CA2046075C - Addition polymerization catalyst with oxidative activation - Google Patents
Addition polymerization catalyst with oxidative activation Download PDFInfo
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- CA2046075C CA2046075C CA002046075A CA2046075A CA2046075C CA 2046075 C CA2046075 C CA 2046075C CA 002046075 A CA002046075 A CA 002046075A CA 2046075 A CA2046075 A CA 2046075A CA 2046075 C CA2046075 C CA 2046075C
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
Addition polymerization catalysts of the formula L ~ MX+ A- prepared by oxidation of a Group 4 or Lanthanide metal derivative of the formula L~ MX2 with an oxidizing agent of the formula (Ox +a)b(A-)d are free of interfering amine or phosphine byproducts. In these formulae:-L independently each occurrence is a ligand or ligand system, especially a n5-cyclopentadienyl group optionally covalently bonded to M throng a substituent;
~ is an integer, especially 1;
M is a Group 24 or the Lanthanide metal, especially titanium or zirconium;
X is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms, especially benzyl;
A- is a monovalent, compatible, noncoordinating anion, especially perfluorotetraphenyl borate;
Ox +a is a cationic oxidizer having a charge of (+a), especially Ag+ or ferrocenium; and b and d are integers selected to provide charge balance.
~ is an integer, especially 1;
M is a Group 24 or the Lanthanide metal, especially titanium or zirconium;
X is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms, especially benzyl;
A- is a monovalent, compatible, noncoordinating anion, especially perfluorotetraphenyl borate;
Ox +a is a cationic oxidizer having a charge of (+a), especially Ag+ or ferrocenium; and b and d are integers selected to provide charge balance.
Description
~~~~"~ a ADDITION POLYMERIZATION CATALYST
WITH O:CIDATIUE ACTIVATION
This inventidn relates to compositions of matter that are useful as catalysts, to a method for preparing the compositions of these catalysts, and to a method of using the compositions as addition polymerization catalysts. More particularly, this invention relates to catalyst compositions, to a method of preparing these catalyst compositions and to a method For polymerizing olefins, diolefins and/or acetylenically unsaturated monomers wherein these catalysts are used.
The use of Z.iegler-Nat~ta type catalysts in the polymerization of addition po.lymerizable manomers is, of course, well known in the prior art. In general, these soluble systems comprise a Group 4 or Lanthanide metal compound and a metal alkyl cocatalyst, particularly an aluminum alkyl cocatalyst.
In EP-A-0277,004 there are disclosed certain bis(cyclopentadienyl) metal compounds formed by reacting a bis(cyclopentadienyl) metal complex with salts of Bronsted acids containing a non-coordinating compatible 38,845-F _1_ anion. The reference discloses the fact that such complexes are usefully employed as catalysts in the nnlwmAri?at;nn of nl°Plr~
r .r.
Disadvantageously it has no~u been found that catalysts prepared according to the foregoing technique are detrimentally affected b,r the presence of by-product amine or phosphine compounds resulting from the catalyst formation. That is, the procedure of EP-A-0277,004 involves an irreversible reaction between a ligand of the metal compound and a ca non of the Bronsted acid salt. In practice such canons are generally trialkyl ammonium or phosphonium ions that result in the formation of a tertiary amine or phosphine by proton transfer tc the ligand during catalyst formation. Such amine or phosphine compounds are undesirable components of the resulting catalyst due to their inhibiting effect on addition polymerizations.
It could be desirable if there were provided a addition polymerization catalyst that is activated in a manner that forms only noninterfering and inert by-products.
In ~J. Am. Ch. Soc. 1~9, ~111-l113 (1987) there is disclosed a process for preparation of cationic zirconium (IV) benzyl complexes by one electron oxidation of dr organometallic compounds. The solvents employed in the preparation of the zirconium metallocenes were tetrahydroiuran or methylene chloride both of which interfere with the desired catalyst formation snd or detrimentall~r of feet subsequent olefin oolymerizations. In addition the reference employed an -3 ~-oxidizing agent containing tetraphenylborate. Such anions, it has now been discovered, are unacceptable for use in an oxidation activation proceas for preparing addition polymerization catalysts.
It has now been discovered that the foregoing and other disadvantages of the prior art ionic olefin polymerization catalysts can be avoided or at least reduced with the catalysts of the present invention. In addition an improved catalyst activation procedure and ~0 im roved addition p polymerization processes are provided according to the present invention. It is, therefore, an object of this invention to provide improved ionic catalyst systems which are useful in the polymerization ~5 of addition polymerizable monomers including olefins, diolefins and/or acetylenically unsaturated monomers.
It is another object of this invention to provide a method for preparing such improved catalysts. Tt is a Further object of this invention to provide an improved 20 polymerization process using such improved catalysts.
Ct is still another object of this invention to provide such an improved catalyst which is not subject to formation of iriterfering compounds. finally it is an object of this invention to provide such an improved 25 catal st ~nhich ma y y permit better control of the product polymer molecular weight and molecular weight distribution.
In accordance with the present invention there ''0 is provided a catalyst useful For addition polymerizations, which catalyst is substantially lacking in amine byproducts, said catalyst corresponding to the formula:
38, 8~+5-.F _3_ 2~~~~~"~
_~_ Lz MX* A°, wherein:
L independently each occurrence is a Iigand or I i ga.nd syst em;
M is a metal of group 4 or Lanthanide series of the Periodic Table of the Elements;
X is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms;
a is an integer greater than or equal to 1; and A- is a monovalent compatible noncoordinating anion.
Preferably M is a metal of group 4 of the Periodic table of the Elements, most preferably titanium or zirconium. Also, preferably X is hydride or C~-C~0 hydrocarbyl.
Further in accordance with the present invention there is provided a process for preparing the 20 above addition polymerization catalyst comprising contacting a derivative of a group 4 or Lanthanide metal corresponding to the Formula:
L~ MX2, wherein 25 L, e, M, and X are as previously defined, with an oxidizing agent which in reduced form is noninterfering with the resulting catalyst, said oxidizing agent comprising a cationic oxidizer and a 30 compatible noncoordinating anion.
The oxidizing agent corresponds to the formula:
(Ox~'a)b~A-)d CI) 38,845-F
~~~~~"~
_5_ wherein:
Ox+a is a non-Bronsted acid, cationic axidizer having a charge of (+a) capable of oxidizing the derivative of a Group ~+ or Lanthanide metal;
A- is as previously defined; and b and d are integers selected to provide charge balance.
The catalysts may be prepared by contacting the derivative of a Group 4 ar Lanthanide metal with the oxidizing agent optionally in an inert diluent such as an organic liquid.
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
The term "ligand or ligand system" refers to any ancillary, electron donating or electron sharing moiety. Such l.igands include anionic ligands and neutral donor l.igands.
Illustrative but nonlimit.ing examples of suitable anionic ligands include: R, -R'(0R'?mOR, (OR')mOR, -PR2, -SR, -OR, -NR2, hydride, and organo-metalloid radicals comprising a Group 14 element wherein each of the hydrocarbyl substituents contained in the organic portion of said arganometalloid, independently, contains From 1 to 20 carbon atoms. In these ligands:
R is a hydrocarbyl, silyl, germyl or a 38,8+5-F -5-~~~~'~"~~~
substituted hydrocarbyl, silyl, or germyl group of from 1 to 24 carbon, silioon, or germanium atoms;
R' is C2_10 alhylono, and m is an integer from zero to ten.
Illustrative but non-limiting examples of suitable neutral donor ligands (L') include: ROR, NR3, PR3, and SR2 wherein R is a_s above defined.
The term "cationic oxidizer" as used herein refers to an organic or inorganic ion having an oxidation potential sufficient to cause a molecular oxidation of the derivative of a Group ~+ or Lanthanide metal so as to form a catalytic species. Generally and preferably the Group 4 or Lanthanide metal of the derivative compound is already in the highest atomic oxidation state. The process of the invention involves a molecular oxidation. Most preferred cationic oxidizers have an oxidation potential of at least -0.20 volt and preferably at least +0.25 volt. Cationic oxidizers are not Bronsted acids.
As used herein, the recitation "compat.ible noneoordinating anion" means an anion which when funotioni.ng as a charge balancing anion in the catalyst system of thi~i .invention does not transfer an anionic subst.ituent or fragment thereof to any cationic species thereby forming a neutral Group ~4 or Lanthanide metal product. "Compatible anions" are anions which are not degraded to neutrality during catalyst preparation or use.
'The recitation ''metalloid", as used herein, includes nonmetals such as boron, phosphorus and the like which exhibit semi-metallic characteristics.
38,845-F -6-_7_ Further preferred derivatives correspond to the formula: L"MX2, wherein:
L" is a derivative of a substituted cyclo-pentadienyl or similar deloealized n-bonding group imparting a constrained geometry to the metal active site and containin a to 20 nonh droP~
g p y o,.n atoms; and M and X are as defined above.
By use of the term "constrained geometry"
herein is meant that the metal atom is forced to greater exposure of the active metal site because of one or more substituents on the cyclopentadienyl or substituted eyelopentadienyl group forming a portion of a ring structure wherein the metal is both bonded to an adjacent covalent moiety and is held in association with the cyclopentadienyl or substituted cyclopentadienyl group through an r15 or other rz-bonding interaction. It is understood that each respective bond between the metal atom and the constituent atoms of the cyclopentadienyl or substituted cyclopentadienyl group need not be equivalent. That is, the metal may be symmetrically or unsymmetrically rz-bound to the cyclopentadienyl or substituted cyelopentadienyl group.
The geometry of the active metal site is Eur~ther defined as follows. 'The eentroid of the cyclopentadienyl or substituted cyelopentadienyl group may be defined as the average of the respective X, Y, and Z coordinates of the atomic centers forming the 3~ cyclopentadienyl or substituted cyelopentadienyl group>
The angle. 0, formed at the metal center between the centroid of the cyclopentadienyl or substituted eyelopentadienyl group and each other ligand of the metal complex may be easily calculated by standard techniques of single crystal X-ray diffraction. Each of 38,845-F _7_ _~_ these angles may increase or decrease depending on the molecular structure of the constrained geometry metal complex. T'hOse OOmplexeS wherein 0:18 Or more of the angles, O, is less than in a similar, comparative complex differing only in the fact that the constrain-s inducing substituent is replaced by hydrogen have constrained geometry for purposes of the present invention. Preferably one or more of the above angles, O, decrease by at least 5 percent, more preferably 7.5 Percent, compared to the comparative complex. Highly preferably, the average value of all bond angles, (3, is also less ~han in the comparative complex.
Preferably, monocyclopentadienyl metal coordination complexes of group 4 or lanthanide metals according ~o the present invention have constrained geometry such that the smallest angle, O, is less than 115°, more preferably less than 110°, most preferably less than 105°.
Highly preferred derivative compounds are monocyclopentadienyl compounds corresponding to the formula:
Y
Gp.h ~ M/
I
(X)2 38,845-F _g_ 2~~~"~
_g_ wherein:
M is titanium or zirconium;
Cps' is a cyclopentadienyl or substituted cyclopentadienyl group bound in an ~5 bonding mode to M;
Z is a divalent moiety comprising oxygen, boron, or a member of group 14 of the Periodic Table of the Elements;
Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y
together form a fused ring system; and X is as previously defined.
After molecular oxidation, the highly preferred catalysts of the invention correspond to the formula:
, Z Y
Cp'~ - M H
A' II
X
~nherein Cp'~, Z, M, X and A' are as previously defined.
Gaeh carbon atom in the cyclopentadienyl radical may be substituted or unsubstituted with the same or a different radical selected from the group consisting of hydroearbyl radicals, substituted-hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected 38,845-F -9-~~~~~~"l from Group 14 of the Periodic Table of the Elements, and halogen radicals, zn addition two or more such substituents may together form a fused ring system.
Suitable hydrocarbyl and substituted-hydrocarbyl radicals, which may be substituted for at least one hydrogen atom in the eyelopentadienyl radical, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals. Suitable organometalloid radicals include mono-, di- and trisubstituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contain from 1 to 20 carbon atoms. More particularly, suitable arganometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like.
Most highly preferred derivative compounds are amidosilane- or amidoalkanediyl- compounds corresponding to the formula:
R~ ~ER'2)m~
N-R
R. ~~ M/
R/ R~ (X)2 wherein:
38 , 845-F -10-' (,~
M is titanium or zirconium, bound to an r15-cyclopentadienyl group;
R' each occurrence is independently selected from hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms;
E is silicon or carbon;
X independently each occurrence is hydride, alkyl, or aryl of up to 10 carbons; and m is 1 or 2.
Examples of the above most highly preferred metal coordination compounds include compounds wherein 1o the R' on the amido group is methyl, ethyl, propyl, but~rl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, ete.; the cyclopentadienyl group is cyciopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, ete.; R' on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, ete.; and X is methyl, neopentyl, trimethylsilyl, norbornyl, benzyl, methyl.benzyl, phenyl, etc. Specific eornpounds include:, (tort-butylamido)(tetramethyl-ray-cyelopentadienyl)-1,2-ethanediylzireonium dimethyl, (teat-butylamido)(tetra-methyl-t15-cyelopentadienyl)-1,2-ethanediyltitanium dimethylbenzyl, (methylamido)(tetramethyl-r~5-~0 cyclopentadienyl)-1,2-ethanediylzireonium dibenzhydryl, (methylamido)(tetramethyl-~~-cyclopentadienyl)-1,2-ethanediyltitanium dineopentyl, (ethylamido)(tetra-methyl-rl~-cyelopentadienyl)-methylenetitanium diphenyl, (tent-butylamido)dibenzyl(tetramethyl-ri5-cyclopenta-dieriyl)silanezirconium dibenzyl, (benzylamido)dimethyl-38,845-P -11-(tetramethyl-rig-cyclopentadienyl)silanetitanium di(trimethylsilyl) and (phenylphosphido)dimethyl(tetra-methyl-ri5.-cyelopontadicil'y'1)silanazir corium dibenzyl.
In the most preferred embodiment --Z-Y- is an amidosilane or amidoalkane group of up to 10 nonhydrogen atoms, that is, (tert-butylamido)(dimethylsilyl), (tert-butylamido)-1-ethane-2-yi, ete.
Derivative compounds which may be used in the preparation of the improved catalyst of this invention are covalently bonded metal compounds that are either devoid of reactive hydrogens (other than hydride leaving groups, X) or wherein potentially reactive hydrogens are protected by bulky protecting groups. Examples of suitable organyl substituents on such metal derivative compounds include norbornyl, neopentyl, trimethylsilyl and diphenylmethyl. Illustrative, but not limiting examples of suitable derivative compounds include:
tetranorbornyltitanium, tetrabenzylzirconium, tetraneopentyltitanium, diphenoxybis(tri-methylsilyl)z.irconium, bis(2,6-diisopropyl-tl-methyl)phenoxy)dibenzyltitanium, tritert-butylsiloxy)trimethylzircanium, dimethoxydibenzhydryl-t.itanium, 'o.is(2,~4,6-trimethflphenoxy)dibenzyltitanium, buta:,cytris((trimethyls.ilyl)methyl)zirconium, d.inorbornyldimethyltitanium, tribenzyltitanium hydride, etc.; cyclopentadienyl and bis(cyelopentadienyl) metal compounds such as bis(eyclopentadienyl)dimethyl-zirconium, cyelopentadienyltribenzylzirconium, cyclopentadienyltrimethyltitanium, cyclopentadienyl-trimethylzirconium, bis(cyclopentadienyl) dineopentyltitanium, cyelopentadienyltri(diphenyl-methyl)zirconium, bis(cyclopentadienyl)diphenyl-zireonium, cyelopentadienyltrineopentyltitanium, bis(cy-38,8+5-E -12-clopentadienyl)di(m-tolyl)zireonium, biseyclopenta-dienyldi(p-tolyl)zirconium; hydrocarbyl-substituted cyelopentadienyi or bis(cyclopentadienyl) compounds such as (pentamethylcyelopentadienyl)-(cyelopentadienyl) dimethylzireonium, bis(ethyleyclopentadienyl)dimethyl-zirconium, (pentamethyleyclopentadienyl)tribenzyl-zirconium, (n-butylcyclopentadienyl)trineopentyl-titanium, cyclopentadienyldimethyltitanium hydride, bis(cyclopentadienyl)bis(diphenylmethyl)zireonium, bis(tert-butylc;rclopentadienyl)bis(trimethylsilyl-methyl)zirconium, bis(cyelohexylcyelopentadienyl) dimethylzirconium, (benzyleyelopentadienyl)di(m-tolyl)methyltitanium, (diphenylcyclopenta-dienyl)dinorbornylmethylzireonium, bis(methyleycla-pentadienyl)diphenylzireonium, (tetraethyleyelo-pentadienyl)tribenzylzirconium, (propylcyelopentadienyl) (cyclopentadienyl)dimethylzireonium, bis(propyleyclo-pentadienyl)dimethylzireonium, (n-butyleyelopentadienyl) dimethyl(n-butoxy)titanium, cyelopentadienyldiphenyl-isopropoxyzirconium, cyelohexylmethyleyelopenta-dienyl)cyclopentadienyldibenzylzirconium, bis((cyelohexyl)methylcyelopentadienyl)dibenzyl-zirconium, b.is(cyclopentadienyl)zireonium dihydride, benzylcyclopentadienyldimethylhaFn.ium, bis(.indenyl)dibenzylz.ireon.ium, (tert-butylamido)di-methyl(tetramethyl-r~7--eyclopentadi.enyl)silane dibenzylz:irconium, (benzylamido)dimethyl(tetraethyl-~5-cyelopentadienyi)silane dibutyltitanium, and the like;
metal hydrocarbyl-substituted cyclopentadienyl metal compounds such as ((trimethylsilyl)-cyelopentadienyi)trimethylzireonium, bis((trimethyl-germyl)cyclopentadienyl)dimethyltitanium, ((trimethyl-stannyl)cyclopentadienyl)tribenzylzireonium, ((penta-trimethylsilyl)cyclopentadienyl)(eyclopenta-38,845-F _~3_ dienyl)dimethylzirconium, bis((trimethylsilyl)cyclo-pentadienyl)dimethylzirconium, penta((trimethyl-sil5~1)cyeloper.ta.di~nyl)tribenzyltitanium, bis((t~i-methylgermyl)cyclopentadienyl)d.iphenylhafnium; halogen-substituted cyclopentadienyl compounds such as ((trifluoromethyl)eyelopentadienyl)(cyelopentadienyl)di-methylzirconium, bis((trifluoromethyl)cyclopenta-dienyl)dinorbornylzirconium, ((trifluoromethyl)eyelo-pentadienyl)tribenzylzirconium; silyl-substituted (cyclopentadienyl)metal compounds such as bis(cyelopentadienyl)di(trimethylsilyl)zireonium, cyelopentadienyltri(phenyldimethylsilyl)zirconium;
bridged cyclopentadienyl-metal compounds such as methylenebis((cyelopentadienyl)dimethylzireonium), ethylene~bis-((cyelopentadienyl)dibenzylzirconium), (dimethylsilylene)-bis-((cyelopentadienyl) dimethyltitanium), methylene-bis-(cyclopentadienyl) di(trimethylsilyl)zirconium, (dimethylsilylene) bis(cyclopentadienyldineopentylhafnium), ethylene-bis-(tetrahydroindenyl)-zirconium dibenzyl and dimethylsilylene(fluorenyl)(cyelopentadienyl)-titanium dimethyl.
Other compounds which are useful in the catalyst compositions of this invention, especially c;ompou nds containing other Group 4 or Lanthanide metals, will, of course, be apparent to those skilled in the art.
Compounds useful as oxidizing agents in the preparation of the compounds of this invention will comprise a cationic oxidizer, and one or more compatible noncoordinating anions, as previously explained.
38,845-F -14-In a preferred embodiment A-c of previous Formula (I) comprises an anion which is a single coordination complex comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom, which anion is bulky and stable under the oxidation and subsequent polymerization conditions, and which anion is compatible with and noncoordinating towards the resulting Group 4 or Lanthanide metal containing catalyst. The anion is employed only to provide charge balance without interfering with the oxidizing ability of Ox+a or the catalytic properties of the resulting catalyst. Any metal or metalloid capable of forming a e,oordination complex which is stable under the reaction conditions of the present invention may be contained in the anion. Suitable metals .include, but are not limited to, aluminum, gold and platinum.
Suitable metalloids include, but are not limited to, boron, phosphorus and silicon. Oxidizing agents containing anions comprising a coordination complex containing a single boron atom are most preferred.
Anions comprising boron which are particularly useful in the preparation of catalysts of this invention rna be re resented b the fol.Lowin Y p Y g general formula:
PBX 1 X2X3Xt;~_ wherein:
B is boron in a valence state of 3;
X1 to X~ are the same or different nonreaetive, organyl or silyl radicals containing from 6 to 20 carbon or silicon atoms. In addition two or more of X1 to X~
may be linked to each other through a stable bridging group. Preferably X1 to X1~ lack reactive hydrogen 38,85-F -15-_ ~~0'~
moieties. That is, the radicals are either devoid of hydrogen, contain only hydrogen in nonactiv ated positions or contain sufficicnt stoic hindrance to protect potentially active hydrogen sites. Examples of suitable radicals for X1 to X4 are perfluorinated hydrocarbyl radicals containing from 6 to 20 carbon atoms, 3,4.5-trifluorophenyl, etc.
A most highly preferred compatible, non-coordinating, anion is tetra(pentafluorophenyl)borate.
Suitable organic cationic oxidizers for use according to the present invention include ferrocenium ions, bis-indenyl Fe(III) ions, and cationic derivatives of substituted ferrocene, and the like molecules.
Suitable metal cationic oxidizers include Ag+1, pd+z~
Pt+', Hg'-'. Hg~+~', Au+ and Cu+. Most preferred cationic oxidizers are ferrocenium and Ag+t cations.
Illustrative, but not limiting, examples of oxidizin~ agents in the o n preparation of the improved catalysts of this invention are Ferrocenium tetra(pentafluorophenyl)borate, gold (I) tetrakis 3,4,5-trifluorophenyl borate, si7.ver tetra(penta-fluorophenyl)borate and 1,1'-dimethy:Lferroeenium tetrakis 3.5-bistr~iF.luorornethylphenyl borate.
Similar lists of suitable compounds containing other metals and metalloids which are useful as oxidizing agents (second components) could be made, but such lists are not deemed necessary to a complete disclosure. In this regard, it should be noted that the Foregoing list is not .intended to be exhaustive and other boron compounds that would be useful as well as useful compounds containing other metals or metalloids 38,845-F -16-_ ~~~~r12~
-1~.-would be readily apparent, from the foregoing general equations, to those skilled in the art.
~~lithout wishing to be bound by any particular theory of operation it is believed that the cationic oxidizer causes the molecular oxidation of the Group 4 or Lanthanide metal derivative, and in the process becomes a neutral species. The oxidized metal derivative loses a hydrogen or hydrocarbyl radical (~R) by a unimolecular elimination reaction. Two ar more such radicals form a hydrogen molecule or a neutral organic species of the formula Rx where x is an integer greater than or equal to 2. These byproducts are of course neutral or noninterfering with any subsequent polymerization reaction and may also be removed from the reaction mixture. This result is much preferred to previously known processes for catalyst activation which resulted in the formation of an amine or similar reaction byproduct.
It should be noted that the two compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the anion, particularly an aryl group, to the metal canon, thereby forming a catalytically inactive species. 'this , could be done by sterie hindrance, resulting from substitutions on the groups attached to the Group 4 or Lanthanide metal as well as substitutions on the aramatie carbon atoms of the anion. It follows, then, that Group a and Lanthanide metal compounds (first components) comp rising, for example, perhydrocarbyl-substituted cyclopentadienyl radicals could be effectively used with a broader range of second compounds than could first components comprisin g less bulky radicals. As the amount and size of the metal 38,845-F _17_ ~~~~"~
substituents are reduced, however, more effective catalysts are obtained with second compounds containing anions c~.hich are more rcsistar~t to degr adation, sue h as those with substituents on the meta and/or para positions of :he phenyl rings. Another means of rendering the anion more resistant to degradation is afforded by f'_uorine substitution, especially perfluoro-substitution, in the anion. Second components containing fluoro-substituted stabilizing anions may, then, be used with a broader range of first components.
In general, the catalyst can be prepared by combining the two components in a suitable solvent at a temperature t,~ithin the range from -100°C to 300°C.
The catal st ma be used to Y y polymerize a-olefins and/or acetylenically unsaturated monomers having from 2 to 18 carbon atoms and/or diolefins having from 4 to 18 carbon atoms either alone or in combination. The catalyst may also be used to polymerize a-olefins, diolefins and/or acetylenically unsaturated monomers in combination with other unsaturated monomers. In general, the polymerization may be accomplished at conditions well known in the prior art For Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0 to 250°C and pressures Frorn atmospheric to 1000 atmospheres (,100 MPa). Suspension, solution, slurry or other process condition may be employed if desired. A
support may be employed but preferably the catalysts are used in a homogeneous manner. It will, of course, be appreciated that the catalyst system will form in situ if the components thereof are added directly to the polymerization process and a suitable solvent or diluent, including condensed monomer, is used in said 38,845-F _18_ _19_ polymerization process. It is, however, preferred to form the catalyst in a separate step in a suitable solvent prior to adding tho sar~a to the polymerization mixture.
As indicated supra, the improved catalyst of the present invention will, preferably, be prepared in a suitable solvent or diluent. Suitable solvents or diluents include any of the solvents known in the prior art to be useful as solvents in the polymerization of olefins, diolefins and acetylenically unsaturated monomers. Suitable solvents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof;
cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyleyelohexane, methyleycloheptane, perfluorinated hydrocarbons such as perfluorinated C~_10 alkanes and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyelopentene, 1-hexane, 3-methyl-1-pentene, ~1-methyl-1-pentene, 1,r4-hexadiene, 1-oc:tene, 1-decene, styrene, divinylbenzene, allylbenzene and v.inyltoluene (including a:11 isomers alone or in admixture).
It is believed that the active catalyst species of the present invention contains a metal center which center remains cationic, unsaturated and has a metal-carbon bond which is reactive with olefins, dialefins and acetylenically unsaturated compounds. Also associated with this metal center is a charge balancing anionic remnant of the formula A-.
38 , 8 ~+5-F -1 g-The catalyst formed by the method of this invention may be retained in solution or separated from the solvent, isolated, and stored for subsequent use.
As previously indicated supra, the catalyst may also be prepared in situ during a polymerization reaction by passing the separate components into the polymerization vessel where the components wil~_ com a~t and react to produce the improved catalyst of this invention.
The equivalent ratio of derivative of a Group ~~ or Lanthanide metal compound to oxidizing agent compound employed is preferably in a range from 0.1:1 to 10:1, more preferably from 0.75:1 to 2:1, most preferably 1.0:1Ø rn most polymerization reactions the equivalent ratio of catalyst:polymerizable compound employed is from 10'12:1 to 10'1:1, more preferably from 10"6:1 to 10'x:1.
A beneficial feature of some of the catalysts of this invention, particularly those based on monocyclopentadienyl substituted titanium compounds in combination with an oxidizing agent comprising boron, is that when the catalysts of this invention are used to copolymerize u-olefins, either alone or .in combination with diolefi.ns, the amount of higher molecular weight olefin or diole.fin incorporated into t;he copolymer is ~;.ignifi.cantly increased when compared to copolymers prepared :dith the more conventional Ziegler-Natta type catalysts. The relative rates of reaction of ethylene and higher a-olefins with the aforementioned titanium-based catalysts of this invention are so similar that the monomer distribution in copolymers prepared with the catalysts of this invention may be controlled by the ratio of monomeric reactants.
38,845-F -20-_21-"Addition polymerizable monomers" usefully polymerized according to the present invention include, for example, et?:ylenically unsaturated monomers, aeetylenic compounds, conjugated or noneonjugated dim es, polyenes, carbon monoxide, ete. Preferred monomers include the C
2-10 a-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, halo- or alkyl substituted styrenes, tetrafluoroethylene, vinylbenzocyclobutane, and 1,4-hexadiene.
Tn general, catalysts can be selected so as to produce polymer products which will be free of certain trace impurities such as aluminum, magnesium and chloride generally found in polymers produced with Ziegler-Natta type catalysts. The polymer products produced with the catalysts of this invention should, then, have a broader range of applications than polymers produced with more conventional Ziegler-Natta type catalysts comprising a metal alkyl such as an aluminum alkyl.
Having described the invention the following examples are provided as further .illustration thereof and are not to be construed as limiting. Unless stated to the contrary a.ll parts and percentages are ex pressed on a weight basis.
Example 1 A cata~.yst mixture was prepared by combining 50 micromoles of bis(cyclopentadienyl)dibenzylzirconium and 50 micromoles of Ferrocenium perfluorotetraphenyl borate in 50 ml purified and deaerated toluene. The mixture 38,845-E~ _2~_ ...22-was agitated for approximately 30 seconds until the blue ferrocenium coloration was discharged.
Polymerization The catalyst was combined with a mixture comprising 2 L of mixed alkane solvent (Isopar E'"
available from Exxon Chemicals Ine.), 75 ml at 50 psi (350 kPa) of hydrogen, and ethylene (31 atmospheres, 3.1 MPa) in a ~+ L reactor. The reactants were previously deaerated and purified and the reactor contents were heated to 170°C. Ten milliliters of the catalyst solution of Example 1 were added. An immediate rapid uptake of ethylene and considerable rise in reactor temperature occurred. (The ethylene uptake was greater than 100 g per minute and the temperature rise was greater than 17°C). At the end of a 10 minute reaction period the reactor contents were removed and devolatilized leaving 46 g of high density polyethylene.
Example 2 To 25 ml of deaerated purified toluene, 25 mieromoles of (tert-butylamido)dimethyl(tetramethyl-rl~
cyelopentadienyl)silanedibenzylzirconium and 25 mieromol.es of ferracenium perfluorotetraphenyl borate were added. The mixture w as agitated for approximately 1 minute until the blue color of the solid ferrocenium salt was discharged.
polymerization A 4 L reactor was charged with 2 L of mixed alkane solvent (Isopar E"') and 300 ml of 1-oetene, heated to 150°C and pressurized with ethylene to 31 atmospheres (3.1 MPa). All components had been 38,845-F -22-~~~~~"~~~
--23_ previously deaerated and purified. 20 ml of the above catalyst solution were added resulting in an immediate rapid uptake of ethylane and a large rise in reactor temperature (approximately 50 g per minute ethylene uptake and temperature rise of 26°C). At the end of a 10 minute period the reactor contents were removed and devolatilized leaving 78 g of ethylene/1-octene copolymer. The 1-octene content of the polymer was 7.5 mole percent as determined by mass balance, Example 3 A catalyst solution was prepared by mixing 10 mieromoles each of (tertbutylamido)dimethyl (r15-2,3,4,5-tetramethyleyelopentadienyl)silane dibenzyl titanium and ferrocenium perfluorotetraphenylborate in 5 milliliters of toluene. After thirty seconds of agitation the blue ferrocenium had been consumed and a greenish brown solution formed.
polymerization Addition of this catalyst solution to a stirred (500 rpm) two liter reactor containing Isopar-E (1000 m1), 1-actene (200 ml), hydrogen (50 ml @ 50 psi, 350 2, kpa) and ethylene (saturated @ 450 psi, 3 Mpa) at 130°C
resulted in a 40°C temperature rise. Ten minutes after addition of the catalyst solution to the reactor' the contents were removed from the reactor and the volatiles stripped to give 104 g of linear low density polyethylene.
Example 4 A catalyst mixture caas prepared from 10 micromoles each of ferrocenium perfluorotetraphenyl-38,845-F -23-~~~~~~~~t~
borate and 2-(n5-cyelopentadienyl)-2-(r~5-fluorenyl) propane dibenzyl zirconium in toluene (5 ml). A
greenish solution :,:as obtained after 1 minute of agitation.
Polymerization This catalyst solution was then added to a stirred (500 rpm) 2 liter reactor containing propylene (200 g), Isopar-E (b00 ml), and 1-octene (200 ml) at 50°C. A temperature rise of 10°C occurred upon addition of catalyst and was maintained for 3 minutes despite circulation of a -10°C ethylene glycol/water mixture through the reactor's internal cooling coils. After 30 minutes the contents of the reactor were removed and devolatilized to ive 1b7 g g of clear, rubbery, syndiotaetic propylene/1-octene copolymer.
38,8+5-F -24-
WITH O:CIDATIUE ACTIVATION
This inventidn relates to compositions of matter that are useful as catalysts, to a method for preparing the compositions of these catalysts, and to a method of using the compositions as addition polymerization catalysts. More particularly, this invention relates to catalyst compositions, to a method of preparing these catalyst compositions and to a method For polymerizing olefins, diolefins and/or acetylenically unsaturated monomers wherein these catalysts are used.
The use of Z.iegler-Nat~ta type catalysts in the polymerization of addition po.lymerizable manomers is, of course, well known in the prior art. In general, these soluble systems comprise a Group 4 or Lanthanide metal compound and a metal alkyl cocatalyst, particularly an aluminum alkyl cocatalyst.
In EP-A-0277,004 there are disclosed certain bis(cyclopentadienyl) metal compounds formed by reacting a bis(cyclopentadienyl) metal complex with salts of Bronsted acids containing a non-coordinating compatible 38,845-F _1_ anion. The reference discloses the fact that such complexes are usefully employed as catalysts in the nnlwmAri?at;nn of nl°Plr~
r .r.
Disadvantageously it has no~u been found that catalysts prepared according to the foregoing technique are detrimentally affected b,r the presence of by-product amine or phosphine compounds resulting from the catalyst formation. That is, the procedure of EP-A-0277,004 involves an irreversible reaction between a ligand of the metal compound and a ca non of the Bronsted acid salt. In practice such canons are generally trialkyl ammonium or phosphonium ions that result in the formation of a tertiary amine or phosphine by proton transfer tc the ligand during catalyst formation. Such amine or phosphine compounds are undesirable components of the resulting catalyst due to their inhibiting effect on addition polymerizations.
It could be desirable if there were provided a addition polymerization catalyst that is activated in a manner that forms only noninterfering and inert by-products.
In ~J. Am. Ch. Soc. 1~9, ~111-l113 (1987) there is disclosed a process for preparation of cationic zirconium (IV) benzyl complexes by one electron oxidation of dr organometallic compounds. The solvents employed in the preparation of the zirconium metallocenes were tetrahydroiuran or methylene chloride both of which interfere with the desired catalyst formation snd or detrimentall~r of feet subsequent olefin oolymerizations. In addition the reference employed an -3 ~-oxidizing agent containing tetraphenylborate. Such anions, it has now been discovered, are unacceptable for use in an oxidation activation proceas for preparing addition polymerization catalysts.
It has now been discovered that the foregoing and other disadvantages of the prior art ionic olefin polymerization catalysts can be avoided or at least reduced with the catalysts of the present invention. In addition an improved catalyst activation procedure and ~0 im roved addition p polymerization processes are provided according to the present invention. It is, therefore, an object of this invention to provide improved ionic catalyst systems which are useful in the polymerization ~5 of addition polymerizable monomers including olefins, diolefins and/or acetylenically unsaturated monomers.
It is another object of this invention to provide a method for preparing such improved catalysts. Tt is a Further object of this invention to provide an improved 20 polymerization process using such improved catalysts.
Ct is still another object of this invention to provide such an improved catalyst which is not subject to formation of iriterfering compounds. finally it is an object of this invention to provide such an improved 25 catal st ~nhich ma y y permit better control of the product polymer molecular weight and molecular weight distribution.
In accordance with the present invention there ''0 is provided a catalyst useful For addition polymerizations, which catalyst is substantially lacking in amine byproducts, said catalyst corresponding to the formula:
38, 8~+5-.F _3_ 2~~~~~"~
_~_ Lz MX* A°, wherein:
L independently each occurrence is a Iigand or I i ga.nd syst em;
M is a metal of group 4 or Lanthanide series of the Periodic Table of the Elements;
X is hydride or a hydrocarbyl, silyl or germyl group having up to 20 carbon, silicon or germanium atoms;
a is an integer greater than or equal to 1; and A- is a monovalent compatible noncoordinating anion.
Preferably M is a metal of group 4 of the Periodic table of the Elements, most preferably titanium or zirconium. Also, preferably X is hydride or C~-C~0 hydrocarbyl.
Further in accordance with the present invention there is provided a process for preparing the 20 above addition polymerization catalyst comprising contacting a derivative of a group 4 or Lanthanide metal corresponding to the Formula:
L~ MX2, wherein 25 L, e, M, and X are as previously defined, with an oxidizing agent which in reduced form is noninterfering with the resulting catalyst, said oxidizing agent comprising a cationic oxidizer and a 30 compatible noncoordinating anion.
The oxidizing agent corresponds to the formula:
(Ox~'a)b~A-)d CI) 38,845-F
~~~~~"~
_5_ wherein:
Ox+a is a non-Bronsted acid, cationic axidizer having a charge of (+a) capable of oxidizing the derivative of a Group ~+ or Lanthanide metal;
A- is as previously defined; and b and d are integers selected to provide charge balance.
The catalysts may be prepared by contacting the derivative of a Group 4 ar Lanthanide metal with the oxidizing agent optionally in an inert diluent such as an organic liquid.
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
The term "ligand or ligand system" refers to any ancillary, electron donating or electron sharing moiety. Such l.igands include anionic ligands and neutral donor l.igands.
Illustrative but nonlimit.ing examples of suitable anionic ligands include: R, -R'(0R'?mOR, (OR')mOR, -PR2, -SR, -OR, -NR2, hydride, and organo-metalloid radicals comprising a Group 14 element wherein each of the hydrocarbyl substituents contained in the organic portion of said arganometalloid, independently, contains From 1 to 20 carbon atoms. In these ligands:
R is a hydrocarbyl, silyl, germyl or a 38,8+5-F -5-~~~~'~"~~~
substituted hydrocarbyl, silyl, or germyl group of from 1 to 24 carbon, silioon, or germanium atoms;
R' is C2_10 alhylono, and m is an integer from zero to ten.
Illustrative but non-limiting examples of suitable neutral donor ligands (L') include: ROR, NR3, PR3, and SR2 wherein R is a_s above defined.
The term "cationic oxidizer" as used herein refers to an organic or inorganic ion having an oxidation potential sufficient to cause a molecular oxidation of the derivative of a Group ~+ or Lanthanide metal so as to form a catalytic species. Generally and preferably the Group 4 or Lanthanide metal of the derivative compound is already in the highest atomic oxidation state. The process of the invention involves a molecular oxidation. Most preferred cationic oxidizers have an oxidation potential of at least -0.20 volt and preferably at least +0.25 volt. Cationic oxidizers are not Bronsted acids.
As used herein, the recitation "compat.ible noneoordinating anion" means an anion which when funotioni.ng as a charge balancing anion in the catalyst system of thi~i .invention does not transfer an anionic subst.ituent or fragment thereof to any cationic species thereby forming a neutral Group ~4 or Lanthanide metal product. "Compatible anions" are anions which are not degraded to neutrality during catalyst preparation or use.
'The recitation ''metalloid", as used herein, includes nonmetals such as boron, phosphorus and the like which exhibit semi-metallic characteristics.
38,845-F -6-_7_ Further preferred derivatives correspond to the formula: L"MX2, wherein:
L" is a derivative of a substituted cyclo-pentadienyl or similar deloealized n-bonding group imparting a constrained geometry to the metal active site and containin a to 20 nonh droP~
g p y o,.n atoms; and M and X are as defined above.
By use of the term "constrained geometry"
herein is meant that the metal atom is forced to greater exposure of the active metal site because of one or more substituents on the cyclopentadienyl or substituted eyelopentadienyl group forming a portion of a ring structure wherein the metal is both bonded to an adjacent covalent moiety and is held in association with the cyclopentadienyl or substituted cyclopentadienyl group through an r15 or other rz-bonding interaction. It is understood that each respective bond between the metal atom and the constituent atoms of the cyclopentadienyl or substituted cyclopentadienyl group need not be equivalent. That is, the metal may be symmetrically or unsymmetrically rz-bound to the cyclopentadienyl or substituted cyelopentadienyl group.
The geometry of the active metal site is Eur~ther defined as follows. 'The eentroid of the cyclopentadienyl or substituted cyelopentadienyl group may be defined as the average of the respective X, Y, and Z coordinates of the atomic centers forming the 3~ cyclopentadienyl or substituted cyelopentadienyl group>
The angle. 0, formed at the metal center between the centroid of the cyclopentadienyl or substituted eyelopentadienyl group and each other ligand of the metal complex may be easily calculated by standard techniques of single crystal X-ray diffraction. Each of 38,845-F _7_ _~_ these angles may increase or decrease depending on the molecular structure of the constrained geometry metal complex. T'hOse OOmplexeS wherein 0:18 Or more of the angles, O, is less than in a similar, comparative complex differing only in the fact that the constrain-s inducing substituent is replaced by hydrogen have constrained geometry for purposes of the present invention. Preferably one or more of the above angles, O, decrease by at least 5 percent, more preferably 7.5 Percent, compared to the comparative complex. Highly preferably, the average value of all bond angles, (3, is also less ~han in the comparative complex.
Preferably, monocyclopentadienyl metal coordination complexes of group 4 or lanthanide metals according ~o the present invention have constrained geometry such that the smallest angle, O, is less than 115°, more preferably less than 110°, most preferably less than 105°.
Highly preferred derivative compounds are monocyclopentadienyl compounds corresponding to the formula:
Y
Gp.h ~ M/
I
(X)2 38,845-F _g_ 2~~~"~
_g_ wherein:
M is titanium or zirconium;
Cps' is a cyclopentadienyl or substituted cyclopentadienyl group bound in an ~5 bonding mode to M;
Z is a divalent moiety comprising oxygen, boron, or a member of group 14 of the Periodic Table of the Elements;
Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y
together form a fused ring system; and X is as previously defined.
After molecular oxidation, the highly preferred catalysts of the invention correspond to the formula:
, Z Y
Cp'~ - M H
A' II
X
~nherein Cp'~, Z, M, X and A' are as previously defined.
Gaeh carbon atom in the cyclopentadienyl radical may be substituted or unsubstituted with the same or a different radical selected from the group consisting of hydroearbyl radicals, substituted-hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected 38,845-F -9-~~~~~~"l from Group 14 of the Periodic Table of the Elements, and halogen radicals, zn addition two or more such substituents may together form a fused ring system.
Suitable hydrocarbyl and substituted-hydrocarbyl radicals, which may be substituted for at least one hydrogen atom in the eyelopentadienyl radical, will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals. Suitable organometalloid radicals include mono-, di- and trisubstituted organometalloid radicals of Group 14 elements wherein each of the hydrocarbyl groups contain from 1 to 20 carbon atoms. More particularly, suitable arganometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like.
Most highly preferred derivative compounds are amidosilane- or amidoalkanediyl- compounds corresponding to the formula:
R~ ~ER'2)m~
N-R
R. ~~ M/
R/ R~ (X)2 wherein:
38 , 845-F -10-' (,~
M is titanium or zirconium, bound to an r15-cyclopentadienyl group;
R' each occurrence is independently selected from hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms;
E is silicon or carbon;
X independently each occurrence is hydride, alkyl, or aryl of up to 10 carbons; and m is 1 or 2.
Examples of the above most highly preferred metal coordination compounds include compounds wherein 1o the R' on the amido group is methyl, ethyl, propyl, but~rl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, ete.; the cyclopentadienyl group is cyciopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, ete.; R' on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, ete.; and X is methyl, neopentyl, trimethylsilyl, norbornyl, benzyl, methyl.benzyl, phenyl, etc. Specific eornpounds include:, (tort-butylamido)(tetramethyl-ray-cyelopentadienyl)-1,2-ethanediylzireonium dimethyl, (teat-butylamido)(tetra-methyl-t15-cyelopentadienyl)-1,2-ethanediyltitanium dimethylbenzyl, (methylamido)(tetramethyl-r~5-~0 cyclopentadienyl)-1,2-ethanediylzireonium dibenzhydryl, (methylamido)(tetramethyl-~~-cyclopentadienyl)-1,2-ethanediyltitanium dineopentyl, (ethylamido)(tetra-methyl-rl~-cyelopentadienyl)-methylenetitanium diphenyl, (tent-butylamido)dibenzyl(tetramethyl-ri5-cyclopenta-dieriyl)silanezirconium dibenzyl, (benzylamido)dimethyl-38,845-P -11-(tetramethyl-rig-cyclopentadienyl)silanetitanium di(trimethylsilyl) and (phenylphosphido)dimethyl(tetra-methyl-ri5.-cyelopontadicil'y'1)silanazir corium dibenzyl.
In the most preferred embodiment --Z-Y- is an amidosilane or amidoalkane group of up to 10 nonhydrogen atoms, that is, (tert-butylamido)(dimethylsilyl), (tert-butylamido)-1-ethane-2-yi, ete.
Derivative compounds which may be used in the preparation of the improved catalyst of this invention are covalently bonded metal compounds that are either devoid of reactive hydrogens (other than hydride leaving groups, X) or wherein potentially reactive hydrogens are protected by bulky protecting groups. Examples of suitable organyl substituents on such metal derivative compounds include norbornyl, neopentyl, trimethylsilyl and diphenylmethyl. Illustrative, but not limiting examples of suitable derivative compounds include:
tetranorbornyltitanium, tetrabenzylzirconium, tetraneopentyltitanium, diphenoxybis(tri-methylsilyl)z.irconium, bis(2,6-diisopropyl-tl-methyl)phenoxy)dibenzyltitanium, tritert-butylsiloxy)trimethylzircanium, dimethoxydibenzhydryl-t.itanium, 'o.is(2,~4,6-trimethflphenoxy)dibenzyltitanium, buta:,cytris((trimethyls.ilyl)methyl)zirconium, d.inorbornyldimethyltitanium, tribenzyltitanium hydride, etc.; cyclopentadienyl and bis(cyelopentadienyl) metal compounds such as bis(eyclopentadienyl)dimethyl-zirconium, cyelopentadienyltribenzylzirconium, cyclopentadienyltrimethyltitanium, cyclopentadienyl-trimethylzirconium, bis(cyclopentadienyl) dineopentyltitanium, cyelopentadienyltri(diphenyl-methyl)zirconium, bis(cyclopentadienyl)diphenyl-zireonium, cyelopentadienyltrineopentyltitanium, bis(cy-38,8+5-E -12-clopentadienyl)di(m-tolyl)zireonium, biseyclopenta-dienyldi(p-tolyl)zirconium; hydrocarbyl-substituted cyelopentadienyi or bis(cyclopentadienyl) compounds such as (pentamethylcyelopentadienyl)-(cyelopentadienyl) dimethylzireonium, bis(ethyleyclopentadienyl)dimethyl-zirconium, (pentamethyleyclopentadienyl)tribenzyl-zirconium, (n-butylcyclopentadienyl)trineopentyl-titanium, cyclopentadienyldimethyltitanium hydride, bis(cyclopentadienyl)bis(diphenylmethyl)zireonium, bis(tert-butylc;rclopentadienyl)bis(trimethylsilyl-methyl)zirconium, bis(cyelohexylcyelopentadienyl) dimethylzirconium, (benzyleyelopentadienyl)di(m-tolyl)methyltitanium, (diphenylcyclopenta-dienyl)dinorbornylmethylzireonium, bis(methyleycla-pentadienyl)diphenylzireonium, (tetraethyleyelo-pentadienyl)tribenzylzirconium, (propylcyelopentadienyl) (cyclopentadienyl)dimethylzireonium, bis(propyleyclo-pentadienyl)dimethylzireonium, (n-butyleyelopentadienyl) dimethyl(n-butoxy)titanium, cyelopentadienyldiphenyl-isopropoxyzirconium, cyelohexylmethyleyelopenta-dienyl)cyclopentadienyldibenzylzirconium, bis((cyelohexyl)methylcyelopentadienyl)dibenzyl-zirconium, b.is(cyclopentadienyl)zireonium dihydride, benzylcyclopentadienyldimethylhaFn.ium, bis(.indenyl)dibenzylz.ireon.ium, (tert-butylamido)di-methyl(tetramethyl-r~7--eyclopentadi.enyl)silane dibenzylz:irconium, (benzylamido)dimethyl(tetraethyl-~5-cyelopentadienyi)silane dibutyltitanium, and the like;
metal hydrocarbyl-substituted cyclopentadienyl metal compounds such as ((trimethylsilyl)-cyelopentadienyi)trimethylzireonium, bis((trimethyl-germyl)cyclopentadienyl)dimethyltitanium, ((trimethyl-stannyl)cyclopentadienyl)tribenzylzireonium, ((penta-trimethylsilyl)cyclopentadienyl)(eyclopenta-38,845-F _~3_ dienyl)dimethylzirconium, bis((trimethylsilyl)cyclo-pentadienyl)dimethylzirconium, penta((trimethyl-sil5~1)cyeloper.ta.di~nyl)tribenzyltitanium, bis((t~i-methylgermyl)cyclopentadienyl)d.iphenylhafnium; halogen-substituted cyclopentadienyl compounds such as ((trifluoromethyl)eyelopentadienyl)(cyelopentadienyl)di-methylzirconium, bis((trifluoromethyl)cyclopenta-dienyl)dinorbornylzirconium, ((trifluoromethyl)eyelo-pentadienyl)tribenzylzirconium; silyl-substituted (cyclopentadienyl)metal compounds such as bis(cyelopentadienyl)di(trimethylsilyl)zireonium, cyelopentadienyltri(phenyldimethylsilyl)zirconium;
bridged cyclopentadienyl-metal compounds such as methylenebis((cyelopentadienyl)dimethylzireonium), ethylene~bis-((cyelopentadienyl)dibenzylzirconium), (dimethylsilylene)-bis-((cyelopentadienyl) dimethyltitanium), methylene-bis-(cyclopentadienyl) di(trimethylsilyl)zirconium, (dimethylsilylene) bis(cyclopentadienyldineopentylhafnium), ethylene-bis-(tetrahydroindenyl)-zirconium dibenzyl and dimethylsilylene(fluorenyl)(cyelopentadienyl)-titanium dimethyl.
Other compounds which are useful in the catalyst compositions of this invention, especially c;ompou nds containing other Group 4 or Lanthanide metals, will, of course, be apparent to those skilled in the art.
Compounds useful as oxidizing agents in the preparation of the compounds of this invention will comprise a cationic oxidizer, and one or more compatible noncoordinating anions, as previously explained.
38,845-F -14-In a preferred embodiment A-c of previous Formula (I) comprises an anion which is a single coordination complex comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom, which anion is bulky and stable under the oxidation and subsequent polymerization conditions, and which anion is compatible with and noncoordinating towards the resulting Group 4 or Lanthanide metal containing catalyst. The anion is employed only to provide charge balance without interfering with the oxidizing ability of Ox+a or the catalytic properties of the resulting catalyst. Any metal or metalloid capable of forming a e,oordination complex which is stable under the reaction conditions of the present invention may be contained in the anion. Suitable metals .include, but are not limited to, aluminum, gold and platinum.
Suitable metalloids include, but are not limited to, boron, phosphorus and silicon. Oxidizing agents containing anions comprising a coordination complex containing a single boron atom are most preferred.
Anions comprising boron which are particularly useful in the preparation of catalysts of this invention rna be re resented b the fol.Lowin Y p Y g general formula:
PBX 1 X2X3Xt;~_ wherein:
B is boron in a valence state of 3;
X1 to X~ are the same or different nonreaetive, organyl or silyl radicals containing from 6 to 20 carbon or silicon atoms. In addition two or more of X1 to X~
may be linked to each other through a stable bridging group. Preferably X1 to X1~ lack reactive hydrogen 38,85-F -15-_ ~~0'~
moieties. That is, the radicals are either devoid of hydrogen, contain only hydrogen in nonactiv ated positions or contain sufficicnt stoic hindrance to protect potentially active hydrogen sites. Examples of suitable radicals for X1 to X4 are perfluorinated hydrocarbyl radicals containing from 6 to 20 carbon atoms, 3,4.5-trifluorophenyl, etc.
A most highly preferred compatible, non-coordinating, anion is tetra(pentafluorophenyl)borate.
Suitable organic cationic oxidizers for use according to the present invention include ferrocenium ions, bis-indenyl Fe(III) ions, and cationic derivatives of substituted ferrocene, and the like molecules.
Suitable metal cationic oxidizers include Ag+1, pd+z~
Pt+', Hg'-'. Hg~+~', Au+ and Cu+. Most preferred cationic oxidizers are ferrocenium and Ag+t cations.
Illustrative, but not limiting, examples of oxidizin~ agents in the o n preparation of the improved catalysts of this invention are Ferrocenium tetra(pentafluorophenyl)borate, gold (I) tetrakis 3,4,5-trifluorophenyl borate, si7.ver tetra(penta-fluorophenyl)borate and 1,1'-dimethy:Lferroeenium tetrakis 3.5-bistr~iF.luorornethylphenyl borate.
Similar lists of suitable compounds containing other metals and metalloids which are useful as oxidizing agents (second components) could be made, but such lists are not deemed necessary to a complete disclosure. In this regard, it should be noted that the Foregoing list is not .intended to be exhaustive and other boron compounds that would be useful as well as useful compounds containing other metals or metalloids 38,845-F -16-_ ~~~~r12~
-1~.-would be readily apparent, from the foregoing general equations, to those skilled in the art.
~~lithout wishing to be bound by any particular theory of operation it is believed that the cationic oxidizer causes the molecular oxidation of the Group 4 or Lanthanide metal derivative, and in the process becomes a neutral species. The oxidized metal derivative loses a hydrogen or hydrocarbyl radical (~R) by a unimolecular elimination reaction. Two ar more such radicals form a hydrogen molecule or a neutral organic species of the formula Rx where x is an integer greater than or equal to 2. These byproducts are of course neutral or noninterfering with any subsequent polymerization reaction and may also be removed from the reaction mixture. This result is much preferred to previously known processes for catalyst activation which resulted in the formation of an amine or similar reaction byproduct.
It should be noted that the two compounds combined for preparation of the active catalyst must be selected so as to avoid transfer of a fragment of the anion, particularly an aryl group, to the metal canon, thereby forming a catalytically inactive species. 'this , could be done by sterie hindrance, resulting from substitutions on the groups attached to the Group 4 or Lanthanide metal as well as substitutions on the aramatie carbon atoms of the anion. It follows, then, that Group a and Lanthanide metal compounds (first components) comp rising, for example, perhydrocarbyl-substituted cyclopentadienyl radicals could be effectively used with a broader range of second compounds than could first components comprisin g less bulky radicals. As the amount and size of the metal 38,845-F _17_ ~~~~"~
substituents are reduced, however, more effective catalysts are obtained with second compounds containing anions c~.hich are more rcsistar~t to degr adation, sue h as those with substituents on the meta and/or para positions of :he phenyl rings. Another means of rendering the anion more resistant to degradation is afforded by f'_uorine substitution, especially perfluoro-substitution, in the anion. Second components containing fluoro-substituted stabilizing anions may, then, be used with a broader range of first components.
In general, the catalyst can be prepared by combining the two components in a suitable solvent at a temperature t,~ithin the range from -100°C to 300°C.
The catal st ma be used to Y y polymerize a-olefins and/or acetylenically unsaturated monomers having from 2 to 18 carbon atoms and/or diolefins having from 4 to 18 carbon atoms either alone or in combination. The catalyst may also be used to polymerize a-olefins, diolefins and/or acetylenically unsaturated monomers in combination with other unsaturated monomers. In general, the polymerization may be accomplished at conditions well known in the prior art For Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0 to 250°C and pressures Frorn atmospheric to 1000 atmospheres (,100 MPa). Suspension, solution, slurry or other process condition may be employed if desired. A
support may be employed but preferably the catalysts are used in a homogeneous manner. It will, of course, be appreciated that the catalyst system will form in situ if the components thereof are added directly to the polymerization process and a suitable solvent or diluent, including condensed monomer, is used in said 38,845-F _18_ _19_ polymerization process. It is, however, preferred to form the catalyst in a separate step in a suitable solvent prior to adding tho sar~a to the polymerization mixture.
As indicated supra, the improved catalyst of the present invention will, preferably, be prepared in a suitable solvent or diluent. Suitable solvents or diluents include any of the solvents known in the prior art to be useful as solvents in the polymerization of olefins, diolefins and acetylenically unsaturated monomers. Suitable solvents include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof;
cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyleyelohexane, methyleycloheptane, perfluorinated hydrocarbons such as perfluorinated C~_10 alkanes and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyelopentene, 1-hexane, 3-methyl-1-pentene, ~1-methyl-1-pentene, 1,r4-hexadiene, 1-oc:tene, 1-decene, styrene, divinylbenzene, allylbenzene and v.inyltoluene (including a:11 isomers alone or in admixture).
It is believed that the active catalyst species of the present invention contains a metal center which center remains cationic, unsaturated and has a metal-carbon bond which is reactive with olefins, dialefins and acetylenically unsaturated compounds. Also associated with this metal center is a charge balancing anionic remnant of the formula A-.
38 , 8 ~+5-F -1 g-The catalyst formed by the method of this invention may be retained in solution or separated from the solvent, isolated, and stored for subsequent use.
As previously indicated supra, the catalyst may also be prepared in situ during a polymerization reaction by passing the separate components into the polymerization vessel where the components wil~_ com a~t and react to produce the improved catalyst of this invention.
The equivalent ratio of derivative of a Group ~~ or Lanthanide metal compound to oxidizing agent compound employed is preferably in a range from 0.1:1 to 10:1, more preferably from 0.75:1 to 2:1, most preferably 1.0:1Ø rn most polymerization reactions the equivalent ratio of catalyst:polymerizable compound employed is from 10'12:1 to 10'1:1, more preferably from 10"6:1 to 10'x:1.
A beneficial feature of some of the catalysts of this invention, particularly those based on monocyclopentadienyl substituted titanium compounds in combination with an oxidizing agent comprising boron, is that when the catalysts of this invention are used to copolymerize u-olefins, either alone or .in combination with diolefi.ns, the amount of higher molecular weight olefin or diole.fin incorporated into t;he copolymer is ~;.ignifi.cantly increased when compared to copolymers prepared :dith the more conventional Ziegler-Natta type catalysts. The relative rates of reaction of ethylene and higher a-olefins with the aforementioned titanium-based catalysts of this invention are so similar that the monomer distribution in copolymers prepared with the catalysts of this invention may be controlled by the ratio of monomeric reactants.
38,845-F -20-_21-"Addition polymerizable monomers" usefully polymerized according to the present invention include, for example, et?:ylenically unsaturated monomers, aeetylenic compounds, conjugated or noneonjugated dim es, polyenes, carbon monoxide, ete. Preferred monomers include the C
2-10 a-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Other preferred monomers include styrene, halo- or alkyl substituted styrenes, tetrafluoroethylene, vinylbenzocyclobutane, and 1,4-hexadiene.
Tn general, catalysts can be selected so as to produce polymer products which will be free of certain trace impurities such as aluminum, magnesium and chloride generally found in polymers produced with Ziegler-Natta type catalysts. The polymer products produced with the catalysts of this invention should, then, have a broader range of applications than polymers produced with more conventional Ziegler-Natta type catalysts comprising a metal alkyl such as an aluminum alkyl.
Having described the invention the following examples are provided as further .illustration thereof and are not to be construed as limiting. Unless stated to the contrary a.ll parts and percentages are ex pressed on a weight basis.
Example 1 A cata~.yst mixture was prepared by combining 50 micromoles of bis(cyclopentadienyl)dibenzylzirconium and 50 micromoles of Ferrocenium perfluorotetraphenyl borate in 50 ml purified and deaerated toluene. The mixture 38,845-E~ _2~_ ...22-was agitated for approximately 30 seconds until the blue ferrocenium coloration was discharged.
Polymerization The catalyst was combined with a mixture comprising 2 L of mixed alkane solvent (Isopar E'"
available from Exxon Chemicals Ine.), 75 ml at 50 psi (350 kPa) of hydrogen, and ethylene (31 atmospheres, 3.1 MPa) in a ~+ L reactor. The reactants were previously deaerated and purified and the reactor contents were heated to 170°C. Ten milliliters of the catalyst solution of Example 1 were added. An immediate rapid uptake of ethylene and considerable rise in reactor temperature occurred. (The ethylene uptake was greater than 100 g per minute and the temperature rise was greater than 17°C). At the end of a 10 minute reaction period the reactor contents were removed and devolatilized leaving 46 g of high density polyethylene.
Example 2 To 25 ml of deaerated purified toluene, 25 mieromoles of (tert-butylamido)dimethyl(tetramethyl-rl~
cyelopentadienyl)silanedibenzylzirconium and 25 mieromol.es of ferracenium perfluorotetraphenyl borate were added. The mixture w as agitated for approximately 1 minute until the blue color of the solid ferrocenium salt was discharged.
polymerization A 4 L reactor was charged with 2 L of mixed alkane solvent (Isopar E"') and 300 ml of 1-oetene, heated to 150°C and pressurized with ethylene to 31 atmospheres (3.1 MPa). All components had been 38,845-F -22-~~~~~"~~~
--23_ previously deaerated and purified. 20 ml of the above catalyst solution were added resulting in an immediate rapid uptake of ethylane and a large rise in reactor temperature (approximately 50 g per minute ethylene uptake and temperature rise of 26°C). At the end of a 10 minute period the reactor contents were removed and devolatilized leaving 78 g of ethylene/1-octene copolymer. The 1-octene content of the polymer was 7.5 mole percent as determined by mass balance, Example 3 A catalyst solution was prepared by mixing 10 mieromoles each of (tertbutylamido)dimethyl (r15-2,3,4,5-tetramethyleyelopentadienyl)silane dibenzyl titanium and ferrocenium perfluorotetraphenylborate in 5 milliliters of toluene. After thirty seconds of agitation the blue ferrocenium had been consumed and a greenish brown solution formed.
polymerization Addition of this catalyst solution to a stirred (500 rpm) two liter reactor containing Isopar-E (1000 m1), 1-actene (200 ml), hydrogen (50 ml @ 50 psi, 350 2, kpa) and ethylene (saturated @ 450 psi, 3 Mpa) at 130°C
resulted in a 40°C temperature rise. Ten minutes after addition of the catalyst solution to the reactor' the contents were removed from the reactor and the volatiles stripped to give 104 g of linear low density polyethylene.
Example 4 A catalyst mixture caas prepared from 10 micromoles each of ferrocenium perfluorotetraphenyl-38,845-F -23-~~~~~~~~t~
borate and 2-(n5-cyelopentadienyl)-2-(r~5-fluorenyl) propane dibenzyl zirconium in toluene (5 ml). A
greenish solution :,:as obtained after 1 minute of agitation.
Polymerization This catalyst solution was then added to a stirred (500 rpm) 2 liter reactor containing propylene (200 g), Isopar-E (b00 ml), and 1-octene (200 ml) at 50°C. A temperature rise of 10°C occurred upon addition of catalyst and was maintained for 3 minutes despite circulation of a -10°C ethylene glycol/water mixture through the reactor's internal cooling coils. After 30 minutes the contents of the reactor were removed and devolatilized to ive 1b7 g g of clear, rubbery, syndiotaetic propylene/1-octene copolymer.
38,8+5-F -24-
Claims (12)
1. A process for preparing an addition polymerization catalyst of the formula:
wherein:
Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an X75 bonding mode to M;
Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the Periodic Table of the Elements;
Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y together form a fused ring system;
M is titanium or zirconium;
X is hydride or hydrocarbyl of up to 20 carbon atoms; and A- is a monovalent compatible noncoordinating anion which does not transfer an anionic substitutent or fragment thereof to a cationic species thereby forming a neutral titanium or zirconium metal product, comprising contacting a metal complex corresponding to the formula:
wherein:
M, Cp*, Z, Y and each X independently are as defined above, with an oxidizing agent which in reduced form is noninterfering with the resulting catalyst, said oxidizing agent corresponding to the formula:
(Ox+a)b(A-)d wherein:
Ox+a is a non-Bronsted acid, cationic oxidizer having a charge of (+a) capable of oxidizing the metal complex;
A- is as previously defined; and b and d are integers selected to provide charge balance.
wherein:
Cp* is a cyclopentadienyl or substituted cyclopentadienyl group bound in an X75 bonding mode to M;
Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the Periodic Table of the Elements;
Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur or optionally Z and Y together form a fused ring system;
M is titanium or zirconium;
X is hydride or hydrocarbyl of up to 20 carbon atoms; and A- is a monovalent compatible noncoordinating anion which does not transfer an anionic substitutent or fragment thereof to a cationic species thereby forming a neutral titanium or zirconium metal product, comprising contacting a metal complex corresponding to the formula:
wherein:
M, Cp*, Z, Y and each X independently are as defined above, with an oxidizing agent which in reduced form is noninterfering with the resulting catalyst, said oxidizing agent corresponding to the formula:
(Ox+a)b(A-)d wherein:
Ox+a is a non-Bronsted acid, cationic oxidizer having a charge of (+a) capable of oxidizing the metal complex;
A- is as previously defined; and b and d are integers selected to provide charge balance.
2. A process as claimed in claim 1, wherein the cationic oxidizer has an oxidation potential of at least +0.20 volt.
3. A process as claimed in claim 2, wherein the cationic oxidizer has an oxidation potential of at least +0.25 volt.
4. A process as claimed in claim 1, wherein Ox+a is selected from the group consisting of ferrocenium;
bisindenyl Fe(III); cationic derivatives of substituted ferrocenium; and metallic canons.
bisindenyl Fe(III); cationic derivatives of substituted ferrocenium; and metallic canons.
5. A process as claimed in claim 4, wherein Ox +a is ferrocenium or Ag+1.
6. A process as claimed in claim 1, wherein A- is:
[BX1X2X3X4]-wherein:
B is boron in an oxidation state of 3, X1, X2, X3 and X4 are the same or different nonreactive, organyl or silyl radicals containing from 6 to 20 carbon or silicon atoms and optionally two or more of X1, X2, X3 or X4 may be linked to each other through a stable bridging group.
[BX1X2X3X4]-wherein:
B is boron in an oxidation state of 3, X1, X2, X3 and X4 are the same or different nonreactive, organyl or silyl radicals containing from 6 to 20 carbon or silicon atoms and optionally two or more of X1, X2, X3 or X4 may be linked to each other through a stable bridging group.
7. A process as claimed in claim 6, wherein X1, X2, X3 and X4 are perfluorinated hydrocarbyl radicals containing from 6 to 20 carbons.
8. A process as claimed in claim 1, wherein each X
independently is hydride, alkyl or aryl of up to 10 carbon atoms; Y is NR'; and Z is (ER'2)m, wherein each R' independently is hydrogen, silyl, alkyl, aryl or a combination thereof having up to 10 carbon or silicon atoms;
and m is 1 or 2.
independently is hydride, alkyl or aryl of up to 10 carbon atoms; Y is NR'; and Z is (ER'2)m, wherein each R' independently is hydrogen, silyl, alkyl, aryl or a combination thereof having up to 10 carbon or silicon atoms;
and m is 1 or 2.
9. A process as claimed in claim 1, wherein X is hydride or C1-C10 hydrocarbyl.
10. A process as claimed in claim 1, wherein X is benzyl.
11. An addition polymerization catalyst substantially lacking in amine or phosphine byproducts prepared according to a process of any one of claims 1-10.
12. The use in an addition polymerization process of a catalyst as claimed in claim 11.
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| Application Number | Priority Date | Filing Date | Title |
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| US54771890A | 1990-07-03 | 1990-07-03 | |
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| EP (2) | EP0698618B1 (en) |
| JP (1) | JP2545006B2 (en) |
| KR (1) | KR100203235B1 (en) |
| CN (1) | CN1032008C (en) |
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| USRE37788E1 (en) * | 1987-01-30 | 2002-07-09 | Exxon Chemical Patents, Inc. | Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts |
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| JPH0780930B2 (en) * | 1985-12-26 | 1995-08-30 | 三井石油化学工業株式会社 | Method for polymerizing α-olefin |
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| US5153157A (en) * | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
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| US4931417A (en) * | 1987-11-09 | 1990-06-05 | Chisso Corporation | Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure |
| US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
| US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
| US5066741A (en) * | 1990-03-22 | 1991-11-19 | The Dow Chemical Company | Process for preparation of syndiotactic vinyl aromatic polymers |
| CA2024830A1 (en) * | 1989-09-29 | 1991-03-30 | Richard E. Campbell, Jr. | Process for preparation of syndiotactic vinyl aromatic polymers |
| DE69018376T3 (en) * | 1989-10-30 | 2002-05-16 | Fina Technology | Manufacture of metallocene catalysts for olefin polymerization. |
| US5034034A (en) * | 1990-08-28 | 1991-07-23 | The Dow Chemical Company | Novel aryl carbonate cyanoaryl ether gas separation membranes |
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1991
- 1991-06-20 JP JP3245282A patent/JP2545006B2/en not_active Expired - Fee Related
- 1991-06-27 BR BR919102815A patent/BR9102815A/en not_active IP Right Cessation
- 1991-07-01 DE DE69121813T patent/DE69121813T2/en not_active Expired - Fee Related
- 1991-07-01 ES ES95115577T patent/ES2267097T3/en not_active Expired - Lifetime
- 1991-07-01 ES ES91305955T patent/ES2091293T3/en not_active Expired - Lifetime
- 1991-07-01 EP EP95115577A patent/EP0698618B1/en not_active Expired - Lifetime
- 1991-07-01 DE DE69133543T patent/DE69133543T2/en not_active Expired - Fee Related
- 1991-07-01 SG SG1996005482A patent/SG52523A1/en unknown
- 1991-07-01 MY MYPI91001193A patent/MY108636A/en unknown
- 1991-07-01 EP EP91305955A patent/EP0468651B1/en not_active Expired - Lifetime
- 1991-07-02 ZA ZA915114A patent/ZA915114B/en unknown
- 1991-07-02 CA CA002046075A patent/CA2046075C/en not_active Expired - Fee Related
- 1991-07-02 RU SU915001125A patent/RU2011652C1/en not_active IP Right Cessation
- 1991-07-02 NO NO912600A patent/NO180720C/en not_active IP Right Cessation
- 1991-07-02 AU AU80145/91A patent/AU651599B2/en not_active Ceased
- 1991-07-02 KR KR1019910011149A patent/KR100203235B1/en not_active IP Right Cessation
- 1991-07-02 CN CN91104485A patent/CN1032008C/en not_active Expired - Fee Related
- 1991-07-02 MX MX9100063A patent/MX9100063A/en not_active IP Right Cessation
- 1991-07-02 FI FI913215A patent/FI105559B/en not_active IP Right Cessation
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1992
- 1992-06-09 US US07/896,732 patent/US5321106A/en not_active Expired - Lifetime
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| JP2545006B2 (en) | 1996-10-16 |
| ES2267097T3 (en) | 2007-03-01 |
| DE69121813D1 (en) | 1996-10-10 |
| KR920002640A (en) | 1992-02-28 |
| EP0698618A3 (en) | 1997-02-12 |
| DE69133543T2 (en) | 2007-08-16 |
| FI105559B (en) | 2000-09-15 |
| ES2091293T3 (en) | 1996-11-01 |
| DE69121813T2 (en) | 1997-04-03 |
| NO180720B (en) | 1997-02-24 |
| BR9102815A (en) | 1992-02-04 |
| EP0698618A2 (en) | 1996-02-28 |
| EP0698618B1 (en) | 2006-08-30 |
| CN1057845A (en) | 1992-01-15 |
| MY108636A (en) | 1996-10-31 |
| NO912600L (en) | 1992-01-06 |
| MX9100063A (en) | 1992-02-28 |
| RU2011652C1 (en) | 1994-04-30 |
| AU8014591A (en) | 1992-01-09 |
| AU651599B2 (en) | 1994-07-28 |
| SG52523A1 (en) | 1998-09-28 |
| KR100203235B1 (en) | 1999-06-15 |
| US5321106A (en) | 1994-06-14 |
| FI913215A0 (en) | 1991-07-02 |
| NO180720C (en) | 1997-06-04 |
| ZA915114B (en) | 1993-03-31 |
| JPH04253711A (en) | 1992-09-09 |
| EP0468651B1 (en) | 1996-09-04 |
| DE69133543D1 (en) | 2006-10-12 |
| CA2046075A1 (en) | 1992-01-04 |
| EP0468651A1 (en) | 1992-01-29 |
| CN1032008C (en) | 1996-06-12 |
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