Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-02-07
2004-05-04
Lu, Caixia (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C502S114000, C502S119000, C502S120000, C502S123000, C502S132000, C502S130000, C502S154000, C502S155000, C526S129000, C526S132000, C526S133000, C526S153000, C526S160000, C526S165000, C526S943000
Reexamination Certificate
active
06730755
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to catalyst supports which are used for olefin polymerizations, especially ethylene polymerization.
BACKGROUND OF THE INVENTION
The use of an aluminoxane as a cocatalyst for ethylene polymerization catalyst was reported by Manyik et al in U.S. Pat. No. (USP) 3,231,550.
Subsequently, Kamisky and Sinn discovered that aluminoxanes are excellent cocatalysts for metallocene catalysts, as disclosed in U.S. Pat. No. 4,404,344.
The use of a supported aluminoxane/metallocene catalyst is further described in, for example, U.S. Pat. No. 4,808,561.
Hlatky and Turner disclosed the activation of bis-cyclopentadienyl metallocene catalysts with boron activators in U.S. Pat. No. 5,198,401.
We have now discovered that the use of a metal oxide support which has been treated with a halosulfonic acid improves the productivity of group 4 metal catalysts which are activated with an aluminoxane or a boron activator.
SUMMARY OF THE INVENTION
In one embodiment, the present invention provides a catalyst support for olefin polymerization comprising:
1) a treated metal oxide support which is prepared by contacting a particulate metal oxide support with a halosulfonic acid; and
2) an activator selected from the group consisting of an aluminoxane and a boron activator, wherein said activator is deposited upon said treated metal oxide support.
In another embodiment, the present invention also provides a supported olefin polymerization catalyst comprising the above defined catalyst support and a group 4 metal catalyst.
The present invention further provides a process to prepare polyolefins using the catalyst technology of this invention. In a highly preferred embodiment, the group 4 metal catalyst is a phosphinimine catalyst.
DETAILED DESCRIPTION
The use of metal oxide supports in the preparation of olefin polymerization catalysts is known to those skilled in the art. An exemplary list of suitable metal oxides includes oxides of aluminum, silicon, zirconium, zinc and titanium. Alumina, silica and silica-alumina are metal oxides which are well known for use in olefin polymerization catalysts and are preferred for reasons of cost and convenience. Silica is particularly preferred.
The metal oxide may be calcined using conventional calcining conditions (such as temperatures of from 200 to 800° C. for time periods of from 20 minutes to 12 hours).
It is preferred that the metal oxide have a particle size of from about 1 to about 200 microns. It is especially preferred that the particle size be between about 30 and 100 microns if the catalyst is to be used in a gas phase or slurry polymerization process and that a smaller particle size (less than 10 microns) be used if the catalyst is used in a solution polymerization.
Conventional porous metal oxides which have comparatively high surface areas (greater than 1 m
2
/g, particularly greater than 100 m
2
/g, more particularly greater than 200 m
2
/g) are preferred to non-porous metal oxides.
The treated metal oxides used in this invention are prepared by directly treating the metal oxide with a halosulfonic acid such as chlorosulfonic acid or fluorosulfonic acid. Fluorosulfonic acid is readily available and the use thereof is preferred.
Activators
The activator used in this invention is selected from 1) aluminoxanes; and 2) boron activators. It is preferred to use an it aluminoxane. Descriptions of suitable activators are provided below.
Aluminoxanes are readily available items of commerce which are known to be cocatalysts for olefin polymerization catalysts (especially group 4 metal metallocene catalysts). A generally accepted formula to represent aluminoxanes is:
(R)
2
AlO(RAlO)
m
Al(R)
2
wherein each R is independently an alkyl group having from 1 to 8 carbon atoms and m is between 0 and about 50. The preferred aluminoxane is methylaluminoxane wherein R is predominantly methyl. Commercially available methylaluminoxane (“MAO”) and “modified MAO” are preferred for use in this invention. [Note: In “modified MAO”, the R groups of the above formula are predominantly methyl but a small fraction of the R groups are higher hydrocarbyls—such as ethyl, butyl or octyl—so as to improve the solubility of the “modified MAO” in aliphatic solvents.]
The halosulfonic acid-treated metal oxide and aluminoxane are contacted together to form a catalyst support according to this invention. This is preferably done using conventional techniques such as mixing the aluminoxane and treated metal oxide together in an aliphatic or aromatic hydrocarbon (such as hexane or toluene) at a temperature of from 10 to 200° C. for a time of from 1 minute to several hours. The amount of aluminoxane is preferably sufficient to provide from 1 to 40 weight % aluminoxane (based on the combined weight of the aluminoxane and the treated metal oxide).
Boron Activators
As used herein, the term “boron activator” refers to both boranes and borate salts which function as activators for olefin polymerization catalysts. These activators are well known to those skilled in the art.
The boranes may be generally described by the formula
B(L)
3
wherein B is boron and each L is independently a substituted or unsubstituted hydrocarbyl ligand. Preferred examples of the ligand L include phenyl, alkyl substituted phenyl and halogen-substituted phenyl with perfluorophenyl being particularly preferred.
The borates may be generally described by the formula
[A] [B(L)
4
]
wherein B is boron and each of the four L ligands is as described above; and
[A] is a carbonium, oxonium, sulfonium or anilinium component of the borate salt. Specific examples of boron activators include:
triethylammonium tetra(phenyl)boron,
tripropylammonium tetra(phenyl)boron,
tri(n-butyl)ammonium tetra(phenyl)boron,
trimethylammonium tetra(p-tolyl)boron,
trimethylammonium tetra(o-tolyl)boron,
tributylammonium tetra(pentafluorophenyl)boron,
tripropylammonium tetra(o,p-dimethylphenyl)boron,
tributylammonium tetra(m,m-dimethylphenyl)boron,
tributylammonium tetra(p-trifluoromethylphenyl)boron,
tributylammonium tetra(pentafluorophenyl)boron,
tri(n-butyl)ammonium tetra(o-tolyl) boron,
N,N-dimethylanilinium tetra(phenyl)boron,
N,N-diethylanilinium tetra(phenyl)boron,
N,N-diethylanilinium tetra(phenyl)n-butylboron,
N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,
di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron,
triphenylphosphonium tetra(phenyl)boron,
tri(methylphenyl)phosphonium tetra(phenyl)boron,
tri(dimethylphenyl)phosphonium tetra(phenyl)boron,
tropillium tetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate,
benzene (diazonium) tetrakispentafluorophenyl borate,
tropillium phenyltrispentafluorophenyl borate,
triphenylmethylium phenyltrispentafluorophenyl borate,
benzene (diazonium) phenyltrispentafluorophenyl borate,
tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate,
triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate,
benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate,
tropillium tetrakis (3,4,5-trifluorophenyl) borate,
benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate,
tropillium tetrakis (1,2,2-trifluoroethenyl) borate,
triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate,
benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate,
tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate,
triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and
benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate.
Readily commercially available ionic activators include:
N,N- dimethylaniliniumtetrakispentafluorophenyl borate,
triphenylmethylium tetrakispentafluorophenyl borate, and
trispentafluorophenyl borane.
The boron activator is preferably used in an equimolar ratio with respect to the transition metal in the catalyst molecule (e.g. if the catalyst is an organometallic complex of titanium, then the B:Ti mole ratio is 1) although the boron activator may be used in lower amounts or in molar excess.
It is also permissible to use a mixture of a boro
Chisholm P. Scott
Donaldson Robert D.
Gao Xiaoliang
Kowalchuk Matthew Gerald
Johnson Kenneth H.
Lu Caixia
Nova Chemicals (Internation) S.A
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