WO1996013532A1

WO1996013532A1 - In situ dehydroxylation of supports and preparation of supported metallocene polyolefin catalysts

Info

Publication number: WO1996013532A1
Application number: PCT/US1995/014363
Authority: WO
Inventors: David George Ward; Patrick Brems
Original assignee: W.R. Grace & Co.-Conn.
Priority date: 1994-10-31
Filing date: 1995-10-25
Publication date: 1996-05-09
Also published as: AU4146896A

Abstract

The present invention provides a method to prepare, in situ, a supported metallocene catalyst precursor on a dehydroxylated support. The method comprises the following steps: (A) reacting reagents (i), (ii) and (iii) in the presence or absence of a solvent, wherein (i) is a compound that is a transitional metal or rare earth metals compound; (ii) is a metal containing reagent, wherein the metal component or the reagent is selected from the group consisting of tin, silicon, germanium and mixtures thereof and the remaining component of the reagent contains a five-member carbon ring, a heterosubstituted five-member carbon ring, or a bridged (ansa) ligand defined as multi cyclic moieties capable of coordinating to the transition or rare earth metals; and (iii) is a hydroxyl group containing support materials; (B) recovering the resulting supported catalyst precursor.

Description

INSITU DEHYDROXYLATION OF SUPPORTS AND PREPARATION OF SUPPORTED METALLOCENE POLYOLEFIN CATALYSTS

This application is a continuation-in-part of U.S. Patent Application Serial No. 08/331,439, filed on October

31, 1994. Background

It has been known to use metallocene compounds of

transition metals as catalysts for polymerization and copolymerization of olefins.

The use of metallocene catalyst systems provides the ability to produce uniform polymers and copolymers of

narrow molecular weight distribution (M D) and narrow compositional distribution.

Solution, slurry, and gas phase polymerization techniques are well known in the field. See, e.q..

Krichelderf, Handbook of Polymer Synthesis, Chapter 1,

Part A, p.7-8 (Marcel Dekker 1992) . However, in order to

use the metallocene catalyst effectively, the active catalytic specie needs to be supported. There are known

supports and known means by which to place the metallocene active specie on the support. These means

involve physically adding the metallocene to the support after the catalyst is prepared. This merely physically

combines the active specie with the support.

A drawback to the use of supported metallocene catalysts is that many oxide supports contain active _

hydroxyl groups. These hydroxyl groups are reactive and tend to deactivate the active, expensive metallocene specie. Accordingly, it is often desirable to deactivate the hydroxyl groups .

In the past, various chemical and/or thermal treatments have been used in an effort to achieve dehydroxylation of the oxide support particles .

Thermal treatments (i.e. , calcining) have been used and are advantageous in that they do not add undesirable

chemicals to the support and that they are relatively simple, inexpensive processes. Unfortunately, thermal treatments are often ineffective for achieving a high degree of dehydroxylation. Further, for many porous

oxide supports (e.g., silica gel) , thermal treatments often result in an undesirable loss of pore volume,

shrinkage of the pores and/or loss of surface area.

Chemical treatments have been attempted. Many types of chemicals have been used such as organo aluminum compounds, magnesium chloride/dehydrating agents

combinations, organosilanes, halosilanes, silanes, etc. These various chemical processes are often expensive and

may result in the addition of undesired or complicating constituents to the oxide support. Thus there remains a need for improved techniques to support metallocene catalytic species while deactivating

the hydroxyl groups present on oxide support materials and avoiding the problems of having undesired chemical constituents or thermal effects.

Accordingly, it is an object of the present

invention to provide novel methods for making supported metallocene precursors in-situ wherein hydroxyl groups

are deactivated. Additionally, another object of the present

invention is to provide a catalyst which is capable of producing polymer with a broad molecular weight.

These and other objects are accomplished by a

catalyst produced by the presently disclosed "in-situ

method" of catalyst preparation as described below and using the present catalyst in solution, slurry and gas phase polymerization processes to obtain desirable novel

polymers .

^•f

Summary of the Present Invention

In accordance with one aspect of the present invention, there is provided a novel composition of matter useful as polyolefin catalyst.

Also provided in accordance with this invention are methods of making and using the novel compositions to

polymerize olefins.

The invention further provides unique catalyst compositions suitable for forming polymers having broad molecular weight distribution and good flow properties

(i.e. , the ability to be processed through dies and other machinery without raising the processing temperature or pressure) . The polymers produced in accordance with the present invention also have reduced presence of polymer degrading and equipment corroding materials, such as

chlorine, in the final polymer product.

The present invention provides a method to prepare, in-situ, a supported metallocene catalyst precursor on a dehydroxylated support. The method comprises the

following steps:

(A) reacting reagents (i) , (ii) and (iii) in the presence or absence of a solvent, wherein

(i) is a compound that is a transition metal compound, optionally containing a five-member carbon s ring, a heterosubstituted five-member carbon ring,

or a bridged (ansa) ligand defined as multi- cyclic moieties capable of coordinating to the transition or rare earth metals;

(ii) is a metal containing reagent, wherein the

metal component of the reagent is selected from the group consisting of tin, silicon, germanium and mixtures

thereof and the remaining component of the reagent is selected from the group of halogen elements, organics,

amides and mixtures thereof, and optionally, containing an additional organic component that contains a five- member carbon ring, a heterosubstituted five-member carbon ring, or be a bridged (ansa) ligand defined as mulit-cyclic moieties capable of coordinating to the transition or rare earth metals; and

(iii) is a hydroxyl group containing support material;

(B) recovering the resulting supported catalyst precursor. Detailed Description of the Invention

Catalyst precursors of the present invention are useful in the polymerization of any olefin in which separate polymerization with a homogeneous catalyst or with a heterogeneous catalyst is possible. Preferably, catalysts of the present invention are useful in the polymerization, copolymerization and terpolmerization of

olefinic monomers, preferably, α-olefins, and most

preferably, propylene and ethylene. The catalyst precursors produced according to the

present invention are described below in terms of the manner in which they are made.

The method to prepare supported catalyst precursors according to the present invention can be described by

the following graphic representations.

Illustration I (InSitu Preparation and Dehyroxylation]

A, optional Support-OH + [CM¹ (optionally, X)] + [MZ (optionally, C)]→

[Support-O-M'X] [MC , optionally Z or X] ]

The terms used in Illustration I are defined below. Support

The Support can be any sufficiently porous inorganic, inorganic oxides and organic materials

containing hydroxyl groups. Suitable inorganic materials include magnesium compounds or their complex salts such as MgCl(OH) and Mg(OH)₂ Inorganic oxide supports, include talcs, clays, and metal oxides from Groups 2-14, actinide, lanthanide Series metals from the Periodic Table; suitable metal oxides are typically Si0₂, Al₂0₃,

MgO, Zr0₂, Fe₂0₃, B₂0₃, CaO, ZnO, BaO, Th0₂ and mixtures

thereof; for example, silica-alumina, silica-titania, silica-titania-alumina, zeolite, ferrite, glass fibers,

magnesia, titania, zirconia, aluminum phosphate gel and

mixtures thereof

Organic Supports include resinous material such as polyvinylaicoho1, starches and mixtures thereof. Preferably, the supports are compositions

conventionally used as catalyst support materials. The degree of porosity in the carrier may be any level that

is achievable in the starting material. Preferably, the carrier particles of the present invention have a pore

volume of at least 0.1 cc/g; preferably more than 1.0 cc/g; and more preferably from about 0.3 to 5 cmVg. Preferably, the carrier particles have a surface area of about 1-1000 m²/g; more preferably in the range of from

100 - 800 m²/g; and more preferably 250-600 m²/g. The typical median particle size for a suitable carrier for

this invention is from 1 to 300 microns, preferably from 5 to 200 microns and more preferably from 25 to 150

microns . Pore volume and surface area, for example, can be measured from volume of nitrogen gas adsorbed in

accordance with BET method. (Refer to J. Am. Chem. Soc, Vol. 60, p. 309 (1983) ) .

C

C represents a ligand defined as one five-member

carbon ring, heterosubstituted five-member carbon ring, or a bridged (ansa) ligand defined as multi-cyclic moieties capable of coordinating to the transition or rare earth metals, M.

The ansa bridge can be selected from the group

comprising carbon, silicon, phosphorus, sulfur, oxygen, nitrogen, germanium, species such as R"₂C, R"₂Si, R"₂Ge, R"₂CR"₂C, R"₂SiR"₂Si, R"₂GeR"_:Ge, R"₂CR"₂Si, R"₂CR"₂Ge, R"₂CR"₂CR"₂C, R"₂SiR"₂Si, diradicals where R is independently selected from the group containing hydride,

halogen radicals, and Cl-20 hydrocarbyl radicals including ethyl, propyl; preferred ansa bridges are Me₂Si (di ethylsilyl) , Ph₂Si (diphenylsilyl) , Me₂C

(isopropylidene) , Ph₂P (diphenylphosphoryl) Me₂SiSiMe₂

(tetramethyldisilane) and the like. Preferably, the ansa bridge has a length of two atoms or less as in methylene, ethylene, diphenysilyl, dimethylsilyl, and

methylphenylsilyl . .

M' represents a metal selected from the group comprising silicon, tin, germanium and mixtures thereof.

M

M represents a metal selected from the group consisting of Groups 3 through 10, lanthanides, actinides

metals of the Periodic Table and mixtures thereof; preferably titanium, zirconium, hafnium, chromium, vanadium, samarium, neodymium and mixtures thereof; most preferably Ti, Zr, and Hf, and mixtures thereof.

The definition of MZ is intended to include any existing Ziegler-Natta catalytic precursors.

X and Z

X and Z represents elements from the halogen group (preferably chlorine, fluorine, bromine and mixtures thereof) ; and substituted and nonsubstituted alkoxys (preferably C1-C20 alkoxys, such as methoxy, ethoxy, isopropyloxy, butoxy and phenoxy) ; alkyls (preferably Cl- C20 alkyls such as ethyl, butyl, octyl, ethylhexyl) ;

aryls (preferably C6-C20 aryls such as phenyl, p-tolyl,

benzyl, 4-t-butylphenyl, 2, 6-dimethylphenyl, 3,5- methylphenyl, 2 , 4-dimethylphenyl, 2, 3-dimethylphenyl) ; alkenyls (preferably C1-C20 alkenyls, such as ethenyl, propenyl, butenyl, pentenyl) ; amides (preferably NR^aR^b , wherein the R^a and R^b can be the same or different and

independently selected from alkyls, alkenyls, aryls, or silanes; preferably C1-C20 alkyls and alkenyls and C6-C20

aryls, including substitued aryls, such as ethyl, butyl, octyl, ethylhexyl) , phenyl, p-tolyl, benzyl, 4-t-

butylpheny1, 2, 6-dimethylphenyl, 3,5-methylphenyl, 2,4- dimethylphenyl, 2, 3-dimethylphenyl) ; and preferred R

groups in the NR²R^b are C1-C5 alkyls, C2-C5 alkenyls, phenyl and napthyl and mixtures thereof.

Preferred amides are dimethylamide, diethylamide, hexamethyldisilazide and mixtures of two or more of the foregoing. PREFERRED CM'X

CM'X is preferably selected from the group comprising (chlorodimethylsilyl) (3-trimethylsilyl) cyclopentadiene, cyclopentadienyltrimethylsilane, indenyltrimethylsilane, indenyltributylstannane, indenyltrimethylgermanium, cyclopentadienyl trimethylgermanium, and mixtures thereof. / /

A

A, may be optionally used to further modify the catalyst and/or support, and can be selected from the

group comprising acid halides, (e.g. , HCl, HBr and HI) ; metal halides (preferably, Al, Si, Sn, Ti, Mg, Cr and mixtures thereof, wherein the halide are Cl, Br, I and

mixtures thereof; organic halides (R'X) , carboxylic acids

(R' (COOH) , esters (R' (COOR" ) , ethers (R' (OR") when n is equal to or greater than 1, alcohols wherein the R'and

R" are the same or different and independently selected from mono or multi-cyclic, halosubstituted and non-

substituted aryls, alkyls, and alkenyl groups and mixtures thereof; preferred are Cl-20 alkenyl groups

(such as ethene, propylene, butene, and pentene) ; Cl-20 alkyl groups (such as a methyl, ethyl, n-propyl, iso-

propyl, n-butyl, n-octyl, and 2-ethylhexyl groups) , C6-20 aryl group (includng substituted aryls) (such as phenyl,

p-tolyl, benzyl, 4-t-butylphenyl, 2,6 dimethylphenyl, 3,5- methylphenyl, 2 , 4-dimethylphenyl, 2,3-dimethylphenyl

groups) and mixtures thereof. More preferred R groups are Cl-5 alkyls, C2-5 alkenyls phenyl and napthyl and

mixtures thereof.

"A" can also be C1-C20 alkylaluminums (preferably C1-C10 alkyl aluminums, and most preferably triethyl aluminum, trimethylaluminum, tributylaluminum and

mixtures thereof) ; C1-C20 alkyl lithium (preferably, Cl- C6 alkyl lithiums, and most preferably n-butyllithium, methyllithium, ethyllithium and mixtures thereof) ; and Grignard reagents, generally represented by the formula

RMgX, where X is selected from the members of the halogen group from the Periodic Table, R is selected from the

group comprising a C1-C20 alkyls and C6-C20 aryls,

preferably C1-C6 alkyls and C6-C10 aryls; preferred Grignard reagents are methyl magnesium chloride, ethyl magnesium chloride, and isopropyl magnesium bromide and mixtures thereof.

Additional suitable "A" compounds for use in this invention is selected from the halogen gases and C1-C5 alkyl alumoxanes such as methylalumoxane, isobutylalumoxane and mixtures thereof.

Preferred A's include CH.C1, tetraydrafuran, t- butylchloride, dialkyl phthalates, ethanol, phenol, ethyl-aluminumdichloride, silicon tetrachloride,

methyllithium, methyl magnesium chloride,

triethylaluminum, methylalumoxane, dibutylphthalate and tin tetrachloride; halogen gases such as Cl₂ Fl₂ and Br₂ and mixtures of two or more of the foregoing. /3

The reaction can be carried over a broad range of temperatures, typically from approximately -78°C to 200°C,

preferably at 0°C to room temperature.

The reaction product will typically have the

following compositional characteristics. The values

provided below are given in weight percent of the final dry catalyst.

CMZ is approximately 0.1% to 50%; preferably 0.1 - 10; most preferably 0.1-5.0;

M'X is approximately 0.1% to 99.8%; preferably 5.0-

50; most preferably 5-15; and

Support is approximately 0.1% to 99.8%.

The reaction described in Illustrations I is

carried out in the presence of a solvent in either a solution or a slurry. The solvents that are desirably

utilized are solvents that do not adversely affect the preparation of the catalyst or, if any residue remains, does not adversely affect polymerization or the properties of the resulting polymer. Preferably, the solvent is a non-polar organic solvent; and most

preferably includes aliphatic hydrocarbons (typically C3 to C12 , such as butane, isobutane, pentane, isopentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and the like); alicyclic hydrocarbons (typically C5-C20, such as cyclopentane, methylcyclopentane, cyclohexane, decalin cycloctane, norbornane, ethyleyelohexane and the

like) ; aromatic hydrocarbons, including substituted aromatics such as benzene, chlorobenzene, xylene, toluene and the like; and petroleum fractions such as gasoline, kerosene, light oils, and the like. It may also be desirable to use tetrahydrofuran or another ether. Mixtures of two or more solvents may also be used, e.g. ,

Exxon's IsoPar ®.

l≤

:ΕRRED PRODUCTS CMZ or CMX

The starting materials can be selected as defined

above to achieve the desired CMZ or CMX. Such CMZ or CMX metallocene catalytic precursors are defined as

organometallic compounds having a transition metal,

including rare earth metals M as defined previously, in coordination with members of at least one five-member carbon ring, heterosubstituted five-member carbon ring, or a bridged (ansa) ligand defined as multi cyclic

moieties capable of coordinating to the transition or

rare earth metals.

The ansa bridge can be selected from the group comprising carbon, silicon, phosphorus, sulfur, oxygen,

nitrogen, germanium, species such as, R³ ₂C, R³ ₂Si, R³ ₂Ge, R³ ₂CR³ ₂C, R³ ₂SiR³ ₂Si, R₂GeR³ ₂Ge, R³ ₂CR³ ₂Si, R³ ₂CR³ ₂Ge, R³ ₂CR³ ₂CR³ ₂C,

R₂SiR³ ₂Si diradicals where R³ is independently selected from the- group containing hydride, halogen radicals, and Cl-20 hydrocarbyl radicals including ethyl and propyl; preferred ansa bridges are Me₂Si (dimethylsilyl) , Ph₂Si (diphenylsilyl) , Me₂C (isopropylidene) , Ph₂P

(diphenylphosphoryl) Me₂SiSiMe₂ (tetramethyldisilane) and

the like. Preferably, the ansa bridge has a length of two atoms or less as in methylene, ethylene, lb diphenysilyl, dimethylsilyl, propylidene and methylphenylsilyl .

The transition metal component of the metallocene

product is selected from Groups 3 through 10, lanthanides and actinides of the Periodic Table and mixtures thereof;

and most preferably, titanium, zirconium, hafnium,

chromium, vanadium, samarium and neodymium and mixtures thereof. Of these Ti, Zr, and Hf and mixtures thereof are most preferable.

In one preferred embodiment, the CMZ metallocene catalyst precursor product is represented by the general

formula (Cp)„MR⁴R⁵ wherein Cp is a substituted or unsubstituted cyclopentadienyl ring, M is a Group 3-6,

lanthanide, actinide series metal from the Periodic Table and mixtures thereof; R⁴ and R⁵ are independently selected halogen, hydrocarbyl group, or hydrocarboxyl groups having 1-20 carbon atoms; m=l-3, p= 0-3 and the sum of

m+n+p equals the oxidation state of M.

In another embodiment the CMX is represented by the formulae:

( C₅R⁶ _m) _pR⁷ _s ( C₅R⁶ MeK_3.p.x and

R _ ( C₅R⁶ _m) ₂MeK ' .

Wherein Me is a Group 3-6, lanthanide, actinide series metal from-the Periodic Table and mixtures thereof; C₅R⁶ _m is a substituted cyclopentadienyl each R⁶, which can be the same or different is hydrogen, alkenyl, aryl, or arylalkyl radical having from 1 to 20 carbon atoms or two carbon atoms joined together to form a part

of a C4 to C6 ring; R⁷ is one or more of or a combination

of a carbon, a germanium, a silicon, a phosphorous or a

nitrogen atom containing radical substitution on and bridging two C₅R^δ _m rings or bridging one C₅R⁶ _m ring back to Me, when p=0 and x=l otherwise x is always equal to 0,

each K which can be the same or different is an aryl alkyl, alkenyl, alkaryl, or arylalkyl radical having from 1-20 carbon atoms or halogen, K' is an alkylidene radical

having from 1 to 20 carbon atoms, s is 0 to 1 and when s

is 0, m is 5 and p is 0, 1, or 2 and when s is 1, m is 4

and p is 1.

In particular, preferred metallocenes are derivatives of a cyclopentadiene (Cp) , including

cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, and l_τl-disubstituted silacyclopentadienes, phosphocyclopentadienes, l-metallocyclopenta-2, 4-dienes, bis (indenyl) ethane and mixtures thereof.

Additional illustrative, but non-limiting, examples of metallocenes represented by the above definition are dialkyl metallocenes such as bis (cyclopentadienyl) titanium I δ

dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadie

nyl) zirconium diphenyl, bis (cyclopentadienyl)hafnium dimet hyl and diphenyl, bis (cyclopentadienyl^titanium di-

neopentyl, bis (cyclopentadienyl) zirconium di neopentyl, bis (cyclopent

adienyl) titanium dibenzyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl)vanadium dimethyl; the mono alkyl metallocenes such as bis(cyclopen

tadienyl) titanium methyl chloride, bis (cyclopentadienyl) ti tanium ethyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium ethyl chloride, bis(cyclope

ntadienyl) zirconium phenyl chloride, bis (cyclopentadienyl)

titanium methyl bromide; the trialkyl metallocenes such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl zirconium trimethyl,

cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafnium trineopentyl, and cyclopentadienyl hafnium

trimethyl; monocyclopentadienyls titanocenes such as, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride;

bis (pentamethylcyclopentadienyl) titanium diphenyl, the carbene represented by the formula bis (^"cyclopentadienyl) ti tanium=CH2 and derivatives of this reagent; substituted

bis (cyclopentadienyl) titanium (IV) compounds such as:

bis (indenyl) titanium diphenyl or dichloride, bis (methyleye lopentadienyl) titanium diphenyl or dihalides; dialkyl, tri

-alkyl, tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds such as bis (1,2-

dimethylcyclopentadienyl) -titanium diphenyl or dichloride, bis (1, 2-diethylcyclopentadienyl) titanium diphenyl or dichloride; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes, such as dimethyl silyldicyclope

ntadienyl titanium diphenyl or dichloride, methyl

phosphine dicyclopentadienyl titanium diphenyl or dichloride,

methylenedicyclopentadienyl titanium diphenyl or dichloride and other dihalide complexes, and the like; as well as bridged metallocene compounds such as isopropyl (cyclopenta

dienyl) (fluorenyl) zirconium dichloride, isopropyl (eye1open tadienyl) (octahydrofluorenyl) zirconium dichloride diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene (cyclopentadienyl) (fluore nyl) zirconium dichloride, diisobutylmethylene(cyclopentadi enyl) (fluorenyl) zirconium

dichloride, ditertbutylmethylene

(cyclopentadienyl) (fluorenyl) zirconium dichloride,

cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diisopropylmethylene (2,5- dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl)hafnium dichloride, diisopropylmethylene(cyclop entadienyl) (fluorenyl)hafnium dichloride, diisobutylmethy lene(cyclopentadienyl) (fluorenyl)hafnium dichloride, ditertbutylmethylene (cyclopentadienyl) (fluorenyl)hafnium

dichloride, cyclohexylidene(cyclopentadienyl) (fluorenyl)ha fnium dichloride, diisopropylmethylene (2, 5- dimethylcyclopentadienyl) (fluorenyl)hafnium

dichloride, isopropyl (cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene(cyclopentadienyl)

(fluorenyl) titanium dichloride, diisopropylmethylene (cyclo

pentadienyl) (fluorenyl) titanium dichloride, diisobutylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ditertbutylmethylene(cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene(cyclopenta dienyl) (fluorenyl) titanium dichloride,

diisopropylmethylene (2, 5 fluorenyl) titanium dichloride, racemic-ethylene bis (1-indenyl) zirconium (IV)

dichloride, racemic-ethylene bis (4, 5, 6, 7-tetrahydro-l- indenyl) zirconium (IV) dichloride, racemic-dimethylsilyl

bis (1-indenyl) zirconium (IV) dichloride, racemic- dimethylsilyl bis (4, 5, 6, 7-tetrahydro-1-indenyl) zirconium (IV) dichloride, racemic-1, 1, 2, 2- tetramethylsilanylene

bis (1-indenyl) zirconium (IV) dichloride, racemic-

1, 1, 2, 2-tetramethylsilanylene bis (4, 5, 6, 7-tetrahydro-l- indenyl)

zirconium (IV), dichloride, ethylidene (1-indenyl

tetramethylcyclopentadienyl) zirconium (IV) dichloride, racemic- dimethylsilyl bis (2-methyl-4-t-butyl-l- cyclopentadienyl) zirconium (IV) dichloride, racemic- ethylene bis (1-indenyl) hafnium (IV) dichloride, racemic-

ethylene bis (4, 5, 6, 7-tetrahydro-1-indenyl) hafnium (IV) dichloride, racemic-dimethylsilyl bis (1-indenyl) hafnium (IV) dichloride, racemic-dimethylsilyl (4,5,6,7- tetrahydro-1- indenyl) hafnium (IV) dichloride, racemic-

1,1,2,2- tetramethylsilanylene bis (1-indenyl) hafnium(IV)

dichloride, racemic-1, 1, 2, 2-tetramethylsilanylene bis ^ ___

(4, 5, 6, 7-tetrahydro-l- indenyl) hafnium (IV), dichloride, ethylidene (l-indenyl-2, 3,4, 5-tetramethyl-l-

cyclopentadienyl) hafnium (IV) dichloride, racemic- ethylene bis (1-indenyl) titanium (IV) dichloride,

racemic-ethylene bis (4, 5, 6, 7-tetrahydro-1-indenyl) titanium (IV) dichloride, racemie- dimethylsilyl bis (1-

indenyl) titanium (IV) dichloride, racemie- dimethylsilyl bis (4, 5, 6, 7-tetrahydro-1-indenyl) titanium (IV)

dichloride, racemic-1, 1, 2, 2-tetramethylsilanylene bis (1- indenyl) titanium (IV) dichloride racemic-1, 1, 2, 2- tetramethylsilanylene bis (4, 5, 6, 7-tetrahydro-l-

indenyl) titanium (IV) dichloride, and ethylidene (1- indenyl-2,3,4, 5-tetramethyl-l-cyclopentadienyl) titanium IV) dichloride. Preferred CMXs or CMZs are bis (cyclopenta¬

dienyl) titanium diehloro, bis (cyclopentadienyl) zirconium, isopropyl (cyclopentaienyl) fluroenyl)zirconium diehloro, bis (1-indenyl) zirconium (IV) diehloro, (4,5,6,7-

tetrahydro-1- indenyl)hafnium(IV)diehloro,

dimethylzireonoeene, dichloroethylenebisindenylzirconium, and dichloroethylene bis (tetrahydroindenyl) zirconium.

POLYMERIZATION The catalytic precursors prepared according to the method of the present invention may be activated by any number of catalytic activators and used to polymerize olefinic materials.

The catalytic activator includes organometallic compounds. Preferably, the metals are selected from the

group including lithium, aluminum, magnesium, zinc and boron. Such catalyst are known for their use in polymerization reactions, especially the polymerization of olefins. These include organo aluminum compounds such

as trialkyl, alkyl hydrido, alkylhalo and alkyl alkoxy

aluminum compounds. Suitably each alkyl or alkoxy group contains 1-16 carbons. Examples of such compounds include trimethylaluminum, triethylaluminum, diethyl aluminumhydride, triisobutylaluminum, trideeyl aluminum, tridodecylaluminum, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, diethyl aluminum chloride, ethyl aluminum dichloride, methyl diethoxy aluminum and methyaluminoxane. The preferred

compound is as an alkyl aluminoxane, the alkyl group having 1 to 10 carbon atoms, especially methyl

aluminoxane.

Additional suitable catalytic activators for use

with this invention are represented by the formulae: _. CT _.KH Q.-Q,.. , ) ] and N" (Q .

[C^*] is an activating cation, which may be a Bronsted acid capable of donating a proton to the transition metal ionic catalytic precursor resulting in a transition metal

5 cation. Such Bronsted acids include but are not limited to ammoniums, oxoniums, phosphoniums and mixtures thereof; preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-

0 dimethylaniline, methyldiphenylamine, pyridine, p-bromo- N,N, -dimethylaniline, p-nitro-N,N-dimethylaniline; phosphoniums from triethylphosphine, triphenylphosphine and diphenylphosphine; oxoniums from ethers such as

diethyl ether, tetrahydrofuran and dioxane; sulfoniums 5 from thioethers such as diethyl thioethers and tetrahydrothiophene; mixtures thereof; most preferably dimethylanilinium and mixtures thereof.

Furthermore, [C^*] may be an abstracting moiety that is capable of reacting with a transition metal catalytic 0 precursor resulting in the transition metal cation.

Acceptable abstracting moiety include but are not limited to silver, carbocations, tropylium, carbeniums, ^{■ •} ferroceniums and mixtures thereof; preferably carboniums

and ferroceniums and mixtures thereof; and most 2i_

preferably triphenyl carbenium. The [C^*] may also include mixtures of the Bronsted acids and the abstracting moiety

species.

[N] is selected from the group consisting of boron,

phosphorus, antimony or aluminum and mixtures thereof, having the n valence state. Preferably, the [N] is boron, aluminum and mixtures thereof.

[__!-_„_!_ are independent, wherein Q_j-Q.^ are RX is defined wherein X is a halogen group element and is typically fluorine, chlorine, and bromine and mixtures thereof; preferred halogens are fluorine, chlorine, iodine and mixtures thereof; and most preferred is

fluorine; and R is mono or multi-cyclic, halosubstituted and non-substituted aryls, alkyls, and alkenyl groups and

mixtures thereof; preferred are Cl-20 alkenyl groups

(such as ethene, propylene, butene, and pentene) ; Cl-20 alkyl groups (such as a methyl, ethyl, n-propyl, iso¬

propyl, n-butyl, n-octyl, and 2-ethylhexyl groups), C6-20 aryl group (includng substituted aryls) (such as phenyl,

p-tolyl, benzyl, 4-t-butylphenyl, 2,6 dimethylphenyl,

3,5- methylphenyl, 2, 4-dimethylphenyl, 2 , 3-dimethylphenyl groups) and mixtures thereof. More preferred R groups are Cl-5 alkyls, C2-5 alkenyls phenyl and napthy1 and

mixtures thereof7^~ lb

Preferred RX compounds are Cl-20 halogenated hydrocarbon groups such as XCH2, X2CH, X3C, C2XnHn-5 (where n = 1-5) , C3HnXn-7 (n = 1-7) and C6XnXn-6 (n = 1- 6) and mixtures thereof; most preferably, FCH₂, CHF₂, F₃C, and fluorosubstituted phenyl, wherein the phenyl can be

mono to pentasubstituted (such as p-fluorophenyl, 3,5- difluorophenyl, pentafluorophenyl, 3 , 4, 5-trifluorophenyl, and 3 , 5-bis (trifluoromethyl)phenyl groups) and mixtures thereof; of these the most preferred is pentafluorophenyl.

Moreover, in this RX, the Q_λ to Q_n may be hydride radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, substituted hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl- and halocarbyl-substituted organometalloid radicals. Additionally, the Q_x to Q_n can simply be the X alone; for example as in ^"BX₄.

In addition, neutral N"(Q_n), can be used in place of the[C^*3^"[ "(Q₁-Q_Iwl)], for example B(C₆F₅)₃. Preferred ^" [t. (C^-Q^) ] are selected from the group consisting of ^"BPhenyl,, ^"B(C₆H₂ (CF₃)₃)₄, ^~B(C_SH₅)₄,

^"AlPhenyl,, ^"Al (C₆H₂ (CF,),) _t , ^~A1(C₆H.)₄, ^"PF₆ ^"BF₄, ^"B(OPh)₄ and mixtures thereof; preferably ^"B(C₆F₅)₄, ^"A1(C₆F₅)₄, ^"A1(C₆H₂(CF₃)₃)₄, ^"Al(C₆H₅)₄, ^"BC₆H₂ (CF₃) ₃) ₄ and mixtures thereof; most preferred are ^"B(C₆F₅)₄, ^"Al(C₆F₅)₄

and mixtures thereof. Preferred _T(Q_n) from the neutral species of the preferred list above of ^"[N"(Q₁-Q_n+1) ] .

The preferred catalytic activators, when not a Lewis acid such as MgCl₂ is present, are the alkylalumoxanes and

the borate activators in combination with an alkyating agent such as TEAL.

Catalytic systems incorporating the present invention are useful to polymerize olefinic materials,

particularly ethylene. Polmerizations of olefinic monomers can be accomplished by an number of well known

techniques by having the olefinic material come into contact with the polymerization catalyst (s) in a reaction

zone under appropriate conditions.

As used herein, "Polymerization" includes copolymerization and terpolymerization and the terms olefins and olefinic monomer includes olefins,

alphaolefins, diolefins, strained cyclic olefins, styrenic monomers, acetylenically unsaturated monomers, cyclic olefins aline or in combination with other unsaturated monomers. While the catalyst system of the present invention is active for this broad range of olefinic monomer feedstock, alpha-olefin polymerizations δ

is preferred, especially the hompolymerization of ethylene and propylene or the copolymerization of ethylene with olefins having 3 to 10 carbon atoms. "Polymerization techniques" for olefin

polymerization according to the present invention can be solution polymerization, slurry polymerization or gas

phase polymerization techniques. Method and apparatus for effecting such polymerization reactions are well

known and described in, for example, Encyclopedia of

Polymer Science and Engineering published by John Wiley and Sons, 1987, Volume 7, pages 480-488 and 1988, Volume 12, pages 504-541. The catalyst according to the present invention can be used in similar amounts and under similar conditions to known olefin polymerization catalyst.

Typically, for the slurry process, the temperature is from approximately 0 degrees C to just below the

temperature at which the polymer becomes soluble in the polymerization medium. For the gas phase process, the

the temperature is from approximately 0 degrees C to just below the melting point of the polymer. For the solution

process, the temperature is typically the temperature from which the polymer is soluble in the reaction medium

up to approximately 275 degrees C. 2^<?

The pressure used can be selected from a relatively wide range of suitable pressures, e.g., from

subatmospheric to about 350 Mpa. Suitably, the pressure

is from atmospheric to about 6.9 Mpa, or 0.05-10 Mpa, especially 0.14-5.5 Mpa. In the slurry or particle form process, the process is suitably performed with a liquid

inert diluent such as a saturated aliphatic hydrocarbon. Suitably the hydrocarbon is a C4 to CIO hydorcarbon,

e.g., isobutane, heptane or an aromatic hydrocarbon liquid such as benzene, toluene or xylene. The polymer

is recovered directly from the gas phase process or by filtration or evaporation from the slurry process or

evaporation from the solution process .

The catalyst of the present invention are

particularly suited for the gas phase or slurry process.

The compositions according to the present invention are used in amounts sufficient to cause polymerization in the feedstocks. Typically, the amount used will be the

range of 0.0005 mmole to 10 mmole/liter of reactor; most preferably from 0.01 mmole to 2.5 mmole/liter of reactor.

The following examples are provided to illustrate

the present invention, but are not to be construed as limiting the invention in any way except as provided in the appended claims . Example A Silica oxide carrier having a particle size of 50μ,

surface area of 300 m²/g and a pore volume of about 1.6

ml/g, such as Sylopol^* 948, (lOg, previously calcined at

800°C for 4 hours) was slurried in 100 ml of hexanes

under an atmosphere of purified argon and cooled to 0°C. And iCl4 (16 mmol) was added and mixed for 15 minutes at

0 C. The slurry was degassed under vacuum briefly and TMS-Cp (16 mmol) was added. The slurry was mixed an additional 30 minutes. After warming to RT, the slurry

was mixed an additional 2 hours. The solid was dried in vacuo .

Example B Silica oxide with MgCl₂, having a particle size of

50μ, surface area of 300 m/g and a pore volume of about 1.6 ml/g, (lOg) such as Sylopol^* 5550 (lOg, a GRACE

Davison product containing approximately 1.6 mmol MgCl2

per gram of support) was slurried in 100 mL of hexanes

under an atmosphere of purified argon and cooled to 0 C. And TiCl4 (16 mmol) was added and mixed for 15 minutes at

0°C. The slurry was degassed under vacuum briefly and TMS-Cp (16 mmol) was added. The slurry was mixed an 3/

additional 30 minutes. After warming to room temperature, the slurry was mixed an additional 2 hours.

The solid was dried in vacuo .

Example C

A 2 L Zipperclave^* reactor was charged with heptanes

(500 mL) and MAO (5 mmol) . The reactor was pressurized with ethylene to 180 psig and the temperature

equilibrated at 75 C. Example A (50 mg) was blown into the reactor under argon pressure. Polymerization was

carried out for 1 hour and was quenched by rapid venting of monomer followed by methanol. The polymer, 7g, was

washed with methanol and dried more than 12 hours in a

vacuum oven at 60 C. Example D

A 2 L Zipperclave^* reactor was charged with heptanes (500 mL) and MAO (5 mmol) . The reactor was pressurized with ethylene to 180 psig and the temperature

equilibrated at 75°C. Example B (50 mg) was blown into the reactor under argon pressure. Polymerization was carried out for 1 hour and was quenched by rapid venting

of monomer followed by methanol. The polymer, 106g, was washed with methanol and dried more than 12 hours in a

vacuum oven at 60 C.

Example E

A 2 L Zipperclave^* reactor was charged with heptanes

(500 mL) and TEAL (2 mmol) , no MAO was used. The reactor was pressurized with ethylene to 180 psig and the

temperature equilibrated at 75 C. Example B (50 mg) was blown into the reactor under argon pressure.

Polymerization was carried out for 1 hour and was quenched by rapid venting of monomer followed by

methanol. The polymer, 128g, was washed with methanol

and dried more than 12 hours in a vacuum oven at 60 C.

This example illustrates that the metallocene according can be activated without MAO in the presence of a Lewis acid support material, e.g. MgCl₂.

Table

APG = aluminum phosphate gel

PVA = polyvinylalcohol

Claims

WE CLAIM : 3-S

1. A method for forming a supported polyolefin catalyst, said method comprising the steps of reacting a

composition containing a transition or rare earth metal, capable of causing polymerization of olefinic materials

and a metal containing reagent of the formula CM' wherein, C is selected from the group comprising a five-

member carbon ring, a heterosubstituted five-member carbon ring, or a bridged (ansa) ligand defined as multi cyclic moieties capable of coordinating to the transition or rare earth metals; and

M' is a metal selected from the group comprising tin, silicon, germanium and mixtures thereof; and a hydroxyl containing support material.

2. The method of claim 1, wherein the method further comprises the step of the CM' reagent further defined a component selected from the group comprising halogen elements, halosubstituted and non-substituted alkoxy, alkyl, alkenyls, and organic component that contains a five-member carbon ring, a heterosubstituted

five-member carbon ring, or a bridged ligand defined as

multi-cyclic moieties capable of coordingating to the transition or rare earth metals and mixtures thereof .

3. The method of claim 1 wherein the support is selected from the group inorganic, inorganic oxides and organic materials containing hydroxyl groups and mixtures

thereof.

4. The method of claim 1 wherein the support is

selected from the group comprising MgCl(OH), Mg(OH)₂, talcs, clays and metal oxides from the Groups 2-14,

actinide, lanthanide series metals from the Periodic

Table, polyvinylalcohol, starches and mixtures theroef .

5. The method of claim 1 wherein CM' is selected

from the group comprising (chlorodimethylsilyl) (3- trimethylsilyl) cyclopentadiene,

cyclopentadienyltrimethylsilane,

indenyltrimethylsilane, indenyltributylstannane, indenyltrimethylgermanium, cyclopentadienyl trimethylgermanium, and mixtures thereof.

6. The method accordingly to claim 1, wherein the reaction of the CM' reagent and the hydroxyl containing

support takes place in the presence of a non-polar organic solvent.

7. The method accordingly to claim 6, wherein the organic solvent is selected from the group comprising

aliphatic hydrocarbons, alicyclic hydrocarons, aromatic hydrocarbons, petroleum fractions and mixtures thereof.

8. The method accordingly to claim 7, wherein the organic solvent is selected from the group comprising butane, isobutane, pentane, isopentane, hexane, octane,

decane, dodecane, hexadecane, octadecane, eyelopentane, methylcyclopentane, cyclohexane, decalin cycloctane,

norbornane, ethylcyclohexane, benzene, chlorobenzene, xylene, toluene, gasoline, kerosene, light oils and

mixtures thereof.

9. The method according to claim 1, wherein in the

transition or rare earth containing component is represented by the formula MZ, wherein M is selected from the group comprising of Groups 3 through 10, lanthanides, actinides series metals of the Periodic Table; and Z is selected from the group comprising halogens, halosubstituted and nonsubstituted C1-C20 alkoxys, alkenyls and alkyls, C6-C20 aryls, and amides. 3 _

10. The method according to claim 9 wherein the M is selected from the group of metals comprising titanium, zirconium, hafnium, chromium, vanadium, samarium,

neodymium and mixtures thereof; and Z is selected from the group comprising chlorine, fluorine, bromine, halosubstituted and non-substituted methoxy, ethoxy, isopropyloxy, butoxy, pentoxy, ehtyl, butyl, octyl,

ethylhexyl, phenyl, p-tolyl, benzyl, 4-t-butlypenyl, 2,6- dimethylphenyl, 3 , 5-methylphenyl, 2 , 4-dimethylphenyl,

2 , 3-dimehtylphenyl, ethyenyl, propenyl, butenyl, pentenyl, and amides of the formul NR^aR , wherein the R^a

and R^b can be the same or different and independently selected from the group of C1-C20 alkyls and alkyls and C6-C20 aryls and mixtures of two or more of the foregoing.

11. The method according to claim 1 wherein the CM' is selected from the group comprising

(chlorodimethylsilyl) (3-trimethylsilyl) eye1opentadiene, eyelopentadienyltrimethylsilane, indenyltrimethylsilane, indenyltributylstannane, indenyltrimethylgermanium, cyclopentadienyl trimethylgermanium, and mixtures thereof. _ ?

12. The method according to claim 1, wherein the reaction mixture further contains reagent A which is selected from the group comprising acid halides, organic

halides, halosubstituted and non-subsituted carboxylic acids, esters, ethers, alkylaluminums, halogen gases,

Grinard reagents, alumoxanes and mixtures thereof.

13. The method according to claim 12 wherein A is selected from the group comprising CH.C1, tetrahydorfuran,

t-butylchloirde, ethanol, phenol,

ethylaluminumdichloride, silican tetrachloride, methyllithium, methyl magnesiumchloride, triethylaluminum, methyalumoxane, dibutylphthalate and

tin tetrachloride, and gases of chlorine, fluorine and

bromine and mixtures of two or more of the foregoing.

14. A composition of matter prepared by any of the methods of Claims 1-13.

15. A polymer prepared by exposing a monomeric and/or comonomeric material to the catalyst composition

prepared in accordance with claims 1-13 in the presence

of a catalytic activator in a reaction zone.

16. A polymer prepared by exposing a monomeric and/or comonomeric material to the catalsyt composition prepared in accordance with claims 1-13 in the presence of a catalytic activator selected from the group comprising trimethylaluminum, triethylaluminum, diethyl aluminumhydride, triisobutylaluminum, trideeyl aluminum, tridodecylaluminum, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, diethyl aluminum chloride, ethyl aluminum dichloride, methyl diethoxy aluminum and methyaluminoxane.

4/

17. A polymer prepared by exposing a monomeric and/or comonomeric material to the catalsyt composition prepared in accordance with claims 1-13 in the presences of a catalytic activator selected from the group of compounds represented by the formula [C⁺]^"[_ (Q.-Q_n÷1) ] and

N"(Q_B) r wherein,

C+ is selected from the group of ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, N, -dimethylaniline, methyldiphenyla ine, pyridine, p-bromo-N,N, -dimethylaniline, p-nitro-N,N- dimethylaniline; phosphoniums from triethylphosphine, triphenylphosphine and diphenylphosphine; oxoniums from ethers such as diethyl ether, tetrahydrofuran and dioxane; sulfoniums from thioethers such as diethyl

thioethers and tetrahydrothiophene; and abstracting moieties selected from the group comprising silver, carbocations, tropylium, carbeniums, ferroceniums and mixtures thereof; preferably carboniums and ferroceniums and mixtures of two or more of any of the foregoing; z

[N] is selected from the group consisting of boron, phosphorus, antimony or aluminum and mixtures thereof, having the n valence state; and

[__-_„,_.] are independent, wherein Q_J-Q_^J are RX wherein each of the Q in the coordinating anion may be the same or different, where in RX is defined where X

fluorine, chlorine, and bromine and mixtures thereof and R is mono or multi-cyclic, halosubstituted and non-

substituted C6-C20 aryls, C1-C20 alkyls, and C1-C20 alkenyl groups and mixtures thereof; and R may be hydride

radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, substituted hydrocarbyl

radicals, halocarbyl and substituted-halocarbyl radicals and hydrocarbyl- and halocarbyl-substituted organometalloid radicals and mixtures of two or more of the foregoing.