US4786697A
Expired / Lapsed
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Molecular weight distribution modification in a tubular reactor
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1987-05-04
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Granted: 1988-11-22
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Expires: 2007-05-04
Abstract
Abstract Polymodal MWD ethylene copolymer comprising at least two modes of differing molecular weights. Each mode has at least one of &upbar& Mw/ &upbar& Mn of less than 2.0, and a &upbar& Mz/ &upbar& Mw of less than 1.8. The polymodal character of the copolymer is achieved by either (1) withdrawing polymer modes from the reactor from at least one takeoff port, and blending such modes with the reactor effluent, or (2) utilizing at least two catalyst species in the reaction to produce modes of differing molecular weights.
Inventors
- 👤 Charles Cozewith
- 👤 Shiaw Ju
- 👤 Gary W. VerStrate
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 23:21
CPC Classifications
C; C10; C10M; C10M143/00; B; B01; B01J; B01J19/00; B01J19/24; B01J19/2415; C08; C08F; C08F10/00; C08F210/00; C08F210/02; C08F210/16; C08F210/18; C08F297/00; C08F297/06; C08F297/08; 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; Y; Y10; Y10S; Y10S526/00; Y10S526/918; Y10S526/922
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
131 words
A method for preparing a polymodal MWD ethylene copolymer which comprises: (a) conducting the polymerization in a substantially mix free reactor; (b) using at least two catalyst species each of which initiates a polymer chain of a different molecular weight than the other catalyst species; (c) using at least one reaction mixture comprising ethylene and at least one alpha-olefin monomer, said reaction mixture being essentially transfer-agent free; (d) in such a manner and under such conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously; the resulting polymer comprising at least two modes of differing molecular weights, each mode having at least one of M w /M n of less than 2 and M z /M w of less than 1.8, the resulting polymer being a polymodal MWD ethylene copolymer.
Claim 2
Independent Claim
131 words
A method for preparing a polymodal MWD ethylene copolymer which comprises: (a) conducting the polymerization in a substantially mix free reactor; (b) using at least two catalyst species each of which initiates a polymer chain of a different molecular weight than the other catalyst species; (c) using at least one reaction mixture comprising ethylene and at least one alpha-olefin monomer, said reaction mixture being essentially transfer-agent free; (d) in such a manner and under such conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously; the resulting polymer comprising at least two modes of differing molecular weights, each mode having at least one of M w /M n of less than 2 and M z /M w of less than 1.8, the resulting polymer being a polymodal MWD ethylene copolymer.
Claim 3
Dependent Claim
43 words
The process according to claim 1 wherein each catalyst species comprises a hydrocarbon-soluble vanadium compound and an 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
61 words
The process according to claim 2 wherein each catalyst species comprises: (a) hydrocarbon-soluble vanadium compound selected from the group consisting of: ##STR4## where x=0-3 and R=hydrocarbon radical; VCl.sub.4 ; VO (AcAc).sub.2, where AcAc=acetyl acetonate V(AcAc).sub.2, where AcAc=acetyl acetonate V(AcAc).sub.3, where AcAc=acetyl acetonate VOCl.sub.x (AcAc).sub.3-x, where x=1 or 2 and AcAc=acetyl acetonate; and VCl.sub.3.nB, where n=2-3 and B=Lewis base capable of forming
Claim 5
Dependent Claim
37 words
hydrocarbon-soluble complexes with VCl 3 ; and (b) organo-aluminum compound selected from the group consisting of: AlR.sub.3 AlR.sub.2 Cl, Al.sub.2 R.sub.3 Cl.sub.3, AlRCl.sub.2, AlR'RCl, Al(OR')R.sub.2, R.sub.2 Al-OAlR.sub.2, and AlR.sub.2 I, where R and R' are hydrocarbon radicals.
Claim 6
Dependent Claim
37 words
hydrocarbon-soluble complexes with VCl 3 ; and (b) organo-aluminum compound selected from the group consisting of: AlR.sub.3 AlR.sub.2 Cl, Al.sub.2 R.sub.3 Cl.sub.3, AlRCl.sub.2, AlR'RCl, Al(OR')R.sub.2, R.sub.2 Al-OAlR.sub.2, and AlR.sub.2 I, where R and R' are hydrocarbon radicals.
Claim 7
Dependent Claim
52 words
The process according to claim 3 wherein a first catalyst species comprises VCl 4 as the catalyst and Al 2 R 3 Cl 3 as the cocatalyst and a second catalyst species comprises VOCl 3 as the catalyst and Al 2 R 4 Cl 3 as the cocatalyst where R is hydrocarbyl.
Claim 8
Dependent Claim
10 words
The process according to claim 4 wherein R is ethyl.
Claim 9
Dependent Claim
14 words
The process according to claim 1 wherein the reactor is a mix free reactor.
Claim 10
Dependent Claim
13 words
The process according to claim 6 wherein the reactor is a tubular reactor.
Claim 11
Dependent Claim
16 words
The process according to claim 1 wherein the reactor is a limited discrete mix free reactor.
Claim 12
Dependent Claim
34 words
The process according to claim 1 wherein the reactor comprises an inlet and an outlet, and wherein the temperature of the reaction mixture at the reactor inlet is about -50° C. to 150° C.
Claim 13
Dependent Claim
22 words
The process according to claim 9 wherein the maximum temperature of the reaction mixture at the reactor outlet is about 200° C.
Claim 14
Dependent Claim
20 words
The process according to claim 3 wherein the catalyst components are premixed, and wherein the polymerization is a solution polymerization.
Claim 15
Dependent Claim
17 words
The process according to claim 11 wherein the catalyst components are aged for at least 0.5 second.
Claim 16
Dependent Claim
22 words
The process according to claim 2 wherein the mole ratio of aluminum to vanadium in the catalyst is about 2 to 25.
Claim 17
Dependent Claim
31 words
The process according to claim 11 wherein the reaction mixture leaving the reactor has a copolymer concentration of about 3 to 15% on a weight copolymer per weight of solvent basis.
Claim 18
Dependent Claim
13 words
The process according to claim 1 wherein the catalyst comprises a Ziegler catalyst.
Claim 19
Dependent Claim
19 words
The process according to claim 10 wherein the maximum outlet temperature of the reaction mixture is about 50° C.
Claim 20
Dependent Claim
23 words
The process according to claim 12 wherein the catalyst comprises components that are premixed and then aged for about 1 to 50 seconds.
Claim 21
Dependent Claim
22 words
The process according to claim 12 wherein the mole ratio of aluminum to vanadium in the catalyst is about 4 to 15.
Claim 22
Dependent Claim
45 words
The process according to claim 18 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 23
Dependent Claim
19 words
The process according to claim 10 wherein the maximum outlet temperature of the reaction mixture is about 70° C.
Claim 24
Dependent Claim
11 words
The process according to claim 1 wherein the polymerization is adiabatic.
Claim 25
Dependent Claim
23 words
The process according to claim 21 wherein one of the active catalyst species provided for at least 65% of the total copolymer produced.
Claim 26
Dependent Claim
15 words
The process according to claim 22 which is continuous and is conducted in hexane solvent.
Claim 27
Dependent Claim
44 words
The process according to claim 1 wherein the mix-free reactor is a tubular reactor and said reaction mixture further comprises diene, and wherein at least one of said ethylene, other alpha-olefin monomer and diene are fed to said tubular reactor at multiple feed sites.
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