# US 5,710,222 A · Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems

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- Number: US 5,710,222 A
- Document ID: US5710222A
- Status: Granted
- Kind: A
- Application number: 07/903,058
- Filed: 1992-06-22
- Granted: 1998-01-20
- Earliest claimed: 1992-06-22
- Assignees: Fina Technology, Inc.
- Inventors: John A. Ewen; B. R. Reddy; Michael J. Elder
- Web page: https://patentgrep.com/patent/US5710222A

## CPC

- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C07F 17/00: Metallocenes
- C08F 110/06: Propene
- C08F 4/61908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/61912: {in combination with an organoaluminium compound}
- C08F 4/61927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/63927: {two cyclopentadienyl rings being mutually bridged}
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65927: {two cyclopentadienyl rings being mutually bridged}
- Y10S 526/943: Polymerization with metallocene catalysts
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

This invention is for a method for varying the melting points and molecular weights of syndiotactic polyolefins by using metallocene catalysts with substituents on the aryl rings of a fluorene ligand in certain positions. Electron donating substituents, for example, dialkylamino, halogen, and alkoxy groups, when present on fluorene at C1, C2, C3 or C2 and C7 render the catalyst less active and decrease the polymer molecular weight. Electron donating substituents, such as alkyl, dialkylamino, halogen or alkoxy, at C4 not only increased the catalyst efficiency but also dramatically increased the polymer molecular weight. Bulky hydrocarbyl substituents, such as alkyl, cyaloalkyl and aryl groups, at C2 and C7 increase the melting point. Bulky substituents such as hydrocarbyl groups like alkyl, cycloalkyl, aryl, alkoxy and dialkylamino groups etc., at C4/C5 decrease the melting point. When multiple substituents are present on fluorene, their effects are additive.

## Claims

### Claim 1

A process for polarizing propylene to produce syndiotactic polypropylene comprising:
a) selecting a metallocene compound described by the general formula:
R"(C.sub.5 H.sub.4)(C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n)MeQ.sub.p
wherein (C.sub.5 H.sub.4) is a cyclopentadienyl ring and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) is a fluorenyl radical; R' is a hydrocarbyl radical, halogen, an alkoxy, an alkoxy alkyl or an alkylamino radical having from 1-20 carbon atoms, each R' may be the same or different; R" is a structural bridge between the (C.sub.5 H.sub.4) and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) rings to impart stereorigidity; Q is a hydrocarbon radical or a halogen; Me is a Group IVB metal; 1.ltoreq.m.ltoreq.4; 0.ltoreq.n.ltoreq.4; and p is the valence of Me minus 2;
wherein R' is an electron donating substituent on the fluorene ligand at C1, C2, or C3 and has the ability to donate electrons equal to or greater than that for methoxy or wherein R' is a methyl group or methoxymethyl group at C4;
b) forming a catalyst comprising the metallocene compound;
c) introducing the catalyst into a polymerization reaction zone containing propylene and maintaining the reaction zone under polymerization reaction conditions; and
d) extracting polypropylene from the reaction zone.

### Claim 2 (depends on 1)

A process as recited in claim 1 wherein R' is at C1, C2 or C3 and is selected from the group consisting of alkyl, dialkylamino, halogen and alkoxy groups.

### Claim 3 (depends on 1)

A process as recited in claim 1 wherein the metallocene compound is selected from the group consisting of isopropylene(1-methoxyfluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylene(2-methoxyfluorenyl)(cyclopentadienyl) zirconium dichloride, isopropylene(3-methoxyfluorenyl) (cyclopentadienyl)zirconium dichloride, and isopropylene(2-dimethylaminofluorenyl)(cyclopentadienyl)zirconium dichloride.

### Claim 4 (depends on 1)

A process as recited in claim 1 wherein R" is an alkylene radical having 1-4 carbon atoms, or arylalkylene or diarylalkylene radical containing 7-20 atoms, a silylene hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine.

### Claim 5 (depends on 4)

A process as recited in claim 4 wherein R" is methylene, ethylene, isopropylene, diarylmethylene, an alkylsilylene or a cycloalkylsilylene.

### Claim 6 (depends on 5)

A process as recited in claim 5 wherein R" is isopropylene or diphenylmethylene.

### Claim 7 (depends on 1)

A process as recited in claim 1 wherein Me is selected from the group consisting of zirconium and hafnium.

### Claim 8 (depends on 1)

A process as recited in claim 1 wherein Q is methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, fluorine, chlorine, bromine or iodine.

### Claim 9 (depends on 8)

A process as recited in claim 8 wherein Q is chlorine or methyl.

### Claim 10

A process for polymerizing propylene to produce syndiotactic polypropylene comprising:
a) selecting a metallocene compound described by the general formula:
R"(C.sub.5 H.sub.4)(C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4-n R'.sub.n)MeQ.sub.p
wherein (C.sub.5 H.sub.4) is a cyclopentadienyl ring and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) is a fluorenyl radical; R' is a hydrocarbyl radical, halogen, an alkoxy, an alkoxy alkyl or an alkylamino radical having from 1-20 carbon atoms, each R' may be the same or different; R" is a structural bridge between the (C.sub.5 H.sub.4) and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) rings to impart stereorigidity; Q is a hydrocarbon radical; Me is a Group IVB metal as positioned in the Periodic Table of Elements; 1.ltoreq.m.ltoreq.4; 0.ltoreq.n.ltoreq.4; and p is the valence of Me minus 2; wherein R' is an electron donating substituent on the fluorene ligand at C.sub.4 or C.sub.5 and has the ability to donate electrons equal to or greater than that for a dimethylamino or methoxy;
b) forming a catalyst comprising the metallocene compound;
c) introducing the catalyst into a polymerization reaction zone containing propylene and maintaining the reaction zone under polymerization reaction conditions; and
d) extracting polypropylene from the reaction zone.

### Claim 11 (depends on 10)

A process as recited in claim 10 wherein R' is selected from the group consisting of alkyl, dialkylamino, halogen and alkoxy groups.

### Claim 12 (depends on 10)

A process as recited in claim 10 wherein the metallocene compound is selected from the group consisting of isopropylene(4-methoxyfluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylene(4-methoxyfluorenyl)(cyclopentadienyl)hafnium dichloride and isopropylene(4-dimethylaminofluorenyl) cyclopentadienyl)zirconium dichloride.

### Claim 13 (depends on 10)

A process as recited in claim 10 wherein R" is an alkylene radical having 1-4 carbon atoms, or arylalkylene or diarylalkylene radical containing 7-20 atoms, a silylene hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine.

### Claim 14 (depends on 13)

A process as recited in claim 13 wherein R" is methylene, ethylene, isopropylene, diarylmethylene, an alkylsilylene or a cycloalkylsilylene.

### Claim 15 (depends on 14)

A process as recited in claim 14 wherein R" is isopropylene.

### Claim 16 (depends on 11)

A process as recited in claim 11 wherein Me is selected from the group consisting of zirconium and hafnium.

### Claim 17 (depends on 10)

A process as recited in claim 10 wherein Q is methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, fluorine, chlorine, bromine or iodine.

### Claim 18 (depends on 17)

A process as recited in claim 17 wherein Q is chlorine or methyl.

### Claim 19 (depends on 11)

A process as recited in claim 11 wherein m=1 and n=0.

### Claim 20

A process for polymerizing propylene to produce syndiotactic polypropylene comprising:
a) selecting a metallocene compound of the general formula:
R"(C.sub.5 H.sub.4)(C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4-n R'.sub.n)MeQ.sub.p
wherein (C.sub.5 H.sub.4) is a cyclopentadienyl ring and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) is a fluorenyl radical; R' is a hydrocarbyl radical, halogen, an alkoxy, an alkoxy alkyl or an alkylamino radical having from 1-20 carbon atoms, each R' may be the same or different; R" is a structural bridge between the (C.sub.5 H.sub.4) and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) rings to impart stereorigidity; Q is a hydrocarbon radical; Me is a Group IVB metal as positioned in the Periodic Table of Elements; 1.ltoreq.m.ltoreq.4; 0.ltoreq.n.ltoreq.4; and p is the valence of Me minus 2; wherein R' is a bulky substituent present on the fluorene ligand at C4 or C5 and is as least as bulky as methoxy or dimethylamino;
b) forming a catalyst comprising the metallocene compound;
c) introducing the catalyst into a polymerization reaction zone containing propylene and maintaining the reaction zone under polymerization reaction conditions; and
d) extracting polypropylene from the reaction zone.

### Claim 21 (depends on 20)

A process as recited in claim 20 wherein R' is selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy and dialkylamino groups.

### Claim 22 (depends on 20)

A process as recited in claim 20 wherein the metallocene compound is isopropylene(4-methoxyfluorenyl)cyclopentadienyl) zirconium dichloride, isopropylene(4-methoxymethylfluorenyl) (cyclopentadienyl)zirconium dichloride or isopropylene(4-dimethylaminofluorenyl)(cyclopentadienyl)zirconium dichloride.

### Claim 23 (depends on 20)

A process as recited in claim 20 wherein R" is an alkylene radical having 1-4 carbon atoms, or arylalkylene or diarylalkylene radical containing 7-20 atoms, a silylene hydrocarbyl compound, a germanium hydrocarbyl compound, an alkyl phosphine, or an alkyl amine.

### Claim 24 (depends on 23)

A process as recited in claim 23 wherein R" is methylene, ethylene, isopropyl diarylmethylene, an alkylsilylene or a cycloalkylsilylene.

### Claim 25 (depends on 24)

A process as recited in claim 24 wherein R" is isopropylene.

### Claim 26 (depends on 20)

A process as recited in claim 20 wherein Me is selected from the group consisting of zirconium and hafnium.

### Claim 27 (depends on 20)

A process as recited in claim 20 wherein Q is methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, phenyl, fluorine, chlorine, bromine or iodine.

### Claim 28 (depends on 27)

A process as recited in claim 27 wherein Q is chlorine or methyl.

### Claim 29 (depends on 20)

A process as recited in claim 20 wherein m=1 and n=0.

### Claim 30

A process for polymerizing propylene to produce syndiotactic polypropylene comprising:
a) selecting a metallocene compound described by the general formula:
R"(C.sub.5 H.sub.4)(C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n)MeQ.sub.p
wherein (C.sub.5 H.sub.4) is a cyclopentadienyl ring and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) is a fluorenyl radical; R' is a hydrocarbyl radical, halogen, an alkoxy, an alkoxy alkyl or an alkylamino radical having from 1-20 carbon atoms, each R' may be the same or different; R" is a structural bridge between the (C.sub.5 H.sub.4) and (C.sub.4 H.sub.4-m R'.sub.m C.sub.5 C.sub.4 H.sub.4-n R'.sub.n) rings to impart stereorigidity; Q is a hydrocarbon radical or a halogen; Me is a Group IVB metal; m=1; n=0; and p is the valence of Me minus 2;
wherein R' is an electron donating substituent on the fluorene ligand at C1, C2 or C3 and has the ability to donate electrons equal to or greater than that for t-butyl, dimethylamino, chlorine, fluorine or methoxy or
wherein R' is a methyl group or methoxymethyl group at C4;
b) forming a catalyst comprising the metallocene compound;
c) introducing the catalyst into a polymerization reaction zone containing propylene and maintaining the reaction zone under polymerization reaction conditions; and
d) extracting polypropylene from the reaction zone.