IE42103B1 - Polymeric dye-receptive additives - Google Patents

Abstract

1522706 Dye-receptive polymers BAYER AG 31 Oct 1975 [15 Nov 1974] 45246/75 Heading C3P A dye-receptive polymer comprises (A) 4 to 10 mol.% of an acrylic or methacrylic acid amide corresponding to the general Formula (I) in which R1 represents H or CH3, R2 represents a linear or branched alkylene radical, optionally substituted by an aryl group, or an arylene radical, and M represents a primary, secondary, tertiary or quaternary ammonium group, a lithium cation or a magnesium cation equivalent; (B) 10 to 50 mol.% of vinyl chloride, vinylidene chloride or vinyl bromide, and (C) 30 to 80 mol.% of at least one other halogenfree compound of general Formula (II) in which R3 represents H or CH3, and R4 represents the group -C#N, where R5 is C1 to C4-alkyl, or the group where R5 is C1 to C4-alkyl, and R6 represents H or CH3. The polymer is produced in an amide containing aprotic solvent, e.g. dimethyl formamide or dimethyl acetamide containing up to 10% by weight of water. Examples are given in which (a) 2-acrylamido-2-methylpropane sulphonic acid /2-methylaminoethanol salt is copolymerized with vinyl or vinylidene chloride and acrylonitrile, methyl methacrylate or N- tert.butyl acrylamide and (b) 4-methylacrylamidobenzene sulphonic acid/triethylamine salt is copolymerized with vinylidene chloride and acrylonitrile.

Description

This invention relates to copolymers having a high sulphonate group content which, with halogen-containing modacrylic polymers, form compatible mixtures from which shaped articles, such as for example fibres or films, with an improved affinity for basic dyes can be produced.

The invention also relates to a process for the production of polymeric dye-receptive additives of this kind.

At present, acrylic and modacrylic fibres, yarns 1o produced therefrom and the sheet-form textiles produced from these materials are mainly dyed with cationic dyes whose basic centres are ionogenically bonded to acid groups of the fibre polymer. Accordingly, the coloristic properties of a fibre are critically determined by its content of acid dye-receptive groups. In many cases, it is possible specifically to increase the concentration of such groups, for example by incorporating comonomers containing carboxyl or sulphonate groups in the chain of the fibre polymer. Favourable dyeing properties are obtained, 2o especially where rational dyeing processes are used, with incorporated amounts of the acid component of from 0.5 to 2.0 mol Jt.

In the technology of fibre production, it is also known that the dyeing properties of fibres and of materials produced from them can be improved by mixing a suitable polymeric component having a very high content of dye-receptive groups with the fibre-forming polymer.

Concentrates'* such as these must satisfy the following requirements if they are to be suitable for use as additives 3° for basically dyeable fibres of acrylic or modacrylic polymers: The polymeric additive must be soluble in the solvents used for spinning and must form compatible mixtures wilii the fibre-forming polymer both in solution and also in the solvent-free fibre.

The additive must be co-ordinated with the base polymer to be finished both in its composition and in its molecular weight in such a way that there is no deterioration in the properties of the fibre, for example embrittlement, reduction of the softening temperature or more unfavourable burning properties in the case of substantially non-inflammable modacrylic fibres.

The polymeric additive with its high content of an acid comonomer component, more especially one containing sulphonate groups, should not be soluble in water, because in that case it could be washed out, for example during wet-spinning processes or during the various aftertreatments to which the fibre is normally subjected.

The use of dye-receptive additives of this kind is particularly significant in the case of fibres of halogencontaining modacrylic polymers produced by processes in which the direct incorporation of ionic dye-receptive comonomers is impossible or substantially impossible.

This is the case, for example, in the emulsion eopolymerisation of acrylonitrile-vinyl chloride or acrylonitrile-vinylidene chloride. in consequence of the above-mentioned requiremetilH In regard to the constitution of the polymeric dye-receptive additives, the following reference points apply to these special systems: The sulphonate-group content of the dye-receptive additive shoiild be adjueted to as high a level as possible, i.e. to concentrations of greater than 4.0 mol $, in order to be able to minimise the quantity added to the fibre to be finished. In order to preclude the solubility of the additive in water, the concentration of the acid component should not exceed an upper critical level amounting to between 12 and 15 mol %.

For reasons of compatibility and for maintaining the substantial non-inflammability of the modacrylic fibre jQ to be finished, a halogen-containing component must be incorporated in the dye-receptive additive.

The polymeric dye-receptive additive should be comparable with the fibre polymer in regard to its average molecular weight, so that molecular weights in the range of from 10,000 to 100,000 have to be achieved.

On account of the high acid group content of the additive, its molecular weight distribution should be as narrow as possible and its chemical inconsistency as low as possible, because otherwise low molecular weight fractions are in danger of being dissolved out of the fibre to a greater extent with water.

The possibilities for producing the polymeric dye-receptive additives which embody the above-mentioned constitutional features are extremely limited in process terms.

Thus, it can be seen from Canadian Patent Specification No. 704,778 that, in the emulsion polymerisation of acrylonitrile-vinyl Chloride, acrylic and methacrylic amides containing sulphonate groups can only be Incorporated in the presence of a corresponding monomer excess, even in the relatively low concentrations referred to above. This applies to a greater or lesser extent to any polymerisation processes which can be carried out in aqueous reaction media, because in cases such as these polymeristion takes place in two phases, especially in eases where the acid comonomer is used in a relatively high concentration, in such a way thar the ionic component predominantly polymerises in aqueon., nolution, Where it is incorporated overproportioi.ally comp-.rc-i with the polymerization in the micelle or in the monomerswollen grain. The polymers formed have a high chemical and molecular inconsistency and contain the sulphonate-group-containing component in a proportion which does not correspond in the least to the predetermined concentration. This tendency is the more pronounced, the higher the concentration of the ncid component.

Copolymers with a high sulphonate group content and, in addition, a high chemical and molecular consistency, are produced more advantageously by polymerisation in a homogeneous phase, solution polymerisation being of particular significance in this respect. However, it is necessary to use particularly polymerisation-active sulphonate-group-containing comonomers which, at the same time, must also show favourable copolymerisation behaviour with the other monomer components present in the system.

Although it is known from East German Patent Specification No. 80 551 that copolymers can be produced from the salts of unsaturated sulphonic acids, more especially from the salts of allyl and methallyl sulphonic acid, with acrylonitrile and vinylidene chloride by a radically initiated solution—polymerisation reaction, the extremely low relative polymerisation reactivities of the above-mentioned sulphonic acid components make it necessary to maintain not only long reaction times, but also oomplioated dosage requirements for the production of useful copolymers.

It has now been found that polymeric dye-receptive additives for fibres of halogen-containing modacrylic—__ polymers can be obtained by copolymerising the monomer components (A), (B) and (C) specified below in certain quantitative ratios.

Accordingly, the present invention relates to a process for the production of polymeric dye-receptive additives with a high sulphonate group content, distinguished by the fact that the following monomer components are copolymerised by radical initiation in an amide-containing aprotic solvent at a temperature In the range of from 20 to 80° C: (A) 4 to 10 mol % of an acrylic or methacrylic acid amide corresponding to the general formula (i); II CH2 = C - C - NH - Rg - SOjM (i) R1 in which Rj represents H or CH^ R2 is a linear or branched alkylene radical optionally substituted hy aryl groups, or an arylene radical, and M represents a primary, secondary, tertiary or quaternary ammonium group, a lithium cation or Mg-cation equivalent; (b) 10 to 50 mol i, of vinyl chloride and/or vinylidene chloride and/or vinyl bromide, and (C) 30 to 80 mol % of at least one other halogen-free, ethylenically unsaturated compound copolymerisable with components (a) and (B) and corresponding to the general formula (ll): In which Β.

(II) Rj represents H or CHj, and R^ represents the group -C=N, the group -C-O-Il,., where Rj is an alkyl radical with up to 4 carbon atoms, or the group 0 -C-NL where Rj is as defined above, and Rg represents H or CH3· This invention also relates to polymeric dye-receptive additives containing, in random distribution, (a) 4 to 10 mol ft of an acrylic or methacrylic acid amide corresponding to the general formula (I): CHg = C - C - NH - Rg - SOjM (i) in which Rj, Rg and M are as defined above; (B) 10 to 50 mol ft of vinyl chloride and/or vinylidene chloride and/or vinyl bromide, and (C) 30 to 80 mol ft of at least one other halogen-free ethylenically unsaturated compound corresponding to the general formula (II): R.

(II) in which Rj and R4 are aa defined above; and having an intrinsic viscosity as measured in dimethyl formamide, of from 0.1 to 3.0 [dl/g].

The inventj.on furthermore relates to acrylic or modacrylic fJ Laments, fibres or films containing an additive as defined above, and to a textile article comprising such filaments, fibres or films.

Solvents suitable for use in the process according to the invention are, above all, amide-containing aprotic solvents of the type preferably used for spinning acrylic and modacrylic polymers. Dimethyl formamide and dimethyl acetamide are mentioned as particularly favourable solvents.

In order, on the one hand, to carry out the reaction 10 the above-mentioned monomers in an economically reasonable manner and, on the other hand, to guarantee a homogeneous reaction in each phase of polymerisation, the ratio by weight of solvent to monomer should be adjusted within certain limits of from 90:10 to 40:60. The preferred j5 range is from 80:20 to 50:50.

It is advantageous for the sulphonate-group-containing acrylic and methacrylic amides mentioned under (a), especially in the form of their ammonium salts, to show a high level of solubility in the amide-containing aprotic solvents 2q which remains intact even in the presence of the other comonomers mentioned under (b) and (c) and in the presence of the polymer formed. This explains their distinctly increased polymerisation activity which is clearly noticeable by comparison with the free sulphonic acids or their alkali and alkaline earth metal salts. A special polymerisation-accelerating effect is observed when ammonium sulphonates formed from amino alcohols, more especially from 2-methylaminoethanol, are used.

Production of the dye-receptive additives by the process according to tbe invention is carried out at temperatures in the range of from 20 to 80°C. Since the above-mentioned aprotic solvents have a high transfer effect whioh becomes distinctly more intense with increasing temperature, reaction temperatures of more than 80°C are not suitable for the production of useful dye-receptive additives, especially since, in that case, the halogencontaining polymer also undergoes fairly heavy discolouration under the effect of the solvent. Polymerisation is preferably carried out at temperatures in the range of from 50 to 60°C.

At temperatures in the above-mentioned range, the polymerisation reaction can only be initiated by particularly active radical starter systems. Suitable starters are, above all, starters of the Redox type, among which the systems ammonium peroxydisulphate/oxalic acid, tert.-butyl hydroperoxide/benzene sulphinic acid and ammonium peroxydisulphate/hydroxy methane sulphinic acid, or their zinc salts, have proved to be particularly effective.

The components of the initiator system are generally used in « concentrations of from 0.01 to 2.0 mol $ and preferably ln concentrations of from 0,05 to 1.0 mol $, based on the total molar quantity of the monomers used.

The choice of the most suitable concentration and the choice of the ratio of oxidising to reducing agent are governed above all by the average molecular weight to be adjusted in the polymeric dye-receptive additive. It has also been found that the polymerisation velocity and also the absolute conversion level can be increased in the presence of thecbove-mentioned, particularly active Redox starter systems providing water is added in a limited concentration to the aprotic solvents. It is possible, without Interfering with polymerisation to any appreciable extent, to add up to 10 % by weight of water, based on the total quantity of solvent used. The optimum effect is obtained with additions of from 5 to 7 $ by weight.

In order to produce polymeric dye-receptive additives 43103 with a high chemical and molecular consistency by the process according to the invention, it is necessary to polymerise the monomer components (A), (B) and (C) in a certain ratio determined by their copolymerisation parameters and to ensure that this ratio remains substantially constant throughout the entire reaction. In many cases, conditions such as these may readily be established by initially introducing all the components of the system and polymerising them in the absence of any further measures up to high conversion levels, on the lines of a batch process. In the context of the invention, this applies in particular to systems in which the halogen-containing component used is vinylidene chloride which, owing to its favourable copolymerisation behaviour with monomers (A) and (C), requires uniform incorporation of all the components of the system.

In cases where vinyl chloride or vinyl bromide are used, polymerisation is more difficult to carry out, because the parameters of the copolymerisation reaction are unfavourable related to most of the comonomers mentioned under (C), In order, in these cases, too, to obtain polymers with a favourable chemical and molecular consistency, it is necessary to develop a strictly adapted dosage scheme for all the components of the system for each polymer composition required, taking Into account the particular polymerisation velocity.

In the process according to the invention, the conversion level should amount to at least 50 ¢, based on the sulphonate-group-containing amide component used.

In most cases, a much higher conversion level is reached, so that the polymer solutions obtained after separation of the volatile monomer fractions may be directly added as dye-receptive additives to modacrylic spinning solutions. - 10 42103 With lower conversions (less than 80 Γ'), the required polymer is best worked up by precipitation, the unreacted sulphonate-group-containing acrylic or methacrylic acid amide being recovered.

The sulphonate-group-containing acrylic and methacrylic amides mentioned under (A), which are reacted with comonomers (B) and (C) to form the polymeric dye-receptive additives according to the invention, may be obtained by known methods: 1. By reacting acrylonitrile or methacrylonitrile with mono-olefinic compounds containing a terminal double bond in the presence of a sulphonating agent. 2. By reacting acrylic or methacrylic acid chloride with the appropriate aminosulphonic acids or their salts in the presence of acid-binding compounds.

Of the acrylic and methacrylic acid amides obtainable by reaction l), 2-acrylamido-2-methyl propane sulphonic acid above all has proved to be particularly suitable for the production of the copolymers according to the invention, because its copolyuerisation behaviour is favourable in the form of its ammonium salts.

Of the compounds obtainable by reaction 2), 4-methacrylamidobenzene sulphonic acid has proved to be eminently suitable for the production of the copolymers according to the Invention.

The acrylic and methacrylic acid amides mentioned under (A) are predominantly incorporated in the form of corresponding ammonium sulphonates which are formed before polymerisation from the free sulphonic acids by neutralisation with primary, secondary and tertiary amines or with quaternary ammonium bases. It is only the high solubility both of the acrylic and methacrylic acid amides containing 21,0 3 ammonium sulphonate groups and of the copolymers formed from them together with components (B) and (C) in the aprotic solvents used which enables polymerisation to be carried out in homogeneous phase, so that the dye-receptive additives according to the invention are actually produced with a high chemical and molecular consistency.

Particularly favourable properties are shown by copolymers containing ammonium structures formed from amines containing hydroxyl groups, for example those formed from 2-methylaminoethanol, diethanolamine or triethanolamine. One striking factor is the very faint natural colour of copolymers such as these which is reflected in the favourable colour of the polymer solutions formed.

This factor promotes their use as dye-receptive additives in the fibre field.

Of the halogen-containing compounds mentioned under (B), vinylidene ohlorlde and vinyl chloride above all are suitable for the production of the polymeric dye-receptive additives. Their incorporation promotes the compatibility of the sulphonate-group-containing polymers with the halogencontaining modacrylic polymers to be finished. Vinylidene chloride has proved to be particularly suitable by virtue of its favourable copolymerisation behaviour, enabling the sulphonate-group-containing component to be uniformly incorporated, above all in the presence of the other comonomer (C).

Of the monomer components mentioned under (C), reference is made above all to acrylonitrile, methyl acrylate and N-tert.-butyl acrylic acid amide. Dye-receptive additives containing these monomers are distinguished by particularly favourable properties. Correspondingly finished modacrylic fibres are not only improved in their colorxstic properties, but they also show more favourable light fastness and increased gloss values.

The average molecular weights fln of the polymeric dye-receptive additives may be adjusted within relatively wide limits of from 5000 to 300,000 in the process according to the invention by varying the catalyst concentration or the initial solvent:monomer ratio. This molecular weight range corresponds to intrinsic viscosities as measured in dimethyl formamide, of from 0.1 to 3.0 [dl/g].

No connection was found between the activity of the dye-receptive additives and their average molecular weight. Nevertheless, it is advantageous for the molecular weights of the copolymers according to the invention to be comparable with those of the modacrylic fibre polymers to be finished in order to preclude any negative influence upon important fibre properties governed by molecular weight, and to guarantee safe completion of the spinning and aftertreatment process under constant conditions. Accordingly, copolymers with average molecular weights fln of from 10,000 to 100,000, corresponding to [ 7] -values of from 0.5 to 2.0 [dl/g], are particularly suitable for use as dye-additives.

Accordingly, preferred copolymers are those which contain, in random distribution, structural units of (a) 4 to 10 mol % of 2-acrylamido-2-methyl propane sulphonic acid in the form of an ammonium salt, (B) 10 to 50 mol $ of vinylidene chloride and/or vinyl chloride, (c) 30 to 80 mol % of acrylonitrile and/or methylacrylate and/or N-tert.-butyl acrylic acid amide, and which have an intrinsic viscosity es measured in dimethyl formamide, of from 0.5 to 2.0 [dl/g].

Unless otherwise indicated, the intrinsic viscosities quoted in the description and in the following Examples were determined at 25°C in dimethyl formamide to which 0.3 % by weight of sodium nitrate had been added in order to eliminate the electrolyte effect [cf. Hans-Georg Elias: •’Makromolekule, page 265, Huthig und Wepf Verlag, Basel-Heidelberg (1971^.

The average molecular weights fin quoted are number averages which may be determined by osmometry.

EXAMPLE 1 The following solutions and mixtures are used for the solution polymerisation process described in the Example: I 13,720 g of dimethyl formamide 1,155 g of deionised water II 3,300 g of dimethyl formamide 1,238 g of 2-acrylamido-2-methyl propane sulphonic acid (AMPS) 437 g of 2-methylaminoethanol ill 4,125 g of acrylonitrile 2,888 g of vinylidene chloride IV 990 g of dimethyl formamide 19.8 g of ammonium peroxy disulphate V 990 g of dimethyl formamide 23,1 g of oxalic acid.

The DMF/water mixture (i) is initially introduced into a 40 litre autoclave of VA-steel equipped with an anchor stirrer, and nitrogen is passed through at 50°C. The AMPS-salt solution (ll) obtained by neutralisation (at 0°C) is combined with the DMF/water mixture (l), followed by introduction of the monomer mixture (ill). After the reaction temperature of 50°C has been reached, a pressure of 1.5 hars is spontaneously adjusted In the now closed autoclave. The polymerisation reaction is initiated by adding the initiator solutions IV and V.

At a stirring speed of 50 rpm, the solution reaches a solids content of 23.0 1> by weight after 12 hours, corresponding to a conversion of 71 1.

The conversion may be further increased by introducing more ammonium peroxy disulphate and oxalic acid. However, it was found that, following separation of the unreacted volatile monomer constituents (acrylonitrile and vinylidene - 15 103 chloride), polymer solutions with conversions of more than 70 jl may be directly added as a dye-receptive additive to spinning solutions of halogen-containing modacrylic polymers.

It ls more advantageous to precipitate the polymer containing sulphonate groups fi'om the solution diluted with water and/or methanol by the addition of an electrolyte.

The polymer obtained at a conversion of 71 % has the following composition: 69.5 mol jl of acrylonitrile .3 mol jl of vinylidene chloride .2 mol jl of AMPS in the form of the ammonium salt of 2-methylaminoethanol [^]DMF = θ*85 [dl/g] EXAMPLE 2 The following solutions and mixtures are used for the polymerisation process described in the Example: I 200 g of dimethyl formamide 75.0 g of 2-acrylamido-2-methyl propane sulphonic acid (AMPS) II III IV 26.5 g of 2-methylaminoethanol 275 g of acrylonitrile 150 g of vinylidene chloride 6l g of dimethyl formamide 1.2 g of ammonium peroxy disulphate 60 g of dimethyl formamide 1.4 g of oxalic acid 900 g of dimethyl formamide are initially introduced into a 2 litre plene-ground glass jar equipped with a reflux condenser cooled kith iced water, a gate paddle stirrer and a gas-inlet pipe, ard nitrogen is passed through at 50°C. The ammonium salt solution (i) and the monomer mixture (ll) are successively combined with the dimethyl formamide. After the reaction temperature of 45° has been reached, polymerisation is initiated by adding solutions 111 and IV.

In order to determine the composition of the polymer formed and its intrinsic viscosity [fl Ih dependence upon the conversion, samples are taken at hourly intervals and the polymer is isolated therefrom by precipitation.

The compositions determined are shown in the following Table: Reaction time [hours] Conversion [%] Polymer [mo acrylo- nitrile composition 1 U vinylidene chloride AMPS salt Viscosity 1.0 15.5 76.3 18.2 5.5 1.08 2.0 25.7 77.2 17.6 5.2 1.08 3.0 33.3 76.7 18.0 5.3 1.08 4.0 37.7 . 76.9 17.9 5.2 1.09 5.0 41.0 76.1 18.6 5.3 1.06 6.0 44.5 76.7 18.2 5.1 1.06 7.0 47.0 76.7 18.2 5.1 1.01 12.0 62.0 76.1 18.7 5.2 1.02 The results show that polymers with a high chemical and molecular consistency are obtained by the described process.

EXAMPLE 3 The following solutions and mixtures are used for the solution polymerisation process described in the Example: I 624 g of dimethyl formamide 52.5 g of deionised water II 150 g of dimethyl formamide 56.4 g of 2-acrylamido-2-methyl propane sulphonic acid (AMPS) - 17 42103 .0 g of 2-methylaminoethanol III 201.5 g of methylacrylate 117.5 g of vinylidene chloride IV 45 g of dimethyl formamide O.75g of ammonium peroxy dleulphate V 45 g of dimethyl formamide 0.9 g of oxalic aoid The DMF/water mixture (I) is initially introduced into a 2 litre glass reaction vessel equipped with a stirrer, a reflux condenser cooled with iced water and a gas-inlet pipe, and nitrogen is passed through at 50°C. The solution (ll) of the AMPS-ammonium salt, prepared at 0°C, is combined with the DMF/water mixture. After the monomer mixture (ill) has been added and the reaction temperature of 55°θ adjusted, the polymerisation reaction is initiated by adding the initiator solutions (IV) and (V).

After 5 hours, the solution is found to have a solids content of 27 ft hy weight, corresponding to a conversion of 87.5 ft. The polymer obtained by precipitation from the polymer solution formed (conversion 87.5 ft) has the following composition: 61.2 mol ft of methylacrylate 31.9 mol ft of vinylidene chloride 6.9 mol ft of acrylamido-2-methyl propane sulphonic acid 25 (in the form of the ammonium salt of 2methylaminoethanol) t^DMF “ 0,64 tdl/e3 EXAMPLE 4 The following solutions and mixtures are used for the 30 solution polymerisation process described in the Example: 1 936 g of dimethyl formamide g of deionised water - 18 42103 281.4 g of N-tert.-butyl acrylic acid amide II 225 g of dimethyl formamide 84.6 g of 2-acrylamido-2-methyl propane sulphonic acid (AMPS) .0 g of 2-methylaminoethanol III 67.5 g of dimethyl formamide 1.5 g of ammonium peroxy disulphate IV 67.5 g of dimethyl formamide 1.8 g of oxalic acid The N-tert.-butyl acrylic acid amide solution (I) is initially introduced into a 2 litre glass reaction vessel equipped with a stirrer, a reflux condenser cooled with iced water and a gas inlet pipe, and nitrogen is passed through at 50°C. The AMPS-ammonium salt solution (ll), obtained at 0°C by neutralisation, is combined with the N-tert.-butyl acrylic acid amide solution (i). After 157 g of vinylidene chloride have been added and the reaction temperature adjusted to 50°C, polymerisation is initiated by adding the initiator solutions (III) and (IV).

After 6 hours, the solution is found to have a solids content of 24 jt by weight, corresponding to a conversion of 75 $.

The polymer obtained hy precipitation from the solution formed after this reaction time has the following composition: 48.3 mol $ of N-tert.-butyl acrylic acid amide 43.3 nol $ of vinylidene chloride 8.4 mol $ of 2-acrylamido-2-methyl propane sulphonic acid (in the form of the ammonium salt of 2-methylaminoethanol) 1-¾ -^DMP = ®·52 [dl/g] EXAMPLE 5 The following solutions and mixtures are used for the solution polymerisation process described in the Example: 48103 g of dimethyl formamide g of deionised water g of dimethyl formamide 70.6 g of 4-methacrylamidohenzene sulphonic acid 29.4 g of triethylamine 87.5 g of acrylonitrile 31.2 g of vinylidene chloride 45 g of dimethyl formamide 0.9 g of ammonium peroxy disulphate 45 g of dimethyl formamide 1.05g of oxalic acid The DMF/water mixture (i) is initially introduced into a 2 litre glass reaction vessel equipped with a reflux condenser cooled with iced water, a stirrer and a gas inlet pipe, and nitrogen is passed through for about 3θ minutes at a temperature of 50°C. The solution (ll) of the triethyl ammonium salt of 4-methacrylamldobenzene sulphonic acid, obtained by neutralisation at 0°C, is combined with the DMF/water mixture. After the monomer mixture (ill) has been added and the reaction temperature of 50°C adjusted, polymerisation is initiated by adding the initiator solutions (IV) and (V).

After 10 hours, the solution is found to have a solids content of 20.5 by weight, corresponding to a conversion of 60 ¢.

I 500 g of 50 g of II 335 g of 70.6 g of 29.4 g of III 187.5 g of 131.2 g of IV 45 g of 0.9 g of V 45 g of A polymer of the following composition is obtained by precipitation from the polymer solution formed (conversion 60 %) 71.5 mol % of acrylonitrile 21.0 mol Jt of vinylidene chloride 7.5 mol % of 4-methacrylamidobenzene sulphonic acid (in the form of the ammonium salt of triethylamine ) = 0-51 [dl/g] EXAMPLE 6 The following solutions and mixtures are used for the solution polymerisation process described in the Example: I 670 g of vinyl chloride 210 g of acrylonitrile Ii 1000 g of dimethyl formamide 90 g of 2-acrylamido-2-methyl propane sulphonic acid (AMPS) 32.5 g of 2-raethylaminoethanol Ill 170 g of dimethyl formamide 4.5 g of ammonium peroxy disulphate IV 170 g of dimethyl formamide 5.25g of oxalic acid V 890 g of dimethyl formamide 195 g of 2-acrylamido-2~methyl propane sulphonic acid (AMPS) 70.5 g of 2-methylaminoethanol VI 570 g of 11.25g of dimethyl formamide ammonium peroxy disulphate VII 570 g of 13.35g of dimethyl formamide oxalic acid VIII 1040 g of acrylonitrile 1700 g of vinyl chloride The acrylonitrile/vinyl chloride mixture (i) is initially introduced into a 12 litre autoclave of VA-steel equipped with an anchor stirrer and four supply vessels connected through metering pumps. The solution (II) of the AMPS ammonium salt is introduced under pressure into the tightly closed reaction vessel. After the reaction temperature of 35°C (internal pressure: 4.0 bars) has been adjusted, polymerisation is initiated by adding the initiator solutions (ill) and (IV). After 30 minutes, solutions (v) to (VIIX) are simultaneously introduced over a period of 10 hours: Solution V: 120 ral/hour Solution VI: 60 al/hour Solution VII: 60 ml/hour Solution VIIX: 300 ml/hour After the 10-hour metering phase, polymerisation is stopped by the addition of 5 g of hydroquinone monomethyl ether and the polymer solution formed is worked up by pre10 cipitating the polymer following evaporation of the volatile monomer constituents.

Composition of the polymer: 72.5 mol $ of acrylonitrile 23.0 mol of vinyl chloride 4.5 mol # of 2-aerylamido-2-methyl propane sulphonic acid (in the form of the ammonium salt 2-methylaminoethanol) [5 ]DMF - x·98 Yield: 1250 g (conzersion: 60 ¢, based on the acrylonitrile and AMPS-salt).

Claims (16)

CLAIMS:

1. A process for the production of a polymeric dye-receptive additive, which comprises copolymerising the following monomers by radical initiation in an amide-containing aprotic solvent at a temperature in the range of from 20 to 80°C: (A) 4 to 10 mol % of an acrylic or methacrylic acid amide corresponding to the general formula (I): CHg = C - C - NH - Rg - SO-jM R, (I) in which Rj represents H or CH,,, Hg represents a linear or branched alkylene radical, optionally substituted by an aryl group, or an arylene radical, and M represents a primary, secondary, tertiary or quaternary ammonium group, a lithium cation or an Mg-cation equivalent; (B) 10 to 50 mol % of vinyl chloride and/or vinylidene chloride and/or vinyl bromide, and (C) 30 to 80 mol % of at least one other halogen-free ethylenically unsaturated compound copolymerisable with components (A) and (b) and corresponding to the general formula (11): R, CHg = C / 5 X R. (II) in which Rj represents H or CH., and 0 R^ represents the group -C“N, the group -C-O-Rj. where Rj is an alkyl radical with up to 4 carbon atoms, or the group 0 R II / 6 -C-N- x where R^ is as defined above, and R g represents H or CH 3 ·

2. A process as claimed in Claim 1, wherein the aprotic solvent is dimethyl formamide or dimethyl acetamide.

3. A process as claimed in Claim 1 or 2, wherein copolymerisation is carried out at a temperature in the range of from 30 to 60°C.

4. A process as claimed in any of claims 1 to 3, wherein a redox system is used as a radical initiator for the copolymerisation reaction.

5. A process as claimed in Claim 4, wherein ammonium peroXydisulphate/oxalic acid is used as the redox system.

6. A process as claimed in Claim 4, wherein tert.-butylhydroperoxide/benzene sulphinic acid is used as the redox system.

7. A process as claimed in any of Claims 1 to 6, wherein up to 10 ft by weight of water is added to the amide-containing aprotic solvent.

8. A polymeric dye-receptive additive comprising in random distribution. (A) 4 to 10 mol ft of an acrylic or methacrylic acid amide corresponding to the general formula (I): R. CHg = C - C - NH - Rg - SOjM 0 (I) in which Rj, Rg and M are as defined in Claim 1, (b) 10 to 50 mol Jt of vinyl chloride and/or vinylidene chloride and/or vinyl bromide, and (C) 30 to 80 mol ft oi at least one other halogen—free ethylenically unsaturated compound corresponding to the general formula (ll): CH„ (11) In which Rj and R^ are as defined in claim 1, and having an intrinsic viscosity [^eeasured in dimethyl formamide, of from 0.1 to 3.0 [dl/g].

9. An additive as claimed in Claim 8, which comprises (A) 4 to 10 mol $ as measured in dimethyl formamide, of from 0.5 to 2.0 [dl/g].

10. An additive as claimed in Claim 8 or 9, wherein M is an ammonium group formed from an aminoalcohol.

11. An additive as claimed in Claim 10, wherein M is 2-methylammonium ethanol.

12. An additive as claimed in Claim 8, substantially as herein described with reference to any of the specific Examples,

13. A process as claimed in Claim 1, substantially as herein described with reference to any of the specific Examples.

14. An additive when produced by a process as claimed in any of Claims 1 to 7 and 13.

15. Acrylic or modacrylic filaments, fibres or films containing an additive as claimed in any of Claims 8 to 12 and 14.

16. A textile article comprising filaments, fibres or films as claimed in Claim 15.