled fabrics

The soil release polymers were used with a concentration of 1% (active substance) in 2 detergent formulations.

Detergent formulation I (in%)

n-alkylbenzenesulfonate powder, sodium salt 5 C13-0xoalcohol with 9 moles of ethylene oxide per mole of 4

Powder soap (industrial soap LIGA MUH) 4

Zeolite WESSALITH P 30

Sodium meta-silicate 3 sodium perborate 15

TAED (tetraacetylethylenediamine) 2

Soil release polymer 1 residue 100% sodium bicarbonate

Detergent formulation II (in%)

n-alkylbenzenesulfonate powder, sodium salt 25 mixed product of fatty alcohol polyalkylene glycol ether and coconut fatty acid salt 15

Ethanol 8

Soil release polymer 1 rest 100% water

The test fabrics (polyester fabric or cotton / polyester fabric from the Krefeld laundry research institute, WfK) were first washed with the formulations described and, after drying, the reflectance values were measured. Then they were soiled with 5 drops of used engine oil. After an exposure time of approx. 18 h, the remission of the soiled pieces of tissue was determined. After another wash with the appropriate formulations, the remission values were finally determined again.

Was washed in Lini-Test laboratory washing machines.

Wash temperature 40 ° C

Washing time 30 minutes

Water hardness 13 ° dH

Detergent concentration 5 g t.q./l liquor ratio approx. 1:83

The following formula was used to calculate the brightening in%: (R3-R2)

Recovery [%] = x 100 (R1-R2)

Rl = remission of the washed tissue

R2 = remission of the oil-contaminated tissue

R3 = remission of the washed oil-contaminated tissue

table

Claims

Claims:

1. dirt-release polymers for fibers containing polyester, characterized in that the dirt-release polymers by the empirical formula I

(CAP) _x (EG / PG) _y (T) ₂ (I) _q (CAR) _r (DEG) _s (En) _t (I)

are described in the

(CAP) for end groups which close the polymer at the end and a.) Sulfoaroyl groups, b.) Groups with the formula M0 ₃ -S- (0) _u - (CH ₂ ) _p - (R0) _v -, in which M for a - alkali, ammonium or substituted ammonium ion, in particular sodium ion, R for ethylene or mixtures of ethylene and propylene, u for 0 or 1, p for 0 or 1 and v for a number from 1 to 100, c .) Poly (oxyethylene) monoalkyl ether groups in which the alkyl group contains 1 to 6 carbon atoms and the polyoxyethylene group consists of 2 to 200 oxyethylene units, or d.) Mixtures thereof

and x for a number from 0 to 2,

(T) for a terephthaloyl group and z for a number from 1 to 50,

(I) for an internal anionic group in the form of its alkali, ammonium or substituted ammonium salt 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, and (En) for 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, stands,

and wherein the 01igo / polyester have molecular weights from 500 to 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.

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 (I) means the sodium salt of the 5-sulfoisophthaloyl group.

5. soil release polymers according to at least one of claims 1 to 4, characterized in that (CAP) means the sodium salt of the sulfobenzoyl group.

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

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

8. soil release 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. are.

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

10. soil release polymers according to at least one of claims 1 to 9, characterized in that they are flowable at room temperature.

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

12. Use of the soil release polymers according to at least one of claims 1 to 10 as a constituent of formulations in textile processing.