CA2178908A1 - Amphiphilic polyesters, process for producing them and their use in washing agents - Google Patents
Amphiphilic polyesters, process for producing them and their use in washing agentsInfo
- Publication number
- CA2178908A1 CA2178908A1 CA002178908A CA2178908A CA2178908A1 CA 2178908 A1 CA2178908 A1 CA 2178908A1 CA 002178908 A CA002178908 A CA 002178908A CA 2178908 A CA2178908 A CA 2178908A CA 2178908 A1 CA2178908 A1 CA 2178908A1
- Authority
- CA
- Canada
- Prior art keywords
- polyesters
- acid
- aliphatic
- acids
- aromatic
- 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.)
- Abandoned
Links
Classifications
-
- 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
-
- 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
Abstract
Amphiphilic polyesters having (a) ester units of polyalkylene glycols with a molar mass of 500 to 7,500 and aliphatic bicarboxylic acids and/or monohydroxy monocarboxylic acids and (b) ester units obtained from aromatic bicarboxylic acids and polyvalent alcohols and with molar masses of 1,500 to 25,000; process for producing the amphiphilic polyesters by polycondensation, in which first of all (a) aliphatic polyesters of polyalkylene glycols with a molar mass of 500 to 7,500 are produced with aliphatic biocarboxylic acids and/or monohydroxy monocarboxylic acids and then, in the aliphatic polyesters thus obtained, (b) aromatic polyesters are produced from aromatic bicarboxylic acids and polyvalent alcohols; the polycondensation sequence is reversed or oligomeric aromatic polyesters (b) are condensed with oligomeric aliphatic polyesters (a); and the use of the amphiphilic polyesters as additives in washing agents, other washing agent additives and washing after treatment agents.
Description
e 0050/44586 - 2~78908 I _- ;rhilir polyesters, preparation thereo~, and use thereof in laundry detergents 5 The present invention relates to _ i rh; 1 i C polyesters, ~L~ sses for preparing them, and their uae as additive in laundry detergents and laundry aftt:L l,Leai ts.
US-A-3 557 039 ii qrl 05~c stable aqueous dispersions of polymers lO preparable by condensation of terephthalic acid or dimethyl terephthalate with ethylene glycol and polyethylene glycol having an average l ~r~ll Ar weight of from 1000 to 4000 . The molar ratio of ethylene terephthalate to polyethylene glycol terephthalate units is within the range from 2 :1 to 6 :1. The dispersions are 15 used for treating the surfaces of polyester articles.
GB-Al 154 730 ~1i qrl os~,q reducing 50il redeposition in the washing of textile material by adding to the wash li~uor, which contains a detergent, polycondensates containing either repeating ester or 20 amide units. ~hese additives are for example condensatioh products known from the above-cited U.S. Patent 3,557,039 and are obtainable by condensation of dimethyl terephthalate, ethylene glycol and polyethylene glycol having 2 - l~rlllAr weight of 1500.
25 EP Applications 185 427, 241 984, 241 985 and 272 033 disclose polyester condensates of polybaaic aromatic carboxylic acids with dihydric alcohols and one-sidedly C1-C4-capped polyethers, which promote soil release from polyester fabrics. These polyesters have hydrophilic end groups which, in the cited applications, are 30 mentioned as the basis of the soil-releasing properties of the polyesters .
P ' iE~hil;c polyesterg of aliphatic polybasic carboxylic acids and/or ~h~dL~ y nrArhnyylic acids with polyethylene glycol 35 are described for example in Polymer Bulletin, Volume 17, 499 - 506 (1987).
US-A-5 142 020 ~l;cr1O~ Amrh;rhilir polyesters obtainable by condensation of (a~ carboxylic acids having at least 2 carboxyl groups, their esters, anhydr des or mixtures, 2 2 ~ 78908 (b) at least dihydric alcohols and/or addition products of from 1 to 5 mol o~ at least one alkylene oxide having 2 or 3 carbon atoms with 1 mol of an at least dihydric alcohol or mixtures and (c) water-soluble addition products of from 5 to 80 mol of at least one alkylene oxide wLth 1 mol of C8-Cz4-alcohols, C8-C18-alkylphenols or C8-C24-alkylamines 10 in a molar ratio of (a):(b):(c) of 100:(from 25 to 2500):(from 5 to 110) at temperatures of at least 120C to weight average ~ l~.r~ r weightg of from 2000 to 50,000. The polyesters are used as grayness-inhibiting and soil-release additive in pulverulent and lis~uid laundry deterge~ts.
It is an ob~ect of the pre~ent invention to provide novel substances and laundry detergent additives.
We have found that this object is achieved by . irh;l;r 20 polyesters containing (a) ester units derived from polyalkylene glycols having a l~clll ~r weight of from 500 to 7500 and aliphatic dicarboxylic acids and/or ~ dL-)~y rh~xylic acids and (b) ester units derived from aromatic dicarboxylic acids and polyhydric alcohols and having molecular weights of from 1500 to 25,000.
The ~mrh;rh;l;r polye6ters are obtained by polyrrmti~n~;n~ to prepare f irs t (a~ aliphatic polyesters of polyalkylene glycols having a molecular weight of from 500 to 7500 with aliphatic dicarboxylic acids and/or monully~ y -_ rboxylic acids and then, within the aliphatic polyester thus obtained, (b~ aromatic polyesters from aromatic dicarboxylic acids and polyhydric alcohols, reversing the order o~ the polycondensation, or rr~n~l~n~n~
oligomeric aromatic polyesters ( b ) with oligomeric aliphatic polyes ters ( a ) .
The ab~ des.:Llbed nn~h~rh;l;s polyesters are used as additive in laundry detergents, other laundry detcrgent additives and laundry aftertreatments.
5 The amphiphilic polyesters having ester units derived from (a) polyalkylene glycols and aliphatic dicarboxylic acids and/or '~dL(~'Y '7 rhr yy1iC acidg (hereinafter called Naliphatic blockN) and (b) aromatic dicarboxylic acids and polyhydric alcohols (hereinafter called naromatic blockN) have soil--release 10 properties in wash liquors and are very readily biodegradable.
The aliphatic blocks (a) are prepared by polycondensatlon of polyalkylene glycols having a ~ ~r r~ r weight of from 500 to 7500 with aliphatic dicarboxylic acids and/or monohydroxy-15 (n~ ~rh~Yylic acids in a conventional manner. Thepolycondensation i5 carried out for example at temperatures of at least 120C, preferably within the t~ ULe range from 150 to 260C, in the presence of customary polycondensation or transesterification catalysts. Typically, the reaction 20 participants are ~ nfl~n~d in an inert gas atmosphere in the presence or absence of further additives, such as antioxidants.
Such processes are known for example from US-A-3 557 039 mentioned at the h~; nn; ng, 25 Suitable catalysts include all Ul~d~ described in the literature for this purpose. When the free polycarboxylic acids or the anhydrides are used in the condensation, p-toluenesulfonic acid i8 the preferred catalyst. When dialkyl dicarboxylates or polycarboxylic esters are used, the customary transesterification 30 catalysts are used, such as, for example, zinc acetate, mixtures of calcium acetate and antimony oxide or tetraalkoxytitanates, such as titanium tetraisobutoxide or titanium tetraisopropoxide.
Other pre~erred catalysts are for example carbonates, acetates and/or Cl-C~-alkoxylates of lithium, sodium, r-gn~a; ~ cobalt, 35 manganese, vanadium, titanium and tin and also tin oxides. The catalysts are generally used in amounts of from 20 to 5000, preferably from 50 to 2000, ppm, based on the components used in the condensation.
40 The condensation can be carried out in the presence of anti-oxidants, for example substituted phenols, such as, for example, 2, 5--di-tert-butylphenol, 2-methylcyclohexyl-4, 6-dimethylphenol, 2, 6--di-tert-butyl-4-methylphenol, pyrogallol, phosphoru3 acid or other antioxidants customary for this purpose. These compounds 45 prevent discoloration of the polyesters due to oxidation during the condensation.
.
4 2 l 78908 Suitable polyalkylene glycols for preparing the aliphatic blocks (a) have number average ler~ r weights of from 500 to 7500, preferably from 1000 to 4500. The polyalkylene glycols are water-soluble. They are preferably derived from ethylene oxide, 5 propylene oxide, n--butylene oxide or isobutylene oxide and are prepared for example by addition of the alkylene oxides to dihydric alcohols. This can be done for example by adding only ethylene oxide or propylene oxide to a dihydric alcohol, such as ethylene glycol or propylene glycol, or by preparing block 10 copolymers by first adding ethylene oxide and then propylene oxide to a dihydric alcohol or vice versa. In the preparation of the polyalkylene glycols, propylene oxide, for example, may be wholly or partly replaced by a butylene oxide. Similarly, random polyalkylene oxides obtainable by addition of a mixed gas of at 15 least two alkylene oxides to a dihydric alcohol can be used as polyalkylene glycols in the preparation of the aliphatic blocks (a). The preferred polyalkylene glycols are ethylene glycol, propylene glycol and block copolymers of ethylene oxide and propylene oxide. - --20Suitable aliphatic dicarboxylic acids contain for example from 2 to 10 carbon atoms. Examples are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. They can be used either 25 alone or mixed, for example as mixtures of oxalic acid and succinic acid or of succinic acid and adipic acid, in the prepar~tion of the aliphatic blocks.
The preparation of the aliphatic blocks of the _ ~ i rh i 1 i r 30 polyesters may be ef fected in the additional presence of mono~ v,.y rhrYylic acids. A further variant comprises using monohydL~,~y ~ rboxylic acids instead of the aliphatic dicarboxylic acid8. The r ~YIL~ rhrl~rylic acids are likewise aliphatic carboxylic acids. Examples are glycolic acid, 35 lactic acid, u~-llydL~ yaLearic acid and (o-hydroxycaproic acid.
They can be used individually or mixed in the preparation of the aliphatic blocks.
The aliphatic blocks are preferably prepared by polycondensation 40 of polyethylene glycol with succinic acid or adipic acid. In this preferred variant, the polycondensation may be carried out in the additional presence of ~-hydroxycaproic acid and/or lactic acid.
The aromatic block (b) of the .~irhilir polyesters is 45 obtainable by polycondensation of aromatic dicarboxylic acids with f or example aliphatic polyhydric alcohols . The polycondensation is carried out by the same methods as used for .
2 1 78~08 preparing the 21iphatic blocks ( a ) . The weight average l F~n~ r weights of the aromatic blocks ~ b ) are customarily within the range from about 192 to 5000, preferably from about 384 to 1500.
5 Suitable aromatic dicarboxylic acids include for example terephthalic acid, phthalic acid and sulfoisophthalic acid. The preferred aroma~ic dicarboxylic acid is terephthalic acid. The dicarboxylic acids may also be used mixed with one another.
10 Suitable aliphatic polyhydric alcohols include for example ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, pen~n~ , glycerol, pentaerythritol, oligoglycerols having 1 ~rl~ r weights of up to 363 and also addition products of from 1 to 5 mol of ethylene 15 oxide and/or propylene oxide with 1 mol of the abovementioned at least dihydric alcohols. Examples of such addition products are ethylene diglycol and propylene diglycol. Also of interest are the addition products of from 1 to 4 mol of ethylene oxide with pentaerythritol, addition products of from 1 to 3-mol of ethylene 20 oxide with 1 mol of glycerol, addition products of from 1 to 3 mol of propylene oxide with 1 mol of glycerol and addition products of f rom 1 to 5 mol of ethylene oxide and/or propylene oxide with 1 mol of oligoglycerol having from 2 to 5 co~-n~n~l~n~ed glycerol units.
Preferred polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol and pentaerythritol. It is of course also possible to use mixtures of polyhydric alcohols in the preparation of the 30 aromatic blocks (b).
The amphiphilic polyesters have weight average ~ le~ r weights of from 1500 to 25,000, preferably from 2500 to 7500. The ratio of the ester units (a): ~b) in the ~ irh;lir! polyesters is 35 within the range from 5: 1 to 1: 2, preferably within the range from 3: 1 to 1: 1.
The amphiphilic polyesters of the invention can be prepared for example by initially, in a first reaction stage, synth~ 7;n~ an 40 aromatic block (b) by, for example, ~ n~lQnq;n~ terephthalic acid or dimethyl terephthalate with polyhydric alcohols to prepare oligomeric alkylene terephthalates having hydrcxy end groups.
Such polycondensates are obtained on carrying out the condensation of the starting materials with a ~olar excess of 45 oH-containing compounds, ie. a molar excess of polyhydric alcohol. The pr~ d~ncates thus obtainable are then reacted in a second reaction stage with an aliphatic dicarboxylic acid, an 0050/4g586 ester of a dicarboxylic acid or an anhydride of a dicarboxylic acid (if the dicarboxylic acids can form anhydrides), a water-soluble polyalkylene glycol and optionally a - ~Lu~yuarboxylic acid or ester to form the 2mrh;~hilir 5 polyester3 of the invention.
Eiowever, the reaction of the first stage can also be carried out by, f or example, reacting terephthalic acid or dimethyl tere-phthalate and polyhydric alcohols to prepare nl ;,~ C alkylene lO terephthalates having carboxy end groups (molar excess of carbox-yl groups in the polycondensation) and then reacting these pre-condensates in a second reaction stage with at least one monohy-droxycarboxylic acid or ester to form a polyester which has car-boxy end groups from the .-~ d mono~lydLu,.y~.~.rboxylic acid 15 and which is subsequently reacted with a polyethylene glycol and optionally an aliphatic dicarboxylic acid or ester to form the amphiphilic polyesters.
The use of the ~ -~ydLo..y~ ,lrboxylic acid in the condensation is 20 facultative. The stage 1 pr~rr~A~nDate having carboxyl end groups can also be reacted directly with at least one polyalkylene glycol and at least one aliphatic dicarboxylic acid.
Eiowever, the ;rh;l;r polyesters of the invention may also be 25 prepared by linking a pr~rnn~ nDate having carboxyl end groups, f ormed f or example f rom terephthalic acid or dimethyl terephtha-late and a polyhydric alcohol, with a separately prepared ali-phatic block of a water-soluble esterification product of 1 mol of a polyalkylene glycol and 2 mol of a monohydroxycarboxylic 30 acid by esterification. The esterification product may addition-ally have been reacted with at least one aliphatic dicarboxylic acid .
A further process variant for preparing the polyesters of the 35 invention comprises initially, in a first reaction stage, reacting at least one polyalkylene glycol and at least one ali-phatic dicarboxylic acid and optionally at least one monohydroxy-rhn~ ylic acid to create a pre~nnflpnnate and, in a second reaction stage, rnnrlonc;ng the pr~rnnti~ncate with a mixture of at 40 least one polyhydric alcohol and at least one aromatic dicarbox-ylic acid or ester to form the amphiphilic polyesters of the invention .
In the preparation of the block =>LLuuLu~c:d polycondensates of the 45 invention, the starting materials are used in such a ratio that the weight ratio of the ester units (a): (b) in the polyester products is within the range from 5: 1 to 1: 2, preferably - ~ 7 2 1 78~08 within the range from 3: 1 to 1: 1. The _~;rhilic polyesters are u~ed as additive in laundry detergents, other laundry detergent additives and laundry aftertreatments. They promote the release of hydrophobic stains in wash liquors, especially in the 5 case of textiles composed of polyester f abric or polyester blend fabrics. Other laundry del eLyellt additives for the purposes of the present invention are to be understood as meaning for example water softeners (eg. sheet--silicates, polycarboxylates or phosphates ) or bleaches . The polyesters to be used according to 10 the invention are particularly effective when the fabric has already been washed or impregnated therewith bef ore becoming stained .
The polyesters of the invention can be present as additive not 15 only in pulverulent but also in li~uid laundry detergent formulations. The anounts of polyester used range for example from O . 05 to 15 ~ by weight, based on the respective formulation.
The amphiphilic polyesters are preferably used in phosphate-free and Le~u- ed phosphate laundry detergents or in laundry 20 aftertreatments, such as fabric conditioners. Reduce~ phv~hate laundry detergents generally include less than 25 i by weight of phosphate .
The polyesters of the invention are soluble or dispersible in 25 water. They can be used in the form of an aqueous solution, as disper3ion or as powder in the preparation of laundry detergents.
A particular advantage of the novel ,~iphi~ polyesters with block structure is the better biodegradability compared with polyesters of purely aromatic carboxylic acids with otherwise the 30 same construction.
The composition of laundry and cleaner detergent formulations can vary greatly. Laundry and cleaner detergent formulations customarily include from 2 to 50 % by weight of surfactants and 35 optionally builders. These figures apply both to li~uid and pulverulent laundry detergents. Laundry and cleaner detergent formulations customary in Europe, the U.S. and Japan are shown in table form for example in Chemical and Engn. News, Vol. 67, 35 (1989). Further data about the composition of laundry and cleaner 40 detergents may be found in WO-A-90/13581 and also in Ullmanns Encyklopadie der t~-hn; ~rh~n Chemie, Verlag Chemie, Weinheim 1983, 4th Edition, pages 63-160. Laundry detergents may additionally contain a bleach, for example sodium perborate, which, if used, may be present in the laundry detergent 45 formulation in amounts of up to 30 ~ ~y weight. Laundry and cleaner detergents may include further customary additives, for example - 1 c.-ri n~ agentg, or pacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, grayness inhibitors and/or bleach activators.
The percentages in the examples are by weight. The polymers of 5 the invention are characterized by det~rmi n; nq the OE~ num~ber and the acid number. These characteristic numbers were determined by standard methods, for example described in E. Muller, Eouben-Weyl, llethoden der organischen Chemie, Georg Thieme Verlag, Stuttgart 1963, Vol. 14/2, p. 17/18.
The molecular weights were determined by gel permeation chromatography (solvent: tetrahydrofuran, column material: PL-gel from Polymer Laboratories, GEI - elution rate: 0.8 ml/min, temperature: 35C). The standard used was narrow-distribution 15 polystyrene. Detection was ef fected with a W detector at 254 rm.
Examples Example l ~ -~
An apparatus suitable for carrying out polycondensations, which was heatable and equipped with a stirrer, a device for working under nitrogen and a stillhead, was charged with 600 g of polyethylene glycol having a number average 1 ~r~ r weight of 25 1500 and 88.0 g of succinic anhydride, followed by 0.86 g of p-toluenesulfonic acid monohydrate and 0 . 86 g of 50 % strength aqueous phosphorus acid, and the contents were heated for 2 hours at 180C while stirring under nitrogen.
30 To this preproduct were then added 127 g of ethylene glycol and 132. 8 g of terephthalic acid and the reaction mixture was heated up in stages to 245C under a stream of nitrogen. The water formed in the course of the polycondensation was distilled of f via a column together with volatiles. Following a condensation time of 35 3 hours and of 4 hours, a further 10 g of ethylene glycol were added each time. After 5 hours the column was removed and sufficient water distilled off until the polycondensate had an acid nu~m~-ber of 2. After 8.5 hour3 of condensation, excess ethylene glycol was distilled off under reduced pressure and the 40 condensation continued ~or 1. 5 hours at 1 mbar and 245C.
The product obtained was a pale beige solid wi~h a weight average r-l ~c~ r weight of 4100.
0050~44586 2~78908 Example 2 Example 1 was repeated using 1.13 g of para-toluenesulfonic acid, 1.13 g of phosphorus acid ~50 % strength), 186 g of ethylene 5 glycol and 265. 6 g of terephthalic acid.
The product obtained was a pale beige solid with a weight average molecular weight of 17, 800 .
10 Example 3 Example l was repeated using 1.13 g of para-toluenesulfonic acid, 1.35 g of phosphorus acid (50 % strength), 260.4 g of ethylene glycol and 3g8.4 g of terephthalic acid.
The product obtained was a pale beige solid with a weight average ~oC~llAr weight of 14,700.
Example 4 - -20Example 3 was repeated with the condensation phase at the end shortened to 1 hour.
The product obtained was a pale beige solid with a weight average 25 ---ler~llAr weight of 10,200.
Example 5 In the apparatus described in Example 1, 750 g of polyethylene 30 glycol having a number average molecular weight of 4000, 41.3 g of succinic anhydride, 1. o g of p-tt~l llc~noc~lll frn; r acid monohydrate and 1. 0 g of 50 % strength aqueous phosphorus acid were mixed and rrln~on~oA at 245C under nitrogen for 2 hours. To this pl~:~lGd~ were then added 87.3 g of ethylene glycol and 35 124.5 g of terephthalic acid and the condensation was continued at the stated temperature while volatiles were distilled off via a column. Following a condensation time of 5 hours the column was removed and the distillation continued until the polycondensation product had an acid number of 3 . 5 . Following a condensation time 40 of 6 hours and of 8 hours a further lO g of ethylene glycol were added each time. After a total of 10.5 hours the excess ethylene glycol was distilled off and the condensation continued at 145C
and l mbar for 1. 5 hours .
45 The product obtained was a pale beige hard solid with a weight average ~ rlll Ar weight of 8400.
'- ~ 10' ' ' 2l789o8 Example 6 In the apparatus described in Example 1, 466.1 g of dimethyl terephthalate, 429.0 g of ethylene glycol and 0.90 g of 5 tetrabutyl orthotitanate were pr~-cnn~ nc~d at from 150 to 180C
for 2 hours while methanol was distilled off and, s~lhs~q~l~ntly, eYcess ethylene glycol was distilled off under reduced pressure.
Following :lo ~ssion with inert gas, 900 g of polyethylene glycol having a number average l~rlll i3r weight of 1500 and 132 g 10 of succinic anhydride were added, and the condensation was initially carried out at atmospheric pressure with a 3tepwise increase in temperature from 180C to 245C. A vacuum was applied from an acid number of 23 and the condensation completed at 1 mbar over 4 hours.
The product obtained was a pale brown solid having a weight average ~ r~ r weight of 6800.
Example 7 Example 5 was repeated with 600 g of polyethylene glycol having a number average molecular weight 4000 being r~n~l~n~ with 33.0 g of succinic anhydride, 1. 05 g of para-toluenesulfonic acid, 2.13 g of phosphorus acid (50 % strength), 169 g of ethylene 25 glycol and 265. 6 g of terephthalic acid.
The product obtained was a pale brown soiid with a weight average molecular weight of 12,400.
30 Example 8 Example 5 was repeated with 600 g of polyethylene glycol having a number average --lerl-l~r weight 4000 being rrn~1~n~ with 33.0 g of succinic anhydride, 1.19 g of para--toluenesulfonic acid, 35 2.38 g of phosphorus acid (50 % strength), 192.6 g of ethylene glycol and 348. 6 g of terephthalic acid.
The product obtained was a pale brown solid with a weight average molecular weight of 13,100.
Example 9 In the apparatus described in Example 1, 600 g of polyethylene glycol having a number average molecular weight of 1500, 128.6 g 4~ of adipic acid, 1.39 g of p-toluenesulfonic acid monohydrate and 1.39 g of 50 % strength aqueous phosphorus acid were mixed and heated under a stream of nitrogen to 180C for 2 hours while the water formed in the course of the condensation was distilled off.
~o this P1~LL~dU~L wa8 then added 160.4 g of ethylene glycol and 39E . 4 g of terephthalic acid and the condensation was continued at 245C. The volatiles were distilled off via a column. After 5 5 hours the column was removed and the reaction mixture was rl~n~d with distillative removal of water until it had an acid nuslber of 3.5, 10 g of diethylene glycol being added after 6 hours and after 8 hours. Following a condensation time of 10.5 hours the excess diethylene glycol was distilled off under 10 reduced pressure.
The product obtained was a pale beige hard solid with a weight average r~ r weight of 9700.
1~ Example 10 Example 9 was repeated using 1.18 g of para--toluenesulfonic acid, 1.18 g of phosphorus acid (50 9~ strength), 186 g of ethylene glycol and 265. 6 g of terephthalic acid. - --20The product obtained was a colorless solid with a weight average molecular weight of 4300.
Example 1 1 Example 6 was repeated using 192. 7 g of adipic acid instead of the succinic anhydride.
The product obtained was a pale brown solid with a weight average 30 l er~ r weight of 8400.
The soiI-release properties of the polymers were determined in a wash test. This was done by measuring the reflectance (instrument: Data color 2000~ of the test fabrics (R1) following 35 3-fold ~L~. -hin~ (Table 1 contains the washing conditions). The fabrics were then stained with used engine oil and the reflectance was determined 24 hours later (R2). This was followed by a further wash before another reflectance measurement (R3). The soil release S in 96 was calculated by the formula 40 s=(R3--R2)/(R1--R2)~100.
.
12 ' ' 2 ~ 78908 ~rable 1: Washing conditions Wa3hing machine Launder-o-meter Detergent liquor 250 ml Detergent dose 6 y/l Wash time 30 min Was h temperature 6 0 C
10 Prewash cycle 3 q~est fabrics 10 g of cotton, 5 g of polyester-cotton 5 g of polyester Staining 0 . 2 g o~ used engine oil on polyester 15 ~able 2 contains the composition of the test detergents used. The detergent formulations indicated in ~able 2 included 1 % of a polycondensate according to Example 11.
~ ~
0050t44586 UU ~ O ~0 O N r~ O Ul r~ I r~l I I O I r-l 1 O_I N r~
IJl ~ O ~D O N ~ O 1~) a~ II r~) ~ I ~ ~ I o I I
_I N ~
o o o o N 1 0 Il') ro II r~ r~) O I I I ~ O r~) -1 N ~ O
--I ~ O ~0 O N ro O Ul O
N ~ ~ 1~ o o ~ o N O~ O I
N ~ 3 ~r_I d' O O ~) O N CD O 11 ) L~ ~r~ In ~ ~ ~ rr~ o I I I ~ r~) _I N ~ ..
~ ~1 ~ O ~0 O N CD O Lll dP ~r r2 1 Ul ~I I --Nl r~ rr) ~
O
~r _I ~ o ~c> o N ~ 0 11'1 r~ c~ I 111 ~ I ~Nl r~ I I r~
Q) ~ ~ ~r o ~D O N r~ O 11 r~l ~ I u~ ~ I ,I r~ I o I I ~
_I ~ O ~D O N rD O 1'1 I,n _, ~ . ~r~ o I I I ,, ~7 ~3 "~
_, ~ r r~
~` r dD
,, ~," O
O _ ~ Ul - 'I~
r~ 1~ ~ C O
+ ~ r~ o dP, ~ o ~
~, m .- . . ,, In O ' J U . p~
- X . 1~ ~ ' C~ r ~, ~, ~" X Id O O O O ~ ~ O
rJ I ~ ~ U 0 ~ U~ U~ L~~ E'l Ul ~ N
2 l 78~08 The results in Table 3 show that in all cases a 80il removal ~ S ) of more than 80 96 takes place when polymer is used.
5 Table 3: sOil release Rl = 81 96 Ex .Comp . Formu- Polymer f ( R2 ) ( R3 ) 5 Ex. lation Example 11 stained washed ( ~ ) 1 1 --- 19.1 29.0 16.0 12 1 1 ~ by weight 19.5 73.6 88.0 2 2 --- 19.6 24.4 7.8 13 2 1 ~ by weight 19.3 71.3 84.3 3 3 ---- 19.4 26.4 11.4 15 14 3 1 ~ by weight 19.4 74.6 89.6 4 4 --- 18.9 27.4 13.7 4 1 ~ by weight 19.7 73.6 87.g 5 S --- 19.6 -33.1 22.0 20 16 5 1 9s by weight 19.3 74.3 89.1 6 6 --- 19.2 23.3 6.6 17 6 1 v6 by weight 18.9 70.9 83.7 7 7 --- 19.1 33.6 23.4 25 18 7 1 ~ by weight 19.0 73.8 88.4 8 8 --- 19.1 44.6 41.2 19 8 1 ~ by weight 18 . 9 78 . 6 96 .1 9 9 --- 18.8 35.2 26.4 g 1 % by weight 18.9 78.4 95.8 10 10 --- 19.0 44.3 40.8 21 10 ~ 1 ~ by weight 21.0 79.2 97.0 The effectiveness o~ polymers was also tested in a branded 35 detergent, Persil color from E~enkel KGaA. The test condition3 chosen corresponded to the data of Table 1. Table 4 contains the respective ~mrh; rh; l; c block copolyesters tested and also the 80il removal results. The amounts of polymer are based on the amounts of detergent used.
The wash results in Table 4 show that the soil removal is distinctly improved with the polymers prepared according to Examples 1 to 11.
5 Table 4: Soil removal in a branded detergent Block polyester prepared S ( 96 ) 5 ( 9~ ) Example according to Example without with 1 9~ o~
polymer polymer 3211 42 g2 -
US-A-3 557 039 ii qrl 05~c stable aqueous dispersions of polymers lO preparable by condensation of terephthalic acid or dimethyl terephthalate with ethylene glycol and polyethylene glycol having an average l ~r~ll Ar weight of from 1000 to 4000 . The molar ratio of ethylene terephthalate to polyethylene glycol terephthalate units is within the range from 2 :1 to 6 :1. The dispersions are 15 used for treating the surfaces of polyester articles.
GB-Al 154 730 ~1i qrl os~,q reducing 50il redeposition in the washing of textile material by adding to the wash li~uor, which contains a detergent, polycondensates containing either repeating ester or 20 amide units. ~hese additives are for example condensatioh products known from the above-cited U.S. Patent 3,557,039 and are obtainable by condensation of dimethyl terephthalate, ethylene glycol and polyethylene glycol having 2 - l~rlllAr weight of 1500.
25 EP Applications 185 427, 241 984, 241 985 and 272 033 disclose polyester condensates of polybaaic aromatic carboxylic acids with dihydric alcohols and one-sidedly C1-C4-capped polyethers, which promote soil release from polyester fabrics. These polyesters have hydrophilic end groups which, in the cited applications, are 30 mentioned as the basis of the soil-releasing properties of the polyesters .
P ' iE~hil;c polyesterg of aliphatic polybasic carboxylic acids and/or ~h~dL~ y nrArhnyylic acids with polyethylene glycol 35 are described for example in Polymer Bulletin, Volume 17, 499 - 506 (1987).
US-A-5 142 020 ~l;cr1O~ Amrh;rhilir polyesters obtainable by condensation of (a~ carboxylic acids having at least 2 carboxyl groups, their esters, anhydr des or mixtures, 2 2 ~ 78908 (b) at least dihydric alcohols and/or addition products of from 1 to 5 mol o~ at least one alkylene oxide having 2 or 3 carbon atoms with 1 mol of an at least dihydric alcohol or mixtures and (c) water-soluble addition products of from 5 to 80 mol of at least one alkylene oxide wLth 1 mol of C8-Cz4-alcohols, C8-C18-alkylphenols or C8-C24-alkylamines 10 in a molar ratio of (a):(b):(c) of 100:(from 25 to 2500):(from 5 to 110) at temperatures of at least 120C to weight average ~ l~.r~ r weightg of from 2000 to 50,000. The polyesters are used as grayness-inhibiting and soil-release additive in pulverulent and lis~uid laundry deterge~ts.
It is an ob~ect of the pre~ent invention to provide novel substances and laundry detergent additives.
We have found that this object is achieved by . irh;l;r 20 polyesters containing (a) ester units derived from polyalkylene glycols having a l~clll ~r weight of from 500 to 7500 and aliphatic dicarboxylic acids and/or ~ dL-)~y rh~xylic acids and (b) ester units derived from aromatic dicarboxylic acids and polyhydric alcohols and having molecular weights of from 1500 to 25,000.
The ~mrh;rh;l;r polye6ters are obtained by polyrrmti~n~;n~ to prepare f irs t (a~ aliphatic polyesters of polyalkylene glycols having a molecular weight of from 500 to 7500 with aliphatic dicarboxylic acids and/or monully~ y -_ rboxylic acids and then, within the aliphatic polyester thus obtained, (b~ aromatic polyesters from aromatic dicarboxylic acids and polyhydric alcohols, reversing the order o~ the polycondensation, or rr~n~l~n~n~
oligomeric aromatic polyesters ( b ) with oligomeric aliphatic polyes ters ( a ) .
The ab~ des.:Llbed nn~h~rh;l;s polyesters are used as additive in laundry detergents, other laundry detcrgent additives and laundry aftertreatments.
5 The amphiphilic polyesters having ester units derived from (a) polyalkylene glycols and aliphatic dicarboxylic acids and/or '~dL(~'Y '7 rhr yy1iC acidg (hereinafter called Naliphatic blockN) and (b) aromatic dicarboxylic acids and polyhydric alcohols (hereinafter called naromatic blockN) have soil--release 10 properties in wash liquors and are very readily biodegradable.
The aliphatic blocks (a) are prepared by polycondensatlon of polyalkylene glycols having a ~ ~r r~ r weight of from 500 to 7500 with aliphatic dicarboxylic acids and/or monohydroxy-15 (n~ ~rh~Yylic acids in a conventional manner. Thepolycondensation i5 carried out for example at temperatures of at least 120C, preferably within the t~ ULe range from 150 to 260C, in the presence of customary polycondensation or transesterification catalysts. Typically, the reaction 20 participants are ~ nfl~n~d in an inert gas atmosphere in the presence or absence of further additives, such as antioxidants.
Such processes are known for example from US-A-3 557 039 mentioned at the h~; nn; ng, 25 Suitable catalysts include all Ul~d~ described in the literature for this purpose. When the free polycarboxylic acids or the anhydrides are used in the condensation, p-toluenesulfonic acid i8 the preferred catalyst. When dialkyl dicarboxylates or polycarboxylic esters are used, the customary transesterification 30 catalysts are used, such as, for example, zinc acetate, mixtures of calcium acetate and antimony oxide or tetraalkoxytitanates, such as titanium tetraisobutoxide or titanium tetraisopropoxide.
Other pre~erred catalysts are for example carbonates, acetates and/or Cl-C~-alkoxylates of lithium, sodium, r-gn~a; ~ cobalt, 35 manganese, vanadium, titanium and tin and also tin oxides. The catalysts are generally used in amounts of from 20 to 5000, preferably from 50 to 2000, ppm, based on the components used in the condensation.
40 The condensation can be carried out in the presence of anti-oxidants, for example substituted phenols, such as, for example, 2, 5--di-tert-butylphenol, 2-methylcyclohexyl-4, 6-dimethylphenol, 2, 6--di-tert-butyl-4-methylphenol, pyrogallol, phosphoru3 acid or other antioxidants customary for this purpose. These compounds 45 prevent discoloration of the polyesters due to oxidation during the condensation.
.
4 2 l 78908 Suitable polyalkylene glycols for preparing the aliphatic blocks (a) have number average ler~ r weights of from 500 to 7500, preferably from 1000 to 4500. The polyalkylene glycols are water-soluble. They are preferably derived from ethylene oxide, 5 propylene oxide, n--butylene oxide or isobutylene oxide and are prepared for example by addition of the alkylene oxides to dihydric alcohols. This can be done for example by adding only ethylene oxide or propylene oxide to a dihydric alcohol, such as ethylene glycol or propylene glycol, or by preparing block 10 copolymers by first adding ethylene oxide and then propylene oxide to a dihydric alcohol or vice versa. In the preparation of the polyalkylene glycols, propylene oxide, for example, may be wholly or partly replaced by a butylene oxide. Similarly, random polyalkylene oxides obtainable by addition of a mixed gas of at 15 least two alkylene oxides to a dihydric alcohol can be used as polyalkylene glycols in the preparation of the aliphatic blocks (a). The preferred polyalkylene glycols are ethylene glycol, propylene glycol and block copolymers of ethylene oxide and propylene oxide. - --20Suitable aliphatic dicarboxylic acids contain for example from 2 to 10 carbon atoms. Examples are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. They can be used either 25 alone or mixed, for example as mixtures of oxalic acid and succinic acid or of succinic acid and adipic acid, in the prepar~tion of the aliphatic blocks.
The preparation of the aliphatic blocks of the _ ~ i rh i 1 i r 30 polyesters may be ef fected in the additional presence of mono~ v,.y rhrYylic acids. A further variant comprises using monohydL~,~y ~ rboxylic acids instead of the aliphatic dicarboxylic acid8. The r ~YIL~ rhrl~rylic acids are likewise aliphatic carboxylic acids. Examples are glycolic acid, 35 lactic acid, u~-llydL~ yaLearic acid and (o-hydroxycaproic acid.
They can be used individually or mixed in the preparation of the aliphatic blocks.
The aliphatic blocks are preferably prepared by polycondensation 40 of polyethylene glycol with succinic acid or adipic acid. In this preferred variant, the polycondensation may be carried out in the additional presence of ~-hydroxycaproic acid and/or lactic acid.
The aromatic block (b) of the .~irhilir polyesters is 45 obtainable by polycondensation of aromatic dicarboxylic acids with f or example aliphatic polyhydric alcohols . The polycondensation is carried out by the same methods as used for .
2 1 78~08 preparing the 21iphatic blocks ( a ) . The weight average l F~n~ r weights of the aromatic blocks ~ b ) are customarily within the range from about 192 to 5000, preferably from about 384 to 1500.
5 Suitable aromatic dicarboxylic acids include for example terephthalic acid, phthalic acid and sulfoisophthalic acid. The preferred aroma~ic dicarboxylic acid is terephthalic acid. The dicarboxylic acids may also be used mixed with one another.
10 Suitable aliphatic polyhydric alcohols include for example ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, pen~n~ , glycerol, pentaerythritol, oligoglycerols having 1 ~rl~ r weights of up to 363 and also addition products of from 1 to 5 mol of ethylene 15 oxide and/or propylene oxide with 1 mol of the abovementioned at least dihydric alcohols. Examples of such addition products are ethylene diglycol and propylene diglycol. Also of interest are the addition products of from 1 to 4 mol of ethylene oxide with pentaerythritol, addition products of from 1 to 3-mol of ethylene 20 oxide with 1 mol of glycerol, addition products of from 1 to 3 mol of propylene oxide with 1 mol of glycerol and addition products of f rom 1 to 5 mol of ethylene oxide and/or propylene oxide with 1 mol of oligoglycerol having from 2 to 5 co~-n~n~l~n~ed glycerol units.
Preferred polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol and pentaerythritol. It is of course also possible to use mixtures of polyhydric alcohols in the preparation of the 30 aromatic blocks (b).
The amphiphilic polyesters have weight average ~ le~ r weights of from 1500 to 25,000, preferably from 2500 to 7500. The ratio of the ester units (a): ~b) in the ~ irh;lir! polyesters is 35 within the range from 5: 1 to 1: 2, preferably within the range from 3: 1 to 1: 1.
The amphiphilic polyesters of the invention can be prepared for example by initially, in a first reaction stage, synth~ 7;n~ an 40 aromatic block (b) by, for example, ~ n~lQnq;n~ terephthalic acid or dimethyl terephthalate with polyhydric alcohols to prepare oligomeric alkylene terephthalates having hydrcxy end groups.
Such polycondensates are obtained on carrying out the condensation of the starting materials with a ~olar excess of 45 oH-containing compounds, ie. a molar excess of polyhydric alcohol. The pr~ d~ncates thus obtainable are then reacted in a second reaction stage with an aliphatic dicarboxylic acid, an 0050/4g586 ester of a dicarboxylic acid or an anhydride of a dicarboxylic acid (if the dicarboxylic acids can form anhydrides), a water-soluble polyalkylene glycol and optionally a - ~Lu~yuarboxylic acid or ester to form the 2mrh;~hilir 5 polyester3 of the invention.
Eiowever, the reaction of the first stage can also be carried out by, f or example, reacting terephthalic acid or dimethyl tere-phthalate and polyhydric alcohols to prepare nl ;,~ C alkylene lO terephthalates having carboxy end groups (molar excess of carbox-yl groups in the polycondensation) and then reacting these pre-condensates in a second reaction stage with at least one monohy-droxycarboxylic acid or ester to form a polyester which has car-boxy end groups from the .-~ d mono~lydLu,.y~.~.rboxylic acid 15 and which is subsequently reacted with a polyethylene glycol and optionally an aliphatic dicarboxylic acid or ester to form the amphiphilic polyesters.
The use of the ~ -~ydLo..y~ ,lrboxylic acid in the condensation is 20 facultative. The stage 1 pr~rr~A~nDate having carboxyl end groups can also be reacted directly with at least one polyalkylene glycol and at least one aliphatic dicarboxylic acid.
Eiowever, the ;rh;l;r polyesters of the invention may also be 25 prepared by linking a pr~rnn~ nDate having carboxyl end groups, f ormed f or example f rom terephthalic acid or dimethyl terephtha-late and a polyhydric alcohol, with a separately prepared ali-phatic block of a water-soluble esterification product of 1 mol of a polyalkylene glycol and 2 mol of a monohydroxycarboxylic 30 acid by esterification. The esterification product may addition-ally have been reacted with at least one aliphatic dicarboxylic acid .
A further process variant for preparing the polyesters of the 35 invention comprises initially, in a first reaction stage, reacting at least one polyalkylene glycol and at least one ali-phatic dicarboxylic acid and optionally at least one monohydroxy-rhn~ ylic acid to create a pre~nnflpnnate and, in a second reaction stage, rnnrlonc;ng the pr~rnnti~ncate with a mixture of at 40 least one polyhydric alcohol and at least one aromatic dicarbox-ylic acid or ester to form the amphiphilic polyesters of the invention .
In the preparation of the block =>LLuuLu~c:d polycondensates of the 45 invention, the starting materials are used in such a ratio that the weight ratio of the ester units (a): (b) in the polyester products is within the range from 5: 1 to 1: 2, preferably - ~ 7 2 1 78~08 within the range from 3: 1 to 1: 1. The _~;rhilic polyesters are u~ed as additive in laundry detergents, other laundry detergent additives and laundry aftertreatments. They promote the release of hydrophobic stains in wash liquors, especially in the 5 case of textiles composed of polyester f abric or polyester blend fabrics. Other laundry del eLyellt additives for the purposes of the present invention are to be understood as meaning for example water softeners (eg. sheet--silicates, polycarboxylates or phosphates ) or bleaches . The polyesters to be used according to 10 the invention are particularly effective when the fabric has already been washed or impregnated therewith bef ore becoming stained .
The polyesters of the invention can be present as additive not 15 only in pulverulent but also in li~uid laundry detergent formulations. The anounts of polyester used range for example from O . 05 to 15 ~ by weight, based on the respective formulation.
The amphiphilic polyesters are preferably used in phosphate-free and Le~u- ed phosphate laundry detergents or in laundry 20 aftertreatments, such as fabric conditioners. Reduce~ phv~hate laundry detergents generally include less than 25 i by weight of phosphate .
The polyesters of the invention are soluble or dispersible in 25 water. They can be used in the form of an aqueous solution, as disper3ion or as powder in the preparation of laundry detergents.
A particular advantage of the novel ,~iphi~ polyesters with block structure is the better biodegradability compared with polyesters of purely aromatic carboxylic acids with otherwise the 30 same construction.
The composition of laundry and cleaner detergent formulations can vary greatly. Laundry and cleaner detergent formulations customarily include from 2 to 50 % by weight of surfactants and 35 optionally builders. These figures apply both to li~uid and pulverulent laundry detergents. Laundry and cleaner detergent formulations customary in Europe, the U.S. and Japan are shown in table form for example in Chemical and Engn. News, Vol. 67, 35 (1989). Further data about the composition of laundry and cleaner 40 detergents may be found in WO-A-90/13581 and also in Ullmanns Encyklopadie der t~-hn; ~rh~n Chemie, Verlag Chemie, Weinheim 1983, 4th Edition, pages 63-160. Laundry detergents may additionally contain a bleach, for example sodium perborate, which, if used, may be present in the laundry detergent 45 formulation in amounts of up to 30 ~ ~y weight. Laundry and cleaner detergents may include further customary additives, for example - 1 c.-ri n~ agentg, or pacifiers, optical brighteners, enzymes, perfume oils, color transfer inhibitors, grayness inhibitors and/or bleach activators.
The percentages in the examples are by weight. The polymers of 5 the invention are characterized by det~rmi n; nq the OE~ num~ber and the acid number. These characteristic numbers were determined by standard methods, for example described in E. Muller, Eouben-Weyl, llethoden der organischen Chemie, Georg Thieme Verlag, Stuttgart 1963, Vol. 14/2, p. 17/18.
The molecular weights were determined by gel permeation chromatography (solvent: tetrahydrofuran, column material: PL-gel from Polymer Laboratories, GEI - elution rate: 0.8 ml/min, temperature: 35C). The standard used was narrow-distribution 15 polystyrene. Detection was ef fected with a W detector at 254 rm.
Examples Example l ~ -~
An apparatus suitable for carrying out polycondensations, which was heatable and equipped with a stirrer, a device for working under nitrogen and a stillhead, was charged with 600 g of polyethylene glycol having a number average 1 ~r~ r weight of 25 1500 and 88.0 g of succinic anhydride, followed by 0.86 g of p-toluenesulfonic acid monohydrate and 0 . 86 g of 50 % strength aqueous phosphorus acid, and the contents were heated for 2 hours at 180C while stirring under nitrogen.
30 To this preproduct were then added 127 g of ethylene glycol and 132. 8 g of terephthalic acid and the reaction mixture was heated up in stages to 245C under a stream of nitrogen. The water formed in the course of the polycondensation was distilled of f via a column together with volatiles. Following a condensation time of 35 3 hours and of 4 hours, a further 10 g of ethylene glycol were added each time. After 5 hours the column was removed and sufficient water distilled off until the polycondensate had an acid nu~m~-ber of 2. After 8.5 hour3 of condensation, excess ethylene glycol was distilled off under reduced pressure and the 40 condensation continued ~or 1. 5 hours at 1 mbar and 245C.
The product obtained was a pale beige solid wi~h a weight average r-l ~c~ r weight of 4100.
0050~44586 2~78908 Example 2 Example 1 was repeated using 1.13 g of para-toluenesulfonic acid, 1.13 g of phosphorus acid ~50 % strength), 186 g of ethylene 5 glycol and 265. 6 g of terephthalic acid.
The product obtained was a pale beige solid with a weight average molecular weight of 17, 800 .
10 Example 3 Example l was repeated using 1.13 g of para-toluenesulfonic acid, 1.35 g of phosphorus acid (50 % strength), 260.4 g of ethylene glycol and 3g8.4 g of terephthalic acid.
The product obtained was a pale beige solid with a weight average ~oC~llAr weight of 14,700.
Example 4 - -20Example 3 was repeated with the condensation phase at the end shortened to 1 hour.
The product obtained was a pale beige solid with a weight average 25 ---ler~llAr weight of 10,200.
Example 5 In the apparatus described in Example 1, 750 g of polyethylene 30 glycol having a number average molecular weight of 4000, 41.3 g of succinic anhydride, 1. o g of p-tt~l llc~noc~lll frn; r acid monohydrate and 1. 0 g of 50 % strength aqueous phosphorus acid were mixed and rrln~on~oA at 245C under nitrogen for 2 hours. To this pl~:~lGd~ were then added 87.3 g of ethylene glycol and 35 124.5 g of terephthalic acid and the condensation was continued at the stated temperature while volatiles were distilled off via a column. Following a condensation time of 5 hours the column was removed and the distillation continued until the polycondensation product had an acid number of 3 . 5 . Following a condensation time 40 of 6 hours and of 8 hours a further lO g of ethylene glycol were added each time. After a total of 10.5 hours the excess ethylene glycol was distilled off and the condensation continued at 145C
and l mbar for 1. 5 hours .
45 The product obtained was a pale beige hard solid with a weight average ~ rlll Ar weight of 8400.
'- ~ 10' ' ' 2l789o8 Example 6 In the apparatus described in Example 1, 466.1 g of dimethyl terephthalate, 429.0 g of ethylene glycol and 0.90 g of 5 tetrabutyl orthotitanate were pr~-cnn~ nc~d at from 150 to 180C
for 2 hours while methanol was distilled off and, s~lhs~q~l~ntly, eYcess ethylene glycol was distilled off under reduced pressure.
Following :lo ~ssion with inert gas, 900 g of polyethylene glycol having a number average l~rlll i3r weight of 1500 and 132 g 10 of succinic anhydride were added, and the condensation was initially carried out at atmospheric pressure with a 3tepwise increase in temperature from 180C to 245C. A vacuum was applied from an acid number of 23 and the condensation completed at 1 mbar over 4 hours.
The product obtained was a pale brown solid having a weight average ~ r~ r weight of 6800.
Example 7 Example 5 was repeated with 600 g of polyethylene glycol having a number average molecular weight 4000 being r~n~l~n~ with 33.0 g of succinic anhydride, 1. 05 g of para-toluenesulfonic acid, 2.13 g of phosphorus acid (50 % strength), 169 g of ethylene 25 glycol and 265. 6 g of terephthalic acid.
The product obtained was a pale brown soiid with a weight average molecular weight of 12,400.
30 Example 8 Example 5 was repeated with 600 g of polyethylene glycol having a number average --lerl-l~r weight 4000 being rrn~1~n~ with 33.0 g of succinic anhydride, 1.19 g of para--toluenesulfonic acid, 35 2.38 g of phosphorus acid (50 % strength), 192.6 g of ethylene glycol and 348. 6 g of terephthalic acid.
The product obtained was a pale brown solid with a weight average molecular weight of 13,100.
Example 9 In the apparatus described in Example 1, 600 g of polyethylene glycol having a number average molecular weight of 1500, 128.6 g 4~ of adipic acid, 1.39 g of p-toluenesulfonic acid monohydrate and 1.39 g of 50 % strength aqueous phosphorus acid were mixed and heated under a stream of nitrogen to 180C for 2 hours while the water formed in the course of the condensation was distilled off.
~o this P1~LL~dU~L wa8 then added 160.4 g of ethylene glycol and 39E . 4 g of terephthalic acid and the condensation was continued at 245C. The volatiles were distilled off via a column. After 5 5 hours the column was removed and the reaction mixture was rl~n~d with distillative removal of water until it had an acid nuslber of 3.5, 10 g of diethylene glycol being added after 6 hours and after 8 hours. Following a condensation time of 10.5 hours the excess diethylene glycol was distilled off under 10 reduced pressure.
The product obtained was a pale beige hard solid with a weight average r~ r weight of 9700.
1~ Example 10 Example 9 was repeated using 1.18 g of para--toluenesulfonic acid, 1.18 g of phosphorus acid (50 9~ strength), 186 g of ethylene glycol and 265. 6 g of terephthalic acid. - --20The product obtained was a colorless solid with a weight average molecular weight of 4300.
Example 1 1 Example 6 was repeated using 192. 7 g of adipic acid instead of the succinic anhydride.
The product obtained was a pale brown solid with a weight average 30 l er~ r weight of 8400.
The soiI-release properties of the polymers were determined in a wash test. This was done by measuring the reflectance (instrument: Data color 2000~ of the test fabrics (R1) following 35 3-fold ~L~. -hin~ (Table 1 contains the washing conditions). The fabrics were then stained with used engine oil and the reflectance was determined 24 hours later (R2). This was followed by a further wash before another reflectance measurement (R3). The soil release S in 96 was calculated by the formula 40 s=(R3--R2)/(R1--R2)~100.
.
12 ' ' 2 ~ 78908 ~rable 1: Washing conditions Wa3hing machine Launder-o-meter Detergent liquor 250 ml Detergent dose 6 y/l Wash time 30 min Was h temperature 6 0 C
10 Prewash cycle 3 q~est fabrics 10 g of cotton, 5 g of polyester-cotton 5 g of polyester Staining 0 . 2 g o~ used engine oil on polyester 15 ~able 2 contains the composition of the test detergents used. The detergent formulations indicated in ~able 2 included 1 % of a polycondensate according to Example 11.
~ ~
0050t44586 UU ~ O ~0 O N r~ O Ul r~ I r~l I I O I r-l 1 O_I N r~
IJl ~ O ~D O N ~ O 1~) a~ II r~) ~ I ~ ~ I o I I
_I N ~
o o o o N 1 0 Il') ro II r~ r~) O I I I ~ O r~) -1 N ~ O
--I ~ O ~0 O N ro O Ul O
N ~ ~ 1~ o o ~ o N O~ O I
N ~ 3 ~r_I d' O O ~) O N CD O 11 ) L~ ~r~ In ~ ~ ~ rr~ o I I I ~ r~) _I N ~ ..
~ ~1 ~ O ~0 O N CD O Lll dP ~r r2 1 Ul ~I I --Nl r~ rr) ~
O
~r _I ~ o ~c> o N ~ 0 11'1 r~ c~ I 111 ~ I ~Nl r~ I I r~
Q) ~ ~ ~r o ~D O N r~ O 11 r~l ~ I u~ ~ I ,I r~ I o I I ~
_I ~ O ~D O N rD O 1'1 I,n _, ~ . ~r~ o I I I ,, ~7 ~3 "~
_, ~ r r~
~` r dD
,, ~," O
O _ ~ Ul - 'I~
r~ 1~ ~ C O
+ ~ r~ o dP, ~ o ~
~, m .- . . ,, In O ' J U . p~
- X . 1~ ~ ' C~ r ~, ~, ~" X Id O O O O ~ ~ O
rJ I ~ ~ U 0 ~ U~ U~ L~~ E'l Ul ~ N
2 l 78~08 The results in Table 3 show that in all cases a 80il removal ~ S ) of more than 80 96 takes place when polymer is used.
5 Table 3: sOil release Rl = 81 96 Ex .Comp . Formu- Polymer f ( R2 ) ( R3 ) 5 Ex. lation Example 11 stained washed ( ~ ) 1 1 --- 19.1 29.0 16.0 12 1 1 ~ by weight 19.5 73.6 88.0 2 2 --- 19.6 24.4 7.8 13 2 1 ~ by weight 19.3 71.3 84.3 3 3 ---- 19.4 26.4 11.4 15 14 3 1 ~ by weight 19.4 74.6 89.6 4 4 --- 18.9 27.4 13.7 4 1 ~ by weight 19.7 73.6 87.g 5 S --- 19.6 -33.1 22.0 20 16 5 1 9s by weight 19.3 74.3 89.1 6 6 --- 19.2 23.3 6.6 17 6 1 v6 by weight 18.9 70.9 83.7 7 7 --- 19.1 33.6 23.4 25 18 7 1 ~ by weight 19.0 73.8 88.4 8 8 --- 19.1 44.6 41.2 19 8 1 ~ by weight 18 . 9 78 . 6 96 .1 9 9 --- 18.8 35.2 26.4 g 1 % by weight 18.9 78.4 95.8 10 10 --- 19.0 44.3 40.8 21 10 ~ 1 ~ by weight 21.0 79.2 97.0 The effectiveness o~ polymers was also tested in a branded 35 detergent, Persil color from E~enkel KGaA. The test condition3 chosen corresponded to the data of Table 1. Table 4 contains the respective ~mrh; rh; l; c block copolyesters tested and also the 80il removal results. The amounts of polymer are based on the amounts of detergent used.
The wash results in Table 4 show that the soil removal is distinctly improved with the polymers prepared according to Examples 1 to 11.
5 Table 4: Soil removal in a branded detergent Block polyester prepared S ( 96 ) 5 ( 9~ ) Example according to Example without with 1 9~ o~
polymer polymer 3211 42 g2 -
Claims (5)
1. Amphiphilic polyesters containing blocks of (a) ester units derived from polyalkylene glycols having a molecular weight of from 500 to 7500 and aliphatic dicarboxylic acids and/or monohydroxymonocarboxylic acids and (b) ester units derived from aromatic dicarboxylic acids and polyhydric alcohols and having molecular weights of from 1500 to 25,000.
2. Amphiphilic polyesters as claimed in claim 1, wherein the weight ratio of ester units (a): (b) is within the range from 5 : 1 to 1 : 2.
3. A process for preparing the amphiphilic polyesters of claim 1 or 2, which comprises polycondensing to prepare first (a) aliphatic polyesters of polyalkylene glycols having a molecular weight of from 500 to 7500 with aliphatic dicarboxylic acids and/or monohydroxymonocarboxylic acids and then, within the aliphatic polyester thus obtained, (b) aromatic polyesters from aromatic dicarboxylic acids and polyhydric alcohols, reversing the order of the polycondensation, or condensing oligomeric aromatic polyesters (b) with oligomeric aliphatic polyesters (a).
4. A process as claimed in claim 3, wherein the weight ratio of (a): (b) is within the range from 3: 1 to 1: 1.
5. The use of the amphiphilic polyesters of claim 1 or 2 as additive in laundry detergents, other laundry detergent additives and laundry aftertreatments.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4403866.6 | 1994-02-08 | ||
| DE4403866A DE4403866A1 (en) | 1994-02-08 | 1994-02-08 | Amphiphilic polyesters, process for their preparation and their use in detergents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2178908A1 true CA2178908A1 (en) | 1995-08-17 |
Family
ID=6509740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178908A Abandoned CA2178908A1 (en) | 1994-02-08 | 1995-01-28 | Amphiphilic polyesters, process for producing them and their use in washing agents |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5777046A (en) |
| EP (1) | EP0743962B1 (en) |
| JP (1) | JPH09509199A (en) |
| AT (1) | ATE171962T1 (en) |
| CA (1) | CA2178908A1 (en) |
| DE (2) | DE4403866A1 (en) |
| DK (1) | DK0743962T3 (en) |
| ES (1) | ES2121623T3 (en) |
| WO (1) | WO1995021880A1 (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4441189A1 (en) * | 1994-11-18 | 1996-05-23 | Basf Ag | Process for the production of fine-particle mixtures of amphiphilic polymers and inorganic solids |
| DE19506634A1 (en) * | 1995-02-25 | 1996-08-29 | Basf Ag | Process for the preparation of finely divided mixtures of amphiphilic polymers and polycarboxylates and their use |
| EP0749998A1 (en) * | 1995-06-21 | 1996-12-27 | Hüls Aktiengesellschaft | Soil release polymers based on oligoesters for releasing oily and fatty stains |
| DE19532717A1 (en) | 1995-09-05 | 1997-03-06 | Basf Ag | Use of modified polyaspartic acids in detergents |
| DE19616096A1 (en) * | 1996-04-23 | 1997-11-06 | Huels Chemische Werke Ag | Use of anionic gemini surfactants in formulations for washing, cleaning and personal care products |
| DE19735715A1 (en) * | 1997-08-18 | 1999-02-25 | Huels Chemische Werke Ag | Amphiphilic polymer useful as soil-release polymer |
| DE10005942A1 (en) * | 2000-02-09 | 2001-08-16 | Basf Ag | Production of graft copolymers used e.g. as coatings by polymerizing vinyl esters in presence of solid polyether comprises using liquid polyalkylene glycol as solvent for radical initiator |
| WO2000018375A1 (en) | 1998-09-30 | 2000-04-06 | Basf Aktiengesellschaft | Application of water-soluble or water-dispersible polymerizates which contain poly-ether and which are used as a coating agent, a binding agent and/or as a film-forming auxiliary agent in pharmaceutical forms of administration |
| DE19936196C2 (en) * | 1999-07-08 | 2003-10-16 | Loewen Entertainment Gmbh | Method for operating a money-operated entertainment device |
| DE10012063A1 (en) | 2000-03-14 | 2001-09-20 | Basf Ag | Soft plasticizer-free capsules for use in pharmaceuticals, cosmetics, detergents or plant protectants are made from a polymers obtained by polymerizing a vinyl ester in presence of a polyether substrate |
| DE10015468A1 (en) | 2000-03-29 | 2001-10-11 | Basf Ag | Hard capsules containing polymers and vinyl esters and polyethers, their use and production |
| DE10041163A1 (en) * | 2000-08-21 | 2002-03-07 | Basf Ag | Hair cosmetic formulations |
| DE10041211A1 (en) | 2000-08-22 | 2002-03-07 | Basf Ag | Use of hydrophilic graft copolymers with N-vinylamine and / or open-chain n-vinylamino units in cosmetic formulations |
| DE10041220A1 (en) * | 2000-08-22 | 2002-03-07 | Basf Ag | Skin cosmetic formulations |
| US20030036497A1 (en) * | 2001-06-25 | 2003-02-20 | Clariant International, Ltd. | Disintegration adjuncts for use in detergent and cleaning compositions |
| DE10245586A1 (en) * | 2002-09-27 | 2004-04-08 | Basf Ag | Use of polymers based on N-vinylcaprolactam |
| US7186789B2 (en) * | 2003-06-11 | 2007-03-06 | Advanced Cardiovascular Systems, Inc. | Bioabsorbable, biobeneficial polyester polymers for use in drug eluting stent coatings |
| DE102004007501A1 (en) | 2004-02-13 | 2005-09-01 | Basf Ag | Amphiphilic block copolymers containing aqueous polymer dispersions, processes for their preparation and their use |
| DE102004018051A1 (en) * | 2004-04-08 | 2005-11-10 | Clariant Gmbh | Detergents and cleaning agents containing dye fixing agents and soil release polymers |
| DE102004029310A1 (en) * | 2004-06-17 | 2005-12-29 | Clariant Gmbh | Highly concentrated, aqueous formulations of oligoesters and polyesters |
| DE102004051455A1 (en) | 2004-10-22 | 2006-04-27 | Clariant Gmbh | Oligoester-based water based pigment preparations, their preparation and use |
| DE102004062200A1 (en) | 2004-12-23 | 2006-07-13 | Basf Ag | Process for the preparation of polyvinyl alcohol-polyether graft copolymers by extrusion |
| DE102005006421A1 (en) * | 2005-02-12 | 2006-08-24 | Clariant Produkte (Deutschland) Gmbh | Polymers and their preparation and use as gas hydrate inhibitors |
| DE102005007287B4 (en) * | 2005-02-17 | 2007-01-25 | Clariant Produkte (Deutschland) Gmbh | Use of polyesters as gas hydrate inhibitors |
| US20070155946A1 (en) * | 2006-01-04 | 2007-07-05 | Corrado Berti | Polyester oligomers, methods of making, and thermosetting compositions formed therefrom |
| DE102007005532A1 (en) | 2007-02-03 | 2008-08-07 | Clariant International Limited | Aqueous oligo- and polyester preparations |
| ES2886584T3 (en) | 2007-06-15 | 2021-12-20 | Ecolab Usa Inc | Fabric conditioning composition and method of use |
| JP5537826B2 (en) * | 2009-03-30 | 2014-07-02 | 三洋化成工業株式会社 | Anti-contamination agent for clothes cleaner and clothes cleaner |
| US8232239B2 (en) | 2010-03-09 | 2012-07-31 | Ecolab Usa Inc. | Liquid concentrated fabric softener composition |
| US8673838B2 (en) | 2011-06-22 | 2014-03-18 | Ecolab Usa Inc. | Solid concentrated fabric softener composition |
| US9506015B2 (en) | 2014-11-21 | 2016-11-29 | Ecolab Usa Inc. | Compositions to boost fabric softener performance |
| US9725679B2 (en) | 2014-11-21 | 2017-08-08 | Ecolab Usa Inc. | Compositions to boost fabric softener performance |
| US9688945B2 (en) | 2014-11-21 | 2017-06-27 | Ecolab Usa Inc. | Compositions to boost fabric softener performance |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3083187A (en) * | 1959-06-22 | 1963-03-26 | California Research Corp | Detergent polyesters |
| GB1088984A (en) * | 1963-06-05 | 1967-10-25 | Ici Ltd | Modifying treatment of shaped articles derived from polyesters |
| US3310512A (en) * | 1965-08-04 | 1967-03-21 | Archer Daniels Midland Co | Water dispersible resins comprising polyalkylene glycol, dicarboxylic acid and polyhydric alcohol |
| GB1154730A (en) * | 1965-10-08 | 1969-06-11 | Ici Ltd | Improvements in the Laundering of Synthetic Polymeric Textile Materials |
| DE3244011A1 (en) * | 1982-11-27 | 1984-05-30 | Cassella Ag, 6000 Frankfurt | POLYESTER DISPERSABLE IN WATER, ITS PRODUCTION AND USE AS A HYDROPHOBIC AGENT |
| US4861512A (en) * | 1984-12-21 | 1989-08-29 | The Procter & Gamble Company | Sulfonated block polyesters useful as soil release agents in detergent compositions |
| 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 |
| ATE73150T1 (en) * | 1984-12-21 | 1992-03-15 | Procter & Gamble | BLOCK POLYESTER AND SIMILAR COMPOUNDS USABLE AS SOIL REMOVER IN DETERGENT COMPOSITIONS. |
| US4713194A (en) * | 1986-04-15 | 1987-12-15 | The Procter & Gamble Company | Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions |
| US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
| GB8629936D0 (en) * | 1986-12-15 | 1987-01-28 | Procter & Gamble | Laundry compositions |
| DE4001415A1 (en) * | 1990-01-19 | 1991-07-25 | Basf Ag | POLYESTERS CONTAINING NON- TONIC SURFACTANTS, THEIR PREPARATION AND THEIR USE IN DETERGENTS |
-
1994
- 1994-02-08 DE DE4403866A patent/DE4403866A1/en not_active Withdrawn
-
1995
- 1995-01-28 EP EP95906354A patent/EP0743962B1/en not_active Expired - Lifetime
- 1995-01-28 JP JP7520926A patent/JPH09509199A/en active Pending
- 1995-01-28 DE DE59503856T patent/DE59503856D1/en not_active Expired - Lifetime
- 1995-01-28 US US08/687,322 patent/US5777046A/en not_active Expired - Fee Related
- 1995-01-28 DK DK95906354T patent/DK0743962T3/en active
- 1995-01-28 WO PCT/EP1995/000300 patent/WO1995021880A1/en active IP Right Grant
- 1995-01-28 CA CA002178908A patent/CA2178908A1/en not_active Abandoned
- 1995-01-28 ES ES95906354T patent/ES2121623T3/en not_active Expired - Lifetime
- 1995-01-28 AT AT95906354T patent/ATE171962T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2121623T3 (en) | 1998-12-01 |
| WO1995021880A1 (en) | 1995-08-17 |
| EP0743962A1 (en) | 1996-11-27 |
| ATE171962T1 (en) | 1998-10-15 |
| DE4403866A1 (en) | 1995-08-10 |
| US5777046A (en) | 1998-07-07 |
| JPH09509199A (en) | 1997-09-16 |
| DK0743962T3 (en) | 1999-06-21 |
| DE59503856D1 (en) | 1998-11-12 |
| EP0743962B1 (en) | 1998-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2178908A1 (en) | Amphiphilic polyesters, process for producing them and their use in washing agents | |
| US5142020A (en) | Polyesters containing nonionic surfactants as cocondensed units, preparation thereof and use thereof in detergents | |
| US5786318A (en) | Soil Release Polymers and detergent compositions containing them | |
| US4785060A (en) | Soil release promoting pet-poet copolymer, method of producing same and use thereof in detergent composition having soil release promoting property | |
| US4849126A (en) | Use of graft polymers based on polyesters, polyester urethanes and polyester amides as grayness inhibitors in detergents | |
| US5217642A (en) | Polyester with tartaric acid, preparation thereof and use thereof as detergent additives, and polyesters of tartaric acid and tetracarboxylic acids | |
| JPH11508319A (en) | Cotton antifouling polymer | |
| CN1070510C (en) | Polyester for bonding of textiles | |
| EP0274907A1 (en) | Anionic end-capped oligomeric esters as soil release agents in detergent compositions | |
| HU216028B (en) | Use of sulfonated polyesters as finishing agents in detergent, rinsing, softening and textile treatment compositions and detergent compositions | |
| JP2004507597A (en) | Flowable, amphiphilic and nonionic oligoesters | |
| JP5678084B2 (en) | Soil release polymer with anti-greying effect and high solution stability | |
| CA2106217A1 (en) | Nonionic soil release agents | |
| EP2670787B1 (en) | Soil release polymers | |
| US4999128A (en) | Soil release polymers having improved performance, stability and economy | |
| EP2670786B1 (en) | Soil release polymers | |
| EP3717613A1 (en) | Renewably sourced soil release polyesters | |
| US8779084B2 (en) | Process for producing polyether-polyester block copolymer | |
| JPH11512136A (en) | Polycarbonate-based dirt-dissolving polymer as a component of a composition for dissolving and removing oily dirt | |
| GB2304727A (en) | Fabric conditioning compositions | |
| JP2005520887A (en) | Copolyesteramide and its use as antifouling agent | |
| WO2024002908A1 (en) | A dishwashing detergent composition, a water-soluble container, and an autodosing automatic dishwashing system | |
| US20240060019A1 (en) | Benefit agent delivery particles | |
| US20240084222A1 (en) | Benefit agent delivery particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |