Polyesters

Abstract

Polyesters according to the following formula (I) are described ##STR00001##
wherein R.sup.1 and R.sup.2 independently of one another are X—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein X is C.sub.1-4 alkyl, the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group or are HO—(C.sub.3H.sub.6), n is based on a molar average a number of from 12 to 120, m is based on a molar average a number of from 1 to 10, and a is based on a molar average a number of from 4 to 9. The inventive polyesters have an advantageous stability in alkaline environment, possess a beneficial solubility and advantageously are clearly soluble in alkaline compositions such as alkaline heavy duty washing liquids and also possess advantageous soil release properties.

Claims

1. A polyester according to the following formula (I) ##STR00012## wherein R.sup.1 and R.sup.2 independently of one another are X—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein X is C.sub.1-4 alkyl, the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is a number of from 40 to 50, m is a number of from 1 to 10, and a is a number of from 5 to 8 and wherein n, m, and a are based on a molar average.

2. The polyester according to claim 1, wherein R.sup.1 and R.sup.2 independently of one another are H.sub.3C—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is a number of from 40 to 50, m is a number of from 1 to 7, and a is a number of from 5 to 8.

3. The polyester according to claim 1, wherein a is a number of from 6 to 7.

4. The polyester according to claim 1, wherein m is a number of from 2 to 5.

5. The polyester according to claim 1, wherein n is a number of from 43 to 47.

6. The polyester according to claim 5, wherein n is a number of from 44 to 46.

7. The polyester according to claim 6, wherein n is 45.

8. The polyester according to claim 1, wherein R.sup.1 and R.sup.2 independently of one another are H.sub.3C—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is a number of from 44 to 46, m is 2, and a is a number of from 5 to 8.

9. The polyester according to claim 8, wherein n is 45, and a is a number of from 6 to 7.

10. The polyester according to claim 1, wherein R.sup.1 and R.sup.2 independently of one another are H.sub.3C—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is a number of from 44 to 46, m is 5, and a is a number of from 5 to 8.

11. The polyester according to claim 10, wherein n is 45, and a is a number of from 6 to 7.

12. A process for the preparation of a polyester according to claim 1, comprising the step of heating dimethyl terephthalate, 1,2-propylene glycol, and X—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m—OH, wherein X is C.sub.1-4 alkyl and preferably methyl, the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to the hydroxyl group —OH and n and m are as defined in claim 1, with the addition of a catalyst, to temperatures of from 160 to 220° C., firstly at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240° C.

Description

Example I

(1) TABLE-US-00001 Amount Amount Raw Material [g] [mol] [Abbreviation] 101.95 0.53 DMT 84.0 1.104 PG 343.5 0.15 H.sub.3C—(OC.sub.2H.sub.4).sub.45—(OC.sub.3H.sub.6).sub.5—OH 0.5 0.0061 NaOAc 0.2 0.0007 IPT

(2) An inventive polyester according to formula (I) is obtained wherein R.sup.1 and R.sup.2 are H.sub.3C—(OC.sub.2H.sub.4).sub.n—(OC.sub.3H.sub.6).sub.m wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is based on a molar average 45, m is based on a molar average 5, and a is based on a molar average a number of from 6 to 7.

Example II

(3) TABLE-US-00002 Amount Amount Raw Material [g] [mol] [Abbreviation] 101.95 0.53 DMT 84.0 1.104 PG 317.4 0.15 H.sub.3C—(OC.sub.2H.sub.4).sub.45—(OC.sub.3H.sub.6).sub.2—OH 0.5 0.0061 NaOAc 0.2 0.0007 IPT

(4) An inventive polyester according to formula (I) is obtained wherein R.sup.1 and R.sup.2 are H.sub.3C—(OC.sub.2H.sub.4)—(OC.sub.3H.sub.6).sub.m wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n is based on a molar average 45, m is based on a molar average 2, and a is based on a molar average a number of from 6 to 7.

Example III

Comparative Example

(5) TABLE-US-00003 Amount Amount Raw Material [g] [mol] [Abbreviation] 44.7 0.23 DMT 38 0.50 PG 301.1 0.14 H.sub.3C—(OC.sub.2H.sub.4).sub.45—(OC.sub.3H.sub.6).sub.2—OH 0.5 0.0061 NaOAc 0.2 0.0007 IPT

(6) A comparative polyester of formula (I′) is obtained

(7) ##STR00010##
wherein R.sup.1′ and R.sup.2′ are H.sub.3C—(OC.sub.2H.sub.4).sub.n′—(OC.sub.3H.sub.6).sub.m′ wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n′ based on a molar average is 45, m′ based on a molar average is 2, and a is based on a molar average a number of from 2 to 3.

Example IV

Comparative Example

(8) TABLE-US-00004 Amount Amount Raw Material [g] [mol] [Abbreviation] 101.95 0.53 DMT 84.0 1.1 PG 206.0 0.1 H.sub.3C—(OC.sub.2H.sub.4).sub.45—(OC.sub.3H.sub.6).sub.2—OH 0.5 0.0061 NaOAc 0.2 0.0007 IPT

(9) A comparative polyester of formula (I′) is obtained

(10) ##STR00011##
wherein R.sup.1′ and R.sup.2′ are H.sub.3C—(OC.sub.2H.sub.4).sub.n′—(OC.sub.3H.sub.6).sub.m′ wherein the —(OC.sub.2H.sub.4) groups and the —(OC.sub.3H.sub.6) groups are arranged blockwise and the block consisting of the —(OC.sub.3H.sub.6) groups is bound to a COO group, n′ based on a molar average is 45, m′ based on a molar average is 2, and a based on a molar average is a number of approximately 10.
Stability Test in Detergent Formulation

(11) 1 wt.-% (based on the total weight of the detergent formulation) of the polyesters of Examples I to IV and of the commercially available soil release polymer “TexCare SRN100” was used in a detergent formulation (the composition of the detergent formulations is given in Table A below) and the pH value was set with caustic to pH 8.2. The turbidity of the 5 formulations was determined. The prepared formulations were stored at 60° C. for 8 days. Afterwards, the hydrolysis of the polyesters was determined and compared to the hydrolysis of the commercially available soil release polymer “TexCare SRN100” by GPC analysis. The results are given in Table B below.

(12) TexCare SRN100 is a polyester comprising —OOC-(1,4-phenylene)-COO— structural units and —O—CH.sub.2CH.sub.2—O— structural units.

(13) TABLE-US-00005 TABLE A Detergent formulation Ingredient wt.-% MPG 15.00 TEA 4.18 NI 7EO 7.28 LAS acid 4.85 SLES 3EO 2.42 Empigen ® BB 0.86 Prifac 5908 0.86 EPEI 3.14 Perfume 1.39 Polyester (selected from the polyesters of 1.00 Examples I to IV and TexCare SRN100) Demineralized water and NaOH to adjust ad 100 to pH 8.2

(14) Key to ingredients used: MPG is mono propylene glycol. TEA is triethanolamine. NI 7EO is C.sub.12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals). LAS acid is C.sub.12-14 linear alkylbenzene sulphonic acid. SLES 3EO is sodium lauryl ether sulphate with 3 moles EO. Empigen® BB is Cocobetaine ex Huntsman. Prifac® 5908 is saturated lauric fatty acid ex Croda. EPEI is Sokalan HP20—ethoxylated polyethylene imine cleaning polymer: PEI(600) 20EO ex BASF. Perfume is free oil perfume. TexCare SRN100 is soil release polymer ex Clariant.

(15) TABLE-US-00006 TABLE B Turbidity of formulation comprising polyester and stability of polyester therein Polyester Turbidity Degree of Hydrolysis TexCare SRN100 clearly soluble 100% Example I (inventive) clearly soluble 45% Example II (inventive) clearly soluble 48% Example III (comparative) clearly soluble 72% Example IV (comparative) turbid 42% %-values for polyesters of Examples I to IV in comparison/relation to TexCare SRN100.
Soil Release Test:

(16) The polyesters of Examples I and II were tested for their soil release performance according to the “Dirty-Motor Oil” Test (DMO-Test).

(17) The polyesters of Examples I and II were used in concentrations of 1 wt.-% (based on the total weight of the detergent formulation used) and the formulations were stored according to the stability test. The formulations were those described above for the stability test. As test fabric a white polyester standard fabric (30A) was used. The prewashed fabrics (the fabrics were prewashed with the stored detergent formulations comprising the polyesters of Examples I and II) were soiled with dirty motor oil. After 1 h the soiled fabrics were washed again with the stored detergent formulations comprising the polyesters of Examples I and II. The washing conditions for the “prewash” and for the washing procedure after soiling with dirty motor oil were as given in Table C.

(18) TABLE-US-00007 TABLE C Washing conditions Washing machine Linitest Hardness of water 15 °H Washing temperature 40° C. Washing time 30 min Detergent concentration 6 g/L

(19) The washing results obtained for the stored formulations comprising the polyesters of Examples I and II are shown in Table D. Table D also shows the washing result obtained for a detergent formulation comprising 1 wt.-% of TexCare SRN100. The composition of this detergent formulation comprising TexCare SRN100 was as described above for the stability test. In case of TexCare SRN100 the conditions for the “prewash” and for the washing procedure after soiling were similar to the conditions used for the detergent formulations comprising the polyesters of Examples I and II but with the exception that in case of TexCare SRN100 the “prewash” and the washing procedure after the soiling of the fabrics with dirty motor oil was done using “fresh” detergent formulation (no alkaline storage).

(20) TABLE-US-00008 TABLE D Test results (washing performance) results for “fresh” formulation Polyester or after storage Washing Performance TexCare SRN100 fresh 100% Example I after storage 96% Example II after storage 107%

(21) The present invention resulted from work undertaken under a joint research agreement between Clariant International Ltd. and Unilever UK Central Resources Limited in the field of polyester soil release polymers and their uses in detergent compositions.