SK277920B6 - Polypropylene, crystalic copolymers and method of their production - Google Patents

Abstract

In this section is described polypropylene, crystalic copolymers of polypropylene or mixture of polypropylene with other polyolefins with prevailingly part of polypropylene with high shock tenacity and high strength in draw which contains the crystalic phase in hexagonal or pseudohexagonal from in mass higher than 65 per cent of weight by measuring with differential calorimeter with specific weight according to DIN 53479 lower then 0,905 g/cm exp.3. These materials are prepared in this way, that polypropylene in solid phase is intensively mixed with stabilizers and/or protective matters against effect of light and/or other additives and with 5 x 10 exp.-4 to 5 x 10 exp.-8 weight parts of mixture crystals of quino-(2,3-b) acridine-7,14-dione-5,12-dihydro with quino-(2,3-b)acridine- -6,7,13,14(5H,12H)tetrone and than is melted, moulded and cooled.

Description

Described is polypropylene, crystalline copolymers of polypropylene or blends of polypropylene with other polyolefins having a predominantly high impact strength and high tensile strength polypropylene comprising a crystalline phase in hexagonal or pseudohexagonal form in an amount greater than 65% by weight with a differential calorimetry to DIN 53479 less than 0.905 g / cm ^J. Said materials are prepared by intensively mixing the polypropylene in the solid phase with light stabilizers and / or light stabilizers and / or other additives and with 5 x 10 ^-4 to 5 x 10 ** parts by weight of quino- (2, 3-b) acridine-7,14-dione-5,12-dihydro-quino- (2,3-b) acridine-6,7,13 _> 14 (5H, 12H) tetron and then melted, molded and allowed to stand cool.

Technical field

The invention relates to polypropylene, in particular to crystalline copolymers and to mixtures with other polyolefins with a predominant amount of polypropylene. These fabrics are characterized by high impact strength and tensile strength, making them suitable for the production of a variety of very durable products. The invention also relates to a process for the preparation of these substances.

BACKGROUND OF THE INVENTION

In the processing of polypropylene by molding in the molten state with subsequent solidification by cooling, either by extrusion or by casting, it is desirable to promote crystallization so that even at higher temperatures rapid and uniform crystal formation occurs. This fact then promotes rapid solidification of the product, thus shortening its production time.

The usual means of achieving this is by adding a so-called heterogeneous nucleating agent, i. a substance which is insoluble in the polymer melt and is a seed for the formation of crystals, as described, for example, in F. L. Binsbergen, Polymer 11 (1979, No. 5, pp. 253-267). The agent may be, for example, an aluminum salt or sodium salts of various organic acids, divalent metal salts and various organic pigments, for example copper phthalocyanines and pigments of the anthraquinone and quinacridone type.

From German patent specification no. 1,188,279, when 0.005 to 0.0005 percent by weight of the gamma-phase linear trans-quinacridone of the formula

H to polypropylene or to a mixture of this material with an ethylene propylene or ethylene butylene blend polymer, the toughness of the resulting material is increased by at least 30%, when more than 0.005% by weight is added, i.e. 5 x 10 ^-5 parts by weight per 100 parts by weight mixture, no further improvement is achieved.

It is further known that isotactic polypropylene can crystallize in various modifications. Usually, a crystalline modification of the polypropylene melt is produced, and a hexagonal or pseudohexagonal modification of β, a three-clinical gamma modification, and a so-called smectic modification, which arises especially during rapid cooling, may also occur.

Hexagonal or pseudohexagonal modification β is produced only under certain conditions and in certain quantities, especially under the following conditions:

(a) crystallization of the melt at a temperature of 100 to 130 ° C;

b) crystallization of oriented melt,

c) crystallizing the melt in the presence of certain nucleating agents.

This method has been described in K. H. Moos and B. Tilger, Angewandte Makromolekulare Chemie 94 (1981), p. 213 to 255.

For example, the nucleating agent may be the aforementioned gamma-phase linear trans-quinacridone as described by HJ Leugering, Macromolecular Chemistry 109 (1967), 204ff and KH Moos and B. Tilger, Angewandte Macromolecular Chemistry 94 (1981), pages 213 to 255).

Direct observation showed that the polypropylene containing the gamma-phase of linear trans-quinacridone in an amount of 1 x 10 ⁴ to 3 x 10 ^-3 parts by weight per 100 parts by weight of polypropylene contains a β-crystalline phase of 40 to 60%. This proportion of β-phase was also confirmed by observation in differential calorimeter and by comparison of the areas of individual vichols, namely ratio of β-form area to total area of α- and β-form.

β-modification of polypropylene has various interesting properties, of which the improvement of impact strength of polypropylene is particularly important. According to J. Brandrup and EH Immergut, Polymer Handbook 2nd Edition, (1975), ΙΠ-10 is a density of 0.922 g / cm ³ compared to a density of α-form of 0.938 g / cm ² with β-form has approximately 30% more spherulite formation than the modification; and.

The invention provides an improved process for the production of polypropylene on an industrial scale such that the crystallization from the melt the polypropylene containing a high proportion of modification β, preferably more than 70%, and have a low density, for example less than 0.905 g / cm ^3, it is these products can be expected to have very good physical properties and very good processing properties.

SUMMARY OF THE INVENTION

The present invention provides polypropylene, crystalline copolymers or mixtures thereof with other polyolefins having a predominantly high impact strength and high tensile strength polypropylene content. Polypropylene contains the crystalline phase in hexagonal or pseudohexagonal form in an amount of more than 65% by weight, as measured by a differential calorimeter, with a specific gravity of these substances according to DIN 53479 of less than 0.905 g / cm ³ , containing 5 x 10 ⁴ to 5 x 10 ⁴ quino- (2,3-b) -acridine-7,14-dione-5,12-dihydro- quino [2,3-b] -acridine-6,7,13,14- (5H, 12H) > tetron per 100 parts by weight of the mixture and, in addition, a stabilizer, light stabilizers and / or other conventional additives.

The ability of the mixed crystals used to promote the crystallization of β-form polypropylene is surprising since such high proportions of β-form in the presence of gamma-phase could never be achieved using linear trans-quinacridone, since the β-phase and linear trans-quinacridone phase is also used as a nucleating agent, but promotes crystallization of polypropylene in crystalline form and.

The invention also relates to a process for the production of these substances, which comprises mixing the polypropylene in the solid phase intensively with stabilizers and / or light-protective agents and / or other additives and with 5 x 10 ⁴ to 5 x 10 ⁸ parts by weight of blended quino- (2,3-b) acridine-7,14-dione-5 crystals,

SK 277920-6

12-Dihydro-quino- (2,3-b) -acridine-6,7,13,14- (5H, 12H) -tetrone is then melted, shaped and allowed to cool.

The linear trans-quinacridone / quinacridone quinone mixed crystals used in the process of the present invention differ in the X-ray diffraction pattern from the gamma linear trans-quinacridone gamma phase in that they do not have thick lines at crystalline lattice spacing, 13.58, 6.41 4.33 and 3.37.10 ^- * cm as well as medium thick lines at 6.70.5.24 and 3.74.10 * cm.

Particularly preferred is the addition of the mixed crystals in an amount that achieves a content of 5.10 < -1 > to 5.10 &^lt; ⁷ > parts by weight per 100 parts by weight of the polypropylene composition.

With this addition, it is possible to provide a crystalline β content of greater than 70% and often greater than 80% with a specific gravity drop of up to 0.904 g / cm ³ .

A high proportion of β modification in the polypropylene material has an impact on the physical properties of the material, for example on the plates of the material, in which an increase in resistance to measurement according to DIN 53455 can be observed, in particular an increase in tensile strength under reduced elongation at break 53452, a reduction of 3.5% of the bending can be observed with the same force, and according to DIN 53453 and DIN 53753, an increase in impact strength can be demonstrated at 23 ° C and -20 ° C.

Polypropylene containing the same amount of gamma linear trans-quinacridone gamma phase has a higher elongation at break and its impact strength and tensile strength have values that lie between the polypropylene without nucleating agent and between the material of the invention. This means that the material produced by the method of the invention has a high strength with increased ductility.

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

The polypropylene blends of the present invention can be obtained by intimately mixing the individual components, the blended crystals being added alone or in the form of a mother blend followed by melt processing, for example by injection molding or extrusion. It is possible to convert the resulting material into a granulate which can be further processed in any desired way. The molding and granule temperatures are in the normal range, and the processing is carried out at a temperature of 200-220 ° C.

The polypropylene blends produced by the process of the invention have low leakage, high impact strength and tensile strength. The melting point is lower than that of conventional polypropylenes, approximately 145-150 ° C. The formation of spherolites is faster than that of conventional types of polypropylenes which crystallize in modification a, which is advantageous for subsequent processing.

The transition to modification occurs when the material is maintained at 150 ° C.

The resulting proportion of β modification results in turbidity of the polypropylene. Upon subsequent transition to modification, it is possible to achieve material re-clarification.

Due to its mechanical and processing advantages, the material produced by the process of the invention is suitable for a variety of processing methods, in particular for extrusion onto films, sheets and fibers, the resulting products having increased mechanical strength. Especially preferred is also processing into hollow articles and injection molding as well as casting very large objects. In the manufacture of these products, cracks occur in materials made of hitherto known materials, so that manufacture is difficult.

The compositions may also contain conventional stabilizing agents without impairing the effect of the nucleating agent.

The invention will be illustrated by the following examples. In all experiments, the mixtures were obtained equally, the comparative samples contained a linear trans-quinacridone gamma phase instead of the mixed crystals.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Polypropylene powder with a flow index (230 kg / m2) of 0.2 g / 10 minutes containing 0.1% calcium stearate, 0.05% tetrakis (2,4-di-tert-butylphenyl) -4, 4'-biphenylenediphosphonite, 0.1% by weight of pentaeritrityltetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.2% by weight of thiodipropionic acid ester are mixed with 5 x 10 -5 to 5 x 10 ⁸ parts by weight of the mixed trans-quinacridone and quinacridonequinone mixed crystals per 100 parts by weight of the mixture, and the resulting mixture is mixed thoroughly. Then the mixture is extruded at 210 ° C using a screw and granulated. 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 layers were added with the following X-ray diffractogram values:

mixed crystal 1 borne crystal 2

(10 ° C) and (io ' ^s < 10.46 (S) 10:16 (WITH) 6.28 6.24 4.60 S, 04 4.13 4.72 3.98 4:38 3.65 S 4.13 3.48 (S) 4.00 3.30 (S) 3.63 (WITH) 2.88 3.47 (WITH) 2.11 3.28 (WITH) 2.09 * 2. 84 2.17 2.11 2.09 2.08 2.6

(S) - thick belts

Plates of 20 x 20 x 0.25 mm were made from the blends thus obtained by melting and pressing at 220 ° C. These plates were cut into 5 mm diameter discs to determine the proportion of crystalline form β in the differential calorimeter.

For each sample, after the first heating, a 220 ° C cooling curve was determined and then a second heating to 23 to 220 ° C was performed in a DSC-2C (Perkin Elmer). Heating and cooling were performed at a rate of 20 K / min. The proportions of the β form were calculated from the area ratios for the β ratio and for the α + β ratio.

SK 277920-6

The values are shown in Table 1 below as a gamma phase linear trans-quinacridone gamma sample.

Table 2

Table 1

MKrtnoawý nuklMÓné opacity! Ieaon * dive area

parts per 100 agent tepleta * C for> ferau parts sneai in · 3> 10 ' SMOsní kryitél 2 114.1 43.2 BMtaaý krydtál 2 120.3 * 0.4 controls * 110.3 41.7 S «I0 ' ³ snow crystals 1 117.0 44.5 web crystal 2 114.0 • 2.3 controls * 117.1 34.5 3 «9» worn cry * t * L l 113.7 W, 9 ncvBý cover 2 114.4 • 3,2 inspection 114.0 ». * 5 r 1U ' ⁷ sox cover i i 113.4 70.4 opened cover 2 114.7 77.4 Itontrula 111. J 64.5 S x 10 '· sauna crystal 1 lll.J 73.1 saaaný kryitdl 2 112.1 69.6 inspection 107.3 36.7 Plates with dimensions of 136 x 136 were then made

proportional share Nuclear Oinidlo ipeciflck * hnotMw »g / ca * N «10 · * xaeaný kxyltdl 1 0.9038 kunyl kxyltál 2 0.9040 inspection 0.9118 3 «10» aneaný kryttdl L 0.9039 ZMMiý kryry *] 2 0,9043 kont rola * 0.9103 You are about'* laeenj crystal 1 0.9037 snowy crystals 2 0.9041 inspection .9085 3 «10 * ⁷ aneany cover 1 0.9036 znean? crystal 2 0.9039 inspection 0.9039 S 10 '· - sounded crystal 1 .9034 item cover 2 0.9039 inspection .9053

x 2 mm. The material was melted to 200 ° C, pressed for two minutes, and then cooled at about 10 K / minute to room temperature. From the 30 x 30 x 2 mm plates thus obtained, the specific gravity was determined according to DIN 53479. The values for the 5 x 10 ⁴ mass fraction were corrected for pigment content.

The results are shown in Table 2 below.

It is apparent from the table that no specific weight of less than 0.9050 was detected in control samples, even with proportions of β 68 or 69% (5 x 25 ^{, 0} ' ⁷⁾ ·

Mechanical properties were also determined for mixtures containing 5 x 10 parts by weight of nucleating agent per 100 parts by weight of the mixture. For this purpose, they were made by pressing plates of 240 x 240 x 3 or 240 x 240 x 4 ³⁰ mm and the plates thus obtained were subjected to the same tests as the above test bodies.

The results obtained are shown in Table 3 below:

Table 3 Propyl Dimension O Nucleation Unit Reagent Control Mixed Crystal 1 Standard

(230 / 2.16) g / 10 min

0.30

00:29

00:29

plate specific gravity 240 x 240 and 4 there g / c · ³ .9059 .9081 .9009 DIN 53479 breakdown voltage N / mm ² 31.0 0.2 * 32.1 * 0.3 27.5 0.6 * DIN 53455 elongation » 11.5 * 0.7 9.0 * 0.7 8.5 * 0.6 DIN 53455 tensile strength N / mm ² 39.8 2.5 * 43.5 1.9 * 46.1 0.7 * DIN 53455 elongation at break 744.4 * 37.6 761.7 * 39.2 652,7 * 12th 9 DIN 53455 bending stress 3,5% N / mm ² 30.7 0.7 * 34.3 0.6 * 29.8 0.7 * DIN 53452 flexural strength N / mm ² 37 .7 * 0.4 41.7X0. 3 36.1 * 0.6 DIN 53452 in a tenacious tenacity mJ / m m ² 5. 7 * 0.3 8.3 * 0.7 13.4 1.8 * DIN 53453 vrubovj) toughness IU / mm ² 1, 5 * 0.2 1.6 * 0.2 2.1 * 0.2 DIN 53453

impact strength + 23 * IU / mm ² 14.6X0.6

21.0 1.4 *

23.6tl.7S ¹ )

DIN 53753 impact strength + 20 * ^2> IU / MI ² 2.6 * 0.2

2.5 * 0.4

3.5 * 0.4

DIN 53753 tensile strength calculated from hardness below Tcl Binclla N / mm ²

69.6x0.fi

77,0x3

63,9X2.2

DIN 53456

• C 90

100

DIN 53460

J) hammer IJ ² 'hammer 0.5 J

Example 2

Following the procedure of Example 1, mixtures of polypropylene having a flow index (230 ° C / 2.16 kg) and 5 g / 10 min and 18 g / 10 min are obtained as stabilizers containing 0.1% by weight of calcium stearate, 0.05% by weight of 2,6-di-tert-butyl-4-methylphenol and 0.05% by weight of pentaeritrityltetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The samples were mixed with 5 x 10 ^- parts by weight of the mixed crystal of Example 1 per 100 parts by weight of the mixture and in the same manner as in Example 1, the proportion of form β was determined. Also in this case, a comparison was made with the same mixture but containing the same amount of the linear gamma trans-quinacridone phase.

The results are shown in Table 4 below: 15

Table 4

nucleating agent 5 m 1O * haaotn. work / 100 haotn, parts polypropylŠA l-foray percentage of flat area 20 aacsný kryštál 5 g / 10 44.5 kum.ru! and 5 g / 10 Min 44.3 crystal 1 18 g / 10 ein 40.2 inspection 1B g / 10 ein 34.2 25 PATENT right

Polypropylene, crystalline copolymers or mixtures thereof with other polyolefins having a predominantly high impact strength and high tensile strength polypropylene content, characterized in that it contains the crystalline phase in hexagonal or pseudohexagonal form in an amount of more than 65% by weight at measured by differential calorimeter, with a specific gravity of these substances according to DIN 53479 of less than 0,905 g / cm ³ , the material contains 5 x 10 "to 5 x 10 * parts by weight of quino- (2,3-b) -acridine-7 mixed crystals, 14-dione-5,22-dihydro with quino- (2,3-b) -acridine-6,7,13,14- (5H, 12H) tetron per 100 parts by weight of the mixture and, in addition, a stabilizer, anti-fouling agents exposure to light and / or other conventional additives.

Claims (3)

Polypropylene, crystalline copolymers or mixtures thereof with other polyolefins having a predominantly high impact strength and high tensile strength polypropylene content, characterized in that it contains the crystalline phase in hexagonal or pseudohexagonal form in an amount of more than 65% by weight at measured by differential calorimeter, with a specific gravity of these substances according to DIN 53479 of less than 0,905 g / cm ³ , the material contains 5 x 10 "to 5 x 10 * parts by weight of quino- (2,3-b) -acridine-7 mixed crystals, 14-dione-5,22-dihydro with quino- (2,3-b) -acridine-6,7,13,14- (5H, 12H) tetron per 100 parts by weight of the mixture and, in addition, a stabilizer, anti-fouling agents exposure to light and / or other conventional additives. Polypropylene according to claim 1, characterized in that it contains 5 x 10 -5 to 5 x 10 ^-7 parts by weight of mixed crystals per 100 parts by weight of the mixture and the proportion of hexagonal or pseudohexagonal crystalline form is higher than 70%. Method for producing polypropylene according to claim 1 or 2, characterized in that the solid phase polypropylene is intensively mixed with stabilizers and / or light-protective agents and / or other additives and with 5 x 10 * to 5 x 10 ** parts by weight. quino- (2,3-b) acridine-7,14-dione-5,22-dihydro mixed with quino- (2,3-b) acridine-6,7,13,14- (5H, 12H) tetrone and then melt, form and allow to cool.