Note: Descriptions are shown in the official language in which they were submitted.
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.
. ~
., .
- . . .
':: ' , ' . - . . ,
1065095
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 -
~ .
,' ' ' .
! ' ' ,: , .
' . , ' , . "
1065095
component (b) have the formula
(5) ~ l ~ Ql ~ ll ~ X
O o
wherein Ql represents -CH=CH-, CH2=C, -CH=f-, -C-CH2- or
CH3 CH2
-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
,'
.. . .
.
1065095
(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
- 6 -
.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
.
,~ . .
' .':'. '' "~ ' ' , ' :.: :. ': '' -.~ '' ' ' ' -
.. . ~ . .. .. . .- - . . . -
106509S
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
. . .
` ' '
- 8 -
.
: :
;.. , , , . ,. , , .. .... , ,.. . . . . , . - . ., - . ` -
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)
' ' .
- 10 -
. . .
: ' . . ~ ,: -' ' ' ~ ' - '
~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
- 12 -
''
1065095
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 -~
' - ~'
,
1065095-
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
~ , ,
- 16 -
.
: ~, . . - ,.. . , .~, ., - . , . . - - - .- . -. - -
, ~ - . : .. . . . .
,. , ... . ,., : , . . . . ... . .. .
.. ; ,~ .. . .,. . . ., .. ,.. , ~ .....
... .
1065095
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
. , .
~ .
,
. . ,. . . " . , . ~:
: , . . , ~ . . - . . . ... -. .- -
10651095
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
- 18 -
, . . . . . . . .
- :
1065095
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
-; ~
- 19 -
. ! , ~
' ',' ' , . '' ' ' ' ' ' " ' . ~ . ''~ .' . ': ' ' ' ,
,
'': ' ' ' - ,.' : , ', , .,' ' ,,, . -J ' ' , '. ' `. '' .
1065095
:
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.
~,
'
'
.
- 20 -
. - , , : , , . .. .- . .. . .
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 -
...
. ,~ , ,
;
-
1065095
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.
'
- 22 -
1065095
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
.
- 23 -
,: ~ '
~'' ..
- : - : ' ~
. .
~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.
.,, :
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- 24 -
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.
106S095
.
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 -
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-
1065095
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.
,-
-,
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1065095
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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10651095
_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.
.
- 29 _
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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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1065095
_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.
.' . ' ' '.. ...
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106509S
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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. . .
1~65(~9~
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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1065095
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.
A ~
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1065~5
~ ple 1~
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
- 37 -
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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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106S095
Example 15
10 g of the dye of the formula
(25) H3C-502 ~ N-N ~ ¦
.
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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1065095
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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- 42 -
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