DE2331395A1 - Vacuole-free acrylonitrile co-polymer films and fibres - contg. reaction prod. of polyacryacrylic ester and dimethylamine, retaining gloss in hot water - Google Patents

Abstract

Vacuole-free fibres and films are prepd. from a mixt. of (a) 80-90 wt. % of a copolymer of acrylonitrile with 20-80 wt. % vinylidene chloride and/or vinyl chloride and/or vinyl bromide and opt. is not >5 wt. % of a monomer with functional acid and/or basic gps. and (b) 20-2 wt. % of a polymer contg. N,N-dimethylacrylamide, formed by reaction of polyacrylic esters with dimethylamine and contg. 90-99 mole % amide. The fibers and films retain their gloss after contact with hot water or steam at increased temp. Film and fibre properties, e.g. shrinkage and flame resistance are not adversely affected.

Description

Bayer Aktiengesellschaft 2331395

Central area of patents, trademarks and licenses

Dn / Ae 509 Leverkusen. Bayerwerk

1 JUNE 8, 1973

Shine stabilized threads and films made from acrylonitrile copolymers

The invention relates to threads and free of vacuoles Films made from a polymer mixture made from an acrylonitrile copolymer with a polymer produced by polymer-analogous reaction of polyacrylic acid-Cj-G, -alkyl esters with dime thylamine.

Films, fibers and threads made from acrylic and modacrylic polymers often lose their gloss and appear matt, if they come into contact with hot water or with steam at elevated temperatures. This is particularly true Dimensions for those made from acrylonitrile / vinylidene chloride from acrylonitrile / ^ inyl chloride and from acrylonitrile / vinyl bromide copolymers manufactured fiber materials that are important for the manufacture of flame-retardant articles. The undesired matting is caused by the smallest cavities, so-called vacuoles, which are located inside the molded body train under the mentioned external conditions. Inevitably, pormarticles such as threads are exposed to the action of hot water or steam during processing exposed, e.g. threads during drawing and crimping, the yarns obtained from them e.g. during dyeing processes and that finished fabrics when washing and ironing. The matting caused by vacuoles is uncontrollable and obvious

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strongly dependent on the external conditions, i.e. on the Intensity and the temperature at which the water comes into action, so that those made from the threads or films Pieces show an uneven appearance of the goods.

It has now been found that in the case of fibers or films made from copolymers of acrylonitrile with 20 - 80 wt .-? 6 vinylidene chloride and / or vinyl chloride and / or vinyl bromide significantly reduces or even completely eliminates the formation of vacuoles can be if one of the spinning solutions aua the acrylonitrile copolymers and organic solvents N, N-dimethyl acrylamide-containing polymers admixed, which by polymer-analogous reaction of polyacrylic acid ester ^ in particular of polyacrylic acid methyl ester, obtained with dimethylamine will. These gloss-stabilizing additives, characterized by their manufacturing process and their Content of Ν, Ν-dimethylacrylamide units with the limit concentrations - £ .90 mol- # and ^ 99 mol-96, unfold their effectiveness, when mixed with the film and fiber-forming acrylonitrile copolymers in an amount of 2-20 wt will.

The invention accordingly relates to vacuole-free fibers and films made from polymer mixtures, consisting of a mixture of:

a) 90-98 wt .- ^ of a Copolymerisate3 of acrylonitrile with 20-80 wt .- # vinylidene chloride and / or vinyl chloride and / or vinyl bromide and optionally with up to 5 wt .- ^ of a monomer with functional acidic and / or basic groups and

b) 2-20 wt .- ^ of a Ν, Ν-dimethylacrylamide units containing Polymer that is produced by polymer-analogous conversion

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of polyacrylic acid esters, preferably of polyacrylic acid methyl ester, is obtained with dimethylamine, with amide components ^ 9O and - ^ 99

The molecular weight of the amide-containing compounds added according to the invention CopolymeriBate can vary within wide limits. In general, polymers with K values (according to H. Fikentscher, Cellulosechemie JJ (1932), p. 58) between 10 100 effective. Polymers with a are particularly favorable K value from 30-80.

The amount added which brings about sufficient gloss stabilization of the film- and fiber-forming base material a) is depends only to a small extent on its composition, but is decisive on the Ν, Ν-dimethylacrylamide content of the polymeric additional component b) determines »the required proportion is lower, the higher the content of N, N-dimethylacrylamide groups is found in the polymer. By a special reaction procedure in the implementation of Polyacrylic acid esters with dirnethylamine succeed in making polymers with amide contents to represent> 90 mol-96, which in their stabilizing effect are often extremely effective even at relatively low additional rates. In most cases it is it is possible with added amounts of 2-10 wt .- # of vacuoles to produce free threads and films.

As a suitable organic solvent to use in the manufacture of spinning solutions of the mixtures according to the invention can be the customary polar solvents named for polyacrylonitrile, such as dimethylformamide, dimethylacetamide, Ethylene carbonate, "^ -butyrolactone, dimethyl sulfoxide, Hexamethyl-phosphoric acid triamide; additionally also come e.g. acetone, cyclohexanone and tetrahydrofuran as solvents.

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It is known that by adding 5-30 parts by weight of a homopolymer from a (meth) acrylamide of the general formula

CH ₂ = C-CO-H

(D

in the

R is hydrogen and CH,

R ₂ and R _{5 are} hydrogen or alkyl with C ₁ to Cg,

or by adding at least 50 copolymers of this type (Meth) acrylamides to 70-95 parts by weight of copolymers of acrylonitrile with vinylidene chloride, or vinyl chloride, the hydrophilicity and the dyeability of threads and fibers is improved from such polymer mixtures. A gloss stabilizing effect of these amide-containing polymers, i.e. the elimination of the disadvantageous formation of vacuoles in the treatment of films and threads made of modacrylic polymers with hot water or steam is not mentioned in DAS 1059614 and is by no means used with the plural of the described amide-containing polymers, but is for dimethylacrylamide homopolymers and some special dimethylacrylamide copolymers characteristic.

Graft polymers, for example made from acrylonitrile and acrylamides, also result as such or as additives to be fiber-forming Acrylonitrile polymers, not the sufficient technical effect, according to the invention by the addition of Ν, Ν-dimethylacrylamide copolymers obtained by polymer-analogous reaction is achieved. The films and threads out

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Differentiate polymer mixtures according to the present invention differs from films and threads made from known polymers in principle, since the films and threads according to the invention consist of polymer mixtures which do not contain any graft polymer.

It is also known, homopolymers or copolymers of N, N-Dimethylacrylamids gloss as stabilizing additives for the copolymers of acrylonitrile with 20 0-80 mol-56 acrylonitrile - 80 wt -. Employ <£ vinylidene chloride and / or vinyl chloride, wherein on the specific effectiveness of which is indicated within the group of polymers containing N-mono- or disubstituted (meth) acrylamides.

It has now been found that other copolymers of Ν, Ν-dimethylacrylamide, especially those by copolymerization materials obtained with (meth) acrylic acid esters, Films and threads free of vacuoles provide the film or fiber-forming base material in higher concentrations are mixed in. For example, gloss stabilization with N, N-dimethylacrylamide / methyl acrylate copolymers, which contain up to 95 moles-96 of the amide component is achieved when the addition amount is at least 12 wt .- #.

It was surprising that polymers produced by polymer-analogous reaction of polyacrylic acid esters ^ in particular of Polyacrylic acid methyl ester, obtained with dimethylamine, with a comparable amide content already in a much lower one Concentration bring about the desired gloss stabilization. In many cases 2-10 wt. 56 are sufficient.

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The copolymerization of Ν, ΙΙ-dimethylacrylamide and Differentiate between acrylic acid methyl ester obtained polymers different from corresponding polymer-analogously converted products with the same average amide content in their chemical uniformity. As fractionation experiments show, have the polymeric reaction products of polyacrylic acid esters and Dimethylamine has a lower chemical uniformity: the amide content in the higher molecular weight fractions increases the mean content clearly decreases, i.e. the degree of conversion of the higher molecular weight polyacrylic acid ester components is noticeable less. Such a polymerization composition is obtained by copolymerizing the monomers according to conventional procedures not adjustable. In general, it is also not aimed for, but in the present case it must be considered favorable to be viewed as this way of. Vacuole-free films and threads are produced with significantly lower additional quantities can be.

The often insufficient dyeability of the claimed threads and films can in a known manner in the present Base material by copolymerization of small amounts, generally about 1-3 wt .- ^, of a monomer with acidic or basic groups, e.g. styrene sulfonic acid, a disulfonimide, Vinyl pyridine or a sulfobetaine.

Adverse influence on the film and fiber properties, e.g. increased shrinkage or reduced flame resistance of the materials is obtained by admixing the Ν, Ν-dimethylacrylamide copolymers obtained by a polymer-analogous reaction not observed and must be a further advantage of the method according to the application for production Vacuole-free films and threads can be viewed.

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· Τ ·

Testing the Ν, Η-dimethylaerylamide-containing polymers Film materials can be used to determine their effectiveness against the formation of vacuoles. The one in fiber production Post-treatment stages run through are in the following Test largely simulated.

1) film formation from dimethylformamide solution (5O ⁰ C)

2) Stretching the film material in boiling water in a ratio of 1 t 4

3) Boiling the film strips stretched on the frame in boiling water (1 hour)

4) drying the sample strips at 50 ^° C. (1 hour)

5) Annealing the film strips at 140 ^° C. (20 minutes)

6) Boiling the films in boiling water (1 hour)

7) drying the film strip at 5O ⁰ C (30 minutes)

Film materials with a stable gloss must no longer show any haze after the last two treatment stages (6 and 7) and should appear clear, transparent and shiny. The film quality is judged on an arbitrary scale, in which 0 no visible opacity caused by vacuoles, 8 means very strong opacity due to numerous vacuoles.

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Note appearance of the film samples

8 strong white, without gloss

7 white, without gloss

6 pale white, without gloss

5 transparent, still clouded, still without gloss

4 transparent, still faintly clouded, with little

shine

3 almost clear, with little gloss

2 almost clear, shiny

1 clear, glossy

0 clear, with high gloss

The K-values listed in the following examples, the polymers were determined (1932), p determined at 25 ⁰ C in 0.5 #iger dimethylformamide solution according to Fikentscher, Gellulosechemie J_3_.

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example 1

Production of a NjN-dimethylacrylamide copolymer by polymer-analogous conversion (additional component A)

A 100 1 VA stirred autoclave is charged with 60 kg of an anhydrous, 15% solution of methyl polyacrylate (K value 70) in dimethylformamide. At 190 ^° C. and a stirring speed of 60 rpm, 9.4 kg t? 13.5 l of dimethylamine (2.0 molar equivalents) are continuously pumped in.

Dosing speed: 4.5 1 / hour. Dosing time t 3.0 hours

Maintaining the reaction mixture after an additional 5 hours at 19O ⁰ C. After a cooling period, the reaction mixture present in the amine components can be removed by distillation and / or by treatment with an acid ion exchanger. The polymeric reaction product with a K value of 68.5 contains 92.5 mol- £ Ν, Ν-dimethylacrylamide.

Example 2

Production of a Ν, Ν-dimethylacrylamide copolymer by polymer-analogous conversion (additional component B)

A 100 1 VA stirred autoclave is charged with 60 kg of an anhydrous, 15% solution of methyl polyacrylate (K value 70) in dimethylformamide. At 19O ⁰ C and a stirring speed of 60 rev / min, in the sealed reaction vessel 6.6 kg 9.7 1 ^ dimethylamine (1.4 molar equivalents) are continuously pumped.

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Dosing speed ι 4.85 l / hour. Dosing time: 2.0 hours

The reaction mixture is then kept at 190 ^° C. for a further 3.5 hours. After this time, the pressure is slowly released at 160 ^° C. in order to drive off most of the amine components present in the reaction mixture. At 190 ⁰ O another 4.7 μg of dimethylamine (1 molar equivalent) are injected, and the polymer-analogous reaction is continued for 3.5 hours. After cooling, the reaction mixture can be made amine-free by distillation and / or by treatment with an acidic ion exchanger. The polymeric reaction product with a K value of 61.5 contains 98.0 mol # N, N-dimethylacrylamide.

Example 3

From the following polymer mixtures, consisting of a copolymer G with 60 wt. - $> acrylonitrile, 38 wt. £ vinylidene chloride and 2 wt Example 1, or additional components A or B prepared according to Example 2, 10 # solutions were prepared in dimethylformamide.

Component A Component B Component C I. - - 100.0 II 2.5 - 97.5 III 5.0 - 95.0 IV 7.5 - 92.5 V 10.0 - 90.0 71 - 2.5 97.5 VII - 5.0 95.0 VIII - 7.5 92.5 IX - 10.0 90.0

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According to the test method explained on items 7 and 8, the gloss-stabilizing effect of components A and B established. The appearance of the film strips according to the different Treatment levels can be assessed as follows »

Movies 1 Hours cooked at 140 ^° C Movies after the tem- annealed 1 hour . cooked wet dried 5 wet dried I. 7th VJI II 7th 7th 4th 7th 7th III 7th 6th 1 6th 6th IV 7th 3 0 VJl 5 V 4th 2 4th CVI 2 VI 2 7th 2 1 0 VII 7th 4th 1 4th 4th VIII 5 3 0 2 2 IX 4th 1 1 1 2 0 0

Glossy films free of vacuoles can contain 7.5% by weight polymeric additional component A, or with 5 wt .- ^ of the component B can be obtained.

Example 4

From a copolymer obtained by emulsion polymerization from 55 wt .- ^ vinyl chloride and 45 wt .- # acrylonitrile with a K value of 68 are obtained with and without addition of 5 »7.5, 10 and 15 parts by weight of the polymer obtained according to Example 1 A 10% solutions are made in dimethylformamide.

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The quality of the films prepared from these solutions is determined after going through the steps explained on pages 7 and 8 Test method assessed as follows!

Addition A Movies 1 7th wet Stde. cooked at 140 ^° C 4th Films after the annealing IO υ UI.U
moist g ( ϊdies dried and tempered 3 5 L vrew.-j / 6th 6th 3 5 5 without 6th 6th 1 4th 3 5.0 5 5 0 3 2 7.5 4th 4th 2 1 0.0 3 2 1 15.0

Example 5

From a copolymer of 64.0 wt .- # acrylonitrile, 33.8 Wt .- ^ vinylidene chloride and 2.2 wt .- # Na-methallyl sulfonate with a K value of 72.1, and the polymer A obtained according to Example 1 with 94.0 wt .- # Ν, Ν-dimethylacrylamide and a K value of 68.5, a 37 # spinning solution was prepared in dimethylformamide, the proportion of the additional component A 10 wt .-? 6, based on the proportion of the base polymer, fraud.

This solution was prepared by the conventional dry spinning method from a 180-hole nozzle (0.25 mm hole diameter) in a 165 ⁰ C hot spinning chimney to form filaments with a spun filament of 9.7 dtex at a withdrawal speed of 200 m / min, spun. Some of the threads obtained were drawn in water at> n 98 ° C. in a ratio of 1 * 3.6, in a washing bath of

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about 80 ⁰ C lösungsaittelfrei washed extensively prepared, and then dried in a hot air dryer at 150 ⁰ C under tension (Sample 1).

The remaining part of the above Päden was stretched in boiling water in a ratio of 1 »4.5, washed, prepared and dried in a hot air dryer at 150 ⁰ C while in! Dryer allowed a shrinkage of Päden of 20 ^ (sample 2). Then the Päden obtained by the two methods were not crimped, cut and fixed in steam at 104 ⁰ C. In accordance with the two processes described, a 37 # spinning solution, which consisted exclusively of the acrylonitrile / vinylidene chloride copolymer, was spun and aftertreated for comparison purposes (samples 3 and 4). In all four parts of the experiment, shiny threads with a round cross-section are obtained.

Scattered light measurements were made on the four Paser samples for assessment the gloss stability carried out. To determine the original gloss of the threads or pasers, 30 mg Pipes cut to a length of 2-3 mm in cuvetteη introduced and covered with immersion oil (η = 1.516), which has approximately the same refractive index as the Paser, in order to exclude the influence of surface structures of the fibers Then with a steroloupe with a photocell attachment against BaSO, as a standard (sensitivity = 1000) determines the number of scattered light.

Lifting the measurement of the output fiber has such parsers are performed, the previously cooked 30 minutes, then squeezed and were dried at 40 ⁰ C in vacuo. An increase in the number of scattered light indicates a susceptibility to vacuoles when treated in boiling water, for example when coloring. Passers with stray light numbers below 10 can

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can be classified as vacuole-free.

1 1 »3, 6th stretched Shrinkage Loyalty payments after 30 min. 2 1 * 4, VJl verstr., $ 20 Starting Cook 3 1 * 3, 6th stretched Shrinkage material sample 4th 1 »4, 5 verstr., 20 # 0 glossy sample 5 0 glossy sample 6th 93 matt sample 6th 93 matt 10

The determination of the scattered light numbers shows that only the threads that contain 10 # of the additional component A also after have retained their shine after boiling water treatment.

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Claims (4)

Claims 1. Vacuole-free fibers and films made from a polymer mixture, characterized in that the polymer blends the end a) 80-98% by weight of a copolymer of acrylonitrile with 20-80 wt .- # vinylidene chloride and / or vinyl chloride and / or vinyl bromide and optionally with up to 5% by weight of a monomer with functional acidic and / or basic groups and b) 2 - 20 wt .-? i of a Ν, Ν-dimethylacrylamide-containing polymer, which is obtained by polymer-analogous reaction of polyacrylic acid esters with dimethylamine and whose amide content is ^ 90 and = 99 M0I96 exist. 2. Vacuole-free fibers and films according to claim 1, characterized characterized in that polyacrylic acid methyl ester is used as the polyacrylic acid ester. 3. vacuole-free fibers and films according to claim 1, characterized in that component b) has a K value (after Fikentscher, CELLULOSECHEMIE IJ. (1932), p. 58) from 10 - 100. 4. Process for the production of vacuole-free fibers and films from solutions of acrylonitrile copolymers, thereby characterized in that 80-98 wt. 56 of a copolymer of acrylonitrile with 20-80 parts by weight of vinylidene chloride and / or vinyl chloride and / or vinyl bromide and 2-20 wt .-? t of a polymer with ^ 90 and = 99 Μο1-? ί Le A 15 095 - 15 - 409884/1203 NjN-dimethylacrylamide units, which are formed by polymer analogues Reaction of polyacrylic acid esters with dimethylamine is obtained in a polar organic solvent dissolves and deforms the solution into threads or films. Le A 15 095 - 16 - 409884/1203