DE1669425B2 - Acrylic bifilar filaments and process for their production - Google Patents

Description

3 4

Compatible A; aylnitrilpolymerisaten evaporated as a solvent. These multilayer films Starting materials, where one component can be produced without difficulty. For the Polymer is used that at least 90% tests will be films with an average acrylonitrile and a maximum of 10% of a borrowed with acrylonitrile thickness of about 50 μ is used copolymerizable, no ionizable groups on- 5 The test is carried out in such a way that the showing monomers in copolymerized form. Two-layer film after drying in strips of holds, characterized in that one is cut as the other 0.5 mm width, which is then in hot Component an acrylonitrile graft polymer with water to be stretched four times, This strip is then under tension for 30 min

pen having high molecular weight graft substrate and ^{treated io in water at 100 0} C and then acrylonitrile or acrylonitrile and fixed with this copolymeri- 30 min at 130 ° C in dry air, sable, no ionizable groups having The improved curling properties are to be

Monomers in graft polymerized form. observe and evaluate if the pretreated

As with acrylonitrile copolymerizable non-ionic film strip alternately 30 min each matable in water at 90 ° C the following monomers may be used advertising 15 and held in dry air at 90 ⁰ C. In the case of: Acrylic acid and methacrylic acid esters with a lower initial length of the strips of, for example, alcohols such as butyl acrylate and 120 mm, the dry air ^{treatment of methacrylic acid methyl ester, vinyl acetate or vinyl 90 0} C results in changes in length that come with herb propionate, styrene, vinyl chloride and Vinylidene chloride. Loops form when treated with water

Under hydrophilic, non-ionizable substrates> o of 90 ⁰ C are more or less regressed, for the grafting with acrylonitrile, such sub- For quantitative evaluation is after the

Punch understood the distance of the setting compared to the known respective treatment hydrophobic polyacrylonitrile measured and increased absorption thread ends of the free hanging thread ability for water and an increased swellability with the number and the inner diameter of the ripple water to have. »5 loops have been shown to be particularly suitable.

high molecular weight hydrophilic products such as The modification of the filmstrip achieved is in-

z. B. polyvinylpyrrolidone, polyoxazolidinone, poly- sequence of the respective polymer combination so vinylacetamide, polyvinylpropionamide or copoly- more effective, the smaller the distance between the thread ends, depending merisate of N-vinylpyrrolidone or N-vinylacetamide, the greater the number of crimped loops and the smaller with ethylene, with (meth) acrylic acid esters, with vinyl 30 is the diameter of these loops. acetate and with styrene. Another measure of the usefulness of graft

The process according to the invention can be carried out as components of modified polymers in such a way that a polymer a), the minimum filament is the reversible change in length of at least 90% of acrylonitrile and at most ' ^{0n /} ₀ of filaments from these graft polymers. The reversible of a nonionic change in length that is heavier than acrylic in water is determined on threads consisting of dimethylnitrile-soluble vinyl compound and a formamide by a wet spinning process - acrylonitrile graft polymer b), which is hydrophilic and which, according to the following methodology, is non-ionizable , in a suitable polar organ- The 1: 6 drawn threads are fixed in

niche solvent dissolves separately. Washed as a solvent for 2 hours in water at 90 ° C, can be used in z. B. Dimethylformamide, 40 drying cabinet at 130 ⁰ C ^l / a hour dried and dimethylacetamide, Dimetbylsulf oxide, Äthylencarbo- their length in a water bath of 7O ⁰ C after 16 hours. the measured. A small weight ensures that the

In the case of the production of threads, the threads will not twist. Subsequently, the thread solutions are first fed separately to a correspondingly selected perforated or slot nozzle, dried ^{in dry air at 70 ° C. for 6 hours.} The supply 45 then again 16 hours in water of 70 ⁰ C is agreement between the two solutions to a thread can introduced and the alternate treatment to according to known methods either before the outlet consistency of the measurements (usually three times) again solutions from the nozzle or repeated after the exit.

from the nozzle. The choice for one of these two can be seen from the tables, as well as the training

Possibilities depend, among other things, on which special effects of crimps and the reversible change in length are to be achieved on the fibers thus formed and on the type and composition of the threads used. The coagulation of Spinnlösun- th graft depends, and the Brauchgen can by a dry or Naßspinnverfah- bility done for reindeer as the preparation of these graft polymers. modified multilayer body is through the

The polymer properties and the improved measured values are demonstrated.

Fiber properties are determined by the following: The preparation of the graft polymers can be performed according to

Investigations of multi-component films are carried out using methods known per se by demonstrating that. The production of these multi-component hydrophilic and non-ionizable polymers or co- or multilayer films is carried out in such a way that the polymer in the form of an aqueous emulsion or first with a film-drawing device a film of poly- 60 solution in a reaction vessel and in counter-acrylonitrile or an acyl nitrile copolymer ( For example, this prepolymer was then a monomer (95% acrylonitrile, 5 % methyl acrylate) from a mixture consisting of at least 90% acrylonitrile and 10% polymer solution in dimethylformamide - a maximum of 10% non-ionizable in water is pulled. After the solvent has evaporated, a vinyl compound which is more difficult to dissolve than acrylonitrile, a graft poly is then added dropwise to this polymer film within a certain time and at an increased merizate liquid using a pulling device under stirring temperature, the polishing of an approximately 10% solution of a graft poly - applied merization with the help of a water-soluble catalyst in dimethylformamide and the gate or catalyst system is started.

Table I. _x . .

Graft polymers made from acrylonitrile on copolymers made from vinylpyrrolidone and ethylene

Graft substrate
Copolymer from

Vinyl pyrroethylene
Mdon

Graft subs stepped

used

lot

30th

16.3

30th

16.3

16.3

16.3

16.3

2.5

7.5
10
20th
30th

Reversible polymer K-value change in length at 70 ⁰ C

72.9 88.1 72.9 81.1 76.4 76.5 79.3

1.28 1.36 1.55 1.93 2.02 3.41 3.72

Ripple Mehrsfhichienfilmstreifen in water at 90 ⁰ C in air at 90 ° C

Thread count and thread count and

length diameter length diameter

of turns of turns

mm mm now mm

110 120 120 120 120 120 70

5/2 0/0 0/0 0/0 0/0 0/0 33 / 0.5

100 90

110 70 45 45 50

6/2 1/10 0/0 7/4 5/5 7/4 46 / 0.5

Table IIA

Graft polymers of acrylonitrile on copolymers of vinyl pyrrolidone and ethyl acrylate

Graft substrate Graft substrate Polymer Reversible Curling of the multilayer film strips Number and in Luit c iei toilet Copolymer from used K value Lengths in water at 90 ° C diameter thread ZahJund Vinyl pyrro acrylic acid lot modification thread of the turns length diameter lidone ethyl ester at 7O ⁰ C length mm of the turns mm mm O / O / % /O mm

37.3
37.3
37.3
37.3

83.9 86.7 85.8 83.6

1.18 2.17 1.50

Comparison: not grafted but admixed polymer 62.7 37.3 13 85.7 0.94

0/0 0/0 0/0 0/0

120 0/0

100 4/4 100 6/3 80 6/3 50 14/2

105

9/1

Table II B

Graft polymers of 95 parts of acrylonitrile and 5 parts of methyl acrylate on copolymers of vinylpyrrolidone and ethyl acrylate

Graft substrate Graft substrate Polymer Reversible Curling of the multilayer film strips Number and in air I at 90 ⁰ C Copolymer from used K value Lengths in water at 90 ⁰ C " diameter thread Number and Vinyl pyrro acrylic acid lot modification thread of the turns length diameter lidon methyl ester at 70 ° C length mm of the turns 0/0 mm mm %% % % mm 0/0 90 6/3 62.7 37.3 8th 93 1.35 120 90 5/3 62.7 37.3 13th 97 1.35 120

Table III

Graft polymers of acrylonitrile on copolymers of vinyl pyrrolidone and methyl methacrylate

Graft substrate Methacrylic Graft substrate Polymer Reversible Curling of the multilayer film strips Number and in air at 9O ⁰ C Copolymer from acid methyl used K value Lengths in water at 90 ^° C diameter thread Number and Vinyl pyrro ester lot modification thread of the turns length diameter lidon V at 70 ⁰ C length mm of the turns 54.5 0/0 mm mm % 48 % /O mm 0/0 50 11/2 45.5 54.5 8th 84.3 1.81 120 0/0 70 7/5 52 7.5 86.7 2.09 120 50 7/4 45.5 10 82.9 2.27 120

^ 7 8

Table IV

Acrylonitrile graft polymers on vinyl acetamide homopolymers

Graft substrate Graft substrate Polymer Reversible Curling of the multilayer film strips Number and in air I WiH) ⁰ C used K value Lengths in water at 90 ^° C diameter thread Number and lot modification thread of the turns length diameter at 70 ° C length mm the twist "" 0/0 mm mm % % mm 0/0 45 5/5 Polyvinyl acetamide 6.5 84.5 1.90 120 0/0 60 5/5 Polyvinyl acetamide 8th 85.2 1.94 120 20th 18/2 Polyvinyl acetamide 12th 83.0 2.09 115

Table V Acrylonitrile graft polymers on copolymers of vinyl acetamide and vinyl acetate Graft substrate Graft substrate polymer Reversible crimping of the multilayer film strips Copolymer of used K-value length in water at 90 ⁰ C in air at 9O ⁰ C Vinylacet- Vinylacetat Amount change of thread count and thread count and

amid length diameter length diameter

the turns of the turn "

%%%% mm mm mm mm

72.1 1.17 120 0/0

83.9 2.04 120 0/0

88.5 1.53 120 0/0

The softening points of all multi-component films and threads tested here are above 240 ° C.

60 40 8th 65 35 8th 65 35 10

70 3/7 55 5/5 30th 15/2

Claims (2)

Deformation of various Acrylic polymer patent claims: th using defined polymers and special spinnerets to fibers and films with 1. Bifilar thread made of acrylonitrile polymers, the desired crimp properties described. Nachsea Components of two differently divided for the procedure of the British patent specification built, compatible Acryhütrilpoly- 8 69 301 is the use of two polymers, Merisaten exist, the one component of which has a different content of ionizable Bifilar thread is a polymer that has at least groups and the desired effects only 90% acrylonitrile and at most 10% one with such concentration ratios of ionizing acrylonitrile copolymerizable, no ionizable io ble groups are achieved in which either the Monomers containing groups in copoly- dyeing properties of the fiber impaired contains merized form, thereby identifying or where the thermoplastic properties draws that the other component will be adversely affected. The coloring properties-Acryhiitrilpfropfpolymerisat is that a hydro- tender fiber is caused by too high a content of philes, no ionizable groups having 15 polymerizates of ionizable comonomers, which in The high molecular weight graft substrate and acrylonitrile of the fiber represent color-affine centers, insofar as nega- or acrylonitrile and copolymerizable with this, tively influenced, as level discolouration only through neglect Ionizable groups containing mono-turn large amounts of so-called retarders Contains in graft polymerized form. can be targeted. Furthermore, the thermo- 2. Process for the production of bifilar thread from plastic properties through the incorporation of too large acrylonitrile polymers through the common use of quantities of ionizable compounds in the polymer spinning of different polymer solutions under sat insofar likewise negatively influenced, as in the case of the use of mutually compatible acrylic treatments of the molded articles Nitrile polymers as starting materials, with a polymer being used as the elevated temperature during yarn or die production as the manufacture of the fabric accelerates irreversible damage that can occur at least 90% acrylonitrile. Particularly disadvantageous for at least 10% of a copolymerizable with acrylonitrile, use of polymers with an increased non-ionizable group-containing mono-content of acidic groups, however, is the highly corromic in copolymerized form, thus the property of the spinning solutions,
30 From Belgian patent specification 6 54 086, an acrylonitrile graft polymer is used, which is known to produce multicomponent threads or a high molecular weight graft substrate with very special properties that have hydrophilic, no ionizable groups and by using acrylonitrile or acrylonitrile as starting materials for these fibers and acrylonitrile copolymers with these copolymers or threads acrylonitrile copolymers with undermerizable, non-ionizable groups with different content of copolymerizable esters of the sending monomers in graft-polymerized form acrylic or methacrylic acid. The desired effect is only achieved at relatively high dosages copolymerizable esters achieved. However, such copolymers have an unfavorable thermoplastic _______ 40 behavior. It is also known from Belgian patent specification 6 53 784, non-reversible crimping multicomponent fibers from acrylonitrile polymers. Compared to such fibers, however, fibers show The subject of the invention is a process for the reversible crimping of a characteristic part before the production of threads from acrylonitrile polymers: the restoration of the original shape by spinning two solutions of an article together, e.g. B. a sweater after wearing acrylonitrile polymers of different combinations through washing and drying.
Settlement. The invention therefore relates to a bifilar thread It is known that threads made of acrylonitrile polymers 50 made of acrylonitrile polymers, the components of which are made from by various measures during a spinning two different built up process with each other to modify. On the one hand, it is possible to consist of acceptable acrylonitrile polymers, with Uniform polymer solutions or copolymers - one component of the bifilar thread is a polymer solutions through certain devices, such as special ones, which contain at least 90% acrylonitrile and a maximum of 10% Hole or slot nozzles to be deformed in such a way that the 55 of a copolymerizable with acrylonitrile, not ionic Form articles in cohaben very special dimensions of monomers which can be grouped, which z. B. on the handle or surface polymerized form, characterized in that properties have a determining effect. Another component is an acrylonitrile graft polygine Modification of films, fibers or foils is merisat that is hydrophilic, not ionizable however, it is possible if different polymers have a high molecular weight graft sub-unit containing 60 groups Forming process combined strat and acrylonitrile or acrylonitrile and with this will. So is z. B. in U.S. Patent 24 39 814 copolymerizable, no ionizable groups described, Viscose of various degrees of ripeness due to pointing monomers in graft-polymerized form to deform special nozzles so that so-called contains. Bifilar thread are obtained, the properties of which 65 the subject matter of the invention is also a method due to the different shrink or (Juellverhal- for the production of bifilar thread from acrylonitrile poly- ten of the components can be determined. merisates through genuine spinning different In British patent 8 69 301 the ner polymer solutions using medium