DE2158581C3 - Syndiotactic polyvinyl chloride fibers and filaments and processes for their manufacture - Google Patents

Description

(A) an initiator system of hydrogen peroxide and an organic sulfinic acid, wherein the so Amount of peroxide compound 03 to 3.0% by weight - tezoger- on the used Monomers - is,

(B) a complexing agent from Cu-II ions and Ethylenediaminetetraacetic acid and π

(c) a lithium or zinc salt

has been made.

3. yarns and fibers according to claim I, characterized in that it consists of a vinyl chloride homo- or copolymer w exist which, when a DS value from 2.1 to 2.5 a Viskosittltszahl [η] 2.2 to 2 , 7 owns.

4. A method for producing threads and fibers according to claim 1 from vinyl chloride homopor. polymerizates or copolymers which contain at least 85 wt .-% vinyl chloride and have a high DS value, by spinning vinyl chloride polymers by the wet or dry spinning process, characterized in that><> that a vinyl chloride polymer with a viscosity number [η] of 2, 0 to 2.9 and a DS value of 2.1 to 24 will be fun.

5. A method for producing threads and fibers according to claim 4 by spinning the v> vinyl chloride homopolymers or copolymers containing at least 85 wt .-% vinyl chloride from a solvent by the wet or dry spinning process, characterized in that a vinyl chloride polymer with a mi Viscosity number [η] of 2.0 to 2 $ and a DS value of 2.1 to 24 is spun, which is obtained by redox-activated precipitation polymerization of vinyl chloride - optionally together with a maximum of 15% by weight of a comonomer - in hi alcohol / Water mixtures at pH values in the range of 2 and 7 and at temperatures between -10 "C and -40 ° C in the presence

(A) an initiator system composed of hydrogen peroxide and an organic sulfinic acid, in which the Amount of peroxide compound 0.3 to 3.0% by weight - based on the amount used Monomers - is,

(B) a complexing agent from Cu-II ions and Ethylenediaminetetraacetic acid and

(c) a lithium or zinc salt

has been made

The invention relates to flame-retardant fibers and threads made from syndiotactic polyvinyl chloride excellent dimensional stability in boiling water and in halogenated solvents of the chemical cleaning, for example in trichlorethylene and perchlorethylene.

Polyvinyl chloride fibers are among the oldest industrially produced synthetic fibers. In comparison with Fibers made of polyamide, polyester and polyacrylonitrile is the textile application of polyvinyl chloride fibers from Remaining of minor importance, since the hitherto used The polyvinyl chloride fibers used had some deficiencies that made their possible applications restricted.

The conventional polyvinyl chloride used for fiber production is produced by the bulk, suspension ^{or emulsion polymerisation process at temperatures between 20 °} C. and 60 ^° C. using peroxides or redox catalysts as initiators for the polymerisation. Fibers spun from these polymers begin to shrink in water at 60 ° C and are only 50 to 60% of their original length in boiling water.

These properties create great difficulties and limitations in processing them Fibers according to the usual processes in the textile industry whenever a thermal treatment the fibers and threads or the textile structures, e.g. B. carried out in fixing processes or in dyeing must become. When using articles made from these polyvinyl chloride fibers, this should be strictly followed make sure that any exposure to higher temperatures is avoided, even under conditions that are suitable for Textiles made from natural fibers or other synthetic fibers are completely harmless, deformations caused by fiber shrinkage.

Attempts to improve the dimensional stability of conventional polyvinyl chloride fibers and threads by means of a heat treatment achieved little success. During this heat treatment, the tear strength drops Fibers to approx. g / dtex, the elongation at break increases to 100% and can even reach higher values. at mechanical stress, these fibers with their low strength and their low modulus of elasticity do not offer any resistance to deformation. The textiles are, for example, exposed to tensile stress longer or bulges form in more stressed areas. Halogenated solvents, some of which are used in chemical or dry cleaning, these swell conventionally Polyvinyl chloride ^ fibers strongly. A treatment with perchlorethylene can therefore textiles from these Fibers shrink significantly and become unusable.

The enumerated here negative characteristics of conventional polyvinyl chloride fibers can be due to the low glass transition temperature Tg of about 65 ° C and explain the poor crystallizability of the polyvinyl chloride produced at temperatures above 20 ⁰ C by conventional polymerization processes. It is known that with decreasing polymerization temperature, syndiotactic linkage of the vinyl chloride molecules (J. Pol. Sci. 39; 321 to 334) increasingly takes place. At the same time, the number of chain branches decreases (Makromol. Chemie 95 (1966), 40 to 51 ). These changes in the microstructure of the polymer bring about a significant increase in the crystallizability of the polyvinyl chloride produced at low temperatures and thus lead to improved dimensional stability of the objects produced from this polyvinyl chloride at high temperatures and in halogen-containing solvents.

In view of the steric structure, preferably methods of infrared spectroscopy are used to distinguish the polyvinyl chlorides (Tieitemperatur-polyvinylchloride) prepared at low temperatures (below 0 ⁰ C) of polyvinyl chlorides, which were prepared at temperatures above 0 ⁰ C.

As already described, there is a direct relationship between the polymerization temperature and the proportion of syndiotactic sequences in the polyvinyl chloride. Both by Fordham (J. Pol. Sci. 41 (1959), pp. 73 to 82) and by Burleigh (JACS 82, (1960) p. 749), the infrared absorption ratio of the CCI oscillation is used to characterize the degree of syndiotactic degree -Bands at 635 cm- 'to 692 cm-', the band at 635 cm - <syndiotactic and the band at 692 cm - ■ isotactic structural units are assigned. The quotient of the extinctions at 635 cm ¹ and 692 cm ¹ is referred to as the DS value (degree of syndiotacticity)

To identify low-temperature polyvinyl chlorides, the degree of syndiotacticity = s is generally used However, they are used in some publications relating to the manufacture of polyvinyl chloride fiber from low-temperature polymers contain no information on the degree of syndiotacticity (DS value) made Ia these cases must be indirect the fiber properties on the steric structure or the crystallizability of the polyvinyl chlorides described getting closed.

Processes are known for the production of polyvinyl chloride in which vinyl chloride (co) polymers are prepared at temperatures below 20 ⁰ C by means of special catalyst systems and spun from dimethylformamide by the NAB or by the dry spinning method. These polymers are in high concentrations, as are customary in spinning solutions, ie more than 15% polymer soluble in dimethylformamide.

Furthermore, the production of fibers from polyvinyl chloride with an AFNOR viscosity index of 450 or above known. The polymer is produced at temperatures below 0 ° C. and from dimethylformamide versponner (see DE-AS 12 89 945).

For the characterization of polyvinyl chlorides is the AFNOR viscosity index is not an internationally common measurement parameter. This AFNOR viscosity index *. leaves calculate from

// Solution

i / solvent

- d. h, from the specific viscosity divided by the measured concentration, which according to the standard amounts to 0.250 g of polyvinyl chloride in 50 ml of cyclohexanone. According to Huggins (JACS 64 (1942), page 2716), the one-point measurement on which the AFNOR viscosity index is based, the viscosity number [η ] π can be calculated:

j «The Huggins constant kn necessary for this calculation. determined Cernia and Ciampa to be 0.4 for polyvinyl chloride (J. Pol. ScL 41 (1959) p. 75). The concentration C in the Huggins equation is given in the dimension gram / deciliter. It shows

When performing the calculation, it is clear that the AFNOR index of 450 has a viscosity number! of [η] = 3.0 ^.

Since the polyvinyl chloride of the said DE-AS with

«Ι an AFNOR viscosity index of at least 450, corresponding to a viscosity number of at least 3.0

- Has a high degree of polymerization and in

Dimethylformamide is soluble to a low level

r »Degree of syndiotacticity or a low ability to crystallize getting closed. Polyvinyl chlorides with a viscosity number above 3 that have a high Have a syndiotactic degree and a high crystallizability are very sparingly soluble. the

the concentration of the spinning solutions must be below 12%. The cost of recovering the solvents are in this case very high in relation to the amount of fiber produced, and an economical one Production process is no longer guaranteed

i "Also include methods of making threads from Highly syndiotactic grade polyvinyl chloride with a molecular weight of 50,000 to 120,000, preferably from 60,000 to 85,000, from the German Auslegeschriften 12 78 066 and 16 69 370 or the

-> ii US-PS 33 88 201 known. According to the relationship between [η] and the molecular weight given in these publications, viscosity numbers of 1.0 to 1.95, preferably 13 to 1.6- are calculated. For a

This is because v> molecular weight of 120,000 results in a maximum [η] of 1.95.

Polyvinyl chlorides with these relatively low viscosity numbers can only be used to make fibers particularly good properties, d. H. high dimensional

Wed stability, in boiling water and halogenated Spin solvents when the polymers have an extraordinarily high DS value or Have crystallizability. Such polyvinyl chlorides are normally grown at temperatures

h> manufactured by -45 ^0C. This low polymerization temperature leads to high energy costs in the production process, which are detrimental to the economy of the process.

If viscosities of 2.0 are also mentioned in Table 2 of US Pat. No. 3,388,201, it is not specifically apparent what degree of syndiotacticity these polymers of viscosity 2.0 have. There, in column 4, line 65, only the reference to "high-DS PVC-solutions" is given. However, since, according to this US patent, it can also be understood to include polymers with a degree of syndiotacticity of 1.8 and, according to Table 1, no DS values above 2.1 are linked to [η] above 2.0, the general teaching goes in the same direction lower viscosities at DS values above 2.0. The person skilled in the art therefore did not feel compelled to undertake investigations which deviate significantly from this teaching. This is all the more so as in the paragraph before Table 2 the dangers of gel formation are pointed out, which are said to occur even more intensely in the case of polymers of higher viscosity.

As has been shown, there are a number of known methods of making polyvinyl chloride fibers of disadvantages. In some cases, the molecular weights of the polyvinyl chlorides used are extraordinary high. The DS value or the crystallizability of these polymers must not be excessively high because otherwise their solubility and thus the economic viability of fiber production would decrease. In which Process for the production of fibers from highly syndiotactic polyvinyl chloride must be carried out at very deep Temperatures are worked. This process is burdened with high energy costs

The invention thus relates to threads and fibers made from vinyl chloride homopolymers or copolymers which contain at least 85% by weight of vinyl chloride and have a high DS value resulting from the usual infrared extinction ratio, with a high modulus of elasticity, high tensile strength and low elongation and high dimensional stability in boiling water, as well as against halogenated hydrocarbons, which is characterized in that the threads and fibers consist of a vinyl chloride homo- or mixed polymer, which in addition to an nC.Worf »AU OI hie 1 ζ« .in »VicLncitötc- roM Γ.0 ", -. η Ο Π ... _ ,. _, - _{L. (J.} _, _

to 23 owns. These threads and fibers preferably consist of a vinyl chloride homopolymer or mixed polymer which, with a DS value of 2.1 to 2.5, has a viscosity number [η] of 2.2 to 2.7.

The invention further relates to threads and fibers of the type mentioned, which are characterized in that they consist of a vinyl chloride polymer with a viscosity number [η] of 2.0 to 23 and a DS value of 2.1 to 23, i.e. through redox-activated precipitation polymerization of vinyl chloride - optionally together with at most 15 wt .-% of a comonomer - in alcohol / water mixtures at pH values in the range of 2 and 7, and at temperatures between - 10 ⁰ C and -40 ⁰ C in the presence of (a) an initiator system composed of hydrogen peroxide and an organic sulfinic acid, in which the amount of peroxide compound is 03 to 3.0% by weight, based on the monomers used, (b) a complexing agent composed of Cu (II) ions and ethylenediaminetetraacetic acid and (c) a lithium or zinc salt has been prepared.

The threads and fibers have high strength with low elongation at break and high heat resistance and good dimensional stability in halogenated dry cleaning solvents. she can be produced by a very economical process.

The polyvinyl chloride fibers of the invention and

threads have a tensile strength of 2.2 to 3.5 g / dtex, an elongation at break of 25 to 55%, a high modulus of elasticity, a shrinkage in boiling water of less than 2% and a low shrinkage in the halogenated solvents of the chemical Cleaning.

The invention also relates to a process for the production of the above-mentioned threads and fibers from vinyl chloride homopolymers or copolymers which contain at least 85% by weight vinyl chloride and have a high DS value by spinning vinyl chloride polymers by the wet or dry spinning process , which is characterized in that a vinyl chloride polymer with a viscosity number [η] of 2.0 to 2.9 and a DS value of 2.1 to 2.5 is spun.

In particular, the process for producing such threads and fibers is carried out by the fact that) a vinyl chloride polymer with a viscosity number [η] of 2.0 to 2.9 and a DS value of 2.1 to 2.5 is spun which is produced by redox activated precipitation polymerization of vinyl chloride - optionally together with at most 15 wt .-% of a comonomer - in alcohol / water mixtures at pH values in the range of 2 and 7, and at temperatures between -10 ⁰ C and -40 ° C in the presence of (a ) an initiator system composed of hydrogen peroxide and an organic sulfinic acid, in which the amount of peroxide compound is 0.3 to 3.0% by weight, based on the monomers used, (b) a complexing agent composed of Cu-II ions and ethylenediaminetetraacetic acid and ( c) a lithium or zinc salt has been produced

To determine the viscosity number, as usual (Cernia and Ciampa: Makromolekulare Chem. 16, (1955), pp. 177 to 182), the relative solution viscosity of polyvinyl chloride in cyclohexanone is measured as a function of the concentration. In a simpler method, the viscosity number [η] can be calculated from a one-point measurement using the Huggins formula.

Παι · nC.Wart w'tw-Λ nonk rlem Air »« * · »» * »«. nawkiMArlen ■■ - - © O- O

Method from the extinctions in the infrared at 635 cm - 'and 692 cm -' determined A DS value of 2.1-2 ^ have polymers that are at ^{-10 ° C to -40 0} C, preferably at -15 ° C to -30 ° Cher.

These polyvinyl chlorides with a high proportion of syndiotactic sequences are redox-activated Precipitation polymerization in alcohol / water mixtures obtained with yields of approx. 60%, the degree of polymerization being adjusted by adjusting the temperature control and peroxide concentration will. For low-temperature vinyl chloride polymerization such a high conversion rate is quite unusual. In general, appropriate for Process yields indicated around 20%. The thermal stability of the polymers according to the invention used in fiber production is extremely high. In a stream of nitrogen is at 170 ° C in three hours only 1% of that in the unstabilized Hydrogen chloride present in the polymers is split off.

In contrast to the previously known low-temperature polyvinyl chlorides the polymers used in the invention do not dissolve in dimethylformamide to a significant extent. A spinning solution can be prepared in dimethylformamide. Obvious is the interaction of the polyvinyl chloride chains with

a high percentage of syndiotactic sequences, and of the commercial polyvinyl chlorides ru compared high viscosity so great that the solvating power of the dimethylformamide at temperatures of 1? Q to 150 ⁰ C is not sufficient that polymers to lö »» n.

In the case of the polyvinyl chlorides used according to the invention it is not only about homopolymers of vinyl chloride, but also about its Copolymers. These must contain at least 85% vinyl chloride. As comonomers above all Things such ethylenically unsaturated compounds are used that reduce the dyeability of the threads facilitate. Such vinyl compounds are e.g. B. vinyl acetate, acrylic ester, methacrylic ester and acrylonitrile, These comonomers increase the dyeability with disperse dyes. Modification with sulfonic acid, vinyl compounds containing disulfimide or carboxyl groups improve the absorption capacity for basic dyes. Such vinyl compounds are e.g. B. styrene sulfonic acid, methallyl sulfonic acid, 3-methacryl loylaminobenzene-N- (benzenesulfonyl) sulfonamide or methacrylic acid. The polyvinyl chlorides can also other polymers are mixed in, which improve the dyeability. Such additions may 15 Do not exceed% by weight.

Thus, highly syndiotactic polyvinyl chlorides - produced by a very economical polymerization process - are spun into fibers and threads.

The table below summarizes data with the help of which the invention in detail is explained.

The listed in column 1 of polyvinyl chloride samples is vinyl chloride homopolymers, which were polymerized at temperatures from -20 ⁰ C to -30 ⁰ C. General explanations of the viscosity numbers [η] (column 2) and the DS value (column 3) have already been made. Experimental details of the main measurement methods are given

i L ucav »!! i icucil.

According to this, about 0.3 to 3.0% by weight of peroxide, based on the amount of monomer used, are used Use. It is preferred to use 0.35 to 1.5% by weight of peroxide compound, based on the monomer.

The polyvinyl chlorides were all spun into threads using the same process, which in turn were all dem were subjected to the same post-treatment process. Spinning and post-treatment processes are communicated below.

The following information is used to explain the measured values in the individual columns:

split
1:
2:

Let the molecular weights of vinyl polymers find out about the concentration of starting radicals, based on the effective monomer concentration, change. The greater the ratio

Concentration on starting radicals
effective monomer concentration

the lower the molecular weights of the 5η resulting present polymers. In the method, the concentration of initiator radicals is essentially determined under constant conditions is considered by the peroxide concentration in the reaction medium, that the concentration of initiator radicals of the peroxide is approximately proportional VerfahLaufende number of the polyvinyl chloride viscosity [η] ^ l

DS value

Spinning solution concentration,% solids in solution

Maximum possible stretch ratio without breaking individual thread capillaries
Tear strength of the drawn threads before post-treatment
Elongation at break of the drawn threads before an aftertreatment
Elimination of hydrogen chloride in a stream of nitrogen at 170 ^° C. within 60 minutes, data in% by weight, based on total PVC
Tear strength of the drawn threads after a treatment time of 30 minutes in boiling water
Elongation at break of the drawn threads after a treatment time of 30 minutes in boiling water
Modulus of elasticity in kp / mm ² ;
determined from the force / elongation diagram in the linear part at low elongation

Cooking shrinkage Its in ^and / or the initial length L ₀ ;

L ₁ corresponds to the length of the thread after a tension-free treatment for 10 minutes in boiling water

.r

- χ 100.

and 14:

and 16:

Shrinkage of the filaments in trichlorethylene, after 20 minutes at 40 and 8O ⁰ C, evaluation analog 12
The threads shrink in air after 1 minute at 130 ^° C. or 150 ^° C., evaluation analogous to 12.

1 2 3 4th 5 6th 7th 8th sample Visc. DS value Conc Stretching F 1 D 1 TS Number [/,] tration Relation dl / g % [g / dtex] % Wt%

1st group
1
2

1.08
1.20

2.20
2.29

25th
23

: 6.5
1: 6.5

1.4
1.65

11th
14th

0.96
14th

1 9 2 J 21 58 11th 581 12th 10 6th 7th 15th 8th Therm o-lock 150 ° sample Visc. DS value Modulus of elasticity KS F 1 D I WS TS 130 ° continuation Number [, J Cooker I. dl / g 4th kp / mnr % | g / dtex] % Ow .-% sample Conc Stretching 1.64 2.30 tration Relation 2.7 11th 0.84 1.72 2.37 % 2.1 11th 0.68 I. group 1.84 2.32 3.15 9 0.63 3 1.92 2.35 19th 1: Il 3.4 9 0.20 4th 20.5 I: 8 5 2.04 2.22 20th 1: 8 3.65 9 0.29 6th 2,! 4 2.3! 20th I: Il , 1 j Q η in 2nd group 2.24 2.45 4.1 8th 0.40 7th 2.30 2.50 19th 1: 10 3.8 9 0.40 8th 2.60 2.10 19th j ■ ι j 5 3.85 9 0.32 9 2.69 2.25 18.5 1: 10 3.55 8th 0.27 10 2.80 2.30 17.5 I: 10 3.9 9 0.41 11th 15.5 I: 11 12th 3.00 2.10 14.5 1: 10 3.2 7th 0.99 13th 3.09 2.33 15th 1: 9.5 2.95 8th 0.37 3rd group 3.24 2.40 3.0 10 - 14th 3.42 2.35 13th 1: 10 3.2 8th 0.44 15, 3.62 2.44 12.5 1: 9 2.8 8th 0.40 16 * 9 10 12.5 1: 7 13 14 16 17th F2 D2 II 1: 8.5 TC S 18th 11th 1: 9 Tri-Schr. g / dtex % 40 ° 80 °

1. uruppe

2
3
4th
5
6th

2nd group
7th

9
10
11th
12th
13th

3rd group
14th

15th
16
17th
18th

0.7

1.2

2.2

1.55

2.5

2.65

2.9
3.5
3.6
3.2
3.2
2.8
3.3

2.5
2.2
2.4
2.6
2.2

32 22 24 28 30 33 27

135 150 210 175 225 240

275 340 355 320 315 290 310

255 220 235 240 210

3.5 2.5 0.5 2

1 0

0.5

0.5

0 1 0

1 0.5

5 3 2 1 0.5

0 1 0 1 2 1 0

0.5

22 25 18 20 23 22 17

7 5 5 3 2.5

0.5

0.5

0 2 1 3 2.5

12 10

The polyvinyl chlorides and polyvinyl chloride threads recorded in the table are divided into three groups The serial numbers 1 to 6 are below in their viscosity numbers, 7 to 13 within and 14 to 18 above the range according to the invention. The DS value of all products is almost the same and lies between 2.1 and 2.5, i.e. h, within the claimed range.

Of the listed values which were determined on the spun threads, some are particularly indicative of the value of the present invention. If one compares the tensile strength of the drawn threads with the viscosity number, the picture is as shown in FIG. 1 represents. The viscosity numbers of the individual polyvinyl chlorides 1-18 are plotted on the ordinate and the maximum achievable thread strengths from column 6 of Table 1 are plotted on the abscissa. At dcf Daisiciiurf; The individual fvieSpunkie clearly shows a broad maximum of the thread tensile strength in the claimed range of the viscosity number between Dj] = 2.0 and [η] = 3.0 ^ L

In principle, the same relationship can be seen in FIG. 2 for those that have shrunk in boiling water Threads, the tensile strength of which was taken from column 9 in table 1. After the shrinking process the tear strengths are overall at a low level.

The properties of the threads made of polyvinyl chlorides with viscosity numbers [ij] <2.0 are generally less favorable compared to the threads according to the invention evaluate. These samples correspond to those produced according to DE-AS 16 69 370 or US-PS 33 88 201 Threads.

At a viscosity number [η] = 1.08, the thermal stability is poor; it only reaches the level of the products according to the invention at [ή] = 1.8. The shrinkage values in boiling water, in trichlorethylene at 40 ^° C. and at 80 ^° C. and in air at 130 ^° C. and 150 ^° C. also show that polyvinyl chlorides with viscosity numbers [η]

and have a comparable DS value, exhibit less favorable behavior a

The strength of the threads in the third group, i.e. That is, threads made of polyvinyl chloride with a viscosity number [η] above 3.0 are at a high level, although not quite as high as in the second group according to the invention. The same applies to the other values. In FIG. 3 shows the relationship between the viscosity number and the maximum possible spinning concentration. This maximum possible spinning concentration results from the solubility of the polyvinyl chlorides in cyclohexanone at 150 to 156 "C ₁ (LL, at the boiling point of the cyclohexanone and the gelling point of the solution on cooling.

With a higher concentration, the spinning solutions tend to gel faster, and spinning disorders can occur. The gelling temperature should not exceed 130 ⁰ C, preferably 115 ° C. The spinning solution concentrations given here are selected so that the gelling temperature is approx. 115 ° C

One can see the F i g. 3 that the maximum spinning solution concentrations of the polyvinyl chlorides with a DS value of 2.4 at a viscosity number of [η] -2JS fall below 15%. In this area, the economic viability of the process for the production of polyvinyl chloride fibers is no longer guaranteed

The fibers according to the invention can both nacn

the wet as well as the dry spinning process can be obtained. For both spinning processes, 15 to 20% gel-free spinning solutions of the highly syndiotactic polyvinyl chloride or a copolymer -) made of at least 85% vinyl chloride at a temperature of 130 to 155 ° C in cyclohexanone. The spinning solutions may contain pigments, fillers, stabilizers or others Products are added.
When wet spinning, the spinning mass is through the

in a heated nozzle in a suitable precipitation bath, e.g. B. a binary or ternary mixture of cyclohexanone, water and a solubilizer or a mixture of water and glycol or glycol ethers, such as. B. ethylene glycol, di- and triethylene glycol, ethylene glycol monomethyl

Ii or monoethyl ether pressed. After intensive washing, the resulting threads are drawn in two stages to improve orientation and crystallinity. A pre-drawing is dissolved in hot water, a post-stretching at temperatures between 100 ⁰ C and 160 ° C on a heated roller, in hot oil, in hot steam or hot air performed the respective total stretching ratio is, as can be seen from Table 1, between 1: 9 and 1: 11, in rare cases even higher. Then the

2 ". Threads still at 180 to 220 ° C in air or steam under

Heat-set tension To improve the heat

and solvent resistance, the threads are finally shrunk in water at 100 to 120 ° C

Even with the dry spinning process, the spinning hole

jo solution have a temperature of 100 to 120 ° C to avoid gelling of the solution and thus spinning disturbances. The spinning solution is heated by the The nozzle is pressed into a spinning shaft heated with air from 150 to 220 ° C and the resulting threads

j5 with a take-off speed of 100 to 300 m / min wound onto spools. The following process steps correspond to the aftertreatment the previously described process.

The fibers according to the invention can on

Due to their good properties, such as the high strength iiv.i Dehr.un ™, the high modulus of elasticity, the very good resistance to organic solvents and boiling water, the excellent dimensional stability at higher temperatures and the inherent flame resistance of PVC in all common textile processing processes will. This further processing can be as pure processing or in a mixture with natural or synthetic fibers, such as. B. wool, cotton, acrylic fibers, rayon and acetate fibers. Possible areas of application are primarily in the field of flame-retardant textiles such as carpets, especially long-pile carpets, decorative fabrics, poister upholstery fabrics, blankets, etc. The good heat retention capacity and the soft, warm feel allow it to be used for underwear and knitwear, especially for children's clothing.

Further areas of application are in the technical sector, where the good resistance of the syndiotactic Polyvinyl chloride fibers against acids, bases, solvents and atmospheric influences to wear comes, so z. B. with filter cloths and protective clothing.

The following are the measuring methods used to characterize the polyvinyl chloride fibers according to the invention contribute significantly, explained in detail:

The DS value of the polyvinyl chloride is determined from the Extinctions of the polymer in the infrared at 635 cm- '

and 692 cm - 'and forming the ratio of

DS =

certainly

Foils made using the following technology are used for measurement:

In each case 300 mg of polyvinyl chloride are dissolved in 5 ml of cyclohexanone at 140 ° C. The solution becomes rapid cooled and poured onto glass plates etched with hydrofluoric acid to form wedge-shaped layers. Through this Keflform ensures that foil areas are created the optimal band intensities for the IR measurement in the transmission range from 25% to 50% result. It is extracted twice with boiling methanol for one hour and then dried in vacuo

The infrared measurement is made with a double-beam grating spectrophotometer (Model Ferkin-Elmer 42) carried out The evaluation takes place after Baseline method, where the baseline is placed between the minima at 775 cm - 'and 555 cm -'.

The viscosity number [η] is determined by known methods. Polyvinyl chloride is dissolved in a concentration range of about c = 0.2% to c = 0.6% in cyclohexanone at 130 ° C. in 30 minutes. The viscosity measurements are carried out at 25 ° C. in an Ubbelohde -Viscometer from Schott and Gen. with capillary I. At least three measurements at different concentrations are necessary from which

'/ TrI -

/ _; solution
solvent

./-l emerges

oxide a. After 30 minutes, add 300 teaspoons of vinyl chloride, the temperature in the reaction space being constant at -25 ° C. Over the course of 2 hours, a mixture of 180 teaspoons of methanol, 180 teaspoons of demineralized water, Ofi teaspoon of sodium hydroxymethylsulfinate, 0.06 teaspoon of sodium lauryl sulphate and a mixture of 200 teaspoons of methanol, 200 teaspoons of deionized water and 2 teaspoons of hydrogen peroxide (30 % ig) entered. Then another 200 teaspoons of vinyl chloride are pressed into the reaction vessel. After 15 hours, the polymer paste is poured into a mixture of 2000 teaspoons of water, 20 teaspoons of LiCl and 2 teaspoons

Sodium pyrosulfite discharged with stirring. The precipitate is spun off with water

washed and dried 305 teaspoons (61% of theory) of a white polymer with a viscosity number are obtained of 2 ^ 5 and a DS value of 2 ^ 0.

The plot-2 ^ i-against C is then obtained

by extrapolation to C = 0 the viscosity number [tjJ (the extrapolation to the velocity gradient G = 0 can be neglected in the present molecular weight range).

Thermostabilities are determined according to the Geddes method (European Pol. Journal, 3 (1967) pp. 267 to 281) measured. A polyvinyl chloride sample of 625 mg is heated to 170 ° C. in a stream of nitrogen Hydrochloric acid released at this temperature in one hour is driven into a receiver with the nitrogen, there absorbed by water and titrated with sodium hydroxide solution. Methyl red serves as an indicator takes place in wt .-% of the split off hydrogen chloride, based on the initial weight.

A) Production of one according to the invention
using syndiotactic polyvinyl chloride

A polymerization vessel equipped with a stirrer is charged as follows (all data are Weight parts):

400 parts of methanol, 900 parts of demineralized water, 0.2 part of copper sulphate, 0.2 part of sodium lauryl sulphate, 0.125 part of it. Ethylenediaminetetraacetic acid, 0.6 TI. Sodium hydroxymethyl sulfinate and 0.1 Tl. ^ H ₂ SO ₄ .

After the reactor has been flushed with nitrogen and cooled to -25 ° C., it is stirred into the reactor Solution a mixture of 20 TI. Methanol, 20 TI. desalinated water and I Tl. 30% hydrogen per-

_v Example !!

100 parts by weight of the TL described under procedure A polymer (viscosity 2J5, DS value 2 ^ 0) are dissolved organisehen a tin stabilizer at 140 ⁰ C in 505 parts by weight of cyclohexanone TL with simultaneous addition of 1.5 parts by weight The TL The spinning solution obtained is filtered at 135 ° C. and the likewise heated spinneret is pressed by means of a heated gear pump d-irch. 38.5 g of solution are conveyed per minute through the 300-hole spinneret with a hole diameter of 0.08 mm, which is 6.35 g PVC corresponds

The precipitation bath consists of a mixture of 20% cyclohexanone, 30% isopropanol and 50% water. The precipitation bath temperature is 60 ° C, the yarn sheet is pulled off with 7 m / min from the nozzle, then washed extensively in water of 60 to 80 ⁰ C. Finally, the thread bundle is stretched in boiling water in a ratio of 1 : 3JS , dried with circulating air at 120 ° C in a heating cabinet and then stretched on a heating roller at 150 ° C in a ratio of 1: 3.0, provided with an antistatic finish and 63 m / min wound onto spools

The threads measured on a Wolpert EZR 3 tearing device with a clamping length of 50 cm, following properties:

Titer - 865 dtex / 300

Strength - 3.8g / dtex
Elongation at break - 9.5%
Modulus of elasticity - 725kp / mm2

In a further operation, the threads are ^{heat-set in steam at 220 °} C. under tension for 4 seconds. The threads are then cut and ^{treated under pressure in water at 120 °} C., with a shrinkage of about 15 to 20%
The tear strength and elongation at break of the staple fibers are measured with the Fafegraph Type 4 at a clamping length of 20 mm.

Ther 3.3dtex Tear resistance 3.25g / dtex Elongation at break 28% modulus of elasticity 325 kp / mm * Shrinkage in boiling Water (KS) 0% Shrinkage in trichloro ethylene at 40 ° C 2% Shrinkage in air from 130 "C 0%

Example 2

100 parts by weight of a polyvinyl chloride polymerized at -25 ° C. with a viscosity number [η] = 2.15 and a DS value of 2.30 are added in 425 parts by weight. Cyclohexanone with the addition of 1.5 parts by weight Dissolved an organic tin stabilizer at 140 ° C. and spun into threads as in Example 1. The threads withdrawn from the nozzle at 7 m / min are drawn after washing in water at approx. 60 ° C in boiling water in a ratio of 1: 4.0, dried in circulating air at 120 ° C and with a heating roller with a surface temperature of 150 ° C in the ratio of 1: 2 £ 6 stretched.

The following textile values were measured:

Titer

Tear resistance
Elongation at break
E-Modules

580dtex200 4.15g / dtex 8% lüiükp / mmz

Titer

Tear resistance
Elongation at break
Modulus of elasticity

tl20dtex / 200

3.7 g / dtex

9%

680 kp / mm *

After the aftertreatment described in Example 1, staple fibers with the values are obtained

Titer 33 dtex

Strength 3.6 g / dtex

Elongation 24%

Ε module 400 kp / mm * shrinkage in boiling

Water (KS) 0% shrinkage in trichloro

ethylene at 40 ° C 2% Shrinkage in air

from 130 ° C 0%

Example 3

100 parts by weight of a polyvinyl chloride polymerized according to regulation A with a viscosity number of [η] = 230 and a DS value of 24 are 1.5 parts by weight of an organic tin stabilizer at 140 ° C. in 470 parts by weight of cyclohexanone contains, solved.

In this experiment, the precipitation bath consists of 50% water and 50% ethylene glycol. The filaments are taken off at 7 m / min from the nozzle (200 hole / 0.1 mm), washed in boiling water 1: stretched 4.0, dried at 15O ⁰ C 1: stretched 2.25

The measurements gave the following values:

230) are at 140 ° C in 525 parts by weight of cyclohexanone, containing 1.5 parts by weight of the organic tin stabilizer, dissolved

The solution from the heated spinning pump through the spinning head of 135 ° C and the nozzle (72 holes with 0.1 mm hole diameter) in a dry spinning cell pressed the supply air temperature at the nozzle is 140 ⁰ C, the temperatures of the air in the shaft be in the upper part 185 ° C, in the lower part 210 ⁰ C. The filaments are drawn off at 300 m / min. Subsequently, the filaments are first in boiling water 1: stretched 1.75, then at 150 ⁰ C for a further 1: 23 post-drawn

The following textile values are measured: Titer I *** dtex Strength 3.7 g / dtex Elongation at break 8% Modulus of elasticity 680 kp / mm *

The staple fibers obtained according to Example 1 have the following properties:

Titer 3.0 dtex

Strength 33 g / dtex Elongation at break 3.0% E-module 350 kp / mm * Shrinkage in boiling

Water 03%

Shrinkage in trichloro

ethylene from »0 ° C 13%

Shrinkage in air
from 130 ° C 0%

Comparative example 1

100 parts by weight of a polyvinyl chloride as prepared according to protocol A, however, having a viscosity of [η] = 3.25 and a DS value of 2.40 at 140 ^e C in 700 parts by weight of cyclohexanone, 13 in the by weight of Part I: an organic tin stabilizer is contained, dissolved in example 1, the filaments are spun, washed and stretched, wherein in the water a draw ratio of 1: 3.0 and such of I at 150 ⁰ C: was adhered to IM. 7 The following textile values were measured:

The staple fibers had the following properties:

Titer 6.6 dtex

Strength 3.1 g / dtex Elongation at break 35% E-module 300 kp / mm *

Shrinkage in boiling
Water 0%

Shrinkage in trichlorethylene of 40 ° C 0.5%

Shrinkage in air
from 130 ° C 0%

Example 4

100 parts by weight of the polyvinyl chloride described under instruction A (viscosity number [η] = 2.5, DS value titer

Tear strength:
strain
Modulus of elasticity

880dtex / 300 23 g / dtex 10% 600 kp / mm ²

The staple fibers also obtained according to Example 1 can be characterized with the following values:

Titer 33 dtex

Strength 2.4 g / dtex

Elongation 30%

Modulus of elasticity 240 kp / mm * shrinkage in boiling

Water 0% shrinkage in trichlorethylene of 40 ° C 2% Shrinkage in air

of 13 (TC 1%

Comparative example 2

In this experiment, polyvinyl chloride with a viscosity number [η] «1.6 dl / g and a DS value of 2.4 is used. 100 parts by weight of this polyvinyl chloride are dissolved in 410 parts by weight of cyclohexanone at 140 ° C. with the addition of 13 parts by weight of an organic tin stabilizer. The analogous to Example 1 wet

The spun threads are drawn in boiling water 1: 3.5 and at 150 ° C1: 2.86
Threads are obtained with the following properties:

Titer 850 dtex / 300 Tear resistance 2 ^ 5g / dtex Elongation at break 11% Modulus of elasticity 420 lcp / mm ²

The further course of the process likewise proceeds as described in Example 1. The staple fibers have the following Characteristics:

Titer 3.3 dtex

Tear strength 2.0 g / dtex Elongation at break 33%

Modulus of elasticity · 210kp / mm2 shrinkage in boiling

Water 0.5% shrinkage in trichloro

Ethylene from 40 ° C 2% Shrinkage in air

from 130 ⁰ C 4%

For this purpose 3 sheets of drawings

Claims (2)

Claims; 1. Threads and fibers made from homopolymers of vinyl chloride or copolymers which contain at least 85% by weight of vinyl chloride and a have a high DS value resulting from the usual infrared extinction ratio, with a high Young's modulus, high tear strength, low elongation and high dimensional stability in boil-in to water, as well as to halogenated hydrocarbons, characterized that the threads and fibers consist of a vinyl chloride homo- or mixed polymer, which in addition to a DS value of 2.1 to 2.5 ι ". has a viscosity number [tj] of 2.0 to 2.9 2. threads and fibers according to claim 1, characterized in that the threads and fibers consist of a vinyl chloride polymer with a viscosity number [ij5 from 2.0 to 2 pounds and a DS value of 2.1> n to 23, which by redox activated precipitation polymerization of vinyl chloride - optionally together with at most 15% by weight of a comonomer - in alcohol / water mixtures at pH values in the range from 2 to 7 and at temperatures between -10 ^° C. and -40 ^° C. in presence