Process for the preparation of an olefin polymer using...

Details Process for the preparation of an olefin polymer using... Process for the preparation of an olefin polymer using...

1999-02-19

2002-03-05

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S008000, C556S011000, C556S012000, C556S014000, C556S021000, C556S027000, C556S028000, C556S043000, C556S053000, C556S081000, C556S087000, C502S117000, C502S152000, C526S126000, C526S160000, C526S943000

Reissue Patent

active

RE037573

ABSTRACT:

The invention relates to a process for the preparation of olefin polymers and copolymers using metallocenes containing specifically substituted indenyl ligands.
The use of chiral metallocenes as a catalyst component in the polymerization of olefins is known and gives highly isotactic polyolefins of high crystallinity and high melting point (cf. Angew. Chem. 97 (1985) 507, German Patent 40 35 886.0).
If achiral metallocenes are used, atactic polymers are obtained which, due to their unbalanced and inadequate product properties, are only of restricted industrial importance.
Of considerable interest are products whose property profile is between these two extremes.
The object was to find a suitable process or a suitable catalyst system which enables the preparation of polymers of reduced crystallinity, increased impact strength, increased transparency, good flow properties at the processing temperature, reduced melting point and high molecular weight.
The main applications of such polymers are plasticizer and lubricant formulations, hot-melt adhesive applications, coatings, seals, insulations, slush-molding compositions or sound-insulation materials.
The invention thus relates to a process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula R
a
—CH═CH—R
b
, in which R
a
and R
b
are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or R
a
and R
b
, together with the atoms connecting them, can form a ring, at a temperature of from −60° to 200° C., at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst formed from a metallocene as transition-metal compound and a cocatalyst, wherein the metallocene is a compound of the formula I
in which
M
1
is a metal from group IVb, Vb or VIb of the Periodic Table,
R
1
and R
2
are identical or different and are a hydrogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
10
-aryl group, a C
6
-C
10
-aryloxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-akylaryl group, a C
8
-C
40
-arylalkenyl group or a halogen atom,
R
3
, R
4
and R
5
are identical or different and R
3
and R
4
and/or R
5
are other than hydrogen and are a C
1
-C
20
-alkyl group, a C
6
-C
20
-aryl group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, it also being possible for these radicals to be halogenated,
R
4
or R
5
may alternatively be hydrogen,
R
6
is
where
R
9
, R
10
and R
11
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, a C
1
-C
10
-fluoroalkyl group, a C
6
-C
10
-aryl group, a C
6
-C
10
-fluoroaryl group, a C
1
-C
10
-alkoxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
8
-C
40
-arylalkenyl group or a C
7
-C
40
-alkylaryl group, or R
9
and R
10
or R
9
and R
11
, in each case together with the atoms connecting them, form a ring,
M
2
is silicon, germanium or tin,
R
7
and R
8
are identical or different and are as defined for R
9
, and
m and n are identical or different and are zero, 1 or 2, where m plus n is zero, 1 or 2.
Alkyl is straight-chain or branched alkyl. Halogen, (halogenated) denotes fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
The indenyl ligands of the metallocene of the formula I used in the process according to the invention are substituted in the 2-position (R
3
) and in at least one of the two positions 5 (R
4
) and 6 (R
5
).
The catalyst to be used for the process according to the invention comprises a cocatalyst and a metallocene of the formula I.
In the formula I, M
1
is a metal from group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.
R
1
and R
2
are identical or different and are a hydrogen atom, a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group, a C
1
-C
10
-, preferably C
1
-C
3
-alkoxy group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-, preferably C
6
-C
8
-aryloxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group, a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group or a halogen atom, preferably chlorine.
R
1
, R
4
and R
5
are identical or different and R
3
and R
4
and/or R
5
are other than hydrogen and are a C
1
-C
20
-, preferably C
1
-C
10
-alkyl group, a C
6
-C
20
-, preferably C
6
-C
12
-aryl group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group or a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group, it also being possible for these radicals to be halogenated.
R
3
, R
4
and R
5
are particularly preferably methyl, trifluoromethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenyl, tolyl, mesityl or xylyl.
R
4
or R
5
may alternatively be hydrogen; if this is the case, R
5
is preferably hydrogen.
R
6
is
═BR
9
, ═AlR
9
, —Ge—, —Sn—, —O—, —S—, —SO, ═SO
2
, ═NR
9
, ═CO, ═PR
9
or ═P(O)R
9
, where R
9
, R
10
and R
11
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-, preferably C
1
-C
4
-alkyl group, in particular a methyl group, a C
1
-C
10
-fluoroalkyl group, preferably a CF
3
group, a C
6
-C
10
-, preferably C
6
-C
8
-aryl group, a C
6
-C
10
-fluoroaryl group, preferably a pentafluorophenyl group, a C
6
-C
10
-, preferably C
1
-C
4
-alkoxy group, in particular a methoxy group, a C
2
-C
10
-, preferably C
2
-C
4
-alkenyl group, a C
7
-C
40
-, preferably C
7
-C
10
-arylalkyl group, a C
8
-C
40
-, preferably C
8
-C
12
-arylalkenyl group or a C
7
-C
40
-, preferably C
7
-C
12
-alkylaryl group, or R
9
and R
10
or R
9
and R
11
, in each case together with the atoms connecting them, form a ring.
M
2
is silicon, germanium or tin, preferably silicon or germanium.
R
6
is preferably ═CR
9
R
10
, ═SiR
9
R
10
, ═GeR
9
R
10
, —O—, —S—, ═SO, ═PR
9
or ═P(O)R
9
and particularly preferably ═SiR
9
R
10
.
R
7
and R
8
are identical or different and are as defined for R
9
.
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
The particularly preferred metallocenes are thus the compounds of the formula A
where
M
1
is Zr or Hf, in particular Zr; R
1
and R
2
are identical or different and are (C
1
-C
3
)-alkyl or chlorine; R
3
and R
4
are identical or different and are (C
1
-C
10
)-, preferably (C
1
-C
4
)-alkyl, which may be halogenated, in particular methyl or butyl, or (C
6
-C
10
) -aryl, in particular phenyl; R
5
is hydrogen, (C
1
-C
10
)-, in particular (C
1
-C
4
)-alkyl, which may be halogenated, or (C
6
-C
10
)-aryl, in particular phenyl; and R
9
and R
10
are identical or different and are (C
1
-C
10
)-, preferably (C
1
-C
4
)-alkyl, in particular methyl, or (C
6
-C
10
)-, preferably (C
6
-C
8
)-aryl, in particular phenyl.
The chiral metallocenes are preferably employed as a racemate. However, it is also possible to use the pure R- or S-form. By means of these pure stereoisomeric forms, optically active polymer can be prepared. However, the meso-form of the metallocenes should be separated off, since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to mirror symmetry at the central metal and is therefore incapable of producing a highly isotactic polymer. If the meso-form is not separated off, atactic polymer is formed in addition to isotactic polymers. For certain applications—for example soft moldings—this may be entirely desirable.
Resolution of the stereoisomers is known in principle.
The above-described metallocenes can be prepared accordance with the following reaction scheme:

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