Patent EP0092809A2 successfully refreshed from Google Patents.
US4716207A
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US
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Nodular copolymers comprising narrow MWD alpha-olefin copolymers coupled by non-conjugated dienes
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1986-09-04
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Granted: 1987-12-29
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Expires: 2006-09-04
Abstract
Abstract A method of preparing a nodular polymer by preparing a copolymer chain and coupling it to a coupling agent. The coupling agent is a non-conjugated diene. Preferably the non-conjugated diene has both double bonds Ziegler catalyst polymerizable. The preferred product comprises a norbornadiene coupled ethylene copolymer wherein the ethylene copolymer has a &upbar& Mz/ &upbar& Mm of less than 2.0 and a &upbar& Mw/ &upbar& Mn of less than 1.8 before coupling.
Inventors
- 👤 Charles Cozewith
- 👤 Shiaw Ju
- 👤 Gary W. VerStrate
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 18:07
CPC Classifications
C; C10; C10M; C10M143/00; C08; C08F; C08F210/00; C08F210/02; C08F210/16; C08F210/18; C08F297/00; C08F297/06; C08F297/08; C08F8/00; B; B01; B01J; B01J2219/00; B01J2219/00049; B01J2219/00051; B01J2219/00074; B01J2219/00087; B01J2219/00099; B01J2219/00159; B01J2219/00186; C10M2205/00; C10M2205/02; C10M2205/022; C10M2205/08; C10M2205/10; C10N; C10N2020/00; C10N2020/01
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
116 words
In a polymerization process for producing a copolymer in the form of polymer chains from a reaction mixture comprising a catalyst, ethylene, and at least one alpha-olefin monomer, the improvement which comprises conducting the polymerization: (a) in at least one mix-free reactor; (b) with essentially one active catalyst species; (c) using at least one reaction mixture which is essentially transfer agent-free; (d) permitting the polymerization to continue until the copolymer is at least 50% completed; (e) introducing into the reaction mixture a coupling agent; and (f) permitting the reaction to continue; thereby incorporating the coupling agent into the polymer so as to form a nodular polymer wherein the polymer chains are linked to the coupling agent.
Claim 2
Dependent Claim
116 words
In a polymerization process for producing a copolymer in the form of polymer chains from a reaction mixture comprising a catalyst, ethylene, and at least one alpha-olefin monomer, the improvement which comprises conducting the polymerization: (a) in at least one mix-free reactor; (b) with essentially one active catalyst species; (c) using at least one reaction mixture which is essentially transfer agent-free; (d) permitting the polymerization to continue until the copolymer is at least 50% completed; (e) introducing into the reaction mixture a coupling agent; and (f) permitting the reaction to continue; thereby incorporating the coupling agent into the polymer so as to form a nodular polymer wherein the polymer chains are linked to the coupling agent.
Claim 3
Dependent Claim
41 words
A process according to claim 1, wherein the catalyst comprises hydrocarbon soluble vanadium compound and or organo-aluminum compound which react to form essentially one active catalyst species, at least one of the vanadium compound and organo-aluminum compound containing a valence-bonded halogen.
Claim 4
Dependent Claim
21 words
A process according to claim 1 wherein the temperature of the reaction mixture is about -50° C. to about 50° C.
Claim 5
Dependent Claim
19 words
A process according to claim 3, wherein the maximum outlet temperature of the reaction mixture is about 200° C.
Claim 6
Dependent Claim
20 words
A process according to claim 4, wherein the catalyst components are premixed, and wherein the polymerization is a solution polymerization.
Claim 7
Dependent Claim
18 words
A process according to claim 5, wherein the catalyst components are aged for at least about 0.5 seconds.
Claim 8
Dependent Claim
22 words
A process according to claim 2, wherein the mole ratio of aluminum to vanadium in the catalyst is about 2 to 25.
Claim 9
Dependent Claim
32 words
A process according to claim 4, wherein the reaction mixture leaving the reactor has a copolymer concentration of about 3 to 15% on a weight of copolymer per weight of solvent basis.
Claim 10
Dependent Claim
13 words
A process according to claim 1, wherein the catalyst comprises a Ziegler catalyst.
Claim 11
Dependent Claim
19 words
A process according to claim 3, wherein the maximum outlet temperature of the reaction mixture is about 50° C.
Claim 12
Dependent Claim
23 words
A process according to claim 8, wherein the catalyst comprises components that are premixed and then aged for about 1 to 50 seconds.
Claim 13
Dependent Claim
22 words
A process according to claim 8, wherein the mole ratio of aluminum to vanadium in the catalyst is about 4:1 to 15:1.
Claim 14
Dependent Claim
45 words
A process according to claim 1, wherein the polymerization is conducted in a solvent for the reaction mixture, and wherein the reaction mixture leaving the reactor has a copolymer concentration of about 3% to 10% on a weight of polymer per weight of solvent basis.
Claim 15
Dependent Claim
116 words
A process according to claim 2, wherein the catalyst comprises: (a) hydrocarbon-soluble vanadium compound selected from the group consisting of: ##STR3## where x=0-3 and R=hydrocarbon radical; VCl 4 ; VO(AcAc) 2 , where AcAc=acetyl acetonate V(AcAc) 3 , where AcAc=acetyl acetonate VOCl x (AcAc) 3-x , where x=1 or 2 and AcAc=acetyl acetonate; and VCl 3 .nB, where n=2-3 and B=Lewis base capable of forming hydrocarbon-soluble complexes with VCl 3 ; and (b) organo-aluminum compound selected from the group consisting of: AlR 3 AlR 2 Cl, Al 2 R 3 Cl 3 , AlRCl 2 , AlR'RCl, Al(OR')R 2 , R 2 Al--OAlR 2 , and AlR 2 I, where R and R' are hydrocarbon radicals.
Claim 16
Dependent Claim
20 words
A process according to claim 2, wherein the catalyst comprises VCl 4 and Al 2 R 3 Cl 3 .
Claim 17
Dependent Claim
19 words
A process according to claim 4, wherein the maximum outlet temperature of the reaction mixture is about 70° C.
Claim 18
Dependent Claim
11 words
A process according to claim 16, wherein the polymerizatin is adiabatic.
Claim 19
Dependent Claim
24 words
A process according to claim 17, wherein the catalyst comprises one active species which provides for at least 65% of the total copolymer produced.
Claim 20
Dependent Claim
15 words
A process according to claim 18, which is continuous and is conducted in hexane solvent.
Claim 21
Dependent Claim
17 words
A process according to claim 1, wherein said polymerization is conducted in at least one tubular reactor.
Claim 22
Dependent Claim
40 words
A process according to claim 20, wherein said copolymer forming reaction mixture further comprises non-conjugated diene, and wherein at least one of said ethylene, other alpha-olefin monomer and non-conjugated diene are fed to said tubular reactor at multiple feed sites.
Claim 23
Dependent Claim
15 words
The process according to claim 1 wherein the coupling agent is a Ziegler diene monomer.
Claim 24
Dependent Claim
22 words
The process according to claim 22 wherein the coupling agent is selected for the group consisting of norbornadiene, vinyl norbornadiene or butenylnorbornadiene.
Claim 25
Dependent Claim
12 words
The process according to claim 13 wherein the coupling agent is norbornadiene.
Claim 26
Dependent Claim
29 words
The process according to claim 22 wherein the coupling agent is incorporated into the reaction mixture at about 0.15 to about 15 wt.% based on the total monomer feed.
Claim 27
Dependent Claim
23 words
The process according to claim 1 wherein the coupling agent is a cationic diene and optionally, a cationic polymerization catayst is added therewith.
Claim 28
Dependent Claim
15 words
The process according to claim 26 wherein the cationic diene is ENB; 1,4-hexadiene or dicyclopentadiene.
Claim 29
Dependent Claim
18 words
The process according to claim 26 wherein the cationic polymerization catalyst is AlRCl 2 wherein R is hydrocarbyl.
Claim 30
Dependent Claim
12 words
The process according to claim 15 or 28 wherein R is ethyl.
Claim 31
Dependent Claim
16 words
A process according to claim 1 wherein said copolymer product is blended with basestock lubricating oil.
Claim 32
Dependent Claim
27 words
A process according to claim 30, wherein said copolymer product is blended with the basestock lubricating oil in an amount of from about 0.001 to 49 wt.%.
Claim 33
Dependent Claim
27 words
A process according to claim 1, wherein said copolymer product is blended with hydrocarbon mineral oil diluent in an amount of from about 5 to 50 wt.%.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-12-28 | 1991-06-29 | 1991-12-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-12-28 | 1995-06-29 | 1995-12-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-12-28 | 1999-06-29 | 1999-12-29 | $7700.00 | Window Closed / Lapsed |