CS729285A3 - Polypropylene and process for preparing thereof - Google Patents

Description

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BACKGROUND OF THE INVENTION The present invention relates to polypropylene and polypropylene derivatives, in particular crystalline copolymers of these mixtures with other polyolefins having a predominantly polypropylene content. These substances are high; tensile strength and tensile strength so that they are suitable for various high-strength products. The invention also relates to a process for the production of these substances. It is desirable to promote crystallization in polypropylene molding in the molten state, followed by solidification in cooling, extrusion or casting, so that rapid and uniform crystal formation occurs at higher temperatures. This fact supports the fast setting of the product? thereby reducing its production time.

A common means of achieving this effect is the addition of a so-called heterogeneous nucleation. a substance which is insoluble in the polymer melt and constitutes a crystal formation as it was. described, for example, in F. L. Binsbergen, Polymer 11 (1970), No. 5, p. 253 - 2a7. For example, the agent may be an aluminum salt or a sodium salt of a variety of organic acids, salts of the latter.

I tk powerful metals and various organic pigments, for example

Pf.t. copper alocyanines and onthrachinone and! quinaltridone. From NSR patent specification δ. It appears that when no 0.005-0.0005 percent by weight of the gamma-phase linear trans-quinacridone of formula H is added.

to polypropylene or to a mixture thereof. with ethylene-propylene or ethylene-butylene blended polymer increases. no more improvement is achieved if more than 0.005% by weight, i.e. 5x10 parts by weight over 100 parts by weight of the mixture is added. Furthermore, it is known that isotactic polypropylene can crystallize in various modifications. Typically, in the crystallization of polypropylene melt the formation of a monoclinic modification a, and hexagonal or pseudohexagonal modification β, triple modification gamma, and so forth may also occur. smectic modification, which arises mainly from rapid cooling.

Hexagonal or pseudohexagonal modification β is formed only under certain conditions and in a certain amount, especially under the following conditions: a) melt crystallization at 100 to 130 ° C, b) melt crystallization, c) melt crystallization at the presence of certain nucleating agents.

This method has been described in the publication. H. Moos, S. Tilger, Angewandte MakromolekulareChemie 94 (1981), pp. 213-255.

For example, the hulling agent may be the aforementioned gamma-phase linear trans-quinacridon as described in H.J. Leugering,

Macromolecular Chemistry 109 (1967), 204 ff and K. H. Moos * and B. Tilger, Angewandte Makromolecular Chemie 94, (1981), pages -213-255). Direct monitoring has shown that polypropylene, which contains a gamma-phase from linear trans-quinacridone in the amount of 3 x 10 < 7 > and 1 * 10 < -1 > % ♦ This proportion of β-phase was also confirmed by monitoring in the differential calorimeter and comparing the areas of the individual peaks, namely the ratio of the β-form area to the total area of α- and β-for-my. properties which are particularly important in improving the impact strength of polypropylene on impact, J. Brandrup and EH Immergut, Polymer Handbook 2nd Edition, (1975), III-10 at a density of 0.922 g / cm @ 2 at compared to the density of the α-form, which is 0.933 g / cm, the β-form having approximately 30% higher formation of ........... j

of spherolites than modifications of a, J

SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for producing polypropylene on a technical scale such that * τΊ

Mf 30 crystallizes the melt, the polypropylene containing the highest beta modification, preferably more than 70% and m-S1 low specific gravity, for example lower than 0.905 ρ / οί, τ5, since these products can be expected to have a very high good physical properties and very good ϋ '! processing properties. SUMMARY OF THE INVENTION The present invention provides polypropylene, crystalline copolymers or mixtures thereof with other high impact polyolefins having high impact strength and high tensile strength, comprising a crystalline material in hexagonal or pseudohexagonal form in an amount greater than 65% by weight. when measured with a differential calorimeter, with a specific weight of these substances according to Dit! 53479 lower

3.times.R @ 0.905 g / cm @ 2, the material contains 5.times.10@-5.times.10@6 parts by weight of quino- (2,3-b) -acridine mixed crystals. -7,14-dione-5,12-dihydro-quino- (2,3-b) -acridine-6,7,13,14- (5H, 12H) -tetron per 100 weight. parts of the mixture and mimotostabilizer, light protective agents and / or other conventional additives.

The invention also relates to a process for the preparation of these substances, wherein the polypropylene in the solid phase is intensively mixed with stabilizers and / or light-protective agents and / or additional additives and with 5 x 1C-5 to 5%. parts by weight of quino (2,3-b) -acridine-7,14-dione-5,12-dihydro-quino- (2,3-b) acridine-6,7,13,14- (511,12H ) tatranka then melts, faces and leaves

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The ability of the used crystals to support crystallization of the polypropylene in the shoe form is surprising since high levels of beta form in the presence of the linear β-linear phase of the linear nucleating agent in the crystalline form have never been achieved in trans-cinnacridone, although The alpha-phano phase of the trans-quinacridone is also used, however, it supports polypropylene alpha crystallization. The mixed crystals of linear chiracridone china-cridonequinone used in the process of the invention differ in the X-ray diffraction pattern from the phaseganine of the linear trans-quinacridone by the fact that they do not have strong lines at the crystal lattice spacing of 13.53, 6.41 , 4.33 and

- R 3.37 .10 cm and also medium-thick lines at 6.70, 5.24-8 - and 3.74. 10 ’cm. The thick lines in the diffraction pattern are in the grid spacing of 10.1 to 10.5, 3.5 to 3.6, 3.45 to 3.5, and 3.3. 10 "8cm.

Particularly preferred is the addition of mixed crystals in an amount at which the contents 5 are reached. 10 ”4 to 5. 10 to 7 parts by weight per 100 parts by weight of the polypropylene composition. In this addition, the crystalline form content of β is greater than 70% and often higher than 80% with a specific gravity of 0.904 g / cm.

The high degree of modification of β in the polypropyle material affects the physical properties of this material, for example on plates of this material, on which an increase in resistance to measurements according to DIN 53455 is observed, in particular an increase in tensile strength at reduced elongation at break. In addition, according to DIN 53452, bending forces can be observed by using the same force of 3.5% and according to DIN 53453 and DIN 53753, the impact strength at 23 ° C - 9 ° C can be demonstrated at -20 ° C. Polypropylene which it contains; the same amount of gamma gamma linear trans-quinidine has higher elongation at rupture and the tensile strength and tensile strength have values that lie between the polypropylene without the nucleating agent and the material of the invention. This means that the material produced by the process of the invention has a high strength with increased ductility. - 'i

The mixed crystals used in the process of the invention are commercially available as quinacridone; pigments.

The polypropylene compositions of the present invention can be obtained by intensively mixing the individual components, wherein the mixed crystals can be added as either a matrix or a mother liquor, followed by melt processing, for example by injection molding or extrusion. It is also possible to convert the resulting material into a granulate which can be further processed in any way. The molding and granulating temperature is within the normal range, for example, at a temperature of 200 to 220 ° C. 10 -

The polypropylene blends produced according to the invention have a high impact strength and a tensile strength. The melting point is lower than conventional polypropylenes, about 145-150 ° C. The formation of spherulites is faster than conventional polypropylene types which crystallize in the modification and which is advantageous for subsequent processing, the transition to modification occurs when the material is maintained at 150 ° C.

The high β modification results in the packaging of polypropylene. Subsequent transition of domodification and recovery of the material can be achieved.

Due to its mechanical advantages and processing advantages, the material produced by the process of the invention is suitable for a variety of processing methods, in particular for extrusion into films, webs and fibers, the resulting products having increased mechanical strength. Particularly advantageous is the treatment of hollow objects and injection molding, as well as the casting of very large articles. The production of these products is effected by materials which are made of 2 known materials for the production of tungsten so that production is difficult.

The compositions may also contain conventional stabilizing additives without compromising the effect of the nucleating agent.

The invention will be illustrated by the following examples. In all experiments the mixtures were obtained in the same way, the comparative samples contained the gamma linear trans-quinacridone instead of the mixed crystals. Example 1

Polypropylene powder with a melt index (230 ° C / 2 16 16 kg) at 0.2 g / 10 min containing 0.1% calcium stearate, 0.05% tetrakis (2,4-di-tert) Bwtylphenyl) -4,4-biphenylylenediphosphonite, 0.1% by weight of pentaerithrityl-tetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2% by weight of thiodiproic acid ester - 12 - 4 - 8 pionics are mixed with 5 x 10 -5 x 10 "by weight mixed linear trans-quinacridone and quinacridone quinone crystals per 100 parts by weight of the mixture, and the resulting mixture is thoroughly mixed. The mixture is then extruded at 210 ° C using an auger. Mixtures with a very low content of mixed crystals can also be obtained by diluting more concentrated mixtures containing the same polypropylene.

Two types of mixed crystals were added with the following X-ray diffraction patterns: mixed crystal 1d (10 "8cm) mixed crystal 2d (10" 8cm) 10.46 (S) 6.28 4.80 4.13 3.98 3, 65 (S) 3.48 (S) 3.30 (S) 2.88 2.11 0 ΛΟ ~ 7 10.16 (S) 6,245,044,724,584,134,003,63 (S) 3,47 (S) 3,28 (S) ooav T- 2.17 2., 11 2.09 2.08 2.06 (S) ... thick strips - 13 - 20 gauge plates were produced from the mixtures thus obtained by melting and pressing at 220 ° C. 20, 0.25 mm These plates were cut in 5 mm diameter discs to determine the crystalline form β in the differential calorimeter.

For each sample, a 220 ° C curve was determined after first heating, and then a second heating to 23 ° C to 220 ° C in the DSC-2C was completed. (Perkin Elmer). Heating and cooling were carried out at a rate of 20 K / minute. The forms of form0 were calculated from the ratio of the areas for the β ratio and for the β-part and + 0.

The values are shown in Table 1 below, using a sample containing the gamma-amino trans-quinacridone phase.

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- 16 - * 136 x 136 x 2 mm plates were then produced. The material was melted at 200 ° C, compressed for two minutes and then cooled to about 10K / min to room temperature. Thus, the specific weight of the obtained platelets having a sxxxá® of 30 x 30 x 2 mm was determined by the method of DBI 53479. The values for the weight fraction of 5 x 10 -4 were corrected for pigment content. The results are given in the following - ". Table 2:

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The procedure of Example 1 is followed to obtain mixtures of polypropylene with a melting index (230 ° C / 2.16 kg) and 5 g / 10 min and 18 g / 10 min. tions. calcium stearate, 0.05% by weight of 2,6-di-tert-butyl-4-methylphenol and 0.05% by weight of pentaeroctityltetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The samples were mixed with 5 x 10 -4 parts by weight of the mixed crystal of Example 1 per 100 parts by weight of the mixture, and the proportion of β was determined in the same manner as in Example 1. Also in this case, a comparison was made with the same mixture but containing the same amount. linear trans-quinacridone phamma-gamma. The results are shown in Table 4 below: »

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Table 4 nucleating agent polypropylene 5 x 10 ~ 4 mass.diff. / / 100 weight, parts β-form percentages area area mixed crystal 5 g / 10 min 84.5 control 5 g / 10 min 48.3 mixed crystal 13 g / 10 min 80.2 control 18 g / 10 min 38.2

Claims (2)

PATENTS 2 r AJ o <c · ro I - 03 ^ »u. Z. * =. a m> * 0 <r- - <m N - <- * II S 0 r ------- J ΓΟ m Polypropylene, crystalline copolymers or mixtures thereof with other polypropylene-based polyolefins having a high impact strength and high tensile strength, characterized in that they contain a crystalline material in the hexagonal or pseudohexagonal form of more than 65% the weight of the differential calorimetry, with a specific gravity of these substances of 53479 below 0.905 g / cm 2, the material contains 5 x 10 6 to 5 x 10 5 parts by weight of mixed quino- (2,3-b) -acridine crystals. 7,14-dione-5,12-dihydro-quino- (2,3-b) -acridine-6,7,13,14- (5K, 12H) -tetronene per 100 'parts by weight of the stabilizer addition, light and / or other additives. 2. Polypropylene according to claim 1, characterized in that it contains 5 * 13 &lt; 5 &gt; x 10 &lt; - &gt; 10 parts by weight of the mixed crystals per 100 parts by weight of the mixture and the hexagonal or pseudohexagonal crystalline form is higher than 70%. Wherein the polypropylene in the solid phase is intensively mixed with the stabilizers and / or light-protective agents and / or the light-stabilizing agent. or other additives and s-4 -3 5 x 10 to 5 x 10 parts by weight of quino- (2,3-b) acridine-7,14-dione-5,12-dihydro-quinoline (2 3-b) acridine-6,7,13,14 (5H, 1211 Jtetron ^ and then melt, face and let cool.