DE2158581B2 - Syndiotactic polyvinyl chloride fibers and filaments and processes for their manufacture - Google Patents

Description

(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 - cheated,

(b) a complexing agent on Cu-II ions and Ethylenediaminetetraacetic acid and

(c) a lithium or zinc salt

has been made.

3. threads and fibers according to claim 1, characterized in that they 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 owns

4. A process for the production of threads and fibers according to claim 1 from vinyl chloride homopolymers or copolymers which contain at least 85% by weight of 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 2.5 is spun.

5. A method for producing threads and fibers according to claim 4 by spinning the 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 viscosity number [η] of 2.0 to 2.9 and a DS value of 2.1 to 2.5 is spun 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 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 0.3 to 3.0% by weight - based on the amount used

Monomers - is,

(b) a complexing agent composed of Cu-II ions and ethylenediaminetetraacetic acid and

(c) a lithium or zinc salt

ι ο has been established

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 penchlorethylene.

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 subordinate B & '- consideration remained, since the hitherto to The polyvinyl chloride fibers used had some deficiencies that made their possible applications restricted.

The conventional polyvinyl chloride used for fiber production is after the bulk, suspension ^{or emulsion polymerization process at temperatures between 20 0} C and 60 ⁰ C using peroxides or redox catalysts as starters for the polymerisation produced Fibers spun from these polymers begin to grow in water at 60 ° C shrink and only have 50 to 60% of their original lapping in boiling water, e. These properties create great difficulties and restrictions on processing them Fibers according to the usual processes in the textile industry whenever a thermal treatment of the fibers and threads or the textile structures, z. B. Runaway in fixing processes or in dyeing must be performed. When using articles From these polyvinyl chloride fibers, care must be taken that any exposure to higher temperatures is avoided because even bsi conditions that apply to textiles made of natural fibers or also to others

If synthetic fibers are completely harmless, deformations are caused by fiber shrinkage.

Attempts to achieve the dimensional stability of conventional polyvinyl chloride fibers and threads by heat treatment have had little success. at After this heat treatment, the tensile strength of the fibers falls to approx. 1 g / dtex, and the elongation at break increases 100% and can reach even higher values. With mechanical stress, these fibers can with their low strength and their low elastic

ho ity module of a deformation offer no resistance. The textiles become longer when they are subjected to tensile stress, for example, or bulges form more stressed areas. Halogen-containing solvents, some of which are used in chemical or dry cleaning

If they are not used, these conventional polyvinyl chloride fibers swell strongly. One treatment therefore, with perchlorethylene, textiles made from these fibers shrink considerably and become unusable.

The negative properties of conventional polyvinyl chloride fibers listed here can be explained by the low glass transition temperature Tg of approx Increasingly, a syndiotactic linkage of the vinyl chloride molecules (]. PoL ScL 39; 321 to 334) occurs. At the same time, the number of chain branches decreases (Malcromol. Chemie 95 (1966), 40 to 51) Significant increase in the crystallization capacity of the polyvinyl chloride produced at low temperatures and thus lead to improved dimensional stability of the objects made from this polyvinyl chloride when heated and in halogen-containing solvents.

In view of the steric structure, preferably methods of infrared spectroscopy are used to distinguish the polyvinyl chlorides (Tiefteraperatur-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 (JA C p. 82, (1960) p. 749) the infrared absorption ratio of the CCl Oscillation bands at 635 cm- 'to 692 cm- ¹ are used, the band at 635 cm-' being assigned syndiotactic and the band at 692 cm- 'isotactic structural units. The quotient of the extinctions at 635 cm- 'and 692 cm-' is referred to as the DS value (degree of syndiotacticity)

DS =

before measurand. This AFNOR viscosity index leaves calculate from

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

There are methods of making polyvinyl chloride fibers known in which vinyl chloride (Coj polymers at temperatures below 20 ° C with the help special catalyst systems and prepared from dimethylformamide after the wet or after the Dry spinning process are spun. These polymers are in high concentrations, as they are at Spinning solutions are common, i.e. more than 15% Polymer soluble in dimethylformamide.

Furthermore, the preparation of fibers of polyvinyl chloride having an AFNOR viscosity index of 450 or more known, the polymer is prepared at temperatures below 0 ⁰ C, and spun from dimethylformamide (vrl DE-AS 12 89 945).

The AFNOR viscosity index is not an internationally accepted solution for the characterization of polyvinyl chlorides

-I.

ι solvents

■ d. h, from the specific viscosity divided by the ίο measurement concentration, which according to the standard is 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 [ή ] are calculated :

'Jspec.

The Huggins constant Ich necessary for this calculation was determined by Cernia unu Ciampa for polyvinyl chloride to be 0.4 (J. PoL ScL 41 (1959) p. 75). The concentration C in the Huggins equation is given in the dimension gram / deciliter. It can be seen when the calculation is carried out that the AFNOR index of 450 has a viscosity number of

[η] = 3.0 — corresponds to

Since the polyvinyl chloride of the aforementioned DE-AS has 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 must have a low degree of syndiotacticity or a low crystallization capacity 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

Furthermore, processes for the production of threads from polyvinyl chloride are highly syndiotactic degrees 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

so 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

Molecular weight of 120,000 results in a maximum [ή] of 1.95.

Polyvinyl chlorides with these relatively low viscosity numbers can only then be incorporated into fibers particularly good properties, d. H. high dimensional stability in boiling water and containing halogens Spinning solvents when the polynurisates one have an extraordinarily high level of DS value or crystallizability. Such polyvinyl chlorides are. usually at temperatures

bi produced from --45 ° C. This low polymerization temperature leads to high energy costs in the production process, which makes the process economically viable burden.

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 Her 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 into FIG Towards lower viscosities with 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 to an even greater extent in the case of polymers of higher viscosity.

As has been shown, the known methods adhere

I l ___ «» ll _ η I '1 L.! 'At ' D 'U.

/.Ui ι IV.I position vwii ι \ jij viiijuiiiisi luiaavi Ii viiii. i \ Ciiit.

of disadvantages. Partly the molecular weights are - '« of the polyvinyl chlorides used are extremely high. The DS value or the crystallizability these polymers must not be excessively high, otherwise their solubility and thus their economic viability the fiber production would decrease. With the -> '> 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 tear strength, 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 homopolymer or mixed polymer which, in addition to a DS value of 2.1 to 2.5 has a viscosity number [η] of 2.0 to 29 These threads and fibers preferably consist of a vinyl chloride homo- or mixed polymer which, with a DS value of 2.1 to 2.5, has a viscosity number [ή] 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 2.9 and a DS value of 2.1 to 25, which by redox-activated Fällungspo- ">" lymerisation of ^v inylchlorid - 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 ° 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 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) μ of a lithium or zinc salt has been produced

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 and threads according to the invention have a tear 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 method of production takes place

pnjrtKA ·. ETH ^ lari nn / J Patern HaHnrnh Haft **; n Vinvlr * hlririH- polymer with a viscosity number [η] of 2.0 to 23 and a DS value of 2.1 to 2.5, which is spun by redox activated precipitation polymerization of vinyl chloride - optionally together with at most 15 percent by ₁ - ¹ Vb of a comonomer - in alcohol / water mixtures at pH values in the range of 2 and 7, and at temperatures between -1O ⁰ C and

- 40 ⁰ C in the presence of (a) an initiator system of water 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

- is, (b) a complexing agent 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.

The DS value is determined by the method outlined above from the absorbances in the infrared at 635 cm- 'and 692 cm-'. Polymers that are at -10 ° C to -40 ° have a DS value of 2.1-23 C, are preferably made ⁰ -30 C at -15 ° C.

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

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 made in dimethylformamide. Obviously isi the interaction of the polyvinyl chloride chains mr

a high percentage of syndiotactic sequences and high in comparison to commercially available polyvinyl chlorides viscosity number so that the solvating power of the Dimeihylformamids even at temperatures of 120 to 150 ⁰ C is not sufficient GRód that solve polymers.

In the case of the polyvinyl chloride used according to the invention it is not only about homopolymers di.s 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 thread 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-methacryloylaminobenzene-N- (benzenesulfonyl) sulfonamide or methacrylic acid. Other polymers can also be added to the polyvinyl chlorides to improve the colorability to enhance. Such additives must not, however, exceed 15% by weight.

This means that highly syndiotactic polyvinyl chlorides - produced using a very economical polymerization process - are spun into fibers and threads.

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

The listed in column 1 of polyvinyl chloride samples is vinyl chloride homopolymers, which were polymerized at temperatures from -20 ⁰ C to -3O 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 most important measurement methods are described separately.

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

in rensgemäB about 03 come to 3.0 wt -% of peroxide, based on the monomer used, for 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:

Jn

Column 1: 2:

9:10:11:

12:

effective monomer concentration

the lower the molecular weights of the resulting present polymers. In which In the process, the concentration of starting radicals is essentially determined by the peroxide concentration in the reaction medium Under constant conditions it is true that the concentration of starting radicals is the Peroxide concentration is roughly proportional to the process and 14:

and 16:

Consecutive number of the polyvinyl chloride Viscosity number [»?] -

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, given 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

Boiling shrinkage KS in% of the initial length L ₀ ;

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

KS =

χ 100.

Shrinkage of the thread in trichlorethylene after 20 minutes at 40 or 80 ^° C., evaluation analogous to 12
The thread shrinks in air after 1 minute at 130 ^° C. or 150 ^° C., evaluation analogous to FIG.

1 sample

2 3 4th 5 Visc. DS value Conc Stretch Number [,,] tration Relation dl / g % 1.08 2.20 25th 1: 6.5 UO 2.29 23 1: 6.5

6th Fl

[g / dtexj

7th Dl

G TS

Wt%

1st group
1

1.4

1.65

11
14th

0.96
1.4

1 9 2 3 21 58 !! 581 KS ! 3 10 6th 14th 7th 15th 8th Therm o-lock 150 ° sample Vis k. DS-Werl Modulus of elasticity Cooker TC F I S. D 1 WS TS 130 ° -locations / .ung Number | _(/ | % Tri-Schr 12th 1 dl / g 4th kp / mm ² 5 40 ° [g / dtex] 90 ° % Wt% 8th IW t sample 1st group Conc Stretching 3.5 / 9 1 1.64 2.30 tration 135 Relation 2.5 5 2.7 39 11 0.84 5 8th 2 1.72 2.37 % 150 0.5 3 2.1 31 11 0.68 5 6th 1st group 3 1.84 2.32 210 2 T 3.15 28 9 0.63 3 5 3 4th 1.92 2.35 19th 175 1: 11 1 1 3.4 30th 9 0.20 2.5 4th 5 20.5 225 1: 8 0 0.5 30th 1.5 5 6th 2.04 2.22 20th 240 I: 8 1 3.65 27 9 0.29 0 2 6th 2nd group 2.14 2.3 i 20th I: 11 0.5 4.1 ΙΛ
y 0.20 0 0 2nd group 7th 2.24 2.45 275 0 0 4.1 22nd 8th 0.40 0 2 7th δ 2.30 2.50 19th 340 1: 10 0 1 3.8 25th 9 0.40 0.5 2.5 8th 9 2.60 2.10 iv 355 i: ϊ 1.5 0 G 3.85 18th 9 0.32 1 1.5 9 10 2.69 2.25 18.5 320 1: 10 0 1 3.55 20th 8th 0.27 0.5 0 10 11 2.80 2.30 17.5 315 1: 10 0.5 2 3.9 23 9 0.41 0 11 12th 15.5 290 1: 11 0 1 22nd 0.5 12th 13th 3.00 2.10 14.5 310 I: 10 0 3.2 17th 7th 0.99 0 2.5 13th 3rd group 3.09 2.33 15th 1: 9.5 0 2.95 8th 0.37 2 2 3rd group 14th 3.24 2.40 255 } 0 3.0 20th 10 - 1 3 14th 15th 3.42 2.35 13th 220 1: 10 0 1 3.2 25th 8th 0.44 3 3! 15th 16 3.62 2.44 12.5 235 1: 9 1 0.5 2.8 23 8th 0.40 2.5 16 17th 9 10 12.5 240 1: 7 0.5 2 28 16 17th IK F2 D2 11 210 1: 8.5 2 24 18th 11 1: 9 g / dtex % 0.7 53 42 2.2 33 1.55 38 2.5 29 2.65 32 2.9 32 3.5 22nd 3.6 24 3.2 28 3.2 30th 2.8 33 3.3 27 2 ^ 32 22nd 32 2.4 30th 2.6 28 12th 29

The polyvinyl chloride and polyvinyl chloride filaments listed in the table are divided into three groups. The serial numbers 1 to 6 are below the viscosity numbers, 7 to 13 are within and 14 to 18 are above the range according to the invention. The DS value of all products is almost the same and lies between 2.1 and 2J5, i.e. Il, within the claimed range.

Some of the values listed, which were determined on the spun threads, are special indicative of the value of the present invention. If you compare the tensile strength of the drawn threads with the viscosity number, you get a picture as shown in FIG. 1. On the ordinate are the Viscosity numbers of the individual polyvinyl chlorides 1-18 and the maximum achievable thread strengths from column 6 of table 1 are plotted on the abscissa. at

Aar r) arct «» 11iin <y At * r <»in7Alnf» n MpRruinlrtP pruiht sirh

clearly a broad maximum of the thread tensile strength in the claimed range of the viscosity number between [η] = 2.0 and [η] = 3.0 ^.

In principle, FIG. 2 shows the same relationship in the case of the threads shrunk in boiling water, the tensile strength of which is shown in column 9 in Table 1 was taken. After the shrinkage process, the overall tear strengths are low Level.

The properties of the threads made of polyvinyl chlorides with viscosity numbers [ij] <2 [beta] are generally to be assessed less favorably in comparison with the threads according to the invention. These samples correspond to the threads produced according to DE-AS 16 69 370 and US Pat. No. 33 88 201.

With a viscosity number [η] = 1.08, the thermostatic ^ üitut Schlsch * sie ^ ** "* ⁰ *** ^ ¹ * *""s * ι * ⁰ * r«, i - ι η Aoe κΐΐνοαιι the products of the invention. also, show the shrinkage values in boiling water, in trichlorethylene at 40 ⁰ C and at 80 "C and in air at 130 ° C and 150 ° C, that polyvinyl chloride having viscosity numbers [η] of 2.0, the described after Processes were produced and have a comparable DS value, exhibit less favorable behavior.

The strength of the threads in the third group, i.e. h_ 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 but of the relationship between viscosity and the maximum possible spin concentration is shown This maximum possible spin concentration results from the solubility of the polyvinyl chloride in cyclohexanone at 150 through 156 ⁰ C, that is, at the boiling point of the Cydohexanons and the gelation of the solution upon cooling.

With higher concentrations, the spinning solutions tend to gel quickly, and it can spin disorders kommea The gelling temperature was 130 ⁰ C, preferably not exceed 115 ⁰ C. The spinning solution concentrations given here are chosen so that the gelling temperature is around 115.degree.

One can see the F i g. 3 that the maximum spinning solution concentrations of the polyvinyl chlorides with a DS value mn 2.4 at a viscosity number of [η] - 23 fall below 154b. 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 according to

the wet as well as the dry spinning process can be obtained. Will be used for both spinning processes 15 to 20% gel-free spinning solutions of the highly syndiotactic polyvinyl chloride or a copolymer -, made from at least 85% vinyl chloride at a temperature of 130 to 155 ° C in cyclohexanone Den Pigments, fillers, stabilizers or other products can optionally be added to the spinning solutions. When wet spinning, the spinning mass is through the

ίο the 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 -> or -monoethyl ether pressed The resulting threads are in two stages after intensive washing to improve orientation and crystallinity stretched. Pre-stretching is carried out in hot water and post-stretching at temperatures

.Ό between 100 ° C and 160 ° C on a heated roller, carried out in hot oil, superheated steam or hot air. The respective total stretching ratio is as shown in Table 1 shows, between 1: 9 and 1: II, in rare cases even above. Then the

r> Threads still below 180 to 220 ° C in air or steam

Heat set tension. To improve the heat

and solvent resistance are final the threads shrunk in water from 100 to 120 ° C.

Even with the dry spinning process, the spinning hole

) o solution have a temperature of 100 to 120 ⁰ C in order to avoid gelling of the solution and thus spinning problems. The spinning solution is pressed out through the heated nozzle into a spinning shaft heated with air at 150 to 220 ° C, and the resulting threads

j5 are taken at a withdrawal 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

■ 40 reason for their good properties, such as the high one Strength and elongation, the higher. Modulus of elasticity, the very good resistance to organic Solvents and boiling water, the excellent dimensional stability at higher temperatures doors and the inherent flame resistance inherent in PVC, all the usual textile. Processing processes are supplied. This further processing can be used as pure processing or in a mixture with natural or synthetic fibers, such as. B. wool, Cotton, acrylic fibers, zeiiwoiie and acetate fibers are made. Possible areas of application are primarily in the field of heavy-duty textiles such as carpets, especially long pile carpets, decorative fabrics, Upholstery materials, blankets, etc. The good heat return hold and the soft, warm grip allow use 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 2, B. for feeding bottles and protective clothing.

Below are the measurement methods used to characterize the polyvinyl of the invention chloride fibers make a significant contribution, in detail tert:

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

and 692 cm ~ 'and formation of the ratio of

DS =

certainly.

Foils are used for the measurement according to the following Technique to be produced:

It contact each dissolved 300 mg of polyvinyl chloride in 5 ml of cyclohexanone at 140 ⁰ C, the solution is rapidly cooled and poured onto the etched with hydrofluoric acid to the glass plates the wedge-shaped layers. This wedge shape ensures that areas of the film are created which, when measured by IR, produce optimal band intensities in the range of 25% to 50%. 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 Perkin-Elmer 42) The evaluation is carried out according to the baseline method, with the baseline between the Minima at 775 cm - 'and 555 cm -' is placed.

The viscosity number [η] is determined by known methods polyvinyl chloride is in the concentration range of about 0.2% to dissolved c = c = 0.6% in cyclohexanone at 130 ⁰ C in 30 minutes, the viscosity measurement is carried out at 25 ⁰ C in an Ubbelohde -Viscometer from Schott and Gen. with capillary I. At least three measurements at different concentrations are necessary from which

'/ «Rl -

■ Solution

solvent

_S pa. — nrti— \ emerges from the plot-2Mjt_ against C one then obtains

by extrapolation to C - 0 the viscosity number [ijl (The extrapolation to the velocity gradient G = O can be carried out in the present molecular weight range be ignored).

Thermostabilities are determined according to the Geddes method (European Pol. Journal, 3 (1967) pp. 267 to 281) measured. A sample of 625 mg polyvinyl chloride is used The heated at 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 an according to the invention using syndiotactic polyvinyl chloride

A polymerization vessel equipped with a stirrer is loaded as follows (all data are parts by weight):

400 tsp. Methanol, 900 tsp. Deionized water, 0.2 t. Copper sulfate, 0.2 tsp sodium lauryl sulfate, 0.125 TI. Ethylenediaminetetraacetic acid, 0.6 TI. Sodium hydroxymethyl sulfinate and 0.1 TI. n-HjSCv

After the reactor was purged with nitrogen and cooled to -25 ⁰ C, it transmits to the stirred solution, a mixture of 20 TL of methanol, 20 TI. desalinated water and 1 TI. 30% hydrogen permeability

oxide a. After 30 minutes, 300 teaspoons of vinyl chloride are added added, whereby the tar temperature in the reaction chamber must be constant -25 "C. In the course of 2 hours. a mixture of 180 teaspoons of methanol, 180 teaspoons of demineralized water, OJB teaspoon of sodium hydroxymethylsulfinate, 0.06 teaspoon of sodium aurybulfate and one further VoratsgeÜB emc mixture of 200 tsp Methanol, 200 teaspoons of demineralized water and 2 teaspoons of hydrogen peroxide (30%) are added. Then another 200 μl of vinyl chloride are poured into the reaction vessel pressed in. 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, washed with water and dried. 305 teaspoons (61% of theory) of a white polymer with a viscosity number of 2JS5 and a DS value of 2 ^ 0 are obtained.

example 1

100 teaspoons by weight of the polymer described under instruction A (viscosity number 23, DS value 230) at 140 ° C. in 505 teaspoons by weight of cyclohexanone with the simultaneous addition of 1.5 teaspoons by weight of an organic tin stabilizer. The spinning solution obtained is nitrated at 135 ° C. and heated by means of a Gear pump pressed through the also heated spinneret. Through the 300-hole spinneret with a Hole diameter of 0.08 mm are delivered per minute 38 ^ g of solution, which corresponds to 635 g of PVC

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 : 3/5 , dried with circulating air at 120 ° C in a heating cabinet and then stretched on a heating roller at! 50 "C iai Yerhlhnis !: 3.0, provided with an antistatic preparation and 63 m / min wound onto spools

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

Titer - 865 dtex / 300

Strength - 3 pounds g / dtex Elongation at break - 9.5% Modulus of elasticity - 725kp / mm *

In a further operation the yarns ii steam at 220 ⁰ C under tension 4 see thermoset Subsequently, the threads are cut and untei pressure in water of 120 ⁰ C treated with s shrink occurs from about 15 to 20%

The tear strength and elongation at break of the staple fibers are measured using the Fafegraph type 4 a clamp of 20 mm.

Titer 33dtex 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 I3O * 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 230 are dissolved in 425 parts by weight of cyclohexanone with the addition of 1.5 parts by weight of an organic tin stabilizer at 140 ° C dissolved 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 Modulus of elasticity

580dtex200

4.15g / dtex

8th%

1010 kp / mm *

Titer l120dtex / 200 Tear resistance 3.7 g / dtex Elongation at break 9% Modulus of elasticity 680 kp / mm ² it staple fibers had to conclude he features: Titer 6.6 dtex strength 3.1 g / dtex Elongation at break 35% Modulus of elasticity 300 kgf / mm ² Shrinkage in boiling water 0% Shrinkage in trichloro 40 "C ethylene 0 ^% Shrinkage in air of 130 ° C 0%

Example 4

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

230) are dissolved at 140 ° C. in 525 parts by weight of cyclohexanone containing 14 parts by weight of the organic tin stabilizer

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 ^° C. The threads are pulled 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:

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

Titer 33 dtex

Strength 3.6 g / dtex

Elongation 24%

Modulus of elasticity 400 kp / mm ² shrinkage in boiling

Water (KS) 0% shrinkage in trichlorethylene at 40 ° C 2% shrinkage in air at 130 ⁰ C 0%

Example 3

100 parts by weight of a polymerized according to procedure A polyvinyl chloride having a viscosity of [η] = 230 and a DS value of 23 at 140 ⁰ C in 470 parts by weight of cyclohexanone containing 13 parts by weight of an organic tin stabilizer, solved

In this experiment, the precipitation bath consists of 50% water and 50% ethylene glycol. The threads are withdrawn from the nozzle (200 holes / 0.1 mm) at 7 m / min, washed, drawn 1: 4.0 in boiling water, dried and drawn at 150 ^° C. 1: 2.25.

The measurements gave the following values:

Titer 190 dtex strength 3.7 glö \ ~ .x Elongation at break 8th% Modulus of elasticity 680 kp / mm ² e obtained according to Example 1 Staple fibers shark following properties: Titer 3.0 dtex strength 33 g / dtex Elongation at break 3.0% Modulus of elasticity 350 kp / mm * Shrinkage in boiling water O ₁ OvO Shrinkage in trichloro ethylene at 40 ° C Shrinkage in air from 130 ⁰ C 0%

Comparative example 1

100 parts by weight of a polyvinyl chloride prepared as in accordance with regulation A, but with a viscosity number of [η] = 3.25 and a DS value of 2.40 are at 14O ⁰ C in 700 parts by weight of cyclohexanone, in the 53 Parts by weight of an organic tin stabilizer are included, dissolved according to example !! the threads are spun, washed and drawn, a draw ratio of 1: 3.0 in the water and a draw ratio of 1: 2.17 ^{at 150 ° C. being maintained.}

The following textile values were measured:

Titer

Tear resistance strain Modulus of elasticity

880dtex / 300

2.9 g / dtex

10%

600 kp / mm *

The get also according to Example 1 ;, s staple fibers ■ • ο can be characterized with the following values:

filter 33 dtex

Strength 2.4 g / dtex

Elongation 30%

E-module 240 kp / mm ² Shrinkage in boiling

Water 0%

Shrinkage in trichloro

ethylene at 40 ° C 2%

Shrinkage in air

from l30 ° C 1%

Comparative example 2

In this experiment, polyvinyl chloride with a viscosity number [η] = 1.6 dl / g and a DS value of tv> 2.4 is used. 100 parts by weight of this polyvinyl chloride are dissolved in an organic tin stabilizer 410 parts by weight of cyclohexanone at 140 ⁰ C with the addition of 13 parts by weight. The analogous to Example 1 wet

sponnenen yarns in boiling water 1: stretched 2.86: 3.5 and at 150 ⁰ C1
Threads are obtained with the following properties:

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

Ε module 210kp / mm2 shrinkage in boiling

Water 0.5% shrinkage in trichloro

ethylene at 40 ° C 2% shrinkage in air

from 130 "C 4%

For this purpose 3 sheets of drawings

Claims (2)

Claims; 1. Threads and fibers made of vinyl chloride horopolymers or copolymers that contain at least 85% by weight vinyl chloride and have a high DS value resulting from the usual infrared extinction ratio, with a high modulus of elasticity, high tensile strength, low elongation and high dimensional stability in boiling water and halogenated hydrocarbons, characterized in that the threads and fibers consist of a vinyl chloride homopolymer or copolymer which, in addition to a DS value of 2.1 to 2, has a viscosity number [η] of 2.0 to 2 $ owns 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 [η] of 2.0 to Z9 and a DS value of 2.1 to 2.5, which is caused 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 ranging from 2 to 7 and at temperatures between - l &'C and -40 ⁰ C in the presence of