Process for producing substantially amorphous...

Details Process for producing substantially amorphous... Process for producing substantially amorphous...

2001-09-18

2004-05-04

Harlan, Robert Deshon (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S161000, C526S172000, C526S351000, C526S348000, C526S348600, C526S943000, C502S117000, C502S152000, C502S155000, C556S053000

Reexamination Certificate

active

06730754

ABSTRACT:

The present invention relates to a new high yield process for producing substantially amorphous propylene-based polymers having high molecular weights. The invention also relates to the novel class of metal complexes used in the above-mentioned process, as well as to the ligands useful as intermediates in the synthesis of said metal complexes.
Metallocene compounds are well-known in the state of the art as catalyst components in olefin polymerization reactions, in association with suitable cocatalysts, such as alumoxanes or aluminum derivatives. For instance, EP 0 129 368 discloses a catalyst system for the polymerization of olefins comprising a bis-cyclopentadienyl coordination complex with a transition metal, wherein the two cyclopentadienyl groups may be linked by a divalent bridging group, such as an ethylene or a dimethylsilandiyl group.
Another class of polymerization catalysts known in the state of the art are the bridged cyclopentadienyl amido catalysts, which usually include monocyclopentadienyl titanium compounds activated by an alumoxane or other suitable cocatalysts (see for instance EP 0 416 815 and EP 0 420 436).
The international patent application WO 98/22486, in the name of the same Applicant, describes bridged and unbridged metallocenes comprising at least a coordinating group containing a six &pgr; electron central radical, directly coordinating a transition metal atom, to which are associated one or more radicals containing at least one non carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te. Said metallocenes are useful as catalyst components for the production of polyethylene and polypropylene.
The international patent application WO 98/37106 describes a polymerization catalyst system comprising a catalytic complex formed by activating a transition metal compound which comprises a group 13, 15 or 16 heterocyclic fused cyclopentadienide ligand and a metal selected from the group consisting of Group 3-9 and 10 metals; said heterocyclic fused cyclopentadienide ligand preferably contains, as endocyclic heteroatoms, one or more B, N, P, O, or S atoms.
The international patent application WO 99/24446, in the name of the same Applicant, describes bridged and unbridged metallocenes comprising at least a heterocyclic cyclopentadienyl group of one of the following formulae:
wherein one of X or Y is a single bond, the other being O, S, NR or PR, R being hydrogen or an hydrocarbon group; R
2
, R
3
and R
4
are hydrogen, halogen, —R, —OR, —OCOR, —SR, —NR
2
or —PR
2
; a is 0-4. These metallocenes may be used as catalyst components in the polymerization of olefins, particularly in the production of homo and copolymers of ethylene.
The international applications WO 98/06727 and WO 98/06728 describe respectively 3-heteroatom and 2-heteroatom substituted cyclopentadienyl-containing metal complexes, useful as catalysts for olefin polymerization; more specifically, these complexes contain a heteroatom-Cp bond, respectively in the 3-position and 2-position of the Cp, and are used for preparing ethylene/1-octene copolymers.
The Applicant has now unexpectedly found a new class of metallocene compounds useful as catalyst components in propylene polymerization, able to produce high molecular weight substantially amorphous propylene (co)polymers in high yields.
An object of the present invention is a process for producing substantially amorphous propylene homopolymers or copolymers comprising contacting propylene, optionally in the presence of one or more olefins selected from the group consisting of ethylene, alpha-olefins of formula CH
2
═CHR′ wherein R′ is a linear or branched C
2
-C
10
alkyl or non conjugate diolefins containing up to 20 carbon atoms, under polymerization conditions with a catalyst system comprising:
A) a titanium complex of formula (I):
wherein: Ti is titanium;
X is a nitrogen or phosphorus atom;
Z is a C, Si or Ge atom; the groups R
1
, equal to or different from each other, are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl and C
7
-C
20
arylalkyl radicals optionally containing Si or heteroatoms belonging to groups 13 or 15-17 of the Periodic Table of the Elements, or two R
1
groups form together a C
4
-C
7
ring;
Y
1
is an atom selected from the group consisting of NR
7
, oxygen (O), PR
7
or sulfur (S), wherein the group R
7
is selected from the group consisting of linear or branched, saturated or unsaturated, C
1
-C
20
alkyl, C
6
-C
20
aryl and C
7
-C
20
arylalkyl radical;
the groups R
2
and R
3
, equal to or different from each other, are selected from the group consisting of hydrogen, halogen, —R, —OR, —OCOR, —OSO
2
CF
3
, —SR, —NR
2
and —PR
2
, wherein R is a linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl or C
7
-C
20
arylalkyl radical; two R can also form a saturated or unsaturated C
4
-C
7
ring, preferably R is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl, p-n-butyl-phenyl or benzyl radical, or R
2
and R
3
form a condensed aromatic or aliphatic C
4
-C
7
ring that can be substituted with one or more R
9
groups wherein R
9
is selected from the group consisting of halogen, —R, —OR, —OCOR, —OSO
2
CF
3
, —SR, —NR
2
and —PR
2
, wherein R has the meaning reported above, or two vicinal R
9
groups form together a condensed aromatic or aliphatic C
4
-C
7
ring;
the groups R
8
, R
4
and R
5
, equal to or different from each other, are selected from the group consisting of hydrogen, halogen, —R, —OR, —OCOR, —OSO
2
CF
3
, —SR, —NR
2
and —PR
2
, wherein R has the meaning reported above, or R
8
and R
4
, R
4
and R
5
or R
5
and R
8
form together a condensed C
4
-C
7
ring that optionally can be substituted with one or more R groups;
the group R
6
is selected from the group consisting of a linear or branched, saturated or unsaturated C
1
-C
20
allyl, C
6
-C
20
aryl and C
7
-C
20
arylalkyl radical, optionally containing heteroatoms belonging to groups 13 or 15-17 of the Periodic Table of the Elements;
the substituents L, equal to or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, —R, —OR, —OCOR, —OSO
2
CF
3
, —SR, —NR
2
and —PR
2
, wherein R has the meaning reported above;
Y
2
is selected from the group consisting of CR
8
or Y
1
; and
m is 0 or 1; when the group Y
2
is a CR
8
group m is l and the 6 membered ring formed is an aromatic benzene ring, when Y
2
is different from CR
8
m is 0 and the carbon atom bonding the R
4
group is directly bonded to the cyclopentadienyl ring and the ring formed is a 5 membered ring; i.e. when m is 1 the compound of formula (I) has the following formula (Ia);
and when m is 0 the compound of formula (I) has the following formula (Ib);
wherein L, X, Z, Y
1
, m, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
8
have the meaning reported above; and
(B) an activating cocatalyst.
The present invention further concerns a titanium complex of formula (I), as reported above, as well as the corresponding ligand of formula (II):
wherein X, Z, Y
1
, m, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
8
have the meaning reported above; the above ligands are particularly useful as intermediates in the preparation of the titanium complexes of formula (I), according to the invention.
The titanium complex of formula (I) may be suitably used according to the present invention in a complexed form, for example in the presence of a coordination molecules such as Lewis bases. Preferred complexes of formula (I) are those belonging to the following three classes (1), (2) and (3), having respectively formula (III), (IV) and (V).
Class (1)
Titanium complexes belonging to class (1) have the following formula (III)
wherein X, Z, Y
1
, L, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
8
have the meaning reported above with the proviso that R
2
and R
3
do not form a condensed aromatic or aliphatic C
4
-C
7
ri

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