Claims
- 1. A process for producing a rubbery copolymer of ethylene, 1-butene and a polyene having (A) an ethylene/1-butene mole ratio of from 86/14 to 95/5, (B) an iodine value of from 2 to 40, (C) an intrinsic viscosity [.eta.], measured in decalin at 135.degree. C., of from 0.8 to 4 dl/g, (D) a weight average molecular weight/number average molecular weight ratio (Mw/Mn) of less than 3, (E) [.eta.]/[.eta.]l of from 0.2 to 0.9 in which [.eta.] is the intrinsic viscosity of the copolymer and [.eta.]l is the intrinsic viscosity of an ethylene/1-butene random copolymer having an ethylene content of 90 mole % and the same weight average molecular weight, determined by a light scattering method, as that of the rubbery copolymer and (F) the polyene is at least one member selected from the group consisting of dicyclopentadiene, 5-vinyl-2-norbornene and 5-ethylidene-2-norbornene; which comprises copolymerizing ethylene, 1-butene and the polyene in an inert hydrocarbon medium at a temperature of from about 40.degree. C. to about [100.degree. C.] 80.degree. C., and at a pressure of from atmospheric pressure to 20 kg/cm.sup.2.G in the presence of a catalyst consisting essentially of
- (a) a vanadium compound of the formula
- VO(OR).sub.n X.sub.3-n
- wherein R represents a C.sub.1 -C.sub.20 alkyl group, X represents a halogen atom, and n represents a positive number within the range of 1.ltoreq.n.ltoreq.1.5, wherein said vanadium compound (a) is at least one compound selected from the group consisting of VO(OCH.sub.3)Cl.sub.2, VO(OC.sub.2 H.sub.5)Cl.sub.2, VO(OC.sub.2 H.sub.5).sub.1.5 Cl.sub.1.5, VO(OC.sub.2 H.sub.5).sub.1.5 Br.sub.1.5, VO(OC.sub.3 H.sub.7 Cl.sub.2, VO(OC.sub.3 H.sub.7).sub.1.5 Cl.sub.1.5, VO(O n-C.sub.4 H.sub.9)Cl.sub.2, and VO(OC.sub.5 H.sub.11).sub.1.5 Cl.sub.1.5, and
- (b) an organoaluminum compound of the formula
- R'.sub.m AlX'.sub.3-m
- wherein R' represent a hydrocarbon group X' represents a halogen atom, and m represents a positive number within the range of 1.2.ltoreq.m.ltoreq.1.4, wherein said organoaluminum compound is a mixture of of C.sub.2 H.sub.5 AlCl.sub.2 and (C.sub.2 H.sub.5).sub.1.5 AlCl.sub.1.5, a mixture of iso-C.sub.4 H.sub.9 AlCl.sub.2 and (iso-C.sub.4 H.sub.9).sub.1.5 AlCl.sub.1.5, or a mixture of C.sub.2 H.sub.5 AlCl.sub.2 and (iso-C.sub.4 H.sub.9).sub.1.5 AlCl.sub.1.5, the Al/V mole ratio in the catalyst being from 5 to 20.
- 2. The process of claim 1 wherein the concentration of the vanadium compound (a) is 0.01 to 5 millimoles/liter medium.
- 3. The process of claim 1 wherein R and R' each independently of the other, represents an alkyl group having from 1 to 3 carbon atoms and X' represents chlorine or bromine.
- 4. The process of claim 3 wherein the copolymerization is carried out under conditions in which the concentration of the vanadium compound (a) is from 0.1 to 2 millimoles/liter, the amount of the organoaluminum compound (b) is adjusted such that the Al/V mole ratio is from 7 to 20, the polymerization temperature is from 50.degree. to 80.degree. C. and the polymerization pressure is from atmospheric pressure to 20 kg/cm.sup.2.G.
- 5. A process for producing a rubbery copolymer of ethylene, 1-butene and a polyene having (A) an ethylene/1-butene mole ratio of from 86/14 to 95/5, (B) an iodine value of from 2 to 40(C) an intrinsic viscosity [.eta.], measured in decalin at 135.degree. C., of from 0.8 to 4 dl/g, (D) a weight average molecular weight/number average molecular weight ratio (Mw/Mn) of less than 3, (E) [.eta.]/[.eta.]l of from 0.2 to 0.9 in which [.eta.]is the intrinsic viscosity of the copolymer and [.eta.]l is the intrinsic viscosity of an ethylene/1-butene random copolymer having an ethylen content of 90 mole % and the same weight average molecular weight, determined by a light scattering method, as that of the rubbery copolymer and (F) the polyene is dicyclopentadiene or 5-vinyl-2-norbornene which comprises copolymerizing ethylene, 1-butene and the polyene in an inert hydrocarbon medium at a temperature of from about 60.degree. C. to about 80.degree. C. and at a pressure of about 7 kg/cm.sup.2.G in the presence of a catalyst consisting essentially of (a) a vanadium compound which is selected from the group consisting of a reaction product of vanadium oxytrichloride with ethanol at a mole ratio of from about 1/1 to about 1/1.5, the reaction product of vanadium oxytrichloride with n-propanol at a mole ratio of about 1/1, of the reaction product of vanadium oxytrichloride with VO(OC.sub.2 H.sub.5).sub.3 at a mole ratio of about 1/1, and (b) an organoaluminum compound which is a mixture of ethylaluminum sesquichloride and ethylaluminum dichloride at a mole ratio of about 7/3 to about 5/5, the vanadium compound (a) and the organoaluminum compound (b) being present in concentrations sufficient to provide an Al/V mole ratio of from about 10/1 to about 15/1.
- 6. A process for producing a rubbery copolymer of ethylene, 1-butene and a polyene having (A) an ethylene/1-butene mole ratio of from 86/14 to 95/5, (B) an iodine value of from 2 to 40, an intrinsic viscosity [.eta.], measured in decalin at 135.degree. C. (C), of from 0.8 to 4 dl/g, (D) a weight average molecular weight/number average molecular weight ratio (Mw/Mn) of less than 3, (E) [.eta.]/[.eta.].sub.l of from 0.2 to 0.9 in which [.eta.] is the intrinsic viscosity of the copolymer and [.eta.]l is the intrinsic viscosity of an ethylene/1-butene random copolymer having an ethylene content of 90 mole % and the same weight average molecular weight, determined by a light scattering method, as that of the rubbery copolymer and (F) the polyene is 5-ethylidene 2-norbornene, which comprises copolymerizing ethylene, 1-butene and the polyene in an inert hydrocarbon medium at a temperature of about 60.degree. C. and a pressure of about 6.4 kg/cm.sup.2.G in the presence of a catalyst consisting essentially of (a) a vanadium compound which is the reaction product between vanadium oxytrichloride and ethanol at a mole ratio of about 1/1, and (b) an organoaluminum compound which is a mixture of ethylaluminum sesquichloride compound and ethylaluminum dichloride at a mole ratio of about 7/3, wherein the concentration of the vanadium compound and the organoaluminum compound in the copolymerization is such that the Al/V mole ratio is about 10/1.
- 7. The process of claim 5 wherein said rubbery copolymer is characterized by (A) an ethylene content of from 86.7 to 94.2 mole %, (B) an iodine value of from 6.5 to 10.8, (C) an intrinsic viscosity of from 1.28 to 1.45 dl/g, (D) a weight average molecular weight/number average molecular weight ratio of from about 2.6 to 2.8, (E) [72 ]/[.eta.]l of from 0.38 to 0.65.
- 8. The process of claim 6 wherein the rubbery copolymer is characterized by (A) an ethylene content of from 86.4 to 93.8 mole %, (B) an iodine value of from 5.5 to 24.0, (C) an intrinsic viscosity of from 1.07 to 2.52, and (D) a weight average molecular weight/number average molecular weight ratio of from about 2.2 to 2.4.
Priority Claims (3)
Number |
Date |
Country |
Kind |
54-44274 |
Apr 1979 |
JPX |
|
54-44275 |
Apr 1979 |
JPX |
|
54-44276 |
Apr 1979 |
JPX |
|
Parent Case Info
This application is a continuation of application Ser. No. 444,061, filed Nov. 23, 1982 and now abandoned, which in turn is a continuation of application Ser. No. 232,389, filed Feb. 7, 1981, now abandoned, which in turn is a division of application Ser. No. 49,207, filed June 15, 1979, also now abandoned.
US Referenced Citations (15)
Foreign Referenced Citations (9)
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2722968 |
Dec 1977 |
DEX |
682924 |
Apr 1964 |
JPX |
43-2924 |
Feb 1968 |
JPX |
49-14542 |
Apr 1974 |
JPX |
856737 |
Dec 1960 |
GBX |
1014874 |
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1112067 |
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1142335 |
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1159554 |
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GBX |
Divisions (1)
|
Number |
Date |
Country |
Parent |
49207 |
Jun 1979 |
|
Continuations (2)
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Number |
Date |
Country |
Parent |
444061 |
Nov 1982 |
|
Parent |
232389 |
Feb 1981 |
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