PT95272B

Monocyclopentadienyl transition metal olefin polymerization catalysts.

Abstract

This record has no abstract on file.

Term

Term ended

Expired 11 September 2005, 21 years ago.

10 claims: 3 independent, 7 dependent

1
1, Processo para a polimerização olefínica, que compreende polimerizar o etileno com um monómero seleccionado entre uma α-olefina em C 3 -C 20 ou uma diolefina em C 5 -C 20 na presença de um sistema catalisador que compreende (A) um composto com a fórmula geral:Mod. 71 - 20.000 ex. - 92/12 ou na qual M é Zr, Hf ou Tl;(C s H s _ y _ x R x ) é um anel ciclopentadienilo que está substituído com zero a cinco grupos R, “x” é 0, 1, 2, 3, 4 ou 5, designando o grau de substituição, e cada Ré, de forma independente, um radical seleccionado entre o grupo que consiste em radicais hidrocarbilo em radicais hidrocarbilo em substituídos, nos quais um ou mais átomos de hidrogénio estão substituídos com um átomo de halogénio, radicais metalóide com substituintes hidrocarbilo em C. x -C 2a , nos quais o metalóide é Ref: JL/PE - 1784 seleccionado entre o Grupo IVA da Tabela Periódica dos Elementos, e radicais halogénio;(JR' Z _ 1 ) é um ligando de heteroátomo, no qual J é um elemento com número de coordenação três do grupo VA ou um elemento com número de coordenação dois do Grupo VIA da Tabela Periódica dos Elementos, cada R' é, de forma independente, um radical seleccionado entre o grupo que consiste em radicais hidrocarbilo em radicais hidrocarbilo em substituídos, nos quais um ou mais átomos de hidrogénio estão substituídos com um átomo de halogénio, e “z” é o número de coordenação do elemento J;cada Q e Q' é, de forma independente, halogénio, hidreto ou um hidrocarbilo em C 1 -C 20 substituído ou não substituído, um alcóxido, um arilóxido, uma amida, uma arilamida, uma fosfida ou uma arilfosfida, desde que, quando Q ou Q' é um hidrocarbilo, esse mesmo Q ou Q' é diferente de C 5 H 5 . y _ x R x ou Q e Q', em conjunto, são um alquilideno ou um hidrocarbilo ciclometalado e M' tem o mesmo significado que M;“y” é 0 ou 1 quando w é superior a 0;y é 1 quando w é 0 ;quando “y” é 1, B é um grupo covalente de ligação em ponte contendo um elemento do Grupo IVA ou VA;L é uma base de Lewis neutra quando “w” designa um número entre 0 e 3;e (B) um alumoxano, com as exclusões: i) a polimerização de etileno com um monómero vinílico aromático;e ii) quando o composto (A) é o dicloreto de (N-tbutilamino) (dimetil) (η 5 -2,3,4,5-tetrametilciclopentadienil) Ref: JL/PE - 1784 silanozircónio, a polimerização de etileno com 1-hexeno ou 4-metil-1-penteno.
2
Processo de acordo com a reivindicação 1, que é uma polimerização em fase líquida.
3
Processo de acordo com a reivindicação 2, no qual o etileno é submetido a uma zona reaccional a pressões entre 1,3 χ 10' 3 bar e 3 445 bar e a uma temperatura de reacção entre -100°C e 300°C.
4
Processo de acordo com a reivindicação 1, no qual a α-olefina é 1-buteno ou 1-octeno.
5
Processo de acordo com a reivindicação 1 ou a reivindicação 4, no qual o alumoxano é metilalumoxano possuindo um grau médio de oligomerização entre 4 e 25.
6
Processo de acordo com qualquer uma das reivindicações anteriores, no qual o polímero resultante possui uma razão Mw/Mn entre 1,5 e 15,0.
7
Processo de acordo com qualquer uma das reivindicações anteriores, no qual o polímero resultante possui um peso molecular médio em peso entre 1 000 e 5 milhões.
8
Utilização de um composto com a fórmula geral:(C 5 H, Ref: JL/PE - 1784 ou na qual M é Zr, Hf ou Tl;(C 5 H 5 . y . x R x ) é um anel ciclopentadienilo que está substituído com zero a cinco grupos R, “x” é 0, 1, 2, 3, 4 ou 5, designando o grau de substituição, e cada Ré, de forma independente, um radical seleccionado entre o grupo que consiste em radicais hidrocarbilo em C^-C^, radicais hidrocarbilo em C^-C^ substituídos, nos quais um ou mais átomos de hidrogénio estão substituídos com um átomo de halogénio, radicais metalóide com substituintes hidrocarbilo em C 1 -C 20 , nos quais o metalóide é seleccionado entre o Grupo IVA da Tabela Periódica dos Elementos, e radicais halogénio;(JR'z-1-y) é um ligando de heteroátomo, no qual J é um elemento com número de coordenação três do grupo VA ou um elemento com número de coordenação dois do Grupo VIA da Tabela Periódica dos Elementos, cada R' é, de forma independente, um radical seleccionado entre o grupo que consiste em radicais hidrocarbilo em Ο χ -Ο 20 , radicais hidrocarbilo em Ο χ -Ο 20 substituídos, nos quais um ou mais átomos de hidrogénio estão substituídos com um átomo de halogénio, e “z” é o número de coordenação do elemento J;cada Q e Q’ é, de forma independente, halogénio, hidreto ou um hidrocarbilo em C^-C^ substituído ou não substituído, um alcóxido, um arilóxido, uma amida, uma arilamida, uma Ref: JL/PE - 1784 fosfida ou uma arilfosfida, desde que, quando Q ou Q' é um hidrocarbilo, esse Q ou Q' é diferente de C 5 H 5 . y _ x R x ou Q e Q', em conjunto, são um alquiiideno ou um hidrocarbilo ciclometalado e M' tem o mesmo significado que M;“y” é 0 ou 1 quando w é superior a 0;y é 1 quando w é 0 ;quando “y” é 1, B é um grupo covalente de ligação em ponte contendo um elemento do Grupo IVA ou VA;e L é uma base de Lewis neutra quando “w” designa um número entre 0 e 3, como um componente de um sistema catalisador na polimerização olefínica de etileno com um monómero seleccionado entre uma α-olefina em C 3 -C 20 ou uma diolefina em C 5 -C 20 , com as exclusões: i) a polimerização de etileno com um monómero vinílico aromático;e ii) quando o composto (A) é o dicloreto de (N-tbutilamino) (dimetil) (η 5 -2,3,4,5-tetrametilciclopentadienil) silanozircónio, a polimerização de etileno com 1-hexeno ou 4-metil-l-penteno.
9
Utilização como reivindicada na reivindicação 8, numa polimerização em fase líquida.
10
Utilização como reivindicada na reivindicação 9, numa polimerização em fase líquida, na qual o etileno é submetido a uma zona reaccional a pressões entre 1,3 χ 10' 3 bar e 3 445 bar e a uma temperatura de reacção entre 100°C e 300°C.

Independent claims10

1,393 paragraphs in 190 sections, as filed

This invention relates to certain group IV B transition metal compounds of the periodic table, a catalytic system comprising a group IV B transition metal compound and an alumoxane, and a process using such catalytic system for the preparation of polyolefins, particularly polyethylene, polypropylene and ethylene and propylene α-olefin copolymers having a high molecular weight. 0 catalytic system is highly ac; low proportion of aluminum to group IV B transition metal as it catalyzes the production of a polyolefin containing low levels of catalyst residues.

As is well known, there are various processes and catalysts for homopolymerization or copolymerization of olefins. For many applications it is vitally important for a polyolefin to have a high average molecular weight for a relatively small molecular weight distribution. A high average molecular weight when accompanied by a low molecular weight distribution provides a high strength polyolefin or ethylene ocolefin copolymer.

Traditional Ziegler-Natta catalytic systems - a transition metal compound co-catalysed by an alkyl aluminum - are capable of producing olefins having a high molecular weight but a high molecular weight distribution.

More recently, a catalytic system has been developed in which the transition metal compound has, as follows: 1.Srfl990 <iv * v __ / 7 /

η.

two or more cyclopentadienyl ring ligands, such a transition metal compound being referred to as a metallocene, which catalyzes the transformation of olefin monomers into polyolefins. Accordingly, group IV B metallocene compounds, particularly titanocene and conirene zir have been used as the transition metal component in that metallocene containing the catalytic system for the production of polyolefins and ethylene copolymers. -olefins. When such metallocenes are co-catalysed with an alkyl aluminum - as is the case with a traditional Ziegler-Natta catalytic system - the catalytic activity of that metallocene catalytic system is generally too low to be of any commercial interest.

It is therefore well known that such metallocenes can be co-catalysed with an alumoxane - rather than alkyl aluminum - to provide a high activity metallocene catalytic system that catalyzes polyolefin production.

A wide range of metallocene-type group IV B transition metalide compounds have been designated as possible candidates for an alumoxane co-catalyzed catalytic system. Hence, although group IV B bis (cyclopentadienyl) transition metal compounds are preferred and metallocenes are rigorously investigated for use in metallocene / alumoxane catalysts for the production of polyolefins, suggestions have been made for mono compounds. transition metal tris (cyclopentadienyl) may also be effective. See, for example, US Pat. 4,522,982; 4,530,914 and 4,701,431. Those mono (cyclopentadienyl) transition metal compounds that have been considered as candidates for a metallocene / alumoxane catalyst are tri (halide) cycloentylene (cyclopentadienyl) trialkyls.

Ref: JL / PE - 1784

11 SEP. nineteen ninety

The most recent international publication No. WO 87/05887 describes the use of a composition comprising a coordinated transition metal to at least one cyclopentadienyl and at least one ligand heteroatom as a metallocene type component for use in a metallocene / alumoxane catalytic system for the polymerization of α-olefins. The composition is broadly defined as a transition metal, preferably from Group IV B of the Peridic Table which is coordinated with at least one cyclopentadienyl ligand and one to three heteroatom ligands, with the balance requirement of coordination being satisfied with cyclopentadienyl or hydrocarbyl. 0 The described metallo / alumoxane catalytic system is illustrated solely with reference to transition metal compounds which are group IV B bis (cyclopentadienyl) transition metal compounds.

More recently, at the Third North American Chemistry Congress held in Toronto, Canada in June 1988 »John Bercaw referred to efforts to use a coordinated Group III B transition metal compound for a bridged ligand. to a simple cyclopentadienyl heteroatom as a catalytic system for olefin polymerization.

Although some catalytic activity was observed under the conditions used, the degree of activity and properties observed in the resulting polymer were discouraging in believing that such a transfer metal compound could be used effectively in commercial polymerization processes.

There is still a need to discover catalytic systems that allow the production of high molecular weight polyolefins with a molecular weight distribution.

-310

Ref: Jl / PE - 1784 Low

SUMMARY GIVES INVENTION fe ^ 1990(

The catalytic system of this invention comprises a group IV B transition metal component of the Periodic Table of Elements (GRG Handbook of Chemistry and Physics, 68th ed. 1987-1988) and an alumoxane component that can be used in phase phase polymerization. solution, pasty or in bulk to produce a medium molecular weight high polyolefin and relatively low molecular weight distribution.

The group 1 'B' transition metal component of the catalytic system is represented by the general formula

Mod. 71-10000 ex. - 89/07

wherein: M is Zr, Hf or Ti and is at its highest oxidation state (+4, d ^ complex);

(G5H5_y_xRx) is 11111 eJlel cyclopentadienyl which is substituted by 0 to 5 substituent groups R 1, x is 0, 1> .2 3, 4 or 15 designating the degree of substitution and each of the substituent groups R is independently a radical selected from a group having consists of hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, hydroxy-4-substituted metalloid radicals *

Ref: JL / PE - 1784 Carbyl in 0 is selected from group IV

A of the Periodic Table of Elements, and halogen radicals or (θ5 ^ 5-.γ_χ &χ) is a cyclopentadienyl ring in which two adjacent groups R are linked to form the ring θ4 ~ ^ 20 c

to provide a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, fluorenyl or octahydrofluorenyl;

(JS *) ê 11111 heteroatom ligand where J is an element with a coordination number of three from group VA or an element with a coordination number of two from group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur and each S 'is independently a radical selected from a group consisting of

Mod. 71-10000 βχ. C 8 -C 8 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom and z is the coordinating number of the element J 1.

Each Q may independently be any univalent anionic ligand such as substituted or unsubstituted C 1 -C 2 halogen, hydride or hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphus provided that when Q is a hydrocarbyl Q is other than ^ 5 ^ 5_y_x^x or Q together may be an alkylidene or a hydrocarbyl with a cyclo metal or any other divalent anionic chelating ligand.

”Yw is O or 1 when w is greater than Qj y is 1 when w is 0; when "y" is 1, B is a covalent linking group containing a group IV A or VA element such as, but not limited to, a dialkyl, arylalkyl or di radical. aryl silicon or germanium, alkyl or aryl phosphine or amine or a hydrocarbyl radical such as methylene, ethylene and the like;

-5Ref: JL / PE - 1784

SEP. nineteen ninety

L is a Lewis base such as diethyl ether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine and the like; ew is a number from 0 to 3; L can also be an if. a transition metal composite of the same type so that the two center metals M and M * are bridged by Q and Q *, where M 'has the same meaning as M and Q' has the same meaning as Q These compounds are represented by the formula:

Mod. 71-10000 ex. -89/07

The alumoxane component of the catalyst may be represented by the formulas: (S1 -Al-O) ^; R4 (R4 -Al-O)mOr corresponding mixtures wherein R1 -R3 are independently a univalent anionic ligand such as C1-4 alkyl or H3let3 and is an integer ranging from 1 to about 50 and preferably from about 1 to about 5. 13 and 25 ·

Catalytic systems of the invention may be prepared by placing the group IV B transition metal componentw and the alumoxane component in common solution in a normally liquid alley or aromatic solvent, which is preferably suitable for use as a polymerization diluent for liquid phase polymerization of an olefin monomer.

A typical polymerization process of the invention -Ref: JL / ΡΕ - 1784

Such an olefin polymerization or copolymerization comprises the steps of contacting ethylene or Î ± -olefins G

-C2C alone or with other unsaturated monomers including C1 -C4 α-olefins (-5 '^ 2O' and or acetylenically unsaturated monomers alone or in combination with other olefins and / or other unsaturated monomers, with a catalyst comprising in a suitable polymerization diluent the group IV B transition metal component illustrated behind; and a methylalumoxane in an amount necessary to provide a molar ratio of aluminum to transition metal of from about 1: 1 to 20,000: 1 or greater; and reacting this monomer in pre. catalyst system at a temperature of from about -100 ° C to about 300 ° C for a time from 1 second to 10 hours to produce a polyolefin having an average molecular weight of about 1000 or less than about 100 ° C. 5-000,000 or greater and a molecular weight distribution of from about 1.5 to about 15 · 0.

Lower molecular weight species may be produced using reduced activity catalytic species; elevated temperatures and / or transfer agents such as hydrogen.

DESCRIPTION OF EORMA BE PERFORMED

Catalytic Component group transition metal component

IV B of the catalytic system is represented by the general formula:

-7Ref: JL / PE - 1784

R) is a cyclopentadienyl ring wherein: M is Zr, Hf or Ti and is in its oxy state. highest donation (+4, άθ complex);

substituted by 0 to five substituent groups R, x is 0, 1, 2, 3, 4 or 5 designating the degree of substitution and each substituent group R is independently a radical selected from the group consisting of C hydrocarbyl radicals. ] _- C20 ' frogacai3 hydrocarbyl suA compound wherein one or more hydrogen atoms is replaced by an act. halogen, metalloid radicals substituted by hydr. wherein the metalloid is selected from the IVA group of the Periodic Table of Elements and the halogen radicals or (Ç5 ^ 5_y_xílx) 0111 cyclopentadienyl ring wherein two adjacent R groups are attached forming the C 1 -C 6 Q ring to provide a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydrindenyl, fluorenyl or octahydrofluorenyl;

(JR ',) is a heteroatom ligand where J is

Λ »Λ. J is an element with a coordinating number of three from group VA or an element with a coordinating number of two from group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen preferred, and each R 'is independently a selec-8Ref: JL / PE - 1784 radical

11 $ T. 90 of the group consisting of C 1 -C 2 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom and z is the coordination number of the element J;

Each Q is independently any univalent anionic ligand such as halogen, hydride or hydrocarbons. substituted or unsubstituted bile, alkoxide, aryl.

oxide, amide, arylamide, phosphide or arylphosphide on the condition that when Q is a hydrocarbyl then Q is different from or both Q together may be a cycloalkylidene or a hydrocarbyl with metal or any other divalent anionic chelation ligand;

y is 0 or 1 when w is greater than 0 and y is 1 when w; = 0; when y is 1, B is a covalent linking group containing an element of group IV A or VA such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine or a hydrocarbyl radical such as methylene, ethylene and the like. L is defined as already indicated.

Examples of group B which are suitable as a constituent group of the group IV B transition metal component of the catalyst system are given in column 1 of Table 1 under heading B.

Examples of hydrocarbyl radicals for Q are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, monyl, decyl, cetyl, 2-ethylhexyl, phenyl, and analogues with the methyl group being Preferred Examples of halogen atoms for Q are chlorine, bromine, fluorine and iodine with chlorine being preferred. Examples of alkoxides and aryloxides for Q have methoxide, phenoxide and substituted phenoxides such as 4-methylphenoxide.

-9Ref: JL / PE - 1784

Examples of amides for Q include dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisopropylamide and the like. Examples of arylamides are diphenylamide and any other substituted phenylamides. Examples of phosphides for Q are diphenylphosphide, dicyclohexylphosphide, diethylphosphide, dimethylphosphide and the like. Examples of alkylated radicals for the Q together are methylidene, ethylidene and propylidene. Examples of group Q which are suitable as a constituent group or element of the group IV B transition metal component of the catalytic system are identified in column 4 of Table 1 under the heading

Suitable substituted hydrocarbyl and hydrocarbyl radicals which may be substituted as an R group by at least one hydrogen atom on the cyclo pentadienyl ring will contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, cyclic hydrocarbon radicals substituted by alkyl, aromatic radicals, alkyl substituted aromatic radicals and cyclopentadienyl rings containing one or more fused saturated or unsaturated rings. Suitable organometallic radicals which may be substituted by an R group with at least one hydrogen atom on the cyclopentadienyl ring include trimethyl silyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like. Examples of cyclopentadienyl ring groups (Ç5H5_y_xRx) Q.huh suitable as a constituent group of the group IV B transition metal component of the catalytic system are identified in column 2 of Table 1 under the heading (θςΗ

Suitable substituted hydrocarbyl and hydrocarbyl radicals which may be substituted as a group

R 'by at least one hydrogen atom in the ligand group

Ref; Heteroatom J will contain from about 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. Examples of heteroatom ligand groups (JR * _i_v) Q.who are appropriate w

as a constituent group of the group IV B transition metal component of the catalytic system are identified in column 3 of Table 1 under the heading (JR ' z ^).

Table 1 shows representative portions of the group IV transition metal component Β ”, the list is illustrative and should not be considered as limiting at any time. A number of end components can be formed by exchanging all possible combinations of the constituent portions. Illustrative compounds are: dichloride dimeti1sililtetrametileiclopentadienil tert-butylamido zircdnio dichloride, dimethylsilyl-tetramethyl-cyclopentadienyl-tert-butylamido hafnium dichloride, dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido zircdnio dichloride, dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido hafnium dichloride; dimethylsilyltrimethylsilylcyclopentadene nyl-tert-butylamido zirconium, dimethylsilyl tetramethylcyclopentadienylphenylamido zirconium dichloride, dichloride dimetilsililtetrametilciclopentadienilfenilamido hafnium di chloride metilfenilsililtetrametilciclopentadienil tert-butylamido zircdnio dichloride, metilfenilsililtetrametilciclopentadienil-tert-butylamido hafnium dichloride Me tilfenilsililtetrametilciclopentadienil-tert-butylamido hafnium dichloride, dimetilsililtetrametilciclopentadienil-pn-butiIfenilamido zircdnio dichloride, dimetilsililtetrametilciclopentadienil-pn-butilfenilamido hafnium. For illustrative purposes the foregoing compounds and exchangers of Table 1 do not include Lewis base ligands (1). The conditions under which bs ligand-containing complexes

-11Ref: JL / PE - 1784

11.SQW n / Lewis acids such as ether and dimers are from. terminated by the steric volume of ligands around the central metal. For example, the t-butyl group in MegSiCMe (Cl) (N-t-Bu) ZrCl 2 has higher steric requirements than the phenyl group in (Si) -le ^ C ^) (NPhJZrClg ^ S ^ The consequently not allowing ether coordination in the first compound Similarly, due to the growth of the steric agitation of the trimethylsilylcyclopentadienyl group in [Me2Si (Me ^ SiG ^ H ^) (N - ^ - BuJZrCl ^ 2 versuof the tetramethylcyclopentadienyl group in Me2 SiMe (Cl2) (N-Bu-ZrCl3), the first compound is dimeric and the last not.

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Ref: JL / PE - 1784 1I. /

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<td>♦ P</td><td>You</td><td>• laughs</td><td> 1</td><td>The</td><td>•P</td><td>• laughs</td><td>•P</td><td>•P</td><td>"P</td><td>•P</td><td>•P</td><td>Φ</td><td> |</td>

triethylplumbylcyclinomethylthio methylateido (when y = 0 pentadienyl)

-13 The<n, · d

02.646

Ref: JL / PE - 1784.

ro o

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>• laughs</td><td></td><td></td><td></td><td> 1</td><td></td><td>at the</td><td>ro</td>

<td></td><td></td><td></td><td></td><td></td><td>O</td><td></td><td>You</td><td>ε</td><td></td><td>O</td><td>• laughs</td><td>P</td><td></td><td>•P·</td><td> ··—-</td>

<td></td><td></td><td></td><td></td><td></td><td>•P</td><td>at the</td><td>P</td><td>ι — 1</td><td></td><td>• laughs</td><td>O:</td><td>X</td><td></td><td>ω</td><td>ο</td>

<td></td><td></td><td></td><td></td><td></td><td>ε</td><td>•H</td><td>laugh</td><td>• laughs</td><td></td><td>ε</td><td>O</td><td>ω</td><td></td><td>ο</td><td>Ρ</td>

<td></td><td></td><td>• laughs</td><td></td><td></td><td>1 — ί</td><td>ro</td><td> +=</td><td>P</td><td></td><td>I — i</td><td>ι — i</td><td>O</td><td>O</td><td>Ρ</td><td>Ό</td>

<td>• laughs</td><td></td><td></td><td>• laughs</td><td>You</td><td>*P</td><td>1 — í</td><td>O</td><td>THE</td><td></td><td>• laughs</td><td>• laughs</td><td>P</td><td>ro?</td><td>• Η</td><td>• Η</td>

<td></td><td>P</td><td>O</td><td>K</td><td></td><td>P</td><td>•P</td><td>ι — i</td><td> 1</td><td></td><td>P</td><td>Ç</td><td>O</td><td>• laughs</td><td>-Ρ</td><td>ι — 1</td>

<td>O</td><td>X</td><td>C5</td><td>O</td><td>O</td><td>Φ</td><td>P</td><td>• laughs</td><td>+ »L</td><td></td><td>ω</td><td>Φ</td><td>•P</td><td>5i</td><td>Φ</td><td>• laughs</td>

<td>OJ</td><td>P</td><td>Fl</td><td>P</td><td>Φ</td><td>•P</td><td>•P</td><td>O</td><td>• laughs</td><td>O</td><td>Ή</td><td>• laughs</td><td>•P</td><td>O</td><td>• Η</td><td>Φ</td>

<td>• Ρ laugh</td><td> 1¾</td>

<td>• laughs • Ρ</td><td>ο</td>

<td>φ</td><td>Ο</td><td></td><td>-ASS</td><td>φ</td><td>Ο</td><td></td><td>• laughs</td>

<td></td><td>ο</td><td></td><td> &</td><td>• Ρ</td><td>Ρ</td><td>laugh</td><td>Ο</td>

<td>t—</td><td>ro</td><td></td><td>Ρ</td><td>Ρ</td><td>ro</td><td>• laughs</td><td>Ρ</td>

<td></td><td>ro</td><td>ι — J</td><td>Ρ</td><td>ε</td><td>σ '</td><td>φ</td><td>• laughs</td>

<td></td><td>laugh</td><td>• Η</td><td>Φ</td><td>ro</td><td> —</td><td>Ρ</td><td>Α</td>

<td>• Ρ</td><td></td><td>ο</td><td></td><td>1 — ί</td><td>ο</td><td></td><td>φ ·</td><td>ro</td><td>γΡ</td><td></td><td>• laughs</td><td>r5</td><td> 1</td><td>ro</td>

<td>Ρ</td><td>Ρ</td><td>ρ</td><td>Ρ</td><td>Ρ</td><td>• ιΡ</td><td>Ç</td><td>-ρ</td><td>• Ρ</td><td>Φ</td><td>• Ρ</td><td>Ρ</td><td>• laughs</td><td>at the</td><td>Φ</td>

<td> 1</td><td>Ρ</td><td>φ</td><td>φ</td><td>«Γ-</td><td>Ρ</td><td>Ρ</td><td>• r—.</td><td> ·—!</td><td>• rH</td><td>ro</td><td>• Ρ</td><td>• laughs</td><td> *-</td><td>at the</td>

<td>ρ |</td><td>φ</td><td>Ρ</td><td>ε</td><td>'Ç</td><td>ηο</td><td>Φ</td><td>ηο</td><td>το</td><td>ηο</td><td>ASS</td><td>ηο</td><td>rr</td><td>laugh</td><td> 1</td>

• tetramstyldisiloxane ethylidene (both 0.)

1,1,4,4-tetramethyldisopropylidene (both ethylene)

13b

626^+6

Ref: JL / PE-178U

TABLE 1 (continued)

13c

Ref: Jl / PE - 1784

Mod. 71-10000 ex.-89/07

/ /

Generally bridged species of the group IV transition metal compound B (y = 1) are preferred. These compounds may be prepared by reacting a cyclopentadienyl lithium compound with a dihalo compound wherein a lithium halide salt is released and a monohalo substituent is covalently bonded to the cyclopentadienyl compound. 0 The cyclopentadiene reaction product thus substituted will then be reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for illustrative purposes, a lithium amide) wherein the halo element of the monohalo substituent group of the product The reaction reaction reacts to release a lithium halide salt and the amine portion of the lithium amide salt is covalently bonded to the cyclopentadienyl reaction product substituent. The resulting amine derived from the cyclopentadienyl product is then reacted with alkyl lithium reagent wherein the unstable hydrogen atoms on the carbon atom of the cyclopentadienyl compound and the nitrogen atom of the covalently bonded amine moiety react with the alkyl group of the alkyl lithium reagent to liberate alkane and produce a dilithium salt of the cyclopentadienyl compound. Accordingly, the bridged species of the Group IV B transition metal compound are produced by reacting the lithium salt of the cyclopentadienyl compound with a Group IV B transition metal, preferably a transition metal halide. of group IV B.

Non-bridged species of the group IV B transition metal compound may be prepared by reacting a cyclopentadienyl lithium compound and an amine lithium salt with a group IV B transition metal halide .

Suitable but not limiting group IV B transition metal compounds which may be used

-14 Ref: JL / PE - 1784

/ in the catalytic system of this invention include bridged species ("yM= 1) wherein the group B bridge is a dialkyl, diaryl or alkylaryl silane or methylene or ethylene. Examples of the most preferred species of bridged group IV B transition metal compounds are bridged compounds of dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene. Most preferred are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.

It The transition metal compounds of the It group

B which are illustrative of non-bridged species ('1and which may be used in the cationic systems of this invention are exemplified by pentamethylcyclopentadienyldi-butylphosphinodinethyl hafnium;

pentamethylcyclopentadienyldi-t-butylphosphinomethyl ethyl hafnium; cyclopentadienyl-2-methylbutoxide dimethyl titanium.

To illustrate the members of the group IV B transition metal component, any combination of the species is selected in Table 1. An example of the bridged species is dimethylsilylcyclopentadienyl-t-butylamido-dichloro zirconium; An example of a non-bridged species is cyclopentadienyl di-t-butylamido-dichlorozirconium.

The alumoxane component of the catalytic system is an oligomeric compound that can be represented by p

the general formula (R -Al-0)m which is a cyclic compound or eg

near. An alumoxane is generally a mixture of both linear and cyclic compounds. In the general formula of alumoxane

methyl, ethyl, propyl, butyl, pentyl or halide inrt is4

-15Ref: JL / FOOT 1784

Preferably R r, R ', R e and R são are each methyl and m m is at least 4. When an alkyl aluminum halide is used in the preparation of α2-5 lumoxane, a or more R may be halide.

As is well known, the alumoxanes po. can be prepared by various processes. For example, a trialkyl aluminum may be reacted with water as a wet inert organic solvent or the trialkyl aluminum may be contacted with a hydrated salt such as hydrated copper sulfate suspended in an inert organic solvent to produce an alumoxane. . In general, a trialkyl aluminum is reacted with a limited amount of water producing a mixture of both linear and cyclic alumoxane species.

Suitable alumoxanes which may be used in the catalytic systems of this invention are those prepared by hydrolysis of an alkylaluminum reagent; such as trimethylaluminum, triethylaluminum, tripopylaluminum; triisobutylaluminum, dimethylaluminum chloride, diisobutylaluminum chloride, diethylaluminum chloride and the like. The preferred alumoxane is methylalumoxane (MAO), particularly methylalumoxanes having a said average degree of oligomerization of 13 to 25%.

CATALYTIC SYSTEMS The catalytic system may include an alkylaluminum and water which may react at least partially with each other and / or with the metallocene compound outside a polymerization vessel in which a reaction may be processed in situ.

Catalytic systems used in the method of the invention comprise a complex formed by a mixture of

-16ULU7U

Ref: JL / PE - 1784

/ /

of a group IV B transition metal component with an alumoxane component. The catalytic system may be prepared by the addition of the required group IV B / transition metal component and alumoxane component to an inert solvent wherein the olefin polymerization may be carried out by a bulk phase polymerization process. solution or paste.

The catalytic system can be conveniently prepared by placing the selected group IV B transition metal component and the selected alumoxane component in any proportions in an aromatic hydrocarbon or alkane solvent - preferably one which is also suitable for use as a polymerization diluent. . When the hydrocarbon solvent used is also suitable as a polymerization diluent the catalytic system may be prepared in situ in the polymerization reactor.

Alternatively, the catalytic system may be prepared in concentrated form and added to the polymerization diluent in a reactor. Or, if desired, the components of the catalytic system may be prepared as separate solutions and added to the polymerization diluent in a reactor in appropriate proportions as required for a continuous liquid polymerization reaction process. Aromatic hydrocarbons and alkanes suitable as solvents for catalytic system formation and also as a polymerization diluent are exemplified by, but not necessarily limited to, chain hydrocarbons.!linear and branched such as isobutane, butane, pentane, hexane, heptane, octane, and the like, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and alkyl substituted aromatic and aromatic analogs and compounds such as benzene, toluene, xylene and the like.

-17Ref: L / PE - 1784

Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene and the like.

According to this invention one can obtain from one. overall, optimal results when the group IV B transition metal compound is present in the polymerization diluent at a concentration of from 0.0001 to 1.0 millimoles / liter diluent and the alumoxane component is present in an amount to provide a ratio mo. aluminum to metal transition from about 1: 1 to 20,000: 1. 0 Sufficient solvent should be such that it provides adequate heat transfer of the catalytic components during the reaction and allows a good mixture.

Catalytic system ingredients - Group IV IV transition metal, alumoxane and polymerization diluent may be added to the reaction vessel rapidly or slowly. The temperature maintained during contact of the catalytic components may vary within a narrow range, for example from -10 ° to 300 ° C. Higher or lower temperatures may also be used.

Preferably, during formation of the catalytic system, the reaction is maintained at a temperature of 25 to 100 ° C, preferably 25 ° C.

At any time, the individual catalytic system components as well as the catalytic system, once formed, are protected from oxygen and moisture. Thus, the reactions are carried out in an oxygen and moisture free atmosphere and when the catalytic system is collected separately it is collected in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are carried out in the presence of a dry and inert gas such as, for example, helium or nitrogen.

-18Ref: JL / PE - 1784.0 /

POLYMERIZATION PROCESS

In a preferred embodiment of the process of this invention, the catalytic system is used in the polymerization of liquid phase (slurry, solution, suspension or bulk phase and corresponding combinations), high pressure fluid phase or gas phase of an olefin monomer. These processes can be used individually or in series. Liquid phase processes comprise the steps of contacting an olefin monomer with the catalytic system in an appropriate polymerization diluent and reacting said monomer in the presence of said catalytic system for a time and temperature sufficient to produce a high molecular weight polyolefin.

Mod. 71-10000 ex.-89/07

The monomer of such a process may comprise isolated ethylene for the production of a homopolyethylene or ethylene in combination with a 3'-olefin having 3 to 20 carbon atoms for the production of an ethylene-copolymer.0olefin. Elevated o-olefin homopolymers such as propylene, butene, styrene and corresponding copolymers with ethylene and / or C1- or higher Î ± -olefins and diolefins may also be prepared. The most preferred conditions for ethylene homo- or co-polymerization are those in which ethylene is subjected to a reaction zone at pressures between 0.019 psia and 50,000 psia and the reaction temperature is maintained at about -100 ° C. ° and 300 ° C. The molar ratio of aluminum to transition metal is preferably 1: 1 to 18,000: 1. A preferred range is 1: 1 to 1000: 1.

reaction time is preferably between 1 min and 1 hour. Without limiting in any way the scope of the invention, a process for carrying out the process of the present invention is as follows: In a stirred tank reactor a liquid 1-butene monomer is introduced. The catalytic system is introduced via piping into either liquid or vapor phase.

-19Ref: JL / PE - 1784

The supply of ethylene gas is carried out both in the reactor vapor phase and in the liquid phase spread as is well known in the art. The reactor contains the liquid phase which is composed substantially of liquid 1-butene together with dissolved ethylene gas and a vapor phase containing vapors of all monomers. Reactor temperature and pressure can be controlled via reflux or vaporization of the o-olefin monomer (self-cooling) as well as by cooling coils, car coatings, etc. The polymerization rate is controlled by the catalyst concentration. The ethylene content of the polymeric product is determined by the ratio of ethylene to 1-butene in the reactor, which is controlled by manipulating the loading rates of these components to the reactor.

EXAMPLES

In the examples illustrating the practice of the invention the analytical techniques described below were used for the analysis of the resulting polyolefin products. Molecular weight determinations for polyolefin products were prepared by Gel Permeation Chromatogra phy (GPO) according to the following technique. Molecular weights and molecular weight distributions were measured using a gel permeation waters 150 chromatograph equipped with a differential refractive index detector and a Chromatix KMX-6 online light scattering photometer. The system was used at 135 ° C with 1,2,4-trichlorobenzene as the mobile phase. Shodex polystyrene gel columns 802, 803, 804 and 805 (Showa Penko America, Inc.) were used. This technique is discussed in Liquid Chromatography of Polymers and Related Materials III, J. Gazes editor, Mareei Pekker, 1981, p. 207 which is incorporated herein by reference. No corrections were made for column expansion; however, they are based on generally accepted standards.

-20Ref '; JL / PE - 1784

National Bureau of Standards Polyethylene 1484 and anionically produced hydrogenated polypropylene (an alternative ethylene-propylene copolymer) corrections which for Mw / Mn (= MWD) were less than 0.05 units Mw / Mn was calculated from of elution times. Numerical analyzes were performed using the Beckman / CIS program known as LALLS® in conjunction with standard gel permeation packaging run on an HP 1000i computer.

The following examples illustrate the specific embodiments of the invention and in no way limit the scope of the invention.

All processes were performed under inert atmospheres of helium or nitrogen. Solvent choices are often optional, for example, in many cases either pentane or 30-60 petroleum ether may be transferred. Lithium amides were prepared from corresponding amines and both n-Buli and MeLi. Published methods for the preparation of LiHC ^Me ^ include CM Pendrick et al. Organometallics, 3,819 (1984) and PH KShler and KH Doll, Z. Naturforsch, 376, 144 (1982). Other lithium-substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and n-Buli or Meli or by reaction of Meli with the fulvene itself. ZrCl 3 and HfCl 4 were purchased from both Aldrich Chemical Company and Cerac. Amines, silanes and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by both Sherring and Ethyl Corp.

EXAMPLES AL OF COMPONENTS B AND GROUP IV B TRANSITION METAL

EXAMPLE A

Compound A; Part.l. Me · HCl · Li (10.Og, 0.078 mol)

-21Ref: JL / PE - 1784 was slowly added to Me2SiCl2 (H-5 mL, 0.095 mol, in 225 mL of tetrahydrofuran (thf) solution). The solution was stirred for one hour to ensure a complete reaction. The solvent thf was then removed via a vacuum tube until cold stored at-196 ° C. Pentane was added to precipitate LiO1. The mixture was filtered through Gelite. The solvent was removed from the filtrate. MeOH / HCl SiMeCl (15-34 g, 0.071 mol) was recovered as a pale yellow liquid.

Part 2. Me4HC5Yes it is2Gl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHR-t-Bu (3-68 g, 0.047 mol, -100 ml thf). The mixture was stirred overnight. The thf was then removed via a cold vacuum tube at -196 ° C. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through celite. The solvent was removed from the filtrate. Me2Si (Me ^HCl ^) (HN-V-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.

Part 5 * MeSi (Me4Hg5) (11.14 g, 0.044 mol) was diluted with -100 ml EtgO. MeLi (1.4 M, 64 mL, 0.090 mol) was added slowly. The mixture was stirred for 1/2 hour after the final addition of MeLi. The ether was reduced to prior volume to filter the product. 0 product, [Me2Yes it is'4C, j) (Nt-Bu) J Li2, was washed with several small portions of ether and then dried in vacuo.

Part 4. Me2Yes it is4Ç5) (Nt-Bu) Li2 (3-0 g, 0.011 mol) was suspended in 150 ml Et20 ZrCl4 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum tube until cold to -196 ° C. Pentane was added to precipitate LiCl. The mixture was filtered through Gelite twice. Pentane was significantly reduced by

-2202040

Ref: JL / PE - 1784

/ volume and the pale yellow solid was filtered and taken with solvent.

Me2Si (Me ^ C ^) (N - ^ - Bu) ZrGl2 (1.07 g, 0.0026 mol) was collected. MegSiCMe ^ G ^) (N - ^ - Bu) Zr012 An additional residue was collected from the filtrate by repeating the recrystallization process. Total yield, 1.94 g, 0.0047 mol.

EXAMPLE B

Compound B: The same procedure as Example A is followed for the preparation of compound A except for the use of HfCl2 instead of ZrCl2 in Part 4. In this manner, when [Me2Si (Me ^ C ^) - (Nt-Bu)] II2 HCl (2.13 g, 0.0081 mole) and HfCl2 (2.59 g, 0.0081 mole) were used to yield MegSi3CMe.4Ç5) (Nt-Bu) HfCl2 (0.98 g, 0.0020 moles).

EXAMPLE C

Compound C: Part 1. Me2SiCl2 (7.5 ml, 0.062 mol) was diluted with -30 ml thf. A solution of N-BuHHCl C Li (7.29 g, 0.056 mol, -100 mL thf) was slowly added and the mixture was allowed to stir overnight. The thf was removed via a vacuum tube to cold at -196 ° C. Pentane was added to precipitate LiCl and the mixture was filtered through Gelite. The pentane was removed from the filtrate leaving a pale yellow liquid, m-BuH2 Cl2 SiMegCl (10.4 g, 0.04 moles).

Part 2. To a solution of LiHN-t-Bu (3.83 g, 0.048 moles, -125 ml) was added t-BuH ^C C ^ SiMe ^l (10.4 g, 0.048 moles) dropwise. The resulting solution was allowed to stir overnight. The thf was removed via a vacuum tube until cold at -196 ° C. Pentane was added to precipitate LiCl and the mixture was filtered through Celite.

pentane was removed from the filtrate leaving a pale yellow liquid, Me2Si (ίί-ΒιιΗΗ σ ^) (NH-Ij-Bu) (11.4 g, 0.045 moles).

-231784 , £/ <0.

UZU4U

Ref: JL / PE

Part 5 · Me2Si (t-BuH)4G5) (NH-t-3u) (11.4 g, 0.04 mol) was diluted in ~ 100 ml Et.2O. MeLi (1.4 M, 70 mL, 0.098 mol) was slowly added. The mixture was allowed to stir overnight. The ether was removed via a vacuum tube to cold at -196 ° C leaving a pale yellow solid [Me2Si (t-BuH)3Ç5) (Nt-Bu)] Li2 (11.9 g, 0.045 moles).

Part 4 · Suspended [l'le2Si (Jt-BuH ^C C) (N-; t -Bu)] Li2 (3.39 g, 0.015 mol) in -100 ml EtgO. ZrCl 4 (3.0 g, 0.015 moles) was slowly added. The mixture was allowed to stir overnight. The ether was removed and pentane was added to precipitate the LiCl. The mixture was filtered through Gelite. The pentane solution was reduced in volume and the solid was filtered off and washed several times with small amounts of pentane. 0 product of the empirical formula Me2Si (t-BuH)5G5) (Ni-Bu) ZrCl2 (2.45 g, 0.0059 moles) was isolated.

EXAMPLE D

Compound D: The same procedure as Example C was followed for the preparation of compound C except for the use of Part 4 HfCl4.2Si (t ^ -BuH. Ç5) (Nt-Bu)] Li2 (5.29 g, 0.012 moles) were used, the product of the empirical formula Me was produced.2Si (Jt-BuH ^ C ^) (Ut-Bu) HfGl2 (1.86 g, 0.0057 moles).

EXAMPLE E

Compound E: Part 1. Me2SiCl2(7-0 g, 0.054 mol) was diluted with -100 ml ether. Me 2 SiC 4 H 4 Li (5 · 9 g, 0.041 moles) was slowly added. Approximately 75 ml of thf was added and the mixture was allowed to stir overnight. The solvent was removed via a vacuum tube to cold at -196 ° C. Pentane was added to precipitate the LiCl. Mix the mixture with Gelite. The solvent was removed from the filtrate providing Me.2Si (Me ^ SiC ^ H ^) C1 (8.1 g, 0.055 moles)

-24Ref; JL / PE - 1784 • 1.Sai790.

) / 'as a pale yellow liquid.

Mod. 71-10000 ex.-89/07

Part.2 MegSiMe ^ SiC ^H ^ JCl (3 · 96 g, 0.017 mol) was diluted in 50 mL of ether. LiHN-jt-Bu (1.36 g, 0.017 moles) was added slowly and the mixture was allowed to stir overnight. The ether was removed under vacuum and pentane was added to precipitate the LiCl. The mixture was filtered through Celite and pentane was removed from the filtrate. MeOH (SiC ^H ^) (NH-_-Bu) (3.7 g, 0.014 mol) was isolated as a pale yellow liquid.

Part 3 «Diluted Me2Si (Me 2 SiO 4 H 4) (δ-t-Bu) (m. (3 x 7 g, 0.014 mol) in ether. MeLi (25 ml, 1.4 M in ether, 0.035 mol) was slowly added. The mixture was stirred at room temperature for 1.5 hours after the final addition of MeLi. The ether was removed by vacuum yielding 4 x 6 g of a white solid formulated as Li.2 [MegSiMe (SiC ^H ^) (N- [Bu])]. 3/42θ β o unreacted MeLi that has not been removed from the solid.

Part 4. Suspended (Nt -Bu) (Nt-Bu)] .3 / 4Et20 (1.44 g, 0.0043 moles) in -50 ml ether. ZrCl 4 (1.0 g, 0.0043 moles) was added slowly and the reaction was allowed to stir for a few hours. The solvent was removed via vacuum and pentane was added to precipitate 0 LiCl. The mixture was filtered through Celite and the filtrate was reduced in volume. The vial was placed in the freezer (-40 ° C) to maximize precipitation of the product. The solid was filtered off yielding 0.273 g of an off-white solid. 0 The filtrate was further reduced in volume and filtered to provide an additional 0.345 g for a total of 0.62 g of the compound of the empirical formula Me.2Si (Me ^ SiO ^ H ^) (N-t-Bu) ZrCl2. The x-ray crystal structure of this product reveals that the compound is dimeric in nature.

-25Ref: JL / PB - 1784

Z

Mod. 71-10000 ex. - 89/07

EXAMPLE g

Compound P: Part 1. Me 4 Cl 2 SiMe 4 was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. LiHNPh (4-6 g, 0.0462 moles) was dissolved in -100 mL of thf. Me.HC was slowly addedçYes it is"

5 2

Cl (10.0 g, 0.0466 moles). The mixture was allowed to stir overnight. The thf was removed via vacuum. Petroleum ether and toluene were added to precipitate the LiCl and filyl; The mixture was extracted through Celite. The solvent was removed leaving a dark yellow liquid, Me2Si (Me ^HCl ^) (NHPh) ((10.5 g, 0.0387 moles).

Part 3. Diluted Me and Me2Yes it is4HC5) (NPHh) (10.5 g, 0.0387 moles) in -60 ml ether. Mls Li (1.4 M in ether, 56 mL, 0.0784 moles) was slowly added and the reaction allowed to stir overnight. The resulting white solid, Li2Me2Yes it is4Ç5) (NPh) .3 / 4Et20 (11.0 g) was filtered and washed with ether.

Part 4- Suspended Li2[Me2Yes it is4Ç5) (NPh) .3 / 4 Et20 (2.81 g, 0.083 mol) in -40 ml ether. ZrCl was slowly added4 (1.92 g, 0.0082 moles) and the mixture was allowed to stir overnight. The ether was removed under vacuum and a mixture of petroleum ether and toluene was added to precipitate the LiCl. The mixture was filtered through Celite the solvent mixture was removed via vacuum and pentane was added. The mixture was placed in the freezer at -40 ° C to maximize precipitation of the product. The solid was then filtered and washed with pentane. 0 MegSiCMe (j) (NPh) ZrCl2.Et20 It was collected as a pale yellow solid (1.89 g).

EXAMPLE G

Compound G: The same procedure was followed as for

-26Ref: JL / PE - 1784

Example P for the preparation of compound? except for the use of HfCl ^ instead of ZrCl ^ in Part 4. Thus ** when Li2 Me2Si (Me2 Cl2) (NPh) .3 / 4Et20 (2.0 g, 0.0059 mol) and HfG1 (1.89 g, 0.0059 mol) were used, produced

Me2Yes it is4Ç5) (NPh) HfCl2.1 / 2Et20 (1.70 g).

Mod. 71-10000 ex. - 89/07

EXAMPLE H

Compound H: Part 1. MePhSiCl was diluted2 (14.9 g, 0.078 mol) in -250 ml of thf. Me 4 Cl 2 HCl (10.0 g, 0.078 moles) was slowly added with a solid. The reaction solution was allowed to stir overnight. The solvent was removed via a vacuum tube to cold at -196 ° C. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through celite and the pentane was removed from the filtrate. MePhSi (Me ^C ^HÍCl) (20.8 g, 0.075 moles) was isolated as a viscous yellow liquid.

Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in -100 ml of thf. MePhSi ((Me ^C ^ ^HjCl (15.0 g, 0.054 mol)) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed via vacuum. of petroleum to precipitate the LiCl. The mixture was filtered through celite and the filtrate evaporated.

MePhSi (Me ^C) (NH-t-Bu) (16.6 g, 0.053 mol) was collected as an extremely viscous liquid.

Part 3. MePhSi (Me MeG ^H) (NH-; t-Bu) (16g, 0.053 moles) was diluted with -100 ml ether. MeLi (76 ml, 0.106 moles, 1.4 M) was slowly added and the reaction mixture was allowed to stir for -3 hours. The ether was reduced in volume and the lithium salt was filtered off and washed with penta to yield 20.0 g of a pale yellow solid formulated as liq.2(MePhSi (Me 4 G 4) (N-jt-Bu)] .3 / 4Et20.

-27Ref: JL / PE - 1784

SERW ^

Part 4. L ± has been suspended2 [l-lePhSi (Me ^) (Nt-BuJ_ 3/4Et20;(5.0 g, 0.0131 moles) in -100 ml Et20 ZrCl 4 (3x6g, 0.0131 moles) was slowly added. The reaction mixture was allowed to stir at room temperature for -1 hours when the reaction mixture slowly darkened. The solvent was removed via vacuum and a mixture added. from: ether from: petroleum and toluene. The mixture was: filtered through Celite to remove LiCl. The filtrate was evaporated to near dryness and filtered. The white solid was taken with petroleum ether. 0 yield of the product, MePhSi (Me ^C ^) (N - Bu) ZrCl2, was 3.82 g (0.0081 mol).

EXAMPLE I

Compound I: Li (MePhSiMe (Cl) (N-t-Bu) J. 3 / 4Et2As described in Example H for the preparation of compound H, Part 3 ·

Part 4. Suspended Li2 pJSi (Me ^ C ^) (N-jfc-Bu) J • 3 / 4Et20 (5.00 g, 0.0131 moles) in -100 ml Et2HfCl 4 (4.20 g, 0.0131 moles) was slowly added and the reaction mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added to precipitate the LiCl. The mixture was filtered through celite. The filtrate was evaporated to near dryness and filtered.

Almost white solid was washed with petroleum ether. Recoido MePhSi (Me4O5) (N- £ -Bu) HfCl2 (3.54 g, 0.0058 moles).

EXAMPLE J

Compound J: MePhSiMe (C ^) (N-t-Bu) HfMe was prepared.2 by adding a stoichiometric amount of MeLi ((1.4 M in ether) to MePhSi (Me2 Cl2) (Nt-Bu) HfCl2 suspended in ether. The white solid could be isolated in near quantitative yield.

-28Z uzoq-u

Ref: JL / PE - 1784

EXAMPLE K

Compound K: Part 1. Me 4 G 5 SiMe 2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.

Part 2. Me 2 Cl 2 Si 4 Cl (10.0 g, 0.047 moles) was diluted with -25 ml Et 2 O. LiHNG ^H ^-pn-Bu.l / 10Et 2 O (7.57 g, 0.047 moles) was slowly added. The mixture was allowed to stir for -3 hours. The solvent was removed via vacuum. Petroleum ether was added to precipitate the LiCl and the mixture was filtered through Gelite. The solvent was removed leaving an orange viscous liquid Me 2 Si (Me 2 Cl 2 H) (HNC 4 H 4 -pn-Bu) (12.7 g, 0.039 mol).

Part 3. (SiCn-H) (HNC-pn-Bu) (12.7 g, 0.039 mol) was diluted with -50 ml of ΕΪ2Ο. MeLi (1.4 M, 55 ml, 0.077 mol) was slowly added. . The mixture was allowed to stir for -3 hours. The product was filtered off and washed with ΕΪ2θ yielding Li2 [Me2 Si (Me2 Cl2) (NC1 H4 -pn-Bu)}. 3/4. <2 <3 as a white solid (13.1 g, 0.033 moles).

Part 4. (Me ^ C ^) (ΝΟθΗ ^ -ρ-n-Bu)] · 3 / 4ΕΪ2θ (3 · 45 g, 0.0087 mol) was suspended in -50 ml EtgO · A Slowly added to ZrCl ^ (2.0 g, 0.0086 mol) and the mixture was allowed to stir overnight. The ether was removed in vacuo and petroleum ether was added to precipitate LiCl. The mixture was filtered through celite. The filtrate was evaporated to dryness to afford a yellow solid which was recrystallized from pentane and identified as Me 2 Si (Me 2 Cl 2) (NC 2 H 4 -pn-Bu 2 Cl 2 · 2 / Et 2 O (4-2 g).

EXAMPLE L

Compound L: Li was prepared2 (Si (Me (O) O)) (NC1 H4 -pn-Bu) .3 / 4Et2 O as described in Example K for the preparation of compound K, Part 3 ·

-29i. SJ1990.

' /

62646

Ref: JL / PE - 1784

Part 4. Suspended Li ^ [Me2Si (Ke ^ C ^) (Ν0θΚ ^ -ρ-n-Bu) J .3 / 4Et2O (3 · 77 g, 0.10095 moles) in ~ 50 ml EtgO. HfCl 4 (3-0 g, 0.0004 moles) was slowly added as a solid and the mixture was allowed to stir overnight. The ether was removed via vacuum and petroleum ether was added to precipitate the LiCl. Mixture was filtered through Celite. Petroleum ether was removed via vacuum affording an off-white solid which was recrystallized from pentane. 0 products have been identified as Me2Si (Me ^ C ^) (ΝΟθΗ ^ -ρ-n-Bu) HfCl2 (1-54 g, 0.0027 moles).

EXAMPLES 1-34 PE POLYMERIZATION

EXAMPLE I

Mod. 71-10000 ex.-89/07

Polymerization - The polymerization was performed in a 1 liter autoclave reactor equipped with a paddle stirrer, an external temperature control water tank, a regulated supply of nitrogen, ethylene, propylene, 1-butene and hexane. and an inlet for the introduction of other solvents, transition metal compound, alu moxane solutions. The reactor was previously dried and degassed prior to use. Typical processing consisted of injecting 400 ml toluene, 6 ml 1.5 M MAO and 0.23 mg of compound A (0.2 ml of a solution of 11.5 mg in 10 ml of toluene) 4 into the reactor. The reactor was then heated to 80 ° C and ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction was stopped by rapid cooling and system ventilation. The solvent was evaporated from the polymer by nitrogen stream. Polyethylene was collected (9 · 2 g, Molecular Weight = 257,200, Molecular Weight Distribution = = 2,275).

EXAMPLE 2

Polymerization - Compound A

-30Hello! B4b

Ref: JL / PE - 1784. ,z<Y <1990 / y / / ' x /

The polymerization was carried out as in Example 1 with the following changes: 300 ml toluene, 3 ml 1.5 Μ MA0 and 0.115 mg of compound A (0.1 ml of 11.5 mg toluene solution in 10 ml). The polyethylene was collected. lene (3.8 g, Molecular Weight = 359.800, Molecular Weight Distribution = 2.425) ·

10,

Mod. 71-10000 ex. -89/07

EXAMPLE 3

Polymerization - Compound AA Polymerization was carried out as in Example 2 using identical concentrations. The difference involved is that the reaction develops at 40 ° C instead of 80 ° C as in the previous example. Polyethylene (2.4, Molecular Weight = 635,000, Molecular Weight Distribution = 3,445) was collected.

EXAMPLE 4

Polymerization - Compound A. Polymerization was carried out as in Example 1 except using 300 ml of hexane instead of 400 ml of toluene. Polyethylene (5 · 4 g, Molecular Weight = 212,600, Molecular Weight Distribution = 2,849) was collected ·

EXAMPLE 5

Polymerization - Compound A Using the same reactor and generally the same procedure as in Example 1, 300 ml of toluene, 200 ml of propylene, 6.0 ml of MA0.1.5 M and 0.46 mg of compound A (O. 4 ml of a toluene solution 11; 5 mg in 10 ml). The reactor was warmed to 80 ° C, ethylene (60 ρβΐ) was added, β was allowed to proceed for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 13 · 3 g of an ethylene propylene copolymer (Molecular Weight = 24,900, Molecular Weight Distribution = 2-027, 73 · 5) was collected.

-31b2b4b

Ref: JL / PE - 1784

UNDER / 100% IR).

Mod. 71-10000 ex.-89/07

EXAMPLE 6

Polymerization - Compound Polymerization was carried out as in Example 5 except for the following changes: 200 ml of toluene and 0.92 ml of compound A (0.8 ml of 11.5 mg toluene solution in 10 ml). The reaction temperature was also reduced to 50 ° C. An ethylene propylene copolymer (6.0 g, Molecular Weight = 83.100, Molecular Weight Distribution = 2.370, 75.7 SCB / 100 ° C per IR) was collected.

EXAMPLE 7

Polymerization - Compound A Using the same reactor and generally the same procedure as in Example 1, 150 ml toluene, 100 ml 1-butene, 6.0 ml 1.5 M MAO and 2.3 mg compound A (2.0 ml) were added to the reactor. ml of a toluene solution

11.5 mg in 10 ml). The reactor was heated to 50 ° C, ethylene (65 psi) was introduced and the reaction was allowed to proceed for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of toluene, 25.4 g of an ethylene-butene copolymer (Molecular Weight = 184,500, Molecular Weight Distribution = 3,424,

23.5 SGB / 10000 ppr15C NMR and 21.5 SCB / 100% by IR).

EXAMPLE 8

Polymerization - Compound The polymerization was carried out as in Example 7 except with the following changes: 100 ml of toluene and 150 ml of 1-butene. An ethylene-batená copolymer% ≤ 30.2 g, Molecular Weight = 143.500, Molecular Weight Distribution = 3.097, 30.8 SCB / 100 ° C was collected per15C NMR and 26.5 SCB / 100 ° C by IR).

-3262646

Ref: JL / PE - 1784 'S & 1920 <

EXAMPLE 9

Polymerization - Compound AA Polymerization was carried out as in Example 7 except with the following changes: 200 ml toluene, 8.0 ml 1.0 M MAO, and 50 ml 1-butene. An ethylene-butene copolymer (24 * 9 g, Molecular Weight = 163.200, Molecular Weight Distribution = 3 · 29θ, 23.3 SCB / 100 ° C) was collected by15C NMR and 18.9 SCB / 100 ° C by IR).

EXAMPLE 10

Polymerization - Compound A. Polymerization was carried out as in Example 9 except replacing 200 ml of toluene with 200 ml of hexane. An ethylene-butene copolymer ((19.5 g, Molecular Weight = 150,600, Molecular Weight Distribution = 3,510, 12.1 SCB / 100 ° C) was collected per15NMR and 12.7 SCB / 100 ° C by IR).

EXAMPLE 11

Polymerization - Compound A. Polymerization was carried out as in Example 10 except with the following changes: 150 ml hexane and 100 ml 1-butene. An ethylene-butene copolymer (16.0 g, Molecular Weight = 116,200, Molecular Weight Distribution = 3,158, 19.2 SCB / 100 ° C was collected per15NMR and 19-4 SCB / 100 ° C by IR).

EXAMPLE 12

Polymerization - Compound A Using the same reactor and the same general procedure as described above, 400 ml of toluene, 5-0 ml of 1.0 M MAO and 0.2 ml of a solution of a pre-activated compound A (11.5 mg of compound A dissolved in 9-0 ml of toluene and 1.0 ml of 1.0 M MAO) to the reactor. The reactor was heated to 80 ° C, ethylene (60psi) was introduced and allowed to

-33Ref: JL / PE-1784VSH 1990 '

The reaction was continued for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 5.4 g of polyethylene (Molecular Weight = 285,000, Molecular Weight Distribution = 2,808) was collected.

Mod. 71-10000 ex. - 89/07

EXAMPLE 15

Polymerization - Compound A Polymerization was performed as in the Example except for aging of compound A for one day. The ethylene powder (2.0 g, Molecular Weight = 260,700, Molecular Weight Distribution = 2,738) was collected.

EXAMPLE 14

Polymerization - Compound A Using the same reactor and the same general procedure as described above, 400 ml of toluene, 0.25 ml of 1.0 M MAO and 0.2 ml of a solution of pre-activated compound A (11.5 mg of compound A dissolved in 9 * 5 ml toluene and 0.5 ml 1.0 M MAO) to the reactor. The reactor was heated to 80 ° C, ethylene (60 psi) was introduced and the reaction allowed to proceed for 50 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 1.1 g of polyethylene (Molecular Weight = 479,600, Molecular Weight Distribution = 5-130) was collected.

EXAMPLE 15

Polymerization - Compound A Using the same reactor and the same general procedure as described above, 400 ml of toluene and 2.0 ml of a pre-active compound A solution of (11.5 mg of compound A dissolved in 9-5 ml) were added to the reactor. toluene (1.5 ml MAO 1.0 M). The reactor was heated to 80 ° C, ethylene (60 psi) was introduced and the reaction was allowed to proceed for 30 minutes followed by rapid cooling and ventilation of the system. After evaporation of the solvent, recover.

-34Ref: JL / PE - 1784

1.6 g of polyethylene (Molecular Weight = 458,800 ', Molecular Weight Distribution = 2,037) ·

Mod. 71-10000 βχ.-89/07

Example 16

Polymerization - Compound A Using the general procedure described above, 400 ml of toluene, 5.0 ml 1.0 MMAO, 0.23 mg of compound A (0.2 ml of toluene solution) was added to the reactor.

11.5 mg in 10 ml). The reactor was heated to 80 ° C, ethylene (400 psi) was introduced and the reaction allowed to proceed for 30 minutes followed by rapid cooling and system ventilation. After evaporation of the solvent, 1θ · 4 g of polyethylene (Molecular Weight = 343,700, Molecular Weight Distribution = 3,674) was collected.

Example 17

Polymerization - Compound A Polymerization was performed in a stirred 100 ml stainless steel autoclave equipped to perform polymerizations at pressures up to 40,000 psi and temperatures up to 300 ° C.

The reactor was purged with nitrogen and heated to 160 ° C. Solutions of compound A and alumoxane were prepared in separate vials. A storage solution was prepared by dissolving 26 mg of compound A in 100 ml of toluene. Compound A solution was prepared by dissolving 0.5 ml of the storage solution in 5.0 ml of toluene. The alumoxane solution consisted of 2.0 ml of a 4% MA0 solution added to 5-0 ml of toluene. The solution of compound A was added to the alumoxane solution, then 0.43 ml of the mixed nitrogen pressure solutions were transferred to a constant volume injection tube. The autoclave was pressurized with ethylene at 1784 bar and stirred at 1500 rpm. The mixed solutions were injected into a stirred reactor under pressure at a temperature rise of 4 ° C. The temperature and pressure

-35 ^ Sffi

Ref: JL / PE - 1784 were recorded continuously for 120 seconds at which time the autoclave contents were subjected to rapid ventilation in a recipient vessel. The reactor was washed with xylene to recover any remaining additional polymer. These washes were combined with the polymer released when the autoclave was vented to produce 0.7 g of polyethylene (Molecular Weight = 245,500 Molecular Weight Distribution = 2,257).

Mod. 71-10000 ex. - 89/07

EXAMPLE 18

Polymerization - Compound B Using the general procedure described in Example 1, 400 ml of toluene, 5.0 ml of 1.0 M- MAO and 0.278 mg of compound B (0.2 ml of 13.9 mg toluene solution in 10 ml) were added to the reactor. ml). The reactor was heated to 80 ° C and ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 10 minutes. The reaction was quenched by rapid cooling and ventilation of the system. The solvent was evaporated from the polymer through a stream of nitrogen. Polyethylene (9 * 6 g, Molecular Weight = 241,200; Molecular Weight Distribution> 2,628) was collected.

Example 19

Polymerization - Compound C Using the general procedures described in Example 1, 300 ml of toluene, 4.0 ml of 1.0 M MAO and 0.46 mg of compound C (0.4 ml of a solution of toluene 11.5 mg in 10 ml) were added to the reactor. The reactor was heated to 80 ° C and ethylene was introduced into the system. The reaction; The polymerization time was limited to 30 minutes. The reaction ceased by rapid cooling and system ventilation. The solvent was evaporated from the polymer by a stream of nitrogen. Polyethylene (1.7 g, Molecular Weight = 278,400; Molecular Weight Distribution = 2,142) was collected.

-36Ref: JL / PE - 1784

1Q

Mod. 71-10000 βχ.-89/07

EXAMPLE 20

Polymerization - Compound D Using the general procedure described in Example 1, 400 ml of toluene, 5-0 ml of 1.0 M MAO and 0.278 mg of compound D (0.2 ml of a 13.9 mg toluene solution in 10 ml) were added. The reactor was heated to 80 ° C and ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction ceased by rapid cooling and system ventilation. The polymer solvent was evaporated by a stream of nitrogen. Polyethylene (1.9g, Molecular Weight = 229,700; Lys Molecular Weight distribution = 2,618) was collected.

EXAMPLE 21

Polymerization - Compound E Using the general procedure described in Example 1, 300 mL of hexane, 9 mL of 1.0M MAO and 0.24 mg of compound E (0.2 mL of a solution of toluene 12.0 mg in .1.0 mL) were added. . The reactor was heated to 80 ° C and ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction ceased by rapid cooling and system ventilation. The solvent of the polymer was evaporated by a stream of nitrogen. Polyethylene (2.2 g, Molecular Weight = 258,200; Molecular Weight Distribution> 2,348) was collected.

EXAMPLE 22

Polymerization - Compound E Polymerization was performed as in Example

1 with the following reactor content: 200 ml toluene,!

100 ml of 1-butene, 9 · θ ml of 1.0 M MAO and 2.4 mg of compound E (2.0 ml of a 12.0 mg toluene solution in 10 ml) at 50 ° C. The reactor was pressurized with ethylene (65 psi) and allowed to if the reaction proceeds for 30 minutes followed by

0 rapid cooling and system ventilation. After evaporation of the solvent 1.8 g of ethylene butene (Molecular Weight = 323,600;

Molecular Weight = 2,463.33 * 5 SCB / 100OC per one copolymer of

IR technique distribution).

62646

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Mod. 71-10000 βχ. · 89/07

EXAMPLE 23

Polymerization - Compound PA Polymerization was carried out as in the Example under the following reactor conditions: 400 ml toluene, 5.0 ml 1.0 M MAO, 0.242 mg compound P (0.2 ml toluene 12.1 mg solution in 10 ml), 80 ml. ° C, 60 psi ethylene, 30 minutes. The process provided 5-3 g of polyethylene (Molecular Weight = 319,900; Molecular Weight Distribution = 2,477).

EXAMPLE 24

Polymerization - Compound The polymerization was carried out as in the Example under the following reactor conditions: 150 mL toluene, 100 mL 1-butene, 9-0 mL 1.0 M MAO, 2.42 mg compound P (2.0 mL of a solution of toluene 12.1 mg in 10 ml), 50 ° C, ethylene at 65 psi, 30 minutes. The process provided

3.5 g of an ethylene-butene copolymer (Molecular Weight ≤ 251,300; Molecular Weight Distribution = 3-341, 33-28 SCB / 10000 by IR technique).

EXAMPLE 25

Polymerization - Compound 0 Polymerization was carried out as in Example 1 under the following reactor conditions: 400 ml toluene, 5.0 ml 1.0 M MAO, 0.29 mg compound G (0.2 ml toluene 14-5 mg solution in 10 ml), 80 ° C, 60 psi ethylene, 30 minutes. The process provided 3-5 g of polyethylene (Molecular Weight = 237,300; Molecular Weight Distribution = 2,549).

-38Ref: JL / PE - 1784 '-Z / ρ? Η /

EXAMPLE 26

Polymerization - Compound GA Polymerization was carried out as in Example 1 under the following reactor conditions: 150 ml of toluene,

100 ml 1-butene, 7.0 ml 1.0 M MAO, 2.9 mg compound G (2.0 ml toluene solution 14.5 mg in 10 ml), 5θ ° 0, ethylene at 65 psi, 3θ minutes. The process provided 1.0% of an ethylene butene copolymer (Molecular Weight = 425.003; Molecular Weight Distribution = 2,816, 27.11 SCB / 100% by IR technique).

Example 27

Polymerization - Compound H Polymerization was carried out as in Example 1 under the following reactor conditions: 400 ml of toluene,

5.0 ml 1.0 M MAO, 0.266 mg of compound H (0.2 ml of a 13-3 mg toluene solution in 10 ml), 80 ° C, 60 psi ethylene, 30 minutes. The process provided 11.1 g of polyethylene (Molecular Weight - 299,800; Molecular Weight Distribution = 2,569).

EXAMPLE 28

Polymerization - Compound H Polymerization was carried out as in Example 1 under the following reactor conditions: 150 ml of toluene,

100 ml 1-butene, 7.0 ml 1.0 M MAO, 2.66 mg compound H (2.0 ml toluene 13.3 mg solution in 10 ml), 50 ° C, 65 psi ethylene, 30 minutes. The process provided

15.4 g of an ethylene-butene copolymer (Molecular Weight = 286,600; Molecular Weight Distribution = 2-980, 45.44 SGB / 10,000 by IR technique).

EXAMPLE 29

Polymerization - Compound I Polymerization was carried out as in Example 1

-59Kll «JL / PE - i / 04

under the following reactor conditions: 400 ml of toluene,

5.0 ml of 1.0 M MA0 and 0.34 mg of compound I (0.2 ml of a 17-0 mg toluene solution in 10 ml) was added to the reactor. The reactor was heated to 80 ° C, ethylene (60 psi) was introduced and the reaction was allowed to proceed for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 0.9 g of polyethylene was collected (Molecular Weight = 377,000; Molecular Weight Distribution = 1,996) ·

Example 30

Polymerization - Compound J Polymerization was carried out as in the Example under the following reactor conditions: 400 ml toluene, 5.0 ml 1.0 M MAQ, O.318 mg compound J (0.2 ml toluene solution 15.9 mg in 10 ml) 80 ° C, 60 psi ethylene, 30 minutes. The process yielded 8.6 g of polyethylene (Molecular Weight = 321,000; Molecular Weight Distribution = 2,803).

EXAMPLE 31

Polymerization - Compound J Polymerization was carried out as in Example ί under the following reactor conditions: 150 ml of toluene,

100 ml 1-butene, 7.0 ml 1.0 M MA0, 3.18 mg compound J (2.0 ml toluene 15.9 mg solution in 10 ml), 50 ° C, 65 parent ethylene, 30 minutes. The process provided

11.2 g of an ethylene butene copolymer (Molecular Weight = 224,800; Molecular Weight Distribution = 2,512, 49 · 57 SCB / 1003 by IR technique, 55.4 SCB / 1003 by NMR technique).

Example 32

Polymerization - Compound KA polymerization was performed as in Example 1

-40Ref: jL / PE - 1784 11 · 7 ° C under the following reactor conditions: 300 ml of toluene,

5.0 ml 1.0 M MAO, 0.272 mg compound K (0.2 ml of a 13.6 mg toluene solution in 10 ml), 80 ° C, 60 psi ethylene, 30 minutes. The process provided 26.6 g of polyethylene (Molecular Weight = 187,300; Molecular Weight Distribution = 2,401).

EXAMPLE 35

Polymerization - Compound K / Polymerization was carried out as in Example 1 under the following reactor conditions: 150 ml of toluene,

100 ml 1-butene, 7.0 ml 1.0 M MAO, 2.72 mg compound K (2.0 ml toluene solution 13.6 mg in 10 ml), 50 ° C, 65 psi ethylene, 30 minutes. The process provided 3-9 g of an ethylene-butene copolymer (Molecular Weight = 207,600; Molecular Weight Distribution = 2,394,33,89 SCB / 1000c by IR technique):

EXAMPLE 34

Polymerization - Compound The polymerization was carried out as in Example 1 under the following reactor conditions: 400 ml of toluene,

5.0 ml 1.0 M MAO, 0.322 mg of compound L (0.2 ml of a 16.1 mg toluene solution in 10 ml), 80 ° C, 60 psi ethylene 30 minutes. The process provided 15-5 g of polyethylene (Molecular Weight # 174,300 Molecular Weight Distribution = 2,193).

EXAMPLE 35

Polymerization - Compound AA Polymerization was carried out as in Example 1 under the following reactor conditions: 250 ml toluene, 150 ml 1-hexene, 7.0 ml 1.0 M MAO and 2.3 mg compound A (2.0 ml of a solution of toluene 11.5 mg in 10 ml) at 50 ° C. The reactor was pressurized with ethylene (65 psi) and gave

-41Ref: JL / PE - 1784

/ /

The reaction was continued for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 26.5 g of an ethylene hexene copolymer (Molecular Weight = 222,800; Molecular Weight Distribution = 3 · 373.39-1 SCB / 10000 by IR technique) was collected.

Example 36

Polymerization - Compound. THE

The polymerization was carried out as in Example 1 under the following reactor conditions: 300 ml of toluene, 100 ml of 1-octene, 7-0 ml of 1.0 M MAO, and 2.3 mg of compound A (2.0 ml of a toluene solution 11.5 mg in 10 ml) to

50 ° C. The reactor was pressurized with ethylene (65 psi) and the reaction was allowed to proceed for 30 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 19.7 g of an ethylene octene copolymer (Molecular Weight = 548,600;

Molecular Weight = 3 · ΟΟ7, 16.5 SCB / 10000 by NMR technique).

Example 57

Polymerization - Comnoato A

The polymerization was carried out as in Example 1 under the following reactor conditions: 300 ml toluene, 100 ml 4-methyl-1-pentene, 7.0 ml 1.0 M MAO and 2.3 mg compound A (2.0 ml solution toluene (11.5 mg in ml) at 50 ° C. 0 The reactor was pressurized with ethylene (65 psi) and allowed to proceed for 3 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 15.1 g of an ethylene-4 copolymer was collected. -methyl-1-pentene (Molecular Weight = = 611,800; Molecular Weight Distribution = 1,683, 1.8 mole determined by C NMR).

-42UZ.UM-U

Ref: JL / PE - 1784

EXAMPLE 58

Polymerization - Compound AA Polymerization was carried out as in the Example under the following reactor conditions: 500 mL toluene, 100 mL of a 2.2 M norbornene solution in toluene solution, 7.0 mL of 1.0 M MAO and 2.5 mg of compound A (2.0 ml of 11.5 mg toluene solution in 10 ml) at 50 ° C. The reactor was pressurized with ethylene (65 psi) and the reaction was allowed to proceed for 50 minutes, followed by rapid cooling and ventilation of the system. After evaporation of the solvent, 12.5 g of an ethylene norbornene copolymer (Molecular Weight = 812,600; Molecular Weight Distribution = 1,711, 0.5 mol% determined by NMR) was collected.

EXAMPLE 59

Polymerization - Compound AA Polymerization was carried out as in Example 1 under the following reactor conditions: 500 ml toluene, 10 ml ml cis -1,4-hexadiene, 7 * 0 ml 1.0 M MAO and 2.5 mg compound A ( 2.0 ml of a solution of toluene 11.5 mg in XO ml) at 50 ° C. The reactor was pressurized with ethylene (65 psi) and allowed to proceed for 50 minutes, followed by rapid cooling and system ventilation. After evaporation of the solvent 15.6 g of an ethylene-cis-1,4-hexadiene copolymer (Molecular Weight = 165.4-00; Molecular Weight Distribution = 2.588.2 mole determined by H2 O) was collected. NMR).

Table 2 summarizes the polymerization conditions used and the properties obtained in the polymers as described in Examples 1-54 above.

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<td>• X</td><td></td><td>co</td><td>co</td><td>co</td><td>co</td><td>faith</td><td>laugh</td><td></td>

<td>CZ2 n</td><td></td><td>LO</td><td>IO</td><td>LO</td><td>LO</td><td>laugh</td><td>faith</td><td>Ό</td>

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<td>THE -</td><td>Q</td><td>laugh</td><td>laugh</td><td>laugh</td><td>laugh</td><td>O</td><td>O</td><td>-P</td>

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<td>Hello</td><td></td><td>co</td><td>you-</td><td> 00</td><td>Created</td><td></td><td></td><td></td>

<td>faith</td><td></td><td>co</td><td>co</td><td>CO</td><td>co</td><td>frog</td><td>THE</td><td>O</td>

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Ref: JL / PE-1784 ο

eco ο>

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<td> ></td><td>O</td><td>faith</td>

<td>THE</td><td>faith</td><td>O</td>

\ ο Α Ο Ο Ο CQ Ο γ-ί fe

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fe fe fe Ρ the fe fe

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οι

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<td></td><td></td><td></td><td></td><td>faith</td><td></td><td></td>

<td>faith</td><td></td><td></td><td></td><td>O</td><td> •</td><td></td>

<td>faith</td><td></td><td></td><td></td><td>O</td><td>THE</td><td></td>

<td></td><td></td><td></td><td></td><td>faith</td><td>TO</td><td></td>

<td>Ο</td><td>CO</td><td>ι — í</td><td>C0</td><td>faith</td><td> 3</td><td></td>

<td> 0-</td><td>THE</td><td>QC</td><td>I'm</td><td>CO</td><td>faith</td><td>Ό</td>

<td>faith</td><td>in</td><td> 04</td><td>QC</td><td>THE</td><td>P</td><td>O</td>

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<td></td><td></td><td></td><td></td><td>O</td><td>faith</td><td>O</td>

<td></td><td></td><td></td><td></td><td>faith</td><td>f></td><td></td>

<td></td><td></td><td></td><td></td><td>faith</td><td>co</td><td>O</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>faith</td>

<td>ΙΩ</td><td>I'm</td><td>OU</td><td>uo</td><td>O</td><td>O</td><td>faith</td>

<td></td><td></td><td></td><td></td><td>faith</td><td>faith</td><td>AND</td>

<td></td><td></td><td></td><td></td><td>O</td><td>O</td><td>faith</td>

_U4i62646

Ref: JL / PE - 1784

It can be seen that the requirements for the alumoxane component can be greatly reduced by premixing the catalyst with the alumoxane before starting polymerization to polymerization (see Examples 12 to 15).

By appropriate selection of (1) Group IV B transition metal component for use in the catalytic system; (2) the type and amount of alumoxane used; (3) the type and volume of polymerization diluent; and (4) reaction temperature; (5) reaction pressure that can drive the polymer product to the desired average molecular weight while still maintaining the molecular weight distribution below about 4.0.

Preferred polymerization diluents for practicing the process of the invention are aromatic diluents such as toluene or alkanes such as hexane.

Resins that are prepared according to this invention may be used to prepare a variety of products including films and fibers.

The invention has been described with reference to its preferred embodiments. Those skilled in the art may, upon reading this description, appreciate changes or modifications that are not outside the scope and spirit of the invention as described above or claimed below.

Contents190

397 members in 27 offices

This recordMember, by publication datePriority claim17 more offices are in the list below

Priority claims8

Priority claims
Document	Office	Kind	Date
40694589	United States of America	A	1989-09-13
40694589	United States of America	A	1989-09-13
53324590	United States of America	A	1990-06-04
53324590	United States of America	A	1990-06-04
406945	–	–	–
533245	–	–	–
US19890406945	–	–	–
US19900533245	–	–	–

Members397

Family members, oldest first
Document	Office	Kind
IL85098D0	Israel	D0	1988-06-30
EP0277003A1	European Patent Office (EPO)	A1	1988-08-03
EP0277004A1	European Patent Office (EPO)	A1	1988-08-03
WO8805792A1	World Intellectual Property Organization (WIPO)	A1	1988-08-11
WO8805793A1	World Intellectual Property Organization (WIPO)	A1	1988-08-11
AU1245288A	Australia	A	1988-08-24
AU1294588A	Australia	A	1988-08-24
NO884210D0	Norway	D0	1988-09-22
NO884210L	Norway	L	1988-09-22
NO884295D0	Norway	D0	1988-09-28
NO884295L	Norway	L	1988-09-28
FI884486A	Finland	A	1988-09-29
FI884487A	Finland	A	1988-09-29
DK548888D0	Denmark	D0	1988-09-30
DK548988D0	Denmark	D0	1988-09-30
PL270367A1	Poland	A1	1988-10-13
DK548888A	Denmark	A	1988-11-30
DK548988A	Denmark	A	1988-11-30
PT86671A	Portugal	A	1989-01-30
PT86672A	Portugal	A	1989-01-30
PL270366A1	Poland	A1	1989-04-17
KR890700612A	Republic of Korea	A	1989-04-26
KR890700618A	Republic of Korea	A	1989-04-26
JPH01501950A	Japan	A	1989-07-06
JPH01502036A	Japan	A	1989-07-13
PL276385A1	Poland	A1	1989-07-24
BR8805025A	Brazil	A	1989-10-17
BR8805026A	Brazil	A	1989-10-17
YU16188A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1990-02-28
YU16288A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1990-02-28
HUT52791A	Hungary	A	1990-08-28
NO903928D0	Norway	D0	1990-09-10
CA2024899A1	Canada	A1	1991-03-14
CA2065745A1	Canada	A1	1991-03-14
NO903928L	Norway	L	1991-03-14
NO953466L	Norway	L	1991-03-14
AU6248390A	Australia	A	1991-03-21
HU905878D0	Hungary	D0	1991-03-28
EP0420436A1	European Patent Office (EPO)	A1	1991-04-03
WO9104257A1	World Intellectual Property Organization (WIPO)	A1	1991-04-04
AU6443990A	Australia	A	1991-04-18
KR910006335A	Republic of Korea	A	1991-04-29
YU178689A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1991-04-30
YU178789A	Yugoslavia, later Serbia and Montenegro (until 2006)	A	1991-04-30
PL286878A1	Poland	A1	1991-05-20
PT95272A	Portugal	A	1991-05-22
AU610863B2	Australia	B2	1991-05-30
US5026798A	United States of America	A	1991-06-25
HUT55791A	Hungary	A	1991-06-28
IL95549D0	Israel	D0	1991-06-30
CA2075035A1	Canada	A1	1991-08-10
CS33491A2	Czechoslovakia (until 1993)	A2	1991-08-13
JPH03188092A	Japan	A	1991-08-16
WO9112285A1	World Intellectual Property Organization (WIPO)	A1	1991-08-22
AU7324491A	Australia	A	1991-09-03
BR9004537A	Brazil	A	1991-09-10
CA2078665A1	Canada	A1	1991-09-21
WO9114713A1	World Intellectual Property Organization (WIPO)	A1	1991-10-03
US5055438A	United States of America	A	1991-10-08
US5057475A	United States of America	A	1991-10-15
PT96743A	Portugal	A	1991-10-31
AU617990B2	Australia	B2	1991-12-12
CA2085581A1	Canada	A1	1991-12-23
WO9200333A2	World Intellectual Property Organization (WIPO)	A2	1992-01-09
EP0468537A1	European Patent Office (EPO)	A1	1992-01-29
NZ235095A	New Zealand	A	1992-01-29
IL85097A	Israel	A	1992-02-16
NO920971D0	Norway	D0	1992-03-12
CA2090872A1	Canada	A1	1992-03-14
CA2090972A1	Canada	A1	1992-03-14
US5096867A	United States of America	A	1992-03-17
WO9200333A3	World Intellectual Property Organization (WIPO)	A3	1992-03-19
IL85098A	Israel	A	1992-03-29
WO9205203A1	World Intellectual Property Organization (WIPO)	A1	1992-04-02
WO9205204A1	World Intellectual Property Organization (WIPO)	A1	1992-04-02
EP0478913A1	European Patent Office (EPO)	A1	1992-04-08
AU8651891A	Australia	A	1992-04-15
AU8754291A	Australia	A	1992-04-15
NO920971L	Norway	L	1992-05-04
IL97198D0	Israel	D0	1992-05-25
DD300233A5	German Democratic Republic (until 1990)	A5	1992-05-27
EP0491842A1	European Patent Office (EPO)	A1	1992-07-01
YU45838B	Yugoslavia, later Serbia and Montenegro (until 2006)	B	1992-07-20
BR9007642A	Brazil	A	1992-07-21
KR920702365A	Republic of Korea	A	1992-09-03
US5153157A	United States of America	A	1992-10-06
EP0513216A1	European Patent Office (EPO)	A1	1992-11-19
PL159193B1	Poland	B1	1992-11-30
PL159196B1	Poland	B1	1992-11-30
US5168111A	United States of America	A	1992-12-01
KR927003669A	Republic of Korea	A	1992-12-18
EP0521908A1	European Patent Office (EPO)	A1	1993-01-13
PL159854B1	Poland	B1	1993-01-29
US5198401A	United States of America	A	1993-03-30
BR9106589A	Brazil	A	1993-06-01
JPH05503546A	Japan	A	1993-06-10
KR930701493A	Republic of Korea	A	1993-06-11
EP0548257A1	European Patent Office (EPO)	A1	1993-06-30
EP0548277A1	European Patent Office (EPO)	A1	1993-06-30
CA2126317A1	Canada	A1	1993-07-08

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	Event	Code
2007-10-10	Annulment/lapse due to non-payment of fees, searched and examined patentLapsedLAPSE DUE TO NON-PAYMENT OF FEESMM4A	MM4A
2001-06-29	Patent granted, date of grantingGrantedFG3A	FG3A
1991-05-22	Laying open of patent applicationBB1A	BB1A