JPH11152304A - Catalyst for polymerization of styrene-based monomer and preparation of styrene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for polymerization of a styrene-based monomer, without requiring a large amt. of an aluminoxane, highly active and good in morphology controllability, which also can give a styrene-based polymer with little amt. of residual metals, good in qualities and high in stereoregularity, advantageously and effectively on an industrial scale, and a preparation method of a styrene-based polymer using the catalyst. SOLUTION: The catalyst for polymerization of a styrene-based monomer is formed using (a) a transition metal compd. (pref. a transition metal compd. having one conjugated five-member ring ligand), (b) a clay, a clay mineral or an ion exchange layered compd., (c) an org. aluminum compd., and, as is required, (d) an alkylation agent. The preparation method of the styrene-based polymer is achieved by homopolymerizing or copolymerizing a styrene-based monomer in the presence of this catalyst for polymerization of a styrene-based monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene monomer polymerization catalyst and a method for producing a styrene polymer, and more particularly, to a method for efficiently producing a styrene polymer having a high syndiotactic structure at low cost. About the method.

[0002]

2. Description of the Related Art In recent years, a styrene-based monomer having a syndiotactic structure (hereinafter referred to as SPS) has been produced by polymerizing a styrene-based monomer mainly using a catalyst comprising a transition metal compound, particularly a titanium compound and methylaluminoxane. Has been proposed (JP-A-62-187708, etc.).

Further, as a method for efficiently producing a styrene-based polymer having a syndiotactic structure without using aluminoxane which is expensive and requires a large amount, a plurality of groups are bonded to a metal. A method using a coordination complex compound comprising an anion and a cation has also been proposed (JP-A-2-415573, JP-A-2-41557).
No. 4, each publication).

[0004]

Conventionally, when a styrene-based monomer is polymerized using a catalyst comprising a titanium compound and an aluminoxane as described above, the activity is not sufficiently exhibited, and it is necessary to improve the activity. Had to use excess aluminoxane. In such a case, a large amount of metal remains in the produced polymer and adverse effects such as a decrease in the mechanical properties of the polymer occur as it is, so that a sophisticated post-treatment technique is required. Furthermore, even when an excess amount of aluminoxane is used, there is a problem that the activity is not improved beyond a certain value. Further, without using aluminoxane, when using a coordination complex compound consisting of an anion and a cation in which a plurality of groups are bonded to a metal,
Although the residual metal content in the polymer can be reduced, there is a problem that the activity is lower than in the case where aluminoxane is used.
Further, in the production method using aluminoxane, there is a problem that the produced polymer tends to adhere to the reactor wall, and there is a possibility that a stable operation of the apparatus may be hindered.

[0005] Therefore, there has been a demand for the development of a production method capable of controlling morphology and obtaining a styrene-based polymer with high activity without using a conventional catalyst system.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be effectively achieved by using a styrene monomer polymerization catalyst comprising a specific catalyst component. And completed the present invention. That is, the present invention provides (1) (a) a transition metal compound,
(B) a clay or clay mineral, and (c) a styrene monomer polymerization catalyst formed using an organoaluminum compound, (2) (a) a transition metal compound, (b) an ion-exchangeable layered compound, and ( c) a styrene monomer polymerization catalyst formed using an organoaluminum compound, (3)
(A) a transition metal compound, (b) a clay or clay mineral,
(C) an organoaluminum compound, and (d) a styrene monomer polymerization catalyst formed using an alkylating agent,
(4) (a) a transition metal compound, (b) an ion-exchange layered compound, (c) an organoaluminum compound, and (d) a catalyst for styrene monomer polymerization formed using an alkylating agent, (5) The above (1) to (1), wherein the (a) transition metal compound is a transition metal compound having one conjugated five-membered ring ligand.
(4) In the styrene monomer polymerization catalyst described in (4), (6) in the styrene monomer polymerization catalyst described in (1) to (5), (a) using a titanium compound as the transition metal compound. A catalyst for producing a styrene-based polymer having a high degree of syndiotactic structure, and (7) a styrene-based monomer in the presence of the catalyst for polymerizing a styrene-based monomer according to any one of the above (1) to (6). A method for producing a styrene-based polymer, characterized by homopolymerizing or copolymerizing the monomer, (8) in the presence of the catalyst for producing a styrene-based polymer according to any one of the above (1) to (6), It is intended to provide a method for producing a styrene polymer having a high syndiotactic structure, characterized by polymerizing a styrene monomer.

[0007]

Embodiments of the present invention will be described below in detail. 1. Various Components of Catalyst for Polymerizing Styrene-Based Monomer (a) Transition Metal Compound As the (a) transition metal compound used in the present invention, various compounds can be used. Alternatively, a Group VIII transition metal compound is preferably used. Further, those represented by the following general formulas (1) to (3) can be mentioned as particularly preferable ones.

Q ¹ _a (C ₅ H _5-ab R ¹ _b ) (C ₅ H _5-ac R ² _c ) M ¹ X ¹ pY ¹ q (1) Q ² _a (C ₅ H _5-ad R ³ _d ) Z ¹ M ¹ X ¹ pY ¹ q (2) M ¹ X ¹ r (3) [wherein Q ¹ represents two conjugated five-membered ring ligands (C ₅ H _{5- ab}
R ¹ _b ) and (C ₅ H _{5 -ac} R ² _c ) represent a linking group, and Q ² represents a conjugated five-membered ligand (C ₅ H _{5-a -d} R ³⁾
_d ) and a binding group that bridges the Z ¹ group. R ¹ , R ² and R ³ each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; , 1 or 2. b, c and d are integers of 0 to 5 when a = 0, and 0 to 4 when a = 1.
And when a = 2, an integer of 0 to 3 is shown.
Further, p + q = valence of M ¹ −2, and r = valence of M ¹ .

M¹Indicates transition metals of Groups IV to VI of the periodic table
Then X¹, Y¹, Z¹Is a covalent bond or an ion
Represents a binding ligand. Note that X¹And Y
¹May be bonded to each other to form a ring structure.
No. ] This Q¹And Q^TwoSpecific examples of (1) methylene
Group, ethylene group, isopropylene group, methylphenyl
Tylene group, diphenylmethylene group, cyclohexylene group
C1-C4 alkylene groups such as cycloalkylene
Group or its side chain lower alkyl or phenyl substituent,
(2) Silylene group, dimethylsilylene group, methylphenyl
Lusilylene group, diphenylsilylene group, disilylene group,
Silylene groups such as tetramethyldisilylene groups, oligos
Rylene group or its lower-chain lower alkyl or phenyl group
(3) germanium, phosphorus, nitrogen, boron or aluminum
Hydrocarbon groups containing minium [lower alkyl groups, phenyl
Group, hydrocarbyloxy group (preferably lower alkoxy
Group)), specifically, (CH_Three)_TwoGe group, (C ₆
H_Five)_TwoGe group, (CH_Three) P group, (C₆H_Five) P group,
(C_FourH₉) N group, (C₆H_Five) N group, (CH_Three) B
Group, (C_FourH₉) B group, (C₆H_Five) B group, (C
₆H_Five) Al group, (CH_ThreeO) Al group, etc.
You. Of these, alkylene groups and silylene groups are preferred.
New

Further, (C ₅ H _5-ab R ¹ _b ), (C ₅ H
_5-ac R ² _c ) and (C ₅ H _5-ad R ³ _d ) are conjugated five-membered ring ligands, and R ¹ , R ² and R ³ are a hydrocarbon group, a halogen atom and an alkoxy group, respectively. , A silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0, 1 or 2.
b, c and d each represent an integer of 0 to 5 when a = 0, an integer of 0 to 4 when a = 1, and an integer of 0 to 3 when a = 2. Here, the hydrocarbon group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 12 carbon atoms. This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group which is a conjugated five-membered ring group, and when there are a plurality of these, two of them are bonded to each other to form a cyclopentadienyl group. A ring structure may be formed together with a part of the pentadienyl group. That is, typical examples of the conjugated five-membered ring ligand are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group. Halogen atoms include chlorine, bromine, iodine and fluorine atoms, and alkoxy groups include
Those having 1 to 12 carbon atoms are preferred. As the silicon-containing hydrocarbon group, for example, -Si (R ⁴ ) (R ⁵ )
(R ⁶ ) (R ⁴ , R ⁵ and R ⁶ are a hydrocarbon group having 1 to 24 carbon atoms) and the like. Examples of the phosphorus-containing hydrocarbon group, the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group are: ^{P- (R 7) (R 8} ), - N (R 7) (R 8) and -
B (R ⁷ ) (R ⁸ ) (R ⁷ and R ⁸ are a hydrocarbon group having 1 to 18 carbon atoms). When there are a plurality of R ¹ , R ² and R ³ , each of the plurality of R ¹ , the plurality of R ² and the plurality of R ³ may be the same or different. In the general formula (1), a conjugated five-membered ring ligand _{(C 5 H 5-ab R} 1 b) and (C ₅ H _5-ac
R ² _c ) may be the same or different.

On the other hand, M¹Is a transition metal of group IV to VI of the periodic table
Indicates the element, specific examples are titanium and zirconium
, Hafnium, niobium, molybdenum, tungsten
The transition metal element of Group IV of the periodic table
Is preferred, and among these, titanium is particularly preferred.
is there. Z¹Is a covalent ligand, specifically an acid
Element (-O-), sulfur (-S-), carbon number 1-20, preferably
1 to 10 alkoxy groups, 1 to 20 carbon atoms, preferably
Or a thioalkoxy group of 1 to 12, carbon atoms of 1 to 40,
Preferably a nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms,
Represents 40, preferably 1 to 18, phosphorus-containing hydrocarbon groups.
You. X¹And Y¹Are covalent ligands
Specifically, a hydrogen atom, a halogen atom, and a carbon number of 1 to 2
0, preferably 1 to 10 hydrocarbon groups, 1 to 2 carbon atoms
0, preferably 1 to 10 alkoxy groups, amino groups, charcoal
A phosphorus-containing hydrocarbon having a prime number of 1 to 20, preferably 1 to 12
Group (for example, diphenylphosphine group) or carbon number
1-20, preferably 1-12, silicon-containing hydrocarbon groups
(E.g., trimethylsilyl group, etc.), having 1-2 carbon atoms
0, preferably 1 to 12 hydrocarbon groups or halogens
Containing boron compound (for example, B (C ₆H_Five)_Four, BF_Four)
You. Of these, halogen atoms and hydrocarbon groups are preferred.
No. This X¹And Y¹Even if they are the same, they are different
May be. In the above general formula (3), M¹
Is a transition metal belonging to Groups IV to VI of the periodic table, as described above.
T, X¹Is a covalent ligand, specifically a halo
Gen atom or alkoxy group. (I) Transition metals represented by the general formulas (1) and (2)
The following compounds may be mentioned as specific examples of the compound.
Wear.

Bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethyl Cyclopentadienyl) titanium dichloride,
Bis (pentamethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyltitanium dichloride, bis (indenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (cyclopentadienyl) titanium chlorohydride, bis (Cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) ethyltitanium chloride, bis (cyclopentadienyl) phenyltitanium chloride, bis (cyclopentadienyl)
Dimethyltitanium, bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) dineopentyltitanium, bis (cyclopentadienyl) dihydrotitanium, (cyclopentadienyl)
Transition metal compounds having no bridging bonding group and two conjugated 5-membered ring ligands, such as (indenyl) titanium dichloride and (cyclopentadienyl) (fluorenyl) titanium dichloride, methylenebis (indenyl) titanium dichloride,
Ethylenebis (indenyl) titanium dichloride, methylenebis (indenyl) titanium chlorohydride,
Ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) methoxychlorotitanium, ethylenebis (indenyl) titanium diethoxide, ethylenebis (indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenyl) ) Titanium dichloride, ethylenebis (2-methylindenyl) titanium dichloride, ethylenebis (2,4-dimethylindenyl) titanium dichloride, ethylenebis (2-methyl-4-trimethylsilylindenyl) titanium dichloride, ethylenebis (2 , 4-Dimethyl-5,6,7-trihydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium Chloride, ethylene (2-methyl -4-t-butyl-cyclopentadienyl)
(3′-t-butyl-5′-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) Titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (2,4-dimethylindenyl) titanium dichloride, isopropylidene (2,4-dimethylcyclopenta Dienyl) (3'5'-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-t-butylcyclopentadienyl) (3'-
t-butyl-5'-methylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3
4-dimethylcyclopentadienyl) titanium chlorohydride, methylene (cyclopentadienyl) (3,4
-Dimethylcyclopentadienyl) dimethyltitanium, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) diphenyltitanium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, methylene ( Cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,3 , 4,5-tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3-methylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) Fluorenyl) titanium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2,5-dimethyl-cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl ) Titanium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenyl Methylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride,
Cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′,
Transition metal compounds having two conjugated five-membered ring ligands bridged by an alkylene group such as 4′-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (4,5 6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylindenyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopenta Dienyl) (3 ',
5'-dimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylenebis (indenyl) titanium dichloride, phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, phenylmethylsilylenebis (2,4 −
Dimethylindenyl) titanium dichloride, phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylene (2
3,5-trimethylcyclopentadienyl) (2 ′,
4 ', 5'-trimethylcyclopentadienyl) titanium dichloride, phenylmethylsilylenebis (tetramethylcyclopentadienyl) titanium dichloride,
Diphenylsilylenebis (2,4-dimethylindenyl) titanium dichloride, diphenylsilylenebis (indenyl) titanium dichloride, diphenylsilylenebis (2-methylindenyl) titanium dichloride, tetramethyldisilylenebis (indenyl) titanium dichloride, tetramethyl Disilylene bis (cyclopentadienyl) titanium dichloride, tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( Tramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) titanium dichloride, Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (2
7-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethyl Silylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2-
Ethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diethylsilylene (2-methylcyclopentadienyl) (2 ′, 7′-diethyl -T-butylfluorenyl) titanium dichloride, dimethylsilylene (2.5
-Dimethylcyclopentadienyl) (2 ', 7'-di-
t-butylfluorenyl) titanium dichloride, dimethylsilylene (2-ethylcyclopentadienyl)
(2 ', 7'-di-t-butylfluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (octahydrfluorenyl) titanium dichloride, dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethylsilylene (ethylcyclopentadienyl) Transition metal compounds having two silylene group-bridged conjugated five-membered ring ligands such as (octahydrofluorenyl) titanium dichloride, dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) titanium dichloride, dimethyl gel Millenbis (indenyl) titanium dichloride, dimethylgermylene (cyclopentadienyl) (fluorenyl) titanium dichloride, methylaluminylenebis (indenyl) titanium dichloride, Phenylamylenebis (indenyl) titanium dichloride, phenylphosphylenebis (indenyl) titanium dichloride, ethylborenebis (indenyl) titanium dichloride, phenylamylenebis (indenyl)
Transition metals having two conjugated five-membered ligands bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as titanium dichloride and phenylamylene (cyclopentadienyl) (fluorenyl) titanium dichloride Compounds, pentamethylcyclopentadienyl-bis (phenyl) aminotitanium dichloride, indenyl-bis (phenyl) aminotitanium dichloride, pentamethylcyclopentadienyl-bis (trimethylsilyl) aminotitanium dichloride, pentamethylcyclopentadienylphenoxytitanium Dichloride, dimethylsilylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) decylaminotitanium dichloride Dimethylsilylene (tetrahydroindenyl) [bis (trimethylsilyl) amino] titanium dichloride, dimethylgermylene (tetramethylcyclopentadienyl) phenylaminotitanium dichloride, pentamethylcyclopentadienyltitanium trimethoxide, pentamethylcyclopenta A transition metal compound having one conjugated five-membered ring ligand such as dienyl titanium trichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) titanium dichloride , (1,1′-dimethylsilylene) (2,
2′-dimethylsilylene) -bis (cyclopentadienyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) dimethyltitanium, (1,1 '-Dimethylsilylene) (2,2'-isopropylidene) -bis (cyclopentadienyl) dibenzyltitanium,
(1,1′-dimethylsilylene) (2,2′-isopropylidene) -bis (cyclopentadienyl) bis (trimethylsilyl) titanium, (1,1′-dimethylsilylene) (2,2′-isopropylidene) -Bis (cyclopentadienyl) bis (trimethylsilylmethyl) titanium, (1,2′-dimethylsilylene) (2,1′-
Ethylene) -bis (indenyl) titanium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) -bis (indenyl) titanium dichloride,
(1,1′-ethylene) (2,2′-dimethylsilylene) -bis (indenyl) titanium dichloride,
Transition having two conjugated five-membered ring ligands in which ligands such as (1,1′-dimethylsilylene) (2,2′-cyclohexylidene) -bis (indenyl) titanium dichloride are double-bridged. Metal compounds, and compounds obtained by replacing the chlorine atom of these compounds with a bromine atom, iodine atom, hydrogen atom, methyl group, phenyl group, etc. In which titanium is replaced by zirconium, hafnium, niobium, molybdenum or tungsten.

The transition metal compounds having one conjugated five-membered ring ligand among the compounds described in (1) and (2) above are particularly preferable among the transition metal compounds described in (1) to (4) above wherein titanium is used as the transition metal. The compound is preferably used in the production of a styrenic polymer having a syndiotactic structure. (II) Specific examples of the transition metal compound represented by the general formula (3) include the following compounds.

Tetra-n-butoxytitanium, tetra-i-propoxytitanium, tetraphenoxytitanium, tetracresoxytitanium, tetrachlorotitanium, tetrapromotitanium, tetra-n-butoxyzirconium, tetra-i-propoxyzirconium, tetra Phenoxy zirconium, tetracrezoxy zirconium, tetrachloro zirconium, tetrabromo zirconium and the like can be mentioned. Among these transition metal compounds, titanium compounds are preferably used in the production of a styrene polymer having a syndiotactic structure.

In the catalyst of the present invention, the component (a)
May be used alone or in combination of two or more. (B) Component Clay or clay mineral As the (b) component, clay or clay mineral is used. Clay is an aggregate of fine hydrated silicate minerals, and refers to a substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. The clay mineral refers to a hydrated silicate that is a main component of clay.

These are not limited to natural products, but may be artificially synthesized products. Ion-exchange layered compound As the component (b), an ion-exchanged layered compound is further used. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and means a compound whose contained ions are exchangeable. Some clay minerals are ion-exchangeable layered compounds.

For example, phyllosilicic acids are mentioned as clay minerals. The phyllosilicic acids include phyllosilicic acid and phyllosilicates. Examples of the phyllosilicate include natural products, such as montmorillonite belonging to the smectite group, saponite, hectorite, illite belonging to the mica group, sericite, and mixed layer minerals of the smectite group and the mica group or the mica group and the vermiculite group. .

Further, as synthetic products, tetrasilicon mica,
Laponite, smecton and the like. In addition, α-
Zr (HPO_Four)_Two, Γ-Zr (HPO_Four)_Two, Α-Ti
(HPO _Four)_TwoAnd γ-Ti (HPO_Four)_TwoClay minerals
Ion-exchange compound having a layered crystal structure
Can be mentioned.

Clays and clay minerals which do not belong to the ion-exchangeable layered compound. Specific examples of the component (b) include, if the montmorillonite content is low, clay, called bentonite, and montmorillonite, which contains many other components. Clay, gairome clay, sepiolite exhibiting a fibrous form, palygorskite, and non-crystalline or low-crystalline allophane, imogolite, and the like.

In the present invention, it is also preferable to carry out a chemical treatment from the viewpoint of removing impurities from the clay, clay mineral and ion-exchangeable layered compound or changing the structure and function. Here, the chemical treatment refers to either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned.

The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as aluminum, iron and magnesium in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic complex, and the like are formed, and the surface area, the interlayer distance, and the like can be changed. By replacing the exchangeable ions between layers with another bulky ion by utilizing ion exchangeability, an interlayer material having an enlarged interlayer can be obtained.

The above-mentioned component (b) may be used as it is, may be one to which water is newly added and adsorbed, or may be one subjected to heat dehydration treatment. As the component (b), clays or clay minerals are preferred from the viewpoint of activity, and phyllosilicic acids are most preferred. Among them, smectite is preferred, and montmorillonite is more preferred. (C) Organoaluminum Compound The organoaluminum compound in the present invention is preferably an alkyl group-containing aluminum compound represented by the following general formula (4), a linear alumoxane represented by the following general formula (5) or And a mixture thereof represented by the following general formula (6).

R ⁹ _m Al (OR ¹⁰ ) _n X _3-mn (4) (wherein R ⁹ and R ¹⁰ each represent an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms) , X represents a hydrogen atom or a halogen atom, and m is 0 <m ≦ 3, preferably 2 or 3, most preferably 3, and n is 0 ≦
n <3, preferably 0 or 1. )

[0024]

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[0025]

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(Wherein, R ¹¹ is a group having 1 to 2 carbon atoms.
It represents 0, preferably 1 to 8 alkyl groups, which may be the same or different. L is 0 ≦ L ≦
40, M is an integer of 2 ≦ M ≦ 10, and N is an integer of 1 ≦ N ≦ 50. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, etc. Aluminoxane such as alkylaluminum, methylalumoxane, ethylalumoxane, isobutylalumoxane, etc., of which halogen or alkoxy group is contained, among which triisobutylaluminum is particularly preferred. (D) Alkylating agent In the present invention, if necessary, an alkylating agent is used as the component (d). The activity may be further improved by using an alkylating agent. Here, there are various alkylating agents. For example, the general formula (7) R ⁹ _m Al (OR ¹⁰ ) _n X _3-mn (7) [wherein R ⁹ and R ¹⁰ Represents an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. Also, m is 0 <m ≦ 3, preferably 2 or 3, and most preferably 3. n is 0 ≦ m ≦ 3.
n <3, preferably 0 or 1. Or an alkyl group-containing aluminum compound represented by the following general formula (8): R ⁹ ₂ Mg (8) wherein R ⁹ is the same as defined above. And an alkyl group-containing magnesium compound represented by the following general formula (9): R ⁹ ₂ Zn (9) wherein R ⁹ is the same as defined above. And the like.

Among these alkyl group-containing compounds, alkyl group-containing aluminum compounds, particularly trialkylaluminum and dialkylaluminum compounds, are preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum Dialkylaluminum halides such as chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-t-butylaluminum chloride, dimethylaluminum methoxide;
Dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, dimethyl aluminum hydride,
And dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. Further, dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium and butylethylmagnesium and dialkylzinc such as dimethylzinc, diethylzinc, ethyl-n-propylzinc and diisopropylzinc are used. I can give it. 2. Preparation method of catalyst (1) Order of addition and contact of each component The order of addition of each component is not particularly limited, and the components can be contacted in the following order. (A) component,
When the component (b) and the component (c) are used, for example,
A method of adding the component (c) after bringing the component (a) into contact with the component (b), a method of adding the component (b) after bringing the component (a) into contact with the component (c), (b) )) The method of adding the component (a) after the component and the component (c) are brought into contact, and the method of simultaneously contacting the three components. Among these, the above-mentioned method of adding the component (a) after bringing the component (b) into contact with the component (c) is preferable.

Further, when the component (d) is used, the order of addition of the component (d) is not particularly limited, but the above three components (a), (b) and (c) are , And preferably the method of adding the component (d) after contacting with the above method. Upon or after contacting the catalyst components, polyethylene,
Polymers such as polypropylene and polystyrene, or solids of inorganic oxides such as silica and alumina may coexist or be brought into contact. (2) Quantitative ratio of each component (b) The number of moles of the transition metal in the component (a) and the mole of the aluminum atom in the organoaluminum compound per 1 kg of the clay, the clay mineral and the ion-exchangeable layered compound of the component. It is desirable that the contact be made at a number of 0.001-0.5 and 0.1-1000, preferably 0.001-0.2 and 1-100. When the number of moles of the transition metal is 0.0001 or less, the polymerization activity of the catalyst is low, and when it is 0.5 or more, the polymerization activity per transition metal is significantly reduced.

When the component (d) is used,
When organic aluminum is used as component (d),
The amount of organoaluminum compound used
Of the transition metal in the component (a) to the aluminum in the component (d)
The molar ratio is 1: 0 (not including 0) to 10000
Is chosen. (3) Contact conditions Contact of each component is carried out in an inert gas such as nitrogen, pentane,
In hydrocarbons such as xane, heptane, toluene and xylene
May be performed. The contact temperature is from -30 ° C to the boiling point of each solvent.
Between points, especially between room temperature and the boiling point of the solvent
Is preferred. 3. Production of styrene-based polymer In the presence of the styrene-based monomer polymerization catalyst, styrene
The homopolymerization or copolymerization of the
A len-based polymer can be produced. In the case of copolymerization,
Copolymerization of styrene monomers, or styrene
-Based monomers and other monomers, such as ethylenically unsaturated bonds
Copolymerization with the containing compound may be mentioned. (1) Styrene monomer In addition to styrene, p-methylstyrene, p-ethylstyrene
Len, p-propylstyrene, p-isopropylstyrene
, P-butylstyrene, p-tert-butylstyrene
, P-phenylstyrene, o-methylstyrene, o-
Ethyl styrene, o-propyl styrene, o-isopro
Pillstyrene, m-methylstyrene, m-ethylstyrene
M-isopropylstyrene, m-butylstyrene,
Mesityl styrene, 2,4-dimethylstyrene, 2,5
-Such as dimethylstyrene and 3,5-dimethylstyrene;
Alkyl styrenes, p-methoxystyrene, o-methoxy
Alkoxystyrenes such as styrene and m-methoxystyrene
Lens, p-chlorostyrene, m-chlorostyrene, o
-Chlorostyrene, p-bromostyrene, m-bromos
Tylene, o-bromostyrene, p-fluorostyrene,
m-fluorostyrene, o-fluorostyrene, o-meth
Halogenated styrenes such as chill-p-fluorostyrene,
Further, trimethylsilyl styrene, vinyl benzoic acid S
Ter, divinylbenzene, and the like. (2) Ethylenically unsaturated bond-containing compound ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-none
1-decene, 4-phenyl-1-butene, 6-
Nyl-1-hexene, 3-methyl-1-butene, 4-methyl
Tyl-1-butene, 3-methyl-1-pentene, 4-methyl
Tyl-1-hexene, 5-methyl-1-hexene, 3,
3-dimethyl-1-pentene, 3,4-dimethyl-1-
Pentene, 4,4-dimethyl-1-pentene, vinyl
Α-olefins such as chlorohexane, 1,3-butadiene
, 1,4-butadiene, 1,5-hexadiene, etc.
Dienes, hexafluoropropene, tetrafluoroe
Tylene, 2-fluoropropene, fluoroethylene,
1,1-difluoroethylene, 3-fluoropropene,
Trifluoroethylene, 3,4-dichloro-1-butene
Halogen-substituted α-olefins such as cyclopentene,
Clohexene, norbornene, 5-methylnorbornene
, 5-ethylnorbornene, 5-propylnorbornene
5,6-dimethylnorbornene, 5-benzylnor
And cyclic olefins such as bornene. (3) Polymerization conditions The polymerization reaction is carried out using butane, pentane, hexane, toluene,
Hydrocarbons such as cyclohexane, liquefied α-olefins, etc.
Or in the absence of a solvent. Warm
The degree is -50 ° C to 250 ° C, and the pressure is particularly limited.
No, but preferably normal pressure to 2000 kgf / cm^Two
Range. Also, water is used as a molecular weight regulator in the polymerization system.
Element may be present. (4) Styrene-based polymer The styrene-based polymer obtained using the above catalyst is a styrene-based polymer.
Chain has a high syndiotactic structure
It is. Here, styrene in the styrenic polymer
Syndiotactic structure with a high degree of linkage is stereochemistry
The structure is highly syndiotactic, ie carbon-
Phenyl which is a side chain to the main chain formed from carbon bonds
In which the phenyl and substituted phenyl groups are alternately located in opposite directions
Has a structure, its tacticity is
Nuclear magnetic resonance with isotope carbon ( ¹³C-NMR method)
Quantified. Tactics measured by this method
Tee is the ratio of the presence of multiple consecutive structural units, such as
In the case of two, it is a diad, in the case of three, a triad,
The case of five can be indicated by a pentad,
The term “styre having a syndiotactic structure” according to the present invention
Is a racemic diad, preferably 75% or more.
Or 85% or more, or 30% for racemic pentad
Syndiotacticity of at least 50%
Polystyrenes and mixtures thereof
Or a copolymer containing these as main components.

[0030]

[Example 1]

(1) Chemical treatment of clay mineral 40 g of commercially available montmorillonite (Kunimine F, Kunipia F) was pulverized by a pulverizer for 4 hours. Pulverized montmorillonite 19.9 in a 500 ml four-necked flask
g of magnesium chloride hexahydrate was dispersed in 100 ml of deionized water in which 20 g of magnesium chloride hexahydrate was dissolved, and treated at 90 ° C. for 0.5 hour with stirring. After the treatment, the solid component was washed with water. This treatment operation was repeated once to obtain montmorillonite treated with magnesium chloride. After drying, it was dispersed in 160 ml of a 6% aqueous hydrochloric acid solution and treated under reflux with stirring for 2 hours. After the treatment, washing with water was repeated until the supernatant became neutral, followed by drying to obtain chemically treated montmorillonite. (2) Synthesis of Premixed Catalyst A chemically treated montmorillonite obtained in (1) (water content: 10% by weight (15%)) was placed in a 100 ml four-necked flask.
Determined from the weight loss of the heat dehydration treatment at 0 ° C for 1 hour))
1.0 g was added and dispersed in 25 ml of toluene to obtain a slurry (A). On the other hand, 25 ml (12.5 mmol) of a toluene solution of triisobutylaluminum (concentration: 0.5 mol / l) was added to a 100 ml four-necked flask. While stirring the mixture, the whole amount of the toluene slurry (A) of the chemically treated montmorillonite was dropped at room temperature over 10 minutes.

After the dropwise addition, the mixture was reacted at room temperature for 0.5 hour.
The temperature was raised, and the reaction was further performed at 100 ° C. for 1 hour. After the reaction,
The supernatant was extracted, and the solid component was washed with toluene.
To this was added 50 ml of toluene to obtain a slurry (B). Subsequently, 13.4 ml of toluene and a toluene solution of triisobutylaluminum (concentration: 2 mol / l) were placed in a 50 ml Schlenk tube.
0.25 ml (0.5 mmol), 6.0 ml of the slurry (B) and 0.4 ml (0.02 mmol) of a toluene solution of pentamethylcyclopentadienyltitanium trimethoxide (concentration: 50 mmol / l) ) Was added successively at room temperature and stirred at the same temperature for 1.5 hours.

Thus, a premixed catalyst was obtained. (3) Polymerization of Styrene In a 30 ml ampoule bottle, 10 ml of styrene and 0.01 ml (0.005 mmol) of a toluene solution of triisobutylaluminum (concentration: 0.5 mol / l) were charged in a nitrogen box.
The ampoule was set in an oil bath at a temperature of 70 ° C., and 10 minutes later, 1.25 ml of the premixed catalyst slurry was charged. After heating polymerization at 70 ° C. for 1 hour, the mixture was taken out of the oil bath, and methanol was added to stop the polymerization. After taking out the polymer and leaving it to stand overnight in methanol, it was vacuum-dried at 200 ° C. for 2 hours.

The obtained polymer had no sticky components and was obtained in a homogeneous granular form. The yield is 1.1
73 grams, yield 21.5 (kg-polymer / gTi
* Hr) and [η] (135 ° C, trichlorobenzene) were 1.37 (deciliter / g). The polymer obtained here was confirmed by ¹³ C-NMR measurement to be a styrene polymer having a syndiotactic structure with a tacticity of 82% in racemic pentad. In addition, Tm was 259 ° C. [Example 2] In the same manner as in Example 1 except that the chemically treated montmorillonite (water content 23% by weight) was used instead of the chemically treated montmorillonite (water content 10% by weight). went. The polymer yield is 0.
629 grams and a yield of 10.5 (kg-polymer / gT
i.Hr). The polymer obtained here has a tacticity of 84% in racemic pentad and a Tm of 2
62 ° C. Comparative Example 1 (1) Synthesis of Premixed Catalyst A nitrogen solution was introduced into a 50 ml Schlenk tube, and while stirring, 7.9 ml of toluene and a toluene solution of triisobutylaluminum (concentration: 2 mol / l) were prepared. 0.25 ml (0.5 mmol),
Silica-supported methylalumoxane (manufactured by Witco)
5 mmol (in terms of aluminum atom) and pentamethylcyclopentadienyltitanium trimethoxide 0.
02 mmol was charged and stirred at room temperature for 0.5 hour. Thus, a premixed catalyst was obtained. (3) Polymerization of Styrene In a 30 ml ampoule bottle, 5 ml of styrene and 0.005 ml (0.0025 mmol) of a toluene solution of triisobutylaluminum (concentration: 0.5 mol / l) were charged in a nitrogen box. The ampoule was set in an oil bath at a temperature of 70 ° C., and after 10 minutes, 0.42 ml of the premixed catalyst was charged while sufficiently stirring the premixed catalyst. 7
After heating polymerization at 0 ° C. for 1 hour, the mixture was taken out of the oil bath, and methanol was added to stop polymerization. The polymer was taken out and immersed in methanol overnight.
Time vacuum drying was performed.

The yield was 0.08 grams, yielding 1.67.
(kg polymer / g-Ti · Hr). The polymer had a sticky component, was obtained in an amorphous shape, and was not a polymer having a syndiotactic structure.

[0035]

According to the styrene monomer polymerization catalyst of the present invention, the activity is high, the morphology is controllable, the quality of the residual metal is small and the quality is good, without using a large amount of aluminoxane. And a highly stereoregular styrenic polymer can be obtained industrially and efficiently.

Claims (8)

[Claims] 1. A styrene monomer polymerization catalyst formed using (a) a transition metal compound, (b) a clay or clay mineral, and (c) an organoaluminum compound. 2. A styrene monomer polymerization catalyst formed using (a) a transition metal compound, (b) an ion-exchange layered compound, and (c) an organoaluminum compound. 3. A transition metal compound, (b) a clay or clay mineral, (c) an organoaluminum compound, and (d)
A styrene monomer polymerization catalyst formed using an alkylating agent. 4. A styrene monomer polymerization catalyst formed using (a) a transition metal compound, (b) an ion-exchangeable layered compound, (c) an organoaluminum compound, and (d) an alkylating agent. 5. The styrene monomer polymerization catalyst according to claim 1, wherein (a) the transition metal compound is a transition metal compound having one conjugated five-membered ring ligand. 6. The styrenic polymer having a high syndiotactic structure according to claim 1, wherein a titanium compound is used as the transition metal compound (a). Production catalyst. 7. Production of a styrenic polymer, wherein a styrenic monomer is homopolymerized or copolymerized in the presence of the styrenic monomer polymerization catalyst according to any one of claims 1 to 6. Method. 8. A styrene-based polymer having a high syndiotactic structure, wherein a styrene-based monomer is polymerized in the presence of the catalyst for producing a styrene-based polymer according to any one of claims 1 to 6. A method for producing a polymer.