Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2000-12-01
2003-06-24
Harlan, Robert D. (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...
C502S117000, C502S152000, C502S155000, C526S089000, C526S128000, C526S160000, C526S161000, C526S171000, C526S317100, C526S320000, C526S336000, C526S347000, C526S348600, C526S943000
Reexamination Certificate
active
06583082
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to polymeric supports suitable for use in association with catalysts, preferably single site type catalysts, activated with aluminoxane. Particularly the supports contain functional groups.
BACKGROUND OF THE INVENTION
There are a number of patents that disclose the use of polymeric supports of olefin polymerization catalysts. Generally the supports are polyolefins as illustrated for example by Atlantic Richfield's U.S. Pat. No. 4,407,727; Quantum's WO 96/35726; and the abstract of Mitsubishi's JP 67407. Polyethylene and polypropylene are not polymers prepared from C
4-12
vinyl monomers and thus the references do not teach or disclose the subject matter of the present patent application.
There are a fairly large number of patents which teach using polymeric supports comprising styrene optionally a cross-linking agent such as divinyl benzene and/or polymeric supports such as poly(methyl methacrylate). These patents are illustrated by U.S. Pat. Nos. 4,623,707; 4,623,912; 5,139,985; 4,900,706; 5,463,000; 5,118,648; 5,498,582; and EP 344 755.
The closest art Applicants are aware relevant to the subject matter of the present patent application are U.S. Pat. No. 5,362,824 issued Nov. 8, 1994 and U.S. Pat. No. 5,461,017 issued Oct. 24, 1995 both to Furtek et al., assigned to Mobil. The patent teaches a polymeric support comprising about 30% of divinyl benzene, about 55% of styrene and about 15% of acetoxy or hydroxy styrene. The support may be used in association with a metallocene catalyst and aluminoxane as an activator. The reference does not suggest functional monomers selected from the group consisting of C
1-8
hydroxy esters of C
3-6
ethylenically unsaturated carboxylic acids, chloride derivatives thereof, chlorostyrene and C
1-8
straight chain, branched or cyclic amines which are unsubstituted or substituted by up to two C
1-4
alkyl radicals at the nitrogen atom.
SUMMARY OF THE INVENTION
The present invention provides a functionalized polymeric support for use in association with a catalyst system comprising a co-catalyst of the formula R
1
2
AlO(R
1
AlO)
m
AlR
1
2
wherein each R
1
is independently selected from the group consisting of C
1-20
hydrocarbyl radicals and m is from 3 to 50, said support comprising the suspension or emulsion polymerization product of a feedstock comprising:
(i) from 0 to 95 weight % of one or more C
4-12
vinyl monomers;
(ii) from 50 to 2 weight % of a crosslinking agent; and
(iii) from 70 to 3 weight % of a functionalized monomer
containing a reactive functional group selected from the group consisting of C
1-8
hydroxy esters of C
3-6
ethylenically unsaturated carboxylic acids, chloride derivatives thereof, chlorostyrene and C
1-8
straight chain, branched or cyclic amines which are unsubstituted or substituted by up to two C
1-4
alkyl radicals at the nitrogen atom; the sum of the weight % of said monomers being 100 weight %, and having a particle size from 0.1 to 1000 microns, surface area of greater than 10 m
2
/g and a pore volume of at least 0.2 cc/g of support.
A further aspect of the present invention provides a supported co-catalyst of the formula R
1
2
AlO(R
1
AlO)
m
AlR
1
2
wherein each R
1
is independently selected from the group consisting of C
1-20
hydrocarbyl radicals and m is from 3 to 50 on the above functional support, wherein the co-catalyst is present on the support in an amount from 0.01 to 0.8 g per g of support.
A further aspect of the present invention provides a catalyst system comprising the above supported co-catalyst, together with a catalyst of the formula:
(L)
n
—M—(X)
p
wherein M is a transition metal; L is a monoanionic ligand independently selected from the group consisting of a cyclopentadienyl-type ligand, a bulky heteroatom ligand and a phosphinimine ligand; X is an activatable ligand; n may be from 1 to 3; and p may be from 1 to 3, provided that the sum of n+p equals the valence state of M, and further provided that two L ligands may be bridged by a silyl radical or a C
1-4
alkyl radical to provide a molar ratio of aluminum to transition metal from 5:1 to 1000:1.
A further aspect of the present invention provides a supported catalyst comprising the above noted support, and a catalyst of the formula:
(L)
n
—M—(X)
p
wherein M is a transition metal; L is a monoanionic ligand selected independently from the group consisting of a cyclopentadienyl-type ligand, a bulky heteroatom ligand and a phosphinimine ligand; X is an activatable ligand; n may be from 1 to 3; and p may be from 1 to 3, provided that the sum of n+p equals the valence state of M, and further provided that two L ligands may be bridged by a silyl radical or a C
1-4
alkyl radical.
A further aspect of the present invention provides the above noted catalyst system together with a co-catalyst of the formula R
1
2
AlO(R
1
AlO)
m
AlR
1
2
wherein each R
1
is independently selected from the group consisting of C
1-20
hydrocarbyl radicals and m is from 3 to 50.
A further aspect of the present invention provides a catalyst system comprising a mixture of a catalyst of the formula:
(L)
n
—M—(X)
p
wherein M is a transition metal; L is a monoanionic ligand selected from the group consisting of a cyclopentadienyl-type ligand, a bulky heteroatom ligand and a phosphinimine ligand; X is an activatable ligand; n may be from 1 to 3; and p may be from 1 to 3, provided that the sum of n+p equals the valence state of M, and further provided that two L ligands may be bridged by a silyl radical or a C
1-4
alkyl radical and a co-catalyst of the formula R
1
2
AlO(R
1
AlO)
m
AlR
1
2
wherein each R
1
is independently selected from the group consisting of C
1-20
hydrocarbyl radicals and m is from 3 to 50 to provide a molar ratio of aluminum to transition metal from from 5:1 to 1000:1 on the above noted support.
A further aspect of the present invention provides the above noted catalyst systems in a gas phase or slurry polymerization, preferably for olefins.
DETAILED DESCRIPTION
The feedstock for the polymeric supports of the present invention comprises:
(i) from 0 to 95, preferably from 60 to 80, weight % of one or more C
4-12
vinyl monomers;
(ii) from 50 to 2, preferably from 25 to 10, weight % of a crosslinking agent; and
(iii) from 70 to 3, preferably from 65 to 15, most preferably from 60 to 15, desirably from 50 to 15 weight % of a functionalized monomer containing reactive functional group selected from the group consisting of C
1-8
hydroxy esters of C
3-6
ethylenically unsaturated carboxylic acids, chloride derivatives thereof, chlorostyrene and C
1-8
straight chain, branched or cyclic amines which are unsubstituted or substituted by up to two C
1-4
alkyl radicals at the nitrogen atom; the sum of the weight % of said monomers being 100 weight %.
Some vinyl monomers include styrene, alpha-methyl styrene, para-methyl styrene and C
1-4
alkyl esters of C
3-6
unsaturated carboxylic acids. The styrenic monomers such as styrene, alpha-methyl styrene, para-methyl styrene may also be referred to as vinyl aromatic monomers. Some C
1-4
alkyl esters of C
3-6
unsaturated carboxylic acids include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate.
Some crosslinking agents include divinyl benzene, divinyl toluene, di- and tri-acrylates and di- and tri-methacrylates such as pentaerythritol trimethacrylate.
Some functionalized monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and pyridine.
The functionalized polymeric supports may be prepared by conventional suspension polymerization techniques. These are well known to those skilled in the art. Generally the monomers are dispersed in water as continuous phase using one or more surfactant or suspending agents which may be ionic such as long chain (e.g. C
12-18
) fatty acids or derivatives thereof (e.g. sulfonates) and salts thereof such as for example, dodecyl benzene sulfonate, or a non ionic surfactant such as polyoxyethylene sorbitan fatty acid ester
Hoang Peter Phung Minh
Kearns Jason Roy
Li Nai-Hong
Lynch David T.
Russell Charles
Harlan Robert D.
Johnson Kenneth H.
The Governors of the University of Alberta
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