CS244307B1

CS244307B1 - Waste material stabilization method from polypropylene fibres preparation

Info

Publication number: CS244307B1
Application number: CS869683A
Authority: CS
Inventors: Nikola Kaloforov
Original assignee: Nikola Kaloforov
Priority date: 1983-11-23
Filing date: 1983-11-23
Publication date: 1986-07-17

Abstract

Predruetom vynálezu je použitie organických fosfonitových a fosfitových stabilizátorov ako přísady s viacfunkčným účinkom pri príprave polypropylénových vlákien z ich odpadov, ktoré možu byť tvrdé (od kompaktných až po strunovité), makké strunovité, nedížené a čiastočne dížené. Je to spósob stabilizácie odpadného materiálu z přípravy polypropylénových vlákien, buď pokrájanému s výhodou predbežne vypratému a odstreďovanému, alebo aglomerovanému, alebo podrtenému, alebo regranulovanému, buď kýblikovému s tavným indexom 3,5 až 17 g/10 min alebo strižovému s tavným indexom 5 až 70 g/10 min, vyznačený tým, že sa ako stabilizátor používá zmes, v ktorej jedna zložka je 0,03 až 0,6 % hmotnostných tetrakis-(2,4-di-terc.-butylfenylJ-4,4‘-bifenyléndifosfonit a ďalšia zložka zmesi je 0,02 až 0,5 % hmotnostných tris- (1-fenyletylfenyl J fosfit. Předkládaný vynález je možné použiť pri výrobě polypropylénových vlákien.The invention is based on the use of organic compounds phosphonite and phosphite stabilizers as an additive with a multifunctional effect in preparing polypropylene fibers thereof waste that can be hard (from compact up to stringy), poppy-stringed, undeveloped and partially cut. It is a method of stabilizing waste material from the preparation of polypropylene fibers, either preferentially pruned washed and centrifuged, or agglomerated, or crushed or regranulated either bucket with fusible with an index of 3.5 to 17 g / 10 min or staple with a melt index of 5 to 70 g / 10 min, indicated by using it as a stabilizer a mixture in which one component is 0.03 to 0.6% by weight tetrakis- (2,4-di-tert-butylphenyl) -4,4‘-biphenylenediphosphonite and another component % of the mixture is 0.02 to 0.5% by weight of (1-phenylethylphenyl J phosphite. The present invention may be used in the present invention production of polypropylene fibers.

Description

244307

SUMMARY OF THE INVENTION The present invention relates to the use of organic phosphonite and phosphite stabilizers and additives with multifunctional action in the preparation of polypropylene fibers from their wastes, which wastes can be hard (from compact to stringed), macerated, coated and partially milled. .

The spinning wastes have the following disadvantages: in the recovery of polymer waste by melting without the use of stabilizers, fibers with poor long-term thermal, processing and light stability, strength, ductility and dispersion properties are prepared. Thus, the untreated fibers from the waste are stressed more than twice: twice for the preparation of fibers - in the ordinary course of production and from waste; in addition, for recycling - either crushing hard and stringed waste, or agglomerating and regranulating untreated amber stringed waste. In the after-reaction mechanism with oxygen and the provision of high temperatures, friction, residence time and other processing conditions and the use of fibers from wastes, the content of stabilizers used decreases more than in conventional fibers. For the aforementioned reasons, the thermo-oxidative, mechanical, mechanochemical, electrostatic, and tedious processes will, in the greater extent, provide additional non-stabilized with suitable waste stabilizers. The precursor of the waste has to some extent a different behavior towards the addition of some additives, including stabilizers, compared to the flood polymer system. For undrawn and partially cut off, the preparation proceeds from the surface to the back of the recycle in the volume of the polymer. It is known that some components (their silicone) preparations impair the dispersion of pigments even when they are in small amounts in polypropylene. Therefore, this non-high-grade waste polymer can be used as a raw material for the preparation of fibers with a certain amount. In the literature, including the patent, data on the multifunctional action of organic phosphite and most phosphonite blends with phosphite stabilizers are lacking to improve the properties of secondary raw material that have been impaired during fiber production and waste recycling. The multifunctional nature of the additives is of practical importance for the desired improvement in the complex properties of polymer systems with a deteriorated pre-deposit such as wastes. The compound tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite is a relatively new stabilizer whose application to polyolefinin has been in recent years. The present invention achieves improved long-term thermal and processing stability, dispersing properties. The shortcomings of the prior art authorizations 197 657, 198 682, 223 416 on waste treatment methods are eliminated by the process of the invention, which opens up the possibility of use with improved light fastness, strength and ductility at the same time as the secondary raw material and its properties in the said author certificates. the addition of small amounts of blends and / or individual stabilizers. This allows the most efficient use of the polymeric material from waste.

This method of using the additives consists in the following: either the waste is crushed (hard and compacted or stringed), preferably pre-washed and centrifuged, or even agglomerated (non-compacted, partially cut and softened) or even regranulated, either wired or fused with an index of 3.5 to 17 g / 10 min, preferably 3.5 to 11 g / 10 min or staple with a melt index of 5-70 g / 10 min, preferably 6-25 g / 10 min, either a mixture or individual stabilizers mentioned in Table 1, which may be in the form of 1 to 30%, preferably 5 to 15%, of a stabilizer in the prior art, preferably in powder or regranulate form. Waste with added stabilizer is used as the raw material in the tomcat or still melts in the melting plant at 170 to 310 ° C, preferably 175 to 230 ° C, and is filtered through a filter of 80 to 1600, optionally with a higher number of holes Regranulate or agglomerate, optionally pulp, may be used, either as a 100% raw material without use (or used for doping) of pigment for fiber preparation or blend: with each other, with fine cut fiber waste, with conventional raw materials. Optionally, finely cut untreated fiber waste may be used which is mixed with the color concentrates and the said stabilizer is added during mixing. In this case, it is suitable to homogenise the polymeric raw material from the waste in the cone mixer or in the spinner prior to reflow and spinning. other suitable equipment. In the case of the use of a non-stabilized polymeric feedstock, it is possible to add both a stabilizer and a fiberized feed. The homogenized overhead, preferably mono-shade, raw material in the base melt screw at temperatures of 190 to 390 ° C or simultaneously in the side screw at these temperatures. They are spun at temperatures of 200 to 330 ° C, preferably 210 to 280 ° C. The weaning time of the untreated fiber is 1 to 60 hours. Thereafter, the fiber is dried at a rate of 70 to 1800 m / min, preferably 100 to 1400 m / min and a cut ratio of 1: 2 to 1: 5.5, preferably 1: 2.8 to 1: 3.5.

As a further possibility, the waste in the form of either an agglomerate or a regranulate or crushed or finely cut fibers or mixed with each other is added in an amount of up to 10%, preferably up to 5%, of the polymer base and mixed in a conical mixer. with a mixing duration of 8 to 40 min, preferably 20 to 30 min, optionally in another suitable mixing device, either with the origin of the 244307 polypropylene or with the concentrate, or part of the abovementioned amount is mixed with the polymer and the other portion pigment concentrate. The added polypropylene content of the a] pigment in the container is reduced in proportion to the added polymer and pigment in the form of waste. Add to the mixing device the stabilizers according to Table 1, either in the conventional state or in the form of 1 to 30%, preferably 5 to 15%, of the stabilizer in the form of either a polymer, preferably a powder or a granulate. The homogenised, preferably mono-solid, raw material is melted either in the base melt at 190 to 390 ° C, or at the inlet - at 200 to 380 ° C or at the same time at both temperatures. conditions as 100% waste material.

The economical advantage of the proposed use of organic phosphonite and phosphite stabilizers is that in the production of polypropylene fibers by wastes by the simultaneous improvement of several necessary properties, separate or small amounts are used, such as raw material, dyed or tinted. a shade of color. In this process, the propylene and expensive pigments are saved. The mixtures used, the individual stabilizers in this invention, color the polymer and have a low volatility. Furthermore, the A + Bako mixture as well as the single stabilizer C at 0.25 ° / o (Table 1) is cheaper than the stabilizer used in the waste treatment of author certificates 197 Further advantages in this process of using the stabilizers shown in Table 1 are lower temperatures of 5 to 110 ° C in hot melt compared to conventional production and improved operational reliability of spinning and spinning. thereby reducing waste

Waste fiber production was used to evaluate efficiency. These fibers are produced by spinning polypropylene with Tiplen H431F. The polypropylene cable produced contained 1.2728% by weight of Cromophtal gelb GR (1.0177% by weight), Cromophtal rot BP (0.1767% by weight), Nylofil schwarz BLN (0.0778% by weight) pigments.

Said wastes with moisture and other odorous constituents were centrifuged to 1.73 to 2.47% moisture, cut, and then evenly dusted with the aforementioned individual and stabilizer mixtures in Table 1. The melting was carried out at temperatures of 220-260 ° C. and a melting time of 2 to 2.5 min in a 80 to 125 mm diameter melting pot and filtering through a 624 aperture filter per 1 cm2. The portion of the prepared regranulate containing 0.25% C (Table 1) was re-melted and a second granulate was obtained at 170-240 ° C, a melting time of 80-100s, and a speed of 280rpm in a mousse twin diameter of 53mm and filtering through filters 1,600 holes per cm 2. The regranulates of all samples according to Table 1 were homogenized in a food mixer for 10 min. The homogenized individual samples were melted in an extruder with a screw diameter of 90 mm and spun. The melting and spinning conditions were: melting zone temperature 240 ° C, spinning temperature 260 ° C, pressure upstream of the pump 7 MPa, pressure downstream of the pump 9 MPa, melting time 15-20 min, single spinning point feeding 300g / min, spinning speed 435m / min, the number of holes in the Y-form in the nozzle 100, the cross-sectional area of the nozzle orifice 0.346 mm, the capillary length 2 mm. Melt indexes were set up on a Gottfert plastomer according to standards. The degree of dispersion 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 Svitev in 1977, pp. 79-82. performed according to common methodologies. The unbonded fiber was left to stand at a mean velocity of 280 m / min at a ratio of 1: 3.154 after standing. The lower galet temperature was 112 ° C and the upper galet was 117 ° C. The efficacy of small amounts of stabilizers alone and their combination in waste was monitored. 244307 Λ ca o

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CO CO CM O CO 05 CO ΙΌ CM * θ '%% * CD rd O c rd rH 244307 7 8 The values obtained were compared with the values, in particular, of waste without addition (0). It can be seen from Table 1 that while adding small amounts of blends and individual stabilizers, several properties of polypropylene fibers are improved, as opposed to sample 0. When the stabilizer mixture is 0.15% A + 0.10% B, the curing properties are additionally improved. fibers - strength increases, ductility decreases, light stability increases from increased strength values determined in relative units and calculated as residual after 60, 120, 180 and more h irradiation under Xenotes 450 conditions. 0.15% A + 0.10% B stabilizer-ro is somewhat higher in thermal stability (considering the degraded degradability index of the regranulate and the undersized fiber below the nozzle as well as the decrease in melt indexes for degradation curves (compared to that of tom-it) a certain amount (0.25%) of stabilizer A. Improvement of melt indexes for degradation curves after a long remelting time (15 min add the degradation of the sample in the plastomer + 4 min for the determination of the melt index of the degraded sample in the plastomer indicates the increased long-term thermal stability of the polymer feedstock from the waste in the presence of a stabilizer. The dispersion or maximum agglomeration of the non-embossed pigment (Table 1) from the waste (Table 2) is higher at the effect of a mixture of stabilizers in the combination of 0.15% A + 0.10% B and the solenoid alone 0.25% And compared to the treatment at the same amounts (0.25%) of the stabilizer C alone - Table 1. The effect of the mixture of 0.15% A + 0.10% B is higher to increase the strength and light stability of the prepared fibers prepared by from their waste compared to the same amount (0.25%) of either A or B or C stabilizers alone.

The aforementioned small amounts of a wide range of agent temperature adjusting agent - customary temperatures for which dispersion and maximum agglomeration are determined up to degradation index temperatures of 280 ° C and above (Table 1). It can be seen from Table 1 that when adding small amounts of said stabilizers, it simultaneously results in an improvement in the new set of properties of the polymeric raw material from the wastes made from it and compared to the non-additive. Tensile strength values determined after 180 and more hours under Xenotest 450 conditions indicated that the 0.15% A ++ 0.10% B compound effect was higher to improve the light-fastness strength than the sum of the single-agent actions. and A and B, and predominantly compared to waste without addition. This is the result of the synergistic effect of the substances in the polymeric system. Furthermore, the action of the aforementioned stabilizers makes it possible to somewhat increase the quality of some of the concentrates, improve the recovery capacity, abrasion, compressibility, workability of workable shades, including pale and reductions in the number of burrs and wastes not only made from wastes but also from conventional materials. In order to improve in particular the light fastness of the wastes instead of the above-mentioned stabilizers, as well as their presence, either 0.03 to 0.3% of 2-hydroxy-4-n-octyloxybenzophenone or 0.03 to 0.3 may be added. % 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole or other substituted hydroxybenzophenones and hydroxybenzotriazoles or sterically hindered amines and organic Ni complexes.

The present invention has an application advantage for optimizing the properties of the preparation of processable polymer systems in this number of polypropylene fibers and plastic products of their various types of waste. The present invention can be used in the manufacture of cable-stranded polypropylene fibers from their wastes. The invention is tested in operating conditions and, when utilized, conventional manufacturing performance and qualitative indicators are achieved.

Table 2 Initial raw material - waste skimmed and not cut from debted and partially cut fibers

Melt Index after Index Limit Stage Maximum- Preparations- Content Degradation Dissolution Aggregate,% by 230 ° C, dation, dubbing, retention parts g / 10 min g / 10 min. mkm% 10.09 40.46 4.02 169.67 3.55 2.76 67 0.48. 1.73

Claims

Method of stabilizing waste material from the preparation of polypropylene fibers, either cut preferably by prewashing and centrifuging, or agglomerated, or crushed, or regranulated, either with a cable having a melt index of 3.5 to 17 g /

OF THE INVENTION / 10 min, preferably 3.5 to 11 g / min, or staple with a melt index of 5 to 70 g / 10 min, preferably 6 to 25 g / 10 min, characterized in that a tetrakis mixture is used as a stabilizer - (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite having the structure t-1 H-t-t or t-t-t in an amount of 0.03 to 0.6% per axis, preferably 0, And tris (1-phenylethylphenyl) phosphite having a structure in an amount of 0.02 to 0.5%, preferably 0.06 to 0.30%.