JPH09169826A - Method for producing propylene-based block copolymer - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a method for producing a propylene-based block copolymer capable of obtaining a molded article having excellent appearance and impact resistance. In the presence of a catalyst for olefin polymerization, the first
In the polymerization step, copolymerization of ethylene and propylene is carried out in a liquid propylene medium, the constitutional unit derived from ethylene is contained in a proportion of 10 to 70 mol%, and the intrinsic viscosity [η] is 5 to 30 dl / a low crystalline or non-crystalline polymer in the range of g is produced, and in the second polymerization step, homopolymerization of propylene is carried out in the coexistence of the low crystalline or non-crystalline polymer, or A method for producing a propylene-based block copolymer, which comprises copolymerizing ethylene with ethylene and / or an α-olefin having 4 to 10 carbon atoms to produce a crystalline polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a propylene-based block copolymer capable of obtaining a molded article excellent in impact resistance and appearance.

[0002]

BACKGROUND OF THE INVENTION Olefin polymers such as propylene polymers are excellent in rigidity, heat resistance and impact resistance, and are therefore used in various fields such as for various molded products.

As a method for further improving the impact strength of such an olefin polymer, for example, a crystalline propylene polymer part and a low (non) crystalline propylene / ethylene random copolymer part (rubber part) are used. There is known a method of producing a block copolymer having As for the block copolymer, the impact resistance and appearance of the molded product are improved when the rubber part has a large molecular weight, and therefore a block copolymer having a large rubber part molecular weight is desired.

When producing a block copolymer, generally, a crystalline propylene polymer part is produced in the first polymerization step and then a rubber part is produced in the second polymerization step. At this time, hydrogen is used to control the molecular weight of the crystalline propylene polymer part,
This hydrogen may be mixed in the polymerization system for producing the rubber part, and it has been difficult to control the molecular weight of the rubber part. Further, it has been difficult to prevent hydrogen from being mixed into the polymerization system for producing the rubber part.

Further, in the block copolymer, when the molecular weight of the rubber portion is high or the content ratio of the rubber portion is high, the dispersibility of the rubber portion is deteriorated, so that fish eyes or spots are generated on the surface of the molded product. . In order to prevent this, the block copolymer is strongly kneaded during molding, or a deactivator such as oxygen is introduced in the second polymerization step to reduce the polymerization activity. As a method of improving the dispersibility of the rubber part, a method of producing the rubber part in the first polymerization step and producing the crystalline propylene polymer part in the second polymerization step is conceivable. There is a problem that the (non) crystalline copolymer is eluted and the particle properties of the polymer are deteriorated to deteriorate the drivability.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior arts, and in a block copolymer even when the molecular weight of the rubber portion is high or the content ratio of the rubber portion is high. A propylene-based block copolymer capable of producing a propylene-based block copolymer that has a high dispersibility in the rubber part of the rubber composition, has little appearance, is excellent in appearance, and has excellent impact resistance. It is intended to provide a way.

[0007]

SUMMARY OF THE INVENTION The method for producing a propylene-based block copolymer according to the present invention is carried out in the presence of an olefin polymerization catalyst,
In the first polymerization step, copolymerization of ethylene and propylene is carried out in a propylene medium, and a constitutional unit derived from ethylene is contained in a proportion of 10 to 70 mol%, and an intrinsic viscosity [η] is 5 to 30 dl / The low crystalline or non-crystalline polymer in the range of g is produced in a proportion of 2 to 40% by weight with respect to the finally obtained block copolymer,
In the second polymerization step, homopolymerization of propylene is performed in the coexistence of the low crystalline or non-crystalline polymer, or propylene and ethylene and / or α-olefin having 4 to 10 carbon atoms are used. Copolymerization is performed to obtain a crystalline polymer in a proportion of 98 relative to the finally obtained block copolymer.
It is characterized in that it is manufactured so that the ratio is up to 60% by weight.

[0008] In the present invention, the ratio of the intrinsic viscosity of the low crystalline or amorphous polymer [eta] and _A, the intrinsic viscosity of the crystalline polymer _{[η] B ([η]} A / [η] _B ) is 1 to 50
Is desirably within the range.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a propylene block copolymer according to the present invention will be specifically described below.

In the present invention, ethylene and propylene are copolymerized in the first polymerization step in the presence of an olefin polymerization catalyst (1) or an olefin polymerization catalyst (2) as will be described later to obtain low crystallinity. Alternatively, an amorphous copolymer is produced, and in the second polymerization step, homopolymerization of propylene is performed in the coexistence of the low crystalline or amorphous copolymer, or propylene and ethylene and / or Copolymerization with an olefin having 4 to 10 carbon atoms is carried out to produce a crystalline polymer.

In the first polymerization step, copolymerization of ethylene and propylene is carried out in a liquid propylene medium to obtain a low crystalline copolymer (low crystalline copolymer part) or an amorphous copolymer (amorphous copolymer). A sex copolymer part) is produced.

In the first polymerization step, the polymerization temperature is usually about -50 to 200 ° C, preferably about 20 to 100 ° C.
And the pressure is usually set to atmospheric pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

In the present invention, the production of the low (non) crystalline copolymer part is carried out in the first polymerization step in the block copolymer production step, and since hydrogen is not mixed into the polymerization system,
It is possible to produce a low (non-) crystalline copolymer part having a large molecular weight. Further, the hydrogen concentration in the polymerization system can be easily adjusted, and the molecular weight of the low (non) crystalline copolymer part can be easily adjusted. When hydrogen is used during the polymerization, the molecular weight of the obtained copolymer can be adjusted, but in the present invention, it is preferable not to use hydrogen in the first polymerization step.

The low crystalline or amorphous copolymer obtained in the first polymerization step contains 10 to 70 mol%, preferably 10 to 60 mol% of a structural unit derived from ethylene.
More preferably, the content is 15 to 55 mol%, and 13
Intrinsic viscosity [η] measured in 5 ° C decalin is 5-30d
1 / g, preferably 5 to 25 dl / g, and more preferably 5.5 to 25 dl / g.

In the first polymerization step, the low crystalline or amorphous copolymer is 2 to 40% by weight, preferably 2.5 to 40% by weight based on the propylene block copolymer finally obtained.
It is produced in an amount of 38% by weight, more preferably 3 to 35% by weight.

In the first polymerization step, the copolymerization of ethylene and propylene is carried out in a liquid propylene medium, so that the obtained low (non) crystalline copolymer is eluted into the medium to form a polymer. The particle properties do not deteriorate.

In the production of the propylene block copolymer according to the present invention, following the first polymerization step, the presence of the low crystalline or amorphous copolymer obtained in the first polymerization step Then, homopolymerization of propylene or copolymerization of propylene and ethylene and / or olefin having 4 to 10 carbon atoms is carried out to produce a crystalline polymer (crystalline polypropylene part).

Examples of the olefin having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene and 4-methyl-1-.
Pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene and the like can be mentioned.

The second polymerization step is usually carried out in a liquid propylene medium. In the second polymerization step, the polymerization temperature is usually about -50 to 200 ° C, preferably about 20 to 200 ° C.
The temperature is 100 ° C., and the pressure is usually atmospheric pressure to 100 kg / c.
It is set to m ² , preferably about ² to 50 kg / cm ² .
The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

When hydrogen is used in the second polymerization, a copolymer having a high melt flow rate can be obtained, and the molecular weight of the propylene-based block copolymer obtained by hydrogenation can be adjusted.

The crystalline polymer obtained in the second polymerization step has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.1 to 20 dl / g, preferably 0.5 to 15 dl / g.
g, more preferably in the range of 0.7 to 10 dl / g.

The constituent unit derived from an olefin other than propylene is 0 to 20 mol%, preferably 0 to 15
It is desirable that the content is mol%, more preferably 0 to 10 mol%.

Low crystallinity obtained in the first polymerization step or
Intrinsic viscosity of amorphous copolymer [η]_AAnd the second polymerization step
Intrinsic viscosity [η] of the crystalline polymer obtained in_BAnd the ratio
([Η] _A/ [Η]_B) Is 1 to 50, preferably 1 to
It is preferably in the range of 30. Obtained in the first polymerization step
Intrinsic Viscosity [η] of Low-Crystalline or Amorphous Copolymer
_AAnd the ultimate viscosity of the crystalline polymer obtained in the second polymerization step.
Degree [η]_BIf the ratio of
The ren block copolymer has excellent moldability.

In the second polymerization step, the crystalline polymer is contained in an amount of 98 to 60% by weight, preferably 97.5 to 62% by weight, based on the propylene block copolymer finally obtained.
More preferably, it is produced in an amount such that the proportion is 97 to 65% by weight.

The propylene block copolymer thus produced has a melt flow rate of 0.1 to 500 g / 10 minutes, preferably 0.2 to 300 g / 10 minutes at 230 ° C. under a load of 2.16 kg. The density is 0.885 to 0.936 g / cm ³ , preferably 0.1.
It is in the range of 900 to 0.933 g / cm ³ , and 135 ° C.
The intrinsic viscosity [η] measured in decalin is usually 30
~ 0.001 dl / g, preferably 10-0.01 dl
/ G, particularly preferably in the range of 5 to 0.05 dl / g.

The amount of the decane-soluble component at 23 ° C. in the propylene block copolymer obtained in the present invention is 40% or less, preferably 38% or less, more preferably 35% or less. The decane-soluble component mainly contains the low (non) crystalline copolymer obtained in the first polymerization step.

The amount of the propylene-based block copolymer soluble in decane at 23 ° C. is measured as follows. That is, the copolymer 3 was placed in a 1 liter flask equipped with a stirrer.
g, 2,6-di tert-butyl-4-methylphenol 20m
Add 500 ml of g and n-decane, and dissolve by heating on an oil bath at 145 ° C. After the copolymer is dissolved, it is cooled to room temperature over about 8 hours and then kept on a water bath at 23 ° C. for 8 hours. The precipitated polymer and the n-decane suspension containing the dissolved polymer are separated by filtration with a G-4 (or G-2) glass filter. The obtained solution was 10 mmHg and 150 ° C.,
It is dried to a fixed amount, and its weight is measured to obtain the soluble component amount of the copolymer in the mixed solvent, which is calculated as a percentage with respect to the weight of the sample copolymer.

In the method for producing a propylene-based block copolymer according to the present invention, in the first polymerization step, low (non)
Since the crystalline copolymer part is produced and the crystalline polymer part is produced in the second polymerization step, the obtained propylene-based block copolymer has a low (non) crystalline copolymer part molecular weight. Of high (low) (non-) crystalline copolymer part, even if the content of low (non-) crystalline copolymer part is high, it is excellent in dispersibility of low (non-) crystalline copolymer part and excellent in impact resistance and appearance. The body can be manufactured.

Next, the olefin polymerization catalyst (1) and the olefin polymerization catalyst (2) used in the present invention will be specifically described. The olefin polymerization catalyst (1) includes (A) a transition metal compound represented by the following general formula (I) or (II), (B) (B-1) an organoaluminum oxy compound, and / or (B- 2) A compound that reacts with the transition metal compound (A) to form an ion pair and, if necessary, (C) an organoaluminum compound, and at least one of the above components is supported on a fine particle carrier. It is a solid catalyst composed of

First, the transition metal compound represented by the general formula (I) will be described.

[0031]

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In the formula, M ¹ represents a transition metal atom of Group IV to VIB of the periodic table, specifically, zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, Preferred is zirconium, titanium or hafnium.

R ^{1 to} R ⁵ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, oxygen. A containing group, a sulfur containing group, a nitrogen containing group, a phosphorus containing group, a hydrogen atom or a halogen atom is shown. Among the groups represented by R ^{1 to} R ⁵ , some of the groups adjacent to each other may be bonded to each other to form a ring together with the carbon atom to which those groups are bonded. Although R ^{1 to} R ⁴ are shown at two places respectively, for example, R ¹ and R ¹ may be the same group or different groups. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

Specific examples of hydrocarbon groups having 1 to 20 carbon atoms as R ^{1 to} R ⁵ include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cyclopentyl , Cyclohexyl, norbornyl, adamantyl, etc. cycloalkyl groups; vinyl, propenyl, cyclohexenyl, etc. alkenyl groups; benzyl, phenylethyl, phenylpropyl, etc. arylalkyl groups; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propyl Phenyl, biphenyl, naphthyl,
Examples thereof include aryl groups such as methylnaphthyl, anthracenyl and phenanthryl.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Fused rings such as indene rings, benzene rings, naphthalene rings,
Examples include a group in which a hydrogen atom on a condensed ring group such as an acenaphthene ring or an indene ring is substituted with an alkyl group such as methyl, ethyl, propyl, or butyl.

Examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups obtained by substituting the above hydrocarbon groups with halogen. Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,
Trihydrocarbon-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted trimethylphenyl and the like And an aryl group.

Further, as the silicon-containing group, other than the above
Examples include groups represented by SiR ₃ [wherein R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; an arylalkoxy group such as phenylmethoxy and phenylethoxy. To be

Further, as the oxygen-containing group, -OSiR
₃ [where R is a halogen atom, having 1 to 1 carbon atoms.
0 alkyl group or aryl group having 6 to 10 carbon atoms].

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur. Further, as the sulfur-containing group, other than the above-mentioned -SR [where R
Is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Further, as the nitrogen-containing group, -N other than the above is used.
R ₂ [where R represents a halogen atom and a carbon atom number of 1 to
Alkyl group of 10 or aryl group having 6 to 10 carbon atoms].

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Further, as the phosphorus-containing group,
PR ₂ [where R is a halogen atom and has 1 carbon atom
To 10 alkyl groups or aryl groups having 6 to 10 carbon atoms].

Examples of the halogen include fluorine, chlorine, bromine and iodine. Among them, a hydrocarbon group is preferable, and in particular, a hydrocarbon group having 1 to 4 carbon atoms of methyl, ethyl, propyl, and butyl, a benzene ring formed by combining hydrocarbon groups, and a hydrocarbon group are preferable. The hydrogen atom on the benzene ring formed by bonding is methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, iso-butyl, tert
It is preferably a group substituted with an alkyl group such as -butyl.

X ¹ and X ² may be the same or different and each represents a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

The hydrocarbon group has 1 to 20 carbon atoms.
Is preferred, and specific examples thereof include the same groups as R ^{1 to} R ⁵ . The halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the same groups as R ^{1 to} R ⁵ .

As the oxygen-containing group and the halogen atom,
The same group or atom as R ^{1 to} R ⁵ can be exemplified. Examples of the sulfur-containing group include the same groups as R ^{1 to} R ⁵ , as well as methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. , Triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate and other sulfonate groups; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethyl Examples include sulfinate groups such as benzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl group and silicon-substituted aryl group as described above. Of these, halogen atoms and C1-20
Is preferably a hydrocarbon group or a sulfonate group.

In the above formula (I), two R ^{5 s} may be bonded to each other to form a bonding group. In this case, the compound represented by the above formula (I) is represented by the following formula (I ′). expressed.

[0050]

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Y ¹ is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, --O--, --CO. -,-
S -, - SO -, - SO 2 -, - Ge -, - Sn -, -
NR ⁶ −, −P (R ⁶ ) −, −P (O) (R ⁶ ) −, −
BR ⁶ — or —AlR ⁶ — [wherein R ⁶ may be the same or different from each other and is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or an alkoxy group].

The hydrocarbon group has 1 to 2 carbon atoms.
A divalent hydrocarbon group of 0 is preferable, and specific examples thereof include methylene, dimethylmethylene, 1,2-ethylene and dimethyl-1,2-.
Ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,
Examples thereof include alkylene groups such as 2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

As the halogenated hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms is preferable, and specifically, the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. And a group obtained by halogenating the hydrocarbon group.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; tetramethyl-1,2-disilyl, tetraphenyl-
Alkyldisilyl groups such as 1,2-disilyl; alkylaryldisilyl groups; and aryldisilyl groups.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Furthermore, the divalent silicon-containing group, the divalent germanium-containing group, and the divalent tin-containing group include any one of silicon, germanium and tin among the groups represented by the following [Chemical Formula 6]. Groups.

Of these, substituted silylene groups such as dimethylsilylene group, diphenylsilylene group and methylphenylsilylene group are particularly preferable. Specific examples of the transition metal compound represented by the above formula (I) include the following compounds.

Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene-bis (1,3
-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, dimethylsilylene -Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-isopropyl-7-methylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-Methyl-4,6-diisopropylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-Methyl-4,5-benzoindenyl)} zirconium dichloride, dimethylsilylene-bis (2 -Methyl-4,5-acenaphthocyclopentadienyl)
Zirconium dichloride, etc.

Furthermore, transition metal compounds in which zirconium metal, titanium metal and hafnium metal in the above compounds are replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal and tungsten metal can be mentioned.

In the present invention, among the transition metal compounds represented by the above formula (I), it is particularly preferable to use the transition metal compound represented by the following formula (III), (IV) or (V).

[0060]

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(In the formula, M ¹ is M in the formula (I).
A transition metal of Groups IV to VIB of the periodic table similar to ¹ and R
¹¹ , R ¹² and R ^{14 to} R ¹⁶ may be the same or different from each other, and are each a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 1.
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups,
It represents a nitrogen-containing group or a phosphorus-containing group, and some of adjacent groups may be bonded to each other to form a ring with the carbon atom to which those groups are bonded, and R ¹³ is 6 carbon atoms.
To 16 in the formula (I), X ¹ and X ² may be the same or different from each other.
Is similar to ¹ and X ^2, Y ¹ is the same as Y ¹ in the formula (I '). )

[0062]

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(In the formula, M ¹ is M in the formula (I).
A transition metal of Groups IV to VIB of the periodic table similar to ¹ and R
²¹ and R ²² may be the same or different from each other,
Hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group represents a group, R ²³ and R ²⁴ may be the same or different from each other, the number of carbon atoms from 1 to 20
Indicates an alkyl group, X ¹ and X ^2, which may be the same or different from each other, are the same as X ¹ and X ² in the formula (I), Y ¹ is, Y in Formula (I ') ^Same as ¹ . )

[0064]

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(In the formula, M ³ is a transition metal of Group IVB of the periodic table, R ^{31 s} may be the same or different from each other, and a hydrogen atom, a halogen atom, or a carbon atom having 1 to 10 carbon atoms. An alkyl group, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, -NR ₂ ,
-SR, -OSiR _3, -SiR ₃ or -PR ₂ groups [wherein, R represents a halogen atom, preferably a chlorine atom, from 1 to 10 carbon atoms, preferably 1 to 3 alkyl groups or carbon atoms, There 6-10, preferably an aryl group] of 6-8, R ³² to R ³⁸ may be the same or different from each other, indicate the same atom or group as the R ^21, these R ³² ~ At least two adjacent groups of the groups represented by R ³⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, and X ⁴ and X
⁵ may be the same or different from each other, a hydrogen atom,
An alkyl group having 1 to 10 carbon atoms, having 1 to 10 carbon atoms
10 alkoxy group, C 6-10 aryl group, C 6-10 aryloxy group, C 2-10 alkenyl group, C 7-40
Represents an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an OH group or a halogen atom, and Z ² represents

[0066]

[Chemical 6]

--O--, --CO--, --S--, --SO--,-
SO_Two-, -Ge-, -Sn-, -NR³⁹-, -P (R
³⁹)-, -P (O) (R³⁹)-, -BR³⁹-Or-A
lR ³⁹-.

However, R ³⁹ and R ⁴⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
A fluoroalkyl group, an aryl group having 6 to 10 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 2 to
An alkenyl group having 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, and an alkylaryl group having 7 to 40 carbon atoms, and R ³⁹ and R ⁴⁰ are , Each may form a ring together with the atom to which they are attached, and M ³ represents silicon, germanium or tin. ) Next, the transition metal compound represented by the general formula (II) will be described.

[0069]

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In the formula, M ² represents a Group IVB transition metal atom, specifically a titanium, zirconium or hafnium atom. Cp is a cyclounsaturated hydrocarbon group or chain such as cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group. Shows a unsaturated hydrocarbon group.

X ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An alkylaryl group, an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms is shown.

Z ¹ is SiR ⁷ ₂ , CR ⁷ ₂ , SiR ⁷ ₂ Si
R ⁷ ₂ , CR ⁷ ₂ CR ⁷ ₂ , CR ⁷ ₂ CR ⁷ ₂ CR ⁷ ₂ , CR ⁷ = C
Shows the _{^{R 7, CR 7 2 SiR 7}} 2 or GERR ⁷ _2. Y
^{2, -N (R 8) -,} - O -, - S- or -P
(R ⁸ )-is shown.

R ⁷ is a group selected from a hydrogen atom or an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group or a combination thereof, and R ⁸ is a group having carbon atoms. An alkyl group having 1 to 10 or an aryl group having 6 to 10 carbon atoms, or 1
Fused ring systems of up to 30 non-hydrogen atoms with one or more R ⁷ may be formed.

W represents 1 or 2. Specific examples of the compound represented by the general formula (II) include (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (methyl amide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (tert-butylamido) dimethyl (tetra Methyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η
⁵ -cyclopentadienyl) silane titanium dichloride,
(Phenyl phosphide) dimethyl (tetramethyl-η ^5-
Examples include cyclopentadienyl) silane zirconium dibenzyl.

The (B-1) organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Good.

These organoaluminum oxy compounds (B-1) can be used alone or in combination of two or more kinds. (B-2) As the compound that reacts with the transition metal compound (A) to form an ion pair (hereinafter, may be referred to as “ionized ionic compound”), JP-A-1-501950 and JP-A-501950 1-502036, Japanese Patent Laid-Open No. 3-17
9005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, and other Lewis acids, ionic compounds, and carborane compounds. You can

As Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , SiO 2 -Al 2
O ₃ can be exemplified.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroferrite Examples include cerium tetra (pentafluorophenyl) borate.

Examples of the carborane compound are dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaunceca) borate, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

The compound (B-2) which reacts with the above transition metal compound (A) to form an ion pair can be used as a mixture of two or more kinds. Hereinafter, one kind of compound selected from the above-mentioned (B-1) organoaluminum oxy compound and (B-2) transition metal compound (A) to form an ion pair is referred to as "activating compound". is there.

As the organoaluminum compound (C) used as necessary, an organoaluminum compound represented by the following formula (VIII) can be exemplified. During ^{_{R d n AlX 3-n ...}} (VIII) ( wherein, R ^d represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
3. In the above formula (VIII), R ^d is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group. Group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (C)
Specifically, trialkyl aluminum, alkenyl aluminum, dialkyl aluminum halide,
Examples thereof include alkylaluminum sesquihalide, alkylaluminum dihalide, and alkylaluminum hydride, and triethylaluminum and triisopropylaluminum are preferable.

As the organoaluminum compound (C), a compound represented by the following formula (IX) can also be used. During ^{_{R d n AlY 3-n ...}} (IX) ( wherein, R ^d are as defined above, Y is -OR ^e group, -
OSiR ^f ₃ group, -OAlR ^g ₂ group, -NR ^h ₂ group, -S
indicates iR ⁱ ₃ group or -N (R ^j) AlR ^k ₂ group, n is ^{1~2, R e, R f,} R g and R ^k are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., R ^h is a hydrogen atom,
A methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ⁱ and R ^j are a methyl group, an ethyl group and the like. ) Among such organoaluminum compounds, R ^d _n
A compound represented by Al (OAlR ^g ₂ ) _3-n , such as E
t ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (is
o-Bu) _{2 and the} like are preferable.

Among the organoaluminum compounds represented by the above formula (VIII) or (IX), the compound represented by the formula R ^d ₃ Al is preferable, and the compound in which R ^d is an isoalkyl group is particularly preferable.

Such an organoaluminum compound (C)
Can be used alone or in combination of two or more. At least one of the above-mentioned (A) transition metal compound, (B-1) organoaluminum oxy compound, (B-2) ionized ionic compound and (C) organoaluminum compound is supported on a fine particle carrier. Used.

Such a fine particle carrier is an inorganic or organic compound and is a granular or fine particle solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm.

Among them, a porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO_Two, Al_TwoO_Three, MgO, Z
rO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, T
hO _TwoOr a mixture thereof, such as SiO_Two-
MgO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two
-V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-MgO
And the like. Among these SiO_TwoYou
And / or Al_TwoO_ThreeThe main component is preferably.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier differ depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably in the range of 100 to 700 m ² / g,
It is desirable that the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The fine particle carrier may be 100 to
It is used by firing at a temperature of 1000 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
Granular or particulate solids of organic compounds having a size of 0 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers containing α-olefins having 2 to 14 carbon atoms such as pentene as a main component, or polymers or copolymers containing vinylcyclohexane and styrene as a main component.

Such a fine particle carrier may contain surface hydroxyl groups and / or water. An olefin polymerization catalyst (solid catalyst) in which at least one component of the (A) transition metal compound, (B) activating compound and (C) organoaluminum compound is supported in the form of fine particles,
Prepared by mixing and contacting the (A) transition metal compound, (B) activating compound, particulate carrier, and (C) organoaluminum compound in an inert hydrocarbon medium or an olefin medium, if necessary. can do.

The olefin polymerization catalyst (1) used in the present invention may be a prepolymerization catalyst prepared by prepolymerizing a small amount of olefin in the solid catalyst. When polymerizing an olefin in the presence of such an olefin polymerization catalyst (1), the transition metal compound (A) usually has a concentration of the transition metal atom in the transition metal compound (A) in the polymerization system of 10 ^−. It is desirable to use an amount of ⁸ to 10 ^-3 gram atom / liter, preferably 10 ^-7 to 10 ^-4 gram atom / liter. When the organoaluminum oxy compound (B-1) is used as the activating compound (B), aluminum in the organoaluminum oxy compound (B-1),
Atomic ratio with transition metal in transition metal compound (A) (Al /
(Transition metal) is usually 5 to 10,000, preferably 10
It is in the range of 5000. When the ionized ionic compound (B-2) is used as the activating compound (B), the molar ratio of the transition metal compound (A) and the ionized ionic compound (B-2) [(A) / (B-2) ] Is usually in the range of 0.01 to 10, preferably 0.5 to 5. When the organoaluminum compound (C) is used, the organoaluminum compound (C)
The atomic ratio (Al / transition metal) between aluminum in the transition metal compound and the transition metal in the transition metal compound (A) is usually 5 to 1000.
The range is 0, preferably 10 to 5000.

In the present invention, (B-1) an organoaluminum oxy compound, (B-2), which is supported on a fine particle carrier.
In addition to the ionized ionic compound or (C) organoaluminum compound, an unsupported organoaluminum oxy compound (B-1), an ionized ionic compound (B
-2) or an organoaluminum compound (C) can be used.

The olefin polymerization catalyst (2) is (Ia)
A solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components;
(II) an organometallic catalyst component (b), and (III) a silicon compound (c) represented by the following formula (i) or a compound (d) having two or more ether bonds existing through a plurality of atoms. Formed from.

[0095] In _{^{R p n -Si- (OR q)}} 4-n ... (i) ( wherein, n is 1, 2 or 3, when n is 1, R
^p represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^{p represents} a secondary or tertiary hydrocarbon group and the other is a hydrocarbon group, and R ^p may be the same or different, and R ^q is a carbon number of 1 to
When 4 is a hydrocarbon group of 4 and 4-n is 2 or 3, R ^q may be the same or different. ) Solid titanium catalyst component (a) which is the catalyst component (Ia)
Can be prepared by contacting the following magnesium compound, titanium compound and electron donor.

Used in the preparation of solid titanium catalyst component (a)
Specific examples of the titanium compound include
The tetravalent titanium compound represented by Ti (OR)_nX_4-n (Wherein, R represents a hydrocarbon group, X represents a halogen atom)
And n is 0 ≦ n ≦ 4) As such a titanium compound, specifically, TiCl
_Four, TiBr_Four, TiI_Four Tetrahalogenated titanium such as
Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five) Cl_Three,
Ti (On-C_FourH₉) Cl_Three, Ti (OC_TwoH_Five) Br_Three, T
i (O-iso-C_FourH₉) Br_ThreeTrihalogenated al such as
Coxy titanium; Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH
_Five)_TwoCl_Two, Ti (On-C_FourH₉)_TwoCl _Two, Ti (OC_TwoH
_Five)_TwoBr_TwoDialkoxytitanium dihalide such as T;
i (OCH_Three)_ThreeCl, Ti (OC_TwoH_Five)_ThreeCl, Ti
(On-C_FourH₉)_ThreeCl, Ti (OC_TwoH_Five)_ThreeBr etc.
Monohalogenated trialkoxy titanium; Ti (OC
H_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (On-C_FourH₉)_Four, T
i (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhexyl)
_FourExamples include tetraalkoxy titanium
it can.

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, and the like. it can. These magnesium compounds may be used alone or may form a complex compound with an organic metal compound described later. Further, these magnesium compounds may be liquid, solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can be derived from metallic magnesium during the catalyst preparation using the above-mentioned method.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride;
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxy magnesium, n-octoxy magnesium, 2-
Examples thereof include alkoxymagnesium such as ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived at the time of preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is used as a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. It may be contacted with a compound having an active carbon-oxygen bond, such as a ketone, an aldehyde or the like.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride and aryloxy magnesium chloride are particularly preferable.

The solid titanium catalyst component (a) used in the present invention is formed by contacting the above magnesium compound with the above titanium compound and electron donor.

Specific examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include the following compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Amines such as tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine;
Pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygen-containing compounds such as coumaran, phthalane, tetrahydropyran, pyran and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol,
C1-C18 alcohols such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol,
Nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone, benzoquinone and the like having 3 to 15 carbon atoms Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, Ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, tetrahydrophthalic acid Diisopropyl, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate,
Di-2-ethylhexyl phthalate, γ-butyrolactone, δ-
C2-30 organic acid esters such as valerolactone, coumarin, phthalide, and ethyl carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl Ether, isopropyl ether,
Butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane, etc. with 2 to 2 carbon atoms
0 ethers; 2-isopentyl-2-isopropyl-1,3-
Dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisopentyl -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-
Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,
3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo- [2,2,1] -heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane Diethers such as 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane and 9,9-dimethoxymethylfluorene; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; acetonitrile, benzonitrile, tolunitrile Nitriles such as; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride, etc. are used.

In addition to these, water, anionic, cationic and nonionic surfactants can also be used.
Further, as the organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0106]

Embedded image

In the above formula, R ¹¹ is a substituted or unsubstituted hydrocarbon group, R ¹² , R ¹⁵ , and R ¹⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ¹³ and R ¹⁴ are hydrogen or a substituted hydrocarbon group. Alternatively, it is an unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R ¹³ and R ¹⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{11 to} R ¹⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C—O—C, COOR, COOH, OH, SO.
_It has groups such as ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate and isopropylmalon. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl Diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; And rocyclic polycarboxylic acid esters.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Long chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate can be mentioned.

Further, as the electron donor, a silicon compound represented by the general formula (i) as described later can also be used. Two or more of these compounds can be used in combination.

When the titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, the carrier compound as described above can be used to prepare the carrier-supported solid titanium catalyst component (a). .

The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum. The solid titanium catalyst component (a) can be produced by bringing the above titanium compound, magnesium compound and electron donor into contact with each other, and any known method can be adopted. it can.

The amount of each of the above components used in preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.01 per mol of the magnesium compound. It is used in an amount of from 10 to 10 mol, preferably from 0.1 to 5 mol, and the titanium compound is from 0.01 to 1000 mol, preferably from 0.1 to 200 mol.
It is used in molar amounts.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is in the range of about 2-200, preferably about 4-100, and the electron donor / titanium (molar ratio) is about 0.0.
1-100, preferably in the range of about 0.2-10,
Desirably, the magnesium / titanium (atomic ratio) is in the range of about 1-100, preferably about 2-50.

Such solid titanium catalyst component (a)
The [catalyst component (Ia)] is a prepolymerized catalyst component (Ib) obtained by prepolymerizing an olefin in the presence of the solid titanium catalyst component (a) and the following organometallic catalyst component (b). It can also be used for polymerization.

As the organometallic catalyst component (b) used in the preparation of the prepolymerization catalyst component (Ib), organometallic compounds of Group I to Group III metals of the Periodic Table are used. Compounds such as

(B-1) An organoaluminum oxy compound similar to the organoaluminum oxy compound (B-1) and an organoaluminum compound similar to the organoaluminum compound (C).

(B-2) A complex alkyl compound of a Group I metal represented by the following formula and aluminum. M ³ AlR ¹⁷ ₄ (in the formula, M ³ represents Li, Na, and K, and R ¹⁷ represents a hydrocarbon group containing usually 1 to 15, preferably 1 to 4 carbon atoms) (b-3) A dialkyl compound of Group II or Group III represented by the following formula.

R ¹⁷ R ¹⁸ M ⁴ (In the formula, M ⁴ represents Mg, Zn or Cd, R ¹⁷ is the same as above, and R ¹⁸ has usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Indicated by the number of hydrocarbon groups contained therein) Among these, organoaluminum compounds are preferably used.

When carrying out the prepolymerization, an electron donor (e) may be used in addition to the solid titanium catalyst component (a) and the organometallic catalyst component (b). As the electron donor (e), specifically, the electron donor previously used in preparing the solid titanium catalyst component (a), the silicon compound (c) represented by the formula (i) described later, and A compound (d) having two or more ether bonds existing through a plurality of atoms, and further, an organosilicon compound represented by the following formula (ci) can be mentioned.

R _n —Si— (OR ′) _4-n (ci) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
As the organosilicon compound represented by the general formula (ci), specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis
o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyl Trimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n -Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, Lee butyl, trimethyl phenoxy silane, methyl tri Lilo carboxylate (Allyloxy) silane, vinyltris (beta-methoxyethoxy silane),
Examples thereof include vinyltriacetoxysilane and dimethyltetraethoxydisiloxane.

These electron donors (e) can be used alone or in combination of two or more. The olefin polymerization catalyst (2) comprises the solid titanium catalyst component (Ia) or the prepolymerization catalyst component (Ib), the organometallic catalyst component (II), the silicon compound (c) or a plurality of atoms. And a compound (d) having two or more ether bonds which are present via

As the organometallic catalyst component (II), the same as the organometallic catalyst component (b) used in the preparation of the prepolymerization catalyst component (Ib) can be used. The silicon compound (c) used as the component (III) is a compound represented by the following formula (i).

[0124] In _{^{R p n -Si- (OR q)}} 4-n ... (i) ( wherein, n is 1, 2 or 3, when n is 1, R
^p represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^{p represents} a secondary or tertiary hydrocarbon group, and the other represents a hydrocarbon group. ^{May be} the same or different, and ^Rq has 1 to 1 carbon atoms.
When 4 is a hydrocarbon group of 4 and 4-n is 2 or 3, R ^q may be the same or different. ) In the silicon compound (c) represented by the formula (i),
Examples of the secondary or tertiary hydrocarbon group include a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, these groups having a substituent, or a hydrocarbon group in which carbon adjacent to Si is secondary or tertiary. Can be mentioned.

Of these, dimethoxysilanes, particularly dimethoxysilanes represented by the following formula (ii) are preferable.

[0126]

Embedded image

(In the formula, R ^p and R ^s are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is secondary carbon or tertiary carbon is shown. ) Specifically, dicyclopentyldimethoxysilane, di-t
-Butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl)
Dimethoxysilane and di-t-amyldimethoxysilane are preferred.

Two or more kinds of these silicon compounds (c) can be used in combination. Examples of the compound (d) having two or more ether bonds existing through a plurality of atoms used as the component (III) (hereinafter sometimes referred to as a polyether compound) include compounds represented by the following formulas: You can

[0129]

Embedded image

In the formula, n is an integer of 2 ≦ n ≦ 10, and R
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and may have a substituent other than a carbon atom in the main chain. Atoms may be included.

As the polyether compound as described above, 1,3-diethers are preferably used, and particularly 2,2-diethers are used.
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3 -Dimethoxypropane, 9,9-
Dimethoxymethylfluorene is preferably used.

These polyether compounds (d) can be used in combination of two or more kinds. When polymerizing an olefin in the presence of such an olefin polymerization catalyst (2), the solid titanium catalyst component (Ia) or the prepolymerization catalyst component (Ib) is (Ia) solid titanium per 1 liter of the polymerization volume. Converted to titanium atoms in the catalyst component or titanium atoms in the (Ib) prepolymerization catalyst component,
Usually, it is used in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol. Also,
In the (II) organometallic catalyst component, the metal atom contained in the (II) organometallic catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500, relative to 1 mol of the titanium atom in the polymerization system.
It is used in a molar amount. Further, (III) the silicon compound (c) or the polyether compound (d) is
(II) Usually about 0.001 to 50 mol, preferably about 0.01 to 20 mol per mol of metal atom in the organometallic catalyst component.
It is used in a molar amount.

During the polymerization, solid titanium catalyst component (a)
The electron donor used in the preparation of and / or the organosilicon compound represented by the above formula (ci) can be used in combination.

The propylene-based block copolymer obtained by the method of the present invention is a softening agent, a filler, a pigment, a stabilizer, a plasticizer, a flame retardant, a lubricant, within a range not impairing the object of the present invention. You may mix | blend an antistatic agent, an electrical property improving agent, etc.

Specific examples of the filler include carbonates such as precipitated calcium carbonate, ground calcium carbonate and magnesium carbonate; aluminum hydroxide, magnesium hydroxide,
Hydroxides such as magnesium oxide; zinc oxide, zinc white,
Oxides such as magnesium oxide; natural silicic acid or silicates such as kaolinite, calcined clay, pyrophyllite, sericite, talc (fine powder), wollastonite, hydrous calcium silicate, hydrous aluminum silicate,
Powdered fillers represented by synthetic silicic acid or silicates such as hydrous silicic acid and anhydrous silicic acid, flaky fillers such as mica, sepiolite, PMF (Processed Mineral Fi)
ber), xonotlite, potassium titanate, elestadite,
Fibrous fillers such as basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, balun fillers such as glass balun and fly ash balun, and organic fillers such as high styrenes, lignin, and re-rubber. .

[0136]

EFFECT OF THE INVENTION The method for producing a propylene block copolymer according to the present invention provides a propylene block copolymer capable of obtaining a molded article which has few spots and is excellent in appearance and impact resistance. Can be manufactured.

[0137]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the following examples, the physical properties of the polymer, Izod impact strength, and appearance (flow mark)
And the number of seeds was measured as follows. Melt flow rate (MFR) 230 ° C. in accordance with ASTM D1238-65T,
It was measured under a load of 2.16 kg.

Intrinsic viscosity [η] Measured in decalin at 135 ° C. Izod impact strength (IZ) According to ASTM D258, it measured at 23 degreeC using the test piece (rear notch) of 1/4 inch in thickness.

Appearance (flow mark) It was visually evaluated using a square plate having a thickness of 2 mm and a length × width of 30 × 12 cm. ◯: Flow marks are less noticeable Δ: Flow marks are slightly conspicuous ×: Flow marks are conspicuously spotted. A film having a thickness of 60 μm and length × width: 10 × 10 cm was used to count spots of 300 μm or more.

[0141]

[Example 1] [Preparation of solid titanium catalyst component] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C for 2 hours to form a uniform solution, and then added to this solution. Phthalic anhydride 22.2g
Was further added, and the mixture was further stirred at 130 ° C. for 1 hour to dissolve phthalic anhydride. The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was added dropwise to 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then again held at 110 ° C. for 2 hours with stirring. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component (A) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was as follows: titanium: 2.3 wt%, chlorine: 61 wt%, magnesium: 19 wt%, DIBP: 12.5 wt%.

[Preparation of prepolymerization catalyst] 400 ml of a four-necked glass reactor equipped with a stirrer under a nitrogen atmosphere, 100 ml of purified hexane, 10 mmol of triethylaluminum, and dicyclopentyldimethoxysilane (DCPMS).
2.0 mmol and the above solid titanium catalyst component (A)
After adding 1.0 mmol in terms of titanium atom, 20 ℃
Propylene was fed into the reactor for 1 hour at a rate of 3.2 N-liter / hour at the temperature of.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. Preliminary polymerization catalyst (B)
I got

[Polymerization] 500 g of propylene was charged into an autoclave having an internal volume of 2 liters, and then ethylene was charged at 20 ° C. so that the ethylene partial pressure would be 1 kg / cm ² -G. At the same temperature, 0.5 mmol of triethylaluminum, 0.5 mmol of DCPMS and 0.005 mmol of the prepolymerization catalyst (B) in terms of titanium atom were charged and copolymerization of propylene and ethylene was carried out. During the polymerization, ethylene was continuously fed so that the ethylene partial pressure was 1 kg / cm ² -G.

After the completion of the copolymerization, the vent valve was opened, the pressure in the polymerization vessel was released until it became normal pressure, and the pressure was further reduced. After the pressure reduction was completed, homopolymerization of propylene was subsequently carried out.
That is, 500 g of propylene and 12 N-liter of hydrogen were charged and polymerization was carried out at 70 ° C. for 30 minutes. After the reaction,
Unreacted gas in the polymerization vessel was purged, and the produced white powder was dried at 80 ° C. under reduced pressure to obtain a polymer. Yield 2
It was 75 g.

[0147]

Example 2 [Preparation of prepolymerization catalyst] 400 ml of a four-necked glass reactor equipped with a stirrer under a nitrogen atmosphere and 100 m of purified hexane.
1, triethylaluminum 1 mmol, DCPMS
0.2 mmol and the solid titanium catalyst component (A)
After adding 0.1 mmol in terms of titanium atom, 20 ℃
Propylene was fed to the reactor for 3 hours at a temperature of 3.7 N-liter / hour.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. The entire amount was transferred to obtain a prepolymerized catalyst (B ').

[Polymerization] Polymerization was conducted in the same manner as in Example 1 except that the prepolymerization catalyst (B ′) was used in place of the prepolymerization catalyst (B) in the “polymerization” of Example 1.

[0150]

Example 3 [Polymerization] 500 g of propylene was charged into an autoclave having an internal volume of 2 liters, and then ethylene was charged at 70 ° C. so that the ethylene partial pressure was 1 kg / cm ² -G. Triethylaluminum 0.5 mmol, DCP at the same temperature
0.5 mmol of MS and 0.002 mmol of the prepolymerized catalyst (B ′) prepared in Example 2 in terms of titanium atom were charged to carry out copolymerization of propylene and ethylene. During the polymerization, ethylene was continuously fed so that the ethylene partial pressure was 2 kg / cm ² -G.

After the completion of the copolymerization, the vent valve was opened, the pressure in the polymerization vessel was released until it became normal pressure, and the pressure was further reduced. After the pressure reduction was completed, homopolymerization of propylene was subsequently carried out.
That is, 500 g of propylene and 12 N-liter of hydrogen were charged and polymerization was carried out at 70 ° C. for 60 minutes. After the reaction,
Unreacted gas in the polymerization vessel was purged, and the produced white powder was dried at 80 ° C. under reduced pressure to obtain a polymer. Yield 2
It was 56 g.

[0152]

[Comparative Example 1] [Polymer] 500 g of propylene and 12 N-liter of hydrogen were charged into an autoclave having an internal volume of 2 liters, and the temperature was raised to 60 ° C., then 0.5 mmol of triethylaluminum,
DCPMS (0.5 mmol) and the preliminary polymerization catalyst (B) were charged in an amount of 0.005 mmol in terms of titanium atom. After the temperature was raised to 70 ° C., the temperature was kept for 35 minutes to polymerize propylene.

After the completion of the polymerization, the vent valve was opened and the pressure inside the polymerization vessel was released until the pressure became normal pressure. After completion of depressurization, ethylene and propylene were subsequently copolymerized. That is, 40 N-liter / hour of ethylene and 1 of propylene
It was fed to the polymerizer at a rate of 60 N-liter / hour.

The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² -G. The temperature is 70 ℃
The temperature was maintained at 80 ° C. and polymerization was carried out for 80 minutes. A small amount of ethanol was added to stop the polymerization reaction, unreacted gas in the polymerization vessel was purged, and the produced white powder was dried at 80 ° C. under reduced pressure to obtain a polymer. The yield was 278g. Table 1 shows the results
Shown in

[0155]

Comparative Example 2 A polymer was produced in the same manner as in Comparative Example 1 except that the preliminary polymerization catalyst (B ′) was used in place of the preliminary polymerization catalyst (B).

The above results are shown in Table 1.

[0157]

[Table 1]

Claims (2)

[Claims] 1. In the first polymerization step, copolymerization of ethylene and propylene is carried out in a liquid propylene medium in the presence of an olefin polymerization catalyst to obtain 10 to 70 mol% of a constitutional unit derived from ethylene. Contained in the ratio of
Production of a low crystalline or non-crystalline polymer having an intrinsic viscosity [η] in the range of 5 to 30 dl / g in a proportion of 2 to 40% by weight with respect to the finally obtained block copolymer. Then, in the second polymerization step, homopolymerization of propylene is carried out in the coexistence of the low crystalline or non-crystalline polymer, or propylene and ethylene and / or α-olefin having 4 to 10 carbon atoms are used. The crystalline polymer is copolymerized with the final block copolymer to obtain 98
A method for producing a propylene-based block copolymer, which comprises producing the propylene-based block copolymer so as to have a proportion of about 60% by weight. 2. The intrinsic viscosity [η] _{A of the} low crystalline or non-crystalline polymer and the intrinsic viscosity [η] of the crystalline polymer.
_The method for producing a propylene block copolymer according to claim 1, wherein the ratio with _B ([η] _A / [η] _B ) is in the range of 1 to 50.