DE1595031A1 - Fiber-forming copolymers based on acrylonitrile and processes for their manufacture - Google Patents

Description

ΓΛΙίΠΑΠ WALIC

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMIURG TELEPHONE = 55547 «8000 MUNICH 15, 26 August 1969 TELEGRAMS, KARPATENT NUSSIAUMSTRASSE

W. 12 415/65 13 / Loe P 15 95 051.9

Monsanto Company St. Louis, Missouri, (V.St.A.)

Fiber-forming copolymers based on acrylonitrile and process for their production

The invention relates to fiber-forming copolymers and to a process for the production of new types flame-retardant, dyeable, fiber-forming copolymers based on acrylonitrile and on the fibers or threads made therefrom.

In particular, the invention relates to specific fiber-forming tetrapolymers of acrylonitrile.

Acrylonitrile polymers have found widespread technical acceptance in the fiber production field. A co

° The reason for the success of these polymers is based on their ® remarkable degree of heat recovery. However, the value or the ^ usefulness of any fiber-forming polymer on the basis of m has to its overall properties, loading a

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^{ω to} satisfy special fiber end use, can be determined. So are acrylonitrile polymers in many

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Respect due to their rather poor flame resistance limited; they are difficult to dye and their warmth and light resistance often does not meet the requirements of a particular end-use. Quite a considerable advance has been made by the interpolymerization of Acrylonitrile achieved with other more autonomous. In general can have a specific property of the fiber in this way can be improved without, however, adversely affecting or worsening the other properties. Vinylidene chloride and vinyl chloride have been used, for example, in combination with acrylonitrile in order to increase fiber resistance, as in US Pat U.S. Patent 2,763,631. These Copolymers show no improvement in colorability and, on the other hand, lead to a deterioration in Fiber properties in terms of heat and light stability and color. In a similar way, additives and mixed monomers, which contain acid groups, used in combination with acrylonitrile to improve the fiber dyeing time In this case, too, the incorporation of acidic monomers leads according to the general 'fiegel to a deterioration in the fiber color, although an improvement in dyeability is achieved.

It has now been established that the use of more than one mixed monomer having a specific function leads to an impairment of the equilibrium of the properties of the fibers. A good balance of

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of the entire properties must for technical exploitation be maintained. For example, if a fiber is required, the strong »very white, heat and light resistant, flame retardant

permanent or flame retardant and at the same time easy to color can create flame retardant or flame retardant Fibers can be reached easily, but usually under deterioration of color and especially under degradation The Vänae- and light stability of the fibers to an extremely low or sand value. If so, a flame retardant Feed material that is purely hand-held or marginal in terms of color and heat and light stability, with pre-enriched properties with regard to the color can be opened only at the expense of the additional Deterioration of the desired color and sensitivity to heat and light are created, then these are properties of the fibers that are already present as manual or limit values usually deteriorated so much that. the polymer no longer has technical capacity or acceptability even if it has good dye acceptability and has good flame retardancy. Up another Difficulty free production of copolymers with well balanced and technically acceptable properties with regard to heat and light stability, color, resistance to flame and good dyeability consists in, the Problem of mutual and economic compatibility

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the various monomers used, Bio experience has shown to a sufficient extent that paper try at this point due to an adherent and inexplicable Incompatibility of a particular monomer in the presence of one or more other mixed monomers always vdßdsr fail »This represents, on a large scale, an explanation show that only very srenige Acrylonitrilpolymerisatmassen traditional fiber production was used.

The object of the invention is therefore to create a process for the production of specific copolymers based on acrylonitrile, the daraas manufactured on Fibers have well-balanced inherent properties, and especially good color, good dyeability, heat and have light stability while being flame resistant or are flame retardant and also the property easy absorption of basic dyes. own.

According to the invention, these purposes are achieved by copolymerization achieved by various vinyl monomers in given concentrations.

The method according to the invention is characterized in that that about 85 wt .- # acrylonitrile, about 10 wt .- # Vinylidene chloride, about 0.7 wt .- ^ sodium p-methallyloxyben- ' zene sulfonate and about 4% by weight of a vinyl monomer

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made of styrene or kethyl acrylate, which is subjected to copolymerization in particular, novel fiber-forming tetrapolymers are produced by the process according to the invention from about 85 wt .-% acrylonitrile, about 10 wt .-% vinylidene chloride, About 0.25 to 1.0 wt. Si of sodium p-methallyloxybenzene sulfate and about 4 wt .-? 6 of the vinyl monomer prepared

Daa quantity ratio (quality relationship) of the various Components is for the successful implementation of the invention important because the substitution of one or more structurally. different or modified monomers a change in fiber properties in one or more Relationships Changed

In addition, satisfactory overall properties require that the weight ratio of the various monomers incorporated into the polymerizaton according to the invention is fairly is precisely regulated · As stated above, the acrylonitrile concentration must about 85% by weight of the total monomer weight messenger. Vinyidbach chloride can range between about 7 and 12 weight percent vary, though. 9 to 11% preferred sodium p-methyllyloxybenzenesulfonate can be in the range from 0.25 to 1.0 # can be used, although 0.7% is preferred. Styrene or methyl acrylate comprise the host of the Polymer structure and are generally in one concentration present in the range of 3 to 7 weight percent. . <

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In the absence of the neutral ionomers. Styrene or

ci ^ ylat it was found that the dyeability of the Acrylonitrile / Vinylidenclilorid-PolymeriBats by incorporation of sodium p-methallyloxybenzenesulfonate not to any significant extent Extent is improved. On the other hand, it supports the uptake of styrene or ethyl acrylate in its absence of sodium p-methallyloxybenzenesulfonate, not the polymer Colorability therefore appears to be that the neutral ionomer , Styrene · and methyl acrylate, to a certain extent with «atrium · p-sothallylO-jQcbenzenesulfonat work together to create the signature of the polymer and the fibers obtained therefrom with regard to the uptake of basic dyes.

The polymers described above can by any customary polymerization process, such as Block polymerization, solution polymerization, or procedures are produced in which the monomers in the üeaktionsmedium can be dispersed, either by bus sponsorship or emulsion takes place. The polymerization is usually catalyzed by known catalysts and is carried out in facilities that are generally used in technology. According to the Preferred Practical The suspension polymerization process is also used applied, the polymer in finely divided

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ITorxa for the subsequent use in fiber formation Garboitsgilnson will be produced. 5 the preferred suspension polymerization process uinf aßf-ansatssvveise execution farms which the monomers with an aqueous medium containing the necessary catalyst and dispersant, suseführ will. One particularly desirable mode of operation involves the semi-batch process in which the polymer is present ionic reaction, which contains the aqueous iodium, with the desired Monomers gradually in the course of the reaction is charged. Eo can also work completely continuously ways are carried out in which the monomers gradually added and the polymer withdrawn continuously will.

The polymerization can be carried out using conventional free radical donating catalysts known in the art are to be catalyzed. These include the organic and inorganic peroxides, which form the peroxy group

contain. Bio peroxy compound can be used within a large can be used. For example, 0.1 to 3, O #, based on the weight of the polymerizable l ^ nomeren, can be used.

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He polymers according to the invention; are preferably stolled using the generally known redox catalyst system. Pie Sedoxsysteiae consist of a pair ν. η compounds, of which one oxidizing and the other a rcdu trim agent is, which are else suitable for mutual conversion in the V / that they free radicals, which are suitable fc to initiate the polymerization, produce · s ~ \ 'the Using a reduction-oxidation system it is also possible to obtain polymerization to a substantial extent at lower temperatures than otherwise required. Suitable activators for the "redox" system are sulfur dioxide, the alkali and. Ammonium bisulfites and sodium formaldehyde sulfoxylate. The preferred catalyst for the Reäoxsystem are salts of peroxydisulfuric acid such as potassium persulfate, usually the catalyst and the activator are used in a ratio which does not exceed 1 to 8 and preferably 1 to 4. The catalyst can] pü. The start of the reaction may be added or it may have been added continuously or in portions during the reaction in order to maintain a uniform catalyst concentration in the reaction mass. The latter procedure is preferred because it results in the formation of a polymer product with more uniform chemical and physical properties. When using the »redox

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initiators in the polymorization reaction according to the invention it was found that sodium p ~ mothallyloxy-benzenesulfonate is not incorporated well, if allowed, with the activator prior to initiating the polymerization reactions to react. It is therefore important to touch the Exclude activator with this monomer ^ This & i? D im generally achieved by das.Uonomerenmaterial and separately supplying the activator to the reaction mixture.

Although the uniform distribution among the reactants in the Heaktionsmacse for the suspension mode of operation can be achieved by vigorous stirring, e3 is generally desirable, the uniform distribution of the Reactants by using inert wetting agents, emulsion stabilizers or dispersants promote i ·. Suitable factors for this Zv / eck sixddie water-soluble S'aljse of fatty acids, e.g. sodium oleate and Potassium stearate, mixtures of water-soluble fatty acid salts, z. 3. the customary soaps produced by the saponification of animal and vegetable oils, the "amine soaps", e.g. B. salts of triethanolamine and dodecylmethylamine, salts of resin acids and mixtures thereof, the water-soluble salts of half-esters of sulfonic acids and long-capped, aliphatic see alcohols, sulfonated carbon dioxide, e.g. alkylaryloulfonates and any other material of a great variety of het? remedies commonly used

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from organic compounds, which are both hydrophobic and also contain hydrophilic residues. The amount of The emulsifying agent or dispersing agent depends on the particular one chosen means, the ratio of monomers to be used and the polymerization conditions. In general, however, 0.1 to 1.0% by weight based on the weight of the Monomers are used.

The dispersion polymerization is preferably carried out in. made of a glass or glass-lined vessel, equipped with a stirrer to stir the contents is. In general, the rotating or rotating agitators are the most effective means of maintaining the intimate Ensure contact between reagents, however other methods can be used successfully can, for example, be reciprocating, rotating, or shaking the reactors. The polymerisation device which generally used, is common in the art, and the adaptation is a special type of apparatus to the reaction under consideration according to the invention is within the range of the skilled person.

Polymerization process for the production of fiber-forming acrylonitrile polymers using organic Poroxydinitiaütren can, for example, the

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Include uses of polymerization regulators to prevent the formation of polymer units of excessively high molecular weight. Suitable regulators are the alkyl and arymencaptans, carbon tetrachloride, chloroform, dithioglycidol and alcohols. The cones can be used in amounts in the range from 0.002 to 2% _t based on the weight of the monomers to be polymerized. Conversions where

the liedox systems are used, usually by the 'presence of about 0.1 to 10 parts per million' of iron improved in the polymerization system.

The polymers, from which the threads according to the invention have specific viscosity values within the range of 0.10 to 0.40. The one used here Specific viscosity value <is determined by the the equation shown below:

jT _m flow time of the polymer solution; in sec . ^ - ^ ⁸ ^ flow time of the solvent in sec.

Viscosity determinations of the polymer solutions and of the solvent are carried out by letting the solutions flow under the action of gravity at 25 ° through a capillary viscosity tube. In this determination, a polymer solution containing 0.1 g of polymer dissolved in 100 ml of N ₁ N'Dimt (ehy! Formamide was used.

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Most polymers for the production of threads are those with uniform physical and chemical properties of relatively high molecular weight,

Experience shows that eiro polymer mass the as described above, has a desirable balance of properties, not suitable for textile use This means that the desired properties found in a particular polymer composition do not always have to be verifiable or be obvious when the polymer is sprayed out and processed or treated to the point v / o it is useful in textile work. In particular, properties such as strength, ■ Elongation, shrinkage, resistance to heat and light are not based on the sum of the polymer properties be predicted. In this regard, it was found that the spinning of the polymers according to the invention after the usual working methods leads in a satisfactory manner to fibers and threads, 'which the necessary * Equilibrium of total properties that the Requirements for the use of textile fibers in blankets, carpets and a wide variety of knitted or varnished fabrics, meet woven and non-woven textile products. The spinning process typically involves ejecting the polymer dope in a koafe bath. The cable or '

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Frets 1 of threads are then washed to remove any remaining lo-

and
to remove solvent / stretched for orientation of the polymer molecules The stretched threads can then be passed through a common finishing bath, dried and taken up

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Additives such as antimony trioxide and organotin compounds can be incorporated into the polymer spinning liquid, so that they are incorporated into the polymer prior to spinning. The additives give the fibers additional stability, if this is necessary or desired.

The invention is explained in more detail below with the aid of examples, in which, unless otherwise stated the parts and percentages listed are based on weight,

example 1

A large reaction vessel equipped with a stirrer, a nitrogen inlet tube, condenser and 'inlets for the monomers, catalyst, activator and sodium p-meth ^ llyloxybenzolsulfonat (SPME), was maintained in .a thermostatically controlled at 40 ⁰ C. it's brought in 'bath. 1000 ml of water and an aqueous solution of ferrous sulfate (0.5 parts per million Fe, based on the Gesamtmonomerengewicht) were then introduced into the Re _n kt ions tube 'and the solution with

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was covered by a nitrogen blanket.

The monomer feeds were made "in" two separate approaches: the first contained 290.5 g of distilled acrylonitrile (AN), 42.0 g of vinylidene chloride (VC ^ and 16.0 g of styrene (S) in a weight ratio of about 83:12: The second monomer feed stream contained 1.75 S of SPME (iiatrium-p-iaothallyloxybenzene sulfonate) dissolved in 240 g of water. The catalyst to be used was prepared by adding 8.75 S ^K 2 ^S 2 ^ 8 * ⁿ * ^ ^m ^ " ^{Water were} dissolved, while ^ the activator solution was obtained by dissolving 7 g of NaHSO? In. 212 g of water to which 28 ml of HpSO * had been added.

Me prepared above monomer, catalyst and activator solutions were gradually added to the heating vessel brqcht for a period of 2 hours, after which the polymerization continues for a further hour- ' zen was left. The polymer thus formed was filtered off from the reaction medium with water washed and dried.

The product of the polymerization reaction consisted of a white Cetrapolymer from AlVVCLp / S / SPME in one Weight ratio of 85.6 / 10.4 / 3.5 / 0.5 · The Heaktion yielded 89% polymer, based on the monomer charge. The polymer had a specific viscosity of 0.148.

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The polymer was then slurried in felt dimethylformamide (DIiJ ¹ ) and then heated to form a clear, colorless spin liquid containing 25% polymer solids. The solution was sprayed into a coagulant bath containing dimethylformamide and water in a ratio of 55 / 4-5 at 55 ° C. The coagulated filaments wurden'pecaschen subjected to stretching inheißem water by 4.75 times and then dried · The thus-prepared F _a sorn were about by a linear density of 3 to / filament, and had eino Fostigkoit of 2.46.

Example 2

According to the manner described in Example 1, an Ali / STC ^ / liA / SPl'E tetrapolymetisate was prepared using methyl acrylate (MA) instead of styrene. The components introduced into the reaction vessel were: H ₂ O / AN / VCl ₂ AiA / SPME / K ₂ S ₂ Oq / SO ₂ / NaHCO ₃ 500 86.5 8.5 4.3 0.7 0.55 2 , 75 2.80 and 0.25 parts per million Pe, based on total monomers. /

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The polymer residence time was 60 minutes at a temperature of 50 ^° C. The resulting tetrapolymer was separated off and spun according to the procedure described in Example 1. /! -

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The fibers and filaments made in accordance with the invention were tested for their flame resistance, color and absorption capacity examined for basic dye, color fastness to light, strength and elongation and it was found that they have an excellent balance of overall properties for technical application, for textile use are required in the manufacture of carpets and blankets, as well as for many other textile purposes.

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Claims (4)

Claims 1) New fiber-forming copolymers, characterized in that that they have about 85 Gev /.- $ 6 acrylonitrile, about 10% by weight vinylidene chloride, about 0.7 Gev /.-? 6 sodium pnethallyloxybenzenesulfonate and etv / a 4 Gev /.-$ o Vinylmonoir.ere, consisting of styrene or methyl acrylate. 2) copolymers according to claim 1, characterized in that that they are in the form of textile fibers or threads. 3) Process for the preparation of flame-retardant, dyeable, fiber-forming copolymers based on acrylonitrile according to claim 1 or 2, characterized in that a monomer mixture of about 85% by weight of 96% acrylonitrile, about 10% by weight of 96% vinylidene chloride is used , etv / ao, 7 Gev /.- 56 Natriura-p-methallyloxybenzenesulfonate and etv / a 4 wt to 70 ⁰ C subjected to the copolymerization. 4) Method according to claim 3, characterized in that the polymerization reaction is dap with a redox catalyst system initiates and sodium p-methallyloxybenzenesulfonate the reaction zone is added without touching the activator. Documents type 7 % l paragraph 2; No. 1 Satt 3 des fo | KUfl04B * 3V. 4,9. 909884/1613