Polyolefin molding composition and molded product

 

(57) Abstract:

Describes a new polyolefin molding composition for thin-walled injection molding, consisting mainly of a polyolefin derived from olefin, with at least 3 C-atoms of the formula Ra-CH=CH-Rbwhere Raand Rbidentical or different, denote hydrogen or C1-15-alkyl straight or branched chain, or Raand Rbform with the associated ring atoms, whereby the polyolefin may contain up to 10 wt.% ethylene and a second olefin with a molar mass of more than 80,000 g/mol, a polydispersity Mw/Mn= 1:8 to 3.5, a viscosity of more than 70 cm3/g, a melting temperature of 130-160C, the length of the isotactic block 30-100 aimed transparency more than 30% of simple and extracted with ether part is less than 2 wt.%. Also described molded product. The technical result - the creation of the molding material with high transparency and rigidity and odorless and yellow. 2 S. and 3 C.p. f-crystals, 6 PL.

The invention relates to a very hard, transparent and rigid polyolefin molding mass for use in injection molding, preferably in thin wall castings PC called statistical copolymers, which is much more transparent compared to the homopolymers. However, there is a negative property, namely the decrease of the melting temperature, hardness, rigidity and resistance under load compared with homopolymers (EP-A-0433987, EP-A-0384263).

For most cases, when injection molding the deterioration of these properties is unacceptable. This is especially true for thin-walled injection molding; to obtain in this way molded products, such as glasses, high hardness is a very important and decisive criterion for the choice of raw materials.

These requirements satisfy the polyolefins, for example polypropylene, which after polymerization is additionally treated with peroxide.

These molding material, denoted as CU-polymers (CR = controlled rheology), have two significant drawbacks:

1) rework peroxide increases the cost of the target products and

2) when interacting with the peroxide formed of low molecular weight fragments, which has an unpleasant odor, which is manifested and made of a polymer molded product. Just in case, for example, glass or food packaging, the smell undesirable.

Nicheskim solution is a polyolefin molding composition according to EP 0485322. Known product can be used, for example, in the automotive industry as shock absorbers. However, the known molding composition has poor morphology of the powder and, therefore, cannot be used to obtain a molded product by injection molding, particularly thin-walled injection molding.

Thus, the objective of this invention to provide a molding material for injection molding, especially for thin-walled injection molding, which does not show known from the prior art negative properties, that is, the molding material in powder form with high transparency and rigidity, and beyond that has no odor and yellow and at the same time with good morphology of the powder.

It is shown that certain polyolefin molding material, which is mainly obtained by polymerization using metallocene catalysts without additional processing as in the case of treatment with peroxide, satisfy the above requirements.

In addition, unexpectedly shown that these polyolefin molding material when compared with CU-polymers directly on the equipment for injection molding significantly reduce the bone compared to CU-polymers, in addition, to reduce the thickness of the walls of the molded parts, which contributes to the saving of raw materials.

Thus, the object of the present invention is a polyolefin molding composition, mainly consisting of polyolefin, which is obtained from an olefin with at least 3 C-atoms of the formula Ra-CH = CH-Rbwhere Raand Rbthe same or different and mean hydrogen or C1-C15-alkyl (straight or branched chain) or Raand Rbform with the associated ring atoms. Polyolefin molding composition may contain up to 10 wt.% ethylene and a second olefin, as defined above, as co monomer.

Polyolefin molding composition has a molar mass Mw of more than 80,000 g/mol, preferably greater than 100,000 g/mol, polydispersity Mw/Mn of from 1.8 to 3.5, preferably from 2.0 to 3.0, the coefficient of viscosity of more than 70 cm3/g, preferably more than 100 cm3/g, a melting point of from 130 to 160oC, preferably from 140 to 160oC, the length of the isotactic block of nout= 30-100, aimed transparency more than 30%, preferably more than 35%, simple and extracted with ether part is less than 2 wt.%, preferably less than 1 weight. %.

is polypropylene.

Polyolefin molding composition according to the invention is used to obtain molded products by injection molding, particularly thin-walled injection molding, with weight polyolefin obtained by polymerization in the presence of a metallocene catalyst using hydrogen in an amount of not more than 3 vol.%.

In addition to the polyolefin molding composition according to the invention may also contain conventional additives, such as for the formation of crystallization centers, stabilizers, antioxidants, UV absorbers, light stabilizers, decontamination officers metals, acceptors radicals, fillers and amplifiers, agents compatibility, softeners, additives to improve processing, emulsifiers, pigments, optical brighteners, flame retardants, antistatics, blowing agents. Especially preferably the use of funds for the formation of crystallization centers. This significantly improves the rigidity and transparency. Well-known specialist, appropriate means for the formation of crystallization centers are available in large industrial scale, for example, pulverized talc, sodium benzoate or derivatives of sorbitol, as aprieta high transparency and high rigidity. Typically, these molding material in the form of a die-cast molded products are used everywhere where high transparency and rigidity. The molding material, in addition, characterized by the absence of odor and yellow.

The use of molding masses according to the invention is a thin-wall injection molding.

The following examples more explain the invention:

Mw- molar srednevekovaja mass (g/mol), some gel chromatography;

Mw/Mnthe polydispersity, defined gel chromatography;

AI index isotacticity (13C-NMR spectroscopy);

nout- average length of isotactic block (13C-NMR spectroscopy);

nPE- the average length of the polyethylene block (13C-NMR spectroscopy);

KB is the coefficient of viscosity, measured at 135oC for 0.1% solution of decahydronaphthalene in a capillary viscometer;

IL (230/2,16) melt index at 230oC, load of 2.16 kg (DIN 53735);

The melting point determination using DSC (20oC/min);

Transparency - die-cast plate 80 x 80 x 1 mm, the measurement noise amount of light);

TVS - indentation hardness of the ball (in the Annex to DIN 53456, molded (4 mm) sample for tensile test of type A according to ISO 3167, the temperature of the casting 240oC);

E - extension tension - indicator section line according to DIN 53497-Z;

Impact strength Izod - ISO 180/IC (measured at 20oC);

The normalized value of yellowness (NZ) - ASTM D 1925-77, DIN 6167 (tested sample: plate, molded by injection molding, HH,0 mm);

Density - the density determination at the 23oC according to DIN 53479, method A;

Heat tested in compression using a ball - on IEC 335/1, section 30.1;

The heat (And Vic) - according to ISO 306 - 1987 or DIN 53460.

Required according to the standard of the samples (molded product) obtained by the injection molding machine Kraus Maffei KM 90/210 C. the temperature of the mass was 2502oC. front Velocity flow were (30020) mm/s, the temperature of the mold (303)oC. Parameters of the cylinder softening: screw diameter 30 mm, the number of revolutions of the screw 420 rpm, injection pressure 2222 bar and the estimated amount of injection at 135 mm stroke length was 95 cm3.

A. Polymerization

Metallocene catalysts obtained as described for example in DE-P 4035883.6 (EP-application N 0485823 A. 1). In experiments on Polimeri.

EXAMPLE 1

A dry 150 DM3the reactor was rinsed with propylene and was loaded at 20oC 80 DM3gasoline fraction with a boiling range 100-120oC. After the filing of 50 l of liquid propylene were added 64 cm3solution methylalumoxane (solution in toluene, based on 100 mmol Al). The contents of the reactor were heated to 40oC and they dosaged hydrogen to achieve its contents in the gas chamber of the reactor 1,2 vol.%. 19, 8 mg rat-dimethylsilane(2-methyl-1-indenyl)circondariale was dissolved in 32 ml of toluene solution methylalumoxane (based on 50 mmol of Al) and were introduced into the reactor. Maintaining a constant hydrogen content in the reactor equal to 1,20,2 about.%, he polymerizable at 40oC 18 h the Polymerization was interrupted by gaseous CO2and the suspension polymer was launched in an attached reactor. The suspension medium was separated from the polymer powder through the filter cartridge and using distillation with water steam, and aqueous suspension of the polymer was separated from water by using pressure suction filter. The powder was dried at 80oC/100 mbar 24 hours Output: 19,6 kg

For powder measured the following parameters: IL (230/2,16) = 32 g/10 min; KV = 142 cm3/g; Mw= 170500 g/mol, Mw/Mn= 2,2; the temperature of the melt is however used the concentration of hydrogen 1,80,2, the number of metallocene was 17.3 mg Obtained 17,9 kg of powdery polymer.

For powder measured the following parameters: IL (230/2,16) = 58 g/10 min; KB = 114 cm3/g; Mw= 126000 g/mol, Mw/Mn= 2,1; melting point 150oC, AI = 96,8%, nout= 53, transparency more than 35%.

EXAMPLE 3

Was repeated example 2, however, 250 g of ethylene was evenly applied to the reactor during the whole time of polymerization (15 hours). Received 18.5 kg of powdery polymer.

For powder measured the following parameters: ethylene content of 1.25 wt.%, nPE< 1,2 (i.e. a large number of ethylene units isolated in the polymer chain). IL (230/2,16) = 49 g/10 min; KV = 131 cm3/g; Mw= 139000 g/mol, Mw/Mn= 2,4; melting point 148oC, the transparency of more than 35%.

EXAMPLE 4

Repeated example 2, however, used metallocen rat-dimethylsilane (2-methyl-4-phenyl-1-indenyl)-ZrCl2the polymerization temperature 50oC and the used amount of hydrogen was 2,95% vol.

Received 17,0 kg of polymer powder.

For powder measured the following parameters: IL (230/2,16) = 30 g/10 min; KB - 147 cm3/g; Mw= 189500 g/mol, Mw/Mn= 2,0; temperat evenly applied to the reactor during the whole time of polymerization. Received 19,5 kg of polymer powder.

For powder measured the following parameters: ethylene content of 3.2 wt.%, nPE< 1,2 (isolated embedding ethylene molecules in the polypropylene chain). IL (230/2,36) = 32 g/10 min; KV = 156 cm3/g; Mw= 194000 g/mol, Mw/Mn= 2,2; melting point 147oC, the transparency of more than 35%.

EXAMPLE 6

Repeated example 4, however, the used amount of hydrogen was (2,30,3).%. Received 16,9 kg of polymer powder.

For powder measured the following parameters: IL (230/2,16) = 19 g/10 min; KV = 169 cm3/g; Mw= 214500 g/mol, Mw/Mn= 2,0; melting point 160oC, the transparency of more than 35%.

EXAMPLE 7

A dry 150 DM3the reactor was rinsed with propylene and filled at 20oC 80 DM3gasoline fraction with a boiling range 100-120oC. After the filing of 50 l of liquid propylene were added 64 cm3methylalumoxane solution in toluene at the rate of 100 mmol Al). The contents of the reactor were heated to 40oC and they dosaged hydrogen to achieve its contents in the reactor of 0.7 vol.%. 11.0 mg rat-dimethylsilane(2-methyl-1-indenyl)circondariale was dissolved in 32 ml of toluene methylalumoxane solution (is). % with the 40oC polymerizable 24 hours the Polymerization was interrupted by gaseous CO2and the polymer suspension was launched in an attached reactor. The suspension medium was separated from the polymer powder through the filter and through the distillation of water vapor, aqueous suspension of the polymer was separated from the water using a suction filter. When 80oC/100 mbar powder was dried 24 h Output: 14,5 kg

For powder measured the following parameters: IL (230/5) = 4.8 g/10 min; KV = 294 cm3/g; Mw= 352000 g/mol, Mw/Mn= 2,3; melting point 151oC, AI = 97,0%, nout= 65, transparency more than 35%.

EXAMPLE 8

At 20oC analogously to example 7 obtained powder polymer with the following properties (yield: 10,1 kg):

IL (230/5) = 2.0 g/10 min; KV = 385 cm3/g; Mw= 485000 g/mol, Mw/Mn= 2,3; melting point 157oC, AI = 97,3%, nout= 70, opacity 35%.

EXAMPLES 9-11

Powder polymer was obtained as in example 7, however, varied the number of hydrogen:

0,40,05% vol. H2(example 9), 0,90,1% vol. H2(example 10) and 1,50,3% vol. H2(example 11).

Output powders were: 18.7 kg (example 9), 16,9 kg (example 10) and 20.6 kg (example 11), the transparency of more than 30%.

2Si indenyl2HfCl2(see EPA-0336127). The polymerization was carried out at 60oC with 0.4 vol.% hydrogen (example 12) and at the 50oC 0.15% hydrogen (example 13). For powders obtained are shown in table 2 data.

The use of molding masses to obtain molded products according to the invention described in the following examples.

EXAMPLE 14

Used a powder of polymer from example 1, which was mixed with 0.07 wt.% the pentaerythritol-tetrakis 3-(3,5-di-tert - butyl-4-hydroxyphenyl)propionate, 0.07 wt.% Tris(2,4-di-tert - butylphenyl)phosphite, 0.1 wt.% a mixture of 90% glycerol monostearate and 10% distearate glycerol (GMS, Atmer 129) and 0.25 wt.% methyldibenzothiophene (MDBS, Millad 3940) as additives to improve oxidation stability, processing and removal from the mold, and also as centers of crystallization and then granulated using a twin-screw extruder ZSK 28 der Fa. Werner und Pfleiderer. The temperature in five heated zones of the extruder was 150oC (input), 210oC, 260oC, 280oC and 260oC (plate filler). The temperature of the mass was 260oC-screw extruder was operated at 280 rpm was Obtained a colorless, presrele way of injection molding.

For these obtained molded products defined the following characteristics: IR (230/2,16) = 35 g/10 min; transparency of 65%, TVS (358 N) = 75 MMO-2; E-module tensile (indicator section) 1610 MMO-2, impact strength Izod 58 MGM-2; NZ = 5,5. The processability of the molding material was tested using thin-wall injection molding (manufacture of cups with a volume of 175 ml with a wall thickness of 0.5 mm) on a machine for injection molding Netstal 110/45. Criteria has been the nature of loss forms, as well as the achieved cycle time without problems during 3 h at maximum speed. Treatment temperature 230oC, a fault-free cycle was 32 injection/min (cycle time of 1.9 sec). The obtained glasses were transparent, light and odorless.

EXAMPLE 15

Worked example 14, but instead of 0.25 wt.% methyldibenzothiophene were injected with 0.3 wt.% talc ultra-thin as centers of crystallization.

For molded defined the following parameters: density = 0,904 g/cm3; IR (230/2,16) = 33 g/10 min; transparency 41%; TVS (358 N) = 71 MMO-2; E-module tensile 1430 MMO-2; impact strength Izod 52 MGM-2; NZ = 6,5.

Experience in manufacturing top is actulaly example 14, however, never used stearate glycerol or sorbitol.

For molded defined the following parameters: density of 0.901 g/cm3; IR (230/2,16) = 33 g/10 min; transparency 35%; TVS (358 N) = 69 MMO-2; E-module tensile 1430 MMO-2, impact strength Izod 68 MGM-2; NZ = 6,5.

Experience of manufacturing cups molding, similar to example 14 showed the cycle time of 2.3 seconds.

EXAMPLE COMPARISON 1

Example 14 was repeated with polypropylene for injection molding (Hostalen PPV 1770 S3A), which is obtained using conventional catalyst of Ziegler-Natta (TiCl4/MgCl2/diethyl ether phthalic acid). The polymer was extracted by a simple ether part 4.2% of atactic polypropylene. The length of the isotactic block was 150,w/Mn= 3.6 and melting point 164oC. obtained from this polymer molded measured the following parameters: density 0,902 g/cm3; IR (230/2,16) = 27 g/10 min; transparency 23%; TVS (356 N) = 64 MMO-2; E-module tensile 1200 MMO-2; impact strength Izod 65 MGM-2; NZ = 8,5.

Experience of manufacturing cups molding, similar to example 14 showed the time of cycle 2, the structure according to examples 1 to 3, molded products of example comparisons are characterized by a significantly lower stiffness (TVS, E-module tensile), lower transparency and a stronger yellow colour (NZ-value).

In the processing of obtaining stakanov the cycle time was longer, the obtained glasses were much less transparent and was found typical for CU-products smell.

EXAMPLE 17

Example 14 is repeated with the polymer of example 2.

For molded defined the following parameters: IL (230/2,16) = 53 g/10 min; transparency of 65%; TVS (358 N) = 65 MMO-2; E-module tensile 1600 MMO-2; impact strength Izod 40 MGM-2; NZ = 5,2.

Experience of manufacturing cups molding, similar to example 14, however, temperature processing 220oC showed the cycle time of 1.7 sec. The obtained glasses were transparent, light as water and odorless.

EXAMPLE 18

Example 15 is repeated, but the polymer was used polypropylene in example 2.

For molded defined the following parameters: IL (230/2,16) = 56 g/10 min; density 0,906 g/cm3; opacity 40%; TVS (358 N) = 75 MMO-2; E-module tensile 1550 MMO-2; shock Vya is a logical example 14, however, when the treatment temperature 220oC showed a cycle time of 1.6 seconds.

EXAMPLE 2 COMPARISON

Example 18 was repeated with polypropylene for injection molding (Hostalen PPW 1780 S2A), which is obtained using conventional catalyst of Ziegler-Natta (TiCl4/MgCl2/diethyl ether phthalic acid).

For this polymer measured the following parameters: 3.7 wt.% atactic polypropylene (simple extraction with ether); IR (230/2,16) = 54 g/10 min; KV = 140 cm3/g; Mw= 161000 g/mol, Mw/Mn= 3,8; melting point 162oC.

For molded products obtained from the moulding mass, not relevant to the invention, measured the following parameters: density 0,907 g/cm3; IR (230/2,16) = 51 g/10 min; opacity 30%; TVS (358 N) = 75 MMO-2; E-module tensile 1400 MMO-2; impact strength Izod 45 MGM-2; NZ = 8,0.

Experience of manufacturing cups molding, similar to example 14 showed a large cycle length 2.0 s, the resulting glasses are much less transparent and was found typical for CU-products smell.

EXAMPLE 19

Repeated example 14, however, used the polymer of example 3. For the obtained molded the shrinkage 1500 MMO-2; impact strength Izod 95 MGM-2; NZ = 6,0.

Experience of manufacturing cups molding, similar to example 14 showed the cycle time of 1.7 seconds, received the cups had excellent transparency and did not detect any smell.

EXAMPLE 20

Repeated example 14, however, used the polymer of example. 4. For the obtained molded product measured the following parameters: density 0,908 g/cm3; IR (230/2,16) = 32 g/10 min; transparency 42%; TVS (358 N) = 84 MMO-2; E-module tensile 1700 MMO-2; NZ = 5,8.

Experience of manufacturing cups molding showed the cycle time of 1.4 seconds.

EXAMPLE 21

Repeated experience of 14, however, used the polymer of example 5. For obtained by molding under pressure of the products measured the following parameters: IL (230/2,16) = 35 g/10 min; transparency 80%; TVS (358 N; = 68 MMO-2; E-module tensile 1550 MMO-2; impact strength Izod: without destruction; NZ = 6,0.

Experience of manufacturing cups molding showed the cycle time of 1.7 seconds.

EXAMPLE 22

Repeated example 14, however, used the polymer of example 6. For obtained by molding under pressure of the products measured the following parameters: IL (23P>-2; NZ = 5,5.

Experience of manufacturing cups molding showed the cycle time of 1.4 seconds.

EXAMPLE 23

Repeated example 14, however, used the polymer of example 5. For obtained by molding under pressure of the products determined the following parameters: IL (230/2,16) = 35 g/10 min; opacity 70%; TVS (358 H) = 66 MMO-2; E-module tensile 1350 MMO-2, impact strength Izod 85 MGM-2; NZ = 6,0.

In the experience of making cups molding the obtained glasses with excellent transparency and odorless.

EXAMPLE 24

Used powder of the polymer of example 8. For measurement of mechanical and optical properties of the produced molded product according to the standard (injection molded products, for measuring TVS pressed plates 4 mm). For this purpose, the polymer powder was thoroughly mixed with 0.3 wt.% pentaerythritoltetranitrate 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 0.05 weight. % of calcium stearate and melted, homogenized and granulated using a twin-screw extruder ZSK 28 firm Werner und Prieiderer. The temperature in five heated zones of the extruder was 150oC (input), 200oC, 270oC, 280oC and 255oC (pleace colorless granules.

For obtained from this molding material products or directly for this molding material defined by the following parameters: IL (230/5) of 5.2 g/10 min; KV = 283 cm3/g; Mw= 346000 g/mol, Mw/Mn= 2,2; melting point 152oC, AI = 97,0%; nout= 65. Transparency 48%; A Vic = 147oC; heat tested in compression using a ball 1.5 mm at 110oC; E-module tensile = 1376 MMO-2; TVS = 74 MMO-2; TVS for injection molded products according to DIN 53456 (358 N): 76 MMO-2.

COMPARING 3

For the obtained molded products made from non-invention molding masses (statistical copolymer Hostalen PPU 5736 S2G Hoechst AG, Frankfurt, Germany (copolymer of ethylene and propylene with ethylene content of 2.3%) performed similar measurements:

IL (230/5) = 56 g/10 min; KV = 183 cm3/g; Mw= 251000 g/mol, Mw/Mn= 3,8; melting point 157oC. Transparency was 50% And the value by Vika 140oC. E-module tensile 1100 MMO-2, indentation hardness ball TVS = 60 MMOs-2.

It is shown that the molded product obtained from statistical copolymers with similar transparency reveals much is but the invention of example 24.

EXAMPLE 4 COMPARISON

Similarly investigated molding the mass of ordinary commodity polypropylene (Hostalen PPN 1060, Hoechst, AG, Frankfurt, FRG):

IL (230/5) = 8 g/10 min; KV = 290 cm3/g; nout= 109; Mw= 280000 g/mol, Mw/Mn= 6,0; melting point 164oC.

Mechanical and optical characteristics obtained from Hostalen PPN 1060 moulded products: transparency 24%; And Vika 152oC; E-module tensile 1300 MMO-2; TVS = 80 MMO-2.

It is shown that under comparable mechanical characteristics and heat resistance, transparency, appropriate product according to the invention, is not achieved.

EXAMPLE 25

Used polypropylene powder of example 8, the molding composition was obtained analogously to example 24, the temperature in sextrader 135oC (input), 175oC, 290oC, 280oC and 250oC (plate filler), the temperature of the mass 280oC-screw extruder was operated at 300 rpm

IL (230/5) = 1.8 g/10 min; KV = 385 cm3/g; Mw= 471000 g/mol, Mw/Mn= 2,7; melting point 156oC; AI = 97,4%, nout= 70; opacity 56%; And Vika 152oC; heat tested in compression using a ball of 1.7 mm is installed from the molding material, combine high transparency, high heat resistance, hardness and rigidity.

EXAMPLES 26-28

Used polypropylene powders of examples 9 (example 26), 10 (example 27) and 11 (example 28).

From powders of polymers obtained molded product according to the invention (as in example 24).

The extruder was operated as follows (see tab. A).

The measurement results for granules and the obtained molded articles are shown in table 3.

EXAMPLES 29 AND 30

Used powders of polymers of examples 12 (example 29) and 13 (example 30). Analogously to example 24 the obtained molded product was obtained by extrusion.

The extruder was operated as follows (see tab. B).

The measurement results for granules and the obtained molded articles are shown in table 4.

EXAMPLE 31

a) Obtaining polymers.

A dry 150 DM3the reactor was rinsed with nitrogen and propylene and at 20oC filled purified from aromatic compounds by gasoline fraction with a boiling range 100-120oC. After addition of 50 l of liquid propylene were added 64 cm3toluene methylalumoxane solution (100 mariaclara content 2,9 about. %; 10,6 mg rat-dimethylsilane(2-methyl-4-phenyl-1-indenyl)percentagea was dissolved in 16 ml of toluene methylalumoxane solution (25 mmol Al) was introduced into the reactor. Maintaining a constant hydrogen content in the gas chamber of the reactor, equal to 2.9%, at the 50oC polymerizable to a residual pressure of propylene of 1 bar. The polymerization reaction was interrupted by gaseous CO2and the suspension polymer was applied to an attached reactor. The suspension medium was separated from the polymer powder through the filter and through the distillation of steam, aqueous suspension of polymer was separated from the water using a suction filter. Powder at 80oC/100 mbar was dried 24 h

Output: 20,8 kg

IL (230/5) = 37 g/10 min; KV = 182 cm3/g; Mw= 197500 g/mol. Mw/Mn= 2,4; melting point 160oC, AI = 98,8%, nout= 100, opacity 35%.

b) Receiving the molding material.

The molding composition was obtained analogously to example 24. The temperature in the extruder was 150oC (input), 200oC, 290oC, 280oC and 260oC (plate filler), the temperature of the mass 275oC-screw extruder was operated at 250 rpm/min For the obtained molded product has the following five-160oC; opacity 54%; And Vika 156oC; heat tested in compression using a ball 1.8 mm at 100oC; E-module tensile 1640 MMO-2; TVS = 84 MMO-2.

A molded product obtained from the molding material, high transparency, heat resistance, hardness and rigidity.

EXAMPLE 32

a) Receiving system socializaton/metallocen.

AA) the Receipt of the marked socializaton carried out according to EP 92107331.8 in the reactor of stainless steel explosion-proof to the pumping system pressure of 60 bar, with a supply of inert gas, maintaining the temperature using the cooling jacket and the second cooling circuit via a heat exchanger on the pumping system. The pumping system sucks the contents of the reactor through a connection in the bottom of the reactor, forcing it to move the pump to the mixer and through the discharge pipe through the heat exchanger back into the reactor. The mixer was connected so that the feed line was narrowed in cross section of the pipe, where there was an increased flow velocity in the turbulent zone which is axially and towards the direction of flow directed onkostwo water under a pressure of 40 bar of argon. Control reactions were carried out through the sampler at the pumping circuit.

In the above-described reactor volume 16 DM3submitted 5 DM3Dean in inert conditions. Added 0,3 DM3(3,1 mol) of trimethylaluminum. Then through the funnel for solids in the reactor was dosaged 250 g of silica gel SD 3216-30 (Grace AG), which was dried at 120oC in argon boiling layer and homogenized using a mixer and pumping system. The total number 45,9 g of water was applied to the reactor in portions of 0.1 cm3every 15 s for 2 hours. The pressure created by the argon and released gases, supported by the valve regulating the pressure, the constant ~ 10 bar. After the introduction of the water pumping system was switched off and stirring is continued for another 5 hours at 25oC. using a suction filter solvent was removed and the solid catalyst was washed with Dean. Then dried in vacuum.

ab) Interaction of socializaton with metallocene rat-dimethylanilines(2-methyl-4 - phenyl-1-indenyl)ZrCl2.

1.5 g of a solid (106 mmol), the receipt of which is described in AA), suspended in a vessel with stirring at 100 cm3toluene and cooled to -30o<75 cm3toluene and bury within 30 minutes to a suspension. Slowly with stirring, was heated to room temperature, and the suspension was stained red.

In conclusion, stirred for 1 hour at 80oC and after cooling to room temperature the mixture was filtered and the solid residue was washed 3100 cm3toluene and 1100 cm3hexane.

The filter residue was dried in vacuum from hexane. Obtained by 12.9 g of free flowing, light red applied catalyst. Analysis showed the content of 10.1 mg zirconocene per gram of catalyst.

b) Polymerization.

2.8 g of the catalyst described in ab), suspended in 50 cm3free from aromatic compounds in the gasoline fraction with a boiling range 100-120oC.

Parallel to this dry 75 DM3the reactor was washed first with nitrogen and then with propylene, and then filled 0,75 DM3(at normal pressure) of hydrogen and 40 DM3liquid propylene. Then was diluted 12 cm3triisobutylaluminum (48 mmol), 100 ml of hexane was introduced into the reactor and the contents stirred for 15 minutes at 30oC.

In conclusion, was introduced into the reactor, the suspension of catalyst, was heated to a temperature of C.

The polymerization was stopped by adding 50 ml of isopropanol. The excess monomer was degirolami, the polymer was dried in vacuum.

As a result 5,0 kg of polypropylene powder.

For powder defined by the following parameters: IL(230/5) = 6,1 g/10 min; KV = 305 cm3/g; Mw= 382000 g/mol, Mw/Mn= 2,2; melting point 150oC, the transparency of more than 35%.

(C) Receiving the molding material.

Forming mass is obtained analogously to example 24. The temperature in the extruder 150oC (input), 200oC, 250oC, 280oC and 270oC (plate filler), the temperature of the mass 270oC, the number of revolutions of the auger 240 rpm

For the molding material and obtained by molding measured the following characteristics: IR (230/5) = 6.5 g/10 min; KV = 285 cm3/g; Mw= 379000 g/mol, Mw/Mn= 2,2; melting point 151oC. Transparency 45%; heat tested in compression using a ball of 1.4 mm at 110oC; And Vika 147oC; TVS = 79 MMO-2; E-module tensile 1487 MMO-2.

1. Polyolefin molding composition for thin-walled injection molding, consisting mainly of a polyolefin derived from olefin with at least 3 C-atoms is od or1-15-alkyl straight or branched chain, or Raand Rbform with the associated ring atoms, whereby the polyolefin may contain up to 10 wt.% ethylene and a second olefin, with a molar mass of more than 80,000 g/mol, a polydispersity Mw/Mnof 1.8 to 3.5, a viscosity of more than 70 cm3/g, melting point 130 - 160C, the length of the isotactic block 30 - 100 aimed transparency more than 30% of simple and extracted with ether part is less than 2 wt.%.

2. Polyolefin molding composition under item 1, characterized in that it has a molar mass of more than 100,000 g/mol, a polydispersity Mw/Mn2 - 3, the coefficient of viscosity of more than 100 cm3/g and a melting point of 140 to 160C.

3. Polyolefin molding composition under item 1 or 2, characterized in that the polyolefin is polypropylene.

4. Polyolefin molding composition according to PP.1, 2 or 3, characterized in that it further comprises means for the formation of crystallization centers, stabilizers, antioxidants, UV absorbers, light stabilizers, decontamination officers metals, acceptors radicals, fillers and amplifiers, combining agents, softeners, additives to improve processing, emulsifiers, pigments, is manufactured by a thin-walled injection molding, characterized in that it is made of polyolefin molding material on PP.1 to 4.

 

Same patents:

The invention relates to polymer mixtures containing olefinic polymer, monotinicity aromatic polymer and the agent compatibility

The invention relates to modified due to the elastomeric grafting polipropilene, their mixtures with modified due to vaccinations isotactic polypropylene, and to their use as agents compatibility or adhesion

The invention relates to thermoplastic polymer compositions based on polyamides, which can find application in mechanical engineering, in particular in the automotive industry, for the manufacture of structural parts of the interior and exterior of the car

The invention relates to polymeric materials, in particular, polymers containing secondary and may find application in the manufacture of waterproofing, roofing materials, floor coverings, i.e. materials for protection of foundations, roofs, floors, different buildings

The invention relates to copolymers of ethylene,-olefin containing from 3 to 18 carbon atoms, and unpaired-omega diene having at least 7 carbon atoms and having two easily curable double bonds, the number of non-conjugate diene is 0.005 to 0.7 mol

The invention relates to the manufacture of abrasive tools on the organic binding of agglomerated, monocrystalline and polycrystalline powders of diamond, cubic boron nitride

The invention relates to the manufacture of abrasive tools on the organic binding of agglomerated, monocrystalline and polycrystalline powders of diamond, cubic boron nitride

The invention relates to the field of artificial leather and reinforced film material on a textile backing and can be used, for example, in the automotive industry for sheltering vehicles, cargo, vans pneumatic and frame structures for various purposes, for the manufacture of flexible tanks, vent pipes

The invention relates to amorphous transparent plate and method of its manufacture

The invention relates to the field of engineering, building materials, efficient sanding of various surfaces: metals, alloys, and materials of mineral origin
The invention relates to the processing of rubber mixtures, in particular for manufacturing reinforced rubber articles such as bodies of rotation

The invention relates to the technology of composite materials, namely obtaining pre-impregnated filler for subsequent molding products using "dry", "wet" winding or hot pressing, and can be used within the aerospace and engineering industries with the development and operation of highly loaded components and structures from overadaptation

The invention relates to the technology of composite materials, namely obtaining pre-impregnated filler for subsequent molding products using "dry", "wet" winding or hot pressing, and can be used within the aerospace and engineering industries with the development and operation of highly loaded components and structures from overadaptation

The invention relates to methods of injection molding of polymers and preformed workpieces used in these processes

The invention relates to foundry, in particular for casting castings with internal thread
Up!