Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
1999-05-06
2001-03-06
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C526S127000, C556S051000
Reexamination Certificate
active
06197984
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention is directed to a method of copolymerizing ethylene with cycloolefin monomers, often referred to as norbornene-type, or NB-type. More specifically, the method employs neutral nickel catalysts and the polymers obtained by the method of this invention are amorphous addition copolymers which may be random or alternating in character.
Addition copolymers of ethylene and norbornene-type monomers are well known and can be prepared using a variety of catalysts disclosed in the prior art. This general type of copolymers can be prepared using free radical catalysts disclosed in U.S. Pat. No. 3,494,897 (Reding et al.); titanium tetrachloride and diethylaluminum chloride as disclosed in East German Patents 109,224 and 222,317 (VEB Leuna); or a variety of vanadium compounds, usually in combination with organoaluminum compounds, as disclosed in European Patent Application No. 156464 (Kajiura et al.). The copolymers obtained with these catalysts are random copolymers. U.S. Pat. No. 4,948,856 issued to Minchak et al. (B.F.Goodrich) discloses preparing generally alternating copolymers by the use of vanadium catalysts which are soluble in the norbornene-type monomer and a co-catalyst which may be any alkyl aluminum halide or alkylalkoxy aluminum halide. European Patent Application No. 0 504 418 Al (Matsumoto et al.) discloses copolymerization of said monomers in the presence of catalysts such as transition metal compounds, including nickel compounds, and a compound which forms an ionic complex with the transition metal compound or a catalyst comprising said two compounds and an organoaluminum compound. More recently, metallocene catalysts were used to prepare copolymers of cycloolefins and &agr;-olefins as disclosed in EP 283,164 (1987) issued to Mitsui Petrochemicals and EP 407,870 (1989), EP 485,893 (1990) and EP 503,422 (1991) issued to Hoechst AG. Most recently PCT published application WO96/23010 discloses processes of polymerizing ethylene, &agr;-olefins and/or selected cyclic olefins which are catalyzed by selected transition metal compounds, including nickel complexes of diimine ligands, and sometimes also a cocatalyst. This disclosure provides, however, that when norbornene or a substituted norbornene is used, no other olefin can be present.
SUMMARY OF THE INVENTION
It is a general object of the invention to provide a novel method of preparing amorphous copolymers of ethylene and at least one norbornene (NB)-type comonomer. These polymers may be random or alternating depending on the choice of catalyst and/or the relative ratio of the monomers used. This method comprises polymerizing said monomers in a diluent or in bulk in the presence of a neutral nickel catalyst which may be represented by the formula
wherein Y may be a saturated or unsaturated hydrocarbyl chain, X may be oxygen or sulfur, E may be phosphorus, arsenic, antimony, oxygen or nitrogen, R and R′ independently each is hydrogen or a hydrocarbyl group, L is a ligand containing a heteroatom P, N or O or L and R together with L may form part of a chelating structure in which case L is an ethylenic double bond.
DETAILED DISCLOSURE OF THE INVENTION
This invention is directed to a new method of preparing substantially amorphous copolymers of ethylene and one or more norbornene (NB)-type comonomers. The resulting copolymers may be alternating or random, depending on the relative proportion of each type of monomer used. This method comprises copolymerizing said monomers in the presence of a catalyst which is a neutral nickel compound bearing a bidentate ligand which chelates the nickel via two hetero-atoms (which may be the same or different) and a hydrocarbyl group (R) or a hydride.
Catalysts employed in the method of this invention may be represented by the formula
wherein Y is a saturated or unsaturated hydrocarbyl chain containing 1 to 3 carbon atoms which may be unsubstituted or substituted with hydrocarbyl groups having up to 20 carbon atoms or functional groups or two adjoining carbon atoms of said hydrocarbyl chain may form part of a cyclic structure, or said hydrocarbyl group may contain a hetero atom;
X is O or S;
E is P, As, Sb, N or O;
R and R′ independently is H or C
1-20
hydrocarbyl group;
n is 0, 1 or 2, and
L is a ligand bearing the heteroatom P, N or O or alternatively L together with R form part of a chelating structure containing a nickel-carbon bond and a neutral two-electron donor moiety. Such a chelating structure would include, for example, where L is a C=C double bond, a ketone, aldehyde, an amide and the like.
Preferably L is a weakly coordinating ligand such as pyridine or a C=C double bond, E is phosphorus (P), X is oxygen (O) and Y is a hydrocarbyl chain containing 2 or 3 carbon atoms.
These catalysts can be prepared in advance or may be generated in situ by mixing the ligand with a suitable nickel complex such as bis (cyclooctadiene) nickel.
The above formula I, which broadly represents the catalysts useful in the method of this invention, includes the below identified sub-categories of such catalysts. These neutral nickel-containing catalysts consist essentially of one or more of the following:
1(a) A dinickel compound of the formula
wherein:
R
3
and each R
4
, independently, is H or C
1-20
hydrocarbyl;
X
1
is O or S;
E
1
is P, As or Sb; and
R
5
and R
6
, independently, is H, C
1-20
hydrocarbyl or a functional group selected from —OR
2
, —Cl, —CO
2
R
2
, —CO
2
M, —C(O)N(R
1
)
2
, —C(O)R
2
, —SR
2
, —SO
2
R
2
, —SOR
2
, —O—SO
2
R
2
, —P(O)(OR
2
)
2-y
(R
1
)
y
, —CN, —NHR
2
, —N(R
2
)
2
,
—Si(OR
1
)
3-x
(R
1
)
x
, —OSi(OR
1
)
3-x
(R
1
)x, —NO
2
, —SO
3
M, —PO
3
M
2
and —P(O)(OR
2
)
2
M, wherein M is alkali or alkaline earth metal, ammonium, quaternary ammonium, phosphonium or arsonium, y is 0, 1 or 2, each R
1
, independently, is H or C
1-20
hydrocarbyl, each R
2
, independently, is C
1-20
hydrocarbyl, and x is 0 or an integer of 1 to 3, or R
5
and R
6
, taken together with the carbon atoms to which they are attached, is a substituted or unsubstituted C
5-8
alicyclic, C
5-8
heterocyclic or C
6-14
aromatic ring, the heteroatom of the heterocyclic ring being selected from O, N and S.
1(b) a nickel compound of the formula
wherein:
R
3
, R
4
, R
5
, R
6
, X
1
and E
1
are defined as above and L
1
is a weakly coordinating ligand, or R
3
and L
1
taken together form a group having the structure
wherein R″ is H, C
1-20
hydrocarbyl or oxyhydrocarbyl or N(R
2
)
2
wherein each R
2
, independently, is C
1-20
hydrocarbyl;
1(c) a nickel compound of the formula
wherein:
R
1
, R
4
, R
5
, R
6,
X
1
and E
1
are as defined above; each R
7
, independently, is H, —OSi(R′″)
3
, C
1-20
alkyl or oxyalkyl, C
6-20
aryl, alkaryl, aralkyl or oxyaryl, —N(R
2
)
2
wherein R
2
is as defined above, or halogen, or both R
7
groups, taken together, form a 5 to 8-membered heterocyclic ring wherein the heteroatom is selected from O, N and S; and
each R′″, independently, is C
1-20
alkyl or oxyalkyl, C
6-20
aryl, alkaryl, aralkyl or oxyaryl;
(2) a mixture comprising:
(i) a nickel compound of the formula
wherein R
3
, R
4
, R
5
, R
6
, X
1
and E
1
are defined as above and L
2
is a strongly coordinating ligand; and
(ii) an acceptor compound which can react with L
2
; and
(3) the mixture comprising:
(i) a nickel compound of the formula
wherein R
4
, R
5
, R
6,
X
1
and E
1
are defined as above; and
(ii) a suitable alkylating or arylating compound.
(4) a nickel compound of the formula:
where E, X, R, L and n are as defined above, Z is a double bond or a carbon atom containing one hydrogen or fluorine or one or two C
1-20
hydrocarbyl groups, provided that one or both hydrocarbyl groups can form a cyclic structure with the carbon atom adjacent to Z, and each of R
5
and R
6
, independently, is H, C
1-20
hydrocarbyl or a functional group selected from —OR
2
, —Cl, —CO
2
R
2
, —CO
2
M, —C(O,N(R
1
)
2
, —C(O)R
2
, —SR
2
, —SO
2
R
2
, —OSO
2
R
2
, —SOR
2
, —P(O)(OR
2
)
2-y
(R
1
)
y
, —CN, —NHR
2
, —N(R
2
)
Bagdasaryan Andrey Khristoforovich
Bykov Viktor Ivanovich
Finkelshtein Eugeny Shmerovich
Makovetsky Kiryll Lvovich
Rhodes Larry Funderburk
Dunlap Thoburn T.
Hudak & Shunk Co. LPA
Nazario-Gonzalez Porfirio
The B. F. Goodrich Company
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