CS219652B1 - Mixture on the base of polypropylene with regulable rheological,stabilization ev.orientation crystallic properties - Google Patents

Abstract

The subject of the invention is a method of improvement and regulation Theological, stabilizing, optionally : orientation properties and crystallinity of polypropylene and mixtures thereof. This method is characterized in that it is polypropylene 0.02 to 0.25%, preferably 0.02 to 0.25%, is added 0.15% poly (ethylene) oxide with molecular weight From 75,000 to 5,000,000, preferably 100,000 to 900,000 with wide as well as narrow distribution 1 molecular weights, or a mixture of 0.1 to 0.5 0.3% poly (ethylene) oxide with 0.1 to 0.5% preferably 0.3 to 0.4% zinc stearate, all concentrations calculated per polymer when mixed into powdered polypropylene prior to pigment manufacture concentrates preferably in use turbocharger. After good mechanical mixing polypropylene with the above as well as with pigments, optionally with other ingredients, the mixture is melted in an extruder and spinning. In addition to the subject features listed There are also other possible variants. The present invention can be used to produce furl . polypropylene fibers or silk as well as i | for other shaped articles.

Description

The present invention is a polypropylene-based composition; The composition of the present invention has a controllable theological, stabilizing, or indicative crystalline properties which contain small amounts of poly (ethylene) oxide or a mixture of poly (ethylene) oxide with zinc stearate.

Modifying the rheology of polypropylene, as well as its blend with pigments and other ingredients, is effective to make the polymers easier and quicker to process. A large number of pigments contribute to the flow properties of the melt mainly by increasing its viscosity, i.e. as a braking element, which means that higher temperatures are required to obtain the correct viscosity. In the last 10-15 years, a very limited number of washing machines have emerged, indicating a greater or lesser impact of the microbial additions of certain individual substances; flowability by melting pure polyolefins. This impact was explained as a result of mutual effect;

| the action of low molecular weight additions with both the above and the lumen structures of the polymers in the melt. i The stages of these interactions work add-ons. The metal with the elemental pure polyolefins is realized by dissolving the polymer with the addition of a co-solvent followed by the following; separation from solution, but only difficult as a result of mechanical mixing, even if mixing is; very large and very intense (G. P. Andrian, N.F. Bakeev, p. V. Kozlov, Vysokomolekuljarnye soedinenija, 1971, A 13, N ° 2, pp. 266-275).

There is a lack of data in the literature, including the patent

Modification and control of two or more properties of polypropylene at the same time as desirable as melt flow, thermal stability and possibly orientation and crystallinity with the effect of small amounts of added substances such as polyethylene oxide and a mixture of poly (ethylene) oxide with stearate; zinc. Of all polyolefins, polypropylene is known to be least resistant to oxidation and thermo-structure. For thick-walled products and coarse-titre fibers, it often occurs; they observe heterogeneous structural formations. Therefore, modifiers are added which provide for a homogeneous structure in the cross-section of the material under investigation. This homogeneity of the structure is particularly needed at higher titers, where only by cooling can a different structure be formed between the surface and the center of the fiber. The preparation of structurally stable and to some extent elastic finished fibers and films requires a compromise between the desire to obtain a high and stable orientation in which the mobility of the molecules is reduced and the desire to obtain elastic properties where the mobility of the molecules is increased. Crushing the are employed, small amounts of poly (ethylene) oxide or a mixture of poly (ethylene) oxide having zinc stearate, and the zlepšeme s not regulated rheology, stabilizers, or ^oriented: Trays properties such as crystallinity polypropylene j! and mixtures thereof with ingredients commonly used in the preparation of fibers and other articles.

The proposed polypropylene-based composition according to the present invention is characterized in that per 100% by weight of polypropylene ^. parts by weight of the polypropylene also comprise: 0.02 to 0.25 parts, preferably 0.02 to 0.15 parts; proportions of poly (ethylene) oxide having a molecular weight of 75 000 to 5 000 000, preferably 100 000 to 900 000 with a wide and narrow molecular weight distribution, or a mixture of 0,1 to ¹ 0,3 proportions of poly (ethylene) oxide with 0 1 to 0.5; preferably 0.3 to 0.4 proportions of both stearate and zinc. Poly (ethylene) oxide as well as mixtures thereof with; Zinc stearate under operating conditions should be added to the polypropylene powder prior to the production of the pigment horses centrates using a turbulent mixer. Further the possibility of additives either before the homogenizer ¹ Ciou in the form of a concentrated granular pripraí down by the polypropylene powder, optionally;

as a pure substance or before granulating the polymer.

¹ The admixture of the additive with the polypropopylene and its mixture is tested in commercial mixing equipment under normal conditions. Then, the mixture is melted in a melter and shaped. The melting point is 190 to 415 ° C. The melt indices were also determined on a Gotfert plastomer according to the standard. The thermal stability of the polypropylene was assessed from the determined degradability index values. The degree of crystallinity was determined by the flotation method and orientation by the optical birefringence method.

As an advantage of the above invention, it appears with the addition of small amounts prístupί Nycha, low cost and non-toxic materials such as poly ^(ethyl-1 only) oxide or a mixture of poly (ethylene) oxide with the zinc stearate to improve and control the melt flow, thermal stability, optionally, the orientation and crystallinity of the polypropylene and mixtures thereof, which are of application importance. The above-mentioned small amounts of poly (ethylene) oxide or its mixtures with zinc stearate are capable of acting over a wide temperature range, indicating the stability of their action. Further changes in melt flow, thermal stability and polymer orientation are abrupt! and non-additively on the added small amounts of poly (ethylene) oxide. For certain small _quantities:; The poly (ethylene) oxide in the polypropylene according to the above-mentioned invention results in a mutual interaction of these components, which is higher than the sum of the effects of the individual substances on the above.

! features. Therefore, in addition to the interactions of the interstructures and the structural plasticization in the mixture according to the above invention, there is also a new effect - synergism of the poly (ethylene) oxide with the polymer, possibly with other constituents of the polymer system. stability, optionally increasing orientation and changing crystallinity. Significantly increasing the flowability of the melt enables the spinning process to be improved and the products to be shaped at all, and the processing temperature of the products is increased, especially at the desired lower temperatures. As an additional advantage when using poly (ethylene) oxide, it is: reducing the necessary energy of the spinner. A further advantage of the above invention is an accessible, simple and economical process using mechanical mixing and melting - both conventional and working steps in the preparation of fibers and plastics products. This eliminates the difficult, uneconomical and unhygienic process in which large amounts of solvent are used to dissolve large amounts of polyolefin for; its good mixing with the agent followed by precipitation of the polymer. Therefore, for the others already mentioned advantageously, the mixture according to the above invention is technically more advantageous.

Example 1

The effectiveness of poly (ethylene) oxide having a molecular weight of 600,000 (A) as well as a combination (A) with zinc stearate (B) in a mixture with unstabilized powdered polypropylene was monitored! TatrenHPF 411 - Table 1

Table 1

Used allowances in shares Degree of crystallinity in% index Degradation bility Melting index at 230 ° C in g / 10 min A B ’ 0.00 0.0 58.19 3.2 32.6 0.02 0.0 58.93 2.1 64.3 0.03 0.0 58.93 0.04 0.0 58.93 2.1 0.05 0.0 58.93 1.9 73.2 0.06 0.0 60,08 0.08 0.0 61,84 0.10 0.0 61,84 1.9 69.8 0.15 0.0 2.0 68.0 0.20 0.0 64.67 2.1 66.1 0.25 0.0 64.67 2.1 65.3 0.20 0.1 58.93 0.20 0.2 58.93 0.20 0.3 56.61 0.20 0.4 56.61

The obtained values were compared with the values of pure Tatren HPF 411 without additions - table

1. Mix the mixture in a TR-400 turbo-mixer at 600 rpm for 5 min. Mechanical mixing of the mixture in a laboratory mixer for 10 min was also [

21965?

[satisfactory. The mixed sample was melted in an extruder with a screw diameter of 16 mm and spun. The melting and spinning conditions were as follows: melting zones and spinner head 240 ° C, pressure before; 20 m / min, spinning speed 130 lm / min, number of holes in the nozzle 20, nozzle hole diameter 0.3 mm, nozzle capillary length 6 mm. It can be seen from Table 1 that, due to the effect of small amounts of poly (ethylene) oxide, it is possible to significantly increase the flowability of the polymer melt and the thermal stability of the polymer. polypropylene. The greatest increase in the flowability of the polymer melt corresponds to its greatest thermal stability. The above changes in the two properties may be associated with an increase in the degree of crystallinity, e.g. with 0.1 to 0.25 J proportions of poly (ethylene) oxide and without increasing the degree of crystallinity, e.g. with an addition of 0.02 to 0.05 proportions of poly (ethylene) oxide. Further, it can be seen that with the addition of small amounts of zinc stearate mixture ^! % of poly (ethylene) oxide, it is possible to slightly detect the degree of crystallinity of the polymer. The above small amounts of reagents act over a wide temperature range - from ordinary temperatures at which crystallinity is determined to in vivo determination temperatures (degradability dex, 280 ° C and above - Table 1).

'Example 2

The procedure is similar to that in Example 1. The only difference is that the efficiency of the micro-amounts of 600,000 molecular weight poly (ethylene) oxide alone in various concentrations in granular and stabilized polypropylene Mosten 55.212 -I- 0.2 proportions of Titan Bayer was evaluated R-KB-2 4- 0.2 aliquots of trilauryltrithiophosphite and stirred for 5 min more. Mosten 55.212 was once ground on an Apex mill with a mesh diameter of. sieve 1.96 mm. Temperature of melting zones and spinning. The head was 300 ° C. This elevated temperature as well as the presence of trilauryltrithiophosphite were needed for the destruction of polypropylene. The values obtained were compared with those of the same poly (ethylene) oxide-free blend - Table 2.

Table 2

Poly / ethylene / oxide with molecular weight

600 000 in shares 0.00 0.02 0.05 0.10 0.15 0.20 0.25 Optical birefringence. 10 ³ 1.14 1.26 2.31 3.38 3.21 2.87 2.40 Degradability index 2.3 2.1 2.1 1.9 1.7 2.0 2.1

The above mixture according to the invention is of application importance for optimizing the properties of the? preparation of processing polymer systems also in this issue of polypropylene fibers and sheaths of diamond products.

It can be seen from the table that, depending on the concentration of poly (ethylene) oxide, the orientation of the above polymer system may increase slightly, to a higher and then to a high value. However, the thermal stability of the polymer ¹ slightly increases.

SUBJECT

Claims (2)

i using mechanical mixing and smelting - common working steps in the preparation of fibers and plastic products. In this way, a difficult, uneconomical and unhygienic procedure is avoided in which large amounts of solvent are used to dissolve a large amount of polyolefin for; its good mixing with the reagent followed by polymer precipitation. Therefore, for the others already mentioned Advantages, the mixture of the present invention is technically preferred. EXAMPLE 1 The effectiveness of 600,000 (A) poly (ethylene) oxide alone as well as the combination of (A) with zinc stearate (B) was mixed with powdered non-stabilized polypropylene. Table 1: Table 1 Used additions in ratios of Crystalline Grade in% Degradation Index Melt Index of 230 ° C in g / 10 min AB '0.00 0.0 58.19 3.2 32, 6 0.02 0.0 58.93 2.1 64.3 0.03 0.0 58.93 0.04 0.0 58.93 2.1 0.05 0.0 58.93 1.9 73 , 2 0.06 0.0 60.08 0.08 0.0 61.84 0.10 0.0 61.84 1.9 69.8 0.15 0.0 2.0 68.0 0.20 0.0 64.67 2.1 66.1 0.25 0.0 64.67 2.1 65.3 0.20 0.1 58.93 0.20 0.2 58.93 0.20 0 0 3 56.61 0.20 0.4 56.61 The values obtained were compared with the pure Tatren HPF 411 without the addition of Table 1. Mixing of the mixtures was carried out in a TR-400 turbolent at 600 rpm for 5 min. Mechanical mixing of the mixers with a laboratory mixer over 10 min was also [21965? [ satisfying. The mixed sample was melted in extruder with a screw diameter of 16 mm and plasticized. The melting and spinning conditions were: melting zone temperature and spinning head 240 ° C, pressure up to 8 MPa, downstream pressure 2 MPa, 20 g / µg dispensing, spinning speed of 130 µm / min, number of holes in nozzle 20, hole diameter of 0.3 mm, capillary length of 6 mm. It can be seen from Table 1 that with the effect of small amounts of poly (ethylene) oxide, the flowability of the polymer melt and the thermal stability of the polymer can be greatly increased. polypropylene. At the same time, the greatest increase in the flowability of the polymer melt corresponds to its highest thermal stability. The aforementioned changes in the two properties may be associated with an increase in [, degree of crystallinity, e.g., 0.1 to 0.25 µl of poly (ethylene) oxide moieties and no increase in the degree of crystallinity, e.g. poly (ethylene) oxide. Furthermore, it can be seen that, in addition to small amounts of zinc stearate mixtures. The degree of crystallinity of the polymer may be slightly increased by the amount of poly (ethylene) oxide. The abovementioned amounts of reagents act in a wide range of temperatures - from the normal temperatures at which the crystallinity is determined up to the degradation temperature of the assay, 280 ° C and above - Table 1. Example 2 Similar procedure to Example 1. Difference It is appreciated that the efficiency of micro-poly (ethylene) oxide alone with a molecular weight of 600,000 in various concentrations of granulated and stabilized polypropylene Mosten 55.212 -i 0.2 parts by weight of Bayer R-KB-2 4- 0.2 parts trilauryltritio- phosphite and stirred for 5 min more. Mosten 55.212 was once ground on an Apex mill with a mesh diameter of 1.96 mm. The temperature of the melting zones and the spinning head was 300 ° C. This elevated temperature as well as the presence of trilauryltrithiophosphite required the prepolymerization of polypropylene. The values obtained matched the values of this same mixture of poly (ethylene) oxide - Table 2. Table 2 Poly / ethylene / oxide with a molecular weight of 600,000 in proportions 0.00 0.02 0.05 0.10 0.15 0, 20 0,25 Optical birefringence. 103 1.14 1.26 2.31 3.38 3.21 2.87 2.40 Degradability Index 2.3 2.1 2.1 1.9 1.7 2.0 2.1 The above mixture according to the invention it has application importance for optimizing the properties of the preparation of processing polymer systems even in this number of polypropylene fibers and sheathing products. It can be seen from the table that, depending on the concentration of the poly (ethylene) oxide, the orientation of the aforementioned polymer system may increase slightly, to higher and then to high values. Here, the thermal stability of the polymer is slightly increased. SUBJECT MATERIALS A blend based on polypropylene with regulatable, stabilizing, or opacifiers! and crystalline properties, characterized in that, for 100 parts by weight of polypropylene. and 0.02 to 0.15 aliquots of poly (ethylene) oxide with a molecular weight of 75,000 to 5,000,000, preferably 100,000 to 900,000, with both broad and narrow With a molecular weight distribution of 0.1 to 0.3 parts of poly (ethylene) oxide with 0.1 to 0.5 parts, preferably 0.3 to 0.4 parts of zinc stearate.