HU221242B1

HU221242B1 - Polypropylene compositions having good transparency and impact resistant

Info

Publication number: HU221242B1
Application number: HU9501376A
Authority: HU
Inventors: Giuliano Cecchin; Floriano Guglielmi
Original assignee: Himont Inc
Priority date: 1988-12-14
Filing date: 1989-12-14
Publication date: 2002-09-28
Also published as: HU9501376D0

Abstract

A találmány szerinti polimerkészítmények a) 70–98 tömeg%-banetilénből, propilénből és/vagy egy CH2=CHR általános képletű ?-olefinből – a képletben R jelentése alkilcsoport – előállított,85–99,5 tömeg% propilént tartalmazó kristályos kopolimert és b) 2–30tömeg%-ban etilénből, propilénből és/vagy egy CH2=CHR általánosképletű ?-olefinből – ahol a képletben R jelentése a fentiekbenmegadott – előállított, 20–70 tömeg% etilént tartalmazó elasztomerkopolimert tartalmaznak; a b) kopolimer xilolban, szobahőmérsékletenrészben oldódik és etiléntartalmának xilolban oldható részéhezviszonyított tömegaránya legfeljebb 1,5; a xilolban oldható rész belsőviszkozitása (I.V.2) kielégíti a 0,2 ? (I.V.2/I.V.1)×(C2–) ? 0,6feltételt, ahol I.V.1 jelentése az (a) kristályos propilénkopolimerbelső viszkozitása, I.V.1 és I.V.2 értékét (dl/g) értékben fejezzükki, és (C–2) jelentése a (b) elasztomer kopolimer etiléntartalmánaktömege. ŕPolymer Compositions of the Invention a) 70-98% by weight of crystalline copolymer containing 85% to 99.5% by weight of propylene, containing from 85% to 99.5% by weight of propylene and / or from an olefin of formula CH2 = CHR, wherein R is alkyl. Containing from 2 to 30% by weight of ethylene, propylene and / or a CH2 = CHR generalized olefin, wherein R is as defined above, contains between 20 and 70% by weight of elastomer copolymer; the copolymer (b) is soluble in xylene, at room temperature and has a weight ratio of ethylene content of up to 1.5 in the xylene soluble part; the internal viscosity (I.V.2) of the xylene soluble part satisfies 0.2? (I.V.2 / I.V.1) × (C2-)? 0.6, wherein I.V.1 is the intrinsic viscosity of the crystalline propylene copolymer (a), expressed as I.V.1 and I.V.2 (dl / g), and (C-2) is the ethylene content of the elastomer copolymer (b). ŕ

Description

BACKGROUND OF THE INVENTION The present invention relates to low temperature, impact resistant and highly transparent polypropylene compositions.

It is known to reduce the crystallinity of polypropylene homopolymers for certain applications by copolymerizing propylene with a small amount of ethylene and / or α-olefins such as butene, pentene and hexene.

Such a process can produce so-called statistically distributed crystalline polypropylene copolymers which are more flexible and more transparent than the homopolymer.

The copolymers thus produced are used in a variety of applications, such as water pipes, water pipes or other liquid food containers, heaters, detergent monolayer bottles, beverage and perfume multilayer bottles, multi-pack food containers and multilayer containers. can be used to make rigid-walled tanks.

However, despite their good transparency, the statistically distributed copolymers of propylene cannot be used in areas requiring more impact-resistant polymers than the corresponding homopolymers, such as those listed above.

It has long been known that the impact resistance of polypropylene can be increased by admixing or post-polymerizing a sufficient amount of propylene-ethylene elastomeric copolymers, but the copolymer thus produced generally loses its transparency.

To overcome this disadvantage, a process has been proposed in which polypropylene is mixed in a melt phase with a propylene-ethylene copolymer of 70 to 85% by weight with a special catalyst (see U.S. Patent No. 4,634,740). It is pointed out in this specification that lower or higher ethylene content does not lead to the desired result. Such a production process further requires separate homopolymer and copolymer synthesis and subsequent blending of the polymers thus obtained. This procedure is clearly costly in terms of investment and operation. A further disadvantage is that the propylene-ethylene copolymer should be prepared in the presence of a less active catalyst in order to avoid the removal of catalyst residues.

In order to overcome the above disadvantages, we have developed a process for producing polypropylene with high transparency and high impact strength. In the process, a high yield stereospecific catalyst loaded on an active magnesium dihalide support is subjected to serial polymerization of propylene and ethylene or a mixture of propylene, ethylene and a higher alpha-olefin.

The process of the present invention eliminates the independent preparation of components, the costly mixing of components in the melt phase, and the independent purification of copolymer components.

U.S. Pat. No. 4,634,740, High-Yield, Stereospecific, Highly Yielded, Magnesium Dihalide Supported by Polymerization of 70 to 85% by weight of Ethylene Propylene Elastomer Polymer compositions containing copolymers have very low impact resistance at low temperatures. Furthermore, the transparency of the formulations obtained by the process was only satisfactory when the ethylene content of the elastomeric copolymer and the elastomeric copolymer were within certain critical limits relative to the intrinsic viscosity of the crystalline copolymer produced at room temperature in xylene.

In the prior art, it has not been taught or suggested so far that high-transparency, low-temperature, impact-resistant, statistically distributed, crystalline propylene copolymer can be produced by high yield serial polymerization in the presence of an active magnesium dihalide support.

In our work, we have developed a process for the preparation of crystalline propylene copolymers that meet the above requirements.

Copolymer compositions prepared by the process of the present invention

a) 70-98% by weight (preferably 85-98% by weight, preferably 80-95% by weight) of ethylene and propylene and / or an α-olefin of the formula CH ₂ = CHR wherein R is 2 C8-C8 straight or branched chain alkyl-crystalline copolymer (I - 85-99.5%, preferably 90-98%, propylene and 0.5-10%, preferably 2-3% - ethylene) Fraction) and

b) 2 to 30% by weight (preferably 2 to 15% by weight, preferably 5 to 20% by weight) of ethylene and propylene and / or an α-olefin of the formula CH ₂ = CHR, wherein R is containing the above-prepared elastomeric copolymer (fraction II) containing 20-70% by weight, preferably 25-60% by weight of ethylene;

the elastomeric copolymer is partially soluble at room temperature in xylene and has a weight ratio of ethylene to xylene soluble in 1.5 or less;

and the intrinsic viscosity (IV2) of the xylene soluble moiety satisfies the following condition:

0.2 <(IV2 / IVL) x C ₂ <0.6, where

IV 1 represents an intrinsic viscosity of the crystalline copolymer (IVL and the values IV2 dl / g are expressed), and C ₂ is the second. mass of ethylene in fraction.

Preferred copolymers of the present invention are xylene soluble at room temperature

10 to 25% by weight (preferably 10 to 15% by weight) and the weight ratio of the copolymer to the amount of ethylene soluble in xylene is 0.3 to 1.5 (preferably 0.3 to 0.9).

As the comonomer content of the copolymers produced by the process of the present invention increases, the hardness of the finished product is reduced, but at the same time it becomes more transparent.

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The elastomeric ethylene copolymer (fraction II) in the compositions of the present invention has a content of 2-30% by weight, preferably 5-20% by weight, which is critical in the sense that smaller amounts do not adequately reduce impact resistance and larger quantities are too hard. will be the finished product.

Criticism of II. fraction composition and molecular weight. If II. The ethylene content of fraction 1 is less than 20% or more than 70% by weight, and the product will not have sufficient impact resistance and / or transparency.

If II. The ratio of the intrinsic viscosity and the intrinsic viscosity and ethylene content of the xylene soluble fraction of the fraction xylene at room temperature does not satisfy the following condition:

0.2 <(IV2 / IVL) x (C ₂₎ <0.6 no satisfactory results are obtained, i.e. the optical properties of the copolymer are not satisfactory value above 0.6, and impact strength below the value of 0.2 is poor.

Fraction I has an intrinsic viscosity of 1-4 dl / g, which corresponds to a melt flow index (Μ.I.) of 80-01 g / 10 min.

The final product has a melt index (?) Of 0.1 to 5 g / 10 min, preferably 0.5 to 30 g / 10 min.

Transparency and strength can be enhanced by the addition of nucleating agents well known in the art.

According to the process of the present invention, the finished copolymer product is prepared by serial polymerization of monomers in the presence of a stereospecific Ziegler-Nattat catalyst on an active magnesium dihalide support. Such catalysts contain as a major component a solid component comprising an at least one halogen-titanium bond on an active magnesium dihalide support and an electron-donor compound.

The catalysts used in the process of the present invention are characterized in that they can be used to produce polypropylene having an isotactic index of greater than 90% in liquid propylene at 70 ° C, and when used in the presence of hydrogen at a suitable concentration, the polymer has a melt index of 1-10. g / 10 min. Such catalysts are well known in the patent literature.

The catalysts disclosed in U.S. Patent 4,339,054 and European Patent No. 45,977 are particularly preferred in the process of the present invention. Such catalysts are also disclosed in U.S. Patent Nos. 4,472,524 and 4,473,660. The solid catalytic component of known catalysts contains an ether, ketone or lecton, or a compound containing nitrogen, phosphorus and / or sulfur, or a mono- or dicarboxylic acid ester as the electron donor compound.

Particularly useful are phthalic acid esters such as diisobutyl, dioctyl or diphenyl phthalate, benzyl butyl phthalate; malonic acid esters such as diisobutyl and diethyl malonate; alkyl and aryl pivalates;

alkyl, cycloalkyl and aryl maleate; alkyl and aryl carbonates such as diisobutyl carbonate; ethyl phenyl and diphenyl carbonate; succinic esters such as mono- and diethyl succinate. Preferred electron donor compounds are phthalic acid esters.

The catalyst components described above can be prepared by various methods.

One method involves, for example, milling the magnesium dihalide (used in anhydrous form with less than 1% by weight of water), the titanium compound, and the electron donor compound under magnesium dihalide activating conditions. The mill is then treated one or more times with excess titanium tetrachloride at 80-135 ° C and then washed with a hydrocarbon such as hexane until all the chlorine ions have disappeared from the wash.

Alternatively, the anhydrous magnesium halide is preactivated by a known method and then treated at 80-135 ° C with an excess of titanium tetrachloride solution containing an electron donor compound. The titanium tetrachloride treatment is then repeated and the solid is washed with hexane or other suitable hydrocarbon to remove unreacted traces of titanium tetrachloride.

In another method, preferably spherical _MgCl2 .nROH compound of the formula: - wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol - treated titanium tetrachloride in an electron donor solution comprising a compound, used in excess. The treatment is carried out at 80-120 ° C. The resulting solid is separated and then treated again with titanium tetrachloride. The solid is separated and washed with some hydrocarbon until all the chlorine ions have disappeared from the wash.

According to a known process, magnesium alcoholates and chloro alcoholates (prepared by the process described in U.S. Patent No. 4,220,554) are treated with an excess of titanium tetrachloride containing an electron-donor compound under the conditions described above. .

Alternatively, magnesium halide and titanium alcoholate (such as MgCl _2. 2Ti (OC ₄ H ₉ ) ₄ complex) are treated with a solution of excess titanium tetrachloride in a hydrocarbon solution containing an electron donor compound. The solid product is separated off and treated again with excess titanium tetrachloride. The solid is separated off and washed with a hydrocarbon such as hexane. The titanium tetrachloride treatment is carried out at 80-120 ° C. Alternatively, the magnesium dichloride and titanium alcoholate complex is reacted with hydropolysiloxane in a hydrocarbon solution, the solid product is separated off and washed at 50 ° C with a silicon tetrachloride solution containing an electron donor compound.

The solid was separated and washed with excess titanium tetrachloride at 80-100 ° C.

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Porous plastics, spherical styrene divinylbenzene or inorganic carriers such as silica or alumina may also be treated with the electron donor titanium tetrachloride solution, these carriers being previously impregnated with organic solvent soluble compounds or magnesium compounds.

Such porous plastics and their impregnation process are described, for example, in Italian Patent 20811 A / 88.

The titanium tetrachloride treatment is carried out at 80-100 ° C, after which the unreacted titanium tetrachloride is separated off, the treatment is repeated, the solid is separated and washed with a hydrocarbon solvent.

In the reaction described above, the molar ratio of MgX ₂ to electron donor compound is generally from 4: 1 to 12: 1.

The amount of electron donor applied to the solid component is generally from 5 to 20 mol% based on the amount of magnesium dihalide.

In the case of plastic and inorganic carriers, the molar ratio of magnesium compound to electron donor compound is higher, generally 0.3-0.8 per electron.

The magnesium to titanium ratio of solid catalyst component (30: 1) to (4: 1) is lower in the case of plastic or inorganic supported compounds, generally (3: 1) to (2: 1).

The titanium compounds useful in the preparation of the solid catalyst component are halides and halogen alcoholates. A preferred titanium compound is titanium tetrachloride.

Satisfactory results can be obtained using titanium trihalides, in particular TiCl ₃ HR, TiCl ₃ ARA, and halogen alcoholates such as TiCl ₃ OR, where R is a phenyl group.

The reactions described above can be used to prepare active magnesium dihalides. Other reactions other than those described above are known in the art. In these reactions, the active magnesium dihalide is prepared from magnesium compounds other than magnesium halides, such as magnesium alcoholates or carboxylates.

The activity of solid magnesium halides is shown by the lack of a high-intensity diffraction line in the spectrum of the solid catalyst component in the spectrum of non-activated magnesium halides (having a specific surface area of less than 3 m ² / g); a halogen line of maximum intensity shifting toward the high intensity diffraction line of the dihalide; or that the high-intensity diffraction line exhibits a broadening half-width that is at least 30% larger than the half-width of the most intense diffraction line.

The most active are those in which the halogen line appears in the X-ray spectrum of the solid catalyst component.

Chlorides are preferred among the magnesium dihalide compounds.

In the case of the most active magnesium dichlorides, the halogen line appears in the X-ray spectrum of the solid catalyst component instead of the diffraction line at 25.6 nm.

Alkylaluminum compounds useful as cocatalysts are trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, and one or more aluminum atoms, each other being oxygen or nitrogen, or SO ₄ or SO _3. linear or cyclic alkylaluminum compounds.

Examples of such compounds are (C ₂ H ₅ ) ₂ Al-O-A1 (C ₂ H ₅ ) ₂ ;

(C ₂ H ₅ ) ₂ A1-N-A1 (C ₂ H ₅ ) ₂ ;

I

C ₆ H ₅ o

II (C, H ₅₎ ₂ OSO A1-A1 (C ₇ H ₅₎ _2;

II

ch ₃

I

CH ₃ (Al-O-) _n Al (CH ₃ ) ₂ ; and the

CH ₃ (Al-O-) _n wherein n is from 1 to 20.

Possible to use A1R ₂ OR 'compounds of formula I, wherein R' is aryl substituted with one or two places, and R is C1-6 alkyl; A1R ₂ H or a compound of formula in which

R has the same meaning as defined above.

The alkylaluminum compound is used in an amount such that the ratio of aluminum to titanium is from 1 to 1000.

Electron donor compounds for use with alkylaluminum cocatalysts are esters of aromatic acids, such as alkyl benzoates and especially 2,2,6,6-tetramethylpiperidine or 2,6-diisopropylpiperidine or at least one Si-OR bond - wherein R is hydrocarbon-containing silicon compounds.

Suitable silicone compounds are (tert-butyl) _2- Si (OCH ₃ ) ₂ , (cyclohexyl) ₂ Si (OCH ₃ ) ₂ or (phenyl) _2- Si (OCH ₃ ) ₂ .

The molar ratio of alkyl aluminum compound to electron donor compound is from 5: 1 to 100: 1.

In the process of the present invention, the polymerization is carried out in at least two steps. In the first step, fraction I, in the presence of the catalyst used in step I, polymerization of fraction I, in the presence of the catalyst in step II. fraction. Polymerization may be carried out by known methods, either continuously or batchwise, in liquid phase, with or without an inert diluent; or by combining a liquid and a gas phase process.

The reaction time and reaction temperature used in the two steps are not critical.

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However, it is preferred that the reaction time is 0.5 to 5 hours and the reaction temperature is 50 to 90 ° C. Molecular weight regulation is accomplished using known regulatory agents, particularly hydrogen.

As described above, the polymerization of α-olefins with propylene may yield a crystalline propylene copolymer or an elastomeric ethylene-propylene copolymer.

The α-olefin is CH ₂ = CHR, wherein R is hydrogen or C 2 -C 8 alkyl. Examples of such olefins are 1-butene, 1-pentene, 1-hexene or 4-methyl-1-pentene.

The following examples illustrate the process of the present invention in more detail.

1-7. examples and

Comparative Examples 1C-6C

The following polymers were analyzed for the prepared polymers:

- intrinsic viscosity was determined in tetrahydronaphthalene at 135 ° C;

flow rate (MI) was determined according to ASTM D 1238, L.;

- ethylene content (C ₂ ) determined by infrared spectroscopy;

- determination of the xylene-soluble and insoluble matter was determined by dissolving the substance in xylene at 125 ° C and then cooling to room temperature, separating the xylene-soluble and insoluble parts by filtration;

- modulus of elasticity was determined by the ASTM D 790 (tangent) method;

Izod impact resistance was determined using the ASTM D 256 (notched) method;

- the bending / fracture transition temperature was determined by its own HIMONT method, which is available upon request;

The transitional bending / breaking temperature is the temperature at which 50% of the specimen, molded with a specified mass of hammer, falls from a specified height.

- turbidity was measured according to ASTM D 1003 on 1 mm thick plates;

extensibility was measured according to ASTM D 638;

- II. the fraction content (% by weight) was determined by comparing the weight of the copolymer formed in the second step with the weight of the finished product;

The mass of the copolymer was determined by measuring the amount of ethylene and propylene introduced into the operation using flow meters calibrated to within ± 1 g.

- intrinsic viscosity (IV2) The intrinsic viscosity (IV2) of the xylene soluble moiety was determined by the following relationship:

IV2 = (IV _sf -IV _si · Χ,) / (1-χ,) where IV _SF is the intrinsic viscosity of the xylene soluble fraction of the final product;

IVSi is the intrinsic viscosity of the xylene-soluble fraction of the product obtained in the first polymerization step; and

X, = S, Q, / SF, where

S1 is the weight (% w / w) of the xylene soluble fraction of fraction I;

SF is the weight (% w / w) of the xylene soluble portion of the finished product; and

Q1 is the weight of fraction I relative to the finished product.

To determine physical and chemical properties, the samples were pelletized and cast; the product without the nucleating agent was pelletized at 230 ° C.

To determine turbidity, the plates were cast at 190 ° C and, depending on the melt index, at 210-230 ° C.

The production conditions and properties of the products of the present invention and the comparative process are set forth in Table 1B and their physico-mechanical properties are shown in Table 2.B. are summarized in Table.

Description of the procedure

The polymerization experiment was carried out in a 22 liter autoclave with a 90-revolutions per minute magnetic stirrer.

The pressure and temperature were kept constant throughout the reaction unless otherwise noted and hydrogen was used as the molecular weight regulator.

The composition of the gas phase (propylene, ethylene, higher alpha-olefm and hydrogen content) was analyzed by continuous gas chromatography.

The process was carried out in two steps. In the first step, the propylene was copolymerized with ethylene or another α-olefin to give a crystalline copolymer (fraction I).

In this step, the polymerization was carried out in liquid propylene slurry at a suitable and constant pressure of the desired comonomer.

In the second step, ethylene was copolymerized with propylene and / or a higher alpha-olefin to give an elastomeric fraction (fraction II).

This operation was carried out in a gas phase with a constant composition of the gaseous reaction mixture.

The procedure was carried out in detail as follows.

A / L. step

The following substances were introduced into the autoclave at room temperature in the order described:

- 16 liters of liquid propylene,

- the desired quantities of ethylene and / or α-olefm and hydrogen gas,

HU 221 242 Bl

- a catalyst system consisting of a solid catalyst component as described below, and

75 ml triethyl aluminum and

- 3.5 g of a mixture of cyclohexylmethyldimethoxysiloxane.

The solid catalyst component was prepared as follows.

625 ml of titanium tetrachloride were introduced into a 1 liter glass flask equipped with a condenser, a mechanical stirrer and a thermometer under anhydrous hydrogen gas. The material was stirred at 0 ° C, and 25 g of spherical MgCl ₂ .2Cl ₂ H ₅ OH carrier prepared by the method described in U.S. Patent No. 4,469,648 were added.

The mixture was heated to 100 ° C over 1 hour. When the temperature of the reaction mixture reached 40 ° C, 9 mmol of diisobutyl phthalate was added. The reaction mixture was then heated at 100 ° C for 2 hours and then allowed to settle. The supernatant was then aspirated. To the solid was added titanium tetrachloride (550 mL) and heated at 120 ° C for 1 h.

The reaction mixture was allowed to settle again and the supernatant was sucked off.

The solid residue was washed with anhydrous hexane at 60 ° C, 6 x 200 mL and then at room temperature with 3 x 200 mL.

The catalyst system described above was fed to the reactor by propylene pressure. The temperature of the reaction mixture was raised to 70 ° C over a period of about 10 minutes and maintained at this value throughout the polymerization. Meanwhile, ethylene and / or higher alpha-olefin and hydrogen gas were introduced to maintain a constant gas phase concentration in the reactor.

When the polymerization is substantially complete, the unpolymerized monomer is removed by blowing the gas mixture at atmospheric pressure.

B / second step

The crystalline propylene copolymer product thus obtained (fraction I) was then sampled through a ball valve on the underside of the autoclave and heated to 70 ° C.

Subsequently, ethylene and propylene and / or a higher carbon olefin was added in a proportion and amount to form a gas phase of the desired composition and pressure (known as the saturation concentration of ethylene, propylene, or higher α-olefin).

During the polymerization, the pressure and composition of the gas phase were maintained constant by introducing a gas mixture containing hydrogen gas, ethylene and propylene and / or higher α-olefins of the desired copolymer composition (fraction II). The amount of individual monomers fed was determined by flowmeters and the composition of the mixture and the amount consumed were recorded / recorded. The feed! the time from the reactivity of the reaction mixture used and the time intervals shown in I and II. varied depending on the amount of copolymer needed to adjust the desired ratio.

After completion of the process, the polymer powder formed was drained, stabilized by a known method, then dried in an oven at 60 ° C under nitrogen and pelletized.

Prior to pelletization, the product was optionally inoculated with a suitable amount of dibenzylidene sorbitol (DBS), generally 2000 ppm.

The reaction conditions and properties of the products obtained are shown in Tables IB and 2B.

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Table 1

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Table 1 (continued)

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HU 221 242 B1

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HU 221 242 Β1

Table 3

Conditions for the preparation of the polymers and analytical results of the polymers obtained IC 2C 3C 4C 5C 6C 7C 1st step Pressure (MPa) 3.08 3.11 3.09 3.10 3.09 3.09 3.08 Time (minutes) 120 120 110 150 240 110 80 Ethylene in the gas phase (mol%) 1.8 2.0 1.6 1.8 1.8 1.6 1.55 Hydrogen in the gas phase (mol%) 0.3 0.6 0.5 0.6 0.4 0.5 0.32 Copolymer intrinsic viscosity IVl (dl / g) - 2.14 2.05 2.41 2.58 2.51 2.44 Ethylene content in copolymer (% by weight) - 3.3 2.2 2.8 2.8 2.1 2.8 Xylene-soluble fraction (% by weight) - 8.5 5.9 5.7 6.5 3.9 6.5 Intrinsic viscosity of the xylene-soluble fraction (dl / g) - 1.2 1.60 1.08 1.35 1.3 1.26 Xylene insoluble fraction (% by weight) - 91.5 94.1 94.3 93.5 96.1 93.5 Intrinsic viscosity of the xylene-insoluble fraction (dl / g) - 2.2 2.05 2.48 2.58 2.54 2.45 Step 2 Pressure (MPa) - 0.91 0.92 0.82 0.80 0.84 0.68 Time (minutes) - 65 25 15 20 23 550 Propylene / * 1-butene (saturation) (g) - 264 237 200 180 86 * 136 Ethylene (saturation) (g) - 19 35 45 55 115 86 Ethylene in the feed mixture (% by weight) - 18 30 40 50 80 67.0 Hydrogen in the gas phase (mol%) - 1.2 2.5 0 0 12.1 4.1 end product II. Fraction content (% by weight) - 8.8 9.3 7.3 7.1 10.5 12.2 Ethylene content (% by weight) 2.8 4.6 5.3 5.6 6.1 9.9 10.6 1-butene content (% by weight) - - - - - 4.0 Internal viscosity (dl / g) 2.6 2.01 1.84 2.53 2.51 2.46 2.44 Flow rate (MI) (g / 10 min) 1.0 3.1 3.9 1.3 1.2 1.6 1.0 Xylene-soluble fraction (% by weight) 6.8 11.2 11.8 11.0 11.0 9.0 11.6 Intrinsic viscosity of xylene soluble fraction IV2 (dl / g) 1.18 1.42 1.40 2.48 2.11 1.35 1.81 Xylene insoluble fraction (% by weight) 93.2 88.8 88.2 89.0 89.0 91 88.4 Intrinsic viscosity IV (dl / g) of the xylene insoluble fraction 2.80 2.16 2.06 2.52 2.64 2.52 2.53 II. Fractional viscosity IV (dl / g) - 1.91 1.23 3.77 3.25 1.38 2.35 IV2 / IV1 xa II. Fraction of ethylene - 0.16 0.18 0.62 0.63 0.44 0.64

Table 4

Physico-mechanical properties of polymers 1 2 3 4 5 6 7 Flexibility modulus (MPa) 905 780 950 910 810 1050 920 Izod impact strength, 0 ° C (J / m) 18.5 24.7 22 34.2 31.5 31.4 58.9 Transient temperature (° C) + 11 +2 + 1.5 -8.5 - -1 -34 Energy, -5 ° C (J) 0.1 p, l 0.15 6.8 - 0.2 13.4 Energy, -10 ° C (J) 0.1 0.1 0.1 0.3 - 0.1 9.8 Tensile strength (MPa) 26.3 24.5 24.8 25.6 18.1 27.7 26.2

HU 221 242 BI

Table 4 (continued)

Polymers are physico-mechanical

Claims

Crystalline propylene copolymer containing from 1 to 5% by weight of ethylene; and

b) 5 to 20% by weight, 25 to 60% by weight, of an elastomeric copolymer containing ethylene.

1. Polymer compositions, which are compositions

(a) from 85 to 99.5% by weight of ethylene, propylene and / or an α-olefin of the formula CH ₂ = CHR, where R is C 2 -C 8 linear or branched alkyl, 70-98% by weight a crystalline copolymer of propylene and

b) 2-30% by weight of ethylene, propylene and / or 25 of an α-olefin of the formula CH ₂ = CHR wherein R is as defined above

containing an elastomeric copolymer containing from 20 to 70% by weight of ethylene;

the copolymer (b) is partially soluble in xylene at room temperature and has a weight ratio of ethylene to xylene soluble fraction of not more than 1.5; the intrinsic viscosity (I.V.2) of the xylene soluble moiety satisfies

0.2 <(IV2 / IVL) x (C ₂₎ <0.6 condition, wherein

I.V.1 is the intrinsic viscosity of the crystalline propylene copolymer (a),

IV 1 and IV2 value (dl / g) is expressed as a value, and (C ₂₎ is the weight of (b) an elastomeric copolymer of ethylene content.

Polymer compositions according to claim 1 which are

(a) 80-95% by weight, 90-98% by weight of propylene and

Polymer compositions according to claim 1, wherein 10 to 25% by weight are soluble in xylene at room temperature and the proportion by weight of ethylene in the xylene soluble portion is from 0.3 to 0.5.

Polymer compositions according to claim 1, wherein 10 to 25% by weight are soluble in xylene at room temperature and the proportion by weight of ethylene in the xylene soluble fraction is 0.3 to 1.5.