JP3202370B2 - Method for producing propylene block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

The present invention relates to a method for efficiently and stably polymerizing a propylene block copolymer having high rigidity and high impact strength with high activity.

[0002]

2. Description of the Related Art Crystalline polypropylene has excellent rigidity and heat resistance, but has a problem of low impact strength, especially low temperature impact strength.

As a method of improving this point, a method of producing a block copolymer by stepwise polymerizing propylene and ethylene or another olefin is already known (JP-B-43-11230, JP-B-44-230). 166
No. 68, JP-B-44-20621, JP-B-49-24
No. 593, JP-B-49-30264, JP-A-48-2
No. 5781, JP-A-50-115296, JP-A-53
-35789, JP-A-54-110072, etc.). However, when propylene and ethylene are polymerized in two or multiple stages, the impact resistance is improved, but on the other hand, since the product contains a copolymerized portion, a large amount of low-crystalline polymer is by-produced. Occurs.

[0004] In general, to increase the impact strength of a block copolymer, the production ratio of a rubbery copolymer has been increased. However, an increase in by-products and an increase in polymer particles have been accompanied. During such time, adhesion to the inner wall of the apparatus or the like occurs, and stable long-term continuous operation of the polymer production apparatus is often difficult.

On the other hand, in order to produce a conventional stereoregular polypropylene block copolymer, a solid component of TiCl ₃ or a solid component containing magnesium, titanium and halogen as essential components is generally used. obtained propylene / ethylene copolymer is usually less uniformity of copolymerization, copolymerization ratios (r _P r
_E ) usually shows a value of 1.5 or more. Therefore, even if the production ratio of the rubbery copolymer in the subsequent stage is increased,
Improvement of impact strength may be insufficient. For the purpose of improvement, a proposal has been made to blend a rubbery copolymer having excellent uniformity in copolymerization (Japanese Patent Laid-Open No. 51-136735).
No. 58-222132, No. 61-12742,
63-150343.

However, a method of blending such a rubbery copolymer having good uniformity requires such a rubbery copolymer to be expensive and to be blended.

Recently, for the purpose of improving low-temperature impact strength, crystalline polypropylene has been produced in the first stage under liquid propylene using a metallocene catalyst, and propylene and ethylene or α-olefin having 4 to 20 carbon atoms have been produced in the second stage. Proposals for copolymerization have been made (EP-43389, EP
P-433990), JP-A-4-114405
No. 0). However, in these proposals, although the low-temperature impact resistance is improved, a fine-particle polymer is generated, and when the number of the later-stage polymers is increased, agglomeration of particles and adhesion to the reactor wall occur. It seems difficult to manufacture.

[0008]

DISCLOSURE OF THE INVENTION The present invention has the above-mentioned problems of the prior art, namely, without blending a rubbery copolymer having good uniformity, generation of fine particles, aggregation of particles, An object of the present invention is to produce a propylene block copolymer having improved impact resistance without causing adhesion to a reactor wall.

[0009]

[Summary of the Invention] <Summary> The present invention makes it possible to produce a rubbery copolymer having good copolymerizability at a later stage of polymerization, and to obtain a sufficient impact resistance. An object of the present invention is to provide a method for stably producing a propylene block copolymer having the same by a gas phase polymerization without blending a rubbery copolymer having excellent uniformity.

Therefore, the process for producing a propylene block copolymer according to the present invention is substantially carried out in the presence of a catalyst obtained by supporting the following components (A) and (B) and (C). In the gas phase, the pre-stage polymerization for producing a crystalline propylene homopolymer or a copolymer of propylene and ethylene having an ethylene content of 5% by weight or less and the polymerization in the presence of the catalyst and the pre-stage polymer are carried out. Continuously, the polymerization ratio (molar ratio) of propylene and at least one comonomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms between propylene and the comonomer
Is carried out in such a manner that the polymerization ratio becomes 0/100 to 80/20, and the polymerization is carried out so that the weight ratio of the polymerization amount of the former stage and the polymerization amount of the latter stage becomes 95/5 to 30/70. That is, it is characterized. Component (A): an organic porous polymer having an average particle size of 5 to 1000 μm and a pore size of 0.006 to 10 μm
m is 0.8 cc / g or more, and the total pore volume of all the pores having a pore diameter of 0.05 to 2 μm is 0.006 what is at more than 50% of the sum of the total pore volume of pores 10 .mu.m, component (B): an organoaluminum oxy compound, component (C): formula ^{_{Q (C 5 H 4-a}} R 1 a) _{(C 5}
H _{^4-b R} 2 ^b) a transition metal compound represented by Mexy. ^{_{[However, (C 5 H 4-a}} R 1 a) and ^{_{(C 5 H 4-b R}} 2
_b ) is a conjugated five-membered ring ligand each of which coordinates to Me (R ¹ and R ² are each independently a hydrocarbon residue having 1 to 20 carbon atoms, a halogen group, an alkoxy group having 1 to 12 carbon atoms) A silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms, and a boron-containing hydrocarbon group having 1 to 12 carbon atoms. A monovalent group selected from the group consisting of a plurality of R ¹
Alternatively, R ² may be bonded at each other end to form a ring), Q is a divalent bonding group bridging between two conjugated five-membered ligands, Me is titanium, X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and up to 2 hydrocarbon groups having 1 to 20 carbon atoms; An amino group optionally substituted with 1 carbon atom
A monovalent group selected from the group consisting of a phosphorus-containing hydrocarbon group of from 20 to 20 and a silicon-containing hydrocarbon group of from 1 to 20 carbon atoms, a is an integer of 0 ≦ a ≦ 4, b is 0 ≦ b ≦ 4 Are respectively shown. <Effect> By the method of the present invention, it has become possible to stably produce a propylene block copolymer having improved impact strength under gas phase polymerization conditions. Therefore, according to the present invention, it is possible to provide a propylene block copolymer having improved impact resistance without blending a rubber having good copolymerizability. [Specific description of the invention] [Catalyst] The catalyst used in the present invention is obtained by supporting the component (B) and the component (C) on the component (A). Here, “the component (A) obtained by supporting component (B) and component (C)” means that component (A) is added to component (B).
In addition to those obtained by supporting only component (C), those obtained by supporting other components other than component (B) and component (C) are included. <Component (A)> The component (A) has an average particle size of 5 to 1000 μm, preferably 10 to 700 μm, and more preferably 20 to 500 μm.
m, an organic porous polymer having a pore size of 0.1.
The total sum of the pore volumes of all the pores having a diameter of 006 to 10 μm is 0.
8 cc / g or more, preferably 1.0 cc / g or more,
And the sum of the pore volumes of all the pores having a pore diameter of 0.05 to 2 μm is 50% or more, preferably 60%, of the sum of the pore volumes of all the pores having a pore diameter of 0.006 to 10 μm. That is all.

The component (A) has a pore size of 0.006 to 0.006.
The sum of the pore volumes of all the pores of 10 μm is 0.8 cc / g
When the amount is less than the above, the amount of the catalyst component that can be impregnated in the component (A) is low, and it is impossible to obtain a sufficient activity per catalyst. A pore having a pore diameter of less than 0.05 μm is a catalyst component,
In particular, it is difficult to impregnate the organic aluminum oxy compound,
In addition, when there are many pores exceeding 2 μm, the catalyst component is detached from the carrier particles at the time of polymerization to start or continue the polymerization,
It is not preferable because it causes the formation of fine particle polymer. Here, the pore volume and the pore diameter were measured using a porosimeter (“Pore Sizer 9310” manufactured by Micromeritex Corporation), and the average particle diameter of the polymer was measured by “Spica II” image analyzer manufactured by Nippon Avionics. Is used to obtain a number average particle size distribution by microscopic observation, and this is converted into a weight average particle size distribution, which means a value at a weight of 50%, that is, D ₅₀ .

The type of the organic porous polymer having the above-mentioned characteristics is arbitrary as long as the above conditions are satisfied. In general, (a) polyethylene, polypropylene, polybutene-1, and ethylene-propylene copolymer are generally used. Copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, propylene-butene-1 copolymer, propylene-hexene-1 copolymer, propylene-
Α-olefin polymers such as divinylbenzene copolymer,
(Ii) aromatic unsaturated hydrocarbon polymers such as polystyrene and styrene-divinylbenzene copolymer; and (iii) polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene ether, and polyethylene. Terephthalate,
Examples include polar group-containing polymers such as polycarbonate.

Of these, α-olefin polymers and aromatic unsaturated compound polymers are preferred because of less side reaction with the catalyst component, and more preferred are α-olefin polymers of the same type as the target polymer. It is united. <Component (B)> The component (B) is an organic aluminum oxy compound. One representative example is alumoxane. Alumoxanes are products obtained by the reaction of one trialkylaluminum or two or more trialkylaluminums with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane, etc. obtained from one type of trialkylaluminum, and methylethylalumoxane, methylbutyl, obtained from two types of trialkylaluminum and water Alumoxane, methylisobutylalumoxane and the like are exemplified.

In the present invention, these alumoxanes can be used in combination of two or more kinds, and alumoxane can be used in combination with other alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is.

It is also possible to use a modified alumoxane by reacting two kinds of alumoxanes or one kind of alumoxane with another organoaluminum compound.

Preferred among these are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane and mixtures of these alumoxanes with trialkylaluminums. Particularly preferred are methylalumoxane and methylisobutylalumoxane.

For the polymerization of propylene,
Chemical shift in the measurement of ²⁷ Al-NMR is 160 to 2
Methyl isobutylalumoxane, which is characterized by being located between 50 ppm and having a line width of at least 3000 Hz, is preferred.

These alumoxanes can be prepared under various known conditions. Specifically, the following method can be exemplified.

(A) a method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether; (b) a salt hydrate having a trialkylaluminum and water of crystallization, for example, copper sulfate; (C) a method of reacting a trialkylaluminum with water impregnated in silica gel or the like; (d) a method of mixing trimethylaluminum and triisobutylaluminum to form toluene, benzene, ether, etc. (E) mixing trimethylaluminum and triisobutylaluminum and reacting them with a salt hydrate having water of crystallization, such as copper sulfate or aluminum sulfate hydrate. Method, (f) impregnate silica gel etc. with water After treatment with bromide, adding treated with trimethylaluminum, method (g) synthesized in methylalumoxane and isobutyl alumoxane known methods, these two components are mixed predetermined amounts, reacted under heating.

Another typical example of the component (B) is an organoaluminum oxy compound represented by the following formula (I).

[0021]

Embedded image (However, R ³ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ⁴ is hydrogen, halogen, a siloxy group, a lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and each of the ^four R ⁴ may be the same or different. )
The component (B) is a reaction product of the following components (i) and (ii).

Component (i) has the general formula

[0023]

Embedded image (Wherein R is an alkylboronic acid represented by
³ represents a hydrocarbon residue having 1 to 10 carbon atoms). component
Specific examples of (i) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, and n-propylboronic acid.
-Butylboronic acid, iso-butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl) phenylboron Acid, etc. Among these, preferred are methylboronic acid, i-butylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. Even more preferred is methylboronic acid.

The component (ii) which reacts with the above component (i) to produce the component (B) is an organoaluminum compound.

The general formula R ⁴ _3-q AlX q or Specific examples of such components (ii)

[0026]

Embedded image Or

[0027]

Embedded image It is represented by (However, R ⁴ has 1 to 1 carbon atoms.
0 represents a hydrocarbon residue; X represents a hydrogen or a halogen group;
⁹ represents hydrogen, halogen or a hydrocarbon residue having 1 to 10 carbon atoms, and q represents 0 ≦ q <3. Specific examples of component (ii) include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, trin-butylaluminum, trin-propylaluminum, triisoaluminum Trialkyl aluminum such as prenyl aluminum,
(B) alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride,
(C) alkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride,
(D) Dimethylaluminum (trimethylsiloxide), dimethylaluminum (trimethylsiloxide), diethylaluminum (trimethylsiloxide)
And alkylaluminum siloxides, and (e) tetraalkylalumoxane such as tetraisobutylalumoxane and tetraethylalumoxane. It is also possible to use a mixture of a plurality of these.

<Component (C)> The component (C) is represented by the general formula Q
Is a ^{_{(C 5 H 4-a R}} 1 a) (C 5 H 4-b R 2 b) a transition metal compound represented by Mexy.

Here, Q represents a bonding group bridging between two conjugated five-membered ring ligands. Specifically, (a) a methylene group,
A C _1-4 alkylene group such as an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group or a cyclohexylene group, or a lower alkyl or a phenyl-substituted side chain thereof;
A silylene group or an oligosilylene group such as a silylene group, a dimethylsilylene group, a phenylmethylsilylene group, a diphenylsilylene group, a disilylene group, a tetramethyldisilylene group, or a lower alkyl or phenyl-substituted side chain thereof, (c) germanium, phosphorus, A hydrocarbon group containing nitrogen, boron or aluminum, that is, a valence excluding the divalent valence of these elements required as a crosslinking group, is a hydrocarbon group, preferably a lower alkyl group or a phenyl group,
Alternatively, a hydrocarbyloxy group, preferably a lower alkoxy group, specifically a (CH ₃ ) ₂ Ge group, (C
₆ H _{5) 2} Ge group, _(CH 3) P _group, (C _{6 H} 5) P
Group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ )
B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H
₅ ) Al group, (CH ₃ O) Al group and the like. Preferred are an alkylene group and a silylene group.

In the above general formula, (C ₅ H
^{_4-a R} ₁ ^a) and _(C 5 H ^{_4-b R} conjugated five-membered ring ligands represented by _{2 b),} although are respectively defined separately, a and b as well as ^{R 1} and ^{R 2} Is the same (details will be described later), it is needless to say that the two conjugated five-membered ring groups may be the same or different.

One specific example of this conjugated five-membered ring group is that a =
0 (or b = 0) is a cyclopentadienyl group (no substituent other than the crosslinking group Q). When the conjugated five-membered ring group has a ≠ 0 (or b ≠ 0) and has a substituent, one specific example of R ¹ (or R ² ) is
Hydrocarbon group (C1-20, preferably C1-1
2), this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are bonded at the other end to form cyclopentadienyl. A ring may be formed together with a part of the dienyl group. Representative examples of the latter are those in which R ¹ (or R ² ) shares the double bond of the cyclopentadienyl group to form a fused six-membered ring, that is, the conjugated five-membered ring group is an indenyl group or It is a fluorenyl group. That is, typical examples of the conjugated five-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ¹ and R ² each represent, in addition to the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a halogen group (eg, fluorine, chlorine, bromine), 1 to 12 alkoxy groups, 1 to 20 carbon atoms
(E.g., a silicon atom is represented by -S
i (R) (R ') (R "), containing 1 to 1 carbon atoms
12 phosphorus-containing hydrocarbon groups (for example, a phosphorus atom is -P
(R) (R ')), a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms (for example, a nitrogen atom is -N (R)
(R '), or a boron-containing hydrocarbon group having 1 to 12 carbon atoms (for example, a boron atom represented by -B
(R) and (R ′)). When a (or b) is 2 or more and a plurality of R ¹ (or R ² ) are present, they may be the same or different.

A and b are integers satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4.

Me is titanium, zirconium and hafnium. Particularly, zirconium is preferable.

X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, Amino group which may be substituted by up to 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms (specifically, for example, a diphenylphosphine group) Or 1-20 carbon atoms,
Preferably, they are 1 to 12 silicon-containing hydrocarbon groups (specifically, for example, a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferred.

Specific examples of the transition metal compound when Me is zirconium are as follows.

(A) Transition metal compounds having two 5-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride, (3) Ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride,
(5) ethylene bis (indenyl) zirconium monomethoxymonochloride, (6) ethylene bis (indenyl) zirconium diethoxide, (7) ethylene bis (indenyl) zirconium dimethyl, (8) ethylene bis (4,5,6, 7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl) zirconium dichloride, (11) ethylenebis (2,4-dimethyl Indenyl) zirconium dichloride, (12) ethylene (2,4
-Dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride;
(13) ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5'-methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclo) (Pentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (15) isopropylidenebis (indenyl) zirconium dichloride, (16)
Isopropylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, (17) isopropylidene (2
-Methyl-4-tertbutylcyclopentadienyl)
(3'-tertbutyl-5'-methylcyclopentadienyl) zirconium dichloride, (18) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (19) methylene (cyclopentane Dienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (20) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (21) methylene (cyclopentadi (Enyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (22) methylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (23) methylene (cyclopentadienyl) (tetramethylcyclo Pentadienyl) zirconium dichloride, (24) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (25)
Isopropylidene (cyclopentadienyl) (2,3
4,5-tetramethylcyclopentadienyl) zirconium dichloride, (26) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (27) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, (28)
Isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (29)
Isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (30) isopropylidene (2,5
-Dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (31) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl)
Zirconium dichloride, (32) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (33) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (3
4) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (35)
Diphenylmethylene (cyclopentadienyl) (3,4
-Diethylcyclopentadienyl) zirconium dichloride, (36) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (37) cyclohexylidene (cyclopentadienyl) (fluorenyl) Zirconium dichloride, (38) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethyldimethylcyclopentadienyl) zirconium dichloride and the like.

(B) Transition metal compounds having a 5-membered ring ligand bridged by a silylene group, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5
6,7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylenebis (2,4-dimethylindenyl) zirconium dichloride, (5) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (6) phenylmethylsilylenebis (indenyl) zirconium dichloride, (7) phenylmethylsilylenebis (4
5,6,7-tetrahydroindenyl) zirconium dichloride, (8) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (9)
Phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (10)
Phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (11) diphenylsilylenebis (indenyl) zirconium dichloride, (12) tetramethyldisilylenebis (indenyl)
Zirconium dichloride, (13) tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, (14) tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, (15) dimethylsilylene (cyclopentane Dienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (16) dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (17) dimethylsilylene (cyclopentadienyl) (tetramethylcyclo Pentadienyl)
Zirconium dichloride, (18) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (19) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, 20) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (21)
Dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (22) Dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (23) Dimethylsilylene (cyclopentane (Dienyl) (octahydrofluorenyl) zirconium dichloride, (24) dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (25) dimethylsilylene (2,5-dimethylcyclopentadienyl) ( (Fluorenyl) zirconium dichloride, (26) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (27) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ( 28) diethylsilylene (2-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride,
(29) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Zirconium dichloride, (30) dimethylsilylene (2
-Ethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (31) dimethylsilylene (diethylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, (32) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (33) dimethylsilylene (dimethylcyclopentadienyl) ) (Octahydrofluorenyl) zirconium dichloride, (34) dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (35) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluoride) Nyl) zirconium dichloride and the like.

(C) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, 2) Dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl)
Zirconium dichloride, (4) phenylaluminum bis (indenyl) zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride, (6) ethylholanobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(D) Further, compounds obtained by replacing chlorine in the compounds (a) to (c) with bromine, iodine, hydride, methyl, phenyl and the like can also be used.

Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified in the above (a) to (d) is changed from zirconium to titanium or hafnium can be used as the component (C).

Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. More preferred are zirconium compounds and hafnium compounds cross-linked with an alkylene group or a silylene group. Particularly preferred are zirconium compounds having a substituent at the 2-position adjacent to the carbon having a bridging group. <Preparation of solid catalyst> The solid catalyst used in the method of the present invention includes:
It is obtained by supporting component (B) and component (C) on component (A). The method of supporting the component (B) and the component (C) on the component (A) is optional, but generally, (a) the component (B) and the component (C) are dissolved in an inert solvent in which they can be dissolved. After mixing with component (A), distilling off the solvent under reduced pressure or under an inert gas stream,
(B) After dissolving the component (B) and the component (C) in an inert solvent, the solution is concentrated within a range in which no solid precipitates, and then the amount of the component ( A) a method of adding (A), a method of sequentially impregnating the solution of the component (B) and the component (C) with the component (A),
Etc. are exemplified.

Since the components (B) and (C) used in the present invention are generally solid, an inert solvent for solubilizing the components (B) and (C) is used in this loading operation. A particularly preferred embodiment is a method in which the component (A) is impregnated with the component (B) and the component (C) to support both components. As the inert solvent, benzene, toluene, xylene, hexane, heptane, octane, decalin, dichloromethane, dichloroethane, chloropropane, chlorobenzene and the like are used. The amount of the inert solvent remaining in the impregnated state is arbitrary, and varies depending on the pore volume of the used organic porous polymer (component (A)). 70% by weight, preferably 5 to 50% by weight. When the content exceeds 70% by weight, the impregnated organic porous polymer cannot maintain an independent particle state, and becomes a state such as agglomeration or sludge, and the subsequent polymerization does not proceed stably or impregnated into the organic porous polymer. It is not preferable because there is a catalyst component that has not been formed and a fine particle polymer is generated during polymerization. The residual amount of the inert solvent affects the activity during the polymerization, particularly during the gas phase polymerization. The remaining amount of about 5% by weight or more makes the activation more stable, so that the polymerization can be easily controlled.

The above-mentioned impregnation operation is usually carried out in an inert atmosphere. However, the impregnation may be carried out while prepolymerizing in the presence of a monomer, or after a small amount of prepolymerization. Alternatively, pre-polymerization may be performed in the gas phase after the impregnation. Such monomers include ethylene, propylene, 1-butene,
1-hexene, 4-methylpentene-1,1,5-hexadiene, styrene, divinylbenzene, etc., or
Mixtures thereof are used. The temperature during the impregnation operation is -7
It is carried out within the range of 8 ° C to 100 ° C, preferably -78 ° C to 50 ° C. The time required for the impregnation step is arbitrary, but is generally within 24 hours, preferably within 10 hours,
It is.

The amounts of component (A) and component (B) used are arbitrary, but generally 0.1 g to 10 g, preferably 1 g, of organic aluminum oxy compound of component (B) per 1 g of component (A). It ranges from 0.3 g to 5 g.
When the amount is less than 0.1 g, the activity per solid catalyst is not sufficiently obtained. When the amount exceeds 10 g, the organic aluminum oxy compound which is not impregnated remains as independent particles, and the particles are combined with the component (C) to obtain an activity. It is not preferable because it expresses to generate a fine particle polymer.

The amount of component (C) used is also arbitrary, but generally it is 1 to 1 in terms of mole ratio per aluminum atom of component (B).
It is in the range of 10,000, preferably 10-3000, more preferably 30-1000. [Use of Solid Catalyst / Polymerization of Olefin] In the method of the present invention, the above-mentioned solid catalyst is applied to gas phase polymerization substantially using no solvent. Further, it is applied to continuous polymerization and batch polymerization.

The polymerization temperature is about -78 to 200 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 50 kg / cm ^2.
-G range. In addition, known means at the time of polymerization,
For example, the molecular weight can be adjusted by selecting the temperature and pressure or by introducing hydrogen.

In the polymerization of the present invention, it is needless to say that the polymerization can be carried out if the solid catalyst and the polymerization monomer are present. However, in order to improve the polymerization activity and to prevent catalyst poisoning, an organic aluminum compound is used. It is also possible to use it.

[0049] Specific examples of such organic aluminum compounds, ^{R 5} _3-n AlX n or ^{R 6} _3-m Al (O
R ⁷ ) _m (wherein, R ⁵ and R ⁶ may be the same or different and each may be a hydrocarbon residue having about 1 to 20 carbon atoms or a hydrogen atom; R ⁷ may be a hydrocarbon residue having about 1 to 20 carbon atoms; X is halogen, n and m are each 0 ≦ n <3, 0 <m <
3) or the following general formula (II) or (III).

[0050]

Embedded image (Where p is a number from 0 to 40, preferably 2 to 25, and R ⁸ is a hydrocarbon residue, preferably a carbon number of 1 to 1).
0, particularly preferably 1 to 4 carbon atoms. )
Specifically, (a) trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum;
(B) alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride; (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride;
(D) aluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum phenoxide, (e) methylalumoxane, ethylalumoxane,
Alumoxanes such as isobutylalumoxane and methylisobutylalumoxane are exemplified. It is also possible to use a mixture of a plurality of these. Of these, trialkylaluminum, alumoxane and the like are preferred.

In addition to the solid catalyst used in the method of the present invention and the above-mentioned organoaluminum compound as an optional component, the third component that can be added includes, for example, H
₂ O, active hydrogen-containing compounds such as methanol, ethanol, and butanol; electron-donating compounds such as ethers, esters, and amines; and alkoxy such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane. Containing compounds,
Examples thereof include Lewis acids such as triphenylboron, tris (pentafluorophenyl) boron, and triphenylcarbyltetrakis (pentafluorophenyl) boron. <Polymerization Step> The polymerization step of the present invention carried out in the presence of the catalyst component comprises at least two steps of a first-stage polymerization and a second-stage polymerization.

Formation of the Catalyst The catalyst used in the method of the present invention is brought into contact with the solid catalyst and the components to be added, if necessary, stepwise or stepwise, inside or outside the polymerization system. Is formed.

[0053] stage polymerization preceding polymerization is supplied to a polymerization system having a propylene homopolymer or a propylene / ethylene mixture the solid catalyst and components that are added as necessary, by polymerizing in one step or multiple stages, propylene crystalline Propylene / ethylene copolymer having an ethylene content of 5% by weight or less, preferably 1.0% by weight or less,
This is a step of forming an amount corresponding to 0 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 90% by weight.

If the ethylene content in the propylene / ethylene copolymer exceeds 5% by weight in the first-stage polymerization, the rigidity of the obtained copolymer decreases, and the amount of low-crystalline polymer by-produced greatly increases. Further, when the polymerization ratio is less than the lower limit of the above range,
Again, the amount of by-products of the low crystalline polymer increases. On the other hand, if the polymerization ratio exceeds the upper limit of the above range, the effect of improving the impact resistance, which is the purpose of the block copolymer, will not be exhibited.

As a polymerization mode of the first-stage polymerization, a gas phase method in which each monomer is substantially in a gaseous state without using a liquid solvent can be adopted. Further, the present invention is also applicable to a method of performing continuous polymerization, batch polymerization or preliminary polymerization. Note that the presence of a small amount of an inert solvent or a liquid monomer is not excluded as long as the gas phase is substantially maintained. As the inert solvent in this case, a singly or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used.

The polymerization temperature is about −78 ° C. to about 200 ° C., preferably 0 to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner. The polymerization pressure is 0 to 90 kg / cm ² G, preferably 0 to 60 kg / cm ² G,
Particularly preferably, 1 to 50 kg / cm ² G is appropriate.

It is preferable to use a solid catalyst in which propylene is preliminarily preliminarily polymerized before the polymerization for the purpose of improving the activity, eliminating the solvent-soluble by-product polymer or preventing the melting point from lowering. At this time, the proportion of the propylene prepolymerized portion in the total polymer is usually 10% by weight or less, preferably 5% by weight or less.

In this case, the polymerization temperature during the propylene prepolymerization is generally the same as or lower than the temperature of the polymerization performed thereafter. Therefore, the temperature during propylene prepolymerization is -30 to 70C, preferably 0 to 50C. The pressure is usually from normal pressure to 20 kg / cm ²
G, preferably normal pressure to 5 kg / cm ² G,
The ratio of the propylene prepolymerized part to the target copolymer is not necessarily limited to this as long as it is within the above-mentioned predetermined range.

The molecular weight of the polymer can be controlled by adding hydrogen to the polymer.

Second- stage polymerization The second-stage polymerization is carried out after the first-stage polymerization, that is, by utilizing the polymerization activity in the first-stage polymerization, that is, at least a part of the polymerization catalyst, to use propylene and ethylene and / or C 4-20. Is further introduced into the polymerization system so that the content of at least one comonomer selected from the group consisting of ethylene and 4-20 α-olefins is 20-100 mol%, preferably 30-80 mol%. Mol%, more preferably 30 to 70 mol% of propylene /
In this step, ethylene and / or an α-olefin copolymer having 4 to 20 carbon atoms is obtained in one or more stages. In this step, 5 to 70% by weight of the total polymerization amount, preferably 10 to 5%
It is desirable to form an amount corresponding to 0% by weight, more preferably 10 to 40% by weight.

The polymerization temperature of the second-stage polymerization is about 0 to 90 ° C., preferably about 40 to 80 ° C. The polymerization pressure is 1 to 5
A range of 0 kg / cm ² G is usually used.

When the polymerization proceeds from the first-stage polymerization to the second-stage polymerization, it is preferable to purge the propylene gas or the propylene / ethylene mixed gas and the hydrogen gas and then proceed to the next step.

In the second-stage polymerization, a molecular weight regulator may or may not be used according to the purpose.

Polymerization Mode The latter polymerization mode according to the method of the present invention can be carried out by any of a batch system, a continuous system, and a semi-batch system. At this time, the polymerization is carried out in a substantially gaseous monomer without using a medium. At this time, as long as a substantial gas state is maintained, it does not exclude that a small amount of the inert solvent or the liquid monomer exists in the polymer and / or the solid catalyst in an impregnated state. [Block copolymer] <Pre-stage polymer> The polymer obtained in the pre-stage polymerization is ¹³ C-
It has a stereoregularity value of [mm] triad fraction of 0.80 or more or [rr] triad of 0.80 or more measured by NMR. [Mm] or [rr] according to the ¹³ C-NMR spectrum of the polymer is JEOL J
The measurement was performed using EOL, FX-200 under the conditions of a measurement temperature of 130 ° C., a measurement frequency of 50.1 MHz, a spectrum width of 8000 Hz, a pulse repetition time of 2.0 seconds, a pulse width of 7 μs, and a cumulative number of 10,000 to 50,000 times. . The analysis of the spectrum was performed using Macromol.
ecules, 21 617 (1988), and Tetsuro Asakura's proceedings of the Society of Polymer Science, 36 (8) 2408 (1987).

Here, the [mm] fraction or [rr] fraction of the triad refers to “triad”, which is a monomer unit in the α-olefin polymer and is the minimum unit of the three-dimensional structure, ie, “trimer unit”. ], [Mm] or [rr] in the total number x of the three stereoisomeric structures that can be taken, ie, [mm] (isotactic), [mr] (heterotactic) and [rr] (syndioctatic). It means the ratio (y / x) of the number y of triads having a structure.

The number average molecular weight (Mn) of the first-stage polymer is 2
It is between 000 and 200,000. Mn is 20,
If it is less than 000, the viscosity at the time of melting becomes insufficient and molding is difficult, and if it exceeds 200,000, the high rigidity targeted by the present invention cannot be maintained. Preferred is between 30,000 and 100,000.

The molecular weight distribution of the obtained polymer is
The ratio of Mw / Mn measured by gel permeation chromatography (GPC) is 3.5 or less, preferably 1
~ 2.8. Generally, a polymer obtained with a catalyst comprising a metallocene compound and an alumoxane has a Mw /
Mn is 3.5 or less. Those exceeding 3.5 are not preferred because relatively low molecular weight substances are relatively increased, and by-product eluted substances are increased and rigidity is hardly increased.

The measurement of gel permeation chromatography (GPC) was carried out according to "Gel Permeation Chromatography" published by Maruzen, Takeuchi. That is, using standard polystyrene of known molecular weight (monodisperse polystyrene manufactured by Toyo Soda), the number average molecular weight (Mn) and weight average molecular weight (M
n) and the value of Mw / Mn was determined. The measurement was performed using 150C-ALC / GPC manufactured by Waters, and three columns of AD80M / S manufactured by Showa Denko were used as columns. As a sample, 200 μl of a sample diluted to 0.2 wt% in o-dichlorobenzene was used. Measurement is 140 ° C, flow rate 1ml
/ Min. <Latter stage polymer> wherein the block copolymer obtained by the process of the present invention is that the copolymerization ratio of the post-stage polymer obtained by cold xylene extraction (r _P Xr _EN) of 2.0 or less . The preferred copolymerization ratio is 1.0 or less. The reaction ratio of the monomer is K. Sog for copolymerization of propylene and ethylene.
a. Similar to Macromol. Chem 191 p2854 (1990), r _P =
2 [PP] / [PE] X, r _EN = 2 [EE] X / [P
E] (where X = propylene / ethylene (the molar ratio charged in the solvent)) is the product of r _P and r _EN . The amount of propylene dissolved in the solvent is determined by Kissin's formula (YV Kissin, "Isospecific polymerization of Ol
efins with Heterogeneous Ziegler-Natta catalysts "
p.3 (1985)). At this time, it is necessary that the value of r _P × r _EN is 2.0 or less, preferably 1.0 or less.

The number average molecular weight of the latter polymer is 5
It is at least 000, preferably at least 90,000. If it is less than 50,000, the effect of improving the impact resistance is small, and the effect of the present invention cannot be obtained. <Measurement of practical physical properties> The practical physical properties of the polymers in each of the following experimental examples were measured using a plastmill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 ml after blending the following additives with the polymers obtained in the respective examples. The composition shown in FIG. 1 was melt-kneaded at 230 ° C. and a rotation speed of 60 rpm for 6 minutes. The resulting mixture was press-molded at 230 ° C. to form a sheet having a thickness of 2 mm. Various test pieces were cut out from this sheet and used for physical property evaluation. Additives: 2,6-di-tert-butylphenol 0.10% by weight RA1010 (manufactured by Ciba-Geigy) 0.05% by weight Measurement and evaluation method (a) Flexural modulus A test piece having a width of 25 mm and a length of 80 mm was cut. , JIS
It measured using the Instron testing machine according to K7203. (B) Izod impact strength According to JIS K7110, three 2 mm-thick test pieces were stacked, and the notched Izod impact strength at 23 ° C. was measured.

[0070]

【Example】

<Example-1> Production of component (C) Dimethylsilylenebis (2-methylindenyl) zirconium dichloride was produced by the following method.

In a 500 ml glass reaction vessel, 4.3 g (33 mmol) of 2-methylindene are dissolved in 80 ml of tetrahydrofuran and, under cooling, 1.
21 ml of a 6M hexane solution was slowly dropped into the reaction vessel. After stirring at room temperature for 1 hour, the mixture was cooled again and 2.1 g of dimethyldichlorosilane was slowly added dropwise. After stirring at room temperature for 12 hours, 50 ml of water was added, the organic phase was separated and dried to give dimethylbis (2- Methylindenyl) silane 3.5
g was obtained.

3.5 g of dimethylbis (2-methylindenyl) silane obtained by the above method was mixed with tetrahydrofuran 7.
0 ml, and cooled to 1.6 M n-butyllithium.
13.9 ml of a hexane solution was slowly added dropwise. After stirring at room temperature for 3 hours, 2.6 g of zirconium tetrachloride (11 mmo
l) / 60 ml of tetrahydrofuran solution was slowly added dropwise, and after stirring for 5 hours, hydrogen chloride gas was blown into the solution, followed by drying. Subsequently, methylene chloride was added to separate a soluble portion, and crystallized at a low temperature to obtain 0.45 g of an orange powder.

Production of Component (B) 1 equipped with a stirrer and a reflux condenser sufficiently purged with nitrogen.
Dehydrated and deoxygenated toluene 10 in a 000 ml flask
0 ml was introduced. Then, on one of the two dropping funnels,
0.72 g (10 mmol) of trimethylaluminum,
1.96 g (10 mmol) of triisobutylaluminum was diluted in 50 ml of toluene, and toluene containing saturated water was introduced into the other, and the mixed aluminum solution and toluene containing saturated water were converted into Al and H ₂ O at 30 ° C. Was fed in equimolar amounts over 3 hours. After the feed ends, 5
The temperature was raised to 0 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 1.9 g of methylisobutylalumoxane as a white solid. Dilute the resulting white solid in toluene
²⁷ As a result of Al-NMR measurement, chemical shift 174pp
m, a spectrum having a half bandwidth of 5844 Hz was shown.

As a component (A) for producing a solid catalyst, a porous polypropylene powder manufactured by Akzo (trade name: "Accurel" 200 to 400 μm)
m-classified product). The pore size of this powder is 0.05
The pore volume between μm and 2.0 μm is 1.89 cc / g,
The total pore volume between 0.006 μm and 10 μm is 2.54
cc / g.

In a 300 ml flask sufficiently purged with nitrogen,
3 g of the above-mentioned porous polypropylene manufactured by Akzo as the component (A), and 2.0 g (0.025 mol) of the methyl isobutylalumoxane synthesized above as the component (B)
Was dissolved in 40 ml of toluene and introduced. Next, dimethylsilylenebis (2
95-methylindenyl) zirconium dichloride.
After introducing 2 mg, toluene was distilled off for 1 hour under a nitrogen stream while stirring at room temperature to obtain a target solid catalyst. When a small amount of this solid catalyst was sampled and dried at 50 ° C. under reduced pressure, the weight was reduced by 7% by weight, and toluene was recovered in the cooling trap.

Production of Propylene Block Copolymer After 80 g of sufficiently dehydrated and nitrogen-purified sodium chloride was introduced into a 1.5-liter internal volume stirred autoclave, the inside of the autoclave was heated to 50 ° C. and replaced with propylene. Then, 0.5 g of the solid catalyst obtained above was introduced, propylene pressure = 7 kg / cm ² G, polymerization temperature = 50 ° C., polymerization time = 4.
The first-stage gas phase polymerization was performed under the following conditions. After completion of the first-stage polymerization, propylene was purged, and then the pressure was increased to 7 kg / cm ² G with a mixed gas of propylene and 1/3 (molar ratio), and polymerization was continued for 1 hour. After the completion of the polymerization, the solid was recovered, the attached salt was washed away with a large amount of water, and then dried. As a result, 42.7 g of a polymer was recovered. Thus, the catalyst activity was 25.1 kg per gram of Zr.
The melting point was 140.5 ° C., and the peak was one peak. When the obtained polymer was subjected to cold xylene extraction, 1
Eight percent by weight dissolved. The cooled xylene insolubles had a number average molecular weight of 110,000, a Q value of 2.30, and ¹³ C-
The [mm] triad fraction measured by NMR is 0.88, and the number average molecular weight of the cold xylene-soluble component is 15
Is 6,000, Q value is 2.75, r _E r _P = 0.6
8. A rubbery polymer having an ethylene content of 72% by weight. The average particle size of the obtained polymer was 2.0 mm.
The fine particles having a size of 9 μm or less were 0.3% by weight or less. The MFR of all the polymers was 4.6. <Example 2> A polymerization operation was performed under the same conditions as in Example 1 except that 30 cc of hydrogen was introduced during the first-stage polymerization. Table 1 shows the results. <Example 3> The polymerization operation was performed in the same manner as in Example 1 except that during the subsequent polymerization, the pressure was increased to 7 kg / cm ² G with a mixed gas in which the molar ratio of propylene and ethylene was 1/1. Table 1 shows the results. <Comparative Example-1> Instead of the solid catalyst obtained in Example-1,
The polymerization operation was carried out under the same conditions as in Example 1 except that 9 mmol of the component (B) was converted into Al atoms and 3 μmol of dimethylsilylenebis (2-methylindenyl) zirconium dichloride of the component (C) was used. Table 1 shows the results. <Example-4> Example 1 was repeated except that 1 mmol of triisobutylaluminum was introduced as the third component before the first-stage polymerization.
The polymerization operation was performed under the same conditions as in Example 1. Table 1 shows the results. <Example-5> A polymerization operation was carried out under the same conditions as in Example-4 except that the post-stage polymerization time was changed to 2 hours. Table 1 shows the results. <Example-6> Production of catalyst component (C) Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was prepared according to J. Orgmet. Chem. (342) 21-29.
1988 and J. Orgmet. Chem. (369) was synthesized according to 359-370 19 89.

Specifically, 5.4 g of bis (indenyl) dimethylsilane was diluted with 150 ml of tetrahydrofuran in a 300 ml flask purged with nitrogen, cooled to −50 ° C. or lower, and then cooled with n-butyllithium (1.6 M). / L) was added dropwise over 30 minutes. After completion of the dropwise addition, the temperature was raised to room temperature over 1 hour, and the reaction was carried out at room temperature for 4 hours to synthesize a reaction solution A.

Into a 500 ml flask purged with nitrogen, 200 ml of tetrahydrofuran was introduced.
After cooling to 50 ° C. or less, 4.38 zirconium tetrachloride
Grams were introduced slowly. Next, after introducing the entire amount of the reaction solution A, the temperature was slowly raised to room temperature over 3 hours. After reacting at room temperature for 2 hours, the temperature was further raised to 60 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in 100 ml of toluene and distilled off again to obtain 3.86 g of crude crystals of dimethylsilylbis (indenyl) zirconium dichloride.

Next, the crude crystals were dissolved in dichloromethane 15
0 ml and introduced into a 500 ml autoclave. After introducing 5 g of platinum-carbon (0.5 wt% platinum supported) catalyst, H ₂ = 50 kg / cm ² G, 50
A hydrogenation reaction was carried out at a temperature of 5 ° C. for 5 hours. After the reaction,
After the catalyst was removed by filtration, the solvent was distilled off under reduced pressure, extracted with toluene, and recrystallized to obtain 1.26 g of the target dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride.

As a component (A) for producing a solid catalyst, a porous polypropylene powder (trade name: “Accurel” <100 μm classifier) manufactured by Akzo was used. The pore size of this powder is 0.05μ ~
The pore volume between 2.0μ is 1.66 cc / g, 0.006
The total pore volume between μ and 10μ was 2.33 cc / g.

In a 300 ml flask sufficiently purged with nitrogen,
As the component (A), 3 g of the above-mentioned porous polypropylene manufactured by Akzo Co., Ltd., and as the component (B), about 1.8 g of methyl isobutylalumoxane synthesized in Example 1 (0.1 g).
(0228 mol) dissolved in 40 ml of toluene.
Next, 42 mg (0.94 mmol) of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized above was introduced as the component (C).
After the introduction, toluene was distilled off for 1 hour under a nitrogen stream with stirring at room temperature to allow the polypropylene particles to flow independently. A part thereof was extracted and dried under reduced pressure at 50 ° C., so that the weight was reduced by 11% by weight, and toluene was recovered in the cooling trap.

The impregnated solid obtained above was preliminarily polymerized with propylene at atmospheric pressure in a flow system. The prepolymerization is performed by cooling with ice water while controlling the flow rate of propylene gas.
Performed between ２０20 ° C. for 30 minutes. The polymerization temperature was controlled by changing the mixing ratio of propylene and nitrogen in the flowing gas in addition to cooling with ice water. After the completion of the prepolymerization, the solid was recovered to obtain 9.5 g of a solid. The Zr content in this solid was 0.76 milligram / gram. Therefore, the prepolymerization yield was 650 grams per Zr.

Production of Propylene Block Copolymer Into a 1.5-liter stirred autoclave, 80 g of sufficiently dehydrated and nitrogen-purified salt was introduced.
The temperature in the autoclave was raised to 30 ° C., and propylene was replaced. Then, 0.6 g of the solid catalyst obtained above was introduced, propylene pressure = 7 kg / cm ² G, polymerization temperature = 30.
The first-stage gas-phase polymerization was performed under the conditions of ° C and a polymerization time of 6 hours. After completion of the first-stage polymerization, propylene was purged, and then 7 kg with a mixed gas of 1/3 (molar ratio) of propylene and ethylene.
/ Cm ² , and post-stage polymerization was performed at 30 ° C. for 1 hour.
Post-treatment of the polymer was performed according to Example-4. Table 1 shows the results. <Example-7> Production of component (C) Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was synthesized by the following method.

In a 500 ml flask sufficiently purged with nitrogen,
After introducing 200 ml of THF and 5 g of fluorene, and cooling the mixture to −50 ° C. or lower, 67 ml of a diluted solution of methyllithium diethyl ether (1.4 M) was added dropwise over 30 minutes.
The temperature was gradually raised to room temperature and reacted for 3 hours. Then
After cooling again to -50 ° C or lower, 10 g of 6,6-dimethylfulvene was added dropwise over 30 minutes. After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was carried out for two days and nights. After the reaction,
_The reaction was stopped by adding 60 ml of ₂ O, the ether layer was separated, dehydrated using anhydrous MgSO ₄ , and the ether was evaporated to dryness to give 2-cyclopentadienyl-2-fluorenylpropane crude crystals. 17.6 g were obtained.

Next, 10 g of the above crude crystals were added to THF 100
Then, the mixture was cooled to -50 ° C or lower, and 46.0 ml (0.0736 mol) of n-butyllithium was added dropwise over 10 minutes. The temperature was returned to room temperature over 1 hour and reacted at room temperature for 2 hours. Next, the solvent was evaporated and dried under a nitrogen stream, and then 100 ml of dichloromethane was added, and the mixture was cooled to -50 ° C or lower. Next, a solution prepared by previously mixing 8.16 g of zirconium tetrachloride in 50 ml of dichloromethane at a low temperature was fed at a stretch. After mixing, slowly raise the temperature over 3 hours,
The reaction was carried out at room temperature for one day. After completion of the reaction, solids were removed by filtration, and the filtrate was concentrated and recrystallized to obtain 4.68 g of a red isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride component (C).

Preparation of Solid Catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 65.5 mg of the component (C) obtained above was used.
The Zr content was 0.88 (milligram / gram), and the prepolymerization yield was 650 (gram / gram Zr).

Production of Propylene Block Copolymer Polymerization was carried out in the same manner as in Example 4 except that 1.0 g of the above solid catalyst was used. Table 1 shows the results. <Reference Example> The polymers obtained in the above Examples and Comparative Examples were melt-mixed with a plast mill, and then pressed into a 2 mm-thick sheet, and the mechanical properties were measured. The results shown in Table 2 were obtained. Was done.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

According to the method of the present invention, a propylene block copolymer having improved impact strength can be stably produced under gas phase polymerization conditions, and a rubber having good copolymerizability can be obtained. As described above, it is possible to provide a propylene block copolymer having an improved impact resistance without blending the propylene block copolymer.

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of the technical contents of the present invention relating to a Ziegler catalyst.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-92621 (JP, A) JP-A-6-25348 (JP, A) JP-A-5-279423 (JP, A) JP-A-4- 114050 (JP, A) Special Table Hei 7-508065 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] A propylene crystalline homopolymer or propylene substantially in a gas phase in the presence of a catalyst obtained by supporting the following components (A) and (B) and (C) on the following components (A): The first-stage polymerization for producing a copolymer of propylene and ethylene having an ethylene content of 5% by weight or less and the polymerization in the presence of the catalyst and the first-stage polymer are continued to produce propylene, ethylene and a C4-20 a second-stage polymerization of polymerizing at least one comonomer selected from the group consisting of α-olefins such that the polymerization ratio (molar ratio) of propylene and the comonomer is in a ratio of 0/100 to 80/20; and The polymerization amount of the former stage and the polymerization amount of the latter stage are 9 by weight ratio.
A method for producing a propylene block copolymer, wherein polymerization is carried out so as to be from 5/5 to 30/70. Component (A): an organic porous polymer having an average particle size of 5 to 1000 μm and a pore size of 0.006 to 10 μm
m is 0.8 cc / g or more, and the total pore volume of all the pores having a pore diameter of 0.05 to 2 μm is 0.006 what is at more than 50% of the sum of the total pore volume of pores 10 .mu.m, component (B): an organoaluminum oxy compound, component (C): formula ^{_{Q (C 5 H 4-a}} R 1 a) _{(C 5}
H _{^4-b R} 2 ^b) a transition metal compound represented by Mexy. ^{_{[However, (C 5 H 4-a}} R 1 a) and ^{_{(C 5 H 4-b R}} 2
_b ) is a conjugated five-membered ring ligand each of which coordinates to Me (R ¹ and R ² are each independently a hydrocarbon residue having 1 to 20 carbon atoms, a halogen group, an alkoxy group having 1 to 12 carbon atoms) A silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms, and a boron-containing hydrocarbon group having 1 to 12 carbon atoms. A monovalent group selected from the group consisting of a plurality of R ¹
Alternatively, R ² may be bonded at each other end to form a ring), Q is a divalent bonding group bridging between the two conjugated five-membered ligands, Me is titanium, X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon group having up to 2 carbon atoms having 1 to 20 carbon atoms; An amino group optionally substituted with 1 carbon atom
A monovalent group selected from the group consisting of a phosphorus-containing hydrocarbon group having from 20 to 20 and a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a is an integer of 0 ≦ a ≦ 4, and b is 0 ≦ b ≦ 4 Are respectively shown. ]