CA1057891A - Polymeric dye-receptive additives - Google Patents

Abstract

POLYMERIC DYE-RECEPTIVE ADDITIVES

Abstract of the Disclosure The invention relates to polymeric dye-receptive additives for modacrylics consisting of 4 - 1o mol % of an acrylic or methacrylic acid amide corresponding of the general formula 1o - 5o mol % of vinyl chloride and/or vinylidene chloride and/or vinyl bromide and 3o - 8o mol % of at least one halogen-free component corresponding to the general formula

Description

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This invention re}ates to copolymers ~aYing a ~igh sulphonate group content whlch, with halogen-containing ~ ~;
modacryllc polymers, ~orm compatible mixture~ rrom which shsped artlcles, such as for exampl~ fibres or ~ilms, with an lmproved arrinity ~or basic dyes can be produced.
The invention al80 relates to a proc~s ~or the production of polymeric dye-receptive additives of this ~ -kind. ~-At present, acrylic and modacrylic iibres, yar~
produced therefrom and the sheet-~orm textiles procluced ~rom these materials are mainly dyed with cationic dye~
whose basic centres are ionogenically bonded to ucid group~ Or the ~ibre polymer. ~ccordingly, the coloristic properties o~ a ~ibre are critically determined by its content o~ acid dye-receptive groups~ In many ¢ases, it i8 pos~ible ~pecifically to in~rease the concentr~tion o~ such groupY, ~or example by incorporating comonomers containing carboxyl or sulphonate groups in the ohain of the fibre polymer. Favourable dyeing properties are obtained, especi~lly where rational dyelng proces~ee are used, with inoorporated amounts oi the acid component o~ irom 0.5 to 2,0 mol ,~.
In the technology oi ~l~re production, lt is also know~ th~t the dyeing properties of ~ibres and o~ materials produoed from them c~n be improved by mi~ing a suitable polymeri¢ component h~ving ~ very high conte~t o~ dye-recepti~e groups wlth the ribre-forming polymer.
nConoe~trates" suoh as these must sstis~y the following requlrement~ lf they are to be suitable ior U5~ a~ additives ~0 for ba~io~lly dyeable i~ibres o~ aorylio or mod~crylio polymers:
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The polymerio additive must be soluble in the 801vent9 u.~ed for Qp~nning and must ~orm compatible mixture~ with the ~lbre~orming polymer both i~ solution and al~o in the solvent-~ree fibre. : ~ .
The addltlve must be oo-ordinated with the ba~e polymer to be ~inished both in lts compos~tlon and in it~
molecular welght in such a way that there i~ no ., d~e~h~$he~ in the properties Or the fibre, ~or ex~mple embrittlement, redu¢tiol~ oi the so~te~ing temperuture or ~ore uniavourable burning properties in the case o~ substantially non-inflammable modacrylic fibre~. q The polymeric additive with it~ high content of an acid comonomer component, more espeoially one cuntaini~g ~ulphonate groups~ should not be soluble in water, beo~u~ in that c~se lt oould be wa~hed ~ut, $or example durl~g wet-spinDing processes or during the various aftertreatments to which the fibre i8 nOrmRlly subJected.
The u~e Or dye-receptive additives o~ this ki~d i8 par~,icularly signl~ic~nt i~ the case Or fibres o~ haloge~-oontalning mod~orylio polymers produced by processes in which the dlreot Incorporation o~ ionio dye reoeptive oomono~ers i8 lmpos~lble or substQntlally lmpossible.
Thl~ i~ the ¢ase~ ~or e~a~ple, ln the emulsion copoly~risation ~ ::
o~ acrrlonitrile-vl~yl chloride or acrylonitrile-vinylidene chlorlde.
I~ con~equence Or the abov0-mentioned.~equirements in regard to ths con~titution o~ the polymeric dye-receptive ~0 ~ddltives~ the ~ollowi~g re~erence points apply to ~hese 9pe¢i~1 8y~te~8:
Th~ ~ulpho~ate-group content o~ the dye-reoeptive . l2-~ .~ . - .

10S7~3~
~dditive should be ~d~u~ted to a~ hlgh a l~vel a~
pos~ible, i.e. to conce~tratio~s o~ greAter th~n 4.0 mol. ~, in order to be able to ~inlm~ 8e the qu~ntity added to the fibre to be i~inishe~. In order to preolude the solubility o$ the ~dditlve ln water, the concentratlon og the ac~d component ~hould not exceed an upper critlcal level amountin~ to between 12 ~nd 15 mol ~.
For reasons Or comp~tibility and ~or mai~taining the substsntial non-inflammability o~ t~e modacrylic ribre to be ~inished9 a h~logen-containing component must be incorporated in the dye-receptive additi~e. ;
The polymeric dye-receptive additive should be comparable with the ~ibre polymer in regard to its averAge molecular wei~ht~ so that molecul~r weights lS in the range oi' ~xom 10,000 t~ 100,000 have to be achieved, On account o~ the high ncid group content of the additive, its molscular weight distribution should be as nnrrow as possible and i~ts chemical inconsistency a~ low as poæsible, be¢au6e othcrwise low molecular weight fr~ctions Are in danger of being dissolved out of the ~ibre to a greater e~te~t with water.
The possibilities ~or producing the poly~erio dye receptive additives which embody the above-mentloned constitutional ~eatures are extremely limited in .25 proce~s terms.
ThuQ, it ca~ be see~ irom Canad~an Patent Speci~ication No. -704,778 that, iD the emulsio~ polymerisation o~ acrylo-: nitrile-vinyl ohloride, acrylic and metha¢rylic Amides containing sulpho~ate gr~up~ can only be incorporated in the presence of a , 30 ¢orre~pondin~ monomer exc28~ even in the relatlvely low con-: ce~trAtio~s reierred to hbo~e. This applies to a greater or 1~sser e~tent to ~ny polymerisatio~ prooe~os:which can be ¢arried out i~ aqueou~ ~eactlon ~edia, because ~n caæe~

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such as these polymeris~ion takes place i~ two phases, e~pecially in o~ses where the acid oomonomer i9 used in a relatively high concentration, in such a way that the ionic oomponent i9 predominantly polymeri~ed in aqueous solution, in which it ls subsequently in¢orporated o~erproportionally ~n the micelle or in the monomer-swollen gr~in in rel~tion to polymerisation. The polymers ~ormed have a high ~hemical ~nd molecul~r incansistency ~ ;
and contain the sulphonate-group-contAining component in ~ proportion which does not correspond in the Ieast to the predetermined concentr~tion. This tendency is the more pronounced, the higher the concentration o~ the acid ¢omponent.
Copolymers with a high ~ulphonate group content and, ln addi.tion, a high chemical and molecular conslstenoy, are produced more adv~nt~geously by polymerisation in a homoge~eou~ pha~e, s~lution polymerisation being of particular signifioance in this r0spect. However, it io nece~ary to use particularly polymerisation-active sulphonate-group-containing comonomer~ which, at the same time, must also show ~a~ourable copolymeri~ation beh~iour with the other monomer components present in the Gystem, Although it i~ known trom East German Patent ...
Specirication No. 80 551 that ~opolymers can be produced from the 5alt6 of unsaturated sulphonic acid~, more espeoially ~rom the salts of allyl and methallyl sulphonic acid, with acrylo~itrile and vinylidene chloride by a radically initiated solution-polymerisation reaction~
the extremely lcw relative polymerisation reactivitie~
of the above-me~tloned sulphonic acid components make it necessary to malntaln not o~ly long reaction time~, but also . .

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complicated dosage requirements for the production of use~ul copolymers.
It has now been ~ound that pol~ymer~c dye-receptive additives for fibres o~ halogen-containing modacrylic polymers can ~e obtained by copol~merising the monomer components (A), (B) and (C) ~peciied below in certain qusntitatlve ratios.
Accordiugly~ the present invention relates to a process for the production Or a polymeric dye-receptive additive with a high sulphonate group content~ which comprises the following monomers copolymerising by radical initlation in an amide-containing aprotic solvent at a temperature in the ran~e o~
~rom 20 to 80 C:

(A) 4 to lO mol ~ oi.an acrylic or methaorylio aoid amide corre~ponding to the general ~ormula (I):
O ., C~ = C - C - NH - R2 ~ S03M (I) al ~ :

in whi~h Rl represent~ H or C}I3~
~2 repre~ents n line~r or branohed alkylene radioal optionally sub~tltuted by aryl groups or an arylene radical~ and M represents a primary~ secondary, tertiary or quaternary ammonium ~roup~ a lithiu~ catio~ or an M~-GJ~tiOn 0qU1~A1ent;

Le A 16 108 - 5 -.. ..

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~L057891L :
n) 1 o to 50 mol ~ Or a member seleo~ed from the group consisting o~ vinyl ohloride~ vinylidene chloride, vinyl bromide, and a mixture thereor (C) 30 to 80 mol ~ o~ at least o;ne other halogen-rree ethylenically unsaturated col~pound copolymerisable with components (A) and (B) and corresponding to the general formula (II):

CH2 _ C . (II) in whioh ~o ~3 represent~ H or CH3, and ]ll~ represonts a radioal seleoted rrom the group consisting o~ -C~N, -~-0-R5, wherein R5 is an alkyl radical with up to 4 carbon atoms, and o ~ H(CH3) where R5 -C-N \ ~

is as defined above.
This invention also relates to a polymerio dye reoeptive additive containing in statistioal distribution:
(A) 4 to 10 mol ~ o~ an acrylic or methacrylio aoid amide corre~pon~1ng to the gen~ral ~ormula (I): :

.

CH2 5 C - C - N~ - Rg - S03M (I) :~

ln whioh ~ 19 R2 ~d M ~ro a~ ~fined above.
., ~ .

.... . , : .
L~ A 16 108 - 6-.

71~

(B) 10 to 50 mol ~ Or a member selected ~rom the group vinyl chloride~ vinylidene chlorideJ vlnyl bromlde, and a mlxture thereof (C) 30 to ~o mol % of at least one other halogen-free ethylenioally unsaturated compound corresponding to the general ~ormula (II):

, CH2 = C \ (II3 in whioh R~ snd ~4 are as defined above.
lo and having ~n intrin~ic vi~ooYit~ [~ ~DM~ a~ m~agured ln dioethyl formamide, o~ ~rom 0,l to 3~0 [dl/~].

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SolYe~ts ~uitable tor uae in the process a¢cordi~g to the invention are, above all, ~mide-containi~g aprotlc ~olvents Or the type preferably u~ed ~or ~pinning acrylic and modacrylic polymers. Di~ethyl iormamide and dimethyl acetamide are mentioned ns particularly favourable ~olYents, In order, on the one hand, to e~rry out the reaotion o~ the abo~e-mentioned monomers i~ an economioally reasonable manner and, on the other hand, to guarantee a homo~eneou reactlon in eac~ phn~c Or polymer~atio~g the ratio by .
-Le A 16 108 - 7 -, .

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w~ig~t o~ ~ol~rent to.~o~o~r ~hould b~ ~dJu~ted ~ithl~
certain limit~ of irom 90:10 to 40:60. The pre~erred range ls ~rom 80:20 to 50:50~
It i~ adYant~geous for the sulphonate-group~containing acrylic and methacryrllc amides ment:loned und~r (A), eæpecially in the ~orm Or their ammonium saltsv to show a high level of solub~lity in the amide-containing aprotic solvents whlch remains intact even in the presence of the other comonomers mentioned under (~) and (c3 and in the presence 0 0~ ~he polymer rormed. This explain~ their distinctlr in¢rea~ed polymeri~ation aotivity whioh is olearly notioeable by oomparison with the free ~ulphonio aoid~
or their alkall and alkal~ne earth metQl s~lts. A speoi~l polymerisAtion-aocelerating efrect i8 observed when 1~ ammonium sulphonates Xormed from amino alcohols, more especially from 2-methylaminoethanol, are used.
Production o~ the dye-receptive additives by the proce~s ~ccording to the invention i~ carried out at temperntures ln the range o~ rrom 20 to 80C. Sinoe the 2e above-mentloned aprotic ~olvents have a hleh tran~er ~*ect whioh become~ dl~tinctly more intense wlth :Increasing te~perature, react10D temperature6 of ~ore than 80C are .
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Le A 16 1O8 - 8 -.
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~35 ~
not ~uit~ble ~or the production o~ u~e~ul dye-receptive. .
~dditives, espec$ally ~lnce, ln that case, the halog~n~
cont~nlng pol~mer al~o undergoes ~airly heavy discolouration under the e~eot oi the solvent. Pol~meri~ation i8 pre~erably carr~ed out ~t temperature~s in the r~nge of irum 30 to 600C.
At temperature~ in the above-mentio~ed range, the polymeri~at~on reaction c~n only be lnitiated by particularly active radical starter ~ystems. Suit~ble starters are, aboYe all, starters o~ the Redox type, among whlch the ~y~tems ammonium peroxodl~ulphQte/oxalic acid, tert.-butyl hydro-peroxide/benzene sulphinio acld ~nd ammonium peroxo-dl~ulphate/hydroxy methane sulphinio acid~ or their ~ino s~lts~ have pro~ed to be p~rticularly ei~ective, The compon~nt~ o~ the initiRtor 8y8tem are generally used in ~;.
concentratio~s o~ ~rom 0.01 to 2.0 mol % and preferably in con¢e~trations o~ ~rom 0005 to 1.0 mol %, based on the total molar quantlty o~ the monomers used.
The choloe of the mo~t ~uitable co~centration ~nd the ohoice of the ratio of oxidislng to reducing agent are governed above all by the avernge moleoular weight to b~ adJusted in the polymeric dye-receptive additlve. It ..
ba~ also been ~qund that the polymerisation veloclty and ~180 the ~bsolute co~ver~ion level can be inoreased in the , 25 prs~ence oi the ~ove-mentioned, p~rticularly ~ctive Redox ~t~rter systems provldi~g w~ter i~ added $n a limited con~entrQtlon to the aprotlc solvents. .It is posslble, witho~t interiering ~ith po~ymerisation to any appreci~ble extent, to add up~to 10 ~ by welght o~ water, b~sed on the totAl qu~n~ . 0~ 801~ent uied. The optimum e~fect i~
obtained w1th addltlons oi ~rom 5 to 7 % by ~eight,.
I~ order to produce polymeric dye-re~eptive addltives ' . '~ ' 9 _ a ~3,j 7~
with a high chemical and moleoular consi~kency by the prooe~s ~ccording to the invention, it 18 necessnry to polymeri~
the mono~er compo~ents (A), tB~ and,~C) in a certain ratio determined by thelr copolymeri~ation parameter~ a~d to e~sure that thi~ ratlo remain~ ~ubstantially ¢onstant throughout the entire reaction, In many cases, condition~ ~uch as ,the~ ~ay readily be estsbllshed by i.nlti~lly introducing all the components of the system and polymerising them i~
the absence of any further measures up to high con~ersion le~els, on the lines Or a batch process. In the oontext ~-~
o~ the invention, this applies in particular to systems in which the halogen-co~taining oomponent used is vinylidene chloride which, owing to its ~avourable copolymerisation behavlour with monomers (A) and (C), requires uni~orm s in¢orporation o~ all the components o~ the ~ystem, In cases where vinyl chloride or vlnyl bromide are used, poly~erisation is more di~ficult to carry out~ because the parameters oi the copolymeris~t~on reaction are unfavouruble related to mo~t o~ the comonomers ment$o~ed under (C). In order, ln these cases, too, to obtain polymers with a Xavourable chemleal and molecular oonsi3tency, it is ~ecessary to develop a strictly adapted dosage scheme ror all the component~ o~ the system for each polymer composition required, taking , 25 into account the p~rticular poiymeri~ation velocity.
In the proces~ aocording to the invention, the eon~ersion level ~hould amount to at least ~0 ~, based on the sulphonate-group-contai~ing amide component used.
In mo~t oase~, a much higher con~ersion level is reached, ~o th~t the polymer solutions obtai~ed may be directly ; . added as dya-rec~pt~e additives to ~odacrylic spinning 801utio~9~ ~ollowlng ~ep~r~tion of the vola$ile monomer ~ - ~o -.; ~ .

1~5'i~

rractions. With lower converslon~ (less than 80 %)~ the required polymer i8 best wor~ed up by precipitat~on~
the unrencted sulphonAte-group-cont~lning acrylic or methacrylic ~cld ~mlde belng recovered.
The sulphonate g~oup-containin,g acrylio ~nd methacrylic amldes mentioned under (A)~ which are reacted wlth comonomer~
(B) ~nd (C) to form the polymeric dye-recept~v~ additlve~
according to the invention, m~y be obt~i~ed by know~
methods:
1. ~y reacting acrylonitrile or mathacrylonitrile wlth mono olefi~ic compounds containlng a terminal double ~ :
bond in the presence of a sulphonating ~gent.

2. By react~ng acrylic or methacryllo aoid chloride with the appropriate amlnosulphonic acids or their salts in the prese~ce Or acid-blnding compound~.
Of the acrylic and methacrylic acid amides obtsinable by reaction 1), 2-acrylamido-2-methyl propane sulphonic ; acid above all has pro~ed to be p~ rticularly suitable ~or the production of the copolymers according to the i~vention, be~ause it~ copolymerisation behaviour is ~avaurable in the form o~ its ~mmoniu~ salts.
0~ the oompound8 obtain~ble by re~otlon 2), 4-methaoryl-amldobenzene sulphoni~ aoid h~s proved to be eminently sultable ~or the production of the copolymer~ ~ocordlng to the in~entio~
The ~orylic and methacryli~ acid amides mentio~ed under (A) ar~ predominantly incorporated in ths ~orm o~
correspo~ding ammonlum ~ulphonates which are iormad before polymerisation Srom the free sulphonic acids by neutr~lisation with prim~ry~ secondsry and tertiary amines or with quaternary am~onium bas~s. It i8 only the high solubility bot~ o~ ~ha scrylic and methacryllc acid a~ides cont~ining . . . .. .

~5'7~'~
a~monium sulyhonate groups and o~ the copolymers ~ormed from them together with components (B) ~nd ~C) in the aprotic solvents used l~hich enables polymeris~tion to be carried out in homogeneous phase, 80 that the dye-receptive additives according to the invention are aetually produced with a high chemical and molecular consistency.
Particularly ~avourable properties are shown by copolymers containi~g ~mmonium structures formed ~rom ami~es containing hydroxyl groups, ~or example those formed rrom 2-methylaminoethanol, diethanolamine or triethanolamine. One striking iactor i8 the very f~int natural colour o~ copolymers such as these which is reflected in the ~avourable colour of ~he polymer solutions ~ormed.
This factor promotes their use as dye-recept~ve additives ln the ~bre field.
or the halogen-containing compounds mentioned under (B), vinylidene chloride and vinyl chloride above all are suit~ble for t~e production oi the polymeric dye-re¢eptive additives.
Their incorporation promote~ the compatibility o~ the sulphonate group-containing polymers w~th the halogen-oontaining modacrylic polymers to be finished. Vinylidene chloride has proved to be particularly suitable by virtue o~ it~ favourable copolymerisatlon behaviour, enabling the , sulphonate-group-containing component to be uniformly incorporated, ~bove all in the presence of the ~ther como~omer (C).
Of the monomer components me~tioned under (C), refere~ce i8 ~ade above all to acrylonitrile, methylacrylate and N-tert,-butyl acrylic acid a~ide. Dye-receptive additives 30 cont~ini~g these monomer~ are distinguished by partlcularly ~avourable propertiss, Corre5pondingly fi~ished modacrylic ~i~re~ are not only improved in their coloris~ic properties, but -: .

~L05'7~.

they fllqo show more favourable light fa3tness ~nd increased gloss values.
The average molecular weights ~ln of the polymeric dye-receptive additi~es may be adjuqted within relatively wide limits of lrom 5000 to 300,000 in the process according to the invention by vAI~ing the catalyst concent~ation or the initial solve~t:monomer r~tio. ~hi~ molecular weight range corresponds to intrinsic v~scosities L ~]DMFP as measured in dimethyl formamide, Or from 0.1 to 3.0 [dl/g].
No connection was ~ound between the activity o~ the dye-receptive additives and their average ~olecular weight.
Nevertheless, it is advantageous ~or the molecular weights of the copolymers according to the invention to be compara~le with those o~ the modacrylic fibre polymers to be finished in order to prcclude any ne~ative in~luence upon import~nt fibre propertie~ governed by molecular weight, and to guarantee safe completion of the spinning and arter-treatment process under constant ~onditions. Accordi~gly9 copol~mers with average molecular weights ~n o~ from 10,000 ~o 100,000, corresponding to ~ ~ values of ~rom 0.5 to 2.0 [dl/g], are particularly suitable ~or use as dye-additive 8 .
Accordingly, preferred copolymers are those which oontain, in ~tatistical distribution, st~uctur~l units of (A) 4 to 10 mol ~ o~ 2-acrylamido-2 methyl propane ~ulphonic acld in the form of an ammonium salt, (B) 10 to 50 mol % of vinylidene chloride and/or vinyl chloride, (C) 30 to B0 m~l % o~ acrylonitrile and/or methacrylate and/or N-tert.~butyl acrylic acid amide, and which h~ve an intrin~io YiSCosity ~ ~]DMF~ ~ measured in dimethyl ~ormamide; o~ ~rom 0~5 to 2.0 ~dl/g¦, .

~L0~7l~1 Unless otherwise indicnted, the intrinsic visoos~ties [~ ]D~lF quoted in the description and in the following Examples were determined at 25C in dimethyl ~ormamide to which 0.3 ~ by weight of sodium nitrate had been added in order to eliminate the electrolyte e~fect (cf. ~ans-Georg Elias: "Malcromole~ule", page 265, ~uthlig und Wepf Verlag, Basel-Heidelberg (1971).
~he average molecular weights ~n quoted are number averages which may be determined by osmometry.

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EXA~IPLE 1 . , , :
q'he following solution~ and mixtures are u~ed for ~he solution polymerisation proces3 described in the E~ample:
I13,720 g o~ dimethyl formamide 19155 g of deionlsed water II3,300 g of dimethyl formamide 1,238 g Or 2-acrylamido2-methyl propane ~ulphonic ~oid PS ) ~37 g of 2-methylaminoethanol III4,125 g of acrylonitrile 2,888 g of ~inylidene chloride IV990 g oi dimethyl formamide l9.B g of ammonium peroxy disulphate Y990 g of dimethyl formamide 2~,1 g of oxalic acld.
The DMF/water mi~ture (I) ~s initially ~ntroduoed into a 40 litre autoolave of VA~steel equipped with an anchor stirrer, and nitroge~ i~ pa~sed t~rough at 50~C. The AMPS-salt solution (II) obtained by neutralication (at 0C) i~ combined with the DMF/water mi~ture (I), followed by introduction o~ the monomer mixture (III). Atter the reaction temperature o~ 50C has been reRched, a prsssure of 1.5 bars i~ spontaneousl~
adJu~ted in the no~ closed autoclave. The polymerisation reaction i9 lnitiAted by adding the in~tiator solutions IV
and V.
At a stirIing speed o~ 50 rpm, the solution reaches a solid3 oontent o~ 23.0 ~ by weight after 12 hours, corresponding to a conver~ion o~ 71 ~.
The aonversion may be further incrcased by introducing :
more ammonium peroxy disulphate and oxalio acid. However, it wns ~ound that, tollowlng ~eparation o~ the unre~cted volntile monomer co~stituents (acrylonitrile and vi~ylidene .. . - -~ ~ - . .

chloride), polymer solution6 wlth conversions of more than 70 % m~y ~e directly added a~ a dye-receptive additive to spinning solutionfi of halogen-containin~ modacrylic polymers.
It is more advantageous to pr0ciplt~te the polymer containing sulphonate groups from the solut~ on diluted with water and/or methanol by the addition oi an electroly~e.
The poly~er obtained at a conversion oi 71 ~ has the following composition:
69.5 mol ~ o~ acrylonitrile 25.3 mol ~ of vinylidene chloride 5,2 mol ~ of AMPS in the ~orm of the ammonium salt oi 2-methylaminoethanol [ 7 JDMF - 0.85 [dl/g~
EXA~PLE 2 The ~ollowing solutions and mixture~ ~re used for the polymerlsation process desoribed in the Example:
I200 g o~ dimethyl ~ormamide 75.0 g oi 2-acrylamidoL2-methyl propane sulphonic acid (AMPS) 26~5 g of 2-mathyl~minoethanol II275 g or acrylonitril~
150 g o~ vinylidene chloride III61 g of dimethyl ~ormamide 1.2 g of ammonium peroxy disulphate IV60 g o~ dimethyl ~ormamide 104 g o~ oxalio acid 900 g o~ dimethyl form~mide are initially introduced into a 2 litre pla~e-ground glas~ jar ~quipped with a reflux conde~ser oooled with iced water, a g~te paddle s~irrer and a gas-inlet pipe, and nitrogen i~ passed through at 50C. The a~monium salt solution (I~ and the monomer mixture (II) ar0 succe~ively oo~b~ned with the dimethyl ~ormamilde. A~ter the Le A 16 108 - 16 -, reaction temper~ture oi 45 ha~ been reaohed~ polymerisa~ion i~ ini tiated by addlng solutions III ~nd IV~
I~ order to determine the compositio~ of the polgmer ~ormed and its intrinsio viscosity [~ ~M~ ~n dependence upon the oo~ver~ion~ ~mple~ are take~ ~t hourly interval~
and the polymer is isolated therefrom by preolpitation.
The compositions determined ~re shown in th~ following Table:

Reaction Converxion Polymer eo 08ition Viscosity [hour~3 [~ J [ m~ ~MPS ~ ~ ]DMF [dl/g]
nitrile chloride salt .. . . ~ __ , , 1.0 15.5 76.318.2 5.5 1~08 2.0 25.7 77.217.6 5.2 1008 .0 3~.3 76.7lB.0 ~.3 1.08 4.0 37.7 76.917.9 5.2 1~09 5.0 41.0 76.118.6 5.3 1.06 6.o 44.5 76~718.g 5.1 1.06 7.0 47.0 76.71 18~2 5.1 1.01 :
12.0 62.0 76.118.7 5.2 1.02 The re~ults show that polymers w~th a high ohemical and moleoul~r consi~tenay are obtained by the desoribed proce 89 .
~
~h~ rollowing solutio~s and mi~tures are used for the 601ution polymerisation process de~cribed in the Example: ;
I 624 g of dimethyl ior~a~ide 52.5 g o~ deioni~ed water

3 ~I 150 g of dimcthyl rormamide 56.4 g o~ 2-acryla~ido-2-methyl prop~ne ~ulphonic aoid (AMPS ) ::
Le A 16 108 - 17 -___ . ' ', ~ ' , ~, I

~05~7~
20.0 g of ~-methylaminoethanol III 201.5 g o~ methacrylate 117.5 g o~ vinylidene chloride IV45 g of dimethyl ~ormamide 0,75g of ammonium peroxy di~ulphate v~5 e Or dimethyl formamide 0.9 g Or ox~lic acid The DMF/water mixture (I) is initi~lly ~ntroduced into a 2 litre glas~ reaction vessel equipped with a stirrer9 a re*lux condenser cooled with iced water and a gas-inlet pipe, and nitrogen i~ passe~ through at 50~C. The solution (II) of the AMPS-ammonium salt, prepared at O~C, i8 combined with the DMF/water ~ix~ure. After the monomer mixture (III) h~s been added ~nd the reaction temperature o~ 55C ad~usted, lS the polymerisation reaction i8 init~ated by addin~ the i~ltiato~ solutions (IV) and (V), After 5 hours, the 801ut~0n iS found to have a solid~
content o~ 27 % by weight, corresponding ~o a oDnversion Or B7.5 %. The polymer obtained by precipitation ~rom the polymer ~olution ~ormed ~conver~ion 87,5 %) has the following compo~ition: :
61,2 ~ol % oi methaorylate 31.~ mol ~ of ~inylidene ohloride 6.9 mol ~ of ~crylamido-2-methyl prop~ne sulphonio ao~d ~in tho ~orm oi the ammonium salt o~
methyl~minoethanol) .
[~]DMF = 0.64 [dl/g]
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The i'ollowin~ solution~ and mixtur~ are used for the 30 ~olut~on polymer1satiQn prooesD de~crlbed in the Ex~mple:
I ~ 936 g o~ di~ethyl formamide 79 g o~ deion~ed water .. : ~. . ...
:.~ ;. . . . .
- .

~S~8~
281.4 g of N-tert.-butyl acrylic a~id amlde II 225 ~ o~ dimethyl formamide 84.6 g o~ 2-aorylamido~2~ethyl propan~ ~ulphonic acid (~AMPS ) 30.0 g o~ 2-methyl~minoethanol III 67.5 g of dimethyl ~ormamidle 1.5 g o~ ~mmonium peroxy disulphate IV 67.5 g of dimethy} for~a~de 1.8 g o~ oxall~ acid ~he N-tert. butyl ~crylio aoid amide solution ~
i8 initially introduced into a 2 litre gla88 reaction vessel equipped with a stirrer, a re~lux condenser oooled with iced w~ter and a gas inlet pipe~ and nitrogen iB pQssed through at 50C. ~he AMPS-~mmonlum s~lt ~olution (II), obtained at 0C by neutrali~ation, i8 oombined with the N-tert.-butyl ~orylio ~cid ~m~de 801utlon (I)~ A~ter 157 g of vinylidene chloride have been added and the reaction temperature ad~usted.
to 50C~ polymerisation i~ initi~ted by adding the initator 801ution8 (III) and ( IV) o Arter 6 hour~ the 801utio~ i 8 round to hav3 a solids oontont oi 24 ~ by weight, corresponding to a oonverslon o$
75 ~. :
The polymer obtal~ed by preoipitution ~ro~ the solution rormed after thls reeotlon time h~s the followlng oompoeitlon:
48.S mol % o~ N-tert.. -butyl Acrylio ~oid amlde - 45.3 mol % of ~inylide~e ohlorid~ :
. .
B.:4 ~ol ~ 9i 2-acrylamido 2-m~thyl.propa~ ~ulpho~lc : .
acid (~n the ~orm OI the a~nvniu~ Balt o~
; 2-methylami~oethanol) ~ ~ 3DMF ' 0.52 [dl/g]

h0 ~ollow~ng solution~ ~d m~xtures ~re u~ed for the solu~lo~ poly~sri~tion proces~ desoribed in the E~mple:

1 9 _ ' .. . . .. . . . .. . . .
:-' " '' ' '7~3^~

I500 g o~ dimethyl ~or~mide 50 g of deionised water II335 g oi dimethyl iormamide 70.6 g of 4-~ethacryl~midobe~zene sulphonio acid 29,4 g o~ tristhylnmine III187~5 g o~ ~crylo~itrile 131.2 g o~ vinylidene chlorilde IY45 g oi dimethyl Iorm~idls : Q.9 g o~ ~mmo~iu~ peroxy d:l~ulphate V45 g of di~ethyl ~or~amide 1.05g Or o~alic acid The ~MF/water m~xturc (I) i8 initlally i~troduced into a 2 litre gl~s~ reaction ves~el equlpped wlth a re~lux conden~er cooled with ioed water, ~ s~irrer and ~ g~ inlet pipe, and nitrogen 1~ pas~ed throu~h ~or about ~0 minutes.
~t ~ temperature oi 50C . q'he ~olution ( II ) of ths triethyl ammonlum s~lt of 4-meth~cryl~midobenzene sulpho~ic aoid, obtalned by neutr~lis~tion at O~C~ i~ oombined with the DMF/water misture. Arter the ~ono~sr ml~ture (III) ha3 been ~dded ~nd the raactlo~ temper~ture o~ 50C ~d~u~ted, polymeri~ation i8 lnltiated by adding the i~iti~tor ~olutions (IV) and (V).
A~er 10 hour3~ the ~olution i8 ~ound to h~ aolias oontent Or 20,5 % by weight, corr~pondl~ to ~ conv~rslon o~ 60 ,~0 ~ polymer oi the iollowing co~posltion 1B ob~ained by : .
preolpita~ fro~ the polymer ~olutio~ formed (oonversion 60 ~):
71.5 ~ol ~ o~ ~cryl~nitrile . . 21~0 ~ol ~ of vinyllde~ ohloride .30 7.5 mol ~.o~ 4-methacryl~midobenzene ~ulphonic Acid (in the ~or~ of ths ~m~onium 6l~1t o~ tr~-athylamine) ]DMF = 0.51 [dl/
- 20 _ '' ~T~
, i " , ~ , .. , " " ~ " ,~ ~
. .

-~5~'3~1L
E~MPLE 6 The ~ollowlng ~olutlons and mixture~ are u~ed for the 801ut~0n polymeri~tion prooe~ described in the Example:
I670 g o~ vlnyl chloride 210 g o$ acrylonitr~le II1000 g of dimethyl ~ormami~de 90 g o~ 2-acrylAmido~-met~yl prop~ne eulphonic ~cid ~AMPS) 32.5 g of 2-methyl~mi~oethanol III170 g oi dime~hyl ~ormam~de

4.5 g of ammonium pero~y disulphate IV170 g of dimethyl ~ormamide

5.25g Or oxalic acid V890 g ot dimethyl formamlde lS 195 g o~ 2-~cryl~mldo-2-methyl prop~ne ~ulphonic acid (AMPS) 70.5 g of 2-meth~l~minoethanol :
VI570 g o~ dimethyl ~or~mide 11.25g oi am~o~iu~ pero~y disulphate VII570 e o~ dimethyl torm~mlde 13n55g of o~lio ~oid VIII1040 8 0~ acrylonitrile 1700 g o~ vlnyl chlorlde .
~he ncrylonitrile/vlnyl ohloride mlxture ~
init~lly l~troduce~ i~to ~ 12.1~tre ~uto~lave o$ VA-~teel equipped with a~ an¢hor stirrer and four supply ves~els oonnected through ~eter~ng pu~p~. ~he solutio~ ~II) o~
th~ ~ S ~mmoniu~ ~alt i8 introduced under pre3sure into th~ ti~htly olosed reaotion ve8sel. After the r~aotion ~0 temp~r~ture o$ 35C (i~ter~nl pre~sure: 4.0 bars) h~s b~èn ~d~u-~ted, pol~eri~atio~ i~ init~ate~ by ~ding th~
l~iti~tor 801utio~ (III) a~d (lV~ ter 30 ~inutes, Ls ~ 1~ 108 - 21 -, . ..
...
, . .

solution~ (v) to ~V~II 3 are simult~neously i~Ltroduced over a perlod OI 10 hour~:
Solution V: 120 ml/hour Solution VI: 60 ~nl/hour Solution VII: 60 ml~hour Solution VIII: 300 ml/hour A~ter the 10-hour metering pha~e, polymerisation is ~topped ~y the ~ddition o~ 5 g ot' hydroquinone mo~omethyl ether ~nd the polymer solution iormed i~ wor~:ed up by pre-clp~tAtillg the polymer follow~g evaporati~n oi the volatile ~onomer consti tuent 8 o Composition of the poly~er:
72.5 mol ~ Or ~crylonitrile 23.0 mol ~ of vinyl ohloride . 4.5 mol ~ of 2-aoryl~mido-2-methyl propane sulpllonic Aoid (in the form o~ th0 ammonium ~alt 2-methylaminoeth~nol) ]~MF - 1-98 [dl/g~
~ield: 1250 g ~oonverslon: 60 ~, ba~ed on the acrylo~itr~le and A~S~alt), ~a~ - 22 -, .: . .. -

Claims (7)

1 A process for the production of a polymeric dye-receptive additive with a high sulphonate group content, which comprises the following monomers copolymerising by radical initiation in an amide-containing aprotic solvent at a temperature in the range of from 2o to 8o° C:
(A) 4 to 1o mol % of an acrylic or methacrylic acid amide corresponding to the general formula (I):

(I) in which R1 represents H or CH3, R2 represents a linear or branched alkylene radical optionally substituted by aryl groups or an arylene radical, and M represents a primary, secondary, tertiary or quaternary ammonium group, a lithium cation or an Mg-cation equivalent;
(B) 1o to 5o mol % of a member selected from the group consisting of vinyl chloride, vinylidene chloride, vinyl bromide, and a mixture thereof (C) 3o to 8o mol % of at least one other halogen-free ethylenically unsaturated compound copolymerisable with components (A) und (B) and corresponding to the general formula (II):

(II) in which R3 represents 11 or CH3, and R4 represents a radical selected from the group consisting of -C?N, wherein R5 is an alkyl radical with up to 4 carbon atoms, and where R5 is as defined above.

2. The process of claim 1, wherein said amide-containing aprotic solvent is dimethyl formamide or dimethyl acetamide.

3. The process of claim 1, wherein said copolymerisation is carried out at a temperature in the range of from 30 to 60°C.

4. The process of claim 1, wherein said radical initiation is effected by a redox catalyst system.

5. The process of claim 4, wherein said redox catalyst system is ammonium peroxodisulphate/oxalic acid.

6. The process of claim 4, wherein said redox catalyst system is tert.-butyl-hydroperoxide/benzene sulphinic acid.

7. The process of claim 1, wherein said amide-containing aprotic sol-vent additionally contains up to lo % by weight of water.