1-olefin isoblock polymer and process for its manufacture

Details 1-olefin isoblock polymer and process for its manufacture 1-olefin isoblock polymer and process for its manufacture

1995-06-05

2002-07-02

Wilson, Donald R. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C502S102000, C526S128000, C526S943000, C526S348200, C526S348500, C526S348600, C526S159000, C526S160000

Reexamination Certificate

active

06413899

ABSTRACT:

DESCRIPTION
The invention relates to a 1-olefin isoblock polymer with long isotactic sequences and to a process for its manufacture.
It is known that polypropylene exists in various structural isomers:
(a) highly isotactic polypropylene in whose molecular chains almost all tertiary C atoms have the same configuration,
(b) isotactic stereoblock PP in whose molecular chains isotactic blocks of opposite configuration alternate regularly with one another,
(c) syndiotactic polypropylene in whose molecular chains every other tertiary C atom has the same configuration,
(d) atactic polypropylene in whose molecular chains the tertiary C atoms have a random configuration, and
(e) atactic-isotactic stereoblock PP in whose molecular chains isotactic and atactic blocks alternate with one another.
A process for the manufacture of isotactic stereoblock polymers is known in which propylene is polymerized with the aid of a metallocene of a metal of group IVb, Vb or VIb of the periodic table (q.v. U.S. Pat. No. 4,522,982). This metallocene is a mono-, di- or tri-cyclopentadienyl or substituted cyclopentadienyl compound of a metal, especially titanium. An aluminoxane is used as cocatalyst.
However, the titanocenes which are preferably used do not have sufficient heat stability in dilute solution to be usable in an industrial process. Moreover, in this process, products with longer isotactic sequences (n greater than 6) are only obtained at very low temperature (−60° C.). Finally, the cocatalysts must be used in comparatively high concentration in order to achieve an adequate catalytic yield, so the catalyst residues contained in the polymer product have to be removed in a separate purification step.
It is further known that stereoblock polymers of 1-olefins with long isotactic sequences can be obtained at industrially favorable polymerization temperatures by means of a catalyst consisting of a metallocene compound with cyclopentadienyl radicals substituted by chiral groups, and of an aluminoxane (q.v. European patent application A 269987).
It is further known that stereoblock polymers of 1-olefins with a broad monomodal or multimodal molecular weight distribution can be obtained when 1-olefins are polymerized using a catalyst consisting of a chiral metallocene containing bridges and of an aluminoxane (q.v. European patent application A 269986). The polymers are particularly suitable for the production of transparent sheets.
It is also known that when a catalyst based on bis-cyclopentadienyl compounds of zirconium and on an aluminoxane is used in the polymerization of propylene, only atactic polymer is obtained (q.v. European patent application A 69951).
Finally, highly isotactic polypropylene can be manufactured by means of soluble stereorigid chiral zirconium compounds (q.v. European patent application A 185 918).
A polymerization process has been found in which a polymer of regular molecular structure and high molecular weight is obtained in high yield at industrially favorable process temperatures.
The invention thus relates to an isoblock polymer of a 1-olefin of the formula RCH═CH
2
, in which R is an alkyl radical having 1 to 28 C atoms, with molecular chains containing isotactic sequences which are separated from one another in each case by one monomer unit of opposite configuration, and with a sequence length of 3 to 50 monomer units.
The invention further relates to a process for the manufacture of the above-mentioned isoblock polymer by the polymerization of a 1-olefin of the formula RCH═CH2, in which R is an alkyl radical having 1 to 28 C atoms, at a temperature of −60 to 100° C. and a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the metallocene is a compound of formula I:
in which
M
1
is a metal of 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
-alkylaryl group, a C
8
-C
40
-arylalkenyl group or a halogen atom,
R
3
, R
4
, R
5
and Re are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
10
-alkyl group, —NR
10
2
, −SR
10
, —OSi
r
R
10
3r+1
, —Si
r
R
10
3r+1
or —PR
10
2
, in which R
10
is a halogen atom or a C
1
-C
10
-alkyl group, or pairs of adjacent radicals R
3
, R
4
, R
5
and R
6
form a ring with the C atoms to which they are bonded, and
R
7
is
in which
R
11
, R
12
and R
13
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
11
and R
12
or R
11
and R
13
form a ring with the atoms to which they are bonded,
M
2
is silicon, germanium or tin,
p is 1, 2 or 3,
R
8
and R
9
are identical or different and are a group═CR
11
R
12
, in which R
11
and R
12
are as defined above, and
m and n are identical or different and are zero, 1 or 2, m+n being zero, 1 or 2.
The isoblock polymer according to the invention is a polymer of a 1-olefin of the formula R-CH═CH2, in which R is an alkyl radical having 1 to 28 C atoms, preferably 1 to 10 C atoms, in particular one C atom, for example propylene, but-1-ene, hex-1-ene, 4-methylpent-1-ene or oct-1-ene. The polymer is especially a propylene polymer.
The molecular chains of this polymer contain isotactic sequences which are separated from one another in each case by one monomer unit of opposite configuration. The molecular chains preferably consist of isotactic sequences which are separated from one another in each case by one monomer unit of opposite configuration. The isotactic sequences have an average length of 3 to 50 monomer units.
As a consequence of this steric structure, the isoblock polymers according to the invention are amorphous or partly crystalline according to the molecular weight and the length of the isotactic sequences. Depending on the crystallinity, the polymers are obtained as granular powders or as compact masses. The partly crystalline isoblock polymers have a low melting point by comparison with isotactic polymers. Isoblock polymers possess rubber-like properties.
The catalyst to be used for the process according to the invention consists of a metallocene compound of formula I and an aluminoxane. In formula I:
M
1
is a metal of group IVb, Vb or VIb of the periodic table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium or hafnium. 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
8
-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
3
, R
4
, R
5
and R
6
are identical or different, preferably different, and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group, —NR
10
2
, —SR
10
, —OSi
r
R
10
3r+1
, —Si
r
R
10
3r+1
or —PR
10
2
, in which R
10
is a halogen atom, preferably a chlorine atom, or a C
1
-C
10
-, preferably C
1
-C
3
-alkyl group, or pairs of adjacent radicals R
3
, R
4
, R
5
and R
6
form a ring with the C atoms to which they are bonded.
R
7
is
═BR
11
, ═AlR
11
, —Ge—, —Sn—, —O—, —S—, ═S═O, ═SO
2
, ═NR
11
, ═CO, ═PR
11
or ═P(O)R
11
, in which R
11
, R
12
and R
13
are id

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