CA1065095A - Anionic sulphonated polyesters, process for their manufacture and their use as dispersants - Google Patents

Abstract

Abstract of the Disclosure Anionic sulphonated polyester are disclosed. They are ob-tained by reaction of (a) at least one n-alkylene, cycloalkylene-, di(alkylene)-arylenediol or polyalkylene glycol.
(b) at least one .alpha.,.beta.-ethylenically unsaturated, aliphatic dicarboxylic acid or a functional derivative thereof, (c) at least one saturated, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or a dimeric unsaturated fatty acid which is different from component (b) or a functional derivative of these acids in an initial step and of (d) at least one water-soluble derivative of sulphurous acid or a salt of oxymethanesulphonic acid in a final step.
These water-soluble polyesters are useful as dispersant in the manufacture of stable aqueous dyestuffs especially of dyes.

Description

1~ 65~D9 5 The invention provides anionic sulphonated polyesters which are obtained by reaction of a) at least one n-Alkylene, cycloalkylene-, di(~lkylene)-arylenediol or polyalkylene glycol, S b~ at least one a, ~-ethylenically unsaturated, aliphatic dicarboxylic acid or a functional derivative thereof, c) at least one saturated, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or a dimeric unsaturated fatty acid which is different from component b) or a functional derivative of these acids in an initial step and of d) at least one water-soluble derivative of sulphurous acid -~ or a salt of oxymethanesulphonic acid in a final step.
; The anionic sulphonated polyesters obtained from ~a), (b), (c) and (d) are water-soluble products which, ~! 15 inter alia as dyeing assistants, possess interesting pro-perties.
^ Types of n-alkylenediols suitable for component (a) are principally those with 2 to 18 carbon atoms, e.g.
ethylene glycol, 1,2-propanediol, trimethylene glycol, tetra-methylene glycol, pentamethylene glycol, hexamethylene glycol, 1,10- and 1,12-octadecanediol and, in particular, 2,3-bu-tanediol. Ethylene glycol is especially preferred. Examples ;l of cycloalkylenediols are 1,2-, 1,3- and especially 1,4-, cyclohexanediols.
,~ ~

~ - 2 - ~ ~
,, .g~ .

':, ., . .~ . , .

lV65~95 The di(alkylene)arylenediols carry both their hyd-roxy groups at the alkyl side chains and their chemical be-haviour is similar to that of the purely aliphatic diols.
In particular they have no acid character, which they can only assume if the hydroxy group is at~ached direct to the aromstic ring (ability to form phenolates), An example of a di(alkyl)arylene diol and in particular of a di(alkyl)-phenylene diol with 1 or 2 carbon atoms in the alkyl group is-1,2-di(hydroxymethyl)-benzene.
The polyalkylene glycols and the n-alkanediols are particularly preferred as component (a). These have, for Example, of the formula (1) H0 - (CnH2n-O)m- H , wherein n is an integer from 2 to 4 and m is an integer from 1 to 200, and, if m is 1, -C H2 ~ represents an un-branched chain, or especially the formula -~ (2) H0 - (C H2 ~) - H
wherein nl is 2 or 3 and ml is an integer from 1 to 10.
Polyethylene glycols with a molecular weight bet-ween c. 2000 and c. 150, in particular between c. 400 and c. 150, above all the polyethylene glycols within this range , and with lower molecular weights, are particularly suitable as component (a). In this connection the values for ml in , formula (2) are between 3 to 5 and 8 to 9.

. ~

., .
- . . .

':: ' , ' . - . . , Triethylene glycol may be cited as a suitable glycol in respect of which ml in formula (2) has values between 3 and S. Good results are also obtained with poly-` ethylene glycols which have a molecular weight of 190 S to 200 and a value for ml in formula (2) of 8 to 9.
Particularly preferred glycols for component (a) are those of the formula . ( nlH2nl~)m ~ H

wherein nl is 2 or 3 and m2 is 1 or 2. Diethylene glycol and especially ethylene glycol have a particularly interes-ting utility.
As component (b) it is advantageous to use those ` dicarboxylic acids or derivatives thereof which have, fo-.
example, the formula (4) X - C - Q - C - X' , ~1 1~ :

. ', . -- . .
. wherein Q represents an ethylenically unsaturated hydro-carbon radical of 2 or 3 carbon atoms which is unsubsti-tuted or substituted by halogen, each of X and X' repre-sents -OY or halogen or together they represent -0- and Y
. 20 represents hydrogen or alkyl of l to 4 carbon atoms.
Further dicarboxylic acids which are preferred for . ' .
. - 4 -~ .
,' ' ' .

! ' ' ,: , .
' . , ' , . "

component (b) have the formula (5) ~ l ~ Ql ~ ll ~ X
O o wherein Ql represents -CH=CH-, CH2=C, -CH=f-, -C-CH2- or -CH2-CH=CH- and Xl represents -Yl or chlorine or both sym~ols Xl together -0- and Yl represents hydrogen, methyl or ethyl.
. The compounds of the formula (5) are derived, for .. example, from the following acids:
maleic, fumaric, methylenemalonic, citraconic, mesaconic, itaconic or glutaconic acid. Derivatives of these acids, for example the esters with an alkyl group of 1 to 4 carbon : atoms, above all the ethyl and methyl esters, or the acid .~ halides, above all the acid chlorides, or especially the . , .
~ acid anhydrides, are also suitable. ~ -Of the acids and derivatives thereof cited herein-~-~ before, maleic acid, above all maleic acid dimethyl ester ., .
-~ or, in particular, maleic anhydride, is particularly pre-ferred.
As component (c) there are used primarily dicarbo-. 20 xylic acid~ of, inter alia, the iormula ,' .. . .
.

(6) X - C - R - C - X' il 11 O O

wherein R represents alkylene of 1 to 20 carbon atoms, cyclo-alkylene of 5 or 6 carbon atoms, phenylene, naphthylene, or the di-decarboxylated radical of a dimeric, ethylenically unsaturated fatty acid which is derived from aliphatic mono-carboxylic acids of 9 to 22 carbon atoms and containing 1 - to 5 ethylenically unsaturated bonds, and X and X' have the meanings assigned to them hereinbefore.
Examples of suitable dicarboxylic acids with an alkylene group of 1 to 20 carbon atoms are malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic acid, ~urther nonanedicarboxylic, decanoicdicarboxylic, undecanoic dicarboxylic acids and finally eicosanoic acid. Particular importance attaches to glutaric, adipic and, above all, se-bacic acid.
Typical dicarboxylic acids with a cycloalkylene " .
group of 5 or 6 carbon atoms include cyclopentane-l,l-dicarboxylic acid, and also hexahydrophthalic, isophthalic and terephthalic acids. Hexahydrophthalic acid and deriva-tives thereof are primarily suitable.
Th~ conventional dicarboxylic acids with a phenylerle group are, for example, phthalic, isophthalic and tere-phthalic acids. Terephthalic acid and derivatives thereof .i .
., - .

r ,, . . . , , ' ': ' ~. '. ' ' '. ' ~

1065~95 are primarily suita~le.
Examples of a suitable dicarboxylic acid with a naphthalene group are na2hthalene-1,2-naphthalene-1,4- and especially naphthalene-1,8-dicarboxylic acids.
The aliphatic monocarboxylic acids of 9 to 22 carbon atoms and with 1 to 5 ethylenically unsaturated bonds, from which R in formu]a ~6) is derived as the di-decarboxylated radical of a dimeric, ethylenically unsaturated fatty acid, are principally d2cenoic, dodecenoic, tetradecenoic, physe-toleic, olelc, elaidic, eicosenic, erucic, linoleic, linolenic, eleostearic and clupadonic acid. These monocarboxylic acids, a lso called fatty acids, can be obtained from natural oils in which they occur above all as glycerides. The dimeric , fatty acids are obtained in known manner by dimerisation of the monocarboxylic acids of the indicated kind. The 50-called dimeric fatty acids always contain a small amount of trimeric and monomeric acids, especially in industrial pro-; ducts.
Derivatives of the dicarboxylic acids which have been described for component (c) are also possible, namely the same derivatives as have been indicated as suitable for component (b).
Preferred components (c) are dicarboxylic acids o, for example. the formula .
,~ . .

' .':'. '' "~ ' ' , ' :.: :. ': '' -.~ '' ' ' ' -.. . ~ . .. .. . .- - . . . -7~ xl - C Rl - 11 -o o wherein Rl represents alkylene of 2 to 8 carbon atoms, cyclohexylene, phenylene or the di-decarboxylated radical of a dimeric, ethylenically unsaturated fatty acid, which is derived from aliphatic monocarboxylic acids of 16 to 22 - carbon atoms and containing 2 to 5 ethylenical]y unsaturated bonds, and Xl has the meaning previous assigned to it.
Examples of pre~erred dicarboxylic acids of the formula (7) are: succinic, glutaric, adipic, pimelic, suberic, lo azelaic, sebacic, phthalic, hexadrophthalic, isophthalic, hexahydroisophthalic, terephthalic, hexahyd-roterephthalic acid as well as dimerised oleic, elaidic, eicosenic, erucic, linoleic, linolenic, eleostearic and clupadonic acids and ,~
the ethyl or methyl esters thereof, acid chlorides or, as the case may be, anhydrodes thereof. Anhydrides have proved especially advantageous.
f The most suitable dicarboxylic acids which are used as component (c) are glutaric, adipic or sebacic acid, - the terephthalic or hexahydrophthalic acid and anhydrides or esters thereof or a dimerised linoleic or linolenic acid, The better results are obtained with terephthalic acid di-methyl ester, hexahydrophthalic acid anhyd_ide, glutaric . . .
` ' ' .
: :
;.. , , , . ,. , , .. .... , ,.. . . . . , . - . ., - . ` -1~)65~95 acid, adipic acid and especially sebacic acid.
Suitable derivatives of sulphurous acid or salts of oxymethanesulphonic acid as component (d~ have the formula .;. .
( ) LM~ 5 ~ EO~S-O-Me)q 1-Z~ q] p-l e-O

`:~ CH2 0H-~ . _ _ 2-p : ' .

wherein Me ~ represents an alkali metal cation or an : ammoniuln cation which is unsubstit-l~ed or substituted by alkyl of 1 to 20 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms, Z represen~s hydrogen or Me ~ and S8-2p) represents the valency of the sulphur atom, and p al~d q . . .
are 1 or 2.
~ By putting 1 for p in formula (8) an oxymethane- .
. sulphonate is obtained. On putting 2 for p in formula (8) there are obtained hydrogen sulphites of q is 1 and pyro-sulphites if q is 2.
Further preferred components (d) have, for example, - the formula (9~ (Me~ qH2_qSqo2q~l ~ ;

_ 9 _ .' , . ' '' .

1065()95 wherein Me~3 represents an alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 4 carbon atom~s, and q is 1 or 2.
Of the components (d) of the ormula (9), parti-cular interest attaches above all to sodium hydrogen sul-- phite and especially to sodiu~ pyrosulphite. In this connection, 1 mole of hydrogen sulphite corresponds to one S03~3 Me~3 equivalent, whereas, for example, 1 mole of pyrosulphite corresponds to two S03~ Me~ equivalents, ]- wherein Me~3 has the meaning previously assigned to it.
Preferred polyesters according to the present inventiol~ are reaction products which are obtained, for example, from 1 mole of component (a) :~
0.05 to 1.45 moles of component (b) 0.05 to 1.45 moles of component (c) and 0.05 to 1,45 S03~ Me~9 equivalents of component (d), wherein M ~ has the meaning previously assigned to it and the sum of the moles of components (b) and (c) is 0.66 to 1.5.
Also preferred are polyesters which are obtained from 1 mole of component (a) 0.40 to 0.49 mole of component (b) ' ' .

. . .

: ' . . ~ ,: -' ' ' ~ ' - ' ~0651~95 0.4O to 0.49 ~ole of component (c) and 0.40 to 0.49 SO3~ N ~ equivalents of component (d), the components (b) and (c) being used in equimolar amounts.
On the basis of the initially described components (a)~ (b), (c) and (d), the anlonic sulphonated polyesters according to tlle invention contain, for example, structural elements of the formulae ,: .
(10) _o~Cnll2n-~~
. ' ' ' .

H
_Q C
O SO Me0 lo ',i ' "~

(12) O O ~:-r Op tionally (13) -C-Q-C-, O O and -. optionally ~! ~14) -C-T-C-' ,.
. , .
' .. . .
- 11 - .

':; , - , - . , i ..

1065~95 wherein n, m, Q, R and Me have the meanings previously assigned to them and T represents the di-decarboxylated radical of a dimeric, ethylenically unsaturated fatty acid which is derived from an aliphatic monocarboxylic acid of 9 to 22 carbon atoms and containing 1 to 5 ethylen-ically unsaturated bonds which are at least partially satu-rated by hydrogen and the group -S03~ Me~9, wherein Me~-+-has the indicated meaning.
Preferred polyesters contain, for example, struc-tural elements of the formulae ~ ~15) tcnll~2nl .
: H

0 503 bIel O

. .
...
~17~ -C-Rl-c-,'' O O
optionally (18) ll Ql ~ ' and O O
: optiona]ly . (1'3~ ~C-Tl-C-'. O O

'' of which, on accourlt of the molar ratios stated herein-before, there are 5 to 145 s~ructural elements of the formulae (16) and (18), 5 to 1~5 structural elements of the formulae (17) and (19~, 5 to 145 structural elements of the formulae (16) and (19) to an average of 100 struc-tural elel~.ents of the formula (15) and of which there are altcgether 66 to 150 structural elements of the formulae (16), (17), (18) ~nd (l~),and wherein nl, Ql, Rl and Me~
have the ~eanings assigned to them hereinbefore and Tl re-presents the di-decarboxylated radical of a dimeric, ethyleni-cally unsaturated fatty acid which is derived from aliphatic monocarboxylic acids o~ 16 to 22 carbon atoms and containing

2 to S ethylenically unsaturated bonds which are at least partially saturated by addition of hydrogen and groups of . 15 the formula -S03~Me~l~, wherein Me~3 has the indicated meaning.
: Polyesters with a particularly interesting utility ~ contain, for example, structural elements o the formulae ., (20) ~~~Cn ~2n ~ ~

,', ' .
(21) 0 2 1 ~ ~ S~ ' . (22a) C~~CH~)4-C~ ~ -'~ O O

: - 13 -.. . . . . ..

lo~sa~s (22b) C (C~l2)8 ~CI
O O

(22c) -C-C 1~ -C-O O
and/or (22 d) -C-c34H6o .'.
optionally : (23) -C-CH-CH-C- , and ` 11 11 ,~ O o optionally ., .

(24 a) -IC~ - [C34~,4 ~V (So3 )vl ~
O O
and/or ~.
(24 b) ~1 [ 34~60~w' ~S03~ Na~) ]-- C-O

of which there are 40 to 49 structural elements of the formulae (21) and (23), 40 to 49 structural elements of ~he formulae (22a), (22b), (22c) and/or (22d) and (24a) and/or (24b)~ 40 to 49 structural elements of the formul.ae (21) and (24a) and/or (24b) to an average of lO0 structural elements ... .

. - 14 -' ' ' ! ' . . . ' . ' ' . ' . ~ ' ' ' ' '' ~; ' ' ' ' ' ~ ' :

t . . ' . ' . . ' :' . ,' ' ~065095 of the formu]a (20), and the structural elements of the formuiae (21) and (23) on the one hand and those of the formulae (22a), (22b), (22c) and/or (22d) and (24a) and/or (24b~ on the other are present in equal numbers, and wherein in the above formulae nl is 2 or 3, m2 is 1 or 2, v is l or 2 and w is 1, 2, 3 or 4.
; The process for the manufacture of Lhe anionic - sulphonated polyesters according to the invention is carried out in such a manner that the components (a), (b), lV (c) and (d) are reacted with one another in the molar . ra~ios stated hereinbefore. .
It is preferable to esterify first the components (a), (b) and ~c) with one another and subsequentl.y to add .
sulphite to the resultant polyes~er by treatment with ..
component (d).
Components (a), (b) and (~) are esterified at 100C to 250C, preferably at 170C to 190C. After thi.s . esterification reaction, water, alcohol or halogen acid . is split off, depending on whether a free acid, esters or acid halides thereof have been used as components (b) and (c). The removal of these elimination products from the reaction mixture can be brought to completion by op,-: ionally terminating the esterification reaction under re~
duced pressure.
: .
- 15 -~
' - ~' , Nor~,ally the esterification reaction lasts from 6 to 24 hours, but mostly 8 to 24 hours, and it i~ advanta--geous to carry it ou~ for the final 2 to 4 hours at a re-duced pressure of 12 to 15 Torr. If desired Gr necessary, the esterificati~n reaction can be speeded up by addition of catalysts. Suitable catalysts are, for example, inor-ganic acids, for instance hydrochloric acid, ~ulphuric acid, phosphoric acid, and above all organic acids, for.
. example organic sulphonic acids and especially p-toluene-sulphonic acid. It is desirable to use 0.1 to 0.3 of these catalysts per mole of component (a).
To prevent polymerisation of the polyester, the ;~ esterification reaction is advantageously carried out in an inert nitrogen atmosphere. In addition, if appropriate7 a polymerisation inhibitor is added. Examples of such in~ibitors are methylene blue, benzthiazine or especially hydroquinone. It is desirable to use 0.01 to 0.1 g of these inhibitors per mole of component (a).
The esterification reaction may be carried out in an inert organic solvent or solvent mixture, Suitable solvents are above all aromatic hydrocarbons, for example , .
toluene, chlorobenzene, o-, m- or p-xylene or a mixt~lre ;~ thereof or also a xylene/toluene or a xylene/benzene mix-ture. Chlorobenzene and, above all, toluene, have proved ~ , , .

: ~, . . - ,.. . , .~, ., - . , . . - - - .- . -. - -, ~ - . : .. . . . .
,. , ... . ,., : , . . . . ... . .. .
.. ; ,~ .. . .,. . . ., .. ,.. , ~ .....

... .

to be most suitable.
However, it is preferable to carry out the esteri-fication reaction without solvents. i.e. in the melt. The procedure desirably in this case is that the component (a) is first put into the reaction vessel and heated to 60C to 90C and then components (b) and (c) are added.
The rate of addition of components (b) and (c) can be adapted to their reaction speeds. As a rule, however, all - three components (a), (b) and (c) are heated together.
The addition of sulphite to the resultant poly-ester obtained from components ~a)~ (b) and (c) is effected by treatment with component (d) in an aqueous medium a~ -50~C to 105C, preferably at 90C to 105C. Component (d) ., .
is normally in the form of a salt of a sulphite which con-tains 60 to 70 percent by weight of sulphur dioxide and which may be diluted with water to a sulphur dioxide content of 5 to 30, preferably 9 to 15, percent by weigh~. The aqueous solution of component (d) is appropriately added to the polyester. I~owever, it is more advantageous to add the polyes~er ~o the solution of the component (d).
; The resultant reaction mixture is normally adjus~ed to a pH of S to 7, preferably 6 to 6.5J by addition cf an ~ -inorganic base9 for example an alkaline earth or, above all, an alkali hydroxide solution, especially sodium hydroxide . , .
~ .
, . . ,. . . " . , . ~:
: , . . , ~ . . - . . . ... -. .- -solution, which ls usually in the form of a di.lute 10%
solution. For this purpose, 50 to 80 g of an aqueous 10% sodium hydroxide solution, which is added to the`re-action mixture over the course of 1 to 2 hours, are norma].ly used.
The addition of sulphite ~o the polyester can be observed by measuring the degree of addition of sulphite, ascertained from the unreac~ed amount of sulphite, in a sample taken from ~he reaction mixture. Usually after 2 to 6 hours the degree of suLphite addition remains stabl2 and is 80 ~o 100%, preferably 9S to 100%.
The anionic sulphonated polyester may be obtained ~ as an aqueous 40 to 60% solution or preferably, after eva-: poration of the solvent, as a resinous or solid substance.
The anionic sulphonated polyesters according to ~ the invention are used preferably as dispersants in the - manufacture of stable, aqueous dispersions. They can also . be used as levelli.ng and retarding agents in conventional dyeing processes. With the use of the anionic sulphonated polyesters it is possible to obtain stable, aqueous dis-. persions of cosmetics, agrochemicals, for example parti-cides, also textile finishing and protective agents, fluores-cent brighteners and especially of dyes. Suitable dyes are ~ primarily the water-insoluble disperse dyes. These are in , . . . . . . . .
- :

particular azo dyes and anthraquinone, acridone, nitro, methine, styryl, a~ostyryl, naphthoperinone, cumarin, quinonaphthalone or naphthoquinone dyes.
~yestuf~ emulsions which contain at least one S anionic sulphona~ed polyester according to the invention possess the advantage of remzining stable over a period of at least 2 months, even at higher, for example dyeing, temperatures.
The present invention also provides retarding agents, levelling agents and especially dispersants, whi~h contain at least one of the anionic sulphonated polyesters according to the invention.
The invention further provides a process for treating, i.e. finishing, or espec~ally for dyeing organic fibrous materials, which comprises treating said materials . ~ .
with stable, aqueous dispersions which contain a finishing ,,i :
or protective agent or especially a dye which has been dispersed with at least one anionic sulphonated polyester according to the invention. In particular, it is possible to dye fibrous materials with stable, aqueous dyestuff dis-`; persions which contain at least one anionic sulphonated polyester accordir.g to the invention by the high temperature exhaustion process, whereby particularly level dyeings are obtained, since no agglomerat;on of the dye and consequently -; ~

. ! , ~
' ',' ' , . '' ' ' ' ' ' " ' . ~ . ''~ .' . ': ' ' ' , , '': ' ' ' - ,.' : , ', , .,' ' ,,, . -J ' ' , '. ' `. '' .

:
no dyestuff deposits occur.
Finally, the present invention also compri.ses the treated and finished, especially dyed, organic fibrous materials, above all textile fibrous materials, for example those of synthetic fibres or blends of natural and synthetic fibres, such as polyester fibres or co~on/polyester blends.
The following Examples illustrate the invention, the peFcentages therein being l~y weight.

~, ' ' .

. - , , : , , . .. .- . .. . .

106S1~9S

Exam~le 1 341.5 g of ethylene glycol (5.5 moles, corresponding to a 10% surplus, .eferred to maleic anhydride and sebacic acid)~
0.5 g of p-toluenesulphonic acid and 0.1 g of hydroquinone are heated in an inert nitrogen atmosphere Lo 80C and the melt is subsequently treated with 245 g of maleic anhydride (2.5 moles) and 505 g of sebacic acid (2.5 moles) 9 in the process of which ~he reaction mixture cools to 45C~
The reaction mi.xture, which is in the form of a thiclc, slightly yellowish suspension, is heated over the course of 1/2 hour to 150C. a clear solution being formed at 105C. Th,s solution is further heated to 190C over the course of 4 hours, with water being split of. from 140C~
The reaction mixture i.s kept at 190C for 1 hour at 760 Torr and for a rurther hour at 15 Torr. The reaction mix-ture is then cooled to 20C to yield 957 g (100% of theor~) of the polyester as a wax-like, yel]owish pasteO The total amount of water that is split off is 134 g (7.43 moles, -~
correspondlng to 99.2% of theory).
The polyester is treated with a solution of 237.5 g of ` sodium metabisulphite (2.5 S03~3 Na63 equivalents) in 1000 ml of water and the reaction mixture is heated to reflux tempe- ;
-~ ~ature, in the process of which a yellowi h emulsion is formed. This emulsion is kept for 1 3/4 hours at re1ux . - 21 -...

. ,~ , , ;

-temperature (98 102C) and during this time 250 g of a 10% aqueous sodium hydroxide solu~ion are added dropwise.
The reaction mixture is then cooled to 20C and 2 slightly cloudy solution is obtained the pH or which is about 6 and the degree of sulphite addition of which, ascertained from the unreacted amount or sulphite, is 95%. This solution is evaporated to yield 1214 g of the anioni.c sulphonated polyester as a white product.

' Example 2 175 g of diethylene glycol (1.65 moles, corresponding to a 10% surplus, referred to maleic anhydride and sebacic : acid), 73.5 g of maleic anhydride ~0.75 mole) and 151.5 g of sebacic acid ~0.75 mole) are heated in an inert nitrogen atmosphere to 150C over the course of 2 hours, with a yellow solution forming at 110C. This solution is further heated for 3 1/2 hours to 190C, with water being split off from 150C. The reaction mixture is cooled to 170C
and then held at this temperature for 3 hours at 15 Torr.
The reaction mixture is subsequently trsated with 0.01 g of hydroquinone and cooled to 70C to yield 348 g (96.6% of theory) of the polyester as a yellow, viscose fluid. The total amount of water split off is 40.5 g ~2.25 moles, corresponding to 100% of theory).
The polyester is added to a solution of 71.25 g of sodium metabisulphite ~0.75 S03~3 Na~3 equivalents, corresponding to the theoretical amount, referred to maleic anhydride) in 300 ml of water. The reaction mixture is heated to :.
reflux temperature within 40 minutes. The reaction mixture, which initially is a white emulsion at 20C, turns into a slightly opalescent solution at 61C, again into a white ~` emulsion at 71C and finally into a slightly turbid solu-tion at 86C. At the onset of reflux (98C) the reaction .

,: ~ ' ~'' ..

- : - : ' ~
. .

~065095 mixture is a clear solution. This solution is kept for 2 1/2 hours at re~flux temperature (98-102C) and during this time 120 g cf a 10% aqueous sodium hydroxide sol-ution are added dropwise. The reaction mixture is cooled to 30C and a white, opalescent, viscous solu~ion is ob-tained; the degree of sulphite addition, ascertained from the unreacted amount of sulphite, is 95%. This solution is evaporated to yield 425 g of the anionic sulphonated poly-ester as a white, resinous product.

.,, :

.

,..
~,. .

' , .
.... . . . , . . .. .. . . . . ....... ., . . . . . ~ .. . ..

. . . . . ~ . ' . . . ~ : . . : ,. : :: :
.

.
Example 3 306 g of a polyethylene glycol with a molecular weight of 200 (1.53 moles, corresponding ~o a 2% .curplus~ referred to maleic anhydride and sebacic acîd) are heated in an inert nitrogen atmosphere to 80C and subsequently treated with 74 g of maleic anhydride (0.75 mole) and 151.5 g of sebaclc acid (0.75 mole). The reaction mix~ure, which is a thick, white suspension, is heated to 150~C wi.thin 1 hour in the course of which a slightly yellowish solution forms at 100C. This solution i5 further heated within 4 hour~s to 190C, with water being split off rom 140C.
The reaction mixture is held at 190C for 3 hours at 15 Torr. The reaction mixture is then treated with 0,015 g of hydroquinone and cooled to 100C to yield 491 g (100%
of theory) of the polyester as a yellowish, viscous li-quid. The total amount of water split off is 38 g (2.11 molesS corresponding to 93.8% of theory).
The polyester is added to a solution of 74.8 g of sodium metabisulphite (0.7875 S0 ~3 Me~3 equivalents, correspondin~
to a 5% surplus, referred to maleic anhydride) in 450 ml of water and the reaction mixture is heated to 90 to 95C.
The pH of the reaction mixture is s-ubsequently adjusted to 6,6 with llS g of a 10% aqueous sodium hydroxide solution, ., whereupon a yellowish solution forms. This solution ls . ~ 25 -. ' , - .:: . . .... . .
.. . . .
. , : ... . ., . ; ., - -- -~, . . : - .. . , , ~ . . .
.. . . . , , , , . :

-heated again to 90 to 95C and held at this temperature for 3 1/2 hours. After this Lime the degree of sulphite addition of the solu~ion is 95%, ascertained from the unreacted amount of sulphite. The solution is evaporated to yield 572 g of the anionic sulphonated polyester as a whlte, resinous substance.

,--, .

, , ., , , -, Example 4 136,5 g of ethylene glycol (2.2 moles, corresponding to a 10% surplus, referred to maleic anhydride and sebacic acid), 98 g of maleic anhydride (l mole), 202 g of sebacic acid (1 mole) and 0.5 g of p-toluenesulphonic acid are dissolved in 500 ml o toluene in an iner~ nitrogen atmos-phere. The solution is heated Lo the boil and kept for ~6 hours at reflux ~emperature (120~C). After 30 hours, 0.5 g of p-toluenesulphonic acid is again added to the reaction mixture. Toluene is then removed from the clears slightly yellowish solution at 40CC and 15 Torr. The residue is dried for 12 hours at 40C and cl Torr to yield 384 g (100% of theory) of the polyester as a ~Tellowish, viscous fluid. The total amount of water split off is 52.4 g (2.91 moles), corresponding to 97% of theory).
Ihe polyester is added to a solution of 90.25 g of sodium metabisulphite (0.95 S03~ Na~ equivalents, corresponding to a 5% less than equivalent amount, referred to maleic anhydride) in 130 ml of water. The reaction mixture is heated to reflux temperature. Then 250 g of a 10% aqueous sodium hydroxide solution are added dropwise within 60 minutes to the reaction mixture, which is in the form of a white emulsion, and a vigorous exothermic reaction ensues, .

. .......................................................................... .

;'', ' , .' ~ ' 106CjO95 the temperature rises to 97C and a clear, yello~ solu-tion forms the degree of sulphi~e addition of which, ascertained from the unreacted amount of sulphite, is 100%. During this reaction any toluene stil] remaining in the starting material is removed. The solution is evaporated to yield 490 g of the anionic, sulphonated polyester as a yellowish, solid substance.

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_xam~le_5 The polyester is manufactured as in Example 4, but with 440 g of a polyethylene glycol with a molecular weight of 200 instead of ethylene glycol. Yield: 697 g (101V/o of theory) of the polyester as a yellow, vlscous fluid. The total amount of water split off is 45 g (2.5 moles~
corresponding to 83.4% of theory).
The pGlyester is added to a solution of 95 g of sodium metabisulp;lite ~1 So3O Naffl equivalent, corresponding to the theoretical amount, referred to maleic anhydride) in 1200 ml of water. The reaction mixture is heated to reflux temperature and treated within 60 minutes ~ith 120 g of a 10% aqueous sodium hydroxide solution. As indi-cated in ~xample ~., a solution forms whose degree of sulphite addition is 100%. The solution is evaporated to yield 800 g of the anionic sulphonated polyester as a white, tacky, rubbery substance.

.

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10651)9S

Example 6 The polyester is manufactured as indicated in Example 5 ~ield: 693 g (lOG.9% of theory) of the polyester as a yellow, viscous oil. The total amount of water split off is 50 g (2.78 moles, corresponding to 92.6% of theory).
The resultant polyester is added to a solution of 104.5 g of sodium metabisulphite (1.1 S03~ Na~) equivalents, corresponding to a 10% surplus referred to maleic an-hydride) in 640 ml of water. The reaction mixture is hea~ed to reflux temperature and the pH is adjusted within 60 minutes to 5.9 by the dropwise addition o~ sodium ~ -hydroxide solution. ~s indicated in Examp]e 4, a solution forms whose degree of sulphite addition is 100%.
The content os this solution is c. 50% on the basis of the water used with the bisulphite and with the sodium hydroxide. There are obtained 1597 g of the anionic sulpho-nated polyester as a c. 50% aqueous solution.
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1065~95 Examp? e 7 313 g of a polyethylene glycol with a molecular weight of 190 (1.65 moles, corresponding to a 10~/o surplus reerred to maleic anhydride and sebacic acid), 88 g of maleic anhydride (0,9 mole), 121.2 g of sebacic acid (0.6 mole) and 0.5 g of p-toluenesulphonic acid are refluxed in 400 m]
- of toluene for 92 hours as indicated in Example 4 and subsequently the toluene is removed from the react-ion mixture. Yield: 514 g of a polyester as distillation resi-due which contains a small amount of toluene and which is in the form of a yel]ow, viscous substance. The total mount ; of water split off is 35 g (1.95 moles, corresponding to 92.6~
The result~nt polyester is added to a solution of 85.5 g of sodium metabisulphite (0.9 S03~3 Na~3 equivalents, corresponding to the theoretical amount referred to ma-leic anhydride) in 400 ml of water. The reaction mixture is heated to reflux temperature and, as indicated in Example 4, treated with 172 g of a 10% aqueous sodium hydroxide solution. The degree of sulphite addition of the resultant ; solution is 100%o There are obtained 1146 g of the anionic sulphonated poly-:
ester, which, as in Example 6, is in the form of a c. 50%
aqueous solution.

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,, .. . : , _xample 8 247~5 g of triethylene glycol (].65 moles, corresponding to a 10% surplus referred to sebacic acid and maleic an-hydride), 66.2 g of maleic anhydride (O.G75 mole), 166,7 g of sebacic acid (0.825 mole ) and 0.5 g of toluenesulphonic acid are ref]ux for 64 hours in 400 ml of toluene as des-cribed in Example 6, and toluene is subsequently removedfrom the reaction mixture. Yield: 456 g of a polyester as yellow viscous distillation residue which contains a small amount of toluene, The total amount of water split off is 41 g (2.28 moles, correspondlng to 98% of theory).
The polyester i~ added to a solu-~ion of 64 g of sodium metabisulphite (0.675 so3~3 Na~ e~uivalents, referred lo maleic anhydride) in 400 ml of water.
The reaction mixture is heated to reflux temperature and :., .
treated, as described in Example 4, with 108 g of a 10%
,- aqueous sodium hydroxide solution. The degree of sulphite addition of tl~e resultant solution is 97.5%. Yield: 1014 g of the anionic sulphonated polyester which, as in Example 6, , ~, .
is in the form of a c. 50% aqueous solution.
.' . ' ' '.. ...
~'' ''' ' ' '' :" ' ' ' ' ' Example 9 341 g of ethylene glycol (5.5 moles, corresponding to a 10% surplus, referred to maleic anhydride and sebacic acid), 294 g of maleic anhydride ~3 moles), and 404 g (2 moles) of sebacic acid are reacted together in the melt in the presence of 0.5 g of p-toluenesulphonic acid and 0.1 g of hydroquinone as described in Example l.
Yield: 913.5 g (100% of theory) of the polyester as a wax-like, beige coloured product. Ths total amount of water split off is 126 g (7 moles, corresponding ~o 100%
; of theory).
~ The polyester is treated with 285 g of a solution of - 285 g of sodium metabisulphite (3 S03~3 Na~equivalents, corresponding to the theoretical amount, referred to maleic anhydride) in 6Q0 ml of water and further processing is effected with the addition of 200 g of a 10% aqueous sodium hydroxide solution as described in Example 1. After evaporation of the resultant solution, whose degree of :
sulphite addition is 93.8%, there are obtained 1210 g of the anionic sulphonated polyester as a white, substantially water-soluble powder. The residue is dissolYed once more - in 9000 ml of water of 70C and the water-insoluble portion is separated by filtration over activated charcoal.
Yield: 1190 g after evaporation.

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106509~

_ ample 10 341 g of ethylene glycol (5,5 moles, corresponding to a 10% surplus, referred to maleic anhydride and sebacic acid), 196 g of maleic anhydride ~2 moles) and 606 g of sebacic acid (3 moles) are reacted ~ogether in the melt as described in Example 1 in the presence OL 0. 5 g of p-toluenesulphonic acid and Q.l g of hydroquinone.
Yield: 988 g (98.9% of tl~eory) of the polyester as a white solid~ The total amount of water split off is 143 g (7.94 moles, corresponding to 99,3% of theory).
The polyester is treated with a solution of 190 g of sodium metabisulphite (2 S03~ Na~9 equivalents, corre-sponding to t~le theoretical amount, referred to maleic anhydride) in 600 ml of water and further processing is effected as described in Example 1 with the addition of 200 g of 10% aqueous sodium hydroxide solution~ After evaporation of the resultant solution, whose degree of sulphite addition is 85.9~/~, there are obtained 1190 g of the anionic sulphonated polyester as a yellowish, viscous substance.

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Example 11 273 g of etl~ylene glycol (4.4 moles, corresponding to a 10% surplus, referred to maleic and terephthalic acid dlmethyl ester), 288 g of ma].eic acid dlmethyl ester (2 moles) and 388 g of terephthalic acid dimethyl ester (2 ~loles) are -reacted toge~her in the melt in the presence of O.S g o~ p-toluene-sulphonic acid and 0.1 g of hydro-quinone as described in Example 1.
Yield: 700 g (101% of theory) of ~he polyester as a white solid.
The polyester is treated with a solu~ion of 190 g 3f sodium metabisulphite (2 S03~ Na~ equivalents, corresponding to the theoretical amount, referred to maleic acid di~lethyl ester) in 800 ml of water and further processing is car-ied out as described in Example 1 with the addition of 200 g of a 10% aqueo1ls sodium hydrox-ide solu~ion.
Ater the suspension has been filtered through ac~ivated charcoal and evaporation of the resultant solution (degree of sulphite addition 77.1%), there are o~tained 760 g of the anionic sulphonated polyester as a yellowish viscose substance.

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Example 12 102 g of ethylene glycol (1.65 ~oles, corresponding to a 10% surplus, referred io maleic anhydride and adipic acid), 88 g of maleic anhydride (0.9 mole) and 87.6 of adipic acid (0.6 mole) are reacted together in the melt in the presence of 0.5 g of p-toluenesulphonic acid and 0.i g of hydro-qUinOlle as in Example 1.
Yield: 240 g (100% of theory) o the ~olyester as a viscous mass. The total amount of water split off (contains traces of ethylene glycol) is 38 g (2.11 moles, corresponding to 100.5% of theory).
The polyes-er is treated with a solution of 85~5 g of sodium metabisulphite (0.9 S0 9 Na~ equivalents, referred to maleic anhydride) in 500 ml of water and further pro_es-sing is carried out as described in Example 1 with the ad-dition of 90 g of a 10% aqueous sodium hydroxide solution.

.. .
- After purification with activated charcoal and evaporation of the resu]tant solution (degree of sulphite addition 83%), there are obtained 316 g of the anionic sulphonated poly-ester as a white solid.

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127.6 g of 1,4-cyclohexanediol (1.1 moles), corresponding to a 10% surplus, referred to maleic anhydride and hexa-hydrophthalic anhydride), 49 g of maleic anhydride (0.5 mole) and 77 g of hexahydrophthalic anhydride (0.5 mole) are heated in a~ inert nitrogen atmosphere within 1 hour to 150C, in the process of which a yellow melt forms at 120C.
This melt is further heated for 4 hours ~o 190C, with water being split off from 140C. The reaction mixture is kept at 190C for 1 hour at 15 Torr.
Yield: 231 g (98% of theory) of the polgester as a yellow iscose fluid. The total amount of water split off is 17.8 g (99% of theory).
The polyester is added to a solution of 47.5 g of sodium metabisulphite (0.5 S03~ Na~3 equivalents, corresponding to the ~heore~ical amount, referred to maleic anhydride) in 200 ml of water. The reaction mixture is heated to reflux temperature within 45 minutes. The reaction mixture, which is initially at 20C a white emulsion, turns into a yel-lowish-white opalescent solution at increasing temperature.
This solution is kept for 90 minutes at reflux temperature (98-102C) during which time 60 g of a 10% aqueous sodium hydroxide solution are added dropwise, The reaction mixture .

1065~95 is cooled to 30C ~o give a yellowish-whlte, viscous solution whose degree of su]phite addition, ascertained from the unreacted amount o~ sulphite, is 100%. Eva-poration of the solution yields 280 g of the an.ionic sulphonated polyester as a white powdery product.

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: . - '' ~ ~' ,, ' 106~095 Example_14 87.3 g of 2,3-butanediol (0.97 mole, corresponding to a 10% surplus, referred to maleic anhydride and glu~aric acid), 43.1 g of maleic anllydride (0.44 mole), 58.1 g of glutaric acid (0.44 mole) are reacted as described in Example 13.
Yield: 156 g (100% of theory) of the polyester as a ye]]owish solid. The total, amount of water split off is 23.5 g (99%
of theory).
The polyester is treated with a solution of 41.9 g of sodium metabisulphite (0.44 S03~ a~ equi,valents, cor-responding to the theoretical amount, referred to maleic anhydride) in 200 ml of water. By proceeding in the same ,~
manner as in Example 13 there is obtained a yellowish-white, viscous solution with a degree of sulphite addition of 100%. Evaporation of the solution yields 212 g of the ' -anionic sulphonated polyester as a yellowish white solid.
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Example 15 10 g of the dye of the formula (25) H3C-502 ~ N-N ~ ¦

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28 ml of waterJ 5Q g of glass-marbles (diameter 1 mm) and 2 g of the anionic sulphonatet polyester according to Example 1 are stirred intensively at 300 rpm until the dye particles haYe a size of 0.5 to 2 ~. The time taken `~ is normally 24 hours. The batch is subsequently treated once more with 3 g of the anionic sulphonated polyester according to Example 1 and with 9 ml of water and stirring ' .`~
; is continued for 2 hours. The batch is sieved off from the glass marbles to give an aqueous dyestuff dispersion the particles of which have a uniform size of 1 to 2~ ant which remains stable for 2 months.
The same results are obtained with the following amounts of ;,' the anionic sulphonated polyester:
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10ti5095 polyester according to Example 2, addition in 2 portions ~2 g + 3 g) polyester according to Example 3, addition in 2 portions (2 g + 3 g) polyester according to Example 4, addition in 2 portions ~2 g + 3 g) polyester according to Example 5, addition in 2 portions ~2 g + 3 g) polyester according to Example 9, addition in 2 portions (2 g + 3 g) ; polyester according to Example 10, addition in 2 portions (2 g + 3 g~
polyester according to Example 11, addition in 2 portions t2 g ~ 3 g) polyester according to Example 12, addition in 2 portions (2 g + 3 g) polyester according to Example 13, addition in 2 portions (2 g + 3 g~
: polyester according to Example 14, addition in 2 portions (2 g + 3 g~
polyester according to Example 6, addition in 2 portions (4 g + 6 g) but with 25 + 7 ml (instead of 28 + 9 ml) of water : polyester according to Example 7, addition in 2 portions (4 g + 6 g) ; but with 25 + 7 ml (instead of 28 + 9 ml) of water polyester according to Example 8, addition in 2 portions --: (4 g + 6 g) but with 25 + 7 ml (instead of 28 ~ g ml) of water.

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Example 16 100 parts of polyethylene glycol terephthalate knitted fabric are treated for 10 minutes at 65C in a dyebath which consis~s of 3000 par~s of water and 6 parts of ammonium sulphate and the pH of which has been adjusted to 5.5 with formic acid. Then 5 parts of a stable dye-stuff dispersion obtained according to Example 15 are added, the temperature is raised within 30 minutes to 130C and dyeing is performed at this temperature for 60 minutes by the high temperature exhaustion process, The dye liquor is then cooled to 90C, drawn off, and the substrate is rinsed and dried.
During the dyeing there occurs no agglomeration of the dye and consequently no deposit on the substrate, so that a level, strong, brilliant, golden yellow dyeing c~f good fastn~ss to rubb ng ls obtained ~;. , .

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Claims (16)

CLAIMS:

1. Anionic sulphonated polyesters which are obtained by reaction of the components (a) a n-alkylene-, cycloalkylene- or di(alkylene)-arylene-diol or polyalkylene glycol, (b) a .alpha.,.beta.-ethylenically unsaturated, aliphatic dicarboxylic acid or a functional derivative thereof and (c) a saturated aliphatic, cycloaliphatic or aromatic dicarboxylic acid or a dimeric unsaturated fatty acid which is different from component (b) or a functional derivative of these acids in an initial step and of the component (d) a water-soluble derivative of sulphurous acid or salt of oxymethanesulphonic acid in a final step.

2. A polyester according to claim 1 the manufacture of which comprises the use of (a) a n-alkylenediol with 2 to 18 carbon atoms, or a poly-alkylene glycol of the formula HO - (CnH2n-O)m- H

wherein n is 2, 3 or 4 and m is an integer from 1 to 200, and, if m is 1, -CnH2n- is an unbranched chain, or a 1,2-, 1,3- or 1,4-cyclohexanediol or a di(alkyl)phenylene-diol with 1 or 2 carbon atoms in the alkyl group as component (a) (b) an unsaturated acid or a derivative thereof of the formula as component (b) wherein Q is an ethylenically unsaturated hydrocarbon radical of 2 or 3 carbon atoms which is un-substituted or substituted by halogen, each of X and X' is -OY
or halogen or both together are -O- and Y is hydrogen or alkyl of 1 to 4 carbon atoms, (c) a saturated acid or a derivative thereof of the formula as component (c) wherein R is alkylene of 1 to 20 carbon atoms, cycloalkylene of 5 or 6 carbon atoms, phenylene, naphthylene or the di-decarboxylated radical of a dimeric, ethylenically unsaturated fatty acid which is derived from aliphatic monocarboxylic acids of 9 to 22 carbon atoms which contain 1 to 5 ethylenically unsaturated bonds, and X and X' each have the above meaning, and (d) a sulphur containing salt of the formula wherein Me? is an alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 20 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms, Z is hydrogen or Me? and (8-2p) represents the valency of the sulphur atom and p and q are 1 or 2.

3. A polyester according to claim 1 the manufacture of which comprises the use of 2,3-butanediol or 1,4-cyclo-hexanediol or of triethylene glycol or of polyethylene glycols with molecular weights of 190 to 200 or of ethylene or diethylene glycol as component (a).

4. A polyester according to claim 1 the manufacture of which comprises the use of a compound of the formula as component (b), wherein Q1 is -CH=CH-, , , or -CH2-CH=CH and X1 is -OY1 or chlorine or both symbols X1 together are -O- and Y1 is hydrogen, methyl or ethyl.

5. A polyester according to claim 1 the manufacture of which comprises the use of a compound of the formula as component (c), wherein R1 is alkylene of 2 to 8 carbon atoms, cyclohexylene, phenylene or the di-decarboxylated ra-dical of a dimeric ethylenically unsaturated fatty acid which is derived from aliphatic monocarboxylic acids of 16 to 22 carbon atoms which contain 2 to 5 ethylenically unsaturated bonds and X1 is -OY1 or chlorine or both symbols X1 together are -O- and Y1 is hydrogen, methyl or ethyl.

6. A polyester according to claim 1 the manufacture of which comprises the use of glutaric acid, sebacic acid, terephthalic acid dimethyl ester or hexahydrophthalic an-hydride as component (c).

7. A polyester according to claim 1 the manufacture of which comprises the use of a compound of the formula , as component (d), wherein Me? is alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms and q is 1 or 2.

8. A polyester according to claim 1 the manufacture of which comprises the use of ethylene or diethylene glycol as component (a), of maleic acid dimethyl ester or maleic anhydride as component (b), of sebacic acid as component (c) and of sodium pyrosulphite as component (d).

9. A polyester according to claim 1 the manufacture of which comprises the use of 1 mole of component (a), 0.05 to 1.45 moles of component (b), 0.05 to 1.45 moles of component (c) and 0.05 to 1.45 SO? Me? equivalents of component (d), wherein Me? is an alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms and the sum of the moles of components (b) and (c) is 0.66 to 1.5.

10. A polyester according to claim 1 the manufacture of which comprises the use of 1 mole of component (a), 0.40 to 0.49 mole of component (b), 0.40 to 0.49 mole of component (c) and 0.40 to 0.49 SO? Na? equivalent of component (d), the components (b) and (c) being used in equimolar amounts.

11. Anionic sulphonated polyesters according to claim 1 which contain structural elements of the formulae -O-(CnH2n-O)m- , and , in which n is 2, 3 or 4 and m is an integer from 1 to 200, and, if m is 1, -CnH2n- is an unbranched chain, Q is an ethylenically unsaturated hydrocarbon radical of 2 or 3 carbon atoms which is unsubstituted or substituted by halogen, Me ? is an alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 20 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms and R is alkylene of 1 to 20 carbon atoms,cycloalkylene of 5 or 6 carbon atoms, phenylene, naphthylene or the di-decarboxyl-ated radical of a dimeric, ethylenically unsaturated fatty acid which is derived from aliphatic monocarboxylic acids of 9 to 22 carbon atoms which contain 1 to 5 ethylenically unsaturated bonds.

12. Anionic sulphonated polyester according to claim 11 which in addition contain structural elements of the formulae and/or wherein Q is an ethylenically unsaturated hydrocarbon radical of 2 or 3 carbon atoms which is unsubstituted or substituted by halogen, and T is the di-decarboxylated radical of a dimeric ethylenically unsaturated fatty acid which is derived from aliphatic monocarboxylic acids of 9 to 22 carbon atoms and containing 1 to 5 ethylenically unsaturated bonds which are at least partially saturated by hydrogen and by groups of the formula -SO? Me? wherein Me? is an alkali metal cation or an ammonium cation which is unsubstituted or substituted by alkyl of 1 to 20 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms.

13. A process for the manufacture of the anionic sulphonated polyesters according to claim 1 which com-prises reacting together (a) a n-alkylene-,cycloalkylene- or di(alkylene)-arylenediol or polyalkylene glycol, (b) a .alpha.,.beta.-ethylenically unsaturated, aliphatic dicarboxylic acid or a functional derivative thereof, (c) a saturated aliphatic, cycloaliphatic or aromatic di-carboxylic acid or a dimeric unsaturated fatty acid which is different from component (b) or a functional derivative of these acids in an initial step and (d) a water-soluble derivative of sulphurous acid or a salt of oxymethanesulphonic acid in a final step.

14. A dispersant which contains an anionic sulphonated polyester according to claim 1.

15. A process for dyeing organic textile materials which comprises the use of a stable aqueous dyestuff dis-persion which contains as dispersant an anionic sulphonated polyester according to claim 1.

16. The organic textile materials dyed according to claim 15.