DE2158581A1 - FIBERS AND FEDES MADE FROM SYNDIOTACTIC POLYVINYL CHLORIDE - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN- Bayerwerk

Central area 0 4 '"ifV- · ¹ " 071 Patents, trademarks and licenses

Reu / Pt

Syndiotactic polyvinyl chloride fibers and filaments

The invention relates to flame retardant fibers and threads syndiotactic polyvinyl chloride with excellent dimensional stability in boiling water and halogenated ones Chemical cleaning solvents, for example in Triehlor- and perchlorethylene.

Polyvinyl chloride fibers are among the oldest industrially produced synthetic fibers. In comparison with fibers made of polyamide, polyester and polyacrylonitrile, the textile use of polyvinyl chloride fibers has remained of secondary importance, as the polyvinyl chloride fibers previously used had some deficiencies that limited their possible uses Λ

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 have only 50 - 60 % of their original length in boiling water »

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These properties create great difficulties and limitations when processing these fibers according to the usual methods in the textile industry, whenever a thermal Treatment of fibers and threads or textiles, structures, e.g. B. carried out in fixing processes or in dyeing must become. When using articles made of these polyvinyl chloride fibers, strict care must be taken to prevent any impact Higher temperatures are avoided, even under conditions that are common for textiles made of natural fibers or for others Synthetic fibers are completely harmless, deformations are caused by fiber shrinkage.

Attempts to achieve the dimensional stability of conventional polyvinyl chloride fibers and filaments by heat treatment have had little success. With this heat treatment, the tensile strength of the fibers drops to approx. 1 g / dtex, the elongation at break increases to 100 % and can even reach higher values.When mechanical stress occurs, these fibers, with their low strength and low modulus of elasticity, cannot resist deformation . The textiles become longer when they are subjected to tensile stress, for example, or bulges form at more heavily stressed areas. Halogen-containing solvents, some of which are used in chemical or dry cleaning, swell these conventional polyvinyl chloride fibers to a great extent. Treatment with perchlorethylene therefore causes textiles made from these fibers to shrink considerably and become unusable.

The negative properties of the conventional polyvinyl chloride fibers listed here can be explained by the low freezing ^{temperature Tg of approx. 65 °} C. and the low crystallization capacity of the conventional polymerisation ^{at temperatures above 20 ° C.}

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explain the polyvinyl chloride produced by the process. It is known that with decreasing polymerization temperature are increasingly a syndiotactic linking of vinyl chloride molecules (J. Pol Be ^ £;.. 321-33 ² O takes place same time, the number increases the chain branches from (Makromol.Chemie £ 5 (1966.. ), 40 - 51) These changes in the microstructure of the polymer cause a 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 of the, preferably methods of infrared spectroscopy at low temperatures (below 0 ⁰ C) produced polyvinyl chloride (low-temperature polyvinylchloride) of polyvinyl "riden prepared at temperatures above 0 ⁰ C are used to distinguish.

As already described, there is a direct relationship between the polymerization temperature and the proportion of syndiotactic sequences in the polyvinyl chloride. Both from Fordham

(J. Pol. Se. 44 (1959) * pp. 73-82) and by Burleigh

(JACS 82, (1960) p. 749) the infrared absorption ratio of the CCl oscillation bands at 635 cm "1 to 692 cm ^{-1 is} used to characterize the syndiotactic degree, the band at 635 cm being syndiotactic and the band at 692 cm " ¹ isotactic structural units can be assigned. f

The quotient of the extinctions at 635 em " ¹ and 692 cm" ^ is referred to as the DS value (degree of syndiotacticity).

DS =

^E 635 cm " ¹

^E 692 cm " ¹

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The degree of syndiotacticity is generally used to identify low-temperature polyvinyl chlorides. However, in some publications that the production of polyvinyl chloride fibers from low-temperature polymers for Have content, no information on the degree of syndiotacticity (DS value) made. In these cases, the steric structure or the crystallization capacity must be influenced indirectly via the fiber properties the described polyvinyl chlorides are closed.

Processes for producing polyvinyl chloride fibers are known in which vinyl chloride (co) polymers are produced at temperatures below 20 ^° C. with the aid of special catalyst systems and are spun from dimethylformamide by the wet or dry spinning process. These polymers are in high concentrations, as are customary in spinning solutions, ie more than 15 % polymer soluble in dimethylformamide.

It is also known to produce fibers from polyvinyl chloride with an AFNOR viscosity index of 450 or above. The polymer is produced at temperatures below 0 ^° C. and spun from dimethylformamide. (DAS 1 289 945) For the characterization of polyvinyl chlorides, the AFNOR viscosity index is not an internationally customary parameter. This AFNOR viscosity index can be calculated from

solution

solvent

i.e., 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 (J.A. C. p. 64 (1942), (2716) can be found in the basis of the AFNOR viscosity index

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One-point measurement of the viscosity number ^ ~ | be calculated: "n spec.

The Huggins constant k ^ required for this calculation determined Cernia and Ciampa to be 0.4 for polyvinyl chloride (J.Pol. Sci. 4l_ (1959) 3. 75). The concentration C in the Hugginsschen The equation is to be given in the dimension gram / deciliter. When performing the calculation, it can be seen that the AFNOR index of 450 corresponds to a viscosity number νοηΓ ^ Ί = 3.0 -.

Since the polyvinyl chloride of the patent mentioned has an AFNOR viscosity index of at least 450, corresponding to a viscosity number of at least 5.0 - has a high degree of polymerization and is soluble in dimethylformamide, it must be concluded that it has a low degree of syndiotacticity or a low crystallization capacity Polyvinyl chlorides with a viscosity number above 3, which have a high degree of syndiotacticity and a high crystallizability, are very poorly soluble. The concentration of the spinning solutions must be below 12 % . In this case, the recovery costs for the solvents are very high in relation to the amount of fiber produced , and an economical production process is no longer guaranteed.

Further, a method for preparing filaments from polyvinyl chloride g syndiotacticity degree with a molecular weight from 50,000 to 120,000, preferably 60,000 to 85,000 known (German Auslegeschrift 1,278,066). According to the information in the cited patent, these molecular weights correspond to viscosity numbers of 1.0-1.9 *, preferably 1.5-1 * 6 -— ·. Polyvinyl chlorides with these relatively low viscosity numbers

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can only then be made into fibers with particularly good properties, i.e. high dimensional stability in boiling water and those containing halogens Spin solvents when the polymers have an extraordinarily high level of DS value or crystallizability exhibit. Such polyvinyl chlorides are normally produced at temperatures of -4-5 ° C. This deep Polymerization temperature leads to high in the production process Energy costs that put a strain on the economic viability of the process.

As has been shown, the known methods of manufacture adhere polyvinyl chloride fibers have a number of disadvantages. Part the molecular weights of the polyvinyl chlorides used are extremely high. The DS value or the crystallization capacity these polymers must not be excessively high, otherwise their solubility and thus the economy of fiber production were losing weight. In the process for the production of fibers from hochsyndiotaktischera polyvinyl chloride must be very work at low temperatures. This process is burdened with high energy costs.

The invention now filaments and fibers made of a polyvinyl chloride Tieftemperaturpolymerisat or -mischpolamerisat containing at least 85 wt.% Vinyl chloride, with a Viskositätszahirno "! 2.0 vis 2.9 and a DS value of 2.1 to 2.5 · Preferably, the viscosity number Γηη I in the range of 2.2 to 2.7. These filaments and fibers are thus characterized in that they are prepared a vinyl chloride polymer containing at least 85 wt.% of vinyl chloride, which is a Viskositätszahlprf] of 2.0 to 2.9 and a DS value of 2.1 has to 2.5, is spun, the redox-activated by precipitation polymerization of vinyl chloride-optionally together with not more than I5 wt.% of a comonomer in alcohol / water-Ge

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mixing is produced, the polymerization at pH values in the range of 2 -and "J at temperatures between -10 ⁰ C and -40 ° C in the presence of (a) an initiator or system of hydrogen peroxide and an organic sulfinic acid , wherein the amount of peroxide compound 0.3 to 3.0 wt. $ based on the monomers used, (b) a complexing agent of Cu-II ions and ethylenediaminetetraacetic acid and (c) a lithium or zinc salt is used.

The threads and fibers have high strength with low elongation at break, high heat resistance and good dimensional stability in the halogen-containing solvents of chemical cleaning. You can look for a very economical one Process are produced. "

The polyvinyl chloride fibers and threads according to the invention have a tensile strength of 2.2-3 * 5 g / dtex, an elongation at break of 25-55 %, a high modulus of elasticity, a shrinkage in boiling water of less than 2 % and a low shrinkage in the halogen-containing ones Chemical cleaning solvents.

Another object of the invention is a process for the production of filaments UIID fibers of vinyl chloride homopolymers or copolymers containing at least 85 wt. # Vinyl chloride, vinyl chloride by spinning g

polymerization, which is characterized in that a vinyl chloride polymer with a viscosity number f'frJ from 2.0 to 2.9 and a DS value of 2.1 to 2.5 is spun »

The process for producing polyvinyl chloride fibers and filaments with high strength, low elongation at break, high heat resistance and with good dimensional stability in halogen-containing solvents by spinning polyvinyl chloride is characterized in that a polyvinyl chloride or a copolymer with at least 85 wt, # vinyl chloride content

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is spun, which is produced by redox-activated precipitation polymerization of vinyl chloride - optionally together with a maximum of 15 wt / l of a comonomer in alcohol / water mixtures, the polymerization at pH values between and.7 - preferably between 2 and 6- and at temperatures between -10 ⁰ C and - ^ O ° C in the presence

(A) an initiator system composed of hydrogen peroxide and a organic oulfinic acid, in which the amount of peroxide compound 0.3 to 3.0 wt.; I -related to the used Monomeric is

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

(c) a lithium or zinc salt,
is carried out.

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

The DS value is determined by the method described above from the absorbances in the infrared at 635 cm and 692 cm · "" *. A DS value of 2.1 - 2.5 have polymers which preferably at ⁰ C to -I5 at -10 ⁰ C to -40 ⁰ C - 30 ⁰ C have been prepared.

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 and peroxide concentration. For low temperature vinyl chloride polymerization is one

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BATH

such a high conversion rate is quite unusual. In general, yields of about? 0,? Are given for corresponding processes. The thermal stability of the polymers that are used in accordance with the invention in fiber production is extremely high. In a nitrogen stream 0 ⁰ C in three hours is only one "# split the existing in unstabillsierten polymers hydrogen chloride at l?.

In contrast to the low-temperature polyvinylchloride known to date, the polymers of the present invention do not dissolve to any appreciable extent in dimethylformamide. A spinning solution cannot be made in dimethylformamide. Obviously, the interaction of the Polyvinylchloridketten with a high percentage of syndiotactic sequences and high in comparison "with commercial polyvinyl chlorides viscosity number is so large that the solvating power of the Dirnethylformamids even at temperatures of 120-150 ⁰ C is not sufficient to dissolve the polymer.

The polyvinyl chlorides of this invention are

not only about homopolymers of vinyl chloride, but also about its copolymers. These must contain at least 85 % vinyl chloride. Ethylenically unsaturated compounds that make the threads easier to dye can be used as comonomers. Such vinyl compounds are e.g. B. vinyl acetate, acrylic ester, methacrylic ester and ^ Acrylonitril.Durch these comonomers the colorability with disperse dyes is increased. Modification with vinyl compounds containing sulfonic acid, disulfimide or carboxyl groups improves the absorption of basic compounds. Dyes. Such

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BATH

Vinyl compounds üind ζ. B. tttyrolsulfonsaure, Methalylsulfon-. acid, 3-foethaorylaylajninobenzol-N- (benzenesulfonyl) suifona] iiid or methacrylic acid. The polyvinyl chlorides of the present Invention, other polymers can also be made to ^ emi improve the dyeability. Such additives are allowed Do not exceed 15 wt. #.

In this way, highly syndiotactic polyvinyl chlorides can be produced after a very economical high polymerization process Fibers and threads are spun.

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

W 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. Explanations of a general kind on the viscosity numbers 1 ¹ Q (column 2) and the DS value (column 3) have already been made. Experimental details of the most important measurement methods are described separately.

The molecular faces of vinyl polymers can be determined via the Concentration of * starting radicals, based on the effective monomer concentration, change. The greater the ratio

Concentration of starting radicals effective monomer concentration

W is, the lower the molecular weights of the resulting present polymers are. In the process, the concentration of starter radicals is essentially determined by the peroxide concentration in the reaction medium. Under constant conditions, is considered that the concentration of starting concentration of radicals is approximately proportional Peroxidkon-. A method according to come about from 0.3 to 3 · 0% by weight of peroxide, based on the monomer used · for use.. Preferably, 0.35 to 1.5 wt _o # peroxide, based on monomer employed.

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The polyvinyl chlorides were all made using the same procedure spun into threads, which in turn all use the same post-treatment process were subjected. Spinning and post-treatment processes will be communicated below *

Serve to explain the measured values in the individual columns the following information:

Column 1: Consecutive number of the polyvinyl chloride 2: Viscosity number [T |] ~
5: DS value

4: concentration of the spinning solution, % solids in the solution ■

5: Maximum possible stretch ratio without breaking ™ Single thread capillaries

6: Tear strength of the drawn threads before an aftertreatment

7: Elongation at break of the drawn threads before an aftertreatment

8: elimination of hydrogen chloride in a nitrogen stream at 170 ⁰ C within 60 minutes * specified in% by weight, based on total PVC.

9: Tear strength of the drawn threads after a treatment time of 50 minutes in boiling water

10: Elongation at break of the drawn threads after a treatment time of 50 minutes in boiling water

2
11: modulus of elasticity in kp / mm;

from the force / strain diagram in the linear part

at low elongation determined ^v g

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

L ^ corresponds to the length of the thread after one Tension-free treatment for 10 minutes in boiling water

KS = - χ 100
and 14: shrinkage of the threads in trichlorethylene after 20 minutes

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ΛΙ

at 40 or 8θ ⁰ C, evaluation is analogous

MMPF of the filaments in air after] and 150 ⁰ C Evaluation analog 12

15 and 16: Shrinkage of the threads in air after 1 minute at 1 ^ 0 ⁰ C

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A 3

QJ CJ O ON co VO LP> LPv CM O C. CVI LPv LPv O LPv LPv CM KN KN VO fHO
τ- .0 O νο ¹ Xi τ- τ- T ^ CM T- O CV) O LfN I. OT T- ο χχ LPv LPv LPv Ss O LfN φ U
M Φ
-ρ ρ-
CQ co ο- LfN LfN NN CM O O O LPv O τ- KN CM τ- φ Ο I ^ CO O ο O LPv m O t ~ O O- O CM KN ω is φ KN NN CM KN KN CM CM CM τ- CM NN CV) O LfN CM CM CM ■ «ί- ϋ co vf CQ-P IfN CM CM CVI CM CM LfN ι σ U ir » KN CM T- O τ- τ- Ο T " O O CM CM -HO
KN O M O O CM T- O T- τ- EH Eh vr • Ρ U.N. LPv IPv IP » Very. Φ KN CJ O CM τ- Ο LP » _O O O LPv O O * - O CM Ui XX \ Α O O O O T— T-MO cn O O O LPv O O LPi O O LfN O O rH
O Θ M rHf-1 fclC KN LPv Γ— CM LPv LPv cvi LPv O τ- LPi O KN ■ «st- T- CM tQ X \ ί-Γ \ τ- CM τ- CM CM f- KN KN KN \ - ON KN LPv CM CVI CV) CM T- j pv ί »t-Ί -ti CVI KN CM CVI CM φ CJ NN CO OS CM CM ^. co O-- O ω ON O ". Ϊ. τ- O
U
(U LPv KN KN CJ NN CVI CM CVI CM O KN CM CM CM KN CM CM LPv LPv NN KN KN KN NN Φ O- CJ CM LfN IPv VO LPv VO CVI KN Vt VO CM CM -P O t - Cj τ- CM CM ON KN KN KN CM CO KN LPv CM CV) CM CVI VO ■ "51" m K "s O CVi O O O KN CJ τ- CVI CM ^ J. O ON -J CO VO VO CJ CTN CVl νί- CM O- Vt- CN f- "^ vj- CO CT O τ ~ O ο O O CM O ° Ο KN OJ O ON NN O O Γ
Ge \ T- Vj- τ- τ- ON ON O ON co ON O O ON O O O co CO T- ON ON CO C- CO Pl LfN LPv VT VO ο- τ- τ- Vf LfA τ- T- co LPv LPv ON LPv O CM co T " X - CM CM KN NN VO Vf V ₁ - KN CO LfN KN CM ON KN KN CM LT, tr ·. NN ** NN KN LfN KN CM LPv «Ι χ— ^ - τ- O O VO t— cn CO x— O χ— ^ - t ~ O CTN O O- ω ON T ~ τ- ON τ— LPi IPv LPv LPv LPv L- \ LPv *. KV ON ο O ON ω O- IfN CVI ■ * " ON LiN vi " NN CVI O ON O ι— OJ LPv τ— IPv _O O O LPv CvJ CJ NN KN KN CJ KN Vj- LPi O LPv NN O NN vj- KN VJ- CJ OJ CJ CVI CJ CJ CM CM CM CM CJ CM KN CM CM CM CVI CM Oil CM CM co O ^. CJ ^. CJ ^. O O Vf CM CVI ο CM VO O- co CJN Vl- T- CVl KN O ON ω O ON CM Vf- VO τ— ^ - X— τ- <- O CM OJ CM VD VO CM O O KN KN KN CVt CVl CM KN NN τ- CVI KN Vf U.N. VO CO ON O KN VO O- co add • ι. O- äddi T- CM ■ vr LfN ms * v 'Z 3dd

The polyvinyl chloride and polyvinyl chloride filaments recorded in the table are divided into three groups. The serial numbers 1-6 are below in their viscosity numbers, 7-15 within and 14-18 above the range according to the invention. The DS value of all products is almost the same and is between 2.1 and 2.5, i.e. within the claimed range.

Of the values listed, which were determined on the spun threads, some are particularly characteristic of the Value of the present invention. If one compares the tensile strength of the drawn threads with the viscosity number, then offers a picture as shown in Figure 1. The viscosity counts of the individual polyvinyl chlorides are shown on the ordinate 1-18 and the maximum achievable thread strengths from column 6 of table 1 are plotted on the abscissa. In the representation the individual measuring points clearly show a broad maximum of the thread breaking strength in the stressed area the viscosity number between fT}] = 2.0 and [o ^] = 5.0 - ~.

In principle, Fig. 2 shows the same relationship with the threads shrunk in boiling water, their tear strength the 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 f rQ <2.0 are compared to those according to the invention To evaluate threads generally less favorable.

If the viscosity number is [Vr {= 1.08, the thermal stability is bad, it only reaches the level of

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ORIGINAL INSPECTED

1S

inventive products. Also, the shrinkage values show in boiling water, in trichlorethylene at 40 ⁰ C and at 80 ⁰ C and in air at IJO ° C and 150 ⁰ C, that polyvinyl chloride having viscosity numbers [V ^] below 2.0, the prepared according to the method described and have a comparable DS value, exhibit less favorable behavior.

The strength of the threads in the third group, ie threads made of polyvinyl chloride with a viscosity number greater than 3 »0, is at a high level, although not quite as high as in the area of the second group according to the invention. The same applies to the other values. In Figure 3, however, the relationship between the viscosity number and the maximum possible spinning concentration is shown. This maximum possible spinning concentration results from the solubility of the polyvinyl chlorides in cyclohexanone at 150-156 ^° C., ie 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 chosen so that the gelling temperature is approx. 115 ° C.

Figure 3 can be seen that the maximum spinning solution concentrations of λ polyvinyl chlorides having a DS value of 2.4 at a viscosity decrease νοη τγ £] = 2.8 under 15%. In this area, the economic viability of the process for the production of polyvinyl chloride fibers is no longer guaranteed.

The fibers of the invention can be used both after the wet as can also be obtained by the dry spinning process. For both

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Spinning method are 15 - 155 ⁰ C prepared in cyclohexanone - 20 $ strength by weight gel-free spinning solutions of high syndiotactic polyvinyl chloride, or a copolymer of at least 85% of vinyl chloride at a temperature of from the 130th Pigments, fillers, stabilizers or other products can optionally be added to the spinning solutions.

During wet spinning, the spinning mass is passed through the heated nozzle into a suitable precipitation bath, for example a binary or ternary mixture of cyclohexanone, water and a solubilizer or a mixture of water and glycol or glycol ether, such as. B. ethylene glycol, di- and triethylene glycol, ethylene glycol monomethyl or monoethyl ether pressed. After intensive washing, the resulting threads are drawn in two stages to improve orientation and crystallinity. A pre-drawing is performed 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. As can be seen from Table 1, the respective total aspect ratio is between 1: 9 and 1: 11, in rare cases even higher. Subsequently, the filaments are still at 180 - heat set 220 ⁰ C in air or steam under tension. To improve the heat and solvent resistance, the threads are then shrunk in water at 100 - 120 ° C.

Also in the dry spinning process, the spinning solution has a temperature of 100-120 ⁰ C hold to avoid gelling of the solution and spinning disturbances. The spinning solution is passed through the heated nozzle into a air of I50 - 220 ⁰ C squeezed heated spinning shaft and the threads are formed at a withdrawal speed of 100 - wound 300 m / min onto spools. The subsequent process steps of the aftertreatment correspond to the procedure described above.

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The fibers according to the invention can due to their good properties, such as high strength and elongation, high modulus of elasticity, very good resistance to organic solvents and boiling water, excellent dimensional stability at higher temperatures and the inherent flame retardancy of PVC can be added to all common textile processing processes. This further processing can be used as pure processing or mixed with natural or synthetic fibers such as 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, Decoration fabrics, upholstery fabrics, blankets, etc. The good heat retention capacity and the soft, warm handle 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, alkalis, solvents and atmospheric influences, e.g. filter cloths and Protective clothing.

Below are the methods of measurement, which contribute significantly to the characterization of polyvinyl chloride according to the invention, described in detail: g The DS value of the polyvinyl chloride of the polymers in the infrared at 655 cm and 692 cm and formation is calculated from the absorbances of the ratio of

cm

ds

^ 692 cm ^l

certainly.

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Foils produced 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.degree. The solution is cooled rapidly and poured onto glass plates etched with hydrofluoric acid to form wedge-shaped layers. This wedge shape ensures that areas of the film are created which, in the IR measurement, result in optimal band intensities in the permeability range of 25 % to 50 % . It is extracted twice for one hour with boiling methanol and then dried in vacuo.

The infrared measurement is carried out with a double-beam grating spectrophotometer (model Perkin-Elmer ^ 2). The evaluation is done according to the baseline method, whereby the baseline
will.

line between the minima at 775 cm "and 555 cm"

The viscosity number pv}] is determined by known methods. Polyvinyl chloride is dissolved in the concentration range from about c = 0.2 % to e = 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 the capillary I. At least three measurements at different concentrations are necessary from which

^ rel ⁼ ^ solution

* \ Solvent

^or * Ή spec. ⁼ n rel " ^Χ r goes.

The viscosity number Γη] is then obtained from the plot against C by extrapolation to C = O. (The extrapolation on the velocity gradient G = O can be neglected in the present molecular weight range)

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Thermal stabilities are measured according to the Geddes method (European Pol. Journal, 3 (1967) pp. 267-281). A polyvinyl chloride sample of 625 mg is heated ^{to 170 °} C. in a stream of nitrogen. The hydrochloric acid released in one hour at this temperature is driven with the nitrogen into a receiver, where it is absorbed by water and titrated with γττ = sodium hydroxide solution. Methyl red serves as an indicator. The information is given in% by weight of the hydrogen chloride split off , based on the initial weight.

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ZO

Example 1 ;

A polymerization vessel equipped with a stirrer is used charged as follows (all details are parts by weight):

^ K) O parts of methanol, 900 parts of deionized water, 0.2 parts of copper sulphate, 0.2 parts of sodium lauryl sulphate, 0.125 parts of ethylenediaminetetraacetic acid, 0.6 parts of sodium hydroxymethylsulphinate and 0.1 part of n ~ H _o £ 0 ^.

After the reactor has been purged with nitrogen and heated to -25 ° C Was cooled, a mixture of 20 parts of methanol and 20 parts of deionized water is added to the stirred solution and 1 teaspoon of 30 # strength hydrogen peroxide. After 350 min. 300 parts of vinyl chloride are added, the temperature in the reaction chamber being constant at -25 ° C. In the course of a mixture of 180 parts of methanol, 180 parts of demineralized water, 0.8 parts of sodium hydroxymethyl sulfinate, 0.06 Tl. Sodium Lauryl Sulphate and a mixture of 200 Tl. Methanol, 200 parts of deionized water and 2 parts of hydrogen peroxide (3O / 6%) are added. After that, again Pressed 200 parts of vinyl chloride into the reaction vessel. After 15 hours the polymer slurry becomes a mixture of 2000 parts of water, 20 parts of LiCl and 2 parts of sodium pyrosulfite discharged with stirring.

The precipitate is spun off, washed with water and dried. 305 parts (61 % of theory) of a white polymer with a viscosity number of 2.55 and a DS value of 2.30 are obtained.

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Example 2:

100 parts by weight of the polymer described in Example 1 (Viscosity number 2.5, DS value 2.30) are at lAo ° C in 505 parts by weight Cyclohexanone with the simultaneous addition of 1.5 parts by weight an organic tin stabilizer solved. The spinning solution obtained is filtered at 135.degree and pressed through the heated spinneret by means of a heated gear pump. Through the 300-hole spinneret with a hole diameter of 0.08 mm, 38.5 g of solution are conveyed per minute, which corresponds to 6.35 g of PVC.

The precipitation bath consists of a mixture of 20 % cyclohexanone,

30 % isopropanol and 50 % water. The felling bath temperature I

is 60 ° C. The thread sheet is pulled off the nozzle at 7 m / min and then washed intensively in water at 60 ° -80 ° C. Finally, the thread bundles in boiling water in the ratio 1: 3.5 stretched, dried with recirculating air of 120 ⁰ C in an oven and then onto a heated roll at 150 ° C in the ratio of 1: 3.0, provided with antistatic preparation and 63 m / min wound onto spools.

The threads have, on a Wolpert EZR 3 tearing device

measured with a clamping length of 50 cm, the following properties:

Titer = 865 dtex / 300 '

Strength = 3.8 g / dtex

Elongation at break = 9.5 %

Modulus of elasticity = 725 kp / mm ²

In a further operation, the threads are exposed to ^{tension in steam at 220 °} C. for 4 seconds. thermoset. The threads are then cut and ^{treated under pressure in water at 120 °} C., with a shrinkage of about 15-20 $.

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I I DÖDÖ I

Zl

The measurement of the tensile strength and elongation at break of the staple fibers is carried out with the Fafegraph type 4 at a Clamping length of 20 mm.

Titer water (KS) 3, , 3 % dtex Tear resistance ; hvlen 3, , 25 g / dtex Elongation at break 2i 1 ,/
> / O modulus of elasticity 325 ')
kp / mm Shrinkage in boiling 0 SchrumDfune: in Trichi oral 2

len

at 40 ° C

Shrinkage in air from 130 ⁰ C 0

Example 3:

100 parts by weight of a polyvinyl chloride polymerized at -25 ° C with the viscosity number f'W] = 2.15 and the DS value of 2.30 are added in 425 parts by weight. Cyclohexanone with the addition of 1.5 parts by weight of an organic tin stabilizer dissolved at 140 ° C. and spun into threads as in Example 2. The stripped with 7 m / min from the nozzle threads are after washing in water at about 60 ° C in boiling water in the ratio of 1: 4.0, and dried in a circulating air of 120 ⁰ C a heating roller with a surface temperature of 150 ° C in a ratio of 1: 2.96 stretched.
The following textile values were measured:

Titer 580 dtex 200

Tensile strength 4.15 g / dtex

Elongation at break 8 %

Modulus of elasticity 1010 kp / mm ²

Le A 13 213 -22-

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After the aftertreatment described in Example 2, staple fibers with the values are obtained

Titer in boiling water (KS) 3.3 dtex strength in trichlorethylene 3.6 g / dtex strain at 40 ° C 24 % Modulus of elasticity in air at 130 ° C 400 p
kp / mm Stump 0 % shrinkage O ei SchrurnDfunE 0 '%

Example 4: ■

100 parts by weight of a polymerized according to Example 1, polyvinyl chloride with a viscosity number vnn [V] = 2.30 and a DS value of 2.5 is at l40 ⁰ C in 470 parts by weight of cyclohexanone, 1.5 parts by weight Contains parts of an organic tin stabilizer, dissolved.

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, stretched 1: 4.0 in boiling water, dried. And stretched 1: 2.25 ^{at 150 ° C.}

The measurements gave the following values: λ

Titer 1120 dtex / 200

Tear strength 3.7 g / dtex

Elongation at break 9 %

Modulus of elasticity 680 kp / mm ²

Le A 13 213 -23-

3 0 9 B 2 2 I 0 9 9 3

The staple fibers had the following properties: boiling water 6.6 dtex 6th Titer Trichlorethylene from 40 ⁰ C 3.1 g / dtex 0
kp / mm strength Air at 150 ^° C 35 ) Elongation at break 300 % Modulus of elasticity 0 % Shrinkage in 0.5 Shrinkage in 0 % Shrinkage in

Example 5:

100 parts by weight of the polyvinyl chloride described in Example 1 (viscosity number (V) 7] = 2.5, DS value 2.50) are at 140 ⁰ C in 525 parts by weight of cyclohexanone, the 1.5 wt. Contains parts of the organic tin stabilizer, dissolved.

The solution is pressed by the heated spinning pump through the spinning head at 135 ° C. and the nozzle (72 holes with 0.1 mm hole diameter) into a dry spinning shaft. The supply air temperature at the nozzle is l40 ⁰ C, the temperatures of the air in the shaft be in the upper part I85 ⁰ C, in the lower part 210 ⁰ C. The filaments are drawn off at 500 m / min. Subsequently, the filaments are first in boiling water 1: stretched 1.75, then at 150 ⁰ C for a further 1: 2.5 post-drawn.

The following textile values are measured:

Titer 190 dtex

Strength 5.7 g / dtex

Elongation at break 8 %

Modulus of elasticity 680 kp / mm ²

Le A 15 215 -24-

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The staple fibers obtained according to Example 2 have the following Characteristics:

Titer in boiling water 3.0 dt ex strength in Trichlorethylene from 40 ⁰ C 3.3 g / dtex Elongation at break in Air at 130 ° C 3.0 % Modulus of elasticity 350 kp / mm shrinkage 0.5 % shrinkage 1.5 % shrinkage 0 %

Example 6:

100 parts by weight of a polyvinyl chloride described according to Example 1, but with a viscosity number of fi ^ = 3 * 25 and a DS value of 2.40 are at 14o ⁰ C in 700 parts by weight of cyclohexanone, in which 1.5 wt . -Parts of an organic tin stabilizer are contained, dissolved. According to example 2, the
Threads spun, washed and drawn, with a draw ratio of 1: 3.0 in water and a draw ratio of 150 ^° C. in water
1: 2.17 was observed.
The following textile values were measured:

Titer 880 dtex / 300

Tear strength 2.9 g / dtex

Elongation 10 %

ο E-module 600 kp / mm

The staple fibers likewise obtained according to Example 2 can be left
characterize themselves with the following values:

Titer 3 * 3 dtex

Strength 2.4 g / dtex

Elongation 30 %

Le A 13 213 " ² ^"

3098 2 2/0993

240 kp / mm 0 2 1 *

Ε module

Shrinkage in boiling water
Shrinkage in trichlorethylene of 40 ^° C. Shrinkage in air of 130 ° C.

Example 7?

In this example polyvinyl chloride with a viscosity number jV] = 1.6 dl / g and a DS value of 2.4 is used. Parts by weight of this polyvinyl chloride are dissolved in 410 parts by weight of cyclohexanone at l40 ⁰ C with the addition of 1.5 parts by weight of an organic tin stabilizer · The Example 2 wet-spun filaments are in boiling water 1: 5 * 5 ⁰ at 150 C 1: 2.86 drawn.

Threads are obtained with the following properties:

Titer 850 dtex / 300

Tear strength 2.55 g / dtex

Elongation at break 11 %

Modulus of elasticity 420 kp / mm ²

The rest of the process also proceeds as in Example 2 described. The staple fibers have the following properties:

Titer 5 * 3 dtex

Tear strength 2.0 g / dtex

Elongation at break '35 %

E-module 210 kp / mm ²

Shrinkage in boiling water 0.5 %

Shrinkage in trichlorethylene of 40 ⁰ C 2 %

Shrinkage in air of 150 ⁰ C 4 %

Le A 13 213 " ²⁶ ~

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Claims (1)

Claims; 1. Threads and fibers made of vinyl chloride homopolymers or Copolymers containing at least 85% by weight of vinyl chloride, with high modulus of elasticity, high tear strength, low elongation and high dimensional stability in boiling Water, as well as halogenated hydrocarbons, characterized in that the vinyl chloride homopolymer or copolymer has a viscosity number R from 2.0 to 2.9 and a DS value from 2.1 to 2.5. 2. threads and fibers according to claim 1, characterized in that for the production of these threads and fibers a vinyl chloride g polymer with a viscosity number [V] of 2.0 to 2.9 and L ^L J a DS value of 2.1 to 2.5 is used, which is produced by redox-activated precipitation polymerization of vinyl chloride, optionally together with a maximum of 15 wt. <6 of a comonomer in alcohol / water mixtures, the polymerization at pH values in the range of 2 and 7 at temperatures between ^{-10 0} C and ^{-40 0} C in the presence of (a) an initiator system of hydrogen peroxide and an organic sulfic acid, wherein the amount of peroxide compound 0.5 to 5.0 wt / l - based on the monomers used - is (b) a complexing agent of Cu-II ions and ethylenediaminetetraacetic acid and (c) a lithium or zinc salt is carried out. 5. threads and fibers according to claim 1, characterized in that that the vinyl chloride homo- or mixed polymer has a viscosity number> i ~] from 2.2 to 2.7. 4. A process for preparing filaments and fibers made of vinyl chloride homopolymers or copolymers which contain at least 85 wt.% Vinyl chloride, vinyl chloride polymerization by spinning, characterized in that a vinyl Le A 15 215 -27- 309822/0993 Chloride polymer with a viscosity number 1 iil from 2.0 to 2.9 and a DS value of 2.1 to 2.5 is spun. 5. A process for preparing filaments and fibers made of vinyl chloride homopolymers or copolymers which contain at least 85 wt.% Vinyl chloride, by spinning on vinyl chloride polymers of a solvent after the wet or dry spinning process, characterized in that a Vinylehloridpolymerisat with a Viskositätszahliiil 2.0 is spun to 2.9 and a DS value of 2.1 to 2.5, which is produced by redox-activated precipitation polymerization of vinyl chloride-if appropriate together with a maximum of 15 wt.; £ of a comonomer in alcohol / water mixtures, the polymerization at pH values in the range of 2 to 7 at temperatures between -10 ⁰ C and -40 ⁰ C in the presence of (a) an initiator system of hydrogen peroxide and an organic sulfinic acid, wherein the amount of peroxide compound -bezogen 0.3 to 3 # 0 wt.% to the monomer used is, (b) a complexing agent from Cu-II ions and ethylenediamine tetraacetic acid and (c) e a lithium or zinc salt is carried out. 6. The method according to claim 1, characterized in that the polymerization in a pH range between 3-6 and at temperatures between -15 ⁰ C and -30 ⁰ C is carried out. Le A 13 213 -28- 309822/099 3