CS229065B1 - Method of preparing polypropylene cable filaments from hard waste thereof,with improved properties - Google Patents

Abstract

A method for producing polypropylene cable ducts fibers when using their hard wastes, which can be from compact to strunove. These wastes are crushed in a crusher, 600 and over 600 kg / h 45 and below 45 kW, and so prepared grit 8 melt index 3.5 to 17 g for 10 min, preferably 3.5 to 9 g / 10 min, is added in an amount of up to 15, preferably to 3% polymer-based and mixed with the original granular polypropylene; \ tor. \ t with a pigment concentrate or part thereof said amounts of pulp are mixed with the polymer and another portion of the pigment concentrator and the resulting mixture is spun at temperatures 220 DEG-325 DEG.

Description

SUMMARY OF THE INVENTION The present invention provides a process for preparing polypropylene cable fibers using their hard wastes, which can range from compact to stringy. The present method makes it possible to improve the processing, thermal, light and long-term stability, the dispersing properties of the waste and the fibers prepared therefrom by adding small amounts of the mixture or of the individual stabilizers. This allows the most efficient use of said wastes.

The occurrence of hard spinning waste results directly from the technological process used to produce the polypropylene cable, as well as from the necessary control. This type of waste has not yet been used with improved properties in polypropylene fibers.

Hard waste obtained by spinning has the following disadvantages:

When the polymer is recovered from the waste by melting without the use of stabilizers, polypropylene is obtained for further processing with an unsuitable high melt index, with deteriorated processing, thermal, light and long-term stability, pigment dispersion and some physical-fire properties. This low-quality polymer is therefore difficult to use as a raw material for fiber processing.

The drawbacks of the prior art methods of using polypropylene fiber wastes are overcome by the process of the invention, which opens the possibility of using hard cable waste with improved properties in cable and staple fibers.

This method consists of the following:

The hard, compact waste with dimensions below 50 x 50 x 10 cm, preferably below 25 x 25 cm or the string waste is crushed in a shredder, preferably with unused blades. The crushed waste has a melt index of 3.5 to 17 g / 10 min. The stabilizers added can be in the form of 3 to 30% stabilizers in the masterbatch of the polymer or regranulate, in the usual state. The crushed hard waste with added stabilizer is used as a raw material in this state or is remelted in the melter at 170 to 300 ° C and filtered through a filter with 200 to 300 ° C.

600, optionally with a greater number of holes per cm. The thus prepared pulp or regranulate can be used either as a 100% raw material without the use of a pigment for the preparation of the fiber or in a mixture with each other, with conventional raw materials, with agglomerate and finely chopped fiber waste.

In case of use of unstabilized pulp or regranulate, it is possible to add a stabilizer even at its spinning. As an alternative, the crushed hard waste in an amount of up to 10%, preferably up to 3%, based on the polymer, is mixed with the cell in a conical mixer with anhydrous granulated polypropylene with stirring for 8 to 40 min, preferably 20 to 30 min. With the aforementioned mixing time, or in another suitable device or part of the abovementioned amount of pulp, the conical mixer is mixed with the polymer and the other part with the pigment concentrate. The content of added polypropylene as well as pigment in a given batch decreases in proportion to the added polymer and pigment in the form of crushed hard waste.

The homogenized gray, preferably mono-shade raw material melts the cell in the basic melting screw at temperatures of 185 to 380 ° C or in the side - at 200 to 370 ° C or simultaneously in both snails. It is fiberized at temperatures of 220 to 325 ° C. The polymer melt index determined on the spinneret is 4.5 to 24 g / 10 min. The standing time of the undiluted fiber is 1 to 60 h, preferably 1 to 3 h. Thereafter, the fiber is divided by an aperture of 80 to Λ 800 m / min and a ratio of 1: 2 to 1: 5.5, preferably 1: 2.6 to 1: 3.5. The cable filament obtained has a strength of 1.05 to 3.3 cN / dtex, an elongation of 35 to 240%, a total titer of 80 to 8,100 dtex. Furthermore, the minimum color fastness was: grade 3 in dry rubbing, grade 4 in shampooing, grade 4 in water.

The economic advantage of the proposed process is that in the production of polypropylene fibers hard waste with improved properties, a cell separate as poles is used, which is colored to the final color shade as well as tinted or in small quantities. This saves polypropylene and expensive pigments. The stabilizer mixtures used in this invention do not stain the polymer, they have low volatility. Further used in the present invention, substances up to 4 parts D ^x in a mixture with either 1 part 3 B ^x or 1 part C ^x or 1 part E ^x or 1 part F are much cheaper than stabilizer A. As another advantage of this In this way, temperatures of 5 to 100 ° C in the melting screws appeared to be lower than in conventional production.

The present invention can be used in the production of polypropylene strand or staple fibers using their hard, poppy stringed, undigested and partially drawn wastes, which can be untreated and not washed or scrubbed, washed and dried in the form of pulp, agglomerate or regranulet, doped or tinted to the final color shade. The polypropylene fiber thus prepared can be classified into quality classes.

^x A, B, C, D, E, F - are abbreviated names of the relevant substances listed in Tables 1 and 2.

Example 1

Waste from the production of cable fibers was used to assess efficiency. These fibers are made by spinning polypropylene under the trade mark Tiplen H531F. The polypropylene cable produced contained 0.9783 h.p. pigments with the trademark Sandorin rot BN (0.9389 h.p.), Graphtol blau 2 GLS (0.0162 h.p.) and Nylofil sehwarz BLN (0.0232 vh.p.).

The solid compact waste, coupled with certain amounts of stringed waste, was crushed in a crusher with a pulp capacity of 600 kg / h and a power consumption of 45 kW. Crushed and homogenized in a cone mixer over 20 min. The waste had a melt index of 10.22 g / 10 min. Mechanical mixing with the stabilizers was carried out in a food mixer for 10 min. It did not observe remelting at temperatures of 170 to 190 ° C, melting time of 80 to 100 s and speed

280 rpm in a fuser and a 53 mm diameter twin screw and filtering through a filter with 1600 holes of about 1 cm. The regranulate was homogenized in a food mixer for 10 min. The homogenized sample was melted in an extruder with a screw diameter of 90 mm and spun. The melting and spinning conditions were: 240 ° C melting zone temperature, 260 ° C spinning temperature, 7 MPa pre-pump pressure, 9 MPa post-pump pressure, 16.5 to 17.5 min melting time, 300 g / min single point spinning spinning speed 435 m / min, number of Y-shaped openings in nozzle 100, nozzle hole cross-section diameter 0.346 mm, nozzle capillary length 2 mm. Ordinary melt indices and melt indices for degustation curves were determined on a Gottfert plastomer according to the standard.

The degree of dlspergy and maximum agglomeration were evaluated microscopically, similar to that described in the Catalog of Analytical-Physical Methods, published by the Research Institute of Chemical Fibers in Svit in 1977, p. 79 to 82. After standing, the undrawn filament was elongated at a mean dump speed of 260 to 280 m / min and at a ratio of 1: 3.154. The efficacy of small amounts of stabilizers alone and their combination in waste was monitored. The values obtained were compared with the values of the waste itself (0). From Table 1 it can be seen that the addition of small amounts of blend and individual stabilizers improves pigment dispersion and maximum agglomeration, melt indexes for regranulate degradation curves, melt index on spinneret and residual fiber strength of 60, 120, 80 and at least 240 h standing at Xenotest 450 compared to sample 0. The sample containing 0.1% C worsens the melt index at the spinneret, melt indices for the regranulate degradation curves and residual strength after 60, 120, 180 and 240 h standing at Xenotest 450 Compared to Sample 0. When adding small amounts of the stabilizer mixture in combination with 0.15% A + 0.1% Be0.29SD + 0.1% E, the melt indices for the regranulate degradation curves and the melt index on the spinneret significantly decrease, points to the best thermal, process and long-term stability achieved.

From the magnitude of the residual strength values after a certain period of ultraviolet radiation in the Xenotte 450 ea, it assessed the specimens for increased light stability. It can be seen that the best light fastness in Xenotest 450 has samples with an effect of 0.15% D + 0.1% F and 0.15% A + + 0.1% B.

It can be seen from Table 1 that the effect of the mixture of substances 0.15% A + 0.1% B on the thermal, processing, light and long-term stability of the waste is higher than the sum of the stabilizing effects of individual substances A and B. with each other, with the polymer and optionally with other components of the polymer system.

With the effect of 0.2% D + 0.1% E, an improvement in dispersion, processing, thermal and long-term stability is observed, which is associated with an improvement in light stability.

Example 2

The procedure is similar to that of Example 1. The only difference is that the efficacy of the stabilizers was monitored using fiber waste containing 0.8569 h.p. pigments of the trade mark Cromophtal rot BR (0.7888 h.p.), Paliogen rot 4790 (0.0332 h.p.) and Nilophil schwarz BLN (0.0349 h.p.). When the fibers were separated, the temperature of the upper galet was 119 ° C and the lower galet was 110 ° C. From Table 2 it can be seen that the addition of small amounts of stabilizers improves dispersion and maximum pigment agglomeration, melt index on the spinneret (samples containing 0.25% D + 0.1% E, 0.25% D + 0, 1% C, 0.3% B), degradation index (sample containing 0.25% D + 0.1% E stabilizers) compared to sample 0.

Improvement of melt indices for degradation curves (Table 1) after a long remelting time of 80 to 100 s in a 53 mm diameter + 16.5 to 17.5 min fusion double extruder in a 90 mm + 15 min screw extruder for degradation of a sample in a Gottefert + plastomer 4 min for the determination of the melt index of a degraded sample in a plastomer Gottefert points to an increased thermal, processing and long-term stability of the polymeric isurea from hard waste. The increased thermal stability of the polymer system allows for color changes to be avoided. The small amounts of the reagent mixture mentioned above operate over a wide temperature range - from ordinary temperatures at which dispersion and maximum agglomeration are determined to degradation index temperatures of 280 ° C and above - Table 1. second

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It can be seen from Tables 1 and 2 that by adding small amounts of said stabilizers, an improvement in the set of properties of the polymeric raw material from hard waste and a new higher stabilizing effect is obtained simultaneously.

Either 0.03 to 0.3% of 2-hydroxy-4-octyioxybenzophenone or 0.03 to 0.3% of 2- (2'-hydroxy) may be added to improve, in particular, the light stability of the wastes in place of and in the presence of the above stabilizers. -3 ', 5'-di-tere.-butylphenyl) -5-chlorobenzotriazole.

The aforementioned embodiment of the invention is of application importance for optimizing properties in the preparation of the processing polymeric systems of this heading, polypropylene fibers and plastic waste products.

Claims (3)

t. Process for the preparation of polypropylene cable fibers using light-hard wastes with improved properties, characterized in that the crushed waste having a melt index of 3.5 to 17 g / 10 min, preferably 3.5 to 11 g / 10 min, is added separately and in particular a mixture of stabilizers in which one component is either 1 to 1. 2 parts of tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylenediophosphonium having a chemical structure or up to 5 parts, preferably 1 to 3 parts of tris- (2,4-di-tert- butylphenyl) phosphite and the chemical structure and the other component of the mixture is either 1 part of the calcium salt of (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester with the chemical structure t-t or ^cHz t-t Θ ABOUT II p-οΙ OC ₂ Hg -c 2. Method according to claim 1, characterized in that the crushed hard waste is added in an amount of up to 10%, preferably up to 3%, based on the polymer and in proportion to either the original granular polypropylene or pigment concentrate, or polymer and another pigment concentrate portion with the addition of a mixture of stabilizers. 2+ J2 or 1 part of pentaeritrite ester of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a chemical structure or 1 to 3 parts of 2,6-di-tert-butyl-4-alkylphenol with a chemical structure structure t — bu HOv / ^{- R} where R is η-0 _3θ ^Η 6ι to η-Ηθ, θ, t-either or 1 part of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecil ester with With the chemical structure all the above stabilizer mixtures are added in an amount of 0.04 to 0.5%, preferably 0.1 to 0.4%, and the mixed, crushed waste with the stabilizer is used in this state or still remelted in the melter at 170 ° C. to 300 [deg.] C., preferably 170 to 230 [deg.] C., the filter is passed through a filter having 200 to 1600, optionally with a greater number of holes per cm, and thus the pulp or regranulet prepared can be used alone or mixed with each other. with conventional raw materials, with agglomerate, as well as with finely chopped fiber waste, it is spun at temperatures of 220 to 325 ° C, preferably 220 to 280 ° C, and is drawn at a speed of 80 to 1800 m / min, with a 1: 2 ratio. to 1: 5.5, preferably 1: 2.6 to 1: 3.5. 3. A process according to claim 1 or claim 2, wherein the stabilizer of 1,1-bis (2-methyl-5-tert-butyl-4-di-tridecilphos) is either 0.1% by weight. onitophenylol) butane with the chemical structure t-bu CH. P-0 · CH. t-bu or a 1: 1 mixture thereof with zinc caprylate with a chemical structure (C HH CCCO ^ Zn), or another component of the mixture is 0.05-0.2% of the phenolic compound of t.