Catalysts for polymerizing styrene and other monomer and...

Details Catalysts for polymerizing styrene and other monomer and... Catalysts for polymerizing styrene and other monomer and...

2000-09-28

2004-11-30

Teskin, Fred (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S124900, C526S125100, C526S126000, C526S127000, C526S153000, C526S160000, C526S161000, C502S129000, C502S132000, C502S171000

Reexamination Certificate

active

06825294

ABSTRACT:

TECHNICAL FIELD
The present invention relates to catalysts for polymerization of styrenes, and to a method for producing styrenic polymers. Precisely, it relates to catalysts for styrene polymerization comprising, as one component, a specific compound, and to an inexpensive and efficient method for producing styrenic polymers with the catalysts, more precisely, to a method for producing styrenic polymers essentially having a syndiotactic structure.
BACKGROUND ART
Recently, metallocene catalysts have been developed and used for styrenic polymer production, which comprise, as the catalyst component, a transition metal compound having a &pgr;-ligand bonded to the center metal element via a group.
To exhibit satisfactory activity, however, the catalysts of that type require a large amount of promoters such as aluminoxanes and the like. Therefore, they are problematic in that the total catalyst costs are inevitably high, and, in addition, the catalyst residue resulting from the promoter used often remains in the polymers produced thereby unfavorably discoloring the polymers.
In that situation, techniques of using clay, clay minerals and the like in place of aluminoxanes have been proposed so as to reduce the amount of the promoters to be used along with the catalysts (Japanese Patent Laid-Open Nos. 301917/1993, 136047/1994, etc.).
At present, however, even these techniques could not as yet provide catalysts having satisfactorily high activity.
DISCLOSURE OF THE INVENTION
The object of the present invention is to provide catalysts for styrene polymerization capable of efficiently and inexpensively producing styrenic polymers, in particular, those essentially having a syndiotactic structure, and to provide a method for producing styrenic polymers.
We, the present inventors have assiduously studied so as to attain the object as above, and, as a result, have found that polymerization catalysts containing, as one component, a specific compound have improved polymerization activity and therefore the amount of the promoters such as oxygen-containing compounds and others to be used with them can be reduced. On the basis of this finding, we have completed the present invention.
Specifically, the invention provides catalysts for polymerization of styrenes and a method for producing styrenic polymers, which are as follows:
1. A catalyst for polymerization of styrenes, which comprises:
(A) a transition metal compound,
(B) an oxygen-containing compound and/or a compound capable of reacting with a transition metal compound to form an ionic complex,
(C) a compound of a general formula (1):
((R
1
)
3
—X—Y)
n
-Z-(R
2
)
m−n
  (1)
wherein R
1
represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R
1
's may be the same or different, and R
1
's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14 of the Periodic Table; Y represents an element of Group 16 of the Periodic Table; Z represents a metal element of Groups 2 to 13 of the Periodic Table; R
2
represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m−1),
and optionally,
(D) an alkylating agent.
2. A catalyst for polymerization of styrenes, which comprises:
(A) a transition metal compound,
(C) a compound of a general formula (1):
((R
1
)
3
—X—Y)
n
-Z-(R
2
)
m−n
  (1)
wherein R
1
represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R
1
's may be the same or different, and R
1
's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14 of the Periodic Table; Y represents an element of Group 16 of the Periodic Table; Z represents a metal element of Groups 2 to 13 of the periodic Table; R
2
represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m−1),
and optionally,
(D) an alkylating agent.
3. The catalyst of above 1 or 2 for polymerization of styrenes, wherein, in (C), X is carbon, Y is oxygen and Z is aluminium.
4. The catalyst of above 1 or 2 for polymerization of styrenes, wherein the compound (C) is a reaction product of <1> at least one selected from compounds of genera formulae (R
1
)
3
—C—R
3
, R
4
—CO—R
5
, or R
6
—CO—R
7
, and <2> a compound of a general formula, Z(R
2
)
m
:
in which R
1
is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an alyloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, or a thioaryloxy group having from 6 to 30 carbon atoms; R
3
is hydroxyl, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, or a thioalyloxy group having from 6 to 30 carbon atoms; R
4
and R
5
each represents hydrogen, halogen, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms or an aromatic hydrocarbon group having from 6 to 30 carbon atoms; R
6
is a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atom, or a thioaryloxy group having from 6 to 30 carbon atoms or an amino group; and R
7
is hydroxy an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, or a thioaryloxy group having from 6 to 30 carbon atoms; or an amino group; and R
1
and R
3
or R
4
and R
5
or R
6
and R
7
may be optionally bonded to each other to form a cyclic structure; Z represents a metal element of Groups 2 to 13 of the Periodic Table; m is an integer, indicating the valency of the metal element Z; and R
2
represents a hydrocarbon group.
5. A catalyst for polymerization of styrenes, which comprises:
(A) a transition metal compound,
(B) an oxygen-containing compound and/or a compound capable of reacting with a transition metal compound to form an ionic complex,
(C1), at least one selected from compounds of general formulae (R
1
)
3
—C—R
3
, R
4
—CO—R
5
, or R
6
—CO—R
7
:
in which R
1
is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, or a thioaryloxy group having from 6 to 30 carbon atoms; R
3
is hydroxyl, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, or a thioaryloxy group having from 6 to 30 carbon atoms; R
4
and R
3
each represents hydrogen, halogen, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms or an aromatic hydrocarbon group having from 6 to 30 carbon atoms; R
6
is a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an ar

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