RU2172327C2 - Composition of olefin (co)polymer, method of preparing thereof (variants), (co)polymerization catalyst of olefins, and method of preparing thereof - Google Patents

Abstract

FIELD: chemistry of polymers. SUBSTANCE: described is olefin (co)polymer composition comprising 0.01-5.0 wt parts of high molecular polyethylene which is ethylene homopolymer or ethylene copolymer with olefin containing 50 wt % or more ethylene units; and 100 wt parts of olefin (co)polymer which is other than high molecular polyethylene in which composition said high molecular polyethylene has characteristic viscosity [η_E] from 15 to100 dl/g measured in tetraline at 135 C or higher, and said high molecular polyethylene is the form of finely dispersed particles having average numerical particle size from 1 to 5000 nm. EFFECT: increased yield of polyethylene, no problem of smell, higher heat resistance, greater melt tension and higher crystallization temperature. 51 cl, 13 dwg

Description

 The invention relates to a composition of a (co) polymer of olefins and a method for its preparation, and to a catalyst for (co) polymerization of olefins and a method for its preparation. More specifically, the present invention relates to a preactivated olefin (co) polymerization catalyst, which is obtained by providing a catalyst for producing a polyolefin having, as a main component, a catalytic component of a transition metal compound containing at least a titanium compound for coating with a polymerizable polyolefin and a polyolefin having a high degree of polymerization, and a method for producing a preactivated catalyst for the copolymerization of olefins and to an olefin copolymerization catalyst having a preactivated catalyst as a main component and a polyolefin composition having a high melt voltage and a high crystallization temperature, which uses an olefin (co) polymerization catalyst and a process for its preparation.

BACKGROUND OF THE INVENTION
Since a polyolefin such as polypropylene, high density polyethylene, linear low density polyethylene or the like has excellent mechanical properties, chemical resistance and the like. and is very suitable for material balance, it is widely used in any processing industry. However, the polyolefin has a small melt stress and a low crystallization temperature. For this reason, processability, such as pneumoforming, foam molding, extrusion molding and the like, is poor and high-speed molding productivity has limitations in various molding methods.

 As a method of increasing the melt voltage and crystallization temperature of polypropylene, a method for ensuring the interaction of polypropylene with an organic peroxide and an additional crosslinking agent in the molten state (Japanese unexamined patent applications NN 59-93711, 61-152754, etc.), a method in which provides the interaction of peroxide with a low decomposition temperature with semi-crystalline polypropylene in the absence of oxygen to produce polypropylene, which has a free end long chain e is branching and does not contain gel (Japanese Unexamined Patent Application No. 2-298536), etc.

 A composition in which polyethylene having a different characteristic viscosity or molecular weight or propylene is mixed and a method for producing such a composition by multistage polymerization have been proposed as another method for improving the viscosity of the melt elastic properties, such as melt stress or the like.

Considered are a method of adding 2-30 parts by weight ultra-high molecular weight polypropylene to 100 wt. including ordinary polypropylene and extruding the product at a temperature that is equal to or higher than the melting temperature and equal to or lower than 210 ^o C (Japanese patent application pending N 61-28694), a method for producing an extrusion sheet made of polypropylene, which is obtained by multistage polymerization and contains two components having a limit viscosity of 2 and various molecular weights (Japanese Patent Application Served No. 1-12770), a method for producing a polyethylene composition that contains 1-10 wt.% poly a yen having a high average viscosity molecular weight and contains three types of polyethylene having different medium viscosity molecular weights, a melting and mixing method or a multi-stage polymerization method (Japanese patent application pending No. 6-261057), a polymerization method of ultra-high molecular weight polyethylene having an ultimate viscosity of 20 dl / g or more, in accordance with the multi-stage polymerization method, using from 0.05 to less than 1 wt.% active titanium-vanadium solid catalyst component enta (Japanese pending patent application N 5-79683), a polymerization method of 0.1-5 wt.% ultra-high molecular weight polyethylene having an ultimate viscosity of 15 dl / g or more using an active titanium catalyst component that has been prepolymerized with 1-butene or 4-methyl-1-pentene in accordance with a multi-stage polymerization process using a polymerization vessel having a special device (Japanese Patent Application Serial No. 7-8890) and the like.

 In addition, a method for producing polypropylene having a high melt voltage, in which propylene is polymerized using a titanium-containing solid catalyst component on a support and a catalyst component based on an organoaluminum compound using a prepolymerized catalyst, which is obtained by prepolymerizing ethylene and a polyene compound (Japanese unexamined patent application N 5-222122), and a method for producing a copolymer of ethylene with a a high melt tension lfa olefin using ethylene containing a pre-polymerized catalyst that contains polyethylene having an ultimate viscosity of 20 dl / g or more, which is obtained by prepolymerizing one ethylene using the same catalyst component (Japanese Unexamined Application for Patent No. 4-55410).

 In accordance with various compositions and preparation methods that are proposed in the prototypes, the melt tension can be increased to some extent, but the remaining odor of the additional crosslinking agent, crystallization temperature, heat resistance, and the like should be improved.

 The method of obtaining a high molecular weight polyolefin should be modified for the following reasons. More specifically, it is difficult to precisely control the degree of (co) polymerization of olefins in order to obtain a small amount of a high molecular weight polyolefin in a multistep polymerization process that must be introduced in the conventional olefin copolymerization step for polymerization. In addition, the polymerization temperature must be reduced in order to obtain a polyolefin having a molecular weight that is large enough. In addition, the production of the final polyolefin composition is reduced.

 In the method of prepolymerizing the polyene compound, it is necessary to obtain the polyene compound separately. In the method of prepolymerizing polyethylene, the dispersibility of the prepolymerized polyethylene in the polyolefin, which is ultimately obtained, is heterogeneous. Therefore, further improvement is required with respect to the stability of the polyolefin composition.

 According to existing analogues, the melt tension and crystallization temperature are not sufficiently improved, as described above. In addition, there are problems that must be resolved with respect to odor and heat resistance. In addition, it is necessary to increase the production of such a polyolefin.

SUMMARY OF THE INVENTION
The aim of the present invention is to provide a polyolefin composition having a high melt voltage and a high crystallization temperature, which is suitable for pneumoforming, foam molding and extrusion molding and which can have high productivity in various molding methods and a method for producing such a polyolefin composition.

 Another objective of the present invention is the creation of a catalyst (co) polymerization of olefins used to obtain a polyolefin composition and a method for producing this catalyst.

 As a result of studies to achieve the above objectives, the present applicants found that the olefin is (co) polymerized using a preactivated catalyst by allowing the catalyst to produce a polyolefin to maintain a small amount of the polyolefin, which must be (co) polymerized and having a specific intrinsic viscosity and a small amount of polyolefin, having a high specific intrinsic viscosity, so that a polyolefin composition is obtained having Exposure to extreme melt tension and high crystallization temperature.

The first aspect of the invention is the composition of (co) polymers of olefins containing 0.01-5.0 parts by weight high molecular weight polyethylene, which is a homopolymer of ethylene or a copolymer of ethylene with an olefin containing 50 wt. % or more of ethylene and 100 parts by weight (co) an olefin polymer other than high molecular weight polyethylene, where the high molecular weight polyethylene has an intrinsic viscosity [η _E ] of 15-100 dl / g, measured in tetraline at 135 ^° C. or higher, and the high molecular weight polyethylene is in the form of fine particles having a number average size particles from 1 to 5000 nm.

Preferably, the intrinsic viscosity [η _E ] is 15-50 dl / g, and more preferably 17-50 dl / g. Preferably, the amount of high molecular weight polyethylene is from 0.02 to 2.0 parts by weight, and more preferably 0.05-1.0 parts by weight. o'clock Preferably, the number average particle size of high molecular weight polyethylene is from 1 to 1000 nm, and more preferably 10-500 nm.

A first aspect of the invention is preferably a composition (olefin copolymer in which the intrinsic viscosity [η _r ] of the composition (olefin copolymer measured in tetralin at 135 ^° C. is 0.2-10 dl / g. Preferably, the intrinsic viscosity [η _r ] is 0.2-8 dl / g, and more preferably 0.7-5 dl / g.

 In a first aspect of the invention, preferably, in the composition of an olefin (co) polymer (o) olefin polymer, excluding high molecular weight polyethylene, is at least one member of the group consisting of a homopolymer of propylene and a copolymer of propylene with an olefin containing 50 wt.% Or more propylene units.

In the first aspect of the invention, preferably, in the composition of the olefin copolymer in the condensed state, where there is no rubber component or inorganic filler, the following relationship is satisfied, expressed by the formula:
log (G '(ω = 10 ^o )) - log (G' (ω = 10 ^-2 )) <2,
where G '(ω = 10 ^o ) is the dynamic modulus of elasticity with a frequency
ω = 10 ^o for the molten product at 230 ^o C and
G '(ω = 10 ^-2 ) - dynamic modulus of elasticity with a frequency
ω = 10 ^-2 .

In the first aspect of the invention, preferably, in the composition of the (co) olefin polymer in a state where no electron beam irradiation occurs, the following relationship is satisfied:
log (N ₁ )> -log (MFR) + 5
where N ₁ is the difference between normal stresses at a shear rate of 4 x 10 ^-1 (s ^-1 ) at 190 ^o C, 230 ^o C and 250 ^o C,
PTR is the melt flow index (unit: g / 10 min).

In a first aspect of the invention, preferably, in the composition of the (co) olefin polymer at 190 ^° C. and 250 ^° C., the following relationship is satisfied:
(N ₁ (190 ^o C) -N ₁ (250 ^o C)) / N ₁ (190 ^o C) <0.6,
where N ₁ (190 ^o C) and N ₁ (250 ^o C) is the difference between normal stresses at a shear rate of 4 x 10 ^-1 (s ^-1 ).

In a first aspect of the invention, preferably, in the composition of the (co) olefin polymer at 190 ^° C. and 250 ^° C., the following relationship is satisfied:
(MS (190 ^° C) -MS (250 ^° C)) / MS (190 ^° C) <3.1,
where MS (190 ^o C) and MS (250 ^o C) is the melt stress at a shear rate of 3 x 10 ^-1 (s ^-1 ).

In a first aspect of the invention, preferably, in the composition of the (co) olefin polymer, the following relationship is satisfied:
(G (t = 10) -G (t = 300)) / G (t = 10) <1,
where G (t = 10) is the relaxation modulus of elasticity at t = 10 (s) and
G (t = 300) - relaxation modulus at t = 300 (s) at 500% elongation of the molten product at 230 ^o C.

 In a first aspect of the invention, preferably, in an olefin (co) polymer composition, the viscosity during stretching increases in the region of large deformations during melting and stretching, which shows the property of strain hardening. The term "large strain region" means more than a certain stress value when the stress-strain relation is no longer linear. The stress in the region of large strains is so large that the strain is disproportionate to the stress.

 In a first aspect of the invention, preferably in the composition of the (co) olefin polymer, fine particles of high molecular weight polyethylene are introduced before or during the (co) polymerization of the olefin.

In a first aspect of the invention, preferably, in the olefin (co) polymer composition, the olefin (co) polymer is a propylene homopolymer or a propylene-olefin copolymer containing 50 wt.% Or more olefin units and the olefin (co) polymer composition satisfies the following relationship between melt tension (MS) at 230 ^° C and intrinsic viscosity [η _E ] measured in tetraline at 135 ^° C:
log (MS)> 4.24 × log (η _T ) -1.20.
In a first aspect of the invention, preferably, in the olefin (co) polymer composition, the olefin (co) polymer is a propylene homopolymer or a propylene-olefin copolymer containing 50% by weight or more of propylene units, and the olefin (co) polymer composition satisfies the following relationship between tension melt (MS) at 230 ^° C. and intrinsic viscosity measured in tetraline at 135 ^° C., [η _E ]:
4.24 × log [η _T ] +0.24> 4.24 × log [η _T ] -1.10
In a first aspect of the invention, preferably, in an olefin (co) polymer composition, the olefin (co) polymer is an ethylene homopolymer or a copolymer of ethylene, with an olefin containing 50% by weight of ethylene units.

 In a first aspect of the invention, preferably, in the composition of the (co) olefin polymer, 0.001 to 2 parts by weight of at least one stabilizer selected from the group consisting of a phenolic antioxidant and a phosphoric antioxidant is added to 100 parts by weight. olefin copolymer compositions.

 In a first aspect of the invention, preferably, in the composition of the (o) olefin polymer, the olefin (co) polymer, excluding high molecular weight polyethylene, is a propylene homopolymer or a propylene-olefin copolymer containing 50% or more by weight of propylene, the olefin copolymer excluding high molecular weight polyethylene obtained by polymerization of propylene or copolymerization of propylene and another olefin having 2-12 carbon atoms in the presence of a preactivated catalyst containing olefin producing an catalyst and polyethylene supported by an olefin producing catalyst, wherein the olefin producing catalyst is formed by a combination of a catalyst component based on a transition metal compound containing at least a titanium compound, 0.01-1000 moles of an organometallic compound (A1) selected from the group consisting of metal, which belongs to group I, group II, group XII and group XIII of the periodic system of elements, published in 1991, in proportion to 1 mole of a transition metal atom and 0-500 moles of electron donor (E1) in relation to 1 mole of the transition metal atom.

 In a first aspect of the invention, preferably in an olefin (co) polymer composition, the composition is obtained by polymerizing propylene alone or by copolymerizing propylene and an olefin having 2-12 carbon atoms in the presence of a preactivated catalyst, the preactivated catalyst further comprising an organometallic compound (AL2) and electron donor (E2), wherein the organometallic compound (AL2) is a metal compound selected from the group consisting of metals belonging to groups I, II, XII and XIII of the periodic system of elements published in 1991, the content of organometallic compounds (AL1) and (AL2) being 0.05-5000 moles per 1 mol of transition metal atom in a preactivated catalyst, and the content of electron donors (E1) and (E2) is 0-3000 moles per 1 mole of a transition metal atom in a preactivated catalyst.

In a first aspect of the invention, preferably, in the olefin (co) polymer composition, the preactivated catalyst supports 0.01-5000 g of polyethylene with an intrinsic viscosity [η _E ] of 15-100 dl / g, measured in tetraline at 135 ^° C., per 1 g the catalytic component of the transition metal compound. Preferably, the amount of supported polyethylene per 1 g of the catalytic component of the transition metal compound is 0.05-2000 g, and more preferably 0.1-1000 g.

In a first aspect of the invention, preferably, in the olefin polymer (co) polymer composition, the preactivated catalyst supports 0.01-100 g of polypropylene (B) and 0.01-5000 g of polyethylene (A) per 1 g of the catalytic component of the transition metal compound, wherein polypropylene (B) has an intrinsic viscosity [η _B ], measured in tetraline at 135 ^° C., of less than 15 dl / g and is a propylene homopolymer or a copolymer of propylene with an olefin containing 50 wt.% Or more of propylene unit, and polyethylene (A) has intrinsic viscosity [η _E ] from 15 to 1000 dl / g, measured in tetraline at 135 ^° C. Preferably, the intrinsic viscosity of the prepolymerized polypropylene is 0.2-8 dl / g, and more preferably 0.5-8 dl / g. The amount of prepolymerized polypropylene per 1 g of the catalytic component of the transition metal compound is from 0.01 to 50 g, and more preferably 0.5-50 g. In addition, it is preferable that the content of the prepolymerized polypropylene is 0.001-2 wt.%, More preferably, 0.005-1.5 wt.%, and most preferably, 0.001-1 wt.%.

 In the first aspect of the invention, preferably, in the composition of the (co) olefin polymer, the (co) olefin polymer, excluding high molecular weight polyethylene, is obtained using 0.01-1000 moles of catalyst, in terms of a transition metal atom in the catalyst, per 1 liter of copolymerization volume of propylene or another olefin.

 In a first aspect of the invention, preferably, in the composition of the (co) olefin polymer, the (co) olefin polymer, excluding high molecular weight polyethylene, is obtained by mixing a) a propylene homopolymer or a copolymer, propylene and an olefin that contains 50 wt.% Or more propylene units, the homopolymer propylene or a copolymer of propylene with an olefin is obtained by polymerization of one propylene and another olefin having 2-12 carbon atoms in the presence of a preactivated catalyst containing an olefin-producing catalyst and polyethylene coating an olefin producing catalyst, wherein the olefin producing catalyst is formed by a combination of a catalytic component of a transition metal compound containing at least a titanium compound, 0.01-1000 moles of an organometallic compound (AL1) selected from the group consisting of metals that belong to the group I, group II, group XII and group XIII of the periodic system of elements, published in 1991, in a ratio of 1 mole of a transition metal atom and 0-500 moles of electron donor (E1) in a ratio of 1 a mole of a transition metal atom and c) a propylene homopolymer or a copolymer of propylene with an olefin, which contains 50 wt.% of propylene units.

A second aspect of the invention is a method for producing an olefin copolymer composition comprising the step of polymerizing or copolymerizing an olefin in the presence of a preactivated catalyst comprising a polyolefin catalyst and polyethylene to form an (o) olefin polymer in which the polyolefin production catalyst contains (i) a catalytic component of a transition metal compound comprising at least a titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), wherein the anical compound (AL1) is a metal compound selected from the group consisting of metals belonging to groups I, II, XII and XIII of the periodic system of elements published in 1991, wherein the content of the organometallic compound (AL1) is 0.01-1000 moles per 1 mol of transition metal atom, the content of the electron donor (E1) is 0-500 mol per 1 mol of transition metal atom and in which polyethylene covers the polyolefin catalyst and contains an ethylene homopolymer or a copolymer of ethylene with an olefin containing 50 wt.%, or more more than ethylene units, and the content of coating polyethylene is 0.01-5000 g per 1 g of the catalytic component of the transition metal compound and the polyethylene has an intrinsic viscosity [η] of 15-100 dl / g, measured in tetraline at 135 ^o C.

 In a second aspect of the invention, preferably, in a method for preparing an olefin (co) polymer composition, the polymerizable or copolymerizable olefin is propylene or an olefin having 2-12 carbon atoms and the (co) polymer of the olefin is a propylene homopolymer or a propylene-olefin copolymer containing 50 wt. % or more units of propylene and an olefin having 2-12 carbon atoms.

 In a second aspect of the invention, preferably, a method for preparing an olefin (co) polymer composition further comprises the step of introducing an organoaluminum compound and an electron donor (E2) into a preactivated catalyst, wherein the content of the organometal compound (AL1) and organoaluminum compound (AL2) in the preactivated catalyst is from 0.05 to 5000 mol.h. per 1 mol of the titanium atom, and the content of electron donors (E1) and (E2) in the preactivated catalyst is 0-3000 mol.h. per 1 mol of a titanium atom in a preactivated catalyst.

 In a second aspect of the invention, preferably, in a method for preparing an olefin copolymer composition, the amount of titanium atom in the catalyst is 0.01-1000 mmol per 1 liter of olefin copolymerization volume.

In a second aspect of the invention, preferably, in a method for preparing an olefin (co) polymer composition, a preactivated catalyst contains 0.01-100 g of polypropylene (B) per 1 g of the catalytic component of the transition metal compound and polypropylene (B) has an intrinsic viscosity [η _B ] less than 25 dl / g, measured in tetraline at 135 ^° C. and is a propylene homopolymer or a copolymer of propylene with an olefin containing 50% by weight or more of propylene units.

 In a second aspect of the invention, preferably, in a method for preparing an olefin (co) polymer composition, the amount of transition metal atom in the catalyst is 0.01-1000 mmoles per 1 liter of olefin (co) polymerization volume.

In a second aspect of the invention, preferably in a method for producing an olefin (co) polymer composition, the method comprises the steps of: (a) a preliminary (co) polymerization process comprising polymerizing or copolymerizing an olefin in the presence of a polyolefin catalyst to obtain 0.01-100 g of polyolefin (B ) having an intrinsic viscosity [η] of less than 15 dl / g measured in tetralin at 135 ^o C, for 1 g of the catalyst component a transition metal compound, wherein the polyolefin producing catalyst comprises: (i) catalytic assembles t a transition metal compound comprising at least a titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), wherein the organometallic compound (AL1) is a metal compound selected from the group consisting of metals belonging to groups I, II, XII and XIII of the periodic system of elements published in 1991, the content of the organometallic compound (AL1) being 0.01-1000 moles per 1 mol of the transition metal atom, the content of the electron donor (E1) is 0-500 moles per 1 mole of transition atom metal; C) the process of preliminary activating (co) polymerization, including the polymerization or copolymerization of an olefin with the formation of 0.01-100 g of polyolefin (A) having an intrinsic viscosity [η] of 15-100 dl / g, measured in tetraline at 135 ^o C, 1 g of the catalytic component of the transition metal compound; and (c) a basic (co) polymerization process comprising polymerizing an olefin having 2-12 carbon atoms in the presence of a preactivated olefin polymerization catalyst, the preactivated catalyst being obtained by coating the catalytic component of the transition metal compound with polyolefins (B) and (A) .

In a second aspect of the invention, preferably, in a method for preparing an olefin (co) polymer composition, the method comprises the step of polymerizing or copolymerizing an olefin in the presence of: (a) a preactivated olefin polymerization or copolymerization catalyst, which is prepared in such a way that the catalytic component of the transition metal compound can be coated with polyolefins (B) and (A), and comprising the steps of: a preliminary (co) polymerization process comprising polymerizing or copolymerizing an olefin in an additive obstacle polyolefin producing catalyst to form 0.01-100 g of polyolefin (B) having an intrinsic viscosity [η] of less than 15 dl / g measured in tetralin at 135 ^o C, for 1 g of the catalyst component a transition metal compound, the polyolefin producing catalyst contains (i) a catalytic component of a transition metal compound comprising at least a titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), wherein the organometallic compound (AL1) is a metal compound selected from the group consisting of metals belonging to groups I, II, XII and XIII of the periodic system of elements published in 1991, the content of the organometallic compound (AL1) being 0.01-1000 moles per 1 mol of transition metal atom, the content of electron donor (E1) is 0-500 moles per 1 mol of transition metal atom; and a pre-activating (co) polymerization process comprising polymerizing or copolymerizing an olefin to form from 0.01 to 100 g of a polyolefin (A) having an intrinsic viscosity [η] of 15 to 100 dl / g, measured in tetraline at 135 ^° C, per 1 g of the catalytic component of the transition metal compound; (c) an organometallic compound (AL2), which is a metal compound selected from the group consisting of metals belonging to groups I, II, XII and XIII of the periodic table of elements published in 1991, wherein the content of organometallic compounds (AL1) and (AL2) is 0.05-5000 moles per 1 mol of transition metal atom in the preactivated catalyst, and (c) electron donor (E2), and the content of electron donors (E1) and (E2) is 0-3000 mol per 1 mol of transition atom metal.

 In a second aspect of the invention, preferably, a method for preparing an olefin (co) polymer composition further comprises the step of introducing 0.001 to 2 parts by weight of at least one stabilizer selected from the group consisting of a phenolic antioxidant and a phosphoric antioxidant into an olefin (co ) a polymer after (co) polymerization of an olefin.

 In a second aspect of the invention, it is preferable to obtain a (co) olefin polymer, including the step of introducing 0-10000 parts by weight (co) polymer of an olefin obtained in a known manner per 100 parts by weight composition (co) polymer of an olefin obtained by the method as defined in the second aspect of the invention, preferably 0-5000 parts by weight and more preferably 0-2000 parts by weight

A third aspect of the invention is an olefin (co) polymerization catalyst comprising a transition metal compound catalyst that contains at least a titanium compound and an olefin (co) polymer (A) coating catalyst in which the olefin (co) polymer (A) has an intrinsic viscosity [η] of 15 to 100 dl / g, measured in tetraline at 135 ^° C. and an olefin (co) polymer (A) content of 0.01-5000 g per 2 g of a titanium-containing solid catalyst component.

A fourth aspect of the invention is a method for producing an olefin (co) polymerization catalyst, comprising the step of polymerizing or copolymerizing an olefin in the presence of a polyolefin producing catalyst to form an olefin copolymer (A) having an intrinsic viscosity [η] of 15 to 100 dl / g, measured in tetraline at 135 ^o C and with the possibility of coating titanium-containing solid catalytic component of 0.01-5000 g of (co) olefin polymer (A) per 1 g of titanium-containing solid catalyst component, in which the catalyst for producing the polyolefin contains (i) a catalytic component of a transition metal compound, including at least a titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), wherein the content of the organometallic compound (AL1) is 0.01- 1000 moles per 1 mol of the titanium atom, and the electron donor content (E1) is 0-500 moles per 1 mol of the titanium atom.

 In the third and fourth aspects of the invention, preferably in the olefin (co) polymerization catalyst, the catalytic component of the transition metal compound is obtained by a combination of 0.01-1000 moles of the organometallic compound (AL1), where the metal is selected from group I, group II, group XII and group XIII a periodic system of elements, published in 1991, per 1 mol of a transition metal atom and 0-500 moles of an electron donor (E1) per 1 mol of a transition metal atom.

 In the third and fourth aspects of the invention, preferably in the olefin (co) polymerization catalyst, the olefin (co) polymer (A) is an ethylene homopolymer or an ethylene-olefin copolymer that contains 50% or more ethylene units.

 In the third and fourth aspects of the invention, preferably, the olefin (co) polymerization catalyst further comprises an organoaluminum compound and an electron donor (E1), wherein the organoaluminum compound is 0.01-1000 moles per 1 mol of titanium atom in the catalyst, and the electron donor content (E1) is 0-500 moles per 1 mol of titanium atom in the catalyst.

In the third and fourth aspects of the invention, preferably, in the (co) olefin polymerization catalyst (co), the polymerizable polyolefin (B) is formed on a layer that is lower than the (co) polymerizable polyolefin (A), wherein the polyolefin (B) has an intrinsic viscosity [η ] less than 15 dl / g, measured in tetraline at 135 ^° C. and a polyolefin (B) content of 0.01-100 g per 1 g of a transition metal compound component.

 In the third and fourth aspects of the invention, preferably in the olefin (co) polymerization catalyst, the catalytic component of the transition metal compound is a titanium-containing solid catalyst component, the main component of which is a titanium trichloride composition or titanetetrachloride.

 In the third and fourth aspects of the invention, preferably in the catalyst for (co) polymerizing olefins, the organometallic compound (AL1) is an organoaluminum compound.

 In the third and fourth aspects of the invention, preferably, in the (co) polymerization of olefins, the electron donor (E1) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur in the molecule, or an organosilicon compound having a Si — O — C bond in the molecule.

 In the third and fourth aspects of the invention, preferably in the olefin (co) polymerization catalyst, the polyolefin (B) is a homopolymer or copolymer of an olefin having 2-12 carbon atoms.

 In the third and fourth aspects of the invention, preferably the olefin (co) polymerization catalyst further comprises an electron donor (E2), wherein the content of electron donors (E1) and (E2) is 0-3000 moles per 1 mol of transition metal atom in the catalyst.

 In the third and fourth aspects of the invention, preferably, in the (co) polymerization of olefins, the electron donor (E2) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur in the molecule, or an organosilicon compound having a Si — O — C bond in the molecule.

 In the third and fourth aspects of the invention, preferably, the olefin (co) polymerization catalyst further comprises an organometallic compound (AL2) and an electron donor (E2), wherein the organometallic compound (AL2) contains a metal selected from the group consisting of metals that belong to group I , group II, group XII and group XIII of the periodic system of elements, published in 1991, and the content of organometallic compounds (AL1) and (AL2) is 0.05-5000 moles per 1 mol of transition metal atom in preliminary activity catalyst, and the content of electron donors (E1) and (E2) is 0–3000 mol per 1 mol of transition metal atom in the preactivated catalyst.

Brief Description of Drawings
In FIG. 1 presents a micrograph with a magnification of 75000x, obtained in the study using a transmission electron microscope (TEM) of the polymer composition from example 26 of the present invention.

 In FIG. 2 is a diagram for explaining a micrograph of FIG. 1.

 In FIG. 3 shows a TEM micrograph of well-known polypropylene.

 In FIG. 4 is a diagram for explaining a micrograph of FIG. 3.

 In FIG. 5 to 7 are graphs showing the rheological properties of the polymer composition of Example 26 of the present invention and the dependence of the dynamic elastic modulus G 'on the frequency ω.

In FIG. 8 and 9 are diagrams of the rheological properties of the polymer composition of Example 26 of the present invention and the relationship between the first normal stress difference N ₁ and shear rate τ.

In FIG. 10 and 11 are diagrams showing the rheological properties of the polymer composition of Example 26 of the present invention and the time dependence of the relaxation modulus G (t); and
in FIG. 12 and 13 are diagrams showing the rheological properties of the polymer composition of Example 26 of the present invention and the time dependence of the viscosity during stretching.

Preferred Embodiments
As used herein, the term “polyolefins” refers to olefin polymers comprising (i) olefin homopolymers containing olefin monomers having 2-12 carbon atoms, (ii) olefin random (co) polymers containing at least 2 olefin monomers and (iii) block o-olefin copolymers containing at least 2 olefin monomers.

 The terms "polyethylenes", "ethylene polymers" and "ethylene copolymers" include ethylene polymers and ethylene copolymers comprising (i) ethylene homopolymers, (ii) random ethylene-olefin copolymers containing 50 wt.% Or more ethylene monomers and (iii) block copolymers of ethylene with olefin containing 50 wt.% or more ethylene monomers.

 The term "polypropylene" refers to (i) propylene homopolymers, (ii) random copolymers of propylene with an olefin containing 50% by weight of propylene monomers and (iii) block copolymers of propylene with an olefin containing 50% by weight of propylene monomers.

 The term "polyolefin composition" refers to a mixture of polyolefins that differ from each other in the form of monomers, molecular weight, disorder, unit in the block copolymer, etc.

 The term "pre-activation" means the activation of a catalyst for the production of polyolefins in activity before polymerization or copolymerization of an olefin. Pre-activation is carried out by polymerization or copolymerization of an olefin in the presence of a catalyst for producing polyolefins with pre-activation due to the fact that the catalyst is coated with a polymerized or copolymerized olefin.

 The term “pre-activated catalyst” means a catalyst containing a conventional catalyst for producing polyolefins and a small amount of at least two polyolefins. The two polyolefins are a polymerization polyolefin having a specific intrinsic viscosity and a polyolefin having a specific and high intrinsic viscosity. The preactivated catalyst is preactivated because the polyolefin production catalyst supports the above two polyolefins. A traditional catalyst for producing polyolefins is a catalyst traditionally used in the manufacture of polyolefins and a conventional catalyst for producing polyolefins contains a catalytic component of a transition metal compound, including at least a titanium compound, an organometallic compound and, if necessary, an electron donor. The catalytic component of the transition metal compound can be any known catalytic component of the production of polyolefins containing the catalytic component of the transition metal compound comprising at least a titanium compound as the main component. Among the catalyst components known in the manufacture, preferably, a titanium-containing solid catalyst component is used. The titanium-containing solid catalyst component may be any of the titanium-containing solid catalyst components containing the titanium trichloride composition. Examples of titanium-containing solid catalytic components include components proposed in the publications of the examined Japanese applications N 56-3356, 59-28573, 63-66323 and others, and the titanium-containing catalytic component on the carrier includes titanium, magnesium, halogen and electron donor as the main components, where the magnesium compound carries titanium tetrachloride, as suggested in Japanese pending applications NN 62-104810, 62-104811, 62-104812, 57-63310, 57-63311, 58-83006, 58-138712 and others.

The organometallic compound may be a compound having an organic group (ligand) of a metal selected from the group consisting of metals of group I, metals of group II, metals of group XII and metals of group XIII of the periodic system of elements published in 1991. Examples of compounds having an organic group (ligand) of the metal include organolithium compounds, organosodium compounds, organomagnesium compounds, organozinc compounds and organoaluminium compounds. The organometallic compound can be used in combination with the above catalytic components of the transition metal compound. Among the examples, it is preferable to use organoaluminum compounds represented by the general formula:
AlR _p ¹ R _q ² X _{3- (p + q))} ,
in which R ¹ and R ² each represents a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen atom, and p and q are positive integers satisfying the expression O <(p + q) ≅ 3 .

 Examples of organoaluminum compounds include trialkylaluminum, such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, triisohexylaluminum or tri-n-octylaluminum; dialkylaluminum monohaloids such as diethylaluminium chloride, di-n-propylaluminium chloride, diisobutylaluminium chloride, diethylaluminium bromide or diethylaluminium iodide; dialkylaluminium hydrides such as diethylaluminium hydride; an alkylaluminium sesquichaloid such as ethylaluminium sesquichloride; monoalkylaluminum dihalo such as ethylaluminum dichloride; and alkoxyalkylaluminum, such as diethoxymonoethylaluminum, preferably trialkylaluminum or di-alkylaluminum monohalo. Such organoaluminum compounds can be used either singly or in combination.

 An electron donor, if required, is used to control the rate of production and / or stereoregularity of the polyolefin. Examples of electron donors include organic compounds having in the molecule any of oxygen, nitrogen, sulfur and phosphorus, such as ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea, isourea, isothiourea, isocyanates, azo compounds, phosphines, phosphites, hydrogen sulfide, thioesters, neoalcohols, silanols and organosilicon compounds containing a Si — O — C bond in the molecule.

 Examples of ethers include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, diisohexyl ether, di-n- octyl ether, diisooctyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran.

 Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol and glycerol.

 Examples of phenols include phenol, cresol, xylene, ethyl phenol and naphthol.

 Examples of esters include monocarboxylic acid esters such as methyl methacrylate, formic acid methyl ester, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, propyl n-acetate, propyl isoacetate, butyl formic acid ester, amyl acetate, butyl n-acetate, octyl acetate, phenyl , ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, toluic acid methyl ester, toluic acid ethyl ester, anisic acid methyl ester, anisic propyl ester to slots, anisic acid phenyl ester, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, methyl naphthoic acid, 2-etilgeksilnaftoynaya acid or ethylphenyl acetate; aliphatic polycarboxylic acid esters such as diethyl succinate, methyl malonic acid diethyl ether, butyl malonic acid diethyl ether, dibutyl maleate or diethyl butyl maleic acid; and aromatic polycarboxylic acid esters such as monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhex -octyl phthalate, di-ethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethyl hexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate or diisobutyl ether of naphthalenedicarboxylic acid.

 Examples of aldehydes include acetaldehyde, propionaldehyde and benzaldehyde.

 Examples of carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valerianic acid or benzoic acid; and acid anhydrides such as benzoic anhydride, phthalic anhydride or tetrahydrophthalic anhydride.

 Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and benzophenone.

 Examples of nitrogen-containing organic compounds include nitriles, such as acetonitrile or benzonitrile; amines such as methylamine, diethylamine, tributylamine, triethanolamine, β- (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine, 2 2,5,5-tetramethylpyrrolidine, N, N, N ', N-tetramethylethylenediamine, aniline or dimethylaniline; amides such as formaldehyde, hexamethylphosphoric triamide, N, N, N ', N', N'-pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide or octamethylpyrophosphorylamide; ureas such as N, N, N ', N'-tetramethylurea; isocyanates such as phenyl isocyanate or toluyl isocyanate; azo compounds such as azobenzene.

 Examples of phosphorus-containing compounds include phosphines such as ethylphosphine, triethylphosphine, di-n-octylphosphine, tri-n-octylphosphine, triphenylphosphine or triphenylphosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite or triphenyl phosphite.

 Examples of sulfur-containing compounds include thioethers such as diethyl thioether, diphenyl thioether or methylene thioether; and thioalcohols such as ethyl thioalcohol, n-propyl thioalcohol or thiophenol.

 Examples of organosilicon compounds include silanols, such as trimethylsilanol, triethylsilanol or triphenylsilanol; and organosilicon compound having Si-O-C bond, such as trimethylmethoxysilane, dimethyldimethoxysilane, metilfenildimetoksisilan, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tsiklopentilmetildimetoksisilan, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane cyclohexylmethyldimethoxysilane cyclohexyltrimethoxysilane, dicyclohexyl dimethoxysilane or 2-norbornylmethyldiethoxysilane.

 The above electron donors can be used either individually or in combination.

In preactivated olefin polymerization catalysts, the polyolefin (A) has an intrinsic viscosity [η] ranging from 15 to 100 dl / g, preferably 17-50 dl / g. The intrinsic viscosity [η] is measured in tetraline at 135 ^° C. The polyolefin (A) is a monopolymer or copolymer containing an olefin having 2-12 carbon atoms, preferably a monopolymer containing ethylene or propylene, or a copolymer of ethylene or propylene with an olefin containing 50 wt.% Or more of ethylene or propylene monomer, preferably at least 70 wt.%, More preferably at least 90 wt.%. Further, the polyolefin (A) is more preferably an ethylene monopolymer or a copolymer of ethylene with an olefin containing 50 wt.% Or more ethylene monomer or, more preferably, at least 70 wt.%, More preferably at least 90 wt.%.

A too low intrinsic viscosity [η] of the polyolefin (A) can hardly provide sufficient melt stress and a sufficient crystallization temperature of the intended polyolefin composition as a final product. The upper limit of intrinsic viscosity [η] is not particularly defining. However, the preferred upper limit may be about 100 dl / g, taking into account manufacturing efficiency and the following reason: when the intrinsic viscosity [η] of the polyolefin (A) is too different from the intrinsic viscosity obtained by the polyolefin composition as a final product, the polyolefin (A) does not can be dispersed in the polyolefin composition, which causes insufficient melt stress. In addition, the intrinsic viscosity [η] of the polyolefin (A), measured in tetraline at 135 ^° C., should be increased to 15 dl / g to provide a high molecular weight final product. For this reason, an ethylene monopolymer or an ethylene olefin copolymer containing 50 wt.% Or more ethylene monomer is preferred from the point of view of polymerization efficiency.

 Although the density of the polyolefin (A) is not particularly determinative, a density of 880-980 g / L is preferred.

 The amount of polyolefin (A) covering the catalytic component of the transition metal compound is from 0.01 to 5000 g per 1 g of the catalytic component, preferably from 0.05 to 2000 g, more preferably 0.1-1000 g. Less than 0, 01 g of polyolefin (A) per 1 g of the catalytic component cannot provide the resulting composition as a final product with a sufficient melt voltage and a sufficient crystallization temperature. More than 5000 g of polyolefin (A) per 1 g of the catalytic component is ineffective and can disrupt the homogeneity of the final product.

 Examples of preferred olefin monomers for polyolefin (A) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and 3-methyl-1-pentene. Among them, ethylene, propylene, 1-butene and 4-methyl-1-pentene are particularly preferred.

The polyolefin (B) is the same as a polymerizable polyolefin having an intrinsic viscosity [η] of less than 15 dl / g measured in tetraline at 135 ^° C. The polyolefin (B) provides the polyolefin (A) contained in the polyolefin composition as a final product with good dispersibility in the composition. The intrinsic viscosity [η] of the polyolefin (B) is preferably lower than that of the polyolefin (A) and higher than that of the polyolefin composition as a final product.

 The amount of polyolefin (B) for coating the catalytic component of the transition metal compound is preferably 0.01-100 g of the catalytic component. In other words, a preferred amount is from 0.001 to 1 wt.% With respect to the polyolefin composition as the final product. Too little polyolefin (B) prevents the dispersion of polyolefin (A) in the polyolefin composition as a final product. Too much polyolefin (B) makes the preparation of preactivated olefin polymerization catalysts less efficient because dispersibility is easily saturated.

 Pre-activated catalysts for olefin polymerization are obtained by pre-activating treatment, allowing the catalytic component of the transition metal compound to support polyolefins (B) and (A). Pre-activating treatment includes the stages of prepolymerization and pre-activating polymerization in the presence of a catalyst for producing polyolefins. Pre-polymerization prepolymerizes the olefin to form polyolefin (B). Pre-activating polymerization polymerizes the olefin to form polyolefin (A). The polyolefin production catalyst is a combination of a catalytic component of a transition metal compound containing at least a titanium compound, an organometallic compound and, if desired, an electron donor.

 In the catalyst for producing polyolefins for pre-activating treatment, the organometallic compound is from 0.01 to 1000 mol parts, preferably 0.05-500 mol. hours, and the electron donor is from 0 to 500 mol. hours, preferably 0-100 mol.h. for 1 mol.h. a transition metal contained in a catalytic component of a transition metal compound containing at least a titanium compound.

 The following method allows the catalytic component of the transition metal compound to support the polyolefins (B) and (A). First, a polyolefin (B) in an amount of from 0.01 to 100 g per 1 g of the catalytic component of the transition metal compound is formed by prepolymerization using 0.01-500 g of a polymerizable olefin in the presence of a polyolefin polymerization catalyst of from 0.001 to 5000 mmol, preferably 0, 01-1000 mmol with respect to the transition metal atom in the catalytic component per 1 liter of olefin polymerization volume. This method does not use or use the largest 500 g of solvent per 1 g of the catalytic component of the transition metal compound. Then, from 0.01 to 5000 g of polyolefin (A) per 1 g of the catalytic component of the transition metal compound is formed by polymerization using 0.01-1000 g of olefin. The term "polymerization volume" refers to the volume of the liquid phase in the polymerization vessel for liquid phase polymerization or the volume of the gas phase in the polymerization vessel for gas phase polymerization.

 The amount of the catalytic component of the transition metal compound is preferably used in the above range with respect to the efficient and controlled polymerization of polyolefin (A). Too small an amount of the used organometallic compound makes the polymerization disproportionately slow down. Too much organometallic compound is ineffective because the resulting polyolefin composition tends to contain a large remainder of the organometal compound as a final product. Too much used amount of electron donor makes polymerization disproportionately slowing down. Too much solvent used requires a large reactor and makes polymerization difficult for effective control.

 Pre-activating treatment is carried out in a liquid phase using solvents. Examples of solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane or dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane or methylcyclohexane; aromatic hydrocarbons such as toluene, xylene or ethylbenzene; inert solvents such as a gasoline fraction or a hydrogenated diesel fuel fraction; and olefins. Preliminary activating treatment is also carried out in a gas phase that does not use a solvent.

 In order to obtain a polyolefin (A) having a high molecular weight and intrinsic viscosity [η] of 15 to 100 dl / g, the pre-activation treatment is carried out, preferably without using hydrogen, although the treatment can be carried out in the presence of hydrogen.

The preliminary polymerization of the polymerizable polyolefin is carried out under the condition that from 0.01 to 100 g of polyolefin (B) is formed per 1 g of the catalytic component of the transition metal compound, usually at a temperature of from -40 to 100 ^o C and a pressure of from 0.1 to 5 MPa over a period of time from 1 minute to 24 hours. Preliminary activating polymerization is carried out under the condition that the formation of polyolefin (A) in an amount of from 0.01 to 5000 g, preferably 0.05-2000 g, more preferably 0.1-1000 g per 1 g of catalytic component of the transition metal compound. This is usually carried out at a low temperature, such as from -40 to 40 ^o C, preferably from -40 to 30 ^o C, more preferably from -40 to 20 ^o C and a pressure of 0.1-5 MPa, preferably 0, 2-5 MPa, more preferably 0.3-5 MPa, for a period of time from 1 minute to 24 hours, preferably from 5 minutes to 18 hours, more preferably from 10 minutes to 12 hours

After pre-activation, additional polymerization can be carried out using 0.01-100 g of polymerizable olefin per 1 g of the catalytic component of the transition metal compound. Additional polymerization maintains high polymerization activity upon pre-activation. The amounts of the organometallic compound, the electron donor, the solvent and the olefin are within the same range as indicated for pre-activation, preferably the amount of the electron donor is from 0.005 to 10 moles, preferably 0.01 to 5 moles. Additional polymerization is preferably carried out at a temperature of from -40 to 100 ^o C and a pressure of 0.1-5 MPa for a period of time from 1 minute to 24 hours. The form of organometallic compounds, electron donors and solvents for additional polymerization may be the same as in the case of pre-activating polymerization. The type of olefin for additional polymerization is identical to the polymerizable olefin.

 The intrinsic viscosity [η] of the polyolefin obtained by additional polymerization is the largest in the range of intrinsic viscosity [η] of the polyolefin (A). The intrinsic viscosity [η] of the polyolefin obtained by additional polymerization is introduced into the final polyolefin.

 To obtain a given polyolefin composition, a preactivated catalyst can be used for the main polymerization using an olefin having 2-12 carbon atoms, either individually or in combination with an organometallic compound (AL2) and an electron donor (E2).

 The olefin main polymerization catalyst contains the above pre-activated catalyst, an organometallic compound (AL2), and an electron donor (E2). The total amount of organometallic compounds (AL1) and (AL2) for the polyolefin production catalyst is 0.05-3000 moles, preferably 0.1-1000 moles per 1 mole of the transition metal atom contained in the preactivated catalyst. The total number of electron donors (E1) and (E2) for the polyolefin production catalyst is 0-5000 moles, preferably 0-3000 moles per 1 mole of the transition metal atom contained in the preactivated catalyst.

 When the total amount of organometallic compounds (AL1) and (AL2) is too small, the reaction rate in the main olefin polymerization becomes too low. Too many organometallic compounds (AL1) and (AL2) are ineffective and, preferably, give a large remainder of the organometallic compounds in the resulting polyolefin composition as the final product. Too many electron donors (E1) and (E2) for the polyolefin catalyst make the reaction rate in the main olefin polymerization extremely low.

 The form of the organometallic compound (AL2) and the electron donor (E2) for preparing the catalyst for the main polymerization of olefin is the same as that of the organometallic compound (AL1) and electron donor (E1). The organometallic compound (AL1) and the electron donor (E1) can be used either individually or in combination. The form of the organometallic compound (AL2) and electron donor (E2) may be the same as for use in the pre-activating treatment, or may differ from those used in the pre-activating processing.

 The olefin main polymerization catalyst may be a combination of a powdery precipitate, an organometallic compound (AL2) and, if desired, an electron donor (E2). The powdery precipitate may be mixed with the solvent in suspension. A powdery precipitate is formed by removing the solvent, unreacted olefin, unreacted organometallic compound (AL1) and electron donor (E1) from the pre-activated catalyst by filtration or decantation. The olefin main polymerization catalyst may also be a combination of another powdery precipitate, an organometallic compound (AL2) and, if desired, an electron donor (E2). This powdery precipitate is formed by evaporation and removal of the solvent and unreacted olefin from the preactivated catalyst, by vacuum distillation or by inert gas flow.

 The polyolefin composition of the invention is obtained as follows. Olefin polymerizes in the presence of a preactivated catalyst or a catalyst for the main polymerization of olefin. The amount of preactivated catalyst or olefin main polymerization catalyst used is from 0.001 to 1000 mmol, preferably 0.005-500 mmol per 1 liter of polymerization volume with respect to the transition metal atom in the preactivated catalyst. The above-defined range of the catalytic component of the transition metal compound provides effective control of olefin polymerization.

Main olefin polymerization can be carried out by a known polymerization method, such as suspension polymerization, bulk polymerization, gas phase polymerization, liquid phase polymerization, or a combination thereof. In the case of suspension polymerization, the olefin is polymerized in solvents such as an aliphatic hydrocarbon, including propane, butane, pentane, hexane, heptane, octane, isooctane, decane or dodecane; alicyclic hydrocarbons, including cyclopentane, cyclohexane or methylcyclohexane; aromatic hydrocarbons such as toluene, xylene or ethylbenzene; inert hydrocarbons such as a gasoline fraction or a hydrogenated diesel fuel fraction; and olefins. In the case of bulk polymerization, the olefin acts as a solvent. In the case of gas phase polymerization, the olefin polymerizes in the gas phase. In the case of liquid phase polymerization, the polyolefin is formed during polymerization in the liquid state. An example of preferred polymerization conditions for the above methods are: temperature from 20 to 120 ^o C, preferably 30-100 ^o C, more preferably 40-100 ^o C, pressure from 0.1 to 5 MPa, preferably 0.3-5 MPa during continuous, semi-continuous or periodic polymerization and polymerization time from 5 minutes to 24 hours. Under these conditions, a polyolefin is effectively formed.

 The polymerization conditions are set to obtain the polyolefin formed in the main polymerization and the polyolefin composition as a final product with an intrinsic viscosity [η] of 0.2 to 10 dl / g, preferably 0.7-5 dl / g, and for regulating the polyolefin (A ) obtained from the used pre-activated catalyst at 0.01-5 wt.% of the composition. Like the known olefin polymerization, the molecular weight of the polymer is controlled by the use of hydrogen in the polymerization.

 The intrinsic viscosity of a given composition of less than 0.2 dl / g leads to poor mechanical properties of the resulting final polyolefin product. An intrinsic viscosity above 10 dl / g impairs the formability.

 When the content of the polyolefin (A) derived from the preactivated catalyst is less than 0.01% by weight of the target polyolefin composition, the melt voltage and crystallization temperature of the polyolefin composition are not sufficiently improved. A content of more than 5% by weight of a polyolefin (A) in a given polyolefin composition is ineffective and the content may impair the homogeneity of the polyolefin composition.

 An olefin having 2-12 carbon atoms is preferred for polymerization in the preparation of the polyolefin composition of the invention. Examples of a preferred olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and 3-methyl-1-pentene. Among them, ethylene, propylene, 1-butene and 4-methyl-1-pentene are particularly preferred. These olefins can be used either individually or in combination.

 The polyolefin obtained by the main polymerization may be an olefin homopolymer, an olefin random copolymer or an olefin block copolymer containing 50% by weight or more of an olefin monomer. The polyolefin is preferably an olefin homopolymer, a statistical olefin copolymer containing 90 wt. % or more of an olefin monomer, or an olefin block copolymer containing 70% by weight of an olefin monomer.

 After the main polymerization of the olefin, if necessary, known processes are carried out such as deactivating the catalyst, removing the catalyst and drying. Then finally the desired polyolefin composition is obtained. The desired polyolefin composition has a high melt voltage and a high crystallization temperature.

 The pre-activation method provides a polyolefin (A) having a high molecular weight, and the polyolefin (A) is uniformly dispersed in the polyolefin composition as a final product. Since the invention uses the above method, the required amount of preactivated catalyst can be obtained at a time. In addition, the main polymerization is carried out by a continuous olefin polymerization process. Therefore, in comparison with the traditional production of polyolefins, a similar performance is achieved.

The polyolefin composition obtained using the pre-activated catalyst in the invention has a high melt voltage. When polypropylene is used as the olefin, the melt stress (MS) of the obtained polypropylene composition has the following ratio with the intrinsic viscosity [η] of the obtained polypropylene composition, measured in tetraline at 135 ^° C:
loq (MS)> 4.24 x loq [η] - 1.05
Too much melt stress affects the formability of the resulting polyolefin composition. Therefore, a preferred range of the invention is:
4.24 loq [η] + 0.05> loq (MS)> 4.24 loq [η] - 1.05,
preferably,
4.24 loq [η] + 0.24> loq (MS)> 4.24 loq [η] - 1.05,
more preferably
4.24 loq [η] + 0.24> loq (MS)> 4.24 loq [η] - 0.93.

The term "melt voltage at 230 ^° C refers to the voltage (cN) of a polyolefin filament measured under the following conditions: the polyolefin is heated to 230 ^° C and using a device called" Melt Voltage II "manufactured by Toyo Seiki Seikaku-Sho Ltd., the polyolefin melt is extruded into the air through a nozzle having a diameter of 2.095 mm at a speed of 200 mm / min to form a strand, and finally, the polyolefin filament stress is measured when the resulting strand is wound at a speed of 3.14 m / min.

 After the main polymerization, if necessary, known processes are carried out such as deactivation of the catalyst, removal of the catalyst and drying. Then finally the desired polypropylene composition is obtained. The following description is an example of a polypropylene (PP) composition.

 Phenolic stabilizers are introduced into the composition to improve the heat resistance, melt stress, and crystallization temperature of the composition. The amount of stabilizer used is 0.001-2 parts by weight, preferably 0.005-1.5 parts by weight. hours, more preferably 0.01-1 parts by weight in relation to 100 wt. including polypropylene (PP) composition. The range of quantities realizes the effect of the stabilizer without inhibiting the properties of the composition as a polyolefin (A). The above range is also preferred in terms of cost.

 Phenolic stabilizers can be any of the known phenolic stabilizers having a phenolic structure. Examples are 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-p-cresol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-p-cresol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl- 6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 2-t-butyl-6- (3'-t-butyl) -5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t -butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl -6 -t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methyl-cyclohexyl) -p-cresol], 2,2 ' Ethylidenebis (4,6-di-t-butylphenol, 2,2'-butylidenebis (2-t-butyl-p-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-t -butylphenyl) butane, triethylene glycolbis [3- (3-t-butyl-5-methyl-4-guildroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4- hydroxyphenyl) propionate], 2,2-thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-3- (3'-5'-di- t-butyl-4'-hydroxyphenyl) propionate, N, N'-hexamethylene bis (3,5-di-t-4-hydroxyhydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate diet yl ether, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl ) propionyloxyethyl] isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis (3,5-di-t-butyl-4-hydroxybenzylphosphoric acid) ethyl) nickel, N, N'-bis [3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-b with [1,1-dimethyl-2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2 , 2-bis [4- [2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane, - (3,5-di-t-butyl-4-hydroxyphenyl) propionate alkyl ether and t .P.

 Particularly preferred examples are 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3 - (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4- methyl phenyl acrylate, 2,2'-ethylidecbis (4,6-di-t-butylphenyl) and the like. Only one phenolic stabilizer may be used, or two or more kinds of phenolic stabilizers may be combined to use.

 In the present invention, a phosphoric antioxidant is mixed as a component that exhibits a high melt stress, a high crystallization temperature of the polypropylene composition to be obtained during molding, thermal oxidation resistance, weather resistance and color change prevention.

 The blended amount is 0.001-2 parts by weight, more preferably 0.005-1.5 parts by weight. hours, most preferably, 0.01-1 wt.h. per 100 parts by weight the polypropylene composition (PP) of component (A), with regard to ensuring the characteristics of the polypropylene composition according to the present invention and the cost of the antioxidant.

 The phosphoric antioxidant that is used for the polypropylene composition of existing analogs can be used without limitation. More specifically, examples are provided below. Only one phosphoric antioxidant can be used, or two or more kinds of phosphoric antioxidants can be used together.

 Examples of biphenylene diphosphonate are tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonate, tetrakis (2,4-di-t-amylphenyl) -4,4'-biphenylene diphosphonate, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphonate, tetrakis (2,6-di-t-butyl-4-methylphenyl) -4,4'-biphenylene diphosphonate , tetrakis (2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl phenyl) -4,4'-biphenylene diphosphonate, tetrakis [2,6-di-t-butyl-4- (2'4'-di -t-butylphenoxycarbonyl) phenyl] -4,4'-biphenylene diphosphonate, tetrakis (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) -4,4'-biphenylene diphosphonate, bis [2,2 'methylene bis (4-methyl -6-t-butylphenyl)] -4,4'-biphenylene diphosphonate, bis [2,2'-methylene bis (4,6) -di-t-butylphenyl)] -4,4'-biphenylene diphosphonate bis [2,2'-ethylidene bis (4-methyl-6-t-butylphenyl)] -4,4'-biphenylene diphosphonate, bis [2,2'-ethylidene bis (4,6-di- t-butylphenyl)] - 4,4'-biphenylene diphosphonate and the like.

 Examples are cathecyl-2,6-di-t-butyl-4-methylphenylphosphite, cathecyl-2,4,6-tri-t-butylphenylphosphite, alpha-naphthylcatecylphosphite, 2,2'-methylenebis (4-methyl-6-t -butylphenyl) -2-naphthylphosphite, 4,4'-butylidene bis (3-methyl-6-t-butylphenyl di-tridecylphosphite), 1,1,3-tris (2-methyl-4-di-tridecylphosphite- 5-t-butylphenyl) butane, trilauryl trithiophosphite, tricyl trithiophosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-hydroxy-9,10-dihydro-9-oxa-10-phosphafenanthrene-10- oxide, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-nonylphenyl) phosphite, tris (mono- or di-nonylphenyl) phosphite, tris (2,4- and-t-butylphenyl) phosphite, tris (2,6-di-t-butyl-4-methylphenyl) phosphite, etc.

 Examples of pentaerythritol diphosphite are distearyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t amylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-5-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl -4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-S-butylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-amylphenyl) pentaerythritol diphosphite, bis (2,6-d -t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis [2,6-di-t-butyl-4- (2 ', 4'-di-t-butylphenoxycarbonyl) phenyl] pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) pentaerythritol diphosphite, etc.

 Examples of tetraoxaspiro [5.5] undecane diphosphite are tetrakis (2,4-di-t-butylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,6-di-t-butyl-4- (2 ', 4'-di-t-butylphenoxycarbonylphenyl) -3,9-bis (1,1-dimethyl-2 -hydroxyethyl) -2,4,8,10-tetraoxaspiro [5, 5] undecandiphosphite, tetrakis (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) -3,9-bis (1,1-dimethyl -2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,4-di-t-amylphenyl) -3,9-bis (1,1-dimethyl-2 - hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,6-di-t-butyl-4-m tilphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,4,6-tri-t -butylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,4,6-tri-t -amylphenyl) -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, tetrakis (2,6-di-t-butyl -4-n-octadecyloxycarbonylethyl-phenyl) - 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2 '-methylene-bis (4-methyl-6-t-butylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'- methylene bis (4,6-di-t-butylphenyl] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'-methylene bis (4,6-di-t-amylphenyl)] - 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [ 5.5] undecane diphosphite, bis [2,2'-ethylidene bis (4-methyl-6-t-butylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2, 4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis- [2,2'-ethylidene bis (4,6-di-t-butylphenyl)] -3,9-bis (1,1- dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'-ethylidene bis (4,6-di-t-amylphenyl)] -3, 9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane- ifosfit etc.

 Examples of 2,2'-bis (4,6-di-t-butylphenyl) phosphite are 2,2'-bis (4,6-di-t-butylphenyl) octylphosphite, 2,2'-bis (4,6- di-t-butylphenyl) nonylphosphite, 2,2'-bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2'-bis (4,6-di-t-butylphenyl) tridecyl phosphite, 2, 2'-bis (4,6-di-t-butylphenyl) myristylphosphite, 2,2'-bis (4,6-di-t-butylphenyl) stearylphosphite, 2,2'-bis (4,6-di-t -butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-bis- (4,6-di-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethylphenyl) phosphite, 2,2'-bis (4,6-di-t -butylphenyl) [2,6-di-t-butyl-4- (2'-4'-di-t-butylphenoxycarbonyl) phenyl] phosphite, 2,2'-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of 2,2'-methylene bis (4-methyl-6-t-butylphenyl) phosphite are 2,2'-methylene bis (4-methyl-6-t-butylphenyl) octylphosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) nonylphosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) laurylphosphite, 2,2'-methylene bis (4-methyl-6- t-butylphenyl) tridecylphosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) myristyl phosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) stearyl phosphite, 2, 2'-methylene-bis (4-methyl-6-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) ( 2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) (2,4,6-tri-t- utylphenyl) phosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethylphenyl) phosphite, 2,2'-methylene bis (4-methyl-6-t-butylphenyl) [2,6-di-t-butyl-4- (2 ', 4'-di-t-butylphenoxycarbonyl) phenyl] phosphite, 2,2'-methylenebis (4- methyl 6-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of 2,2'-methylene bis (4,6-di-t-butylphenyl) phosphite are 2,2'-methylene bis (4,6-di-t-butylphenyl) octylphosphite, 2,2'-methylene- bis (4,6-di-t-butylphenyl) nonylphosphite, 2,2'-methylene bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2'-methylene bis (4,6-di t-butylphenyl) tridecylphosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) myristylphosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) stearylphosphite, 2, 2'-methylene-bis (4,6-di-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) ( 2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-methylene-bi (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethylphenyl) phosphite, 2,2'-methylene bis (4,6-di-t-butylphenyl ) [2,6-di-t-butyl-4- (2'-4'-di-t-butylphenoxycarbonyl) phenyl] phosphite, 2,2'-methylene-bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of 2,2'-methylene bis (4,6-di-t-amylphenyl) phosphite are 2,2'-methylene bis (4,6-di-t-amylphenyl) octylphosphite, 2,2'-methylene bis (4,6-di-t-amylphenyl) stearyl phosphite, 2,2'-methylene bis (4,6-di-t-amylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2 ' methylene bis (4,6-di-t-amylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-methylene bis (4,6-di-t-amylphenyl ) (2,4,6-tri-t-amylphenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) (2,6-di-t-butyl-4-n- octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) [2,6-di-t-butyl-4- (2'-4'-di-t-butylphenoxycarbonyl ) -phenyl] phosphite, 2,2'-methylene-bis (4,6-di-t-amylphenyl) ( 2,6-di-t-butyl-4-n-hexadecyloxycarbonyl-phenyl) phosphite and the like.

 Examples of 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) phosphite are 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) octylphosphite, 2,2'-ethylidene- bis (4-methyl-6-t-butylphenyl) nonylphosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) lauryl phosphite, 2,2'-ethylidene bis (4-methyl- 6-t-butylphenyl) tridecyl phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butyl phenyl) myristyl phosphite, 2,2'-ethylidene bis (4-methyl-6- t-butylphenyl) stearyl phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-ethylidene bis (4 -methyl-6-t-butylphenyl) (2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butyl enyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) (2,6-di-t-butyl-4-n -octadecyloxycarbonylethylphenyl) phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) [2,6-di-t-butyl-4- (2'-4'-di-t-butylphenoxycarbonyl) -phenyl] phosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) phosphite, etc.

 Examples of 2,2'-ethylidene bis (4,6-di-t-butylphenyl) phosphite are 2,2-ethylidene bis (4,6-di-t-butylphenyl) octylphosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) nonylphosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) lauryl phosphite, 2,2'-ethylidene bis (4,6-di-t -butylphenyl) tridecylphosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) myristyl phosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) stearyl phosphite, 2,2 '-ethylidene-bis (4,6-di-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) (2 6-di-t-butyl-4-methyl-phenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite 2,2'- ethylidene bis (4,6-di-t-butylphenyl) (2,6-di-t-butyl-4-n-octadecyloxycarbonylethylphenyl) phosphite, 2,2'-ethylidene bis (4,6-di-t- butylphenyl) [2,6-di-t-butyl-4- (2-4'-di-t-butylphenoxycarbonyl) phenyl] phosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl ) (2,6-di-t-butyl-4-n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of 2,2'-ethylidene bis (4,6-di-t-amylphenyl) phosphite are 2,2'-ethylidene bis (4,6-di-t-amylphenyl) octylphosphite, 2,2'-ethylidene- bis (4,6-di-t-amylphenyl) stearyl phosphite, 2,2'-ethylidene bis (4,6-di-t-amylphenyl) (2,4-di-t-amylphenyl) phosphite, 2,2 ' Ethylidene bis (4,6-di-t-amylphenyl) (2,4,6-tri-t-amylphenyl) phosphite, 2,2'-ethylidene bis (4,6-di-t-amylphenyl) ( 2,6-di-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-ethylidene-bis (4,6-di-t-amylphenyl) [2,6-di-t-butyl- 4- (2 ', 4'-di-t-butylphenoxycarbonyl) phenyl] phosphite, 2,2'-ethylidene bis (4,6-di-t-amylphenyl) (2,6-di-t-butyl-4 n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of 2,2'-thio-bis (4-methyl-6-t-butylphenyl) phosphite are 2,2'-thio-bis (4-methyl-6-t-butylphenyl) octylphosphite, 2,2'-thio- bis (4-methyl-6-t-butylphenyl) nonylphosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) laurylphosphite, 2,2'-thio-bis (4-methyl-6- t-butylphenyl) tridecylphosphite, 2,2'-thiobis (4-methyl-6-t-butylphenyl) myristylphosphite, 2,2'-thiobis (4-methyl-6-t-butylphenyl) stearylphosphite, 2, 2'-thio-bis (4-methyl-6-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) ( 2,6-di-t-butyl-4-methylphenyl) phosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) (2,4,6-tri-t-butylphenyl) phosphite, 2,2'-thio-bis (4-methyl-6-t-but ilphenyl) (2,6-di-t-butyl-5-n-octadecyloxycarbonylethyl-phenyl) phosphite, 2,2'-thiobis (4-methyl-6-t-butylphenyl) [2,6-di-t -butyl-4- (2'-4'-di-t-butylphenoxycarbonyl-phenyl] phosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) (2,6-di-t- butyl-4-n-hexadecyloxycarbonylphenyl) phosphite and the like.

 Examples of fluorophosphite are 2,2'-bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-bis (4- t-amyl-6-methylphenyl) fluorophosphite, 2,2'-bis (4-S-eicosylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2 ' methylene bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2'-methylene bis (4-methyl-6-nonylphenyl) fluorophosphite, 2,2'-methylene bis (4,6-dinonylphenyl ) fluorophosphite, 2,2'-methylene-bis (4-methyl-6-cyclohexylphenyl) fluorophosphite, 2,2'-methylene-bis (4-methyl-6- (1'-methylcyclohexyl) phenyl) fluorophosphite, 2,2 '-isopropylidene-bis (4-nonylphenyl) fluorophosphite, 2,2'-buty liden bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-methylene bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylene bis (4,6-di-t- amylphenyl) fluorophosphite, 2,2'-ethylidene bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene bis (4-ethyl-6-t-butylphenyl) fluorophosphite, 2,2 ' Ethylidene bis (4-S-butyl-6-t-butylphenyl) fluorophosphite, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-ethylidene bis (4 , 6-di-t-amylphenyl) fluorophosphite, 2,2'-methylene bis (4-methyl-6-t-octylphenyl) fluorophosphite, 2,2'-butylidene bis (4-methyl-6- (1 ' -methylcyclohexyl) phenyl) fluorophosphite, 2,2'-methylene bis (4,6-dimethylphenyl) fluorophosphite, 2,2'-thio-bis (4-t-o cytylphenyl) fluorophosphite, 2,2'-thio bis (4,6-di-S-amylphenyl) fluorophosphite, 2,2'-thio bis (4,6-di-isooctylphenyl) fluorophosphite, 2,2'-thio bis (5-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-methyl-6-alpha-methylbenzylphenyl ) fluorophosphite, 2,2'-thio-bis (3-methyl-4,6-di-t-butylphenyl) fluorophosphite, 2,2'-thio-bis (4-t-amylphenyl) fluorophosphite, etc.

 Examples of diphosphite are bis [2,2'-methylene bis (4,6-di-t-butylphenyl)] ethylene glycol diphosphite, bis [2,2'-methylene bis (4,6-di-t-butylphenyl )] -1,4-butanediol diphosphite, bis [2,2'-methylene bis (4,6-di-t-butylphenyl)] - 1,6-hexanediol diphosphite, bis [2,2'-methylene bis (4-methyl-6-t-butylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'-methylene-bis (4,6-di-t-butylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [ 5.5] undecane diphosphite, bis [2,2'-methylene-bis (4,6-di-t-amylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2, 4,8,10-tetraoxaspiro [5.5] undecane-dif sphite, bis [2,2'-ethylidene bis (4-methyl-6-t-butylphenyl)] -3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10- tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'-ethylidene bis (4,6-di-t-butylphenyl)] - 3,9-bis (1,1-dimethyl-2-hydroxyethyl) - 2,4,8,10-tetraoxaspiro [5.5] undecane diphosphite, bis [2,2'-ethylidene bis (4,6-di-t-amylphenyl)] -3,9-bis- (1, 1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane bisphosphite, bis [2,2'-methylene bis (4,6-di-t-butylphenyl] -N , N'-bis (2-hydroxyethyl) oxamide diphosphite and the like.

 Examples of triphosphite are tris [2,2'-methylene bis (4,6-di-t-butylphenyl)] -glycerol triphosphite, tris [2,2'-methylene bis (4,6-di-t-butylphenyl )] - trimethylol ethane triphosphite, tris [2,2'-methylene bis (4,6-di-t-butylphenyl] -trimethylol propane triphosphite, tris [2,2'-bis (4,6-di-t- butylphenyl)] -triethanolamine triphosphite, tris [2,2'-bis (4,6-di-t-amylphenyl)] -tri-ethanolamine triphosphite, tris [2,2'-methylene bis (4,6- di-t-butyl-phenyl)] -triethanolamine-triphosphite, tris [2,2'-methylene-bis (4,6-di-t-amylphenyl)] -triethanolamine-triphosphite, tris [2,2'-ethylidene- bis (4,6-di-t-butylphenyl)] -triethanolamine triphosphite, tris- [2,2'-ethyl den-bis (4,6-di-t-amylphenyl)] -triethanolamine triphosphite, tris [2,2'-methylene-bis (4,6-di-t-butylphenyl)] -N, N ', N' 'tris (2-hydroxyethyl) isocyanurate triphosphite and the like.

 Examples of a phosphoric antioxidant are tetrakis [2,2'-methylene bis (4,6-di-t-butylphenyl) -erythritol tetrafosphite, tetrakis [2,2'-methylene bis (4,6-di-t-butylphenyl )] -pentaerythritol-tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethylphosphite, bis (2,4-di-t-butyl-6-methylphenyl) -2-ethylhexylphosphite, bis (2, 4-di-t-butyl-6-methylphenyl) stearylphosphite, 2,4,6-tri-t-butylphenyl-2-ethyl-2-butyl-1,3-propanediolphosphite and the like.

 For compositions according to the present invention, other than phosphoric antioxidants can be used so as to achieve the objectives of the present invention.

 Examples of the antioxidant are the well-known phenolic antioxidants and thio-antioxidants that are used for polypropylene compositions. Examples of thio-antioxidants include dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dilauryl stearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), dioctadecyl disulfide, distearyl iodide

 These phenolic and thio antioxidants can be used alone or in combination with two or more kinds of phenolic antioxidants.

 The amount of such antioxidants used is for each 0.001-1.5 parts by weight. per 100 parts by weight polypropylene composition, preferably 0.005-1 parts by weight, particularly preferably 0.01-0.5 parts by weight

 For compositions according to the present invention, stabilizers other than the above stabilizers may be used so as to fulfill the objectives of the present invention.

 Examples of stabilizers include a halogen absorber. The halogen absorber acts to capture the halogen remaining as a catalyst residue in the polypropylene contained in the composition. The use of a halogen absorber improves the compositions of the invention with respect to heat resistance, odors, color, corrosion resistance, weather resistance, and the like.

 Halogen absorbers can be any metal salts of fatty acids, metal salts of alkanoyl lactic acid, metal salts of aliphatic hydroxy acids, hydrotalcites, salts of complex lithium aluminum hydroxide, metal oxides, metal hydroxides, metal carbonates, aliphatic metal phosphates, epoxy compounds, aliphatic amines, aliphatic hindered amine compounds, aminotriazine compounds and the like.

 Examples of halogen absorbers include metal salts of aliphatic acids such as acetic acid, propionic acid, butyric acid, valerianic acid, alpha methylbutyric acid, hexanoic acid, sorbic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, 9-decene acid, undecanoic acid, undecylenic acid, lauric acid, linderic acid, myristic acid, fiseteric acid, myristoleic acid, palmitic acid, palmitoleic acid acid, hygiroic acid, stearic acid, petrozelinic acid, oleic acid, elaidic acid, cis-11-octadecenoic acid, vaccenic acid, linoleic acid, alpha-eleostearic acid, beta-eleostearic acid, punicinic acid, linolenic acid, gamma , moroctinic acid, stearidonic acid, stearolic acid, arachinic acid, gadoleic acid, cis-11-eicosenoic acid, arachidonic acid, behenic acid, cetoleic acid, erucic acid, brassidic acid I acid, clupanodonic acid, lignoceric acid, selacholeic acid, 4,8,12,15,18,21-tetrahexanoic acid, cerotic acid, ximenic acid, montanoic acid, melissic acid, lumequinic acid; metal salts of alkanoyl lactic acids such as dodecanoyl lactic acid, tetradodecanoyl lactic acid, octadecanoyl lactic acid; metal salts of aliphatic hydroxy acids such as glycolic acid, lactic acid, hydroacrylic acid, alpha-hydroxybutyric tartronic acid, glyceric acid, malic acid, tartaric acid, methovic acid, grape acid, citric acid, 2-hydroxytetradecanoic acid, ipurelic acid, 2-hydroxyhex acid, jalapinolic acid, uniperic acid, ambrettolic acid, 9,10,16-trihydroxyhexadecenoic acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-guide oksioktadekanoevaya acid, 9,10-digidroksioktadekanoevaya acid, ricinoleic acid, kamlolenovaya acid, licanic acid, 22-gidroksidokozanovaya acid or phrenosinic acid; alicyclic metal carboxylates, such as metal naphthenates; aromatic metal carboxylates derived from aromatic carboxylic acids such as benzoic acid or p-t-butylbenzoic acid; alicyclic metal hydroxylates derived from alicyclic hydroxy acids, such as oxynaphthenic acid; aromatic metal hydroxylates derived from aromatic hydroxyl acids such as salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid or 3,5-di-t-butyl-4-hydroxybenzoic acid; a number of metal aminocarboxylates; metal salts of lithium / aluminum complex hydroxide basic aluminum / lithium hydroxycarbonate hydrate and basic aluminum / lithium hydroxy sulfate hydrate; metal oxides; metal hydroxides; metal carbonates and metal phosphates.

 Examples of a metal salt of an aliphatic phosphate are (mono- or di-mixed) hexyl phosphate, (mono-di-mixed) octyl phosphate, (mono or di-mixed) -2-ethylhexyl phosphate, (mono or di-mixed) decyl phosphate, (mono - or di-mixed) lauryl phosphate, (mono- or di-mixed) myristyl phosphate, (mono- or di-mixed) palmityl phosphate, (mono- or di-mixed) stearyl phosphate, (mono- or di-mixed) oleyl phosphate, (mono - or di-mixed) linolein phosphate, (mono- or di-mixed) linoleyl phosphate, (mono or di-mixed) docosyl phosphate, (mono or di-mixed) erucil osfat, (mono- or di-mixed) tetrakozilfosfat, (mono- or di-mixed) geksakozilfosfat, (mono- or di-mixed) oktakozilfosfat etc.

 Examples of a metal salt of aromatic phosphate are bis (p-t-butylphenyl) phosphate, mono (p-t-butylphenyl) phosphate, 2,2'-methylene bis (4,6-di-t-butylphenyl) phosphate, 2,2 'methylene bis (4,6-di-t-amylphenyl) phosphate, 2,2'-ethylidene bis (4,6-di-t-butylphenyl) phosphate, 2,2'-ethylidene bis (4, 6-di-t-amylphenyl) phosphate and the like.

 Additional examples are tribasic sulfate, hydrazone, alkene, cyclic ester, organometallic compounds, benzhydrol, epoxy compounds such as a condensation product of epichlorohydrin and bisphenol A, a condensation product of 2-methylepichlorohydrin and bisphenol A, triglycidyl isocyanurate, epoxidized with oil epoxidized castor oil and the like, and hydroxylamine.

Examples of an aliphatic amine are octylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, cocoaamine, thallium amine, soy amine, N, N-dicacao-amine, N, N-dithallowamine, N, N-disoyamine, N-lauryl-N, N-dimethylamine, N-myristyl-N, N-dimethylamine, N-palmityl-N, N-dimethylamine, N-steapyl-N, N-dimethylamine, N-cacao-N, N-dimethylamine, N-tallow-N, N-dimethylamine, N-soya-N, N-dimethylamine, N-methyl-N, N-dithylamine, N-methyl-N, N-dicacaoamine, N-oleyl-1,3-di-aminopropane, N-tallow 1,3- diaminopropane, hexamethylenediamine
etc.

 Examples of ammonium chloride are N-lauryl-N, N, N-trimethylammonium chloride, N-palmityl-N, N, N-trimethylammonium chloride, N-steapyl-N, N, N-trimethylammonium chloride, N-docosyl-N, N, N-trimethylmethyl N-cocoa-N, N, N-trimethylammonium chloride, N-tallow-N, N, N-trimethylammonium chloride, N-co-N, N, N-trimethylammonium chloride, N, N, N-triethyl-N-benzylammonium chloride, N -lauryl-N, N-dimethyl-N-benzylammonium chloride, N-myristyl-N, N-dimethyl-N-benzylammonium chloride, N-cacao-N, N-dimethyl-N-benzylammonium chloride, N, N-di, N, N-di-N -dimethylammonium chloride, N, N-dicacao-N, N-dimethylammonium chloride, N, N-dithylamine-N, N-dimethylammonium chloride, N, N-diiso-N, N-dimethylamine onyxchloride, N, N-bis (2-hydroxyethyl) -N-lauryl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-stearyl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-oleyl-N-methylammonium chloride, N, N-bis (2-hydroxyethyl) -N-cocoa-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-laurol-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-stearyl-N-methyl-ammonium chloride, N, N-bis (polyoxyethylene) -N-oleyl-N-methylammonium chloride, N, N-bis (polyoxyethylene) -N-stearyl-N-methylammonium chloride, N, N- bis (polyoxyethylene) -N-cocoa-N-methylammonium chloride and the like.

 Examples of betaine are N, N-bis (2-hydroxyethyl) laurylaminobetaine, N, N-bis (2-hydroxyethyl) tridecylaminobetaine, N, N-bis (2-hydroxyethyl) myristylaminobetaine, N, N-bis (2-hydroxyethyl) pentadecylaminobetaine , N, N-bis (2-hydroxyethyl) palmitylaminobetaine, N, N-bis (2-hydroxyethyl) stearylaminobetaine, N, N-bis (2-hydroxyethyl) oleylaminobetaine, N, N-bis (2-hydroxyethyl) docosylaminobetaine, N , N-bis (2-hydroxyethyl) octocosylaminobetaine, N, N-bis (2-hydroxyethyl) cocoaaminobetaine, N, N-bis (2-hydroxyethyl) taroaminobetaine and the like.

 Hexamethylenetetramine. Alkanolamine such as triethanolamine, triisopropanolamine and the like.

 Examples of N- (2-hydroxyethyl) amine are N- (2-hydroxyethyl) laurylamine, N- (2-hydroxyethyl) tridecylamine, N- (2-hydroxyethyl) myristylamine, N- (2-hydroxyethyl) pentadecylamine, N- (2 -hydroxyethyl) palmitylamine, N- (2-hydroxyethyl) stearylamine, N- (2-hydroxyethyl) oleylamine, N- (2-hydroxyethyl) docosylamine, N- (2-hydroxyethyl) octacosylamine, N- (2-hydroxyethyl) cocoamine , N- (2-hydroxyethyl) tall amine, N-methyl-N- (2-hydroxyethyl) laurylamine, N-methyl-N- (2-hydroxyethyl) tridecylamine, N-methyl-N- (2-hydroxyethyl) myristylamine, N-methyl-N- (2-hydroxyethyl) pentadecylamine, N-methyl-N- (2-hydroxyethyl ) palmitylamine, N-methyl-N- (2-hydroxyethyl) stearylamine, N-methyl-N- (2-hydroxyethyl) oleylamine, N-methyl-N- (2-hydroxyethyl) docosylamine, N-methyl-N- (2 -hydroxyethyl) octacosylamine, N-methyl-N- (2-hydroxyethyl) cocoamine, N-methyl-N- (2-hydroxyethyl) tall amine and the like.

 Examples of N, N-bis (2-hydroxyethyl) aliphatic amine are N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) tridecylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N-bis (2-hydroxyethyl) peptadecylamine, N, N-bis (2-hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl) stearylamine, N, N-bis (2-hydroxyethyl) oleylamine, N, N-bis (2-hydroxyethyl) docosylamine, N, N-bis (2-hydroxyethyl) octacosylamine, N, N-bis (2-hydroxyethyl) cocoaamine, N, N-bis (2-hydroxyethyl) tall amine, etc. . Mono- or di-ester of N, N-bis (2-hydroxyethyl) aliphatic amine and aliphatic acid such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid and the like.

 Examples of the simple ether are polyoxyethylene laurylamino ether, polyoxyethylene stearylamino ether, polyoxyethylene oleylamino ether, polyoxyethylene cacaoamino ether, polyoxyethylenated alumino ether and the like.

 Examples of diaminoalkyl are N, N, N ′, N′-tetra (2-hydroxyethyl) -1,3-diaminopropane, N, N, N ′, N′-tetra (2-hydroxyethyl) -1,6-diaminohexane, N -lauryl-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-stearyl-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N -cacao-N, N ', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N-tallow-N, N', N'-tris (2-hydroxyethyl) -1,3-diaminopropane, N , N-dicacao-N ', N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N, N-dithallow-N, N'-bis (2-hydroxyethyl) -1,3-diaminopropane, N- cocoa-N, N ', N'-tris (2-hydroxyethyl) -1,6-diaminohexane, N-tallow-N, N', N'-tris (2-hydroxyethyl) -1,6-diaminohexane, N, N-dicacao-N ', N'-bis (2-gi roksietil) -1,6-diaminohexane, N, N-ditallou-N ', N'-bis (2-hydroxyethyl) -1,6-diaminohexane, and the like

 Examples of the aliphatic amide are oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, montanoic acid amide, N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearyl amide amide β-stearyleruic acid, N-oleyl palmitic acid amide, N, N'-methylene-bis-lauric acid amide, N, N'-methylene-bis-myristic acid amide, N'N'-methylene-bis-palmitic acid amide, amide N, N'-methylene-bis-palmitoleic acid, N, N'-methylene-b isstearamide, N, N'-methylene-bis-12-hydroxystearate acid amide, N, N'-methylene-bis-oleic acid amide, N, N'-methylene-bis-behenic acid amide, N, N 'amide -methylene-bis-erucic acid, amide of N, N'-methylene-bis-montanoic acid, amide of N, N'-ethylene-bis-lauric acid, N, N'-ethylene-bis-myristic acid, amide N, N 'ethylene bispalmitic acid, N, N'-ethylene-bis-palmitoleic acid amide, N, N'-ethylene-bis-stearic acid amide, N, N'-ethylene-bis-12-hydroxystearic acid amide, amide N , N'-ethylene-bis-oleic acid, N, N'-ethylenebis-behenic acid amide, N amide, N'-ethylene-bis-erucic acid, an amide of N, N'-ethylene-bis-montanoic acid, N, N'-hexamethylene-bis-stearamide, an amide of N, N'-hexamethylene-bis-oleic acid, an amide N, N'-hexamethylene-bis-behenic acid, N, N'-distearic acid amide, N, N'-dioleyl oxalic acid amide, N, N'-distearyl succinic acid amide, N, N'-dioleyl succinic acid amide, N , N'-distearyl adipic acid, N, N'-dioleyl adipic acid amide, N, N'-distearyl sebacic acid amide, N, N'-dioleyl sebacic acid amide and the like.

 Examples of the aliphatic amide are N, N-bis (2-hydroxyethyl) laurylamide, N, N-bis (2-hydroxyethyl) tridecylamide, N, N-bis (2-hydroxyethyl) myristylamide, N, N-bis (2-hydroxyethyl) pentadecylamide, N, N-bis (2-hydroxyethyl) palmitamide, N, N-bis (2-hydroxyethyl) stearylamide, N, N-bis (2-hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) dococylamide, N, N-bis (2-hydroxyethyl) octacocamylamide, N, N'-bis (2-hydroxyethyl) cocoamide, N, N-bis (2-hydroxyethyl) tall amide, etc.

 Examples of the polyoxyalkylene aliphatic amide are polyoxyethylene lauryl amide ether, polyoxyethylene stearyl amide ether, polyoxyethylene oleyl amide ether, polyoxyethylene coco amide ether, polyoxyethylene amide ether and the like.

 Examples of the hindered amine compound are 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-aryl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6 6-tetramethylpiperidine, 1- (4-t-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-methacrylyloxy -1,2,2,6,6-pentamethylpiperidine, 1-benzyl-2,2,6,6-tetramethyl-4-piperidylmaleate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis - (1,2,2,6,6-pentamethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl- 4-piperidyl) cevacate bis (2,2,6,6-tetramethyl- 4-piperidyl) fumarate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) cevacate, bis (1-aryl-2,2,6,6-tetramethyl-4-piperidyl) phthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) tsevacate, 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperiazinone), 2-methyl -2- (2,2,6,6-tetramethyl-4-piperidyl) imino-N- (2,2,6,6-tetramethyl-4-piperidyl) imino-N- (2,2,6,6 -tetramethyl-4-piperidyl) propionamide, 2-methyl-2- (1,2,2,6,6-pentamethyl-4-piperidyl) imino-N- (1,2,2,6,6-pentamethyl-4 -piperidyl) propionamide, 1-propargyl-4-beta-cyanoethyloxy-2,2,6,6-tetramethylpiperidine, 1-acetyl-2,2,6,6-tetramethyl-4-piperidyl acetate, (trimellitic acid) - tris (2,2,6,6- tetramethyl-4-piperidyl) (ester), 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibutyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) dibenzyl malonate, bis (1,2,3,6-tetramethyl-2,6-diethyl-4-piperidyl) dibenzyl malonate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate and the like.

 Examples of the hindered amine compound are bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1,2,2,6,6- pentamethyl-4-piperidyl) -1,5-dioxaspiro [5.5] undecane-3,3-dicarboxylate, bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [ 5.5] undecane-3,3-dicarboxylate, 1,3-bis [2,2 '- [bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-dioxacyclohexane-5,5-dicarboxylate )], bis (2,2,6,6-tetramethyl-4-piperidyl) -2- [1-methylethyl [1,3-dioxacyclohexane-5,5-dicarboxylate]], 1,2-bis [2,2 '- [bis (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-1,3-dioxacyclohexane-5,5-dicarboxylate]], b is (2,2,6,6-tetramethyl-4-piperidyl) -2- [2- (3,5-di-t-butyl-4-hydroxyphenyl)] ethyl-2-methyl-1,3-dioxacyclohexane- 5,5-dicarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) -1,5-dioxaspiro [5.11] heptadecane-3,3-dicarboxylate and the like.

 Examples of the hindered amine compound are hexane-1 ', 6'-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine), toluene-2', 4'-bis (4-carbamoyloxy- 1-n-butyl-2,2,6,6-tetramethylpiperidine), dimethyl bis (2,2,6,6-tetramethylpiperidin-4-hydroxy) silane, phenyl-tris (2,2,6,6-tetramethylpiperidine -4-hydroxy) silane, tris (1-propyl-2,2,6,6-tetramethyl-4-piperidyl) phosphite, tris (1-propyl-2,2,6,6-tetramethyl-4-piperidyl) phosphate, phenyl- [bis (1,2,2,6,6-pentamethyl-4-piperidyl)] phosphonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-but otetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butantetracarboxylic acid amide, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) - 1,2,3,4-butanetetracarbonamide and the like.

 Examples of the hindered amine compound are 2-dibutylamino-4,6-bis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] -3-undecylmethoxy) -S-triazine , 2-Dibutyl-amino-4,6-bis (9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethoxy) -S-triazine tetrakis (9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,4-butantetracarboxylate, tetrakis (9-aza -3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -1,2,3,4-butantetracarboxylate, tridecyl-tris (2,2,6 , 6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tridecyl-tris (1,2,2,6,6-pentamethyl-4- piperidyl) -1,2,3,4-butanetetra carboxylate, di (tridecyl) bis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, di (tridecyl ) -bis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butantetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [5.1.11.2] geneikosan-21-one, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane and the like.

 Examples of the hindered amine compound are poly (2,2,6,6-tetramethyl-4-piperidyl acrylate), poly (1,2,2,6,6-pentamethyl-4-piperidyl acrylate), poly (2,2,6,6 -tetramethyl-4-piperidylmethacrylate), poly (1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate), poly [[bis (2,2,6,6-tetramethyl-4-piperidyl) itaconate] ] vinyl butyl ether]], poly [[bis (1,2,2,6,6-pentamethyl-4-piperidyl) itaconate] [vinyl butyl ether]], poly [[bis (2,2,6,6-tetramethyl-4 -piperidyl) itaconate] [vinylilocyl ether]], poly [[bis (1,2,2,6,6-pentamethyl-4-piperidyl) itaconate] [vinylilctyl ether]] dimethyl succinate-2- (4-hydroxy-2,2, 6,6-tetramethylpiperidyl ) -ethanol - condensation products, etc.

 Examples of the hindered amine compound are poly [hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [ethylene - [[2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[1,3,5-triazine-2,4-diyl] - [(2,2,6,6-tetramethyl -4-piperidyl) imino]] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imiyo]], poly [[6- (diethylimino) -1,3,5-triazine-2,4- diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [[2,2,6,6-tetramethyl-4-piperidyl imino]], poly [[6 - [(2- ethylhexyl) imino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-te tramethyl-4-piperidyl) imino]], poly [[6 - [(1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-2,4-diyl] - [(2,2 , 6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6- (cyclohexylimino) -1,3,5-triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl imino]], poly [[6 -morpholino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4- piperidyl) imino]], poly [[6- (butoxyimino) -1,3,5-triazin-2,4-di-yl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[1,1,3,3-tetramethyl-butyl) oxy] -1,3,5-triazine-2,4-diyl] - [(2,2,6,6-tetramethyl-4-piperidyl) imino ] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and the like.

 Examples of the hindered amine compound are poly [hydroxy [6 - [(1-piperidyl) -1,3,5-triazine-2,4-diyloxy-1,2-ethanediyl] [(2,2,6,6-tetramethyl- 3-oxo-1,4-piperidyl) -1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl) -1,2-ethanediyl]], poly [ hydroxy [6- [1,1,3,3-tetramethylbutyl) imino] -1,3,5-tri-azin-2,4-diyloxy-1,2-ethanediyl] - [(2,2,6,6 -tetramethyl-3-oxo-1,4-piperidyl) -1,2-ethanediyl] [(3,3,5,5-tetramethyl-2-oxo-1,4-piperidyl) -1,2-ethanediyl]] poly [[6 - [(ethylacetyl) imino] -1,3,5-triazine-2,4-diyl] [(2,2,6, 6-tetramethyl-4-piperidyl) imino) hexamethylene [(2, 2,6,6-tetramethyl-4-piperidyl) imino]], poly - [[6 - [(2,2,6,6-tetramethyl-4-pi eridyl) butylimino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl- 4-piperidyl) imino]] and the like.

 Examples of the hindered amine compound are 1,6,11-tris {(4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5- triazin-2-yl} amino] undecane, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl} amino] undecane, 1,6,11-tris [{4,6-bis (N-octyl-N- (2,2,6,6-tetramethyl-4 -piperidyl) amino) -1,3,5-triazin-2-yl} amino] undecane, 1,6,11-tris {4,6-bis (N-octyl-N- (1,2,2,6 , 6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl} amino] undecane, 1,5,8,12-tetrakis [4,6-bis (N- (2,2 , 6,6-tetramethyl-4-piperidyl) butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [4, 6 bis (N- (1,2,2,6,6-penta methyl-4-piperidyl) butylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane and the like.

 Examples of aminotriazine compounds are 2,4,6-triamino-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-6-phenyl-1, 3,5-triazine, 1,4-bis (3,5-diamino-2,4,6-triazinyl) butane, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl ) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, etc.

 Examples of metals for the above metal salts include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc or aluminum. Such metal salts may exist as a middle salt or a base salt. Examples of preferred metal salts include metal salts of fatty acids, metal salts of alkanoyl lactic acid, metal salts of aliphatic hydroxy acids, hydrotalcites, salts of complex lithium aluminum hydroxide, metal oxides, metal hydroxides, metal carbonates, aliphatic metal phosphates, epoxy compounds, aliphatic amines, aliphatic amides hindered amine compounds, aminotriazine compounds or mixtures thereof. Such halogen absorbers can be either individually or in combination of two kinds or more.

 The input amount of halogen absorbers is 0.001-2 parts by weight. per 100 wt. including polypropylene composition (PP) as component A, preferably 0.005-1.5 parts by weight, particularly preferably 0.01-1 parts by weight

 For compositions according to the present invention, polypropylene additives other than the above halogen absorbers can be used so as to achieve the objectives of the present invention. Examples of additives include light stabilizers, metal deactivators, brighteners, nucleating agents, lubricants, antistatic agents, anti-fogging agents, anti-sticking agents, anti-dropping additives, radical generators such as peroxide, flame retardants, flame retardants, pigments, organic and inorganic inorganic fillers, such as talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, silicon dioxide, titanium dioxide, sulfide zinc atom, barium sulfate, magnesium sulfate, calcium silicate, aluminum silicate, fiberglass, potassium titanate, carbon fiber, carbon black, graphite or metal fiber, resins such as silane-containing, titanate-containing, boron-containing, aluminate-containing or zirconate-aluminate-containing additives, treated with a surfactant such as sizing and organic fillers such as wood flour, cellulose, regenerated paper, synthetic fiber or natural fiber.

 The resulting polypropylene compositions can be mixed with a number of additives or synthetic fiber, if required. Examples of additives include antioxidants, ultraviolet absorbers, antistatic agents, nucleating agents, lubricants, flame retardants, anti-stick additives, coloring agents, organic and inorganic fillers. Then the composition is usually subjected to heat treatment, melting and mixing. Further, the compositions are formed with granulation to obtain granules and are used to produce a number of molded products.

EXAMPLES
Further, the present invention is described in more detail using examples and comparative examples.

 The definitions of terms and measurement methods used in the examples and comparative examples are as follows. In addition, in the following examples and comparative examples, polypropylene can be denoted by the abbreviation PP, and polyethylene by the abbreviation PE.

(1) Intrinsic viscosity [η]: ultimate viscosity in tetralin at 135 ^° C., measured with an Oswald viscometer manufactured by Mitsui Toatsu Chemicals Inc. (unit: dl / g).

 (2) Melt voltage (MS): Values measured using the "Melt Voltage P" instrument manufactured by Toyo Seiki Seisaku-sho, Ltd. (unit: cH).

(3) Crystallization temperature (Tc): values measured using a Perkin-Elmer Ltd. differential scanning calorimeter VII from a temperature showing the maximum heat absorption during crystallization of the polypropylene composition after the temperature rises from room temperature to 240 ^° C. with a temperature rise rate of 30 ^o C / min, then holding the temperature at 230 ^o C for 10 min, lowering the temperature to -20 ^o C at a speed of 20 ^o C / min, maintaining the temperature of -20 ^o C for 10 min, raising the temperature to 230 ^o C at a speed 20 ^o C / min, maintaining a temperature of 230 ^o C for 10 min, lowering the temperature to 150 ^o C at a speed of 180 ^o C / min and further lowering the temperature at a speed of 5 ^o C / min (unit: ^o C).

(4) Heat resistance: granules of the polyolefin composition are obtained by mixing 0.1 wt.h. 2,6-di-t-butyl-p-cresol and 0.1 parts by weight calcium stearate with 100 parts by weight polyolefin composition, melting and mixing and then granulating the mixture at 230 ^o C using an extruder having a screw diameter of 40 mm

 The melt flow rate (MFR) (unit: g / 10 min) of granules obtained as described above and granules obtained by further processing of the above melt, mixing and granulating using an extruder more than two times, is determined in accordance with table procedure 14 1 JIS K7210 standard. The difference between the MFI of the final granules obtained and the MFI of the initially obtained granules (MFI of the final granules - MFI of the initial granules = ΔPTR) is calculated as heat resistance.

 A smaller difference (ΔPTR) indicates better heat resistance.

 (5) Resistance to discoloration: using the same granules that are used to determine heat resistance, the yellowing index (VI) of granules obtained first and granules obtained by further processing with granulation more than two times is determined in accordance with the method of JIS K7103 standard and counted the difference between the yellowing index at the beginning of the obtained granules and the yellowing index of the final granules (ΔVI = VI final granules - VI initial granules).

 A smaller VI difference indicates better color fastness.

EXAMPLE 1
(1) Obtaining a catalytic composition comprising a transition metal compound
0.3 L of decane, 48 g of anhydrous magnesium chloride, 170 g of orthotitanate-n-butyl and 195 g of 2-ethyl-1-hexanol are mixed in a stainless steel polymerisation reactor with a stirrer, then dissolved with stirring at 130 ^° C. for 1 h with the formation of a homogeneous solution. The homogeneous solution is heated to 70 ^o C, then 18 g of diisobutyl phthalate is added to it with stirring. After 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to obtain a solid precipitate and a temperature of 70 ^° C. was maintained for another 1 hour. The solid was separated from the solution and washed with hexane to obtain a solid.

All solid product is mixed with 1.5 L of titanium tetrachloride dissolved in 1.5 L of 1,2-dichloroethane. Then 36 g of diisobutyl phthalate is added and the mixture is stirred for 2 hours at 100 ^° C. with reaction. The liquid phase is removed by decantation at the same temperature, then 1.5 L of 1,2-dichloroethane and 1.5 L of titanium tetrachloride are added and kept at 100 ^° C. for 2 hours with stirring. Then, after washing with hexane and drying, a supported titanium catalyst component (a catalyst component of a transition metal compound) is obtained containing 2.8% by weight of titanium.

(2) Obtaining pre-activated catalyst
After creating an atmosphere of gaseous nitrogen, a 5 L stainless steel polymerization reactor equipped with an inclined turbine stirrer is charged with 2.8 L of n-hexane, 4 mmol of triethyl aluminum (organometallic compound (AL1)) and 9.0 g of a supported titanium catalyst component, obtained as shown above (5.26 mmol per 1 mol of Ti atom), and then 20 g of propylene are fed for preliminary polymerization for 10 min at -2 ^o C.

The polymer formed in the prepolymerization obtained under the same conditions is analyzed, and it is established that 2 g of propylene becomes polypropylene (B) per 1 g of the titanium catalyst component on the support and the intrinsic viscosity [η _B ] of polypropylene (B), measured in tetraline at 135 ^° C. equals 2.8 dl / g.

After the reaction period, unreacted propylene is removed from the reaction vessel. After replacing the gas-phase part in a polymerization reactor with nitrogen gas for 2 hours, ethylene is continuously fed so as to maintain an internal pressure at 0.59 MPa with an internal temperature of -1 ^° C for preliminary activation.

The polymer formed in the pre-activated polymerization, charged under the same conditions, is analyzed, and it is established that there is 24 g of polymer per 1 g of the titanium catalyst component on the carrier, and the intrinsic viscosity [η _T2 ] measured in tetraline at 135 ^o C, equals 31.4 dl / g.

The amount of (W ₂ ) polyethylene (A) per 1 g of supported titanium catalyst component formed in the preliminary activating polymerization with ethylene can be calculated as the difference between the amount of polymer formed (W _T2 ) 1 g of titanium catalyst component on the carrier after the preliminary activating treatment and the amount of formed polypropylene (B) (W ₁ ) per 1 g of the titanium catalyst component on the carrier after prepolymerization according to the following formula:
W ₂ = W _T2 - W ₁
The intrinsic viscosity [η _E ] of polyethylene (A) formed in the pre-activating polymerization with ethylene can be calculated from the intrinsic viscosity [η _B ] of polypropylene (B) formed in the prepolymerization and the intrinsic viscosity [η _T2 ] of the polymer formed in the preliminary activating processing according to the following formula:
[η _E ] = [η _T2 ] × W _T2 - [η _B ] × W ₁ ) / (W _T2 -W ₁ ) = [η _E ]
In accordance with the above formulas, the amount of polyethylene (A) formed in the pre-activating polymerization with ethylene is 22 g per 1 g of the supported titanium catalyst component, and the intrinsic viscosity [η _E ] is 34.0 dl / g.

After completion of the reaction period, unreacted ethylene is discharged out of the polymerization reactor. After replacing the gas-phase part of the polymerization reactor with nitrogen gas and adding 1.6 mmol of diisopropyl dimethoxysilane (electron donor (E1)), 20 g of propylene are fed and kept for 10 min at 1 ^° C for additional polymerization after preliminary activating treatment.

The polymer formed in the additional polymerization, obtained under the same conditions, is analyzed, and it is established that there is 26 g of polymer per 1 g of the titanium catalyst component on the support and the characteristic viscosity [η _T3 ], measured in tetraline at 135 ^° C., is 29 , 2 dl / g. The resulting amount (W ₃ ) of polypropylene formed in the additional polymerization, calculated as shown above, is 2 g per 1 g of the titanium catalyst component on the support, and the intrinsic viscosity [η _C ] is 2.8 dl / g.

 After completion of the reaction period, unreacted propylene is discharged out of the polymerization reactor. The gas-phase part of the polymerization reactor is replaced with nitrogen gas once to obtain a suspension of the pre-activated catalyst of the main copolymerization.

(3) Preparation of polypropylene composition (main) propylene copolymerization
After creating a nitrogen gas atmosphere in a polymerization reactor of stainless steel 500-liter stirred tank is loaded at 20 ^o C to 240 liters of n-hexane, 780 mmoles of triethylaluminum (organometallic compound (AL2)), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1 / 2 amounts of a suspension of pre-activated catalyst obtained as shown above. Then, after 55 l of hydrogen were introduced into the reaction reactor and the temperature was raised to 70 ^° C, propylene was continuously fed into the reaction reactor so as to maintain the gas phase pressure in the polymerization reactor at 0.79 MPa for 2 hours at a polymerization temperature of 70 ^° C to conduct the main polymerization of propylene.

After the polymerization period has ended, 1 liter of methanol is introduced into the polymerization reactor and the catalyst deactivation reaction is carried out at 70 ^° C. for 15 minutes. After removal of the unreacted gas, the solvent separates and the polymer is dried to obtain 40.1 kg of a polymer having an intrinsic viscosity [η _T ] of 1.97 dl / g.

The resulting polymer is a polypropylene composition containing 0.25 wt.% Polyethylene (A) according to preliminary activating polymerization as (A) component, and the intrinsic viscosity [η _T ] of polypropylene as (c) component is 1.89 dl / g.

0.1 wt. including 2,6-di-t-butyl-p-cresol and 0.1 parts by weight calcium stearate is mixed with 100 wt.h. the resulting polypropylene composition. The mixture is granulated at 230 ^° C. using an extruder having a screw diameter of 40 mm to obtain granules. Various physical properties of the granules are determined, which are as follows: MFR - 3.5 g / min, crystallization temperature - 122.5 ^o C and melt tension - (MS) - 4.9 cN. Detailed physical properties are given in table 1.

EXAMPLE 2 AND COMPARATIVE EXAMPLE 1
Polypropylene compositions are prepared using the same conditions as in Example 1, except that the conditions for pre-activating polymerization with ethylene are modified with a change in the amount of polyethylene (A) formed to produce test samples of Example 2 and Comparative Example 1.

 The various physical properties of the obtained polypropylene compositions are given in table 1.

COMPARATIVE EXAMPLE 2
The polypropylene composition is obtained using the same conditions as in example 1 (2), except that the preliminary activating polymerization with ethylene is replaced by 220 g of propylene being fed into the polymerization reactor in three stages: 80 g when initiating the preliminary activating polymerization, 80 g — 30 minutes after initiation and 60 g — 1 hour after initiation to obtain the test sample of comparative example 2.

 The various physical properties of the obtained polypropylene composition are given in table 1.

COMPARATIVE EXAMPLE 3
The polypropylene composition is obtained using the same conditions as in example 1, except that the preliminary activated polymerization with ethylene of the catalyst component on a carrier containing titanium is not carried out.

 The various physical properties of the obtained polypropylene compositions are given in table 1.

COMPARATIVE EXAMPLE 4
After creating an atmosphere of gaseous nitrogen in a stainless steel polymerization reactor equipped with an inclined turbine stirrer, 10 kg of a powdered propylene homopolymer having an intrinsic viscosity [η _T ] of 1.67 dl / g and an average particle size of 150 μm is obtained by suspension polymerization of propylene in n- hexane using a catalyst prepared by a combination of a catalytic titanium component containing a composition of titanium chloride, diethylaluminium chloride and diethylene glycol dimethyl ether as a third th component. Then, after a 10-fold repetition of the operation of evacuating the polymerization reactor and supplying nitrogen gas at atmospheric pressure, a 70 wt.% Toluene solution of 0.35 mol of di-2-ethylhexylperoxydicarbonate (conversion agent) is introduced and mixed with nitrogen gas atmosphere with stirring at 25 ^° C. The temperature in the polymerization reactor rises to 120 ^o C and maintained for 30 minutes for the reaction. After the completion of the reaction period, the temperature in the polymerization reactor rises to 135 ^° C. and post-treatment is carried out at the same temperature for 30 minutes. After processing, the polymerization reactor is cooled to room temperature and then opened to produce polypropylene.

0.1 wt. including 2,6-di-t-butyl-p-cresol and 0.1 parts by weight calcium stearate is mixed with 100 wt.h. the resulting polypropylene composition. The mixture is granulated at 230 ^° C. using an extruder having a screw diameter of 40 mm to form granules to obtain a test sample of comparative example 4.

 The obtained various physical properties of the granules obtained in examples 1-2 and comparative examples 1-4 are shown in table 1.

EXAMPLE 3
(1) Obtaining a catalytic composition comprising a transition metal compound
37.5 L of decane, 7.14 kg of anhydrous magnesium chloride, 35.1 L of 2-ethyl-1-hexanol are mixed in a stainless steel polymerisation reactor with a stirrer and then dissolved with stirring at 140 ^° C. for 4 hours to obtain a uniform solution. 1.67 kg of phthalic anhydride is added to the homogeneous solution and additional stirring and mixing is carried out for 1 h at 130 ^° C with the dissolution of phthalic anhydride in a homogeneous solution.

After cooling the entire homogeneous solution obtained to room temperature (23 ^° C), the entire homogeneous solution is added dropwise in 200 L of titanium tetrachloride, maintained at -20 ^° C for more than 3 hours. After the addition, the solution is heated to 110 ^° C for more than 4 hours. When the temperature rises to 110 ^° C., 5.03 L of diisobutyl phthalate is added and stirred for 2 hours at 110 ^° C. for the reaction. After 2 hours of reaction, the solid is collected by hot filtration. The solid was resuspended in 275 L of titanium tetrachloride and maintained at 110 ^° C. for 2 hours again for reaction.

 After the reaction, the solid again is collected by hot filtration. The solid is washed with n-hexane sufficiently so that titanium radicals are not detected in the washing liquid. Then the solvent is separated by filtration and the solid part is dried under reduced pressure to obtain a titanium catalyst component on a support (catalytic component of a transition metal compound) containing 2.4 wt.% Titanium.

(2) Obtaining pre-activated catalyst
After filling a 30 L stainless steel polymerization reactor with an inclined turbine stirrer with gaseous nitrogen, 18 L of n-hexane, 60 mmol of triethyl aluminum (organometallic compound (AL1)) and 150 g of a titanium catalyst component on a support obtained as shown above ( 75.16 mmol per 1 mol of titanium atom), then 210 g of propylene are fed with preliminary polymerization for 20 min at -1 ^o C.

The polymer formed in the preliminary polymerization, obtained under the same conditions, is analyzed, and it is established that 1.2 g of polypropylene (B) per 1 g of the titanium catalyst component on the support and the intrinsic viscosity of polypropylene (B) [η _B ] measured in tetraline at 135 ^° C., 2.7 dl / g.

After completion of the reaction period, unreacted propylene is discharged out of the polymerization reactor. After replacing the gas-phase part with nitrogen gas, ethylene is fed continuously into the polymerization reactor for 3 hours in such a way as to maintain the internal pressure at 0.59 MPa and the internal temperature at -1 ^° C for preliminary activating polymerization.

The polymer formed in the pre-activating polymerization, obtained under the same conditions, is analyzed, and it is established that there is 33.2 g of polymer per 1 g of the titanium catalyst component on the support and the intrinsic viscosity [η _T2 ] measured in tetraline at 135 ^o C equals 29.2 dl / g.

It was found that the amount of polyethylene (A) formed in the preliminary activating polymerization with ethylene per 1 g of the catalyst component on the carrier containing titanium is 32 g per 1 g of the titanium catalyst component on the carrier, and the intrinsic viscosity [η _E ] is 30, 2 dl / g.

After completion of the reaction period, unreacted ethylene is discharged out of the polymerization reactor. After replacing the gas phase part with nitrogen gas once and introducing 22.5 mmol of diisopropyldimethoxysilane (electron donor (E1)) into the polymerization reactor, 385 g of propylene is fed and kept for 20 minutes at 0 ^° C for additional polymerization after preliminary activating treatment. After the completion of the reaction period, unreacted propylene is discharged out of the reaction vessel and the gas-phase part of the reaction vessel is replaced with nitrogen to obtain a suspension of the preactivated main copolymerization catalyst.

The polymer formed in the additional polymerization obtained using the same conditions is analyzed, and it is established that there is 35.4 g of polymer per 1 g of the titanium catalyst component on the support and the characteristic polymer viscosity [η _T3 ] measured in tetraline at 135 ^o C is 27.6 dl / g.

Based on the above results, it turns out that the amount of polypropylene formed during the additional polymerization is 2.2 g per 1 g of the supported titanium catalyst component, and the intrinsic viscosity [η _C ] is 2.8 dl / g.

(3) Obtaining a polypropylene composition (main copolymerization of propylene)
In a 110-liter horizontal gas-phase polymerization reactor with a stirrer (length / diameter = 3.7), an atmosphere of gaseous nitrogen is created, after which 25 kg of polypropylene powder is loaded and then 0.61 g / h of a suspension of preactivated catalyst is continuously supplied in the form of a titanium the supported catalyst component and a 15 wt.% n-hexane solution of triethyl aluminum (organometallic compound (AL2)) and diisopropylmethoxysilane (electron donor (E2)) so that the corresponding molar ratios the bonds become 90 and 15 with respect to the titanium atoms in the titanium supported catalyst component.

Further, at a polymerization temperature of 70 ^° C., hydrogen is supplied so as to have a hydrogen: propylene ratio of 0.006 in the polymerization reactor, and propylene is supplied so as to maintain the pressure inside the polymerization reactor at 2.15 MPa during continuous gas phase polymerization of propylene for 150 hours .

 During the polymerization, the polymer is withdrawn from the polymerization reactor at a rate of 11 kg / h in order to maintain the polymer level in the polymerization reactor at 60% by volume.

The selected polymer is treated by contacting with nitrogen gas containing 5 volume% water vapor at 100 ^° C. for 30 minutes to obtain a polymer having an intrinsic viscosity [η _T ] of 1.80 dl / g.

The content of polyethylene (A) formed during the preliminary activating treatment in the polymer is 0.18 wt.%, And the intrinsic viscosity [η _P ] of polypropylene is 1.75 dl / g.

Then, using the same conditions as in Example 1, polymer granules are obtained using an extruder. Various physical properties of the granules are determined, which turn out to be the following: PTR - 6.0 g / 10 min, crystallization temperature - 122 ^o C and melt stress (MS) - 2.5 cN.

EXAMPLE 4
The polypropylene composition is obtained using the same conditions as in example 3, except that the ratio of hydrogen: propylene in the gas phase is changed to 0.008 to change the MFI in example 3 to obtain the test sample of example 4.

 The various physical properties of the obtained polypropylene composition are given in table 2.

COMPARATIVE EXAMPLE 5
The polymer is prepared using the same conditions as in Example 3, except that preliminary activating polymerization with ethylene is not carried out to obtain the test sample of Comparative Example 5.

 The various physical properties of the obtained polymer are shown in table 2.

EXAMPLE 5
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 3.

(2) Obtaining pre-activated catalyst
A suspension of the pre-activated catalyst is obtained using the same pre-activating polymerization conditions as in Example 3 (2), except that the reaction temperature is 0 ^° C., 30 g of propylene is supplied in addition to ethylene and the reaction temperature is maintained for 45 minutes.

The catalyst obtained by pre-activating processing is analyzed, and it is established that there is 23.2 g of polymer per 1 g of titanium catalyst component on the support and the characteristic polymer viscosity [η _T2 ], measured in tetraline at 135 ^° C., is 21 , 5 dl / g, and a random copolymer of ethylene with propylene (A) having an intrinsic viscosity [η _A ] of 22.5 dl / g and a content of propylene polymerization unit of 0.7 wt% (constant at C-NMR) is formed in amount of 22 g per 1 g of titanium catalytically on the component carrier for pre-activation treatment.

The polymer obtained by additional polymerization after pre-activating treatment using the same conditions is analyzed, and it is established that there is 25.3 g of polymer per 1 g of titanium catalyst component on the support and the intrinsic viscosity of the polymer [η _T3 ] measured in tetraline at 135 ^° C., it equals 19.9 dl / g, and a polymer having an intrinsic viscosity [η _C ] of 2.2 dl / g is formed in an amount of 2.1 g per 1 g of the titanium catalyst component on the support with additional polymerization.

(3) Obtaining a polypropylene composition (main copolymerization of propylene)
A polymer having an intrinsic viscosity [η _T ] of 1.54 dl / g and an ethylene polymerization unit of 0.8 wt.% Is obtained with a productivity of 11.6 kg / h when gas phase polymerization is carried out for 150 hours continuously using the same conditions as in example 3 (3), except that the suspension of the preactivated catalyst obtained as described above (2) is used as the suspension of the preactivated catalyst, the ratio of hydrogen: propylene in the gas phase is 0.012 and ethylene is fed into nenie to propylene so that its ratio to the propylene concentration in the polymerization reactor is continuously maintained at 0.003.

The content of the ethylene-propylene random copolymer (A) in the polymer formed by the pre-activation treatment is 0.12 wt. %, and the intrinsic viscosity of the propylene-ethylene copolymer [η _P ] is 1.52 dl / g.

Then, using an extruder under the same conditions as in Example 1 (3), granules of a polypropylene composition are obtained. Various physical properties of the granules are determined, which are as follows: MFI - 15.4 g / 10 min, crystallization temperature - 121.2 ^o C and melt stress (MS) - 1.4 cH.

COMPARATIVE EXAMPLE 6
The polymer is prepared using the same conditions as in Example 5, except that preliminary activating polymerization with ethylene and propylene is not carried out to obtain a test sample of comparative example 6.

 The various physical properties of the obtained polymer are shown in table 2.

COMPARATIVE EXAMPLE 7
Only preliminary activating polymerization with ethylene in Example 1 (2) is carried out without preliminary polymerization with propylene or additional polymerization. To the resulting suspension of the preactivated catalyst, 1 l of methanol is added to deactivate the catalyst for 1 h at 70 ^o C. After the reaction, the polyethylene is separated from the suspension by filtration, then dried under reduced pressure to obtain 200 g of polyethylene having an intrinsic viscosity [η _E ] 32 5 dl / g

20 kg of polypropylene obtained by the main polymerization of propylene without preliminary activating polymerization with ethylene or additional polymerization with propylene in Example 1 (2) are mixed and 50 g of the above polyethylene are mixed. Next, 20 g of 2,6-di-t-butyl-p-cresol and 20 g of calcium stearate are loaded into a Henschel mixer with a capacity of 100 l and mixed for 3 minutes. The mixture is then granulated using an extruder having a screw diameter of 40 mm at 230 ^° C. to obtain a test sample of comparative example 7.

Various physical properties of the obtained granules are determined, which are as follows: characteristic viscosity [η _T ] - 1.97 dl / g, MFR - 3.5 g / 10 min, crystallization temperature - 116.2 ^o C and melt stress (MS) - 1.0 cH.

EXAMPLE 6
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 3.

(2) Obtaining pre-activated catalyst
A suspension of the preactivated catalyst is obtained using the same conditions as in Example 3.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
The same conditions as in Example 3 are used, except that hydrogen is supplied so as to have a hydrogen: propylene ratio of 0.002 in the polymerization reactor (1), and furthermore, propylene is supplied so as to maintain the internal pressure of the polymerization reactor at 1.77 MPa for the polymerization process (1).

The polymer obtained by the polymerization process using the same conditions is analyzed, and it is established that the MFI is 1.1 g / 10 min, the intrinsic viscosity [η _T ] of the polymer, measured in tetraline at 135 ^° C., is 2.39 dl / g The intrinsic viscosity [η _P ] of polypropylene in the polymerization process (1) is 2.32 dl / g.

The polymer obtained in the above process is fed continuously to the polymerization reactor (II) at 60 ^° C. so as to maintain a hydrogen: propylene ratio and a hydrogen: ethylene ratio in the polymerization reactor of 0.003 and 0.2, respectively, and maintain the pressure inside the polymerization reactor at 1.57 MPa for the polymerization process (II).

 During the polymerization, the polymer is withdrawn from the polymerization reactor at a rate of 9.4 kg / h in order to maintain the polymer level in the polymerization reactor at 60% by volume.

The selected polymer is processed by contact with nitrogen gas containing 5% vol. steam at 100 ^° C. for 30 minutes to obtain a polymer having an intrinsic viscosity [η _T ] of 2.69 dl / g.

The content of polyethylene (A) formed during the preliminary activating treatment in the polymer is 0.21 wt.%, And the intrinsic viscosity [η _P ] of the composition of the propylene-alpha-olefin block copolymer (c) is 2.63 dl / g.

 The polymerization ratio between the polymerization process (1) and the polymerization process (II) is calculated by preparing copolymers having different reaction quantitative ratios of ethylene: propylene in advance and using them as reference samples to obtain a calibration curve of the IR absorption spectrum and determining the reaction quantitative ratio of ethylene: propylene in the polymerization process (II) for further calculation by the amount of ethylene content in the entire polymer. The results are shown in table 3.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. Various physical properties of the granules are determined, which turn out to be the following: MFR - 0.52 g / 10 min, crystallization temperature - 121.9 ^o C and melt stress (MS) - 5.2 cN.

EXAMPLE 7
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
A suspension of pre-activated catalyst is obtained under the same conditions of pre-activating polymerization, as in example 1.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
After creating a nitrogen gas atmosphere in a polymerization reactor of stainless steel 500-liter stirred tank it is loaded at 20 ^o C to 240 liters of n-hexane, 780 mmoles of triethylaluminum (organometallic compound (AL2), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1 / 2 the amount of suspension of the preactivated catalyst obtained as described above Then, after introducing 100 L of hydrogen into the polymerization reactor and raising the temperature to 70 ^° C, propylene is continuously fed into the polymerization reactor so that s to maintain the pressure gas phase portion at 0.79 MPa for 90 minutes at a temperature of 70 ^o C to conduct the polymerization of the polymerization process (1). After the polymerization process (1) The propylene feed is stopped and the temperature inside the polymerization reactor was lowered to 30 ^o C and then hydrogen and unreacted propylene are removed, and a portion of the polymerized suspension is selected to determine the MFI, which is 7.5.

After increasing the temperature inside the polymerization reactor to 60 ^° C, 30 L of hydrogen are introduced into it and ethylene and propylene are fed in such a way as to have an ethylene supply of 35 wt.% Continuously for 2 hours. The fully supplied amount of ethylene is 7.5 kg.

After the polymerization period is completed, 1 liter of methanol is introduced into the polymerization reactor and the catalyst is deactivated for 15 minutes at 70 ^° C. Then, after removing the unreacted gas, the solvent is separated off and the polymer is dried to obtain 40.5 kg of a polymer having an intrinsic viscosity [η _T ] of 1.95 dl / g.

The obtained polymer is a propylene-alpha-olefin block copolymer composition containing 0.26 wt.% Polyethylene (A) in accordance with preliminary activating polymerization as (a) component, and the intrinsic viscosity [η _P ] of the propylene block copolymer composition with alpha-olefin as (c) component is 1.87 dl / g.

 The polymerization ratio between the polymerization process (I) and the polymerization process (II) is calculated by obtaining copolymers having different reaction quantities of ethylene: propylene in advance, using them as reference samples to obtain a calibration curve of the IR absorption spectrum and determining the reaction quantity of ethylene: propylene in the polymerization process (II) and further calculation by the amount of ethylene content in the entire polymer. The results are shown in table 3.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. Various physical properties of the granules are determined, which turn out to be the following: PTR - 3.0 g / 10 min, crystallization temperature - 121.5 ^o C and melt stress (MS) - 2.1 cH.

EXAMPLE 8
The polymerization process (I) is carried out using the same conditions as in Example 7 (3), except that the conditions for obtaining the main (co) polymer composition, i.e. after feeding in such a way as to have a ratio of propylene: ethylene = 0.3 in the first stage, 50 l of hydrogen are introduced into the polymerization reactor, and the temperature rises to 60 ^o C, propylene is fed continuously for 90 minutes at a polymerization temperature of 60 ^o C and maintaining the pressure of the gas phase inside the polymerization reactor at 0.79 MPa. After the polymerization process (I), the flow of propylene and polyethylene is stopped and the temperature inside the reactor drops to 30 ^o C, then hydrogen and unreacted propylene are removed. Part of the polymerized suspension is selected to determine the MFI, which is equal to 3.0.

After raising the temperature inside the reactor to 60 ^° C, 50 l of hydrogen are introduced into the polymerization reactor and ethylene and propylene are fed in such a way as to have an ethylene supply of 35 wt.% Continuously for 2 hours. The total amount of ethylene supplied is 8.2 kg.

After completion of the polymerization period, 1 L of methanol is introduced into the polymerization reactor, and the catalyst is deactivated for 15 minutes at 70 ^° C. Then, after removal of the unreacted gas, the solvent is separated off and the polymer is dried to obtain 40.5 kg of a polymer having an intrinsic viscosity [η _T ] of 2.08 dl / g.

The obtained polymer is a propylene-alpha-olefin block copolymer composition containing 0.24 wt.% Polyethylene (A) in accordance with preliminary activating polymerization as (a) a component and an intrinsic viscosity [η _P ] of the propylene-alpha block copolymer composition the α-olefin as (c) the component is 2.00 dl / g.

 The polymerization ratio between the polymerization process (I) and the polymerization process (II) is calculated by obtaining copolymers having previously different reaction quantitative ratios of ethylene: propylene, using them as reference samples to obtain a reference spectrum curve. IR absorption, determination of the reaction quantitative ratio of ethylene: propylene in the polymerization process (II) and further calculation by the amount of ethylene content in the entire polymer. The results are shown in table 3.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. Various physical properties of the granules are determined, which turn out to be the following: MFR - 2.0 g / 10 min, crystallization temperature - 116.8 ^o C and melt stress (MS) - 2.5 cH.

COMPARATIVE EXAMPLE 8
Using the same conditions as in comparative example 5, a suspension of a titanium catalyst on a support is obtained. Using a suspension of a titanium catalyst on a support, a propylene-alpha-olefin block copolymer composition is prepared using the same conditions as in Example 6 (3) to obtain a test sample of Comparative Example 8.

 The various physical properties of the resulting propylene-alpha-olefin block copolymer composition are shown in Table 3.

COMPARATIVE EXAMPLE 9
Using the same conditions as in comparative example 3, a suspension of a titanium catalyst on a support is obtained. Using a suspension of a titanium catalyst on a support, a propylene-alpha-olefin block copolymer composition is prepared using the same conditions as in Example 7 (3) to obtain a test sample of Comparative Example 9.

 The various physical properties of the resulting composition of the block copolymer with alpha olefin are shown in table 3.

COMPARATIVE EXAMPLE 10
Using the same conditions as in comparative example 3, a suspension of a titanium catalyst on a support is obtained.

 Using a suspension of a titanium catalyst on a support, a propylene-alpha-olefin block copolymer composition is prepared using the same conditions as in Example 8 (3) to obtain a test sample of Comparative Example 10.

 The various physical properties of the resulting propylene-alpha-olefin block copolymer composition are shown in Table 3.

EXAMPLE 9
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
A suspension of the preactivated catalyst is obtained using the same conditions as in Example 1.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
After providing an atmosphere of nitrogen gas in the polymerization reactor of stainless steel 500-liter stirred tank it is loaded at 20 ^o C to 240 liters of n-hexane, 780 mmoles of triethylaluminum (organometallic compound (AL2), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1 / 2 amount of a suspension of the preactivated catalyst obtained as described above. The feed is carried out in such a way as to have a ratio of hydrogen: propylene and propylene: ethylene equal to 0.04 and 0.03, respectively, and the temperature rises about 60 ^o C, after which polypropylene, hydrogen and ethylene are fed continuously for 2 hours while maintaining the pressure of the gas phase inside the polymerization reactor at 0.79 MPa with the copolymerization of propylene with alpha-olefin.

After the completion of the polymerization period, 1 liter of methanol is introduced into the polymerization reactor and the catalyst is deactivated for 15 minutes at 60 ^° C. Then, after removal of the unreacted gas, the solvent is separated off and the polymer is dried to obtain 41.0 kg of a polymer having an intrinsic viscosity [η _T ] of 1.91 dl / g.

The resulting polymer is a composition of a random copolymer of propylene with an alpha olefin containing 0.24 wt. % of polyethylene (A) according to the preliminary activating polymerization as (a) a component and the intrinsic viscosity [η _P ] of a copolymer of propylene with alpha-olefin as (c) a component is 1.83 dl / g.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. Various physical properties of the granules are determined, which are as follows: MFI - 3.7 g / 10 min, crystallization temperature - 115.2 ^o C and melt stress (MS) - 1.8 cH.

EXAMPLE 10
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 3.

(2) Obtaining pre-activated catalyst
A suspension of the preactivated catalyst is obtained using the same conditions as in Example 3.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
Into a horizontal gas-phase continuous reactor with a capacity of 110 l (length: diameter = 3.7) with a stirrer, 25 kg of polypropylene powder are introduced and then a suspension of the preactivated catalyst in the form of a titanium catalyst component on a carrier at a rate of 0.81 g / h and 15 wt. A% n-hexane solution of triethylaluminum (organometallic compound (A 2)) and diisopropyl dimethoxysilane (electron donor (E2)) are fed continuously so as to have molar ratios of titanium atoms in the supported titanium catalyst component of 90 and 15, respectively.

Under conditions of a polymerization temperature of 60 ^° C., hydrogen and ethylene are fed in such a way as to have an ethylene: propylene ratio of 0.02 in the polymerization reactor. Then, when propylene is supplied in such a way as to maintain the pressure inside the polymerization reactor at 1.77 MPa, gas-phase polymerization of propylene is carried out continuously for 150 hours.

 During the polymerization, the polymer is withdrawn from the polymerization reactor at a rate of 12 kg / h in order to maintain the polymer level inside the polymerization reactor at 60% volume.

The selected polymer is processed by contact with nitrogen gas containing 5% vol. water vapor at 100 ^° C. for 30 minutes to obtain a polymer having an intrinsic viscosity [η _T ] of 1.95 dl / g.

The content of polyethylene (A) formed during the preliminary activating treatment in the polymer is 0.22 wt.%, And the intrinsic viscosity [η _P ] of the composition of the propylene-alpha-olefin block copolymer (c) is 1.89 dl / g.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. The various physical properties of the granules are determined, which are as follows: MFI - 3.2 g / 10 min, crystallization temperature - 110.0 ^o C and melt stress (MS) - 1.9 cN.

EXAMPLE 11
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
A suspension of the preactivated catalyst is obtained using the same conditions as in Example 1.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
After providing an atmosphere of gaseous nitrogen in a 500 l stainless steel polymerization reactor with a stirrer, 240 l of n-hexane, 780 mmol of triethyl aluminum (organometallic compound (AL2)), 78 mmol of diisopropyl dimethoxysilane (electron donor (E2)) are loaded into it at 20 ^° C. 1/2 the amount of suspension of the preactivated catalyst obtained as described above. Then, hydrogen, propylene, butene-1 and ethylene are fed in such a way as to have a ratio of hydrogen: propylene, hydrogen: ethylene and propylene: butene-1 equal to 0.08, 0.025 and 0.038, respectively, the temperature rises to 60 ^o C and propylene , hydrogen, ethylene and butene-1 are fed continuously for 2 hours while maintaining the pressure of the gas phase inside the polymerization reactor at 0.79 MPa with copolymerization of propylene with alpha-olefin.

After the completion of the polymerization period, 1 liter of methanol is introduced into the polymerization reactor and the catalyst is deactivated for 15 minutes at 60 ^° C. Then, after removal of the unreacted gas, the solvent is separated off and the polymer is dried to obtain 39.6 kg of a polymer having an intrinsic viscosity [η _T ] of 1.67 dl / g.

The obtained polymer is a propylene-alpha-olefin copolymer composition containing 0.25 wt.% Polyethylene (A) in accordance with preliminary activating polymerization as (a) a component and an intrinsic viscosity [η _P ] of the propylene-alpha-olefin copolymer composition (c) the component is 1.59 dl / g.

Then using an extruder using the same conditions as in example 1, polymer granules are obtained. Various physical properties of the granules are determined, which turn out to be the following: PTR - 7.6 g / 10 min, crystallization temperature - 110.3 ^o C and melt stress (MS) - 1.3 cH.

COMPARATIVE EXAMPLE 11
Using the same conditions as in comparative example 3, a suspension of a titanium catalyst on a support is obtained. Using a suspension of a titanium catalyst on a support, a propylene-alpha-olefin block copolymer composition is prepared using the same conditions as in Example 9 (3) to obtain a test sample, a comparative example. eleven.

 The various physical properties of the resulting propylene-alpha-olefin block copolymer composition are shown in Table 4.

COMPARATIVE EXAMPLE 12
Using the same conditions as in comparative example 5, a suspension of a titanium catalyst on a support is obtained. Using a suspension of a titanium catalyst on a support, a propylene-alpha-olefin block copolymer composition is prepared using the same conditions as in Example 10 (3) to obtain a test sample of Comparative Example 12.

 The various physical properties of the resulting propylene-alpha-olefin block copolymer composition are shown in Table 4.

EXAMPLE 12
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
Using the same conditions as in example 1, a preliminary activating polymerization with ethylene and an additional polymerization with propylene are carried out without preliminary polymerization with propylene.

The polymer obtained in the process of pre-activating polymerization under the same conditions is analyzed and determined that there is 22.2 g of polyethylene (A) per 1 g of the titanium catalyst component on the support and the intrinsic viscosity [η _E ] of the polymer, measured in tetraline at 135 ^o C is 32.5 dl / g.

The polymer formed during the preliminary activating polymerization using the same conditions and then subjected to additional polymerization is analyzed and determined that there is 2.0 g of polymer per 1 g of the titanium catalyst component on the carrier only during additional polymerization and the intrinsic viscosity [η _E ] of the polymer measured in tetraline at 135 ^° C. is 2.3 dl / g.

Obtaining a polypropylene composition (main (co) polymerization of propylene)
Using the obtained pre-activated catalyst, the main polymerization of propylene is carried out using the same conditions as in Example 1 to obtain polypropylene. The resulting polypropylene is granulated using the same conditions as in example 1, to obtain the test sample of example 12.

 The various physical properties of the obtained polypropylene are given in table 5.

COMPARATIVE EXAMPLE 14
A preactivated catalyst is obtained using the same conditions as in Example 1, except that preactivation polymerization with propylene or preactivation polymerization with ethylene is not carried out, but only additional polymerization with propylene is carried out. The obtained preactivated catalyst is used for the main polymerization of propylene using the same conditions as in Example 1 to obtain polypropylene. The resulting polypropylene is granulated using the same conditions as in example 1, to obtain the test sample of comparative example 14.

 The various physical properties of the material of comparative example 14 are given in table 5.

EXAMPLE 13 AND COMPARATIVE EXAMPLE 15
Polypropylene compositions having different contents of polyethylene (A) are obtained using the same conditions as in Example 1, except that the preliminary activating polymerization with propylene is not carried out and the conditions of the preliminary activating polymerization with ethylene are changed. Polypropylene compositions are processed using the same procedure as in Example 1 to obtain test samples of Example 13 and Comparative Example 15.

 The various physical properties of the materials of example 13 and comparative example 15 are given in table 5.

EXAMPLE 14
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 3.

(2) Obtaining pre-activated catalyst
The preliminary activating polymerization with ethylene and the additional polymerization with propylene are carried out using the same conditions as in Example 3, except that the preliminary polymerization with propylene is not carried out.

The polymer obtained by pre-activating polymerization under the same conditions is analyzed and it is determined that there is 32.0 g of polyethylene (A) per 1 g of the titanium catalyst component on the support and the intrinsic viscosity [η _E ] of the polymer, measured in tetraline at 135 ^° C. equals 29.8 dl / g.

The polymer formed by pre-activating polymerization using the same conditions and further with additional polymerization is analyzed and determined that there is 2.2 g of polymer per 1 g of the titanium catalyst component on the support only with additional polymerization and the intrinsic viscosity [η _E ] of the polymer, measured in tetraline at 135 ^° C. is 3.4 dl / g.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
Using the obtained pre-activated catalyst, the main polymerization of propylene is carried out using the same conditions as in Example 3 to obtain polypropylene. The resulting polypropylene is granulated using the same conditions as in example 3, to obtain the test sample of comparative example 14.

 The various physical properties of the obtained polypropylene are given in table 5.

COMPARATIVE EXAMPLE 16
The propylene copolymer composition is obtained using the same conditions as in Example 3, except that the preliminary activating treatment (2) is not carried out and the polymerization of propylene is carried out in the presence of a solid titanium catalyst obtained in (1) under the same conditions as in (3) to obtain a test sample of comparative example 16.

 The various physical properties of the obtained polypropylene are given in table 5.

EXAMPLE 15
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
The preliminary activating polymerization with a gas mixture of ethylene and propylene is carried out using the same conditions as in Example 5, except that no preliminary polymerization with propylene or additional polymerization with propylene is carried out.

The ethylene-propylene copolymer formed by preliminary activating polymerization using the same conditions is analyzed and determined to contain 0.8 wt.% Of a polymerization unit of propylene (determined by ¹³ C-NMR), there is 25 g of a copolymer of ethylene with propylene per 1 g of titanium catalytic component on the carrier and the intrinsic viscosity [η _E ] of the polymer, measured in tetraline at 135 ^° C., is 30.0 dl / g.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
Using the obtained pre-activated catalyst, the main polymerization of propylene is carried out using the same conditions as in Example 1 to obtain polypropylene. The resulting polypropylene is granulated using the same conditions as in example 1, to obtain the test sample of example 15.

 The various physical properties of the obtained polypropylene are given in table 6.

COMPARATIVE EXAMPLE 17
The composition of the (co) propylene polymer is obtained using the same conditions as in example 1, except that the preliminary activating treatment (2) is not carried out, and the polymerization of propylene is carried out in the presence of a solid titanium catalyst obtained in (1) in the same conditions as in (3), to obtain a test sample of a comparative example. 17.

 The various physical properties of the obtained polypropylene are given in table 6.

COMPARATIVE EXAMPLE 18
The composition of the (co) propylene polymer is obtained by polymerization of propylene using the same conditions as in Example 1, except that pre-activation with propylene or additional polymerization with propylene is not carried out, pre-activation polymerization with ethylene is replaced by pre-activation treatment with a gas mixture of ethylene and propylene, and 240 g of propylene are introduced into the polymerization reactor to obtain a test sample of comparative example 18.

 The various physical properties of the obtained polypropylene are given in table 6.

EXAMPLE 16 AND COMPARATIVE EXAMPLE 19
Polypropylene compounds having different contents of polyethylene (A) are obtained using the same conditions as in Example 1, except that no preliminary activating polymerization with propylene or additional polymerization with propylene is carried out and the conditions for preliminary activating polymerization with ethylene are changed. Polypropylene compounds are processed using the same procedure as in Example 1 to obtain test samples of Example 16 and Comparative Example 19.

 The various physical properties of the samples of example 16 and comparative example 19 are shown in table 6.

EXAMPLE 17
(1) Obtaining a catalytic composition comprising a transition metal compound
The titanium supported catalyst component is prepared using the same conditions as in Example 3.

(2) Obtaining pre-activated catalyst
The preliminary activating polymerization with ethylene is carried out using the same conditions as in Example 3, except that no preliminary polymerization with propylene or additional polymerization with propylene is carried out.

The polymer obtained in the process of preliminary activating polymerization using the same conditions is analyzed and determined that there is 29 g of polyethylene (A) per 1 g of the titanium catalyst component on the carrier and the intrinsic viscosity [η _E ] of the polymer, measured in tetraline at 135 ^o C equals 35.5 dl / g.

(3) Obtaining a polypropylene composition (main copolymerization of propylene)
Using the obtained pre-activated catalyst, the main polymerization of propylene is carried out under the same conditions as in example 5, to obtain polypropylene.

 The resulting polypropylene is granulated using the same conditions as in example 1, to obtain the test sample of example 17.

 The various physical properties of the obtained polypropylene are given in table 6.

EXAMPLE 18
The conditions of example 1 are repeated, except that 0.1 wt.h. phosphorus-type antioxidant tris (2,4-di-t-butylphenyl) phosphite is added per 100 wt. including the obtained polypropylene composition instead of 0.1 parts by weight the phenolic antioxidant of 2,6-di-t-butylcresol in Example 1 (3), the granules are obtained by granulation using an extruder at 230 ^o C. Various physical properties of the granules are determined, which are as follows: MFR - 3.6 g / 10 min, the crystallization temperature is 119.5 ^o C and the melt stress (MS) is 2.1 SN. Detailed physical properties are given in table 7.

EXAMPLE 19
The conditions of Example 2 are repeated, except that the phosphoric type antioxidant Tris (2,4-di-t-butylphenyl) phosphite is added per 100 parts by weight. the obtained polypropylene composition instead of the phenolic type of the oxidant 1,6-di-t-butyl-p-cresol in example 2 (3). The result is a polypropylene composition to obtain the test sample of example 19.

 The various physical properties of the obtained polypropylene are given in table 7.

COMPARATIVE EXAMPLES 20-23
Polypropylene compositions are obtained by repeating comparative examples 1 to 4, except that the phosphorus type antioxidant tris (2,4-di-t-butylphenyl) phosphite is added per 100 parts by weight the obtained polypropylene composition instead of the phenolic type of the antioxidant 2,6-di-t-butyl-p-cresol, to obtain test samples of comparative examples 20 to 23.

 The various physical properties of the obtained polypropylene are given in table 7.

EXAMPLES 20-21
Polypropylene compositions are obtained using the same conditions as in example 3 and example 5, except that the phosphorus type antioxidant tris (2,4-di-t-butylphenyl) phosphite is added per 100 parts by weight the obtained polypropylene composition instead of the phenolic type of 2,5-di-t-butyl-p-cresol oxidant, to obtain test samples of examples 20 and 21.

 The various physical properties of the obtained polypropylene are given in table 8.

COMPARATIVE EXAMPLES 24-26
Polypropylene compositions are obtained using the same conditions as in comparative examples 5 to 7, except that the phosphorus type antioxidant tris- (2,4-di-t-butylphenyl) phosphite is added per 100 wt. including the obtained polypropylene composition instead of the phenolic type of the antioxidant 2,6-di-t-butyl-p-cresol, to obtain test samples of examples 24 to 26.

 The various physical properties of the obtained polypropylene are given in table 8.

EXAMPLE 22
The polypropylene composition is obtained using an extruder using the same conditions as in example 1, except that 0.09 wt. including phosphorus type antioxidant Tris (2,4-di-t-butylphenyl) phosphite and 0.01 wt.h. the phenolic type of antioxidant 2,6-di-t-butyl-p-cresol is added per 100 parts by weight the resulting polypropylene composition instead of 0.1 parts by weight the phenolic type of antioxidant 2,6-di-t-butyl-p-cresol in Example 1 (3).

Various physical properties of the obtained polypropylene composition are determined, which turn out to be the following: characteristic viscosity [η _T ] - 1.97 dl / g, MFI - 3.5 g / 10 min, crystallization temperature - 120.7 ^o C and melt stress (MS) - 2.8 sn. Detailed physical properties are given in table 9.

EXAMPLE 23
The polypropylene composition is obtained using an extruder, as in example 1, using the same conditions as in example 1 (3), except that 0.08 wt.h. phosphorus type antioxidant tris (2,4-di-t-butylphenyl) phosphite and 0.02 wt.h. dimyristylthiodipropionate is added per 100 wt. including the obtained polypropylene composition instead of 0.1 parts by weight phenolic type antioxidant 2,6-di-t-butyl-p-cresol.

Various physical properties of the obtained polypropylene composition are determined, which turn out to be the following: characteristic viscosity [η _T ] - 1.97 dl / g, MFI - 3.5 g / 10 min, crystallization temperature - 119.8 ^o C and melt stress (MS) - 2.5 cN. Detailed physical properties are given in table 9.

EXAMPLE 24
(1) Preparation of a catalyst composition comprising a transition metal compound

 The titanium supported catalyst component is prepared using the same conditions as in Example 1.

(2) Obtaining pre-activated catalyst
A suspension of the preactivated catalyst is obtained using the same conditions as in Example 1.

(3) Obtaining a polypropylene composition (main (co) polymerization of propylene)
After creating an atmosphere of gaseous nitrogen in a 500 l stainless steel polymerization reactor with a stirrer, 240 l of n-hexane, 780 mmol of triethyl aluminum (organometallic compound (AL2)), 78 mmol of diisopropyl dimethoxysilane (electron donor (E2)) are loaded into it at 20 ^° C 1/2 the amount of suspension of the preactivated catalyst obtained as described above. Then, after 95 l of hydrogen were introduced into the polymerization reactor and the temperature was raised to 70 ^° C, propylene was fed continuously for 45 minutes while maintaining the gas phase pressure inside the polymerization reactor at 0.79 MPa with the polymerization process (I) being carried out. After completion of the polymerization process (I), the supply of propylene is stopped and the temperature inside the polymerization reactor drops to 30 ^o C. Hydrogen and unreacted gas are discharged. A portion of the polymerization suspension is selected and analyzed to determine the MFI and intrinsic viscosity [η _T1 ] measured in tetralin at 135 ^° C., which is 6.5 g / 10 min and 1.78 dl / g, respectively. The intrinsic viscosity [η _P1 ] obtained in the polymerization process (I) is 1.59 dl / g.

Then, 45 L of hydrogen is introduced into the polymerization reactor and the temperature in the polymerization reactor rises to 70 ^° C, then propylene is continuously supplied for 60 minutes while maintaining the polymerization temperature at 70 ^° C and the gas phase pressure inside the polymerization reactor at 0.98 MPa with polymerization process (II). After completion of the polymerization process (II), the flow of propylene is stopped and the temperature inside the polymerization reactor drops to 30 ^o C. Hydrogen and unreacted propylene are removed. A portion of the polymerization suspension is selected and analyzed to determine the MFI and intrinsic viscosity [η _T2 ] measured in tetraline at 135 ^° C., which is 3.1 g / 10 min and 2.01 dl / g, respectively. The intrinsic viscosity [η _P2 ] obtained in the polymerization process (II) is 2.29 dl / g.

Then 30 l of hydrogen is introduced into the polymerization reactor and the temperature inside the polymerization reactor rises to 70 ^° C, then propylene is fed continuously for 90 minutes while maintaining the polymerization temperature at 70 ^° C and the gas phase pressure inside the polymerization reactor at 0.98 MPa with polymerization process (III).

After completion of the polymerization process (III), the supply of propylene is stopped and the temperature in the polymerization reactor is reduced to 30 ^o C. Hydrogen and unreacted propylene are removed. After the polymerization period is completed, 1 liter of methanol is introduced into the polymerization reactor and the catalyst is deactivated for 15 minutes at 70 ^° C. Then, after removing the unreacted gas, the solvent is separated off and the polymer is dried to obtain 39.1 kg of a polymer having an intrinsic viscosity [η _T3 ] of 2.33 dl / g. The intrinsic viscosity [η _P3 ] of the polymer obtained in the polymerization process (III) is 3.86 dl / g.

The resulting polymer is a polypropylene polymer composition containing 0.25 wt.% Polyethylene (A) in accordance with pre-activating polymerization as (a) a component and an intrinsic viscosity [η _P ] (c) of the component is 2.25 dl / g.

 Mass ratios of the polymerization process (I), the polymerization process (II) and the polymerization process (III) are calculated by the magnesium content of the powder at each stage and are given in table 10.

Then, using the same conditions as in Example 1, polymer granules are obtained using an extruder. Various physical properties of the granules are determined, which turn out to be the following: PTR - 1.3 g / 10 min, crystallization temperature - 122.3 ^o C and melt stress (MS) - 9.9 cH.

 The various physical properties of the obtained polypropylene composition are given in table 10.

COMPARATIVE EXAMPLE 27
Using the same conditions as in comparative example 3, a suspension of a titanium catalyst on a support is obtained.

 Using a suspension of a titanium catalyst on a support, a polypropylene composition is obtained using the same conditions as in example 24 (3) to obtain a test sample of comparative example 27.

 The various physical properties of the obtained polypropylene composition are given in table 10.

EXAMPLE 25
50 wt.% Of the polypropylene composition of Example 1 and 50 wt.% Of the polypropylene composition of Comparative Example 3 are mixed, then 0.1 wt.% Of 2,6-di-t-butyl-p-cresol and 0.1 wt.% Are mixed calcium stearate. The mixture is granulated using an extruder having a screw diameter of 40 mm at 230 ^° C. The various physical properties of the obtained granules are shown in Table 11.

EXAMPLE 26
Polypropylene compositions are obtained using the same conditions as in example 1, except that the amount of preactivated catalyst containing high molecular weight polyethylene is changed to 0.24 wt.% And 0.46 wt.%. The resulting polypropylene compositions are analyzed as follows.

(1) Transmission electron microscope (TEM) studies
Research using a transmission electron microscope (TEM) is carried out as follows. The granule samples are heated for 3 minutes in a hot press at 200 ^° C, pressed for 5 minutes under a pressure of 50 kg / cm ² and hardened in a cold press at 50 ^° C for 3 minutes to obtain a plate-like test sample 1 mm thick. After stripping, the test samples are processed by electronically etching the steam with an aqueous RuO ₄ solution to give contrast for TEM studies. An aqueous RuO ₄ solution is obtained by dissolving 0.6 g of NaIO ₄ (guaranteed reagent from Uvako Pur Chemical Industrial, Ltd.) and 0.1 g of RuCl nH ₂ O (of the same company) in 10 ml of pure water. The test sample is installed in a closed container with an aqueous solution of RuO ₄ and remains in it for 48 hours at room temperature for etching. Although the pickling is carried out in this invention with steam from an aqueous solution, other methods can be used with the same success to obtain the same effect, such as pickling by soaking in an aqueous solution of RuO ₄ or sublimated gas from RuO ₄ crystals. The etched sample is cut to obtain thin-layer sections with a thickness of approximately 80 nm using an ultra-microtome company Jeol Ltd. using a knife angle of 45 ^o . Ultrathin sections are examined using a TEM brand JEM-100CX firm Jeol Ltd. with an accelerating voltage of 100 kV.

 A micrograph obtained with the above TEM at 75000x magnification is shown in FIG. 1. As seen in FIG. 1, a high molecular weight polyethylene having a number average particle size of about 70 nm is dispersed in the surrounding polymer. It is observed that high molecular weight polyethylene has a lamellar structure.

 In FIG. 1 is a drawn diagram of FIG. 1 with explanation to facilitate understanding. The globular and lamellar structure of high molecular weight polyethylene is added for clarification.

 On the other hand, the particles are not dispersed in well-known conventional polypropylenes, as shown in the micrograph of FIG. 2 and its drawn diagram in FIG. 4.

(2) Rheological studies
2.1. Obtaining a sample for research using a rheometric mechanical spectrometer RMS-800.

PMS-800 test pellets (mixture with 0.1 wt.% Thermal stabilizer: 2,6-di-t-butyl-p-cresol (BHT) and 0.1 wt.% Lubricant: calcium stearate) are pressed into a plate with a diameter 25 mm at 200 ^o C. The plate is installed in the PMS-800 for measurements.

2.2. Drawing viscosity
(i) Thermostabilizer (BHT: 0.1 wt.%, lubricant calcium stearate: 0.1 wt.%) is added to the powder and mixed in a Henschel mixer for 3 minutes.

(ii) The above mixture is granulated using an extruder having a diameter of 40 mm at a temperature of 230 ^o C.

(iii) Filaments having a uniform diameter are obtained from the above pellets using a melt tension gauge with a hole diameter of 3 mm, supplied by Toyo Seiki Seisaku-sho, Ltd., at a temperature of 210 ^° C. and an extrusion speed of 5 mm / min after preheating for 5 min before extrusion.

 Next, rheological properties are explained.

1. Regarding G '
In relation to the molten product, the dynamic elastic modulus G 'is determined at 230 ^° C with deformation in the linear frequency range from 10 ^-2 to 10 ² [rad / s] using a RMS-800 rheometric mechanical spectrometer made by Reometrix Incorporated having a parallel plate with a diameter 25 mm attached to it. The results are shown in FIG. 5 to 7.

 As shown in FIG. 5 and 6 (vertical axes: dynamic elastic modulus G ′, horizontal axes: frequency ω), the G ′ polymer of the present invention (hereinafter abbreviated as “HMS-PP”) has a second low-frequency plateau that is not observed with a conventional polymer ( "Conv. PP"). The height of the second plateau increases in accordance with the amount of pre-treated PE. It is known that the second plateau is observed for copolymers or polymers filled with inorganic compounds having a configuration in which rubber particles are dispersed in the plastic phase in the form of islands. This is considered as caused by the mechanism of prolonged softening, derived from the dispersed phase structure. It is believed that the second plateau appears due to the fact that in the material of the invention HMS-PP disperses the number of particles of high molecular weight PE at a submicron level. The abbreviation "HIMONT LCB-PP" in FIG. 5 denotes electron beam crosslinked polypropylene obtained by the electron beam radiation method Gimont Incorporated. It is important that the electron-beam-cross-linked polypropylene does not have a second plateau anywhere.

2. Regarding N ₁
The first difference in normal stresses N _{1 of the} molten product at 190 ^o C, 230 ^o C and 250 ^o C is determined in the range of shear rates from 10 ^-2 to 10 [s ^-1 ] using a RMS-800 rheometric mechanical spectrometer manufactured by Reometrix Incorporated, having a conical plate with a diameter of 25 mm and with a taper angle of 0.1 rad attached to it.

 Measurement begins 30 minutes after setting the sample and stabilizing the temperature. The time to reach a constant flow state is determined by preliminary measurement.

Preliminary measurement: a constant flow is applied to the samples 150 [S] at 0.01 [s ^-1 ] and 100 [S] at 0.1 [s ^-1 ], and the minimum time to reach a certain viscosity is determined.

As can be seen in FIG. 8 (vertical axis: first normal stress difference N ₁ , horizontal axis: shear rate), FIG. 9 (vertical axis: first difference in normal stresses N ₁ , horizontal axis: PTR), N ₁ for the material of the invention HMS-PP is higher than that of traditional polypropylene (Conv. PP) and increases in accordance with the amount of pre-treated PE. A PP having N _i higher than that of a traditional PP is a PP obtained by the electronic radiation method of Gimont Incorporated. But, as shown in FIG. 9. (vertical axis: the first difference in vertical stresses N ₁ , horizontal axis: temperature), N ₁ for a traditional PP or PP obtained by the electron beam radiation method decreases with increasing temperature, while the temperature dependence of the material of the invention (HMS-PP) is negligible.

3. Regarding G (t)
The relaxation elastic modulus G (t) of the molten product at 230 ^o C is determined at a strain of 500% and a time scale of 330 [s] using a RMS-800 rheometric mechanical spectrometer manufactured by Reometrix Incorporated, having a conical plate with a diameter of 25 mm with a taper angle of 0, 1 glad attached to it. In particular, the samples are installed between conical plates having a taper angle of 0.1, and the lower plate is rotated by an angle of 28.65 ^o , which at this moment corresponds to a strain of 500%. The angle of 28.65 ^o is determined as follows. 500% strain means that the strain is expressed 5. According to the formula τ = Kα × θ, in which Kα is the deformation constant and θ is the angle of displacement (rad), θ is equal to / Kα. In this case, Kα = 10 in accordance with 1 / 0.1, provided that the taper angle is 0.1. Therefore, θ becomes equal to 5/10, i.e. 0.5 (rad), equal to 28.65 ^o .

 As shown in FIG. 10 and 11 (vertical axis: relaxation modulus G (t), horizontal axis: time), the slope of the curve G (t) of the material of the invention (HMS-PP) is almost the same as that of traditional PP, in the field of small times, but the slope is averaged over the region of large times and in the region of large times there is a plateau. The limiting section is not observed within the measurement scale (330 [s] or less), and the starting point of the longer-term plateau shifts toward small times in accordance with an increase in the amount of pre-treated PE.

 The slope of the G (t) curve for PP obtained by the electron beam radiation method of Gimont Incorporated is average compared to the slope of the G (t) curve of traditional PP or the material of the invention, but there is no longer-term plateau and there is no limit section, as in the case traditional PP.

 A longer-term plateau of the G (t) curve is also observed for PP with a two-modal molecular weight distribution.

4. Regarding viscosity when stretched
Threads having a uniform diameter are preheated for 5 minutes in a silicone oil bath at 180 ^o C and stretched at a constant strain rate (0.05, 0.10, 0.30) using a melt rheometer manufactured by Toyo Seiki Seisaku sho, Ltd., with the measurement of viscosity during stretching. Using the above viscometer, the tension and diameter of the thread are measured with the passage of time (the diameter of the thread is measured using a CCD camera).

 In FIG. 12 (vertical axis: drawing viscosity, horizontal axis: time), a case is presented in which a polypropylene composition is obtained using the same conditions as in Example 1, except that the amount of preactivated catalyst containing high molecular weight polyethylene is changed to 0 , 46 wt.%, And the amount of hydrogen changes. The viscosity when drawing the resulting polypropylene composition is determined at different strain rates (τ). The measurement results are given in table 12.

 In FIG. 13 (vertical axis: drawing viscosity, horizontal axis: time), a case is presented in which a polypropylene composition is obtained using the same conditions as in comparative example 3, except that the amount of hydrogen changes.

 The viscosity when drawing the resulting polypropylene composition is determined at different strain rates (τ). The measurement results are given in table 13.

 As indicated above, the viscosity value during extrusion of traditional PP tends to a constant value, even when a large deformation during extrusion is applied (table 13). Whereas in the case of the material of the invention HMS-PP, strain hardening is observed with an increase in viscosity beyond a certain strain value (see table 12). The increase in viscosity is an advantage in injection molding or pneumoforming having a large deformation. Strain hardening is observed in PP obtained by the electron beam radiation method or in the ionomer of Gimont Incorporated. However, the phenomenon is not observed in a block polypropylene composition. Table 14 confirms the individual features of the formula.

 As indicated previously, it is confirmed that the HMS-PP material of the present invention exhibits or significantly observes the above advantage compared to the control PP without the addition of a preactivated catalyst containing high molecular weight polyethylene regardless of the propylene homopolymer, random propylene copolymer or block propylene copolymer. This is probably due to the interaction between the molecules of dispersed high molecular weight polyethylene and polypropylene molecules.

 It is also confirmed that, even when the powder of the preactivated catalyst containing high molecular weight polyethylene is mixed with the base polypropylene, the above rheological properties are not manifested.

 Since this invention can be implemented in several forms without departing from the spirit of its main characteristics, therefore, the present embodiments of the invention are illustrative, but not limiting, since the scope of the invention is determined by the appended claims and not by the foregoing description, and all changes that are included within the limits and boundaries of the claims, or equivalents of such limits and boundaries, therefore are covered by the claims.

Claims (49)

1. The composition of the (co) polymer of olefin, including 0.01 to 5.0 wt.h. high molecular weight ethylene polymer, which is a homopolymer of ethylene or a copolymer of ethylene with an olefin containing 50 wt.% or more units of ethylene, and 100 wt.h. (co) an olefin polymer other than a high molecular weight ethylene polymer, wherein said high molecular weight ethylene polymer has an intrinsic viscosity (η _E ) measured in tetraline at 135 ^° C. of 15-100 dl / g, and said high molecular weight ethylene polymer is in the form dispersed small particles having a number average particle size of 1 to 5000 nm.  2. The olefin (co) polymer composition according to claim 1, wherein the number average particle size of the high molecular weight ethylene polymer is 10 to 500 nm. 3. The olefin (co) polymer composition according to claim 1, wherein the intrinsic viscosity (η _T ) of the olefin (co) polymer composition measured in tetraline at 135 ^° C. is 0.2-10 dl / g.  4. The composition of the (co) olefin polymer according to claim 1, wherein the (co) olefin polymer other than a high molecular weight ethylene polymer is at least one representative selected from the group consisting of a propylene homopolymer and a propylene copolymer with an olefin containing 50 wt.% Or more units of propylene. 5. The composition (co) of the olefin polymer according to claim 1, where the following dependence is satisfied in the condensed state, when the rubber component or inorganic filler is not contained, as expressed by the following formula:
log (G '(ω = 10 ^o )) - log (G' (ω = 10 ^-2 )) <2,
where G '(ω = 10 ^o ) is the dynamic modulus of elasticity with a frequency ω = 10 ^{o of the} molten product at 230 ^o C and
G '(ω = 10 ^-2 ) is the dynamic modulus of elasticity with a frequency of ω = 10 ^-2 . 6. The composition (co) of the olefin polymer according to claim 1, where the following dependence is satisfied in a state where irradiation by electron flow does not occur:
log (N ₁ )> - log (MFR) + 5,
where N ₁ is the first difference in normal stresses at a shear rate of 4 • 10 ^-1 (s ^-1 ) at 190 ^o C, 230 ^o C and 250 ^o C;
MFR is an indicator of melt flow. 7. The composition (co) of the olefin polymer according to claim 1, where at 190 and 250 ^o C the following dependence is satisfied:
(N ₁ (190 ^o C) - N ₁ (250 ^o C)) / N ₁ (190 ^o C) <0.6,
where N ₁ (190 ^o C) and N ₁ (250 ^o C) is the first difference in normal stresses at a shear rate of 4 • 10 ^-1 (s ^-1 ). 8. The composition (co) of the olefin polymer according to claim 1, where at 190 ^o C and 250 ^o C the following dependence is satisfied:
(MS (190 ^° C) - MS (250 ^° C)) / MS (190 ^° C) <3.1,
where MS (190 ^o C) and MS (250 ^o C) is the melt stress with a shear rate of 3 • 10 ^-1 (s ^-1 ). 9. The composition (co) of the olefin polymer according to claim 1, where the following relationship is satisfied:
(G (t = 10) - G (t = 300)) / G (t = 10) <1,
where G (t = 10) is the relaxation elastic modulus with t = 10 (s) and
G (t = 300) - relaxation modulus with t = 300 (s), with the condition of 500% deformation of the molten product at 230 ^o C.  10. The olefin polymer (co) polymer composition according to claim 1, wherein the stretching viscosity increases in the region of large deformations during melting and stretching, showing curing during deformation.  11. The olefin (co) polymer composition according to claim 1, in which fine particles of said high molecular weight ethylene polymer are added before or during (co) polymerization of the olefin. 12. The composition of the (co) olefin polymer according to claim 1, in which the (co) olefin polymer other than a high molecular weight ethylene polymer is at least one representative selected from the group consisting of a propylene homopolymer and a propylene-olefin copolymer, containing 50 wt.% or more units of propylene, and said olefin (co) polymer composition satisfies the following relationships between melt stress (MS) at 230 ^° C and intrinsic viscosity (η _T ) measured in tetraline at 135 ^° C, where the melt stress measured under such conditions when the olefin (co) polymer composition is heated to 230 ^° C. and the molten olefin (co) polymer composition is extruded into the air through a nozzle having a diameter of 2.095 mm at a speed of 200 mm / min to form filaments and finally the tension of the obtained filaments of the composition (co) the olefin polymer is measured when the resulting yarn is wound at a speed of 3.14 m / min:
log (MS)> 4.24 × log (η _T ) -1.20.
13. The olefin (co) polymer composition according to claim 1, wherein the olefin (co) polymer is an ethylene homopolymer or a copolymer of ethylene with an olefin containing 50 wt.% Or more of ethylene units.  14. The composition of the (co) polymer olefin according to claim 1, where per 100 parts by weight of the composition of the (co) polymer of the olefin is introduced 0.001 to 2 parts by weight of at least one stabilizer selected from the group consisting of a phenolic antioxidant and phosphoric antioxidant.  15. The composition of the (co) olefin polymer according to claim 1, in which the (co) olefin polymer other than a high molecular weight ethylene polymer is at least one representative selected from the group consisting of a propylene homopolymer and a propylene-olefin copolymer, containing 50 wt.% or more units of propylene, the propylene polymer is obtained by polymerizing propylene alone or by copolymerizing propylene with an olefin containing from 2 to 12 carbon atoms, in the presence of a pre-activated catalyst comprising a field production catalyst olefins coated with a high molecular weight ethylene polymer, which is an ethylene homopolymer or an ethylene-olefin copolymer, and said polyolefin production catalyst is formed by combining a catalyst component comprising a transition metal compound containing at least one titanium compound, from 0.001 to 1000 mol of an organometallic compound (AL1) selected from the group comprising metal, which belongs to Group I, Group II, Group XII and Group XIII of the Periodic System, published in 1991, per 1 mol l the transition metal atom, and from 0 to 500 mol of the electron donor (E1) per 1 mol of the transition metal atom.  16. The olefin (co) polymer composition of claim 15, wherein the preactivated catalyst in addition to (AL1) and (E1) comprises an organometallic compound (AL2) and an electron donor (E2), said organometallic compound (AL2) is a compound metal selected from the group comprising metals belonging to groups I, II, XII and XIII of the Periodic system published in 1991, the content of organometallic compounds (AL1) and (AL2) is from 0.05 to 5000 mol per 1 mol of transition atom metal in pre-activated ca catalyst, and the content of electron donors (E1) and (E2) is from 0 to 3000 mol per mol of the transition metal atom in the preactivated catalyst. 17. The olefin (co) polymer composition according to claim 15 or 16, wherein the preactivated catalyst comprises an olefin polymerization catalyst coated with from 0.01 to 5000 g of high molecular weight ethylene polymer with an intrinsic viscosity (η _E ) of from 15 to 100 dl / g measured in tetraline at 135 ^o C, per 1 g of the catalytic component of the transition metal compound. 18. The olefin (co) polymer composition according to claim 15 or 16, wherein the preactivated catalyst comprises an olefin polymerization catalyst coated with from 0.01 to 100 g of propylene polymer (B) and from 0.01 to 5000 g of high molecular weight ethylene polymer ( A) per 1 g of the catalytic component of the transition metal compound, said propylene polymer (B) has an intrinsic viscosity measured in tetraline at 135 ^° C. (η _B ) of less than 15 dl / g and is a propylene homopolymer or a propylene-olefin copolymer, including units of propylene in the quantity TBE 50 wt.%, and said high molecular weight ethylene polymer (A) has an intrinsic viscosity (η _E), measured in tetraline at 135 ^o C, of from 15 to 100 dl / g.  19. The composition of the (co) olefin polymer according to claim 15 or 16, wherein the (co) olefin polymer, other than a high molecular weight ethylene polymer, is prepared using from 0.01 to 1000 mmol of a catalyst, calculated as a transition metal atom in the catalyst , per 1 liter of (co) polymerizable volume of propylene or another olefin.  20. The composition of the (co) olefin polymer according to claim 1, in which the (co) olefin polymer, other than a high molecular weight ethylene polymer, is a mixture of (b) a propylene polymer, which is a propylene homopolymer or a copolymer of propylene with an olefin containing 50 wt. .% or more units of propylene, and (a) a propylene polymer that is a propylene homopolymer or a copolymer of propylene with an olefin containing from 2 to 12 carbon atoms, which is obtained in the presence of a preactivated catalyst containing a preparation catalyst polyolefins coated with a high molecular weight ethylene polymer and said polyolefin production catalyst is formed by combining a catalytic component of a transition metal compound containing at least a titanium compound, from 0.01 to 1000 mol of an organic metal compound (AL1) selected from the group of metals, related to I, II, XII and XIII groups of the Periodic system, published in 1991, per 1 mol of a transition metal atom, and from 0 to 500 mol of an electron donor (E1) per 1 mol of a transition metal atom. 21. A method for producing an olefin (co) polymer composition, comprising: (a) preparing a preactivated catalyst that comprises a polyolefin producing catalyst coated with a high molecular weight ethylene polymer, wherein said polyolefin producing catalyst comprises (i) a catalytic component of a transition metal compound, which comprises at least one titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), said organometallic compound (AL1) is a compound metal selected from the group comprising a compound of metals of the I, II, XII and XIII groups of the Periodic system published in 1991, the content of the organometallic compound (AL1) is from 0.01 to 1000 mol per mol of the transition metal atom, the content of electron donor (E1 ) is from 0 to 500 mol per 1 mol of a transition metal atom, wherein said high molecular weight ethylene polymer is an ethylene homopolymer or a copolymer of ethylene with an olefin containing ethylene units in an amount of 50 wt.% or more and having a characteristic elm a bone measured in tetraline at 135 ^° C. (η _E ) equal to 15 to 100 dl / g, and wherein said preactivated catalyst comprises an olefin production catalyst coated with a high molecular weight ethylene polymer, and the content of high molecular weight ethylene polymer is from 0.01 to 5000 g per 1 g of the catalytic component of the transition metal compound; and (b) a basic polymerization process that involves the preparation of an olefin polymer other than a high molecular weight ethylene polymer in the presence of said preactivated catalyst.  22. The method of obtaining the composition (co) of the olefin polymer according to item 21, in which the olefin polymer, other than a high molecular weight ethylene polymer, is a propylene homopolymer or a copolymer of propylene with an olefin containing from 2 to 12 carbon atoms containing 50 wt.% or more propylene units.  23. The method for preparing the olefin (co) polymer composition according to claim 21, which, in addition to adding (AL1) and (E1), includes the step of adding an organoaluminum compound (AL2) and an electron donor (E2) to the preactivated catalyst, in which the content of the organoaluminum compound (AL1) and (AL2) in a preactivated catalyst is from 0.05 to 5000 mol per 1 mol of a metal titanium atom, and the content of electron donors (E1) and (E2) in a preactivated catalyst is from 0 to 3000 mol per 1 mol titanium atom in p re-activated catalyst.  24. The method for preparing the olefin (co) polymer composition according to claim 21, wherein the content of the titanium atom in the catalyst is from 0.01 to 1000 mmol per 1 liter of olefin subjected to (co) polymerization. 25. A method for producing an olefin (co) polymer composition comprising the following steps: (a) a preliminary polymerization process, which comprises producing propylene polymer (B) in the presence of a polyolefin production catalyst, wherein said polyolefin production catalyst contains (i) a catalyst component comprising a compound a transition metal that contains at least one titanium compound, (ii) an organometallic compound (AL1) and (iii) an electron donor (E1), said organometallic compound (AL1), in which ll is a metal selected from the group comprising metals belonging to groups I, II, XII and XIII of the Periodic system published in 1991, the content of the organometallic compound (AL1) is from 0.01 to 1000 mol per 1 mol of transition metal atom, the content of the electron donor (E1) is from 0 to 500 mol per 1 mol of the transition metal atom, wherein said propylene polymer (B) is a propylene homopolymer or a propylene-olefin copolymer containing 50 wt.% or more propylene units and having a characteristic viscosity (η _B ), measured in tetraline at 135 ^° C., equal to less than 15 dl / g, and wherein said prepolymerized catalyst comprises a polyolefin catalyst coated with a propylene polymer (B) and a propylene polymer content ( B) is from 0.01 to 100 g per 1 g of the catalytic component of the transition metal compound; (b) a pre-activating polymerization process, which involves producing a high molecular weight ethylene polymer (A) in the presence of a pre-polymerized catalyst to obtain a pre-activated catalyst, wherein said high molecular weight ethylene polymer (A) is an ethylene homopolymer or an ethylene-olefin copolymer containing 50 wt. . % or more of ethylene units and having an intrinsic viscosity (η _E ) measured in tetraline at 135 ^° C. of 15 to 100 dl / g, and wherein said preactivated catalyst comprises a pre-polymerized catalyst coated with a high molecular weight ethylene polymer (A) and the content of the high molecular weight ethylene polymer (A) is from 0.01 to 5000 g per 1 g of a catalytic component comprising a transition metal compound; and (c) a basic polymerization process that involves the preparation of an olefin polymer having 2 to 12 carbon atoms in the presence of a preactivated catalyst. 26. A method for producing an olefin (co) polymer composition comprising the following steps: (a) a prepolymerization process that includes producing propylene polymer (B) in the presence of a polyolefin production catalyst, wherein said polyolefin production catalyst contains (i) a catalytic component of a transition compound a metal which contains at least a titanium compound, (ii) an organometallic compound (AL1) and an electron donor (E1), said organometallic compound (AL1) is a metal compound alla selected from the group comprising metals belonging to groups I, II, XII, and XIII of the Periodic system published in 1991, the content of said organometallic compound (AL1) is from 0.01 to 1000 mol per 1 mol of transition metal atom, the content said electron donor (E1) is from 0 to 500 mol per mol of a transition metal atom, wherein said propylene polymer (B) is a propylene homopolymer or a propylene-olefin copolymer containing 50 wt.% or more propylene units and having a characteristic matic viscosity (η _B), measured in tetraline at 135 ^o C, equal to at least 15 dl / g, and wherein the prepolymerizing the catalyst comprises a catalyst producing polyolefin coated propylene polymer (B), and the content of the propylene polymer (B) is from 0.01 to 100 g per 1 g of the catalytic component of the transition metal compound; (b) a pre-activating polymerization process that involves producing a high molecular weight ethylene polymer (A) in the presence of said pre-polymerized catalyst to obtain a pre-activated catalyst, wherein said high molecular weight ethylene polymer (A) is an ethylene homopolymer or an ethylene-olefin copolymer containing 50 wt.% or more ethylene units and having an intrinsic viscosity (η _E), measured in tetraline at 135 ^o C, of from 15 to 100 dl / g, said pre-activated catalyst contains a pre-polymerized catalyst coated with a high molecular weight ethylene polymer (A) and a high molecular weight ethylene polymer (A) is from 0.01 to 5000 g per 1 g of the catalytic component of the transition metal compound, and (c) a basic polymerization process which comprises the preparation of an olefin polymer having from 2 to 12 carbon atoms in the presence of: (I) said preactivated catalyst; (II) an organometallic compound (AL2), which is a metal compound selected from the group consisting of metals belonging to groups I, II, XII, and XIII of the Periodic Table published in 1991, the total content of organometallic compounds (AL1) and (AL2 ) is from 0.05 to 5000 mol per 1 mol of a transition metal atom in a preactivated catalyst; and (III) electron donor (E2), the total content of electron donors (E1) and (E2) is from 0 to 3000 mol per 1 mol of transition metal atom.  27. The method of obtaining the composition (co) of the olefin polymer according to item 21, which further includes the step of adding from 0.001 to 2 parts by weight at least one stabilizer selected from the group consisting of a phenolic antioxidant and a phosphorus-containing antioxidant to an olefin (co) polymer after olefin (co) polymerization.  28. A method of obtaining a composition (co) of an olefin polymer, comprising the step of adding from 0 to 2000 parts by weight composition (co) polymer of an olefin obtained by a known method, to 100 parts by weight the composition (co) of the olefin polymer obtained by the method according to item 21. 29. A catalyst for preparing a composition of (o) olefin polymer according to claim 1, comprising a catalytic component of a transition metal compound that contains at least one titanium compound and a high molecular weight ethylene polymer (A) that covers a catalyst component in which a high molecular weight ethylene polymer (A ) has an intrinsic viscosity (η _E), measured in tetraline at 135 ^o C, of from 15 to 100 dl / g, and the content of said high molecular weight ethylene polymer (a) is 0.01 to 5,000 g per 1 g of the catalytic component of a transition metal compound.  30. The olefin (co) polymerization catalyst of claim 29, wherein the catalytic component of the transition metal compound is prepared by combining a transition metal compound of at least one titanium compound and from 0.01 to 1000 mol of an organometallic compound (AL1), where the metal is selected from the group comprising metal belonging to I, II, XII and XIII groups of the Periodic system, published in 1991, per 1 mol of transition metal atom, and from 0 to 500 mol of electron donor (E1) per 1 mol of transition atom metal.  31. The olefin (co) polymerization catalyst of claim 29, wherein the high molecular weight ethylene polymer (A) is an ethylene homopolymer or a copolymer of ethylene with an olefin that contains 50 wt.% Or more of ethylene units. 32. The olefin (co) polymerization catalyst according to Claim 29, wherein the propylene polymer (B) also coates the catalytic component of the transition metal compound, said propylene polymer (B) is a propylene homopolymer or a propylene-olefin copolymer containing 50 wt.% Or more propylene units and having an intrinsic viscosity (η _B ) measured in tetraline at 135 ^° C. of less than 15 dl / g and the content of said propylene polymer (B) is from 0.01 to 100 g per 1 g of the catalytic component of the transition compound metal.  33. The olefin (co) polymerization catalyst according to Claim 29, wherein the catalytic component of the transition metal compound is a titanium-containing solid catalyst component, the main component of which is a titantrichloride composition or titantetrachloride.  34. The olefin (co) polymerization catalyst of claim 29, wherein the organometallic compound (AL1) is an organoaluminum compound.  35. The olefin (co) polymerization catalyst according to claim 30, wherein the electron donor (E1) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur in the molecule, or an organosilicon compound having a Si — O — C bond in the molecule.  36. The olefin (co) polymerization catalyst according to claim 32, wherein the propylene polymer (B) is a propylene homopolymer or a copolymer of propylene with an olefin containing from 2 to 12 carbon atoms.  37. The olefin (co) polymerization catalyst according to claim 30, wherein it further comprises an electron donor (E2), wherein the content of said electron donors (E1) and (E2) is 0 to 3000 moles per 1 mol of transition metal atom in the catalyst.  38. The olefin (co) polymerization catalyst according to claim 37, wherein the electron donor (E2) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur in the molecule, or an organosilicon compound having a Si — O — C bond in the molecule.  39. The olefin (co) polymerization catalyst according to claim 30, wherein it further comprises an organometallic compound (AL2) and an electron donor (E2), wherein in said organometallic compound (AL2) the metal is selected from the group consisting of metals belonging to group I , group II, group XII and group XIII of the periodic system of elements published in 1991, the content of organometallic compounds (AL1) and (AL2) is 0.05 to 5000 moles per 1 mol of transition metal atom in a preactivated catalyst, and the content of electron Norov (E1) and (E2) is 0 - 3000 moles per 1 mol of transition metal atom in a preactivated catalyst.  40. A method of producing a catalyst for (co) polymerizing an olefin according to clause 29, comprising the step of producing a high molecular weight ethylene polymer (A) in the presence of a polyolefin catalyst, wherein said polyolefin catalyst contains (i) a catalytic component of a transition metal compound that contains at least at least one titanium compound, (ii) an organometallic compound (AL1) and an electron donor (E1), the content of said organometallic compound (AL1) is from 0.01 to 1000 mol per 1 mol of titanium atom, and The holding of the indicated electron donor (E1) is from 0 to 500 mol per 1 mol of the titanium atom and in which the high molecular weight ethylene polymer (A) covers the catalytic component of the transition metal, in a ratio of 0.01 to 5000 g of high molecular weight ethylene polymer (A) per 1 g of the catalytic component of the transition metal compound.  41. The method for producing the olefin (co) polymerization catalyst according to claim 40, wherein the catalytic component of the transition metal compound is obtained by combining 0.01 to 1000 moles of the organometallic compound (AL1) and 0 to 500 moles of the electron donor (E1) with respect to 1 mol of the titanium atom wherein said organometallic compound (AL1) contains a metal selected from group I, group II, group XII and group XIII of the periodic table of elements published in 1991.  42. A method of producing a catalyst for (co) polymerizing an olefin according to claim 40, wherein the high molecular weight ethylene polymer (A) is an ethylene homopolymer or a copolymer of ethylene with an olefin containing 50 wt.% Or more of ethylene units. 43. The method of producing the olefin (co) polymerization catalyst according to claim 40, further comprising the step of coating the catalytic component of the transition metal compound with a propylene polymer (B) to the step of coating the catalytic component of the transition metal compound with a high molecular weight ethylene polymer (A), wherein said polymer propylene (B) is a propylene homopolymer or a copolymer of propylene with an olefin containing 50 wt. % or more units of propylene and having an intrinsic viscosity (η _B ) measured in tetraline at 135 ^° C. of less than 15 dl / g, and the content of propylene polymer (B) is from 0.01 to 100 g per 1 g of catalytic component of the transition metal compound.  44. The method for producing the olefin (co) polymerization catalyst according to claim 40, wherein the catalytic component of the transition metal compound is a titanium-containing solid catalyst component, the main component of which is a titanium trichloride composition or titantetrachloride.  45. A method of producing a catalyst for (co) polymerizing an olefin according to claim 40, wherein the organometallic compound (AL1) is an organoaluminum compound.  46. The method of producing the olefin (co) polymerization catalyst according to claim 40, wherein the electron donor (E1) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur in the molecule, or an organosilicon compound having a Si — O — C bond in the molecule.  47. A method of producing a catalyst for (co) polymerizing an olefin according to claim 43, wherein the propylene polymer (B) is a propylene homopolymer or a copolymer of propylene with an olefin containing from 1 to 12 carbon atoms.  48. The method of producing a catalyst for (co) polymerizing an olefin according to claim 40, wherein it further comprises the step of introducing an electron donor (E2) into the catalyst, wherein the content of the electron donor (E1) and (E2) is 0 to 3000 moles per 1 mol of transition metal atom in the catalyst.  49. A method for producing an olefin (co) polymerization catalyst according to claim 48, wherein the electron donor (E2) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur or an organosilicon compound having a Si — O — C bond in the molecule.  50. A method for producing an olefin (co) polymerization catalyst according to claim 40, further comprising the step of adding to the catalyst an organometallic compound (AL2) and an electron donor (E2), wherein said organometallic compound (AL2) comprises a metal selected from the group consisting of metals related to groups I, II, XII, and XIII of the Periodic system published in 1991, the content of organometallic compounds (AL1) and (AL2) is from 0.05 to 5000 mol per 1 mol of transition metal atom in the catalyst, and the content of electron donors (E1) and (E2) is from 0 to 3000 mol per 1 mol of a transition metal atom in a preactivated catalyst. Priority on points and signs:
10/18/1995 according to claim 1, wherein the determination of the number average particle size was introduced from 10/17/1996;
10/18/1995 according to claims 3, 4, 13, 15 - 26, 29 - 50;
08/09/1996 according to claims 14, 27;
10/17/1996 according to claims 2, 5 - 12, 28.

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