[go: up one dir, main page]

WO2014019659A1 - Polyesters - Google Patents

Polyesters Download PDF

Info

Publication number
WO2014019659A1
WO2014019659A1 PCT/EP2013/002195 EP2013002195W WO2014019659A1 WO 2014019659 A1 WO2014019659 A1 WO 2014019659A1 EP 2013002195 W EP2013002195 W EP 2013002195W WO 2014019659 A1 WO2014019659 A1 WO 2014019659A1
Authority
WO
WIPO (PCT)
Prior art keywords
molar average
groups
polyester according
molar
average
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2013/002195
Other languages
French (fr)
Other versions
WO2014019659A8 (en
Inventor
Dirk Fischer
Thomas Lindner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP13741676.4A priority Critical patent/EP2880076B1/en
Priority to US14/418,703 priority patent/US20150203630A1/en
Priority to JP2015524661A priority patent/JP6465798B2/en
Priority to PL13741676T priority patent/PL2880076T3/en
Priority to MX2015001510A priority patent/MX2015001510A/en
Priority to ES13741676.4T priority patent/ES2671447T3/en
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to CN201380040917.8A priority patent/CN104603175B/en
Priority to BR112015002039A priority patent/BR112015002039A2/en
Publication of WO2014019659A1 publication Critical patent/WO2014019659A1/en
Anticipated expiration legal-status Critical
Publication of WO2014019659A8 publication Critical patent/WO2014019659A8/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/78—Preparation processes
    • 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
    • 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

Definitions

  • the invention relates to new polyesters and a process for their preparation.
  • the polyesters are useful as soil release agents in laundry detergent and fabric care products.
  • soil release agent is applied to materials that modify the fabric surface minimizing the subsequent soiling and making the cleaning of the fabric easier on further washing cycles.
  • Laundry detergent compositions containing polyesters have been widely disclosed in the art.
  • EP 0 964 015 A1 discloses soil release oligoesters that may be used as soil release polymers in detergents and that are prepared using polyols comprising 3 to 6 hydroxyl groups.
  • EP 1 661 933 A1 is directed to at room temperature flowable, amphiphilic and nonionic oligoesters prepared by reacting dicarboxylic acid compounds, polyol compounds and water-soluble alkylene oxide adducts and their use as additive in washing and cleaning compositions.
  • many of the polyesters described in the prior art are in need of improved stability in an alkaline environment. Especially in alkaline heavy duty washing liquids polyesters often show turbidity upon incorporation and by alkaline hydrolysis thereby also losing soil release power. Therefore, it was the object of the present invention to provide new polyesters which 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.
  • R and R 2 independently of one another are H 3 C-(OC2H4)n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group or are HO-(C 3 H 6 ) or HO-(C 4 H 8 ),
  • n is based on a molar average a number of from 40 to 50
  • m is based on a molar average a number of from 1 to 7, and
  • a + b is based on a molar average a number of from 4 to 9.
  • R and R 2 independently of one another are H 3 C-(OC2H4) n -(OC 3 H6) m wherein the -(OC2H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group or are HO-(C 3 H 6 ) or HO-(C 4 H 8 ),
  • n is based on a molar average a number of from 40 to 50
  • m is based on a molar average a number of from 1 to 7
  • a + b is based on a molar average a number of from 4 to 9.
  • the variable "a” based on a molar average preferably is a number of from 2.8 to 8.1 and the variable "b" based on a molar average preferably is a number of from 0.4 to 2.7.
  • the sum "a + b" based on a molar average preferably is a number of from 5 to 8.
  • the variable "a” based on a molar average preferably is a number of from 3.5 to 7.2 and the variable "b" based on a molar average preferably is a number of from 0.5 to 2.4.
  • the sum "a + b" based on a molar average more preferably is a number of from 6 to 7.
  • the variable "a" based on a molar average preferably is a number of from 4.2 to 6.3 and the variable "b" based on a molar average preferably is a number of from 0.6 to 2.1.
  • the variable "a" based on a molar average is a number of from 4.8 to 5.6 and the variable "b" based on a molar average is a number of from 1.2 to 1.4.
  • variable "m" based on a molar average preferably is a number of from 2 to 5 and more preferably is 3.
  • variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45.
  • R and R 2 independently of one another are H3C-(OC 2 H4)n-(OC 3 H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
  • n is based on a molar average a number of from 44 to 46
  • m is based on a molar average
  • a + b is based on a molar average a number of from 5 to 8
  • polyesters wherein the variable "a” based on a molar average is a number of from 3.5 to 7.2 and the variable "b" based on a molar average is a number of from 0.5 to 2.4 are particularly preferred.
  • the polyesters wherein the variable "a” based on a molar average is a number of from 3.5 to 7.2 and the variable "b" based on a molar average is a number of from 0.5 to 2.4 are particularly preferred.
  • R 1 and R 2 independently of one another are H 3 C-(OC2H 4 ) n -(OC3H6)m wherein the -(OC2H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
  • n is based on a molar average a number of from 44 to 46
  • m is based on a molar average
  • a + b is based on a molar average a number of from 6 to 7
  • polyesters wherein the variable "a” based on a molar average is a number of from 4.2 to 6.3 and the variable "b" based on a molar average is a number of from 0.6 to 2.1 are especially preferred.
  • variable "n" based on a molar average preferably is 45.
  • R 1 and R 2 independently of one another are H3C-(OC2H 4 ) n -(OC3H6)m wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to a COO group,
  • n is based on a molar average 45
  • a + b is based on a molar average a number of from 6 to 7,
  • a based on a molar average is a number of from 4.8 to 5.6
  • b based on a molar average is a number of from 1.2 to 1.4
  • structural units indexed with "b" preferably is of from 70 : 30 to 90 : 10 and more preferably is 80 : 20.
  • the structural units indexed with "a” and the structural units indexed with “b” preferably are distributed blockwise, alternating or
  • the groups -0-C 2 H 4 - in the structural units "H 3 C-(OC2H4)n-(OC 3 H6)m" are of the formula -O-CH 2 -CH 2 -.
  • the groups -O-C3H6- in the structural units indexed with "a”, in the structural units "H 3 C-(OC2H4)n-(OC3H 6 ) m " and in the structural units HO-(C 3 H 6 ) are of the formula -0-CH(CH 3 )-CH 2 - or -0-CH 2 -CH(CH 3 )-, i.e. are of the formula
  • the groups -0-C 4 H 8 - in the structural units indexed with "b" and in the structural units HO-(C 4 H 8 ) are of the formula -O-CH(CH 3 )-CH(CH 3 )-, i.e. are of the formula
  • the inventive polyesters may be used in substance, i.e. as such, but may also be provided as aqueous solutions.
  • the aqueous solutions are e.g. beneficial with respect to their handling and e.g. the metering of the inventive polyester is very easy.
  • the aqueous solutions comprise the inventive polyesters in an amount of from 25 to 70 weight-% based on the total mass of the aqueous solution.
  • a further subject matter of the invention is an aqueous solution comprising an inventive polyester in an amount of from 25 to 70 weight-% based on the total mass of the aqueous solution.
  • aqueous solutions may even consist of the inventive polyester and water.
  • inventive polyesters may advantageously be used in washing or laundry detergent compositions.
  • these washing or laundry detergent compositions may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent compositions.
  • optional ingredients include, but are not limited to builders, surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for washing or laundry detergent compositions.
  • 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.
  • alkaline compositions such as alkaline heavy duty washing liquids and also possess advantageous soil release properties.
  • inventive polyesters possess advantageous foam suppressing properties. This is not only advantageous when the washing or laundry detergent compositions comprising the inventive polyesters are applied but also advantageously reduces foaming during handling of the inventive polyesters.
  • the inventive polyesters may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG), and H 3 C-(OC2H4)n-(OC3H 6 ) m -OH, wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC 3 H 6 ) groups is bound to the hydroxyl group -OH and n and m are as defined for the inventive polyesters, 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.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • BG 2,3-butylene glycol
  • H 3 C-(OC2H4)n-(OC3H 6 ) m -OH wherein
  • a further subject matter of the invention is a process for the preparation of the inventive polyesters which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG) and H 3 C-(OC 2 H 4 )n- (OC 3 H6)m-OH, wherein the -(OC 2 H 4 ) groups and the -(OC 3 H 6 ) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the inventive polyesters, 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
  • Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
  • H3C-(OC2H 4 ) n -(OC3H6)m-OH and a catalyst are added to a reaction vessel, heated under inert gas, preferably nitrogen, to a temperature of from 160 °C to 220 °C to remove methanol and then pressure is reduced to below atmospheric pressure, preferably to a pressure of from 200 to 900 mbar and more preferably to a pressure of from 400 to 600 mbar for completion of the transesterification, and
  • the reaction in a second step the reaction is continued at a temperature of from 210 °C to 240 °C and at a pressure of from 0.1 to 10 mbar and preferably of from 0.5 to 5 mbar to form the polyester.
  • Sodium acetate (NaOAc) and tetra isopropyl orthotitanate (IPT) is preferably used as the catalyst system in the inventive process.
  • the polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG) and methyl
  • the synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.
  • DMT Dimethyl terephthalate
  • PG 1,2-propylene glycol
  • BG 2,3-butylene glycol
  • NaOAc sodium acetate
  • IPT tetraisopropyl orthotitanate
  • the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream.
  • methanol is released from the reaction and is distilled out of the system (distillation temperature ⁇ 55 °C). After 2 h at 210 °C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 h.
  • Example I The mixture is heated up to 230 °C. At 230 °C the pressure is reduced to 1 mbar over 160 min. Once the polycondenzation reaction has started, a 1 ,2-propylene glycol / 2,3-butylene glycol mixture is distilled out of the system. The mixture is stirred for 4 h at 230 °C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150 °C. Vacuum is released with nitrogen and the molten Polymer is transferred into a glass bottle.
  • Example I Example I:
  • R and R 2 are H 3 C-(OC 2 H4)n-(OC3H6)m wherein the -(OC 2 H 4 ) groups and
  • the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
  • n is based on a molar average 45
  • m is based on a molar average
  • a + b is based on a molar average a number of from 6 to 7,
  • a based on a molar average is a number of from 4.8 to 5.6
  • b based on a molar average is a number of from 1.2 to 1.4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Polyesters
The invention relates to new polyesters and a process for their preparation. The polyesters are useful as soil release agents in laundry detergent and fabric care products.
The term "soil release agent" is applied to materials that modify the fabric surface minimizing the subsequent soiling and making the cleaning of the fabric easier on further washing cycles.
Laundry detergent compositions containing polyesters have been widely disclosed in the art.
DE 10 2007 013 217 A1 and WO 2007/079850 A1 disclose anionic polyesters that may be used as soil release components in washing and cleaning compositions.
DE 10 2007 005 532 A1 describes aqueous formulations of soil release oligo- and polyesters with a low viscosity. The aqueous formulations may e.g. be used in washing and cleaning compositions.
EP 0 964 015 A1 discloses soil release oligoesters that may be used as soil release polymers in detergents and that are prepared using polyols comprising 3 to 6 hydroxyl groups. EP 1 661 933 A1 is directed to at room temperature flowable, amphiphilic and nonionic oligoesters prepared by reacting dicarboxylic acid compounds, polyol compounds and water-soluble alkylene oxide adducts and their use as additive in washing and cleaning compositions. However, many of the polyesters described in the prior art are in need of improved stability in an alkaline environment. Especially in alkaline heavy duty washing liquids polyesters often show turbidity upon incorporation and by alkaline hydrolysis thereby also losing soil release power. Therefore, it was the object of the present invention to provide new polyesters which 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.
Surprisingly this object is solved by polyesters according to the following formula (I)
Figure imgf000003_0001
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6) or HO-(C4H8),
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a + b is based on a molar average a number of from 4 to 9.
Therefore, a subject matter of the present invention are polyesters according to the following formula (I)
Figure imgf000003_0002
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6) or HO-(C4H8),
n is based on a molar average a number of from 40 to 50, m is based on a molar average a number of from 1 to 7, and a + b is based on a molar average a number of from 4 to 9.
In these inventive polyesters wherein the sum "a+b" based on a molar average is a number of from 4 to 9, the variable "a" based on a molar average preferably is a number of from 2.8 to 8.1 and the variable "b" based on a molar average preferably is a number of from 0.4 to 2.7.
In the inventive polyesters the sum "a + b" based on a molar average preferably is a number of from 5 to 8.
In these preferred inventive polyesters wherein the sum "a+b" based on a molar average is a number of from 5 to 8, the variable "a" based on a molar average preferably is a number of from 3.5 to 7.2 and the variable "b" based on a molar average preferably is a number of from 0.5 to 2.4.
In the inventive polyesters the sum "a + b" based on a molar average more preferably is a number of from 6 to 7. In these preferred inventive polyesters wherein the sum "a+b" based on a molar average is a number of from 6 to 7, the variable "a" based on a molar average preferably is a number of from 4.2 to 6.3 and the variable "b" based on a molar average preferably is a number of from 0.6 to 2.1. Among these inventive polymers those polymers are preferred wherein the variable "a" based on a molar average is a number of from 4.8 to 5.6 and the variable "b" based on a molar average is a number of from 1.2 to 1.4.
In the inventive polyesters variable "m" based on a molar average preferably is a number of from 2 to 5 and more preferably is 3.
In the inventive polyesters the variable "n" based on a molar average preferably is a number of from 43 to 47, more preferably is a number of from 44 to 46 and even more preferably is 45. Inventive polyesters according to formula (I)
Figure imgf000005_0001
wherein
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 3, and
a + b is based on a molar average a number of from 5 to 8
are particularly preferred. Among these particularly preferred inventive polyesters the polyesters wherein the variable "a" based on a molar average is a number of from 3.5 to 7.2 and the variable "b" based on a molar average is a number of from 0.5 to 2.4 are preferred.
Inventive polyesters according to formula (I)
Figure imgf000005_0002
wherein
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 3, and
a + b is based on a molar average a number of from 6 to 7
are especially preferred. Among these especially preferred inventive polyesters the polyesters wherein the variable "a" based on a molar average is a number of from 4.2 to 6.3 and the variable "b" based on a molar average is a number of from 0.6 to 2.1 are preferred.
In the above-mentioned particularly preferred and especially preferred inventive polyesters the variable "n" based on a molar average preferably is 45.
Figure imgf000006_0001
wherein
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 3,
a + b is based on a molar average a number of from 6 to 7,
a based on a molar average is a number of from 4.8 to 5.6, and b based on a molar average is a number of from 1.2 to 1.4
are extraordinarily preferred.
In the inventive polyesters the molar ratio of structural units indexed with "a" :
structural units indexed with "b" preferably is of from 70 : 30 to 90 : 10 and more preferably is 80 : 20.
In the inventive polyesters the structural units indexed with "a" and the structural units indexed with "b" preferably are distributed blockwise, alternating or
statistically and more preferably are distributed statistically. The groups -0-C2H4- in the structural units "H3C-(OC2H4)n-(OC3H6)m" are of the formula -O-CH2-CH2-.
The groups -O-C3H6- in the structural units indexed with "a", in the structural units "H3C-(OC2H4)n-(OC3H6)m" and in the structural units HO-(C3H6) are of the formula -0-CH(CH3)-CH2- or -0-CH2-CH(CH3)-, i.e. are of the formula
CH3 CH3 — O— CH CH2 or — O— CH2 CH
The groups -0-C4H8- in the structural units indexed with "b" and in the structural units HO-(C4H8) are of the formula -O-CH(CH3)-CH(CH3)-, i.e. are of the formula
CH3 CH3 — O— CH CH
The inventive polyesters may be used in substance, i.e. as such, but may also be provided as aqueous solutions. The aqueous solutions are e.g. beneficial with respect to their handling and e.g. the metering of the inventive polyester is very easy. Preferably, the aqueous solutions comprise the inventive polyesters in an amount of from 25 to 70 weight-% based on the total mass of the aqueous solution.
Therefore, a further subject matter of the invention is an aqueous solution comprising an inventive polyester in an amount of from 25 to 70 weight-% based on the total mass of the aqueous solution. These aqueous solutions may even consist of the inventive polyester and water.
The inventive polyesters may advantageously be used in washing or laundry detergent compositions. Besides the inventive polyesters these washing or laundry detergent compositions may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in laundry detergent compositions. Examples of optional ingredients include, but are not limited to builders, surfactants, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, color protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotopes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for washing or laundry detergent compositions.
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. In washing or laundry detergent
compositions they result in a beneficial washing performance, in particular also after storage. Furthermore, the inventive polyesters possess advantageous foam suppressing properties. This is not only advantageous when the washing or laundry detergent compositions comprising the inventive polyesters are applied but also advantageously reduces foaming during handling of the inventive polyesters.
The inventive polyesters may advantageously be prepared by a process which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG), and H3C-(OC2H4)n-(OC3H6)m-OH, wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the inventive polyesters, 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.
Therefore, a further subject matter of the invention is a process for the preparation of the inventive polyesters which comprises heating dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG) and H3C-(OC2H4)n- (OC3H6)m-OH, wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to the hydroxyl group -OH and n and m are as defined for the inventive polyesters, 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.
Reduced pressure preferably means a pressure of from 0.1 to 900 mbar and more preferably a pressure of from 0.5 to 500 mbar.
In a preferred embodiment of the invention the inventive process is characterized in that
a) dimethyl therephthalate, 1 ,2-propylene glycol, 2,3-butylene glycol,
H3C-(OC2H4)n-(OC3H6)m-OH and a catalyst are added to a reaction vessel, heated under inert gas, preferably nitrogen, to a temperature of from 160 °C to 220 °C to remove methanol and then pressure is reduced to below atmospheric pressure, preferably to a pressure of from 200 to 900 mbar and more preferably to a pressure of from 400 to 600 mbar for completion of the transesterification, and
b) in a second step the reaction is continued at a temperature of from 210 °C to 240 °C and at a pressure of from 0.1 to 10 mbar and preferably of from 0.5 to 5 mbar to form the polyester. Sodium acetate (NaOAc) and tetra isopropyl orthotitanate (IPT) is preferably used as the catalyst system in the inventive process.
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.-%). General procedure for the preparation of the inventive polyesters
The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG) and methyl
polyalkyleneglycol using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.
Transesterification
Dimethyl terephthalate (DMT), 1 ,2-propylene glycol (PG), 2,3-butylene glycol (BG), methyl polyalkyleneglycol, sodium acetate (anhydrous) (NaOAc) and
tetraisopropyl orthotitanate (IPT) are weighed into a reaction vessel at room temperature.
For the melting process and homogenization, the mixture is heated up to 170 °C for 1 h and then up to 210 °C for a further 1 h sparged by a nitrogen stream. During the transesterification methanol is released from the reaction and is distilled out of the system (distillation temperature < 55 °C). After 2 h at 210 °C nitrogen is switched off and the pressure is reduced to 400 mbar over 3 h.
Polycondenzation
The mixture is heated up to 230 °C. At 230 °C the pressure is reduced to 1 mbar over 160 min. Once the polycondenzation reaction has started, a 1 ,2-propylene glycol / 2,3-butylene glycol mixture is distilled out of the system. The mixture is stirred for 4 h at 230 °C and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150 °C. Vacuum is released with nitrogen and the molten Polymer is transferred into a glass bottle. Example I:
Figure imgf000011_0001
An inventive polyester according to formula (I) is obtained wherein
R and R2 are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and
the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 3, and
a + b is based on a molar average a number of from 6 to 7,
a based on a molar average is a number of from 4.8 to 5.6, and b based on a molar average is a number of from 1.2 to 1.4.

Claims

Patent Claims:
1. Polyester according to the following formula (I)
Figure imgf000012_0001
wherein
R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group or are HO-(C3H6) or HO-(C4H8),
n is based on a molar average a number of from 40 to 50,
m is based on a molar average a number of from 1 to 7, and
a + is based on a molar average a number of from 4 to 9.
2. Polyester according to claim 1 , characterized in that a based on a molar average is a number of from 2.8 to 8.1 and b based on a molar average is a number of from 0.4 to 2.7.
3. Polyester according to claim 1 , characterized in that the sum a + b based on a molar average is a number of from 5 to 8.
4. Polyester according to claim 3, characterized in that a based on a molar average is a number of from 3.5 to 7.2 and b based on a molar average is a number of from 0.5 to 2.4.
5. Polyester according to claim 1 , characterized in that the sum a + b based on a molar average is a number of from 6 to 7.
6. Polyester according to claim 5, characterized in that a based on a molar average is a number of from 4.2 to 6.3 and b based on a molar average is a number of from 0.6 to 2.1.
7. Polyester according to claim 5 or 6, characterized in that a based on a molar average is a number of from 4.8 to 5.6 and b based on a molar average is a number of from 1.2 to 1.4
8. Polyester according to one or more of claims 1 to 7, characterized in that m based on a molar average is a number of from 2 to 5.
9. Polyester according to claim 8, characterized in that m based on a molar average is 3.
10. Polyester according to one or more of claims 1 to 9, characterized in that n based on a molar average is a number of from 43 to 47.
11. Polyester according to claim 10, characterized in that n based on a molar average is a number of from 44 to 46.
12. Polyester according to claim 11 , characterized in that n based on a molar average is 45.
Polyester according to one or more of claims 1 to 12, characterized in that I R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46
m is based on a molar average 3, and
a + b is based on a molar average a number of from 5 to 8.
14. Polyester according to claim 13, characterized in that a based on a molar average is a number of from 3.5 to 7.2 and b based on a molar average is a number of from 0.5 to 2.4.
15. Polyester according to claim 13, characterized in that
R and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average a number of from 44 to 46,
m is based on a molar average 3, and
a + b is based on a molar average a number of from 6 to 7.
16. Polyester according to claim 15, characterized in that a based on a molar average is a number of from 4.2 to 6.3 and b based on a molar average is a number of from 0.6 to 2.1.
17. Polyester according to one or more of claims 13 to 16, characterized in that n based on a molar average is 45.
18. Polyester according to one or more of claims 1 to 17, characterized in that R1 and R2 independently of one another are H3C-(OC2H4)n-(OC3H6)m wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) groups is bound to a COO group,
n is based on a molar average 45,
m is based on a molar average 3,
a + b is based on a molar average a number of from 6 to 7,
a based on a molar average is a number of from 4.8 to 5.6, and b based on a molar average is a number of from 1.2 to 1.4.
19. Polyester according to one or more of claims 1 to 6 and 8 to 17,
characterized in that the molar ratio of structural units indexed with "a" : structural units indexed with "b" is of from 70 : 30 to 90 : 10.
20. Polyester according to one or more of claims 1 to 19, characterized in that the molar ratio of structural units indexed with "a" : structural units indexed with "b" is 80 : 20.
21. Polyester according to one or more of claims 1 to 20, characterized in that the structural units indexed with a and the structural units indexed with b are distributed blockwise, alternating or statistically.
22. Polyester according to claim 21 , characterized in that the structural units indexed with a and the structural units indexed with b are distributed statistically.
23. Process for the preparation of a polyester according to one or more of claims 1 to 22, characterized in that it comprises heating dimethyl terephthalate, 1 ,2-propylene glycol, 2,3-butylene glycol, and H3C-(OC2H4)n-(OC3H6)m-OH, wherein the -(OC2H4) groups and the -(OC3H6) groups are arranged blockwise and the block consisting of the -(OC3H6) 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.
PCT/EP2013/002195 2012-07-31 2013-07-24 Polyesters Ceased WO2014019659A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US14/418,703 US20150203630A1 (en) 2012-07-31 2013-07-24 Polyesters
JP2015524661A JP6465798B2 (en) 2012-07-31 2013-07-24 polyester
PL13741676T PL2880076T3 (en) 2012-07-31 2013-07-24 Polyesters
MX2015001510A MX2015001510A (en) 2012-07-31 2013-07-24 Polyesters.
ES13741676.4T ES2671447T3 (en) 2012-07-31 2013-07-24 Polyesters
EP13741676.4A EP2880076B1 (en) 2012-07-31 2013-07-24 Polyesters
CN201380040917.8A CN104603175B (en) 2012-07-31 2013-07-24 Polyester
BR112015002039A BR112015002039A2 (en) 2012-07-31 2013-07-24 polyesters

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12005550 2012-07-31
EP12005550.4 2012-07-31
DE12005550.4 2012-07-31

Publications (2)

Publication Number Publication Date
WO2014019659A1 true WO2014019659A1 (en) 2014-02-06
WO2014019659A8 WO2014019659A8 (en) 2016-01-07

Family

ID=46829597

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/002195 Ceased WO2014019659A1 (en) 2012-07-31 2013-07-24 Polyesters

Country Status (9)

Country Link
US (1) US20150203630A1 (en)
EP (1) EP2880076B1 (en)
JP (1) JP6465798B2 (en)
CN (1) CN104603175B (en)
BR (1) BR112015002039A2 (en)
ES (1) ES2671447T3 (en)
MX (1) MX2015001510A (en)
PL (1) PL2880076T3 (en)
WO (1) WO2014019659A1 (en)

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2016075179A1 (en) * 2014-11-11 2016-05-19 Clariant International Ltd Laundry detergents containing soil release polymers
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric
WO2021160851A1 (en) 2020-02-14 2021-08-19 Basf Se Biodegradable graft polymers
WO2021165493A1 (en) 2020-02-21 2021-08-26 Basf Se Alkoxylated polyamines with improved biodegradability
EP3933017A1 (en) 2020-07-03 2022-01-05 The Procter & Gamble Company Fabric and home care product comprising a sulfatized esteramine
WO2022087035A1 (en) 2020-10-23 2022-04-28 The Procter & Gamble Company Laundry detergent composition comprising polyvinyl alcohol acetal polymer
EP4006131A1 (en) 2020-11-30 2022-06-01 The Procter & Gamble Company Method of laundering fabric
WO2022136389A1 (en) 2020-12-23 2022-06-30 Basf Se Amphiphilic alkoxylated polyamines and their uses
EP4134421A1 (en) 2021-08-12 2023-02-15 The Procter & Gamble Company Detergent composition comprising detersive surfactant and graft polymer
EP4134420A1 (en) 2021-08-12 2023-02-15 The Procter & Gamble Company Detergent composition comprising detersive surfactant and biodegradable graft polymers
WO2023064749A1 (en) 2021-10-14 2023-04-20 The Procter & Gamble Company A fabric and home care product comprising cationic soil release polymer and lipase enzyme
EP4321604A1 (en) 2022-08-08 2024-02-14 The Procter & Gamble Company A fabric and home care composition comprising surfactant and a polyester
WO2024094803A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024094802A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024094800A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024119298A1 (en) 2022-12-05 2024-06-13 The Procter & Gamble Company Fabric and home care composition comprising a polyalkylenecarbonate compound
EP4386074A1 (en) 2022-12-16 2024-06-19 The Procter & Gamble Company Fabric and home care composition
WO2024129520A1 (en) 2022-12-12 2024-06-20 The Procter & Gamble Company Fabric and home care composition
EP4458933A1 (en) 2023-05-05 2024-11-06 The Procter & Gamble Company A fabric and home care composition comprising a propoxylated polyol
EP4458932A1 (en) 2023-05-04 2024-11-06 The Procter & Gamble Company A fabric and home care composition
EP4484536A1 (en) 2023-06-26 2025-01-01 The Procter & Gamble Company Fabric and home care composition
EP4549540A1 (en) 2023-11-02 2025-05-07 The Procter & Gamble Company Fabric and home care composition
EP4549541A1 (en) 2023-11-02 2025-05-07 The Procter & Gamble Company Fabric and home care composition
EP4553137A1 (en) 2023-11-08 2025-05-14 The Procter & Gamble Company A fabric and home care composition comprising a polyester
EP4570892A1 (en) 2023-12-15 2025-06-18 The Procter & Gamble Company A laundry detergent composition
EP4570893A1 (en) 2023-12-15 2025-06-18 The Procter & Gamble Company Fabric and home care composition
WO2025168447A1 (en) 2024-02-07 2025-08-14 Evonik Operations Gmbh Polyesters as dispersants for agricultural actives
EP4610340A1 (en) 2024-03-01 2025-09-03 The Procter & Gamble Company A laundry detergent composition comprising a polyester
EP4624554A1 (en) 2024-03-26 2025-10-01 The Procter & Gamble Company Fabric care compositions
EP4624555A1 (en) 2024-03-26 2025-10-01 The Procter & Gamble Company Fabric and home care compositions
EP4636063A1 (en) 2024-04-19 2025-10-22 The Procter & Gamble Company A unit dose laundry detergent product
EP4660287A1 (en) 2024-06-06 2025-12-10 The Procter & Gamble Company Use of a polysaccharide ester in a laundry detergent composition
EP4663732A1 (en) 2024-06-10 2025-12-17 The Procter & Gamble Company Use of graft polymer in a laundry detergent composition
EP4663733A1 (en) 2024-06-10 2025-12-17 The Procter & Gamble Company Use of a graft polymer in a laundering process
WO2025255814A1 (en) 2024-06-14 2025-12-18 The Procter & Gamble Company Detergent particles containing polymer and surfactant
WO2025255813A1 (en) 2024-06-14 2025-12-18 The Procter & Gamble Company Detergant particles containing surfactant and water-soluble polymer

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX380468B (en) * 2012-07-31 2025-03-12 Clariant Int Ltd POLYESTERS.
EP2966160A1 (en) 2014-07-09 2016-01-13 Clariant International Ltd. Storage-stable compositions comprising soil release polymers
US10240107B2 (en) 2014-11-11 2019-03-26 Clariant International Ltd. Laundry detergents containing soil release polymers
EP3489340A1 (en) 2017-11-28 2019-05-29 Clariant International Ltd Renewably sourced soil release polyesters
EP3802765B1 (en) 2018-05-24 2024-12-18 Clariant International Ltd Soil release polyesters for use in detergent compositions
CN116065394B (en) * 2023-03-30 2023-07-11 张家港市德宝化工有限公司 Bio-based moisture-absorption sweat-release multifunctional finishing agent and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220156A2 (en) * 1985-10-18 1987-04-29 The Procter & Gamble Company Fabric softener composition
EP0964015A1 (en) 1998-06-12 1999-12-15 Clariant GmbH Soil release oligoester
WO2001058980A1 (en) * 2000-02-11 2001-08-16 E.I. Du Pont De Nemours And Company Continuous process for producing poly(trimethylene terephthalate)
DE10127146A1 (en) * 2001-06-02 2002-12-05 Zimmer Ag Production of polybutylene terephthalate from butanediol and terephthalic acid involves using a catalyst solution containing alkyltitanate, butanediol and a dicarboxylic or hydroxycarboxylic acid
EP1661933A1 (en) 2004-11-24 2006-05-31 SASOL Germany GmbH Liquid, amphiphilic and nonionic oligoesters
WO2007079850A1 (en) 2005-12-21 2007-07-19 Clariant Produkte (Deutschland) Gmbh Anionic soil release polymers
DE102007005532A1 (en) 2007-02-03 2008-08-07 Clariant International Limited Aqueous oligo- and polyester preparations
DE102007013217A1 (en) 2007-03-15 2008-09-18 Clariant International Ltd. Anionic Soil Release Polymers
WO2012104156A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Soil release polymers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1191499A (en) * 1967-09-29 1970-05-13 Ici Ltd Production of Aromatic Polyesters
US4702857A (en) * 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
EP0185427B1 (en) * 1984-12-21 1992-03-04 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
EP2135931B1 (en) * 2008-06-16 2012-12-05 The Procter & Gamble Company Use of soil release polymer in fabric treatment compositions
US8779084B2 (en) * 2009-07-01 2014-07-15 Solvay (China) Co., Ltd. Process for producing polyether-polyester block copolymer
PL2670788T3 (en) * 2011-01-31 2015-08-31 Unilever Nv Alkaline liquid detergent compositions
WO2012104157A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Soil release polymers
MX380468B (en) * 2012-07-31 2025-03-12 Clariant Int Ltd POLYESTERS.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220156A2 (en) * 1985-10-18 1987-04-29 The Procter & Gamble Company Fabric softener composition
EP0964015A1 (en) 1998-06-12 1999-12-15 Clariant GmbH Soil release oligoester
WO2001058980A1 (en) * 2000-02-11 2001-08-16 E.I. Du Pont De Nemours And Company Continuous process for producing poly(trimethylene terephthalate)
DE10127146A1 (en) * 2001-06-02 2002-12-05 Zimmer Ag Production of polybutylene terephthalate from butanediol and terephthalic acid involves using a catalyst solution containing alkyltitanate, butanediol and a dicarboxylic or hydroxycarboxylic acid
EP1661933A1 (en) 2004-11-24 2006-05-31 SASOL Germany GmbH Liquid, amphiphilic and nonionic oligoesters
WO2007079850A1 (en) 2005-12-21 2007-07-19 Clariant Produkte (Deutschland) Gmbh Anionic soil release polymers
DE102007005532A1 (en) 2007-02-03 2008-08-07 Clariant International Limited Aqueous oligo- and polyester preparations
DE102007013217A1 (en) 2007-03-15 2008-09-18 Clariant International Ltd. Anionic Soil Release Polymers
WO2012104156A1 (en) * 2011-01-31 2012-08-09 Unilever Plc Soil release polymers

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2016075179A1 (en) * 2014-11-11 2016-05-19 Clariant International Ltd Laundry detergents containing soil release polymers
CN107109301A (en) * 2014-11-11 2017-08-29 科莱恩国际有限公司 Laundry detergent compositions comprising soil release polymers
JP2017534730A (en) * 2014-11-11 2017-11-24 クラリアント・インターナシヨナル・リミテツド Laundry detergent containing soil release polymer
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric
WO2021160851A1 (en) 2020-02-14 2021-08-19 Basf Se Biodegradable graft polymers
WO2021165493A1 (en) 2020-02-21 2021-08-26 Basf Se Alkoxylated polyamines with improved biodegradability
EP3933017A1 (en) 2020-07-03 2022-01-05 The Procter & Gamble Company Fabric and home care product comprising a sulfatized esteramine
WO2022006485A1 (en) 2020-07-03 2022-01-06 The Procter & Gamble Company A fabric and home care product comprising a sulfatized esteramine
WO2022087035A1 (en) 2020-10-23 2022-04-28 The Procter & Gamble Company Laundry detergent composition comprising polyvinyl alcohol acetal polymer
EP4006131A1 (en) 2020-11-30 2022-06-01 The Procter & Gamble Company Method of laundering fabric
WO2022136389A1 (en) 2020-12-23 2022-06-30 Basf Se Amphiphilic alkoxylated polyamines and their uses
EP4134421A1 (en) 2021-08-12 2023-02-15 The Procter & Gamble Company Detergent composition comprising detersive surfactant and graft polymer
EP4134420A1 (en) 2021-08-12 2023-02-15 The Procter & Gamble Company Detergent composition comprising detersive surfactant and biodegradable graft polymers
WO2023019153A1 (en) 2021-08-12 2023-02-16 The Procter & Gamble Company Detergent composition comprising detersive surfactant and graft polymer
WO2023019152A1 (en) 2021-08-12 2023-02-16 The Procter & Gamble Company Detergent composition comprising detersive surfactant and biodegradable graft polymers
WO2023064749A1 (en) 2021-10-14 2023-04-20 The Procter & Gamble Company A fabric and home care product comprising cationic soil release polymer and lipase enzyme
EP4321604A1 (en) 2022-08-08 2024-02-14 The Procter & Gamble Company A fabric and home care composition comprising surfactant and a polyester
WO2024036126A1 (en) 2022-08-08 2024-02-15 The Procter & Gamble Company A fabric and home care composition comprising surfactant and a polyester
WO2024094803A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024094802A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024094800A1 (en) 2022-11-04 2024-05-10 The Procter & Gamble Company Fabric and home care composition
WO2024119298A1 (en) 2022-12-05 2024-06-13 The Procter & Gamble Company Fabric and home care composition comprising a polyalkylenecarbonate compound
WO2024129520A1 (en) 2022-12-12 2024-06-20 The Procter & Gamble Company Fabric and home care composition
EP4386074A1 (en) 2022-12-16 2024-06-19 The Procter & Gamble Company Fabric and home care composition
EP4458932A1 (en) 2023-05-04 2024-11-06 The Procter & Gamble Company A fabric and home care composition
EP4458933A1 (en) 2023-05-05 2024-11-06 The Procter & Gamble Company A fabric and home care composition comprising a propoxylated polyol
WO2024233240A1 (en) 2023-05-05 2024-11-14 The Procter & Gamble Company A fabric and home care composition comprising a propoxylated polyol
EP4484536A1 (en) 2023-06-26 2025-01-01 The Procter & Gamble Company Fabric and home care composition
WO2025006207A1 (en) 2023-06-26 2025-01-02 The Procter & Gamble Company Fabric and home care composition
EP4549540A1 (en) 2023-11-02 2025-05-07 The Procter & Gamble Company Fabric and home care composition
EP4549541A1 (en) 2023-11-02 2025-05-07 The Procter & Gamble Company Fabric and home care composition
WO2025096273A1 (en) 2023-11-02 2025-05-08 The Procter & Gamble Company Fabric and home care composition
WO2025096272A1 (en) 2023-11-02 2025-05-08 The Procter & Gamble Company Fabric and home care composition
EP4553137A1 (en) 2023-11-08 2025-05-14 The Procter & Gamble Company A fabric and home care composition comprising a polyester
WO2025101680A1 (en) 2023-11-08 2025-05-15 The Procter & Gamble Company A fabric and home care composition comprising a polyester
EP4570892A1 (en) 2023-12-15 2025-06-18 The Procter & Gamble Company A laundry detergent composition
EP4570893A1 (en) 2023-12-15 2025-06-18 The Procter & Gamble Company Fabric and home care composition
WO2025128416A1 (en) 2023-12-15 2025-06-19 The Procter & Gamble Company Fabric and home care composition
WO2025128415A1 (en) 2023-12-15 2025-06-19 The Procter & Gamble Company A laundry detergent composition
WO2025168447A1 (en) 2024-02-07 2025-08-14 Evonik Operations Gmbh Polyesters as dispersants for agricultural actives
EP4610340A1 (en) 2024-03-01 2025-09-03 The Procter & Gamble Company A laundry detergent composition comprising a polyester
EP4624554A1 (en) 2024-03-26 2025-10-01 The Procter & Gamble Company Fabric care compositions
EP4624555A1 (en) 2024-03-26 2025-10-01 The Procter & Gamble Company Fabric and home care compositions
WO2025207550A1 (en) 2024-03-26 2025-10-02 The Procter & Gamble Company Fabric care compositions
WO2025207301A1 (en) 2024-03-26 2025-10-02 The Procter & Gamble Company Fabric and home care compositions
EP4636063A1 (en) 2024-04-19 2025-10-22 The Procter & Gamble Company A unit dose laundry detergent product
WO2025221588A1 (en) 2024-04-19 2025-10-23 The Procter & Gamble Company A unit dose laundry detergent product
EP4660287A1 (en) 2024-06-06 2025-12-10 The Procter & Gamble Company Use of a polysaccharide ester in a laundry detergent composition
WO2025255062A1 (en) 2024-06-06 2025-12-11 The Procter & Gamble Company Use of a polysaccharide ester in a laundry detergent composition
EP4663732A1 (en) 2024-06-10 2025-12-17 The Procter & Gamble Company Use of graft polymer in a laundry detergent composition
EP4663733A1 (en) 2024-06-10 2025-12-17 The Procter & Gamble Company Use of a graft polymer in a laundering process
WO2025255814A1 (en) 2024-06-14 2025-12-18 The Procter & Gamble Company Detergent particles containing polymer and surfactant
WO2025255813A1 (en) 2024-06-14 2025-12-18 The Procter & Gamble Company Detergant particles containing surfactant and water-soluble polymer

Also Published As

Publication number Publication date
BR112015002039A2 (en) 2017-07-04
EP2880076B1 (en) 2018-04-18
WO2014019659A8 (en) 2016-01-07
JP6465798B2 (en) 2019-02-06
PL2880076T3 (en) 2018-10-31
CN104603175B (en) 2016-11-09
US20150203630A1 (en) 2015-07-23
MX2015001510A (en) 2015-04-08
ES2671447T3 (en) 2018-06-06
CN104603175A (en) 2015-05-06
JP2015527446A (en) 2015-09-17
EP2880076A1 (en) 2015-06-10

Similar Documents

Publication Publication Date Title
EP2880076B1 (en) Polyesters
EP2880073B1 (en) Polyesters
EP3167032B1 (en) Storage-stable compositions comprising soil release polymers
CA2953273C (en) Alkaline laundry liquid composition comprising polyesters
FI91972B (en) 1,2-propylene-terephthalate-polyoxyethylene-terephthalate polyesters useful as soil removal agents with terminal groups and compositions containing these
EP3717613B1 (en) Renewably sourced soil release polyesters
TW200550B (en)
US20170275420A1 (en) Polyesters, Manufacturing Process Thereof and Their Use
JP2004507597A (en) Flowable, amphiphilic and nonionic oligoesters

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13741676

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015524661

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 14418703

Country of ref document: US

Ref document number: MX/A/2015/001510

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2013741676

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015002039

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112015002039

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150129