DE2846923A1 - ACRYLIC FIBER AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

Meissner & Meissner

PATENT AGENCY OFFICE

BERLIN - MUNICH

PATENT LAWYERS

DIPL.-ING. W. MEISSNER (BLN) DIPL-ING. P. E. MEISSNER (MCHN) DIPL-ING. H.-J. PRESTING (BLN)

HERBERTSTR. 22, 1000 BERLIN 33

Your sign Your letter from our sign Berlin, the

(o7o) E.

Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa S.p.A.

18, Via Montebello, Milano, Italy

Acrylic fiber and method of making it

The invention relates to an acrylic fiber, ie a fiber which is formed from acrylonitrile (ACN) copolymers, in which acrylonitrile is generally present in amounts not less than 85 % , and a process for its production.

When such fibers come from a solution in a water-miscible organic solvents such as dimethylformamide (DT'IF) and the like. Solvents such as dimethylacetamide or Dimethyl sulfoxide, wet spun, show the fibers that Tendency to become opaque, i.e. they lose their shine; this deficiency lowers the dyeing yields. Such an opacity is independent of the Ueg on which the spinning varnish is produced; it does not only occur when the spin paint is released by loosening the Copolymer is produced in the spinning solvent, but also, and in particular, the monomers directly in the

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Spinning solvents are polymerized, as is generally the case in the art.

The comonomers used are usually acrylonitrile and a sulfonated comonomer with the function of making the fiber To give the desired colorability, it is usually the sodium salt the allyl or methallyl or vinyl sulfonic acid, as well as also optionally another comonomer with ethylenically unsaturated Groups, preferably a vinyl ester such as methyl acrylate, methacrylate and vinyl acetate, are used.

By spinning the viscous spin paint in an aqueous bath, especially if the solvent used is DMF, obtain a fiber which lacks the desirable gloss, probably because of the presence in the fiber as such small cavities (micro-cavities), the disturbing effects of which are difficult to eliminate by subsequent treatments are.

It is known from the art that the gloss of the fiber can be influenced by various factors Measures can be improved, e.g. by

1) increasing the percentage of solids in the spin finish;

2) lowering the percentage vinyl ester content in the polymerizate;

3) increasing the percentage of sulfonate in the copolymer;

4) Adding a certain amount of water to the spinning solution.

However, such measures have negative consequences for both

Progress of generation as well as physical

Textile coloring properties of the fiber, i.e. in the first case

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are spinning problems due to the high viscosity of the Solutions evoked; in the second case the result is a low B. Plasticity of the fiber, in the third case, coloring problems arise because of the excessive difficulty of absorbing the color one, in the fourth case there is a low stability (tendency to gel) because of the coagulation effect of water.

Surprisingly, it has now been found according to the invention that the problem of the opacity of the fiber can be satisfactorily solved and fibers having excellent gloss and high Dye yields can be obtained without having to take any of the measures indicated above, if instead the normal sulfonates such as allyl or piethallyl sodium sulfonate an unsaturated monomer is used which has a sulfo group

-3
contains and in the presence of 2.1 ο moles per liter of azobisiso

-1

butyronitrile at a concentration of 2.1o moles per liter in DfIF, which contains "6 moles per liter of water, homopolymerized at a temperature of 67 C and up to a conversion in homopolymer of more than 3o-40 % after 11 hours. Such monomers are hereinafter referred to as "significantly homopolymerizable sulfonomers"; this term is to be understood that the above precise definition applies to the behavior of the monomer during homopolymerization. These sulfonated monomers should also be sufficiently soluble in the polymerization mixture and in the solvent so that a continuous Copolymerization can be carried out in an organic solvent in a homogeneous phase.

Preferably the significantly homopolymerizable monomer is a derivative, generally a salt (preferably alkali or Ammonium salt) of an acid of the general formula

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CH ₉ = C - CONH - C - C - SO-H R. CH-R- ^R 6

^R 4

uorin R _{1 is} a hydrogen atom or a short-chain alkyl radical and R ", R", R ,, R, - and R ,, which can be the same or different from one another, is a hydrogen atom or an alkyl, cycloalkyl or aryl radical.

A typical example of these derivatives is the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid of the formula

CH ₂ -CH- CONH - C (CH ₃ J ₂ - CH ₂ - SO ₃ Na

which has a homopolymerization capacity under the specified conditions of more than 5o % compared to 4 "fo, which result under the same conditions for sodium allyl sulfonate.

Other preferred monomers belonging to the class of acrylamidoalkanesulfonic acid derivatives are explained below.

If these sulfoderivatives are introduced in proportions, which correspond to a number of acid milli-equivalents in the fiber which are adequate for a regular progress of the dyeing are, a sufficiently glossy fiber is using the classic ternary copolymerization process obtained in organic solvent in a homogeneous phase, while with the SuIfomonomeren previously used and above were mentioned, as is well known, the introduction of a considerably larger amount of acid milli-equivalents is necessary, whereby one

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negative consequences with regard to the dyeing behavior of the fiber has to be accepted if a sufficiently shiny fiber is to be obtained.

Further, it is possible to obtain a fiber which is glossy and excellent in dyeing yields while keeping the figure the acid milli equivalent is significantly reduced, and produce shiny fibers that are even below normal Have saturation points if, instead of the single-phase ternary copolymerization process, one of the following uses both procedures:

a) Mixing two solutions that result from separate binary interpolymerizations, on the one hand from acrylonitrile with sulfonated monomer and, on the other hand, acrylonitrile with vinyl ester;

b) Production of a copolymer from a binary acrylonitrile / sulfocomonomer, Mix the resulting solution with a solution of acrylonitrile monomer and vinyl ester monomer in suitable Mixing and subsequent interpolymerization of the whole.

By using the second of the two preferred methods mentioned, it is also possible to increase the degree of utilization of the sulfomonomer even to more than 90%. "Degree of utilization ¹¹ here means the percentage of monomer that becomes part of the copolymer molecule. As a result, the alkalis in the process contain

Coagulating baths and uash baths - much smaller amounts of the Sulfocomonomers, solvent recovery is simplified and there is no waste of sulfomonomic and spinning solvent, which is equally advantageous from an ecological point of view.

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-Ίο-

In the present description, the term "copolymer" - Unless otherwise stated- used to designate a polymeric product, in the formation of which more than one (1) monomer participates.

The proportions of acrylonitrile and vinyl ester do not differ from those that are used if the conventional ones are used sulfonated monomers used. However, only 30-33 sulfonic acid milliequivalents in 1 kg of fiber are sufficient the invention works to provide a shiny fiber while using, for example, sodium allyl sulfonate at least 100 meq / kg are required. As for one

regular staining between 35 and 55 meq / kg are required, ■ pjrt-scßrifi-

the _A is evident by using this class of sulfonated monomers according to the invention.

These sulfonated monomers also have the ideal properties for use in the two aforementioned preferred processes, which are also claimed, especially if a binary copolymer of acrylonitrile / sulfonated monomer with a content of the latter monomer above 8-1o % is obtained should and the solvent is DMF; then it is necessary to use a continuous interpolymerization process proceeding in a homogeneous phase.

Uenn, on the other hand, sodium allyl sulfonate, for example, among the Above-mentioned conditions is used, there are significant disadvantages, uie

a) insufficient gloss of the fiber;

b) less use of sulfonates;

the.

c) Operational complications, the _A industrial engineering practice

make the process difficult.

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ORIGiMAL INSPECTED

The aim of the invention are therefore acrylic fibers, which by copolymers of acrylonitrile, methyl acrylate and a significantly homopolymerizable sulfocomonomer are formed and 85 to 95% by weight of ACN (acrylonitrile), 4.5 to 12% by weight of methyl acrylate and 0.5 to 3 percent by weight of the sulfonated comonomer. All percentages given below are percentages by weight.

The two binary copolymers, which were mentioned in connection with the definition of the two preferred methods, contain in the first 65 to 95 % acrylonitrile and 5 to 35 % 2-acrylamido-2-methylpropane sodium sulfonate and in the second 85 to 95, 5 % acrylonitrile and 4.5 to 15 % methyl acrylate, the proportion in which the two solutions of the polymers or monomers are mixed being 2 to 15 parts by weight of the first and between 85 and 98 parts by weight of the second. All parts given below are parts by weight.

Another object of the invention are the material compositions, which are formed by the spinnable viscous solutions which the ternary copolymers or

the mixtures of binary copolymers contain (as already mentioned), from which solutions the fiber is obtained; The aim is also the process for their production, in particular in the two preferred configurations described above, namely as separate copolymerizations of ACN and des sulfonated monomer in the spinning solvent and the mixing of the two polymeric solutions, or correspondingly the interpolymerization of acrylonitrile with the sulfonated monomer, the mixing of those resulting from the first interpolymerization Solution that includes both the binary copolymer and

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which contains unreacted monomers with a second solution of acrylonitrile and ethyl acrylate monomers and carrying out a second interpolymerization phase with the resulting mixed Solution. ;

The proportions in terms of weight percent are as follows used in different cases.

For the interpolymerization of the ACN with the sulfomonomer, the total percentage of the monomers is between 25 and 40 % of the total mass of the first solution and the sulfocomonomer is 5 to 35 % of the total mass of the two monomers.

For the interpolymerization of ACN with the vinyl monomer, the total percentage of the monomers is 25 to 40 % and the vinyl monomers 84 to 95 % of the total of the i-ionomers.

The second solution of the monomers used in the second preferred process has a total weight concentration of acrylonitrile and methyl acrylate which is still between 25 and 40 % of the total mass, the acrylonitrile being present between 84 and 95 % of the total of the two monomers.

The mixed solution comprises between 2 and 15 parts of the solution resulting from the first interpolymerization and between 85 and 98 parts of the second monomer solution. The second interpolymerization phase can be initiated as soon as the first phase has ended and after the complete mixing of the solution obtained in the first phase with the second solution in suitable proportions.

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The first of the two methods is used to mix the two solutions of the copolymers in the appropriate proportions towards the end of the copolymerization of the two binary copolymers forming mixtures, i.e. from acrylonitrile / sulfonated Monomer and acrylonitrile / methyl acrylate.

The results obtained according to the invention, in particular the progress from the point of view of the gloss properties of the Fiber, in the light of this, among other things, can be achieved by using the previous sulfonated comonomers, such as sodium allyl sulfonate, are extremely surprising.

Research carried out suggest that the significant homopolymerizable monomers form homopolymeric segments in the copolymer chain, and other sulfomonomers do not to do. Such segments are likely to facilitate the elimination of the spinning solvent from the coagulated bodies and consequently give the filaments a more compact and hollow shape. Additive space-free structure. Although the applicant believes that such phenomena occur and produce the surprising results of the invention or contributing to these is not intended here to be influenced by any interpretation of the mechanism by which the Invention could work, since it is sufficient that its results can be backed up experimentally and have been proved by experience what from the following Examples will emerge.

These examples show the different binary and ternary Copolymers of the invention from polymerizations in known reactor types equipped for this purpose in homogeneous Phase obtained in an organic solvent.

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The fibers have been obtained therefrom under the conditions described below using mixtures from solvent (DMF) and water as coagulating baths and generation a thread count of 3.3 dtex per filament.

Spinning conditions

a) spinneret

A spinneret with 175 openings with a diameter of 65 Microns were used to get the desired 3.3 dtex fineness per filament in the finished fiber.

b) spinneret feed

A knurled micropump was used, which was 0.6 cm per revolution dispensed and the number of revolutions was adjusted so that the amount of polymeric solution was delivered into the spinning head, necessary to produce the desired thread count was.

c) coagulation

The coagulation is carried out in a vat with a length of about 1 m, which was kept at 12-13 C and at a constant content of 60% water and 40% DMF.

d) collecting

The yarn is taken from the coagulating tub by means of a roller / pin device withdrawn at a speed of 10 m / min.

e) Uaschen

The yarn runs from the coagulating tub through a series of washing containers, which are filled with demineralized water and kept at 5o C, in countercurrent until the remaining DMF is less than 0.5 %, calculated on the dry yarn basis.

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f) V / extend

The yarn is taken from the washing containers into a stretching tub the same dimensions as the coagulating tub, including the stretching tub contains demineralized water kept at 95-1oo C, uo the yarn of an extension of up to one Draw ratio of 5.6; from here it will travel at a speed of 56 m / flin. collected. After stretching the yarn passes through a finishing tub, uo emollient Agents and antistatic agents suitable for this purpose are applied.

g) drying

After finishing, the yarn is placed on a belt dryer, with which the yarn can freely contract by around 20% while drying in air at 13o C.

The fiber thus obtained is ready and can be used for the present Cases are subject to fixed controls, i.e.

1) The cross section of the filament after coagulation is microphotographed.

2) The dye yield on the finished dry fiber is determined determines the amount of dye that is required in the Fiber according to the various examples to obtain the same shade of color as that of a preferred fiber according to This invention obtained and used as a basis for comparison if they are stained with a given Firyi'ge dye is. The fiber of the example is used as a preferred comparison fiber 2 is selected, and the color shade which is obtained in all cases corresponds to that which this fiber assumes If it is dyed with 1.4 g of dye per 100 g of dry fiber "

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The color chosen for this control is a dark brown shade, that by using a mixture of the following three dyes is obtained in the following proportions:

- Yellou Maxilon 3 RL = 5o %

- Red Plaxilon GRL = 24 %

- Blue Maxiion GRL = 26 % .

The indicated shade of color in the fiber of Example 2 has been obtained by dyeing until the dye is consumed

3
is, of 5 g of fiber in 2oo cm of a solution containing o, o7o g of this dye mixture, uas corresponds to 1.4 g of dye per 100 g of fiber. Only the number of grams of dye per 100 g fiber is given under point 2). It can be seen that the higher this number, the more opaque the fiber will be,

3) The dynamometric properties of the finished fiber will be determined in the usual way.

Illustrative and non-limiting examples are described below.

example 1

This example specifies the conditions for the ternary single-phase interpolymerization process and the control values for a fiber obtained from a ternary interpolymer which, as the sulfonated compound, is 2-acrylamido-2-methylpropane sodium sulfonate with the percentage that is required to obtain a glossy To obtain fiber free of microspaces or voids with excellent dyeing yields; This percentage is 1.5 % and corresponds to a number of 65 sulfonic acid flilli equivalents per kg of fiber, it is only

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slightly higher than the minimum of 55 required for a regular coloration. The bath composition of the fiber is 90, 5 % acrylonitrile, 8 % methyl acrylate and 1.5 % 2-acrylamido-2-methylprαpan-sodium sulfonate.

This ternary polymer is obtained by copolymerization at 67 ° C. and for 11 hours of 3.72 parts by weight of ACN, 2.92 parts of ffiefehylacrylate and 0.34 parts of the sulfonated monomer in 2 parts of water and 64 parts of DFIF in the presence of 0.024 parts of azobisisobutyronitrile and o, o1 parts of malic acid stabilizer. Towards the end of the polymerization, the solution contains 19 % of a copolymer composed of 90.5 % ACN, 8 % API, 1.5 % 2-acrylamido-2-methylpropane sodium sulfonate, the degree of utilization of the latter being 80 % of that in the charge that has reached polymerization is.

The spinning varnish containing 21% polymer, which is obtained after distillation and recovery of the unreacted volatile monomers, is spun under the conditions already given; a fiber is obtained which has the following control data:

a) j see photo no. 1 (Fig. 1)

b): 1.4 g

c) Thread count in dtex = 3.2
Strength in g / dtex = 3.7
Extensibility = 32
Loop strength in g / dtex = 1.5

These control data confirm a very shiny fiber with excellent Dye yields obtained from a polymer containing 65 milli-equivalents of acid, a value that is only slightly higher than the maximum normally used in acrylic fibers.

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The example shows that it is possible to obtain a shiny fiber even by using the normal single-phase ternary I'lischpolymerisationsverfahren applied: This would be with allylsulfonat not possible because, as you can see from the comparison example 5, at 65 acid millie equivalents the fiber becomes more opaque because of the presence of microspaces along the thread edge is; as shown by Example 6, in order to obtain such a number of plilli equivalents, it is a shiny fiber To produce it, it is necessary to add 3% water to the spinning solution.

Example 2

This example concerns the conditions for producing a fiber by the first preferred polymerisation process and the control data for the fiber obtained.

In this example the fiber does not get out one after the other classical single-phase and ternary fluid polymerization processes as in Example 1, but by fishing in suitable proportions of the final polymerization mixtures from the separate preparation of two binary copolymers: Acrylonitrile / sulfoderivat and acrylonitrile / flethylacrylate.

The fiber finally obtained in this case contains 90.9 % ACN, 1.8% methyl acrylate, 1.1% 2-acrylamido-2-methylpropanesodium sulphonate, which corresponds to 48 milli-equivalents of acid per kg of polymer; this number represents the average content of acrylic fibers and guarantees excellent results from the point of view of dyeability.

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This example explains the preferred embodiment of the Invention, as far as the properties of the fiber are taken into account to be pulled.

The two binary copolymers that build up the fiber have been obtained under the following conditions.

The binary copolymer of acrylonitrile / sulfoderivat is prepared by copolymerizing 27.2 parts of acrylonitrile and 4.8 parts of 2-acrylamido-2-methyl propane sodium sulfonate in 2 parts of water and 66 parts of DMF in the presence of at 67 ° C. for 11 hours 0.027 parts of azobisisobutyronitrile and 0.015 parts of malic acid stabilizer. Towards the end of this polymerization, the mixture contains 21 % of a copolymer composed of 85 % ACN and 15 % sulphate derivative, which corresponds to 655 sulfonic acid milliequivalents per kg of polymer.

The second binary copolymer of acrylonitrile / methyl acrylate is prepared by copolymerizing at 67 ° C for 11 hours 3o.8 parts of ACN and 3.2 parts of methyl acrylate in 2 parts of water and 64 parts of DMF in the presence of o, o24 parts of azobisisobutyronitrile and o, o1o parts of malic acid stabilizer. Towards the end of this polymerization, the mixture contains 17.2 % of a copolymer composed of 91.3 % ACN and 8.7 % methyl acrylate.

At the end of the two polymerizations, 1 part of the final polymerization solution of the binary copolymer of acrylonitrile / sulfonated! Derivative mixed with 15.7 parts of the final polymerization solution of the second ACN / APl binary copolymer. After mixing, the unreacted volatile monomers are eliminated and recovered by distillation; a solution is obtained which contains 21 % of a polymer which consists of

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-2ο-

9 o, 9 % ACN, B % AM, 1.1 % sulfonated) derivative and 48 acid meq per kg fiber and a sulfonate usage rate of 65 / g corresponds.

Spinning this solution under the same conditions as in the previous example provides a fiber that has the following Control data has:

a) see photo no. 2 (Fig. 2)

b) = 1.4 g

c) Fineness of thread in dtex = 3.3
Strength in g / dtex = 3.6
Extensibility, % = 29
Loop strength in g / dtex = 1.55

From the data of this example it is clear that the use of 2-acrylamido-2-methylpropane sodium sulfonate and using the first preferred flash polymerization method provides a fiber which is still perfectly glossy and shows excellent dyeing yields, where a number sulfonic acid milli-equivalents per kg fiber is achieved, which is lower than that of Example 1 and between 4o and 5o, which are optimal values for dyeing with basic Corresponds to dyes.

Example 3

In this example, a fiber is produced by the polymerization process of Example 1, but the percentage by weight of the sulfonated derivative in the copolymer is reduced to 0.75% , which corresponds to only 33 acid meq per kg of fiber, i.e. even lower than in normal acrylic fibers . What was said about Example 2 is confirmed, because the fiber is still shiny, free of microspaces and still has good dyeing yields.

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This example is indicative of the excellent results, those with significantly homopolymerizable sulfomonomers in the direction of on glossy acrylic fibers can be obtained by wet spinning in a bath consisting of organic solvent and water consists.

1 part of the Endpolymerisationslösung of v in Example 2 / erwendeten first binary ACN / sulfonate Flischpolymerisats is mixed with 23.5 parts of a Endpolymerisationslösung containing 17% of a copolymer © WFC & ätt _t the _f G from 91% acrylonitrile and 8.4 parts of methyl acrylate composed iH

After mixing, the same procedure as in Example 2 is followed; The finished fiber is composed of 91.25 % ACN, 8 % acrylate and 0.75 % 2-acrylamido-2-methylpropane sodium sulfonate and has the following control data:

a) see photo no. 3 (Fig. 3)

b) = 1.4 g

c) Fineness of thread in dtex = 3.1
Strength in g / dtex = 3.6
Extensibility, % - 31

Loin strength in g / dtex = 1.6

These control data show a good degree of gloss of the fiber despite the low acid milliequiv / alent content, despite the absence won water in the spinning varnish and despite the use won baths consisting of mixtures of water and dimethylformamide, from which very difficult glossy fibers are obtained, if Nikrorraumes are obtained without adding water to the spinning varnish conventional monomers are used.

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Example 4

In this example the data is for the creation of a fiber according to the previously preferred interpolymerization process , i.e. a two-phase polymerization process.

The fiber obtained has the same final composition as that of Example 2, namely 9o, 9 % ACN, 5% methyl acrylate and 1.1 % 2-acrylamido-2-methylpropane sodium sulfonate, which corresponds to 48 acid meq per kg, and has the same gloss and same dyeing yields as the fiber of example 2; furthermore, the utilization rate of the sulfonated monomer is very high, ie over 90 %. In order to obtain this fiber, a binary copolymer of acrylonitrile / sulfonated derivative, similar to that of Example 2, is produced in a first polymerization phase. Towards the end of the first polymerization, 1 part of this solution is mixed with 23.1 parts of a mixture which contains 3.o.94 parts of acrylonitrile, 3.06 parts of methyl acrylate, 2 parts of water and 64 parts of DHF.

The mixture obtained is subjected to the copolymerization conditions at 67 ° C. for 11 hours in the presence of 0.024 parts of azobisisobutyronitrile and 0.1 parts of malic acid stabilizer. Towards the end of the polymerization, the mixture contains 17.14 % of a polymer which contains 9a, 9 % ACN, 8 % APl and 1.1 % sulfonated derivative, including 48 acid meq per kg, which corresponds to a degree of utilization of the sulfonate of 90.5 %,

The solution is distilled under vacuum to eliminate and recycle the unreacted volatile monomers; A solution is obtained which contains 21 % polymer, which is spun under the same conditions as in the previous examples. The fiber produced in this way has the following control data:

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ORIGINAL INSPECTED

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a) see photo no. 4 (Fig. 4)

b) = 1.4 g

c) Fineness of thread in dtex = 3.2
Strength in g / dtex = 3.6
Extensibility, % = 32
Loop strength in g / dtex = 1.6

The control data are essentially identical to those of Example 2.

Example 5 : comparative example

This example does not illustrate the invention, but serves the comparison »The control data are given for a fiber made using sodium allyl sulfonate as the monomer and Application of the single-phase ternary polymer used in Example 1 sation process can be obtained.

The fiber obtained in this example is composed of 91.05% AGN, 8 % methyl acrylate, 0.95% sodium allyl sulfonate, which corresponds to 65 acid meq per kg of polymer, ie the same value as in Example 1.

The fiber has a gloss which is considerably inferior to that of Example 1 because of the presence of microspaces along the fiber edges, although it contains the same number of acid-meq per kg of fiber. To obtain this fiber, 3o.8 parts of acrylonitrile, 2.9 parts of methyl acrylate and 0.3o parts of sodium allylsulfonate are added at 67 ° C. for 11 hours in 2 parts of water and 64 parts of DP ¹ IF in the presence of 0.024 parts of azobisisobutyronitrile and o , o1 parts of malic acid stabilizer polymerized.

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Towards the end of the polymerization, the solution contains 18 % of a polymer composed of 91.05 % ACN, 8 % AP! and o, 95 % sodium allylsulfonate is composed, which corresponds to 65 acid-meq per kg and a sulfonate utilization rate of 60 % .

The spinning solution, which contains 21 % polymer and is obtained after distillation and recovery of the unreacted monomers, is spun under the same conditions as in the previous examples; a fiber is obtained with the following control data:

a) see photo no. 5 (Fig. 5)

b) = 1.6 g

c) Fineness of thread in dtex = 3.34
Strength in g / dtex = 3.4
Elongation, % = 35
Loop strength in g / dtex = 1.65

The control data underline the fact that when sodium allyl sulfonate is used, the acid milli equivalent per kg Polymer is the same (65), the fiber obtained is less shiny because of the presence of microspaces along the outer edge of the fiber; therefore, the dyeing yield is comparable to that of Example 1, i.e., compared to that of Example 1 Use of 2-acrylamido-2-methylpropane sodium sulfonate is reduced.

Example 6: comparative example

This example is also not an explanatory example for the invention, but serves as a comparison and gives the control data for a fiber made from the same spinning solution as

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in the previous example 5 is obtained, to which, however, 3 Geu .- / & U are added.
Control data:

a) see photo no. 6 (Fig.6)

b) = 1.4 g

c): Fineness of thread in dtex = 2.95

Strength in g / dtex = 3.7
Elongation, % = 32
Loop strength in g / dtex = 1.7

The control data show that in order to obtain a complete fiber from a copolymer, the 65 acid millie equivalent and which is derived from sodium allyl sulfonate, it absolutely it is necessary to add 3 Geu .- ^ water to the spinning varnish.

Example 7 : l / comparison example

In this further comparative example, the control data are given for a fiber made using sodium allyl sulf onate and application of the first preferred interpolymerization process and preparation of a first binary interpolymer from ACN / sulfonate, which has approximately the same amount of acid milli equivalents as the first copolymer of Example 1 contains, has been obtained.

This first copolymer is composed of 90 % acrylonitrile and 10 % sodium allylsulphonate, corresponding to 695 acid millie equivalents per kg of polymer.

The second mixed polymer to be mixed with the first is a mixed polymer containing 91 % ACN and 9 % methyl acrylate. The final polymerization solutions with the respective two copolymers are mixed in the required proportions in order to obtain a fiber that is 9o.9 %

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Contains acrylonitrile, 8 % acrylate and 1.1 % sodium allyl sulfonate, which corresponds to 77 meq per kg fiber.

The under the same conditions as in the previous examples produced fiber gave the following control data:

a) see photo no. 7 (Fig. 7)

b) η 1.55 g

c) Fineness of thread in dtex = 3.2 strength in g / dtex = 3.6 elongation, % = 3o, 5
Loop strength in g / dtex = 1.5o

From the control data it was found that if sodium allyl sulfonate is used even in an amount greater than that of the 2-acrylamido-2-methylpropane sodium sulfonate in Example 2 (i.e. 77 acid-meq versus 65) the resulting fiber has less gloss and lower staining yields due to the presence of microspaces, actually fewer, but of larger dimensions than those of the example

Example B.

Example 1 is repeated, but using 2-acrylamido-2-propanesulfonic acid as a significantly homopolymerizable sulfomonomer.

The fiber composition in this case is 90, 74 % ACN, 8 % methyl acrylate, 1.26 % sulfomonomer. The copolymer is obtained by flow polymerization under the conditions described in Example 1 of 3o.79 parts of ACN, 2.92 parts of methyl acrylate and 0.29 parts of 2-acrylamido-2-propanesulfonic acid in the same way

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Mixed solvent and with the same catalyst and stabilizer uiia obtained in Example 1.

As in Example 1, the fiber contains 65 sulfonic acid meq per kg, The control data are essentially identical to those of Example 1.

Example 9

The procedures of Example 1 using 2-acrylamido-2-phenylethanesulfonic acid are found to be significantly homopolymerizable Sulfomonomer repeated.

The copolymerized amounts of monomer are 3o, 7o parts ACN, 2.92 parts of methyl acrylate and 0.38 parts of 2-acrylamido-2-phenylethanesulfonic acid; all other components are as in example 1 and 8.

The fiber, which contains 65 sulfonic acid meq per kg and has the same control agents as that of Example 1, is composed of 90, 33 % ACN, 8 % methyl acrylate and 1.67 % sulfomonomer.

Example 1o

The procedures of Example 2 are repeated, however using 2-acrylamido-2-propanesulfonic acid as significant homopolymerizable sulfomonomer.

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The finished fiber contains 91.7 % ACN, 8 % methyl acrylate, 0.93% sulfomonomer and 48 sulfonic acid meq per 1 kg.

The binary copolymer of ACN / sulfomonomer is obtained as in Example 2, the only differences being that 27.9 parts of ACN and 4.1 parts of sulfomonomer are used. The binary copolymer obtained is composed of 87 ^[/ b ACFJ and 13% of sulphonic derivative and has rneq 655 per kg. The second copolymer corresponds to that of Example 2. All other instructions of Example 2 are followed.

The fiber control data are as in Example 2,

Example 11

The way of working !! of Example 2 are made using 2-Acrylamido-2-phenylethane sulfonic acid as a significant urine polymerizable Monomer repeated.

The finished fiber contains 90 % , 77% ACN, 8 % methyl acrylate and 1.23 % sulfoderivat as well as 48 sulfonic acid-meq per kg.

The binary copolymer of ACN / sulfomonomer is obtained as in Example 2, the only differences being that 27 parts of ACN and 5. o parts of sulfomonomer are used. The binary copolymer obtained is composed of 83.3 % ACN and 16.7 % sulfoic derivative and has 655 meq per kg. The second copolymer is that of Example 2, all other conditions of Example 2 are followed.

The fiber control values are as in Example 2.

9090 1 9/0703

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Claims (1)

Meissner & Meissner PATENT Attorney Bu R G BERLIN - MÖNCHEN PATENT LAWYERS DIPL-ING. W. MEISSNER (BLN) DIPL-ING. P. E. MEISSNER (MCHN) DIPL-ING. H.-J. PRESTING (BLN) HERBERTSTR. 22, 1000 BERLIN 33 Your sign Your letter from our sign Berlin, the (o7o) E. Snia Viscosa Claims 1.High gloss acrylic fiber made from a polymeric material containing monomer units of acrylonitrile, at least one vinyl ester and at least one, by definition, significantly homopolymerizable sulfocomonomer having. 2. Fiber according to claim 1, characterized in - net that the significantly homopolymerizable sulfocomonomer is a derivative of at least one acrylamidoalkanesulfonic acid. 3. Fiber according to claim 2, characterized in - net that the salt of an acrylamidoalkanesulfonic acid The alkali and / or ammonium salt of 2-acrylamido-2-methylpropanesulfonic acid is. 4. Fiber according to claim 1, characterized in that that the vinyl ester is methyl acrylate, vinyl acetate and / or methyl methacrylate is. 909819/0709 BORO MONKS: TELEX: TELEGRAM: PHONE: BANK ACCOUNT: CHECK ACCOUNT: ST. ANNASTR. 11 1 - 856 44 INVENTION BERLIN BERLIN 31 W. MEISSNER, BLN-W 8000 MONKS 22 INVEN d BERLIN 030/891 60 37 BERLINER BANK AG. 122 82 -109 TEL .: 089/22 35 44 030/892 23 82 3695716000 ORIGINAL INSPECTED 5. Fiber according to claim 1, characterized in that that the monomer units are contained in the following percentages by weight of the total mass: Acrylonitrile 85 to 95.5 % Vinyl ester 4 to 12 % significantly homopolymerizable sulfomonomer 0.5 to 3 %. 6. Fiber according to claim 1, characterized in that that the copolymer material is essentially a ternary copolymer. 7. Fiber according to claim 1, characterized in that that the copolymer material is a mixture of binary Copolymers is. 8. fiber according to claim 1, characterized in that that the copolymer material is composed of binary and non-binary copolymers. 9, Method of making an acrylic fiber with high gloss, characterized in that a viscous spinning solution is prepared in a water-miscible organic spinning solvent of a copolymer material which has monomer units of acrylonitrile, at least one vinyl ester and at least one according to definition significantly homopolymerizable sulfocomonomer, and spins this solution in a coagulating bath that consists of a mixture of water and the spinning solvent. 909819/0709 1o. Process according to Claim 9, characterized in that the significantly homopolymerizable sulfocomonomer is a derivative of at least one acrylamidoalkanesulfonic acid. 11. The method according to claim 9, characterized in - v \. ^ ——————— net ' that' is used as the spinning solvent dimethylformamide, dimethylacetamide and / or dimethyl sulfoxide. 12. The method according to claim 9, characterized in that the viscous solution uird obtained by mixing zuei solutions of binary copolymers which has been obtained by copolymerizing in the same spinning solvent of acrylonitrile and the vinyl ester on the one hand and acrylonitrile and the significantly homopolymerizable sulfo-comonomer on the other hand . 13. The method according to claim 12, characterized in that the first binary polymerizate 65 to 95 % (Geu .- $ £) acrylonitrile units and 5 to 35 Geu.-JS units of the sulfononomer, the second copolymer 85 to 95.5 % acrylonitrile units and 4.5 to 15% by weight vinyl ester units and mixing in proportions of 2 to 15 parts by weight of the first copolymer and 85 to 98 parts by weight of the second copolymer. 14. The method according to claim 9, characterized in that the viscous spinning solution is prepared by mixing acrylonitrile with the significantly homopolymerizable sulfocomonomer in the spinning solvent, mixing the resulting solution with a solution of acrylonitrile and vinyl ester and copolymerizing the whole. 90B819 / 0709 15, composition consisting of viscous solutions of mixtures of binary copolymers which have been obtained by the method according to claim 12. 16. Composition consisting of viscous solutions from binary and non-binary copolymers which have been obtained according to the method of claim 14. 909819/0709