JP3309786B2 - Polypropylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene composition containing a stereoregular polypropylene having a specific structure and an α-olefin copolymer. More specifically, the present invention relates to a polypropylene composition which, when used as a molding material, has a very good balance between rigidity and impact resistance, and exhibits high heat resistance and toughness.

[0002]

2. Description of the Related Art Crystalline polypropylene has mechanical properties,
It is widely used in various molding fields because it has excellent chemical resistance and is very useful in balance with economic efficiency. However, when a propylene homopolymer is used as the crystalline polypropylene, the rigidity is increased but the impact resistance is insufficient. Therefore, a method of adding ethylene-propylene rubber, ethylene-propylene-diene rubber, or the like to a propylene homopolymer, or a method of producing a so-called block copolymer by subsequently copolymerizing ethylene and propylene after homopolymerization of propylene. Thus, although the impact resistance has been improved, it is desired to further improve the rigidity-impact resistance balance. Further, there is a strong demand for improved performance of polypropylene, particularly improved heat resistance and high toughness, in order to expand restricted uses of conventional polypropylene.

On the other hand, it is known that isotactic polypropylene can be obtained by polymerizing propylene using a catalyst comprising a combination of a metallocene and an aluminoxane different from a conventional catalyst system. It is also known to produce a so-called block copolymer by homopolymerizing propylene and subsequently copolymerizing ethylene and propylene using a similar catalyst.

JP-A-4-337308 discloses an example in which dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride is used as a metallocene. JP-A-6-287257 discloses dimethylsilyl. Example using bis (methylcyclopentadienyl) hafnium dichloride, JP-A-5-202152
Japanese Patent Application Laid-Open No. 6-206921 and Japanese Patent Application Laid-Open No.
c-ethylenebisindenyl hafnium dichloride,
Examples using rac-dimethylsilylbisindenyl hafnium dichloride and rac-phenylmethylsilylbisindenyl hafnium dichloride and JP-A-6-172414 disclose dimethylsilylenebis (2-methylindenyl) zirconium dichloride and An example using silylene bis (tetrahydroindenyl) zirconium dichloride is described.

[0005]

The propylene / ethylene block copolymers obtained using these metallocenes show some improvement in impact resistance, but still have room for improvement in rigidity and heat resistance. There is. Therefore, in the polypropylene composition obtained by the conventional method, there has been a problem to further improve the balance between rigidity and impact resistance, heat resistance and toughness.

The inventors of the present invention have conducted various studies to solve the above-mentioned problems in the prior art, and as a result, a polypropylene composition containing a stereoregular polypropylene having a specific structure and an α-olefin copolymer has been used as a molding material. The present inventors have found that when used, they have a very good balance between rigidity and impact resistance, and exhibit high heat resistance and toughness, and have reached the present invention.

[0007]

According to the present invention, the present invention contains 20 to 95% by weight of a stereoregular polypropylene and 5 to 80% by weight of an α-olefin copolymer, and the polypropylene has a nuclear magnetic resonance spectrum a) Isotactic pentad fraction (mmmm) of 0.940 to 0.9
95, (b) Syndiotactic pentad fraction (rr
rr) is 0 to 0.01 and (c) 0 to 0.10 mol% of heterogeneous bonds resulting from the 2,1 insertion reaction and the 1,3 insertion reaction.
And (d) a weight average molecular weight (M _w ) of 50,0
00～1,000,000 and (e) a weight average molecular weight number average molecular weight of (M _w) (M _n) for the ratio (M _w / M _n) Yotsute that is 1.5 to 3.8, wherein And the α-olefin copolymer is α-olefin 10 to 90
% And at least one other α-olefin 90
There is provided a polypropylene composition comprising from 10 to 10% by weight.

[0008] The stereoregular polypropylene used in the polypropylene composition of the present invention should satisfy the above requirements (a) to (e). However, a propylene / α-olefin copolymer containing 5% by weight or less of α-olefin can be equally used instead of stereoregular polypropylene as long as the above requirements (a) to (e) are satisfied.
Therefore, as long as the above requirements (a) to (e) are satisfied, the propylene / α-olefin copolymer containing 5% by weight or less of α-olefin is replaced with stereoregular polypropylene to obtain the polypropylene composition of the present invention. It should be understood that the use of the components of the product is also included in the scope of the present invention.

The propylene / α-olefin copolymer usable in the present invention contains 5% by weight or less of α-olefin, and the α-olefin has 2 to 12 carbon atoms.
Α-olefin, preferably ethylene, 1-butene, 4
-Methyl-1-pentene, particularly preferably ethylene, 1
-Butene is used. In addition, not only one kind but also two or more kinds of α-olefins other than propylene can be used in combination, and polyenes can be used in an amount of less than 1% by weight.

Among the requirements for the stereoregular polypropylene used in the present invention, (a) to (c) are calculated based on the measurement results of ¹³ C nuclear magnetic resonance spectrum according to the following method. That is, it is determined by measuring at 67.20 MHz and 130 ° C. using a mixed solution of o-dichlorobenzene / brominated benzene = 8/2 by weight at a polymer concentration of 20% by weight. As a measuring device, for example, JEOL
A JEOL-GX270 NMR measurement device manufactured by Co., Ltd. is used.

In the present invention, "isotactic pentad fraction (mmmm)" and "syndiotactic pentad fraction (rrrr)" are defined by A. Zamberg (A. Z.
ambelli) et al., "Macromolecules 6 , 925 (1973)" means the isotactic and syndiotactic fractions in pentad units in the polypropylene molecular chain measured by ¹³ C nuclear magnetic resonance spectrum. I do. The method for determining the assignment of peaks in the measurement of the ¹³ C nuclear magnetic resonance spectrum followed the assignment proposed in “Macromolecules 8 , 687 (1975)” by A. Zambelli et al.

The isotactic pentad fraction (mmm) of the requirement (a) for the stereoregular polypropylene in the present invention.
As described above, m) is the ratio of propylene monomer units having five consecutive meso bonds present in all propylene monomer units in the polypropylene molecule.
Therefore, this isotactic pentad fraction (mmm
The higher the value of m), the higher the isotacticity.
The above polypropylene has an isotactic pentad fraction (mmmm) of 0.940 to 0.995, preferably 0.990 to 0.995, and particularly preferably 0.960 to 0.995.
0.995.

The syndiotactic pentad fraction (rr) of requirement (b) of the stereoregular polypropylene in the present invention is used.
rr) is the ratio of five consecutive racemic-bonded propylene monomer units present in all propylene monomer units in the polypropylene molecule. Therefore, a lower syndiotactic pentad fraction (rrrr) indicates lower syndiotacticity. In the above polypropylene, the syndiotactic pentad fraction (rrrr) is from 0 to 0.01, preferably from 0 to 0.007, particularly preferably from 0 to 0.004.

In the present invention, "2,1 insertion reaction and 1,1,
"Heterogene bond due to three insertion reactions" means T. Tsutsu
proposed by i) such (POLYMER, 30, 1350 (1989 )) has been 2,1 insertion reaction and 1 in the polypropylene molecular chain measured by ¹³ C nuclear magnetic resonance spectra according to the method,
(3) The percentage of heterogeneous bonds caused by the insertion reaction.

The heterogeneous bond resulting from the 2,1 insertion reaction and the 1,3 insertion reaction of requirement (c) of the stereoregular polypropylene in the present invention is 0 to 0.10 mol%, preferably 0 to 0.08 mol%. %. In addition, when a known ordinary titanium-based catalyst is used for the polymerization of propylene, the polymerization proceeds by a 1,2-insertion reaction, whereas when a known metallocene catalyst is used, a certain degree of a 2,1-insertion reaction is used. And a 1,3 insertion reaction has occurred, and it is known that a certain amount of heterogeneous bonds is present in the obtained polypropylene.

From the above requirements (a) to (c), the stereoregular polypropylene used in the present invention has almost no heterogeneous bond or racemic bond chain, and has a very highly controlled meso bond chain. It can be confirmed that it shows extremely high isotacticity.

Among the requirements for the stereoregular polypropylene in the present invention, the weight average molecular weight (M _w ) of (d) and
The ratio (M _w / M _n ) of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ) of (e) is based on the results of gel permeation chromatography (GPC) measurement according to the following method. calculate. That is, the polymer concentration is 0.05% by weight.
O-dichlorobenzene solution was used, and the column was a mixed polystyrene gel column (for example, PSKgel manufactured by Tosoh Corporation).
GMH6-HT), and measured at 135 ° C. As the measuring device, for example, GPC-150C manufactured by Waters Corporation is used.

The weight average molecular weight (Mw) which is the requirement (d) of the stereoregular polypropylene in the present invention is 50,000.
0 to 1,000,000, preferably 100,00
0 to 1,000,000.

The ratio weight average molecular weight is a requirement of stereospecific polypropylene (e) in the present invention the number average molecular weight of _{(M w) (M n)} (M w / M n) is from 1.5 to 3.8 And preferably 1.5 to 3.5. The ratio of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ) (M _w /
M _n ) is a measure of the molecular weight distribution. A large (M _w / M _n ) ratio results in a wide molecular weight distribution, and a small ratio results in a narrow molecular weight distribution.

The essential requirement of the stereoregular polypropylene in the present invention is the above-mentioned five requirements. However, due to having these structural characteristics, particularly the characteristics of requirements (a) to (c), the present invention The melting point of polypropylene is 155 to 168.
° C, 160-168 ° C, and even 16
2 to 168 ° C.

Here, the melting point of the polypropylene was raised from room temperature to 230 ° C. under a heating condition of 30 ° C./min using a DSC-7 differential scanning calorimeter manufactured by Perkin-Elmer Co., Ltd. for 10 minutes at the same temperature. After holding, at -20 ° C / min -2
After the temperature was lowered to 0 ° C and kept at the same temperature for 10 minutes,
The temperature at which the peak at the time of melting under the temperature increasing condition of ° C./min was defined as the melting point.

The α-olefin copolymer, which is an essential component of the polypropylene composition of the present invention, contains one type of α-olefin in order to obtain a molded article having excellent impact resistance.
90% by weight, preferably 20-90% by weight, and 90-10% by weight of at least one other α-olefin,
Preferably, it must be contained in an amount of 80 to 10% by weight. Further, in order to obtain a molded product having more excellent impact resistance, an α-olefin copolymer obtained by randomly copolymerizing one α-olefin and another α-olefin is preferable. In addition, any of amorphous and crystalline forms can be used as the copolymer.

The α-olefin contained in the α-olefin copolymer is an α-olefin having 2 to 12 carbon atoms, preferably ethylene, propylene, 1-butene, 4-methyl-1-pentene, -Pentene, 1-hexene, 1-octene, particularly preferably ethylene and propylene. As the copolymer, not only two kinds but also three or more kinds of α-olefin copolymers can be used. Further, a copolymer obtained by copolymerizing polyenes in an amount of less than 10% by weight can be used. Can also be used.

Examples of the above-mentioned α-olefin copolymer used in the composition of the present invention include ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene / 1-hexene random copolymer. Coalescence, ethylene / 1-octene random copolymer, ethylene / 1-butene / 1-hexene random copolymer, ethylene / 1-
Butene / 1-octene random copolymer, ethylene / propylene / 1-butene random copolymer and propylene / 1-butene random copolymer, and the like.
Further, the use of two or more of the above is also possible.
It is also possible to use olefin / polyene random copolymers such as propylene / polyene random copolymers and ethylene / propylene / polyene random copolymers.

The polypropylene composition of the present invention has a stereoregularity of 20 to 95% by weight, preferably 50 to 95% by weight.
95% by weight, particularly preferably 80 to 95% by weight, and α-olefin copolymer 5 to 80% by weight, preferably 5 to 80% by weight.
-50% by weight, particularly preferably 5-20% by weight. When the stereoregular polypropylene and the α-olefin copolymer are within the above range, the rigidity-impact balance of the molded article produced by using the obtained polypropylene composition becomes good, and high heat resistance and high heat resistance are obtained. It has both toughness and achieves the object of the present invention.

That is, when the polypropylene composition of the present invention is used as a molding material, it has a flexural modulus of 950.
MPa or higher and Izod impact strength of 115 J / m
² or more, exhibits an excellent balance between rigidity and impact resistance, and has a deflection temperature of 105 ° C. or more and a toughness of 1
It shows high performance of 2.0 MPa or more.

The method for producing the polypropylene composition of the present invention is not particularly limited. Typical methods include (I) a method of producing a stereoregular polypropylene and an α-olefin copolymer and then mixing them using a conventional mixing apparatus, and (II) a method of polymerizing propylene in the presence of a catalyst. Subsequently, a method for producing the polypropylene composition of the present invention at once can be exemplified by a multi-stage polymerization method in which an α-olefin is copolymerized in a state where polypropylene and a catalyst are mixed.

(I) Stereoregular polypropylene and α-
A method for producing each of the olefin copolymers and then mixing them using a usual mixing apparatus. First, as for the method for producing the stereoregular polypropylene used in the present invention, any method can be adopted as long as the obtained polypropylene satisfies the above requirements. Although it is possible, at this time, a method of producing using a metallocene catalyst can be adopted. This method will be described below.

The metallocene catalyst used in this method is a catalyst comprising the following compounds (A) and (B) or a catalyst comprising the following compounds (A), (B) and (C). Compound (A): a transition metal compound having at least one π-electron conjugated ligand. Compound (B): aluminoxane, the transition metal compound (A)
At least one compound selected from an ionic compound and a Lewis acid that react with to form an ionic complex. Compound (C): an organoaluminum compound.

The compound (A) is usually called a metallocene and has a π-electron conjugated ligand, that is, an η-cyclopentadienyl structure, an η-benzene structure, an η-cycloheptatrienyl structure, or an η-cyclooctaene. A transition metal complex in which at least one or more ligands having a tetraene structure are coordinated with a transition metal.

Although any metallocene can be used in the present invention as long as an isotactic polypropylene having the above-mentioned requirements can be obtained, the preferred metallocene is represented by the general formula Q (C ₅ H _4-m R ¹ _m ) _{(C 5 H 4-n R} 2 n) M
In XY _{[wherein, (C 5 H 4-m} R 1 m) and _{(C 5 H 4-n R} 2 n)
Each represents a substituted cyclopentadienyl group; m and n are integers of 1 to 3; R ¹ and R ² may be the same or different; each is a hydrocarbon group having 1 to 20 carbon atoms; Q represents a hydrocarbon group containing two or more carbon atoms on a cyclopentadienyl ring or a hydrocarbon group forming one or more hydrocarbon rings which may be substituted by a hydrocarbon; (C ₅ H _4-m R ¹ _m ) and (C ₅ H
_{4-n represents} a divalent, hydrocarbon, unsubstituted silylene or hydrocarbon-substituted silylene group bridging R ² _n ), wherein M represents titanium, zirconium or hafnium, and X and Y
May be the same or different, and each represents a hydrogen, a halogen, or a hydrocarbon group].

More preferably, in the above general formula:
R ¹ and R ² may be the same or different, each is an alkyl group having 1 to 20 carbon atoms, Q is a dialkylsilylene group, M is zirconium or hafnium, and X and Y are the same or different. Alternatively, a chiral transition metal compound showing a halogen or a hydrocarbon group may be used.

An example of such a metallocene is dimethylsilylene (3-t-butylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, rac-ethylenebis (indenyl) zirconium dimethyl, rac-
Ethylenebis (indenyl) zirconium dichloride, rac-dimethylsilylenebis (indenyl) zirconium dimethyl, rac-dimethylsilylenebis (indenyl) zirconium dichloride, rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (tetrahydroindenyl) )
Zirconium dichloride, rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) ) Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-
Ethylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl -4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2
-Methyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-
4-naphthylindenyl) zirconium dichloride,
rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4, 5-benzoindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride Rac-dimethylsilylenebis (2-ethyl-4-
Phenylindenyl) zirconium dichloride, ra
c-dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl)
Hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl)
Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) hafnium dichloride, dimethylsilylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) Zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethyl Cyclopentadienyl) titanium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (2,3,
5-trimethylcyclopentadienyl) (2 ′, 4 ′,
5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2 , 3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dimethyl.

Among these metallocenes, particularly preferred are dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride and dimethylsilylene (2,4-dimethyl Cyclopentadienyl) (3 ′, 5 ′
-Dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethyl Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Trimethylcyclopentadienyl) hafnium dichloride and dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dimethyl.

In the synthesis of these chiral metallocenes, a non-chiral metallocene having a non-chiral structure may be by-produced. However, in actual use, it is not necessary that all of the metallocene be a chiral metallocene, and the meso-form may be mixed. It does not matter. However, when using a mixture with the meso form, it depends on the mixing amount of the meso form and the propylene polymerization activity,
In some cases, it is necessary to remove the atactic polypropylene polymerized from the meso form by a known method such as solvent extraction so that the obtained polypropylene satisfies the above essential requirements.

The transition metal compound (A) can be used as a catalyst by combining it with the compound (B) or with the compounds (B) and (C). It is also possible. As such a fine particle carrier, a granular or spherical fine particle solid which is an inorganic or organic compound and has a particle diameter of 5 to 300 μm, preferably 10 to 200 μm is used.

Among them, as the inorganic compound used for the carrier, SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZnO and the like or a mixture thereof, for example, SiO ₂ -Al
₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO _2-
Al ₂ O ₃ -MgO and the like. In these, S
Those containing iO ₂ or Al ₂ O ₃ as a main component are preferred.

The organic compounds used for the carrier include ethylene, propylene, 1-butene and 4-methyl-
Examples thereof include a polymer or copolymer of an α-olefin having 2 to 12 carbon atoms such as 1-pentene, and a polymer or copolymer of styrene or a styrene derivative.

Compound used as a catalyst component in the production of stereoregular polypropylene used in the composition of the present invention
(B) is at least one compound selected from aluminoxane, an ionic compound which reacts with the transition metal compound (A) to form an ionic complex, and a Lewis acid.

Aluminoxane is an organoaluminum compound represented by the following general formula (1) or (2).

[0041]

Embedded image

Here, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
Alkyl group such as ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, allyl group, 2-methylallyl group, propenyl group, isopropenyl group, 2-
Examples thereof include an alkenyl group such as a methyl-1-propenyl group and a butenyl group, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and an aryl group. Among these, an alkyl group is particularly preferred, and each R ³ may be the same or different. P is an integer of 4 to 30, preferably 6 to 30, and particularly preferably 8 to 30.

The above-mentioned aluminoxanes can be prepared under various known conditions. Specifically, the following method can be exemplified. (I) A method in which a trialkylaluminum is directly reacted with water using an organic solvent such as toluene or ether. (Ii) A method of reacting a trialkylaluminum with a salt having water of crystallization, such as copper sulfate hydrate or aluminum sulfate hydrate. (Iii) A method of reacting trialkylaluminum with moisture impregnated in silica gel or the like. (Iv) A method in which trimethylaluminum and triisobutylaluminum are mixed and directly reacted with water using an organic solvent such as toluene or ether. (V) A method in which trimethylaluminum and triisobutylaluminum are mixed and reacted with a salt having water of crystallization, for example, copper sulfate hydrate or aluminum sulfate hydrate. (Vi) A method of impregnating silica gel or the like with water, reacting triisobutylaluminum, and further reacting trimethylaluminum.

Examples of the ionic compound and Lewis acid which form an ionic complex by reacting with the transition metal compound (A) include JP-A-1-501950 and JP-A-2001-501950.
No. 502036, JP-A-3-179005,
JP-A-3-179006, JP-A-3-20770
No. 3, JP-A-3-207704 and the like.

The ionic compound usable in the present invention is a salt of a cationic compound and an anionic compound. The anion reacts with the transition metal compound (A) to cationize the transition metal compound and form an ion pair, thereby stabilizing the transition metal cation species.
Examples of such anions include an organic boron compound anion and an organic aluminum compound anion.
Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.

Of these, ionic compounds containing a boron atom as an anion are preferable. Specifically, triethylammonium tetrakis (pentafluorophenyl) borate and triethylammonium tetrakis (pentafluorophenyl) borate are preferred.
n-butylammonium, triphenylammonium tetrakis (pentafluorophenyl) borate, methylanilium tetrakis (pentafluorophenyl) borate, dimethylanilium tetrakis (pentafluorophenyl) borate, trimethylanilium tetrakis (pentafluorophenyl) borate, etc. No.

As the Lewis acid, a boron atom-containing Lewis acid is preferable, and a compound represented by the following general formula can be used. BR ⁴ R ⁵ R ⁶ (wherein R ⁴ , R ⁵ and R ⁶ each independently have a substituent such as a fluorine atom, an alkyl group or a fluorine atom, a methyl group, a trifluoromethyl group, etc. Indicates a good phenyl group).

Examples of the compound represented by the above general formula include trifluoroboron, tri (n-butyl) boron, triphenylboron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [ (4-fluoromethyl) phenyl] boron, tris (3,5-difluorophenyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (pentafluorophenyl) boron and the like. Fluorophenyl) boron is particularly preferred.

Here, the transition metal compound (A) and the compound (B)
When aluminoxane is used as the compound (B), the ratio of the transition metal atom in the transition metal compound (A) is 1
The Al atom in the aluminoxane is 1 to 50,0 mol
The range is from 00 mol, preferably from 10 to 30,000 mol, particularly preferably from 50 to 20,000 mol.

When an ionic compound or Lewis acid is used as the compound (B), the ionic compound or Lewis acid is used in an amount of 0.01 to 2,2 mol per mol of the transition metal atom in the transition metal compound (A). 000 mol, preferably 0.1 to 50
It is used within a range of 0 mol. Any of the above compounds (B) can be used alone or in combination.

Further, the (C) organoaluminum compound used as one component of the polymerization catalyst according to the present invention includes:
There is a compound represented by the following general formula. ^{_{AlR 7 t R 8 t '×}} 3- (t + t') ( wherein, R ⁷ and R ⁸ is an alkyl group having 1 to 10 carbon atoms,
Represents a hydrocarbon group such as a cycloalkyl group or an aryl group or an alkoxy group, X represents a halogen atom, and t and t 'represent any number of 0 <t + t'≤3).

Examples of the compound represented by the above general formula include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, dimethylaluminum chloride, dimethylaluminum bromide , Diethylaluminum chloride, dialkylaluminum halides such as diisopropylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide,
Examples thereof include alkyl aluminum sesquihalides such as isopropyl aluminum sesquichloride, and one or more kinds thereof can be used.

The amount of the organoaluminum compound to be used is such that the Al atom in the organoaluminum compound is 0 to 10,000 mol, preferably 0 to 5,000 mol, particularly 0 to 5,000 mol per mol of the transition metal atom in the transition metal compound (A). Preferably 0 to 3.0
The range is 00 mol.

Thus, compound (A) and compound (B)
By using a specific catalyst consisting of a combination of the compounds (A), (B) and (C), propylene is polymerized to produce a stereoregular polypropylene used in the composition of the present invention. However, a known propylene polymerization process can be used as the propylene polymerization method, butane, pentane, hexane, heptane, aliphatic hydrocarbons such as isooctane, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, Slurry polymerization method in which propylene is polymerized in an inert solvent such as aromatic hydrocarbons such as toluene, xylene and ethylbenzene, gasoline fraction and hydrogenated diesel oil fraction, bulk polymerization using propylene itself as a solvent, and propylene A gas-phase polymerization method in which the polymerization is carried out in a gas phase can be used.

In the polymerization of propylene, the above-mentioned catalyst comprises the compound (A) and the compound (B), or the compound (A),
Compound (B) and compound (C) previously mixed in an inert solvent may be supplied to the polymerization reaction system, or compound (A) and compound (B), or compound (A) may be added to the polymerization reaction system. ,
The compound (B) and the compound (C) may be supplied separately. Furthermore, prior to the main polymerization of propylene, a small amount of α-olefin is added to a compound (A) and compound (B) or a catalyst obtained by combining compound (A), compound (B) and compound (C) in an inert solvent. Specifically, the α-olefin is used in an amount of 1 g to 10 mol per mol of the transition metal in the compound (A).
After the polymerization reaction of about kg,
Carrying out the main polymerization of propylene is also effective in obtaining polypropylene in a good particle shape, and is included in the scope of the present invention.

As the α-olefin which can be used for the above preactivation, an α-olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, propylene, butene, pentene, hexene, octene, 4-octene, Methyl-1-
Pentene, etc., particularly ethylene, propylene, 4
-Methyl-1-pentene is preferably used.

The specific catalyst used in the present invention or the preactivated specific catalyst thus prepared is used for the polymerization of propylene by the above-mentioned polymerization method. Polymerization conditions similar to those for propylene polymerization using a Ziegler-based catalyst described above are employed. That is, the polymerization temperature is from -50 to 150 ° C, preferably from -10 to 100 ° C, and the polymerization pressure is from atmospheric pressure to
The reaction is carried out at 7 MPa, preferably 0.2 MPa to 5 MPa in the presence of hydrogen, usually for about 1 minute to 20 hours.
The amount of hydrogen is 0.1 kPa to 5 MPa, preferably 1 kPa to 5 MPa, as the hydrogen partial pressure in the gas phase in the polymerization vessel.
3 MPa is an appropriate amount.

After the polymerization of propylene is completed, if necessary, post-treatment steps such as a known catalyst deactivation treatment step, catalyst residue removal step, and drying step are performed, and then the stereoregular polypropylene used in the present invention is obtained. The polypropylene must have the above five requirements. Unless these requirements are satisfied, the object of the present invention cannot be achieved.

That is, if the above-mentioned metallocene is used and propylene is polymerized under the above-mentioned polymerization conditions, the stereoregular polypropylene used in the present invention is not always obtained. Depending on the type of metallocene, the optimum polymerization may not be obtained. You need to select a condition. As the optimum polymerization conditions, a relatively low polymerization temperature is often selected in the range of the polymerization conditions described above.

The method for producing the α-olefin copolymer used in the present invention is not particularly limited, and a known copolymerization method can be used. An α-olefin copolymer obtained by random copolymerization of an α-olefin under similar polymerization conditions using a catalyst similar to that for producing the above-mentioned polypropylene used in the composition of the present invention is used. This is also a preferred embodiment of the present invention.

The composition of the present invention can be produced by mixing a predetermined amount of the polypropylene and the α-olefin copolymer produced as described above, and then sufficiently kneading them.
Examples of the mixing device include a high-speed stirring device such as a Henssel mixer (trade name) and a super mixer, and examples of the kneading device include a Banbury mixer, a roll, a co-kneader, and a single-screw or twin-screw extruder. The mixing conditions are not limited. For example, mixing can be performed at room temperature to 100 ° C, preferably at room temperature to 60 ° C, for 1 minute to 1 hour, preferably 3 minutes to 30 minutes. The kneading conditions are not limited, but, for example, a residence time in the extruder of 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes can be used. 180-300 ° C as kneading temperature,
Preferably, 200-280 degreeC can be illustrated.

(II) After the propylene is polymerized in the presence of a catalyst, the polypropylene composition of the present invention is formed at once by a multistage polymerization method in which α-olefin is copolymerized in a state where the polypropylene and the catalyst are mixed. Production Method The catalyst exemplified in the above method (I) or the preactivated specific catalyst is used in the first-stage polymerization or copolymerization mainly using propylene by the polymerization method described above. As the polymerization conditions in the one-stage polymerization or copolymerization, the same polymerization conditions as in the polymerization of propylene with a known Ziegler catalyst are usually employed. That is, polymerization is -50 to 150 ° C.
Preferably at a temperature of -10 to 100 ° C and atmospheric pressure to 7M
It is usually carried out at a pressure of Pa preferably 0.2 MPa to 5 MPa in the presence of hydrogen for about 1 minute to 20 hours. In addition,
The amount of hydrogen is 0.1 k as the partial pressure of hydrogen in the gas phase in the polymerization vessel.
An appropriate amount is Pa to 5 MPa, preferably 1 kPa to 3 MPa.

In the above first stage polymerization or copolymerization, the polymerization is carried out so that the polypropylene satisfying all the above requirements (a) to (e) accounts for 20 to 95% by weight of the target polypropylene composition. Conditions need to be adjusted.
The first stage polymerization or copolymerization can be carried out in multiple stages.

Following the first stage polymerization or copolymerization,
In the second stage, the copolymerization of two or more α-olefins is carried out in one or more stages under the same range of polymerization conditions as in the first stage. Here, one stage of polymerization means a continuous or temporary supply break of the monomer.

In the second stage copolymerization, the α-olefin copolymer having an α-olefin content other than propylene of 10 to 90% by weight accounts for 5 to 80% by weight of the total composition. Conditions need to be adjusted.

After the completion of the second-stage copolymerization, if necessary, post-treatments such as known catalyst deactivation treatment, removal of catalyst residues, and drying are performed, and then the polypropylene composition of the present invention is obtained.

The thus obtained polypropylene composition of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, an inorganic or organic material. After blending various additives such as a filler and various synthetic resins, the mixture is heated and melt-kneaded using a melt-kneading machine, and further provided as a pellet cut into granules.

These pellet-shaped molding materials are molded by various known polypropylene molding methods, for example, techniques such as injection molding, extrusion molding, foam molding, and hollow molding. Various industrial injection molded parts, various containers, Various molded products such as a non-stretched film, a uniaxially stretched film, a biaxially stretched film, a sheet, a pipe, and a fiber can be manufactured.

[0069]

Next, the present invention will be described specifically with reference to examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. (1) Isotactic pentad fraction (mmmm):
It was measured by the method described above. (2) Syndiotactic pentad fraction (rrr
r): Measured by the method described above. (3) Amount of heterogeneous binding (IV): measured by the method described above. The lower measurable value was 0.02 mol%. (4) Weight average molecular weight ( _Mw ): Measured by the method described above. (5) Number average molecular weight ( _Mn ): Measured by the method described above. (6) Melting point: measured by the method described above (unit: ° C.). (7) Rigidity: A JIS type evaluation test piece was prepared from the polypropylene composition using an injection molding machine at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C., and the test piece was placed in a room with a relative humidity of 50% and a room temperature of 23 ° C. After leaving for 72 hours, JISK7203
The flexural modulus was measured (unit: MPa). (8) Impact resistance: An evaluation test piece was prepared in the same manner as in (7), and the Izod impact strength was measured according to JIS K7210 (unit: J / m ² ). (9) Heat resistance: An evaluation test piece was prepared in the same manner as in (7),
According to JIS K7207, the deflection temperature (HDT) under a stress of 0.451 MPa was measured and used as a measure of heat resistance.
The higher the temperature (HDT), the better the heat resistance (unit: ° C.). (10) Toughness: In a uniaxial tensile test of an evaluation test piece, it was considered that the material strength up to the fracture after the yield point represents toughness, and (strength at break-strength at yield) was used as a measure of toughness.
That is, the composition pellets obtained in the same manner as in the above (7) were heated and melted for 3 minutes at 230 ° C. and 4.0 MPa in a press machine, and then melted at 30 ° C. and 14.8 MPa. After cooling for 0.5 minutes, the thickness taken out of the mold is 0.5mm
A test piece having a length of 50 mm and a width of 6 mm was punched out from the compression-molded sheet. Using a Toyo Seiki strograph, the test piece was stretched in the longitudinal direction at a displacement rate of 10 mm / min at 40 ° C., and the yield point strength at that time was defined as Sy (unit: MPa). Next, the necked portion of the tensile test specimen whose yield point strength was measured was cut with scissors, and then the test specimen was stretched in the longitudinal direction again at 40 ° C. at a displacement speed of 10 mm / min. The strength at which the test piece broke was defined as the breaking strength Sb (unit: MPa). Here, (Sb-Sy) was used as a measure of toughness (unit: MPa). The higher the value, the higher the toughness.

Example 1 (1) Production of stereoregular polypropylene A stainless steel polymerization vessel equipped with a stirrer and having an inner volume of 100 dm ^{3 and having} a stirrer was replaced with nitrogen gas, and then 50 dm ³ of n-hexane was introduced into the polymerization vessel. , Methylaluminoxane in toluene solution (manufactured by Tosoh Akzo Co., Ltd., trade name: MMAO, concentration:
2 mol / dm ³ ) as 7.6 mol in terms of Al atom, and chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) hafnium as a metallocene Dichloride 1.
48 mmol and meso-form dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 3', 5'-
A mixture of 0.05 mmol of trimethylcyclopentadienyl) hafnium dichloride at 20 ° C. with 1 dm ³ of toluene
Was put in. Subsequently, the temperature in the polymerization vessel was set to 30 ° C., and hydrogen was supplied so that the hydrogen partial pressure in the gas phase portion in the polymerization vessel became 0.1 MPa, and then the pressure in the polymerization vessel was reduced to 0.4 MPa.
Propylene was continuously supplied into the polymerization vessel for 4 hours so as to maintain the above-mentioned condition, thereby polymerizing propylene. During the polymerization, the temperature in the polymerization vessel was kept at 30 ° C. After the polymerization was completed, unreacted propylene was discharged from the polymerization vessel, and then 2-propanol ³ dm ³
Was charged into a polymerization vessel, and stirred at 30 ° C. for 10 minutes to deactivate the catalyst. Subsequently, an aqueous solution of hydrogen chloride (concentration: 12mo
was added l / dm ³⁾ 0.2dm ³ and methanol 8dm ^3, 6
Treated at 0 ° C. for 30 minutes. After the treatment, the stirring was stopped and the aqueous phase was removed from the lower part of the polymerization vessel. Then, the same operation was repeated by adding the same amount of aqueous hydrogen chloride solution and methanol. Then, an aqueous solution of sodium hydroxide (concentration: 5 mol / dm ³ ) was added.
02Dm ^3, water 2 dm ^3, and the methanol was 2 dm ³ added,
The mixture was stirred at 30 ° C. for 10 minutes. After post-treatment, except for the aqueous phase portion from the polymerization reactor under stirring was stopped, additional water 8Dm ³
After stirring for 10 minutes at 30 ° C. and removing the aqueous phase twice, the polymer slurry was extracted from the polymerization vessel, filtered and dried to obtain 5.2 kg of stereoregular polypropylene used in the present invention. I got The physical properties of the obtained polypropylene were measured by the methods described above, and the results are shown in Table 1.

(2) Production of α-olefin copolymer (ethylene / propylene copolymer) In (1), toluene was replaced with 50 dm ^{3 of} n-hexane.
And a gaseous mixture consisting of 35 mol% of propylene and 65 mol% of ethylene was continuously supplied to the polymerization reactor at a supply rate of 8 dm ³ / min without adding hydrogen, instead of propylene. A part of the mixed gas present in the gas phase in the polymerization vessel was polymerized through a valve attached to the polymerization vessel so as to maintain the temperature at 50 ° C. and maintain the pressure in the gas phase in the polymerization vessel at 0.4 MPa. (1) Except for performing random copolymerization of ethylene and propylene while continuously discharging outside the vessel,
The same polymerization operation and purification operation as those described above were performed to obtain an α-olefin copolymer dissolved in toluene. Subsequently, the temperature in the polymerization vessel was raised to 60 ° C., and then reduced pressure to 40 ° C.
The dm ³ toluene was distilled off. Further, the temperature in the polymerization vessel was set to 30
After the temperature was lowered to 70 ° C., 70 dm ³ of methanol was added to obtain 2.5 kg of an amorphous ethylene / propylene copolymer consisting of 53.8% by weight of ethylene and 46.2% by weight of propylene.
The amorphous ethylene / propylene copolymer was taken out of the polymerization vessel and crushed into flakes.

(3) Production of polypropylene composition 4.6 kg of the polypropylene obtained in (1), 0.7 kg of the amorphous ethylene / propylene copolymer obtained in (2), tetrakis [methylene-3- (3 ′) -5'-di-t-butyl-4 '
-Hydroxyphenyl) propionate] methane 5.3
g and 5.3 g of calcium stearate were mixed to prepare a polypropylene composition containing 86.8% by weight of polypropylene and 13.2% by weight of an ethylene / propylene copolymer. This composition was formed into pellets using a single screw extrusion granulator set at a screw diameter of 40 mm and an extrusion temperature of 230 ° C. The mechanical properties of the obtained composition in a pellet state were measured by the method described above, and the results are shown in Table 1.

Example 2 (1) Production of Stereoregular Polypropylene A stainless steel polymerization vessel equipped with a stirrer blade and having an inner volume of 100 dm ^{3 and having} a stirrer was replaced with nitrogen gas, and then a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) ,Product name:
MMAO, concentration: 2 mol / dm ³ ) in terms of Al atom, 0.5 m
ol, hydrogen partial pressure in the polymerization vessel at 20 ° C is 0.06MP
After hydrogen was charged into the polymerization reactor so as to obtain a, and then 30 kg of liquefied propylene was supplied, chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5) was used as a metallocene. '-Trimethylcyclopentadienyl) zirconium dichloride (0.033 mmol) and dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 3 ', 5'-trimethylcyclopentadienyl) zirconium as meso form Dichloride 0.
A 002 mmol mixture was injected into the polymerization vessel together with 0.1 dm ³ of toluene at 20 ° C. by pressurizing with nitrogen to initiate polymerization of propylene. During the polymerization, the temperature in the polymerization vessel was kept at 30 ° C.
4 hours after the start of polymerization, 2-propanol 3 dm
³ was injected into the polymerization vessel and the polymerization was terminated at 30 ° C. for 5 minutes. After that, unreacted propylene was discharged from the polymerization vessel to the outside. Subsequently, 50 dm ³ of n-hexane was charged into the polymerization vessel, and after that, the same post-treatment as in Example 1 was performed to obtain 6.6 kg of stereoregular polypropylene used in the present invention. The physical properties of the obtained polypropylene were measured by the methods described above, and the results are shown in Table 1.

(2) Production of α-olefin copolymer (ethylene / propylene copolymer) Except that in (2) of Example 1, a mixed gas consisting of 40 mol% of propylene and 60 mol% of ethylene was supplied into the polymerization vessel. In the same manner, an amorphous ethylene / propylene copolymer (ethylene content: 46.0% by weight) was obtained.

(3) Production of polypropylene composition 4.25 kg of stereoregular polypropylene obtained in (1), (2)
0.75 k of the amorphous ethylene / propylene copolymer obtained in
g, tetrakis [methylene-3- (3'-5'-di-t
-Butyl-4'-hydroxyphenyl) propionate] methane 5.0 g and calcium stearate 5.0 g
g was mixed to prepare a polypropylene composition containing 85% by weight of polypropylene and 15% by weight of an ethylene / propylene copolymer. This composition is screwed 40 mm in diameter
The pellets were formed using a single screw extrusion granulator set at an extrusion temperature of 230 ° C. The mechanical properties of the obtained composition in a pellet state were measured by the method described above, and the results were shown in Table 1.
Shown in

Comparative Example 1 As a metallocene, a chiral dimethylsilylene (2,4-
Example 1 except that dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride was used and the polymerization temperature was 70 ° C.
Propylene was polymerized in the same manner as in (1) to obtain 6.6 kg of polypropylene. About the obtained polypropylene,
Physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1. An amorphous ethylene / propylene copolymer (ethylene content: 45.0% by weight) was obtained in the same manner as in (2) of Example 1. When an attempt was made to obtain a pellet of the polypropylene composition in the same manner as in (3) of Example 1, since the molecular weight of the polypropylene component was too low, the molten resin dripped from the outlet of the granulator and the desired pellet was obtained. Did not.

Example 3 After a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 100 dm ³ and equipped with a stirrer was replaced with nitrogen gas, 50 dm ³ of n-hexane and a toluene solution of methylaluminoxane (Tosoh Akzo Co., Ltd.) were introduced into the polymerization vessel. Product name: MMAO, concentration:
2 mol / dm ³ ) as 7.6 mol in terms of Al atom, and chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) hafnium as a metallocene Dichloride 1.
48 mmol and meso-form dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 3', 5'-
A mixture of 0.05 mmol of trimethylcyclopentadienyl) hafnium dichloride is mixed with 1 dm ³ of toluene for 20 minutes.
Charged at ° C. Subsequently, the temperature in the polymerization vessel was set to 30 ° C., and hydrogen was supplied so that the hydrogen partial pressure in the gas phase portion in the polymerization vessel became 0.1 MPa, and then the pressure in the polymerization vessel was reduced to 0.4 MPa.
Propylene was continuously supplied into the polymerization vessel for 4 hours so that the first stage polymerization was carried out. During the polymerization, the temperature in the polymerization vessel was kept at 30 ° C.

After a lapse of 4 hours, unreacted propylene and hydrogen are discharged from the polymerization vessel, the temperature in the polymerization vessel is set to 50 ° C., and 65 mol% of propylene and ethylene are adjusted so that the pressure in the polymerization vessel is maintained at 0.8 MPa. A mixed gas of 35 mol% was continuously supplied into the polymerization vessel for 5 minutes to perform the second stage copolymerization. During the polymerization, the temperature in the polymerization vessel was kept at 50 ° C. After the completion of the copolymerization, ³ dm ³ of 2-propanol was charged into the polymerization vessel and stirred at 30 ° C. for 10 minutes to deactivate the catalyst. Subsequently, an aqueous solution of hydrogen chloride (concentration: 12 mol / d
m ³⁾ was added 0.2Dm ³ and methanol 8dm ^3, 60 ℃
For 30 minutes. After the treatment, the stirring was stopped and the aqueous phase was removed from the lower part of the polymerization vessel. Then, the same operation was repeated by adding the same amount of aqueous hydrogen chloride solution and methanol. Then, an aqueous solution of sodium hydroxide (concentration: 5 mol / dm ³ ) 0.02 d
m ^3, water 2 dm ^3, and the methanol was 2 dm ³ added, 30 ° C.
For 10 minutes. After the treatment, the stirring was stopped and the aqueous phase was removed from the lower part of the polymerization reactor. Then, 8 dm ³ of water was further added, the mixture was stirred at 30 ° C. for 10 minutes, and the operation of removing the aqueous phase was repeated twice. After raising the temperature inside to 50 ° C,
Under reduced pressure, hexane was distilled out of the polymerization vessel, and the polypropylene composition of the present invention containing 86.7% by weight of polypropylene and 13.3% by weight of α-olefin copolymer 6.
0 kg was obtained. The mechanical properties of the obtained polypropylene composition were measured by the method described above, and the results are shown in Table 1.

[0079]

[Table 1]

Comparative Example 2 The procedure of Example 3 was repeated, except that the metallocene and methylaluminoxane were used as the catalysts. The magnesium chloride supported titanium catalyst component obtained in the same manner as in Example 3 of JP-A-62-104812 was used. Using a catalyst obtained by combining 1.0 mmol in terms of Ti, 150 mmol of triethylaluminum, and 30 mmol of diisopropyldimethoxysilane as the third component of the catalyst, the hydrogen partial pressure before the start of polymerization was 0.0
Propylene was polymerized in the same manner except that the polymerization pressure was 4 MPa, the polymerization pressure was 0.8 MPa, and the polymerization temperature was 70 ° C.

After the polymerization of propylene, the temperature in the polymerization vessel was lowered to 30 ° C., and unreacted hydrogen and propylene in the polymerization vessel were discharged to the outside of the polymerization vessel, and then the inside of the polymerization vessel was replaced with nitrogen twice. Further, a part of the polypropylene slurry in the polymerization vessel was taken out and dried, and then the physical properties of the polypropylene were measured. Subsequently, in a state where the polypropylene slurry (including the catalyst) is present in the polymerization reactor, hydrogen is supplied to the polymerization reactor in a volume of 1.4 liters, and then the temperature in the polymerization reactor is increased to 60 ° C. Was simultaneously supplied at 0.56 kg / hr and propylene gas at 1.25 kg / hr, and ethylene-propylene random copolymerization was carried out for 2 hours. After the completion of the copolymerization, the temperature in the polymerization reactor was lowered to 30 ° C., and unreacted hydrogen, ethylene and propylene in the polymerization reactor were discharged outside the polymerization reactor. Further take out the slurry in the polymerization vessel from the polymerization vessel,
After being separated into most of the solvent and the block copolymer (including a small amount of solvent) by centrifugation, the copolymer portion was heated and dried with heating nitrogen at 100 ° C. to obtain an ethylene-propylene block copolymer powder. . The mechanical properties of the obtained block copolymer were measured by the method described above, and the results are shown in Table 2.

Example 4 A stainless steel polymerization vessel equipped with a stirrer and having an inner volume of 100 dm ^{3 and having} a stirrer was replaced with nitrogen gas, and then a toluene solution of methylaluminoxane (trade name: M, manufactured by Tosoh Akzo Co., Ltd.)
MAO, concentration: 2 mol / dm ³ ) in terms of Al atom
1, the hydrogen partial pressure in the polymerization vessel at 20 ° C. is 0.06 MPa
Hydrogen was charged into the polymerization reactor so as to obtain 30 kg of liquefied propylene, and then chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5 ′) was used as a metallocene. -Trimethylcyclopentadienyl) zirconium dichloride (0.033 mmol) and meso-form dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 3', 5'-trimethylcyclopentadienyl) zirconium dichloride 0.0
A 02 mmol mixture was injected into the polymerization vessel together with 0.1 dm ³ of toluene at 20 ° C. by pressurizing with nitrogen to initiate polymerization of propylene. During the polymerization, the temperature in the polymerization vessel was kept at 30 ° C.

After 4 hours, the temperature in the polymerization vessel was lowered to 30 ° C., and after unreacted propylene was discharged from the polymerization vessel, 50 dm ³ of n-hexane was charged into the polymerization vessel. ° C, and 65 mol% of propylene and 35 mol of ethylene so that the pressure in the polymerization vessel is maintained at 0.6 MPa.
% Of the mixed gas was continuously supplied into the polymerization vessel for 5 minutes to perform the second-stage copolymerization. During the polymerization, the temperature in the polymerization vessel was kept at 40 ° C. After completion of the copolymerization, Example 3
Was carried out in the same manner as in the above to obtain a polypropylene composition of the present invention containing 83.7% by weight of polypropylene and 16.3% by weight of an α-olefin copolymer. The mechanical properties of the obtained polypropylene composition were measured by the method described above, and the results are shown in Table 2.

Comparative Example 3 In Example 4, chiral dimethylsilylene (2,4-dimethylcyclopentadienyl) was used as the metallocene.
(3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride was used, and the polymerization temperature in the first stage was 7
A propylene / α-olefin block copolymer was obtained in the same manner as in Example 4 except that the temperature was changed to 0 ° C. When trying to obtain pellets for measuring the mechanical properties of the obtained block copolymer, the molecular weight of the polypropylene component was too low, so the molten resin dripped from the granulator outlet,
The desired pellet was not obtained.

Comparative Example 4 An ethylene / propylene block copolymer was produced according to Example 2 described in JP-A-4-337308. The mechanical properties of the obtained block copolymer were measured by the method described above, and the results are shown in Table 2.

[0086]

[Table 2]

[0087]

As is clear from the above-described embodiment,
Since the polypropylene composition of the present invention has both high heat resistance and high toughness in addition to a good rigidity-impact resistance balance, it is possible to expand the application fields limited by conventional polypropylene.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tsutomu Shioda 2--17, Tatsumidaihigashi, Ichihara-shi, Chiba (56) References JP-A-8-12827 (JP, A) JP-A-7-196734 (JP, A JP-A-10-1573 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08F 4/64-4/69

Claims (7)

(57) [Claims] The present invention contains 20 to 95% by weight of a stereoregular polypropylene and 5 to 80% by weight of an α-olefin copolymer, and the polypropylene is characterized by (a) isotactic pentad fraction ( mmmm) is 0.940 to 0.995, (b) the syndiotactic pentad fraction (rrrr) is 0 to 0.01, and (c) a heterogeneous bond resulting from the 2,1 insertion reaction and the 1,3 insertion reaction. Is 0
0.10 mol%, and (d) a weight average molecular weight (M
_w) is 50,000 to 1,000,000, and (e) a weight average molecular weight number average molecular weight of (M _w) (ratio _{M n) (M w / M} n) is at 1.5 to 3.8 And wherein said α-olefin copolymer comprises 10 to 90% by weight of α-olefin and 10 to 90% by weight of at least one other α-olefin, wherein the polypropylene comprises , (A) a transition metal compound having at least one π-electron conjugated ligand, and (B) an aluminoxane, an ionic compound which reacts with the transition metal compound to form an ionic complex, and one selected from Lewis acids A polymer obtained by polymerizing propylene using a catalyst comprising the above compound or a catalyst comprising an organoaluminum compound (A), (B) or (C), wherein the α-ole The fin copolymer comprises: (A) a transition metal compound having at least one π-electron conjugated ligand;
A catalyst comprising at least one compound selected from aluminoxane, an ionic compound which reacts with the transition metal compound to form an ionic complex, and a Lewis acid; or
(A), (B) and (C) obtained by copolymerizing two or more α-olefins using a catalyst comprising an organoaluminum compound, wherein (A) the π-electron conjugated ligand Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) Enil)
(3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2, 4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Hafnium dichloride and dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
A polypropylene composition, which is at least one compound selected from the group consisting of hafnium dimethyl. 2. Polypropylene has an isotactic pentad fraction (mmmm) of 0.960 to 0.995, and a syndiotactic pentad fraction (rrrr) of 0 to 0.000.
2. The polypropylene composition according to claim 1, wherein the heterogeneous bond resulting from the 4,2,1 insertion reaction and the 1,3 insertion reaction is 0 to 0.08 mol%. 3. The polypropylene composition according to claim 1, wherein the polypropylene has a melting point of 155 to 168 ° C. 4. The α-olefin copolymer is an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, an ethylene / 1-hexene random copolymer, an ethylene / 1-octene random copolymer, Ethylene / 1-butene / 1-hexene random copolymer, ethylene / 1-butene / 1-octene random copolymer, ethylene / propylene / 1-butene random copolymer, propylene / 1-butene random copolymer, and The polypropylene composition according to any one of claims 1 to 3, which is an α-olefin / polyene random copolymer. 5. A molded article molded from the polypropylene composition according to any one of claims 1 to 4. 6. A method for producing a polypropylene composition, comprising: (i) (A) a transition metal compound having at least one π-electron conjugated ligand and (B) an aluminoxane, and reacting with the transition metal compound to form an ionic complex. Propylene is polymerized using a catalyst comprising one or more compounds selected from an ionic compound and a Lewis acid which form propylene, or a catalyst comprising (A), (B) and (C) an organoaluminum compound, (Ii) (A) a transition metal compound having at least one π-electron conjugated ligand and (B) an aluminoxane, an ionic compound which reacts with the transition metal compound to form an ionic complex, and a Lewis acid Or a catalyst comprising (A), (B) and (C) an organoaluminum compound Using, by copolymerizing two or more kinds of α- olefins, a step of obtaining the α- olefin copolymer, wherein the α- olefin copolymer α- olefin 10-90 wt% and at least 1
Comprising from 10 to 90% by weight of another α-olefin of the kind, wherein in the steps (i) and (ii), (A) π
The transition metal compound having at least one electron conjugated ligand is dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4 -Dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethyl Cyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Selected from the group consisting of trimethylcyclopentadienyl) hafnium dichloride and dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dimethyl] And (iii) mixing a predetermined amount of the polypropylene and the α-olefin copolymer; and comprising the above steps, wherein the polypropylene composition is 20 to 95% by weight of stereoregular polypropylene and α-olefin copolymer. 5 to 80% by weight, and the polypropylene had a (a) isotactic pentad fraction (mmmm) of 0.940 to 100% by nuclear magnetic resonance spectrum.
0.995, (b) Syndiotactic pentad fraction (rrrr) is 0 to 0.01, and (c) 0 to 0.10 mol of heterogeneous bonds resulting from 2,1 insertion reaction and 1,3 insertion reaction.
%, And (d) a weight average molecular weight (M _w ) of 50,
000～1,000,000 and (e) a weight average molecular weight number average molecular weight of (M _w) ratio _{(M n) (M w /} M n) is from 1.5 to 3.8, and wherein the The manufacturing method described above. 7. A method for producing a polypropylene composition, comprising: (i) (A) a transition metal compound having at least one π-electron conjugated ligand, and (B) an aluminoxane, and reacting with the transition metal compound to form an ionic complex. Propylene is polymerized using a catalyst comprising one or more compounds selected from an ionic compound and a Lewis acid which form propylene, or a catalyst comprising (A), (B) and (C) an organoaluminum compound, And (ii) copolymerizing two or more α-olefins under the condition that the obtained polypropylene and the catalyst are mixed to obtain an α-olefin copolymer, wherein the α-olefin copolymer is obtained. The olefin copolymer comprises from 10 to 90% by weight of an α-olefin and from 10 to 90% by weight of at least one other α-olefin; In the steps (i) and (ii), the transition metal compound (A) having at least one π-electron conjugated ligand is dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′- Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) ) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Hafnium dichloride and dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Selected from the group consisting of hafnium dimethyl]; and the polypropylene composition contains 20 to 95% by weight of stereoregular polypropylene and 5 to 80% by weight of an α-olefin copolymer, and the polypropylene has nuclear magnetic properties. According to the resonance spectrum, (a) the isotactic pentad fraction (mmmm) was 0.940 to 0.995,
(B) Syndiotactic pentad fraction (rrrr) is 0
0.01 and (c) 0 to 0.10 mol% of heterogeneous bonds resulting from the 2,1 insertion reaction and the 1,3 insertion reaction, and (d) the weight average molecular weight (M _w ) is from 50,000 to One,
000,000 and (e) a weight average molecular weight number average molecular weight of (M _w) ratio _{(M n) (M w /} M n) is 1.5 to 3.
8. The method according to claim 1, wherein