Renewably Sourced Soil Release Polyesters

Abstract

A renewably sourced soil release polyester

comprising two or more structural units (a1), one or more structural units (a2) and either one or two terminal structural groups (a3)

##STR00001##

wherein G.sup.1 is one or more (OC.sub.nH.sub.2n) with n being a number of from 2 to 10, preferably from 2 to 6 and more preferably (OC.sub.2H.sub.4), (OC.sub.3H.sub.6), (OC.sub.4H.sub.8) or (OC.sub.6H.sub.12), R.sup.1 is a C.sub.1-30 alkyl, preferably C.sub.1-4 alkyl and more preferably methyl, p is, based on a molar average, a number of from 1 to 200, preferably from 2 to 150 and more preferably from 3 to 120, q is, based on a molar average, a number of from 0 to 40, preferably from 0 to 30, more preferably from 0 to 20, and most preferably from 0 to 10,
where the (OC.sub.3H.sub.6)- and (OC.sub.2H.sub.4)-groups of the terminal group (a3) may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically, either of the groups (OC.sub.3H.sub.6) and (OC.sub.2H.sub.4) can be linked to R.sup.1 and O, adjacent structural units (a1) are connected by the structural unit (a2), in the case that only one terminal group (a3) is present in the polymer, the other terminal group is selected from the group consisting of OH, OCH.sub.3, and G.sup.1OH and both terminal groups may be only linked to a structural unit (a1).

Claims

1. A polyester comprising two or more structural units (a1), one or more structural units (a2) and either one or two terminal structural groups (a3) ##STR00013## wherein G.sup.1 is one or more (OC.sub.nH.sub.2n) with n being a number of from 2 to 10, R.sup.1 is a C.sub.1-30 alkyl, p is, based on a molar average, a number of from 1 to 200, q is, based on a molar average, a number of from 0 to 40, where the (OC.sub.3H.sub.6)- and (OC.sub.2H.sub.4)-groups of the terminal group (a3) may be arranged blockwise, alternating, periodically and/or statistically, either of the groups (OC.sub.3H.sub.6) and (OC.sub.2H.sub.4) can be linked to R.sup.1 and O, adjacent structural units (a1) are connected by the structural unit (a2), in the case that only one terminal group (a3) is present in the polymer, the other terminal group is selected from the group consisting of OH, OCH.sub.3, and G.sup.1OH and both terminal groups may be only linked to a structural unit (a1).

2. The polyester according to claim 1, characterized in that the sum of p and q, based on a molar average, is a number of from 5 to 150.

3. The polyester according to claim 1, characterized in that R.sup.1 is methyl.

4. The polyester according to claim 1, characterized in that G.sup.1 is (OC.sub.2H.sub.4) or (OC.sub.3H.sub.6).

5. The polyester according to claim 1, characterized in that it additionally comprises one or more structural units (a4), which may be indirectly linked to structural units (a1) or other structural units (a4) via the structural units (a2), or directly linked to a terminal group: ##STR00014##

6. The polyester according to claim 1, characterized in that the average molecular weight (M.sub.w) is from 2000 to 20000 g/mol.

7. The polyester according to claim 1, characterized in that the average number of structural units (a1) is from 2 to 60.

8. The polyester according to claim 1, characterized in that the total amount of terminal group (a3), based on the total weight of the polyester, is at least 40 wt. %.

9. The polyester according to claim 1, characterized in that the total amount of repeating structural units (a1) and (a2) and of terminal group (a3), based on the total weight of the polyester, is at least 50 wt. %.

10. The polyester according to claim 5, characterized in that the amount of structural units (a4), based on the total weight of the polyester, is from 0.1 wt.-% to 50 wt.-%.

11. The polyester according to claim 1, characterized in that the structural units are exclusively selected from the group consisting of structural units (a1) and (a2).

12. A process for the preparation of a polyester comprising two or more structural units (a1), one or more structural units (a2) and either one or two terminal structural groups (a3) ##STR00015## wherein G.sup.1 is one or more (OC.sub.nH.sub.2n) with n being a number of from 2 to 10, R.sup.1 is a C.sub.1-30 alkyl, p is, based on a molar average, a number of from 1 to 200, q is, based on a molar average, a number of from 0 to 40, where the (OC.sub.3H)- and (OC.sub.2H)-groups of the terminal group (a3) may be arranged blockwise, alternating, periodically and/or statistically, either of the groups (OC.sub.3H.sub.6) and (OC.sub.2H.sub.4) can be linked to R.sup.1 and O, adjacent structural units (a1) are connected by the structural unit (a2), in the case that only one terminal group (a3) is present in the polymer, the other terminal group is selected from the group consisting of OH, OCH.sub.3 and G.sup.1OH and both terminal groups may be only linked to a structural unit (a1) characterized in that it comprises the steps of heating furan-2,5-dicarboxylic acid, one or more alkylene glycols, and R.sup.1(OC.sub.2H.sub.4).sub.p(OC.sub.3H.sub.6).sub.qOH, 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.

13. (canceled)

14. A liquid laundry detergent comprising at least one polyester according to claim 1.

15. A process for washing a fabric comprising the step of contacting the fabric with a polyester comprising two or more structural units (a1), one or more structural units (a2) and either one or two terminal structural groups (a3) ##STR00016## wherein G.sup.1 is one or more (OC.sub.nH.sub.2n) with n being a number of from 2 to 10, R.sup.1 is a C.sub.1-30 alkyl, p is, based on a molar average, a number of from 1 to 200, q is, based on a molar average, a number of from 0 to 40, where the (OC.sub.3H.sub.6)- and (OC.sub.2H.sub.4)-groups of the terminal group (a3) may be arranged blockwise, alternating, periodically and/or statistically, either of the groups (OC.sub.3H.sub.6) and (OC.sub.2H.sub.4) can be linked to R.sup.1 and O, adjacent structural units (a1) are connected by the structural unit (a2), in the case that only one terminal group (a3) is present in the polymer, the other terminal group is selected from the group consisting of OH, OCH.sub.3, and G.sup.1OH and both terminal groups may be only linked to a structural unit (a1).

Description

EXAMPLES

[0109] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages given are percentages by weight (% by wt. or wt.-%).

[0110] Polymer Preparation

[0111] General Procedure for the Preparation of the Polyesters of the Examples

[0112] The polyester synthesis may be carried out by the reaction of 2,5-furandicarboxylic acid or its ester, alkylene glycols, alkyl capped polyalkylene glycols and optionally dimethyl terephthalate (DMT) using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a (trans)esterification and the second step is a polycondensation.

[0113] (Trans)Esterification

[0114] The reactants were weighed into a reaction vessel at room temperature under a nitrogen atmosphere. The mixture was heated to an internal temperature of 65 C. for melting and homogenization, followed by the addition of 200 l tetraisopropyl orthotitanate.

[0115] Within 2 hours, the temperature of the reaction mixture was continuously increased to 210 C. under a weak nitrogen flow and held at this temperature for 2 hours. During the transesterification, methanol was released from the reaction and was distilled out of the system, whereas in the case of an esterification water is released from the reaction and distilled out of the system. After 2 h at 210 C., nitrogen was switched off and the pressure reduced to 400 mbar over 3 h.

[0116] Polycondensation

[0117] The mixture was heated up to 230 C. At 230 C. the pressure was reduced to 1 mbar over 160 min. Once the polycondensation reaction had started, the glycol or mixture of glycols was distilled out of the system. The mixture was stirred for 4 h at 230 C. and a pressure of 1 mbar. After the end of this time period, the inner pressure of the reaction vessel was set back to 1 bar using N.sub.2 and the polymer melt was subsequently removed from the reactor and allowed to solidify.

Key to Reactants Used in the Examples 1 to 14

[0118]

TABLE-US-00001 mPEG750 is mono hydroxy-functional polyethylene glycol monomethyl ether, average molecular weight 0.75 KDa (Polyglykol M 750, Clariant). mPEG2000 is mono hydroxy-functional polyethylene glycol monomethyl ether, average molecular weight 2 KDa (Polyglykol M 2000, Clariant). mPEG5000 is mono hydroxy-functional polyethylene glycol monomethyl ether, average molecular weight 5 KDa (Polyglykol M 5000, Clariant). EG is ethylene glycol PG is propylene glycol FDCME is furan-2,5-dicarboxylic acid dimethyl ester FDCA is furan-2,5-dicarboxylic acid FDBE is furan-2,5-dicarboxylic acid dibutyl ester DMT is dimethyl terephthalate IPT is tetraisopropyl orthotitanate NaOAc is sodium acetate

TABLE-US-00002 TABLE I Polymer examples 1 to 6 Component 1 2 3 4 5 6 FDCME 184.15 69.06 36.83 18.42 36.83 36.83 FDCA FDBE DMT 19.42 EG 12.41 PG 121.74 45.65 15.22 30.44 30.44 30.44 mPEG750 100 mPEG2000 500 250 100 100 mPEG5000 100 IPT 0.2 0.2 0.1 0.1 0.1 0.1 NaOAc 0.5 0.5 0.25 0.3 0.3 0.3

TABLE-US-00003 TABLE II Polymer examples 7 to 13 Component 7 8 9 10 11 12 13* FDCME 11.05 14.73 92.08 108.82 92.08 FDCA 4.59 FDBE 40.23 DMT EG PG 18.26 3.65 7.3 9.13 60.87 71.94 60.87 mPEG750 mPEG2000 100 20 12 10 200 181.82 250 mPEG5000 IPT 0.08 0.016 0.016 0.016 0.2 0.2 0.2 NaOAc 0.2 0.04 0.04 0.04 0.5 0.5 0.5 *In this example the polycondensation temperature was 210 C.

[0119] Liquid laundry detergent compositions containing exemplary polyesters A series of exemplary liquid laundry detergent compositions, both excluding and including soil release polymer, were prepared according to Table III.

Key to Ingredients Used in the Compositions of Table A

[0120]

TABLE-US-00004 LAS is C.sub.12-14 linear alkylbenzene sulfonate, sodium salt SLES 2EO is sodium lauryl ether sulfate with 2 moles EO (Genapol LRO, Clariant). NI 7EO is C.sub.12-15 alcohol ethoxylate 7EO nonionic (Genapol LA070, Clariant) Fatty Acid is a C.sub.12-18 stripped palm kernel fatty acid SRP is a polyester prepared according to examples from Tables I and II

TABLE-US-00005 TABLE III Liquid laundry detergent compositions for performance testing wt.-% a.m. Ingredient 1 2 LAS 5.20 5.20 SLES 2EO 6.50 6.50 NI 7EO 5.20 5.20 Fatty Acid 2.80 2.80 Glycerol 2.40 2.40 Ethanol 1.20 1.20 Sodium citrate 1.70 1.70 Sodium tetraborate decahydrate 2.00 2.00 SRP 0.00 1.00 Demin water and NaOH to adjust pH ad 100 ad 100 pH Value 8.4 8.4 Appearance at room temperature clear clear

[0121] Soil Release Test

[0122] The inventive liquid laundry detergent compositions containing the polyesters of component a) and prepared according to the compositions listed in Table III, were tested for their soil release performance according to the Dirty-Motor Oil Test (DMO-Test) using a Lini Apparatus. The conditions for the test are listed in Table B.

TABLE-US-00006 TABLE IV Washing conditions - Soil Release Test Equipment Linitest Plus (SDL Atlas) Water hardness 14 dH Washing temperature 40 C. Washing time 30 min Detergent concentration 4.3 g/l Soiled Fabric:Liquor Ratio 1:40

[0123] As test fabric, white polyester and polycotton standard swatches (WFK 30A and WFK 20A, from WFK Testgewebe GmbH) were used. The fabrics were prewashed three times with the stored liquid laundry detergent compositions. The swatches were then rinsed, dried and soiled with 25 l of dirty motor oil. After 1 hour the soiled fabrics were washed again with the same stored liquid laundry detergent compositions used in the pre-washing step. After rinsing and drying the washed swatches, a measurement of the remission of the stained fabric at 457 nm was made using a spectrophotometer (Datacolor 650).

[0124] The soil release performance is shown as an improvement in soil removal of the swatches washed with one of the formulations 2 from Table III compared with formulation 1 of Table III:

R=R.sub.form 2R.sub.form 1

[0125] The washing results obtained for the liquid laundry detergent compositions comprising the inventive soil release polymers are shown in Table V, expressed as R along with the 95% confidence intervals.

TABLE-US-00007 TABLE V Washing results Biosourced Example wt.-% excl. Polyester Polycotton No. (a3) R 95% CI R 95% CI 1 100 4.1 1.3 11.2 0.5 2 100 3.4 0.85 11.5 1.2 3 100 1.1 0.50 8.3 0.8 4 70 7.9 0.7 17.9 0.7 5 100 0.9 0.5 9.0 0.3 6 100 1.6 0.6 5.3 1.2 7 100 2.9 0.5 9.3 0.6 8 100 2.4 0.5 11.5 0.3 9 100 3.6 0.8 8.7 1.1 10 100 1.8 0.3 5.8 0.7 11 100 4.5 0.5 9.2 0.6 12 100 2.7 0.5 10.9 0.6 13 100 3.1 0.8 8.8 0.9

[0126] Biosourced Material Content Calculation

[0127] The weight content of bio-sourced material shown in Table V is related to the hydrophobic block of the polymer and calculated according to the theoretical composition comprising the structural units (a1), (a2) and optionally (a4). The excess of used glycol and MeOH of the transesterification are therefore not taken into account in the calculation. The used EG, PG (a2) and furan (a1) components are assumed to be 100% bio sourced.

[0128] The biosourced material content, biosourced wt.-%, is then calculated as:

Biosourced wt.-%=100(a4) wt.-%

[0129] Where (a4) wt.-% is the weight percentage of structural units (a4) in the resulting polymer.