EP0427696A2 — Process and catalyst for producing syndiotactic p…

Claim 1

Independent Claim 160 words

A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst having an unbalanced metallocene cation and a stable noncoordinating counter anion for said metallocene cation, said metallocene cation being characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, one of said ring structures being a substituted or unsubstituted cyclopentadienyl ring and the other of said ring structures being a substituted cyclopentadienyl group which is sterically different from said first cyclopentadienyl group, and both of said cyclopencadienyl groups being in a stereorigid relationship relative to said coordinating metal atom to prevent rotation of said rings. (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.

Claim 2

Dependent Claim 160 words

A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst having an unbalanced metallocene cation and a stable noncoordinating counter anion for said metallocene cation, said metallocene cation being characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, one of said ring structures being a substituted or unsubstituted cyclopentadienyl ring and the other of said ring structures being a substituted cyclopentadienyl group which is sterically different from said first cyclopentadienyl group, and both of said cyclopencadienyl groups being in a stereorigid relationship relative to said coordinating metal atom to prevent rotation of said rings. (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.

Claim 3

Dependent Claim 17 words

The process of Claim 1, wherein said transition metal atom is a titanium, zirconium or hafnium atom.

Claim 4

Dependent Claim 12 words

The process of Claim 2, wherein said ethylenically unsaturated monomer is propylene.

Claim 5

Dependent Claim 34 words

The process of Claim 3, wherein said polymerization reaction is carried out under conditions in which any aluminoxane concentration is maintained at a level providing an Al/Me mole ratio of no more than 10.

Claim 6

Dependent Claim 18 words

The method of Claim 4, wherein said polymerization process is carried out in the absence of added aluminoxane.

Claim 7

Dependent Claim 213 words

A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst characterized by the formula: [R˝(C p R n )(C p R′ m )MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that (C p R′ m ) is a sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atom) or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.

Claim 8

Dependent Claim 213 words

A process for the syndiotactic propagation of a polymer chain derived from an ethylenically unsaturated monomer comprising: (a) providing a metallocene catalyst characterized by the formula: [R˝(C p R n )(C p R′ m )MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that (C p R′ m ) is a sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atom) or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound and maintaining said reaction zone under polymerization conditions to produce syndiospecific polymerization of said monomer.

Claim 9

Dependent Claim 16 words

The process of Claim 6, wherein Me is titanium, zirconium or hafnium and k is 1.

Claim 10

Dependent Claim 11 words

The process of Claim 7, wherein Q is a methyl group.

Claim 11

Dependent Claim 14 words

The method of Claim 6, wherein said ethylenically unsaturated monomer is a C₃+ hydrocarbon.

Claim 12

Dependent Claim 15 words

The method of Claim 7, wherein said ethylenically unsaturated monomer is a vinyl aromatic compound.

Claim 13

Dependent Claim 12 words

The method of claim 10, wherein said vinyl aromatic compound is styrene.

Claim 14

Dependent Claim 15 words

The Method of Claim 6, wherein said ethylenically unsaturated monomer is a substituted vinyl compound.

Claim 15

Dependent Claim 13 words

The method of Claim 12, wherein said substituted vinyl compound is vinyl chloride.

Claim 16

Dependent Claim 15 words

The method of Claim 6, wherein said ethylenically unsaturated monomer is a C₃+ alpha olefin.

Claim 17

Dependent Claim 189 words

A process for the production of syndiotactic polypropylene, comprising: (a) providing a metallocene catalyst characterized by the formula: [R˝ (C p R n ) (C p R′ m ) MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that the (C p R′ m ) is a sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst with propylene in a polymerization reaction zone and maintaining said reaction zone under polymerization conditions to produce syndiotactic polypropylene.

Claim 18

Dependent Claim 189 words

A process for the production of syndiotactic polypropylene, comprising: (a) providing a metallocene catalyst characterized by the formula: [R˝ (C p R n ) (C p R′ m ) MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that the (C p R′ m ) is a sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b, or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, k is from 0 to 2; and (b) contacting said catalyst with propylene in a polymerization reaction zone and maintaining said reaction zone under polymerization conditions to produce syndiotactic polypropylene.

Claim 19

Dependent Claim 34 words

The process of Claim 15, wherein said polymerization reaction is carried out under conditions in which any aluminoxane concentration is maintained at a level providing an Al/Me mole ratio of no more than 10.

Claim 20

Dependent Claim 18 words

The method of Claim 16, wherein said polymerization process is carried out in the absence of added aluminoxane.

Claim 21

Dependent Claim 108 words

A metallocene catalyst for use in the syndiotactic propagation of a polymer chain comprising an unbalanced metallocene cation and a stable noncoordinating counter anion for said metallocene cation, said metallocene being characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, one of said ring structures being a substituted or unsubstituted cyclopentadienyl ring and the other of said ring structures being a substituted cyclopentadienyl group which is sterically different from said first cyclopentadienyl group, and both of said cyclopentadienyl groups being in a stereorigid rela tionship relative to said coordinating metal atom to prevent rotation of said rings.

Claim 22

Dependent Claim 108 words

A metallocene catalyst for use in the syndiotactic propagation of a polymer chain comprising an unbalanced metallocene cation and a stable noncoordinating counter anion for said metallocene cation, said metallocene being characterized by a cationic metallocene ligand having sterically dissimilar ring structures joined to a positively charged coordinating transition metal atom, one of said ring structures being a substituted or unsubstituted cyclopentadienyl ring and the other of said ring structures being a substituted cyclopentadienyl group which is sterically different from said first cyclopentadienyl group, and both of said cyclopentadienyl groups being in a stereorigid rela tionship relative to said coordinating metal atom to prevent rotation of said rings.

Claim 23

Dependent Claim 20 words

The catalyst of Claim 18, wherein said stereorigid relationship is imparted by a structural bridge extending between said cyclopentadienyl groups.

Claim 24

Dependent Claim 176 words

A metallocene catalyst for use in the syndiotactic propagation of a polymer chain comprising an unbalanced metallocene cation and a stable noncoordinating anion for said metallocene cation characterized by the formula: [R˝(C p R n ) (C p R′ m ) MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that (C p R′ m ) is sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, and k is from 0 to 2.

Claim 25

Dependent Claim 176 words

A metallocene catalyst for use in the syndiotactic propagation of a polymer chain comprising an unbalanced metallocene cation and a stable noncoordinating anion for said metallocene cation characterized by the formula: [R˝(C p R n ) (C p R′ m ) MeQ k ]⁺[P]⁻ wherein: each C p is a cyclopentadienyl or substituted cyclopentadienyl ring; each R is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms; each R′ is the same or different and is a hydrocarbyl radical having 1-20 carbon atoms and is selected such that (C p R′ m ) is sterically different ring than (C p R n ); R˝ is a structural bridge between the C p rings imparting stereorigidity to the catalyst; Me is a group 4b, 5b or 6b metal from the Periodic Table of Elements; each Q is a hydrocarbyl radical having 1-20 carbon atoms or is a halogen; P is a stable noncoordinating anion; n is from 0 to 4, m is from 1 to 4, and k is from 0 to 2.

Claim 26

Dependent Claim 16 words

The catalyst of Claim 20, wherein Me is titanium, zirconium or hafnium and k is 1.

Claim 27

Dependent Claim 14 words

The catalyst of Claim 20, wherein said transition metal is titanium, Zirconium or hafnium

Claim 28

Dependent Claim 23 words

The catalyst of Claim 20, wherein R′ m is selected such that (C p R′ m ) forms a fluorenyl or indenyl radical.

Claim 29

Dependent Claim 46 words

The catalyst of Claim 20 wherein R˝ is selected from the group consisting of an alkylene radical having 1-4 carbon atoms, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrdocarbyl radical.

Claim 30

Dependent Claim 11 words

The catalyst of Claim 24 wherein Q is a methyl group.

Claim 31

Dependent Claim 22 words

The process of Claim 25 wherein Rm is selected such that (C p R′ m ) forms a fluorenyl or indenyl radical.

Claim 32

Dependent Claim 20 words

The catalyst of Claim 26 wherein R˝(C p R n )(C p R′ m ) forms an isopropylidene (cyclopentadienyl-1-fluroenyl) radical.

Process and catalyst for producing syndiotactic polymers

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