JP2008516025A - Elastomer polyolefin composition - Google Patents

Abstract

A) Crystalline with a polydispersity index (PI) of 4.5-6 and an isotactic pentad (mmmm) content of more than 96% measured by ¹³ C NMR with xylene insolubles at 25 ° C Propylene homopolymers or crystalline copolymers of propylene containing less than 3% ethylene or C ₄ -C ₁₀ α-olefins or combinations thereof; B) 35% to 70% propylene or C ₄ -C ₁₀ Olefin polymer compositions containing 15-40% partially amorphous ethylene copolymer containing α-olefins or combinations thereof, and optionally small amounts of dienes (mass basis unless otherwise stated). The olefin polymer composition exhibits an elongation at break value in the range of 150-600% according to ISO 527.

Description

  The present invention relates to elastomeric polyolefin compositions and processes for their preparation.

As is known, isotactic polypropylene is endowed with a special combination of excellent properties, but has the disadvantage of insufficient impact resistance at relatively low temperatures and low elongation properties.
According to the teachings of the prior art, the addition of rubber can eliminate defects without noticeably affecting other polymer properties. This can be obtained by changing the synthesis process or by blending polypropylene and rubber.

  A change in the synthesis process involves polymerizing propylene to an isotactic polymer and then copolymerizing an ethylene and propylene mixture in the presence of the isotactic polymer. Representative methods and compositions of the prior art are described in US Pat. No. 3,200,173, USP 3,629,368, USP 3,670,053, USP 6,313,227 and European Patent Application 0 077 532. In the issue.

  The polyolefin composition described in the European patent application EP 03007669.9 (published as WO2004 / 087807) has high rigidity and good impact resistance. The balance of properties included (A) a highly crystalline propylene homopolymer or copolymer with a broad polydispersity index and (B) an elastomeric ethylene copolymer, collected at 90 ° C. as a result of temperature programmed elution fractionation (TREF) The ethylene content of the fraction is achieved by a composition that satisfies a specific relationship. The disadvantage of this composition is that it does not have sufficient elongation.

  The polyolefin composition described in European Patent Application EP 401 2148.5 has a high elongation at break and good impact resistance. The disadvantage is that the stiffness is not very high when the elongation is high. A composition having a high value of elongation at break contains a large amount of elastomeric polymer.

  It has now been found that it is possible to obtain a polypropylene composition having a particularly advantageous balance of properties, in particular a high elongation at break and good impact resistance, without causing a significant reduction in the stiffness properties. .

  An advantage of the composition according to the invention is that high elongation properties are achieved with a relatively low content of elastomeric polymer in the composition. Another advantage is that the composition has a relatively high stiffness despite the fact that the composition exhibits high elongation at break values.

  Another advantage is that the articles prepared with the composition according to the present invention have good impact resistance at both ductile-brittle transition temperature and Izod impact resistance, so that they can be used for several applications at low temperatures without breaking the article. It is possible to do.

  The composition according to the invention can be easily converted into various finished or semi-finished products, in particular by using injection molding and thermoforming techniques. A particular balance of properties and a high value of elongation at break make the composition suitable for the automotive industry, in particular for bumpers.

Thus, the present invention
A) having a polydispersity index (PI) value of 4.5-6, preferably 4.5-5.5, and a content of isotactic pentad (mmmm) measured by ¹³ C NMR in xylene insolubles at 25 ° C. 60 to 85 wt% of a crystalline propylene homopolymer or a crystalline copolymer of propylene containing 3 wt% or less of ethylene or C ₄ -C ₁₀ α-olefins or combinations thereof higher than 96%, preferably higher than 98% %, Preferably 65-80 wt%, more preferably 65-75 wt%;
B) 15% of a partially amorphous copolymer of ethylene containing 35 wt% to 70 wt%, preferably 40 to 55 wt% of propylene or C ₄ -C ₁₀ α-olefins or combinations thereof and optionally a small amount of diene. -40 wt%, preferably 20-35 wt%, more preferably 25-35 wt%
The present invention relates to an olefin polymer composition to be contained.

The olefin polymer composition according to the invention exhibits an elongation at break value of 150 to 600%, preferably 200 to 500% according to ISO 527.
A particularly preferred feature of the composition of the present invention is that the molecular weight distribution measured by GPC in component (A) as expressed by the ratio Mw (average) / Mn (average) is in the range of 6-9;
The value of the Mz (average) / Mw (average) ratio measured by GPC in component (A) is 2.5 or more, in particular 2.5 to 4.5, typically 3 to 4;
The flexural modulus (ISO 178) is 700-1500 Mpa, more preferably 900-1300 Mpa;
The melt flow rate (MFR) is 0.5 to 45 g / 10 min, more preferably 2 to 20 g / 10 min (ISO 1133, 230 ° C., 2.16 kg load).

The composition according to the invention preferably exhibits an impact resistance value at a ductile-brittle transition temperature of less than -50 ° C. The Izod impact resistance of the composition is preferably greater than 12 kJ / m ² at 23 ° C. and greater than 7 kJ / m ² at 0 ° C.

  The term “copolymer” as used herein refers to both polymers having two different repeating units in the chain and polymers containing two or more different repeating units in the chain, such as terpolymers.

Component (A) is preferably a propylene homopolymer.
The stereoregularity of the polymer of component (A) is an isotactic type.
The copolymer of components (A) and (B) comprises repeating units derived from ethylene and / or butene-1, pentene-1, 4-methyl-pentene-1, hexene-1 and octane-1, or combinations thereof. Including. A preferred comonomer is ethylene. The total amount of copolymerized ethylene is preferably 9 to 20 wt%. Copolymer (B) may optionally contain repeat units derived from conjugated or non-conjugated dienes such as butadiene-1,1,4-hexadiene, 1,5-hexadiene and ethylidene-norbornene-1. When present, the diene is typically present in an amount of 0.5 to 10 wt% based on the weight of the copolymer.

As mentioned above, the composition of the present invention can be prepared by a polymerization process comprising at least two stages. In the first stage, the relevant monomers polymerize to form component (A), and in one or more subsequent stages ethylene-propylene, ethylene-propylene and one or more C ₄ -C ₁₀ α-olefins, A mixture of ethylene and one or more C ₄ -C ₁₀ α-olefins and optionally a diene polymerizes to form component (B).

  Thus, the present invention also relates to a process for pre-preparing the composition by continuous polymerization comprising at least two continuous steps. Components (A) and (B) are prepared separately in each step except the first step in a continuous process performed in the presence of the polymer formed in the preceding process and the catalyst used in the preceding process. The The catalyst is added only in the first step, but its activity remains active in all subsequent steps. Component (A) is preferably prepared in one or two polymerization stages. Although the order of the polymerization stages is not an important process feature, it is preferred that component (A) be prepared before component (B).

Polymerization can occur in liquid phase, gas phase or liquid-gas phase.
For example, it is possible to carry out a propylene polymerization stage using liquid propylene as a diluent and to carry out subsequent copolymerization stages in the gas phase without intermediate stages except for partial degassing of propylene.

  Examples of suitable reactors are continuous operation stirred reactors, loop reactors, fluidized bed reactors or horizontal or vertical stirred powder bed reactors. Of course, the reaction can also be carried out in a plurality of reactors connected in series.

  Polymerization can also be carried out in a cascade in which stirred gas phase reactors in which the powder reaction bed continues to move by means of a vertical stirring device are connected in series. The reaction bed generally contains the polymer polymerized in each reactor.

The propylene polymerization to form component (A) may be one or more C ₄ -C such as ethylene and / or butene-1, pentene-1, 4-methylpentene-1, hexene-1 and octene-1 or combinations thereof. _It may be carried out in the presence of ₁₀ α-olefin.

As mentioned above, the copolymerization of ethylene with propylene (preferred) and / or other C ₄ -C ₁₀ α-olefins to form component (B) may be carried out in the presence of dienes.
Component (B) is partially soluble in xylene at ambient temperature (ie 25 ° C.). The amount of xylene solubles of component (B) at ambient temperature is typically in the range of 60-92 wt%. The intrinsic viscosity of the xylene solubles is typically in the range of 1.8-4 dl / g, preferably 2.5-3.5 dl / g.

The reaction time, pressure and temperature associated with the polymerization process are not critical, but better if the temperature is 20-150 ° C, especially 50-100 ° C. The pressure may be ambient pressure or higher.
The molecular weight is adjusted using a known regulator, particularly hydrogen.

  The composition of the present invention may be produced by a gas phase polymerization process performed in at least two interconnected polymerization zones. This type of process is described in European patent application 782 587.

  In particular, the process includes feeding one or more monomers to the polymerization zone under reaction conditions in the presence of a catalyst and collecting the polymer product from the polymerization zone. In this process, the growing polymer particles flow upwards under rapid fluidization conditions through one (first) polymerization zone (riser) and exit the riser to another (second) polymerization. Enters the conversion zone (downcomer), descends in high density form under the action of gravity through the downcomer, exits the downcomer and is reintroduced into the upcomer, thus the polymer between the upcomer and the downcomer Is established.

  Within the downcomer, the density of solids increases and approaches the bulk density of the polymer. In this way, the pressure can increase along the direction of flow, allowing the polymer to be reintroduced into the riser without the assistance of special mechanical means. In this manner, a “loop” circulation is established, defined by the pressure balance between the two polymerization zones and the head loss introduced into the system.

  Generally, rapid fluidization conditions in the riser are established by feeding a gas mixture containing the relevant monomers to the riser. The gas mixture is preferably supplied below the reintroduction point of the polymer to the riser using suitable gas dispersion means. The gas conveying speed to the riser is faster than the conveying speed under operating conditions, and is preferably 2 to 15 m / s.

  Generally, the polymer and gaseous mixture exiting the riser are conveyed to a solid / gas separation zone. Solid / gas separation can be performed using conventional separation means. From the separation zone, the polymer enters the downcomer. The gaseous mixture exiting the separation zone is compressed, cooled and conveyed to the riser with the addition of a makeup monomer and / or molecular weight regulator, as appropriate. The conveyance may be performed by a recycling line for the gaseous mixture.

  Control of the polymer circulation between the two polymerization zones can be done by metering the amount of polymer exiting the downcomer using means suitable for controlling the flow of solids such as mechanical valves.

Operating parameters such as temperature are useful in gas phase olefin polymerization processes, for example 50-120 ° C.
This process can be carried out under operating pressures between 0.5 and 10 MPa, preferably 1.5-6 MPa.

  Advantageously, the one or more inert gases are maintained in the polymerization zone in an amount such that the total partial pressure of the inert gases is preferably 5-80% of the total gas pressure. The inert gas can be, for example, nitrogen or propane.

  Various catalysts are fed to the riser at any point in the riser. However, the catalyst may be fed to any point in the downcomer. The catalyst may be in any physical state, and thus a catalyst that is in either a solid or liquid can be used.

Preferably, the polymerization catalyst is a Ziegler-Natta catalyst comprising a solid catalyst component. The solid catalyst component is
a) Mg, Ti and halogen, and at least two electron donor compounds, and at least one electron donor compound present in an amount of 15 to 50 mol% with respect to the total amount of the electron donor, Selected from esters of succinic acid that cannot be extracted in excess of 20 mol% at least, wherein at least another electron donor compound can be extracted in excess of 30 mol% under the same conditions;
b) alkylaluminum compounds, and in some cases (but preferably)
c) one or more electron donor compounds (external donor)
including.

  Succinates that cannot be extracted more than 20 mol% are defined as non-extractable succinates. An electron donor compound that can extract more than 30 mol% is defined as an extractable electron donor compound.

Preferably, a succinic acid ester that cannot be extracted more than 15 mol% and another electron donor compound that can extract more than 35 mol% are used.
The non-extractable succinic acid ester is preferably the following formula (I):

Wherein the groups R ₁ and R ₂ are the same or different from one another and optionally contain a C ₁ -C ₂₀ linear or branched alkyl group, alkenyl group, cycloalkyl group, aryl group, aryl containing heteroatoms An alkyl group or an alkylaryl group; the groups R _{3 to} R ₆ are the same or different from each other and are hydrogen or a C ₁ -C ₂₀ linear or branched alkyl group, alkenyl group, cyclo An alkyl group, an aryl group, an arylalkyl group or an alkylaryl group; the groups R _{3 to} R ₆ bonded to the same carbon atom are bonded together to form a ring, provided that R _{3 to} R ₅ are simultaneously If hydrogen, R ₆ is a primary branch having 3 to 20 carbon atoms, secondary or tertiary alkyl group, cycloalkyl group, aryl group, arylalkyl group or alkylaryl group or Sometimes a linear alkyl group having at least 4 carbon atoms containing a hetero atom)
Selected from succinic acid esters.

  Preferably, the amount of non-extractable succinic acid ester is 20 to 45 mol%, more preferably 22 to 40 mol%, based on the total amount of electron donor compound. Among the non-extractable succinic acid esters described above, particularly preferred is the following formula (II):

Wherein the groups R ₁ and R ₂ are the same or different from one another and optionally contain a C ₁ -C ₂₀ linear or branched alkyl group, alkenyl group, cycloalkyl group, aryl group, aryl containing heteroatoms An alkyl group or an alkylaryl group; the groups R ₃ and R ₄ are the same or different from one another and optionally contain a C ₁ -C ₂₀ alkyl group, cycloalkyl group, aryl group, arylalkyl group or alkyl containing heteroatoms Aryl groups, at least one of which is a branched alkyl group)
It is a succinic acid ester. The compound is a type (S, R) or (R, S) stereoisomer that exists in pure or mixed form with respect to the two asymmetric carbon atoms defined by the structure of formula (II).

  Among the extractable electron donor compounds, particularly preferred are organic mono- or di-carboxylic esters such as benzoates, malonic esters, phthalates and certain succinic esters. These are described, for example, in US Pat. No. 4,522,930 and European Patent 45977. Particularly suitable are phthalate esters. Alkyl phthalates such as diisobutyl, dioctyl and diphenyl phthalate and benzyl-butyl phthalate are preferred.

The extraction rate test was performed as follows.
A. Preparation of the Solid Catalyst Component 250 ml of TiCl ₄ is introduced at 0 ° C. into a nitrogen-purged 500 ml _4- neck round bottom flask. While stirring, 10.0 g of microspherical MgCl ₂ * 2.8C ₂ H ₅ OH (operating at 3,000 rpm instead of 10,000 rpm according to the method described in Example 2 of US Pat. No. 4,399,054) Prepared). An additional 4.4 mmol of the given electron donor compound is added.

The temperature is raised to 100 ° C. and maintained at this temperature for 120 minutes. The agitation is then stopped and the solid product is allowed to settle and the supernatant liquid is siphoned off.
Add 250 ml of fresh TiCl ₄ . The mixture is allowed to reach 120 ° C. in 60 minutes with stirring and then the supernatant liquid is siphoned off. The solid (A) is washed 6 times with anhydrous hexane (6 × 100 ml) at 60 ° C., dried under vacuum, and quantitative analysis of Mg and electron donor compound is performed. Thus, the ratio (ratio A) of the electron donor compound to Mg is determined.
B. Treatment of Solid (A) As described in 190 ml anhydrous n-hexane, 19 mmol AlEt ₃ and 2 g A in a 250 ml jacketed glass reactor equipped with mechanical stirrer and filtration membrane under nitrogen atmosphere. The catalyst component prepared in is introduced. The mixture is heated to 60 ° C. with stirring (stirring speed 400 rpm) for 1 hour. The mixture is then filtered, washed 4 times with n-hexane at 60 ° C. and finally dried under vacuum at 30 ° C. for 4 hours. The solid is then quantitatively analyzed for Mg and electron donor compounds. Thus, the ratio (ratio B) of the electron donor compound to Mg is determined.

The extraction rate of the electron donor compound is expressed by the following formula:
Extracted ED (%) = (ratio A-ratio B) / ratio A.
Calculate according to

  Preferred examples of the non-extractable succinic acid esters described above are pure or mixed (S, R) (S, R) forms, possibly racemic, and examples of succinic acid esters to be used in the catalyst components described above. Are diethyl 2,3-bis (trimethylsilyl) succinate, diethyl 2,2-sec-butyl-3-methyl succinate, diethyl 2- (3,3,3-trifluoropropyl) -3-methyl succinate, diethyl 2,3-bis (2-ethylbutyl) succinate, diethyl 2,3-diethyl-2-isopropyl succinate, diethyl 2,3-diisopropyl-2-methyl succinate, diethyl 2,3-dicyclohexyl-2-methyl succinate , Diethyl 2,3-dibenzyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3-di-t-butyl succinate , Diethyl 2,3-diisobutyl succinate, diethyl 2,3-dineopentyl succinate, diethyl 2,3-diisopentyl succinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2 , 3- (9-fluorenyl) succinate, diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2-t-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexyl succinate, diethyl 2-isopentyl- 3-cyclohexyl succinate, diethyl 2-cyclohexyl-3-cyclopentyl succinate, diethyl 2,2,3,3-tetramethyl succinate, diethyl 2,2,3,3-tetraethyl succinate, diethyl 2,2,3 , 3-tetrapropyl succinate, diethyl 2,3-diethyl-2,3-diisopropyl succinate, diisobutyl 2,3-bis (trimethylsilyl ) Succinate, diisobutyl 2,2-sec-butyl-3-methyl succinate, diisobutyl 2- (3,3,3-trifluoropropyl) -3-methyl succinate, diisobutyl 2,3-bis (2-ethylbutyl) Succinate, diisobutyl 2,3-diethyl-2-isopropyl succinate, diisobutyl 2,3-diisopropyl-2-methyl succinate, diisobutyl 2,3-dicyclohexyl-2-methyl succinate, diisobutyl 2,3-dibenzyl succinate , Diisobutyl 2,3-diisopropyl succinate, diisobutyl 2,3-bis (cyclohexylmethyl) succinate, diisobutyl 2,3-di-t-butyl succinate, diisobutyl 2,3-diisobutyl succinate, diisobutyl 2,3-di Neopentyl succinate, diisobutyl 2,3-diisopentyl succinate, diisobutyl 2,3- (1,1,1-trifluoro-2- Propyl) succinate, diisobutyl 2,3-n-propyl succinate, diisobutyl 2,3- (9-fluorenyl) succinate, diisobutyl 2-isopropyl-3-ibutyl succinate, diisobutyl 2-terbutyl-3-ipropyl succinate Diisobutyl 2-isopropyl-3-cyclohexyl succinate, diisobutyl 2-isopentyl-3-cyclohexyl succinate, diisobutyl 2-n-propyl-3- (cyclohexylmethyl) succinate, diisobutyl 2-cyclohexyl-3-cyclopentyl succinate, Diisobutyl 2,2,3,3-tetramethyl succinate, diisobutyl 2,2,3,3-tetraethyl succinate, diisobutyl 2,2,3,3-tetrapropyl succinate, diisobutyl 2,3-diethyl-2, 3-diisopropyl succinate, dineopentyl 2,3-bis (trimethylsilyl) succi , Dineopentyl 2,2-di-sec-butyl-3-methyl succinate, dineopentyl 2- (3,3,3-trifluoropropyl) -3-methyl succinate, dineopentyl 2,3 bis (2-ethylbutyl) ) Succinate, dineopentyl 2,3-diethyl-2-isopropyl succinate, dineopentyl 2,3-diisopropyl-2-methyl succinate, dineopentyl 2,3-dicyclohexyl-2-methyl succinate, dineopentyl 2,3-dibenzyl succinate , Dineopentyl 2,3-diisopropyl succinate, dineopentyl 2,3-bis (cyclohexylmethyl) succinate, dineopentyl 2,3-di-t-butyl succinate, dineopentyl 2,3-diisobutyl succinate, dineopentyl 2,3- Dineopentyl succinate, Dineopentyl 2,3-diisopentyl succinate, Dineopentyl 2,3- (1,1,1-trifluoro-2-propyl) succinate, dineopentyl 2,3-n-propyl succinate, dineopentyl 2,3 (9-fluorenyl) succinate, dineopentyl 2-isopropyl-3-isobutyl succinate, dineopentyl 2-t-butyl-3-isopropyl succinate, dineopentyl 2-isopropyl-3-cyclohexyl succinate, dineopentyl 2-isopentyl-3-cyclohexyl succinate, dineopentyl 2-n-propyl-3- (cyclohexylmethyl) succinate, dineopentyl 2-cyclohexyl-3-cyclopentyl succinate, dineopentyl 2,2,3,3-tetramethyl succinate, dineopentyl 2,2,3,3-tetraethyl succinate, dineopentyl 2,2,3,3-tetrapropyl succinate Dineopentyl 2,3-diethyl-2,3-diisopropyl succinate A.

  Particularly preferred are diethyl 2,3-dibenzyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3-diisobutyl succinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diisobutyl 2,3-dibenzyl succinate, diisobutyl 2,3-diisopropyl succinate, diisobutyl 2,3-bis (cyclohexylmethyl) succinate, diisobutyl 2,3-n-propyl Succinate, dineopentyl 2,3-diethyl-2-isopropyl succinate, dineopentyl 2,3-diisopropyl-2-methyl succinate, dineopentyl 2,3-dicyclohexyl-2-methyl succinate, dineopentyl 2,3-dibenzyl succinate , Dineopentyl 2,3-diisopropyl succinate, dineopen Til 2,3 bis (cyclohexylmethyl) succinate, dineopentyl 2,3-diisobutyl succinate, dineopentyl 2,3-n-propyl succinate, dineopentyl 2-isopropyl-3-cyclohexyl succinate.

The alkyl-Al compound (b) is preferably selected from trialkylaluminum compounds such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum . Mixtures of trialkylaluminum compounds with alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt ₂ Cl and Al ₂ Et ₃ Cl ₃ can also be used.

  The external donor (c) may be the same type as the succinic acid esters of the formulas (I) and (II) or may be a different type. Suitable external electron donor compounds include silicon compounds, ethers, esters such as phthalates, benzoates and succinates having a structure different from formula (I) or (II), amines, heterocyclic compounds and especially 2 , 2,6,6-Tetramethylpiperidine, ketones and general formula (III):

Wherein R ^I and R ^II are the same or different and are a C ₁ -C ₁₈ alkyl group, a C ₃ -C ₁₈ cycloalkyl group or a C ₇ -C ₁₈ aryl group; R ^III and R ^IV are the same Or is different and is a C ₁ -C ₄ alkyl group)
1,3-diethers or 1,3-diethers belonging to a ring structure or polycyclic structure in which the carbon atom at the 2-position consists of 5, 6 or 7 carbon atoms and contains 2 or 3 unsaturations Can be mentioned.

Ethers of this type are described in European patent applications 361493 and 728769.
A particularly preferred class of external donor compounds is of the formula R _a ⁷ R _b ⁸ Si (OR ⁹ ) _c , where a and b are integers from 0 to 2, c is an integer from 1 to 3, (A + b + c) is 4. R ⁷ , R ⁸ and R ⁹ are optionally C ₁ -C ₁₈ hydrocarbon groups containing heteroatoms). Particularly preferred is a branched chain having 3 to 10 carbon atoms, where a is 1, b is 1, c is 2, and at least one of R ⁷ and R ⁸ is optionally containing heteroatoms. A silicon compound which is an alkyl group, an alkenyl group, an alkylene group, a cycloalkyl group or an aryl group, and R ⁹ is a C ₁ -C ₁₀ alkyl group, particularly methyl. Examples of such preferred silicon compounds are cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and (1, 1,1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, 3,3,3-trifluoropropyl-2-ethylpiperidyl-dimethoxysilane and (1,1,1-trifluoro-2 -Propyl) -methyldimethoxysilane. Further preferred are silicon compounds in which a is 0, c is 3, R ⁸ is a branched alkyl or cycloalkyl group optionally containing a heteroatom and R ⁹ is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and hexyltrimethoxysilane.

Particular preferred examples of silicon compounds are cyclohexylmethyldimethoxysilane and dicyclopentyldimethoxysilane.
Preferably, the electron donor compound (c) is in such an amount that the molar ratio between the organoaluminum compound and the electron donor compound (c) is 0.1 to 500, more preferably 1 to 300, especially 3 to 100. Used in

As described above, the solid catalyst component contains Ti, Mg, and halogen in addition to the electron donor. In particular, the catalyst component comprises a titanium compound having at least one Ti-halogen bond and the above-described electron donor compound supported on Mg halide. The magnesium halide is preferably MgCl ₂ in active form, which is widely known in the patent literature as a support for Ziegler-Natta catalysts. U.S. Pat. Nos. 4,298,718 and 4,495,338 are the first disclosures of the use of these compounds in Ziegler-Natta catalysts. From these patents it is known that the magnesium dihalide in active form used as a support or co-support in the catalyst component for olefin polymerization is characterized by an X-ray spectrum. Here, the strongest diffraction lines appearing in the spectrum of inactive halides are reduced in intensity and replaced with halos, with the maximum intensity of halos moving towards an angle lower than the angle of the stronger line.

Preferred titanium compounds are TiCl ₄ and TiCl ₃ and further the formula Ti (OR) _{n -y} X _y (where n is the valence of titanium, y is a number between 1 and n, and X is a halogen And R is a hydrocarbon group having 1 to 10 carbon atoms) Ti-halo alcoholates can also be used.

The preparation of the solid catalyst component can be carried out according to several methods well known and described in the prior art.
According to a preferred method, the solid catalyst component is a titanium compound of the formula Ti (OR) _ny X _y where n is the valence of titanium and y is a number between 1 and n, preferably Addition of TiCl ₄ to the formula MgCl ₂ · pROH, where p is a number between 0.1 and 6, preferably 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms It can be prepared by reacting with magnesium chloride derived from the compound. The adduct is suitable in spherical form by mixing the adduct with alcohol and magnesium chloride in the presence of an immiscible inert hydrocarbon under stirring conditions at the melting point (100-130 ° C) of the adduct. Can be prepared. The emulsion is then quenched to cause the addition compound to solidify in the form of spherical particles.

Examples of globular addition compounds prepared according to this procedure are described in US Pat. Nos. 4,399,054 and 4,469,648. The adducts thus obtained can be reacted directly with Ti compounds or heat controlled dealcohols (80 to 80) so as to obtain adducts whose molar number of alcohol is generally lower than 3, preferably between 0.1 and 2.5. 130 ° C.). The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholized or the like) in cold TiCl ₄ (generally 0 ° C.) and the mixture is heated to 80-130 ° C. This temperature is maintained for 0.5-2 hours. The treatment with TiCl ₄ can be performed one or more times. The electron donor compound may be added during the treatment with TiCl _4.

Regardless of the method of preparation used, the final amount of electron donor compound is preferably a molar ratio with respect to MgCl ₂ of 0.01 to 1, more preferably 0.05 to 0.5.
The catalyst components and catalysts described above are described in International Publication Pamphlets WO 00/63261, WO 01/57099 and WO 02/30998.

  Other catalysts that can be used in the process according to the invention are metallocene-type catalysts, such as those described in US Pat. No. 5,324,800 and EP-A-0 129 368, which are particularly advantageous. Is a bridged bis-indenyl metallocene as described, for example, in US Pat. No. 5,145,819 and EP-A-0 485 823. Other classifications of suitable catalysts include European Patent Publication EP-A-0 416 815 (Dow), EP-A-0 420 436 (Exxon), EP-A-0 671 404, EP- It is a so-called constrained geometry catalyst as described in A-0 643 066 and international publication pamphlet WO 91/04257.

The catalyst may be previously contacted (prepolymerized) with a small amount of olefin.
The composition of the present invention may further contain additives common in the art such as antioxidants, light stabilizers, heat stabilizers, nucleating agents, colorants and fillers.

In particular, the addition of nucleating agents significantly improves important physical-mechanical properties such as flexural modulus, heat distortion temperature (HDT), tensile strength at yield point and transparency.
Typical examples of nucleating agents are p-tert-butylbenzoate, 1,3- and 2,4-dibenzylidene sorbitol.

The nucleating agent is preferably added to the composition of the present invention in an amount ranging from 0.05 to 2 wt%, more preferably from 0.1 to 1 wt%, based on the total amount.
Addition of inorganic fillers such as talc, calcium carbonate and mineral fibers also improves mechanical properties such as flexural modulus and HDT. Talc can also have a nucleating effect.

Hereinafter, although an Example demonstrates a detail, this invention is not limited to these.
The data regarding the polymerizable substance of an Example are determined by the following method.
-MFR: Determined according to ISO 1133 (230 ° C, 2.16 kg).
-Intrinsic viscosity [η]: Measured in tetrahydronaphthalene at 135 ° C.
-Mn (number average molecular weight), Mw (mass average molecular weight) and Mz (z average molecular weight): Measured by gel permeation chromatography (GPC) in 1,2,4-trichlorobenzene. Specifically, a sample was prepared at a 70 mg / 50 ml concentration of stabilized 1,2,4 trichlorobenzene (250 μg / ml BHT (CAS REGISTRY NUMBER 128-37-0); then the sample was taken to 170 ° C. over 2.5 hours Heated and solubilized; measured with Waters GPCV2000 at 145 ° C, flow rate 1.0 ml / min using the same stabilizing solvent, 3 Polymer Lab columns (Plgel, 20 μm mixed ALS, 300 x 7.5 mm) Used in series.
-Ethylene content: measured by IR spectroscopy.
- decision of isotactic pentad content of each xylene insoluble fraction 50mg dissolved in C ₂ D ₂ Cl ₄ of 0.5 mL.
¹³ C NMR spectra were acquired on a Bruker DPX-400 (100.61 Mhz, 90 ° pulse, 12 s delay between pulses). Approximately 3000 transients were recorded for each spectrum and the mmmm pentad peak (21.8 ppm) was used as a control.
Microstructural analysis was performed as described in the literature (Polymer, 1984, 25, 1640, by Inoue Y. et al. And Polymer, 1994, 35, 339, by Chujo R. et AL).
-Polydispersity index (PI)
This is a measurement of the molecular weight distribution of the polymer. To determine the PI value, the RMS-800 parallel plate rheometer model marketed by Rheometrics (USA) operating at frequencies increasing from 0.01 rad / sec to 100 rad / sec, temperature 200 ° C The modulus separation at low elasticity values, eg 500 Pa, was determined. From the elastic modulus separation value, PI is the following formula:
PI = 54.6 × (elastic modulus separation) ^-1.76
(Where elastic modulus separation (MS) is:
MS = (frequency at G '= 500 Pa) / (G "= frequency at 500 Pa)
Where G ′ is the storage modulus and G ″ is the loss modulus.
Xylene soluble and insoluble at -25 ° C
2.5 g of polymer is dissolved in 250 ml of xylene at 135 ° C. with stirring. After 20 minutes, the solution is cooled to 25 ° C. with stirring and then allowed to settle for 30 minutes. The precipitate is filtered through filter paper, the solution is evaporated in a stream of nitrogen and the residue is dried under vacuum at 80 ° C. until constant mass. Thus, the mass% of the polymer-soluble and insoluble components at room temperature (25 ° C.) was calculated.
-Flexural modulus: measured in accordance with ISO 178.
-Izod impact resistance: measured according to ISO 180/1 A.
-Determination of the ductile / brittle transition temperature: determined according to the internal method MA 17324 available as required.
According to this method, the biaxial impact resistance is determined by the impact of an automatic computer controlled hammer.
Circular test species are obtained by cutting with a circular hand punch (38 mm diameter). They are conditioned at 23 ° C. and 50 RH for at least 12 hours and then placed in a thermostatic bath for 1 hour at the test temperature.
The force-time curve is detected during the impact of a hammer (5.3 kg, 1.27 cm diameter hemispherical punch) against a circular seed placed on the ring support. The machine used is CEAST 6758/000 type model No.2.
The D / B transition temperature means a temperature at which 50% of the sample is brittlely broken in the impact test.
A plaque for measuring D / B having dimensions of 127 × 127 × 1.5 mm is prepared according to the following method.
The injection molding machine is a Negri Bossi ™ type (NB 90) with a gripping force of 90 tons. The mold is a rectangular plaque (127 × 127 × 1.5 mm).
The main process parameters are:
Back pressure (bar): 20
Injection time (s): 3
Maximum injection pressure (MPa): 14
Hydraulic injection pressure (MPa): 6-3
First holding hydraulic pressure (MPa): 4 ± 2
First retention time (s): 3
Second holding hydraulic pressure (MPa): 3 ± 2
Second retention time (s): 7
Cooling time (s): 20
Mold temperature (℃): 60
The melting temperature is between 220 ° C and 280 ° C.
-Elongation at break and elongation at yield: determined according to ISO 527.
[Example 1]
Preparation of the solid catalyst component 250 mL of TiCl ₄ was introduced at 0 ° C. into a 500 mL _4- neck round bottom flask purged with nitrogen. While stirring, 10.0 g of microspherical MgCl ₂ .2.8C ₂ H ₅ OH (according to the method described in US Pat. No. 4,399,054, Example 2 but operated at 3000 rpm instead of 10000 rpm) The following internal electron donor compounds were added: 1.67 mmol diethyl 2,3-diisopropyl succinate (racemic) and 1.37 mmol diethyl 2,3-diisopropyl succinate (meso) as non-extractable succinate 4.56 mmol diisobutyl phthalate. The temperature was raised to 100 ° C. and this temperature was maintained for 120 minutes. The agitation was then stopped, the solid product was allowed to settle, and the supernatant liquid was siphoned off. Then 250 ml of fresh TiCl ₄ was added. The mixture was allowed to react at 120 ° C. for 60 minutes and then the supernatant liquid was siphoned off. The solid was washed 6 times with anhydrous hexane (6 × 100 ml) at 60 ° C.

Prior to introduction to the catalyst system and prepolymerization polymerization reactor, the solid catalyst components described above were mixed with aluminum triethyl (TEAL) and dicyclopentyldimethoxysilane (DCPMS) for 24 minutes at 12 ° C and TEAL against the solid catalyst components. Contact was made in such an amount that the mass ratio was equal to 11 and the mass ratio TEAL / DCPMS was equal to 3.

The catalyst system was then prepolymerized by maintaining a suspension in liquid propylene for about 5 minutes at 20 ° C. before introduction into the first polymerization reactor.
Polymerization Polymerization experiments are carried out in a continuous mode with three reactors in series with a device that moves the product from one reactor to the next reactor. The first reactor is a liquid phase reactor, and the second and third reactors are fluidized bed gas phase reactors. Component (A) is prepared in the liquid phase in the first reactor and component (B) is prepared in the gas phase in the two reactors.

Hydrogen is used as a molecular weight modifier.
The gas phase (propylene, ethylene and hydrogen) is continuously analyzed by gas chromatography.

At the end of the experiment, the powder is removed and dried under a stream of nitrogen.
The main polymerization conditions and analytical data of the polymers produced in the three reactors are reported in Table 1.

  The polymer particles are then introduced into a rotating drum and mixed with 0.15 wt% Irganox B 225 (consisting of about 50% Irganox 1010 and 50% Irgafos 168, from Ciba Specialty Chemicals) and 0.05 wt% Ca stearate. To obtain a nucleating composition. Irganox 1010 is pentaerythrityl tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate and Irgafos 168 is tris (2,4-di-tert-butylphenyl) phosphite.

8500ppm talc is also added as a nucleating agent.
The polymer particles are then extruded in a twin screw extruder in a nitrogen atmosphere at a rotational speed of 250 rpm and a melting temperature of 200-250 ° C.

The properties of the polymer thus obtained are reported in Table 2.
[Comparative Example 1]
Comparative polymer composition of Comparative Example 1
A) crystalline isotactic propylene homopolymer 68 wt% with MFRL 80 g / 10 min;
B) Propylene / ethylene copolymer 32wt% containing 42wt% ethylene
Make from.

The polymerization process is characterized in that the catalyst component does not contain an extractable electron donor compound and a non-extractable electron donor compound, but contains only one electron donor compound diethyl 2,3-diisopropyl succinate (racemate). Except for this, the same procedure as in Example 1 is performed. The molar amount of diethyl 2,3-diisopropyl succinate (racemic) present in the catalyst component is equal to the total amount of internal electron donor compound of Example 1. The catalyst system preparation and prepolymerization treatment are performed in the same manner as in Example 1. Propylene homopolymer is prepared in the liquid phase in two reactors instead of just one reactor. The polymerization conditions are reported in Table 1.
[Comparative Example 2]
Comparative polymer composition of Comparative Example 2
A) 68 wt% crystalline isotactic propylene homopolymer;
B) Propylene / ethylene copolymer 32wt% containing 47wt% ethylene
Make from.

  The polymerization process is carried out in the same manner as in Example 1 except that the catalyst component does not contain an extractable electron donor compound and a non-extractable electron donor compound but contains only one kind of electron donor compound. That is, the mass ratio of 9.1 mmol diisobutyl phthalate and TEAL / DCPMS is equal to 5.

The polymerization conditions are reported in Table 1.
Tables 2 and 3 report the properties of the two comparative polymer compositions of Comparative Examples 1 and 2, which are stabilized and nucleated like the composition of Example 1.

Claims (5)

A) a crystalline propylene homopolymer having a polydispersity index of 4.5 to 6 and an isotactic pentad (mmmm) content of more than 96% measured by ¹³ C NMR in xylene insolubles at 25 ° C. 3 wt% or less of ethylene or C ₄ -C ₁₀ alpha-olefins or crystalline copolymers 60～85Wt% propylene containing these combinations;
B) Olefin polymer composition comprising 15 to 40 wt% of partially amorphous copolymer of ethylene containing 35 wt% to 70 wt% propylene or C ₄ -C ₁₀ α-olefins or combinations thereof, and optionally a small amount of diene An olefin polymer composition having an elongation at break of 150 to 600% in accordance with ISO 527.   The olefin composition of claim 1, wherein the crystalline homopolymer or copolymer is in an amount of 65-80 wt% and the amorphous copolymer is in an amount of 20-35 wt%.   Component (A) is a composition of Claim 1 whose molecular weight distribution shown by Mw (average) / Mn (average) ratio measured by GPC is 6-9. A polymerization process for preparing an olefin polymer composition according to claim 1 comprising at least two successive steps, wherein components (A) and (B) are formed in a preceding step excluding the first step. A solid catalyst prepared individually in a continuous process in which each process is carried out in the presence of a polymer and a catalyst used in the preceding process and in the presence of a polymerized Ziegler-Natta catalyst containing a solid catalyst component Ingredients
a) At least one electron donor compound that contains Mg, Ti and halogen and at least two electron donor compounds and is present at 15 to 50 mol% with respect to the total amount of electron donors cannot be extracted more than 20 mol% Selected from esters of succinic acid, characterized in that at least the other electron donor compound can be extracted in an amount of more than 30 mol%;
b) an alkylaluminum compound;
A polymerization process optionally comprising c) one or more electron donor compounds. In the solid catalyst component, the non-extractable electron donor is represented by the following formula (I):
Wherein R ₁ and R _{2 which} are the same or different from each other are a C ₁ -C ₂₀ linear or branched alkyl group, alkenyl group, cycloalkyl group, aryl group, arylalkyl group optionally containing a hetero atom. Or an alkylaryl group;
The same or different groups R _{3 to} R ₆ are each hydrogen or a C ₁ -C ₂₀ linear or branched alkyl group, alkenyl group, cycloalkyl group, aryl group, arylalkyl group or alkyl containing a hetero atom. An aryl group;
The groups R _{3 to} R ₆ bonded to the same carbon atom may form a ring together, provided that when R _{3 to} R ₅ are simultaneously hydrogen, R ₆ represents 3 to 20 carbon atoms. From primary branched, secondary or tertiary alkyl groups, cycloalkyl groups, aryl groups, arylalkyl groups or alkylaryl groups or linear alkyl groups having at least 4 carbon atoms and optionally containing heteroatoms As long as it is selected)
The process of claim 4 selected from the following succinic acid esters.