Claims
- 1. A block copolymer having a number-average molecular weight of about 1,000 to about 600,000 and a molecular weight distribution of 1.05 to 1.40 in which a random copolymer segment (A) is bonded to a polymer segment (B), with the ratio of (A) to (B) being 15/85 to 97/3 by weight, said random copolymer segment (A) being composed of the constitutional units represented by the formulas I and II below: ##STR6## wherein the amount of I in said segment (A) is from 30 to 80 wt% and the amount of II in said segment (A) is from 70 to 20 wt%, and said polymer segment (B) being composed of the constitutional units represented by the formula ##STR7## wherein R is a hydrocarbyl of 1 to 20 carbon atoms, said block copolymer formed by a process which comprises the steps of:
- (a) performing living polymerization of ethylene and propylene in a polymerization zone at a temperature of less than -50.degree. C. in the presence of a catalyst comprising beta-diketone vanadium chelate and an organoaluminum compound, to provide a living ethylene-propylene random copolymer;
- (b) reacting said ethylene-propylene copolymer with a halogen to provide an ethylene-propylene random copolymer having halogenated terminal groups;
- (c) contacting said halogenated copolymer produced in step (b) with metallic magnesium; and
- (d) polymerizing the product of step (c) with a methacrylate ester of the formula ##STR8## wherein R is as defined above, to form said block copolymer.
- 2. The block copolymer of claim 1 wherein said catalyst used in step (a) is formed by introducing to said polymerization zone (i) a beta-diketone vanadium chelate of the formula: ##STR9## wherein R.sub.1 and R.sub.2 are the same or different and are each alkyl or aryl, and (ii) an organoaluminum compound of the formula R.sub.2 AlX, wherein R is an alkyl group of 1 to 8 carbon atoms and X is a halogen atom.
- 3. The block copolymer of claim 2 wherein said vanadium chelate comprises a member selected from the group consisting of V(acetylacetonate).sub.3, V(benzoylacetylactonate).sub.3, and V(dibenzoylmethanate).sub.3.
- 4. The block copolymer of claim 2 wherein said organoaluminum compound comprises a member selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride.
- 5. The block copolymer according to claim 1 wherein said vanadium chelate is used in an amount of from 1.times.10.sup.-4 to 0.01 mol per 1 mol of said ethylene and propylene and wherein said organoaluminum compound is used in an amount of from about 1.times.10 to 0.1 mol per 1 mol of said ethylene and propylene.
- 6. The block copolymer according to claim 5 wherein said step (a) polymerization temperature is -65.degree. C. or below.
- 7. The block copolymer according to claim 6 wherein said organoaluminum compound is used in an amount of from 5 to 25 mol per 1 mol of said vanadium chelate.
- 8. The block copolymer according to claim 1 wherein from 2 to 5 moles of said halogen are employed in step (b) per mole of said organoaluminum compound.
- 9. The block copolymer according to claim 1 wherein said halogenated copolymer and said metallic magnesium are contacted in the presence of tetrahydrofuran or diethylether solvent, under reflux for 1 to 10 hours.
- 10. The block copolymer of claim 9 wherein from about 0.001 to 0.1 part by weight of said metallic magnesium is employed per part by weight of said halogenated copolymer.
- 11. The block copolymer according to claim 1 wherein said polymerization step (d) is performed at a temperature of from -50.degree. to -100.degree. C.
- 12. A block copolymer having a number-average molecular weight of about 1,000 to about 600,000 and a molecular weight distribution of 1.05 to 1.40 in which a random copolymer segment (A) is bonded to a polymer segment (B), with the ratio of (A) to (B) being 15/85 to 97/3 by weight, said random copolymer segment (A) being composed of the constitutional units represented by the formulas I and II below ##STR10## wherein the amount of I in said segment (A) is from 30 to 80 wt% and the amount of II in said segment (A) is from 70 to 20 wt%, and said polymer segment (B) being composed of the constitutional units represented by the formula ##STR11## wherein R is hydrocarbyl of 1 to 20 carbon atoms, said block copolymer formed by a process which comprises the steps of:
- (a) performing living polymerization of ethylene and propylene in a polymerization zone at a temperature of less than -50.degree. C. in the presence of a catalyst comprising a beta-diketone vanadium chelate and an organoaluminum compound, to provide a living ethylene-propylene random copolymer; and
- (b) polymerizing the product of step (a) with a methacrylate ester of the formula ##STR12## wherein R is as defined above, to form said block copolymer.
- 13. The block copolymer of claim 12 wherein said catalyst used in step (a) is formed by introducing to said polymerization zone (i) a beta-diketone vanadium chelate of the formula: ##STR13## wherein R.sup.1 and R.sup.2 are the same or different and are each alkyl or aryl, and (ii) an organoaluminum compound of the formula R.sub.2 AlX, wherein R is an alkyl group of 1 to 8 carbon atoms and X is a halogen atom.
- 14. The block copolymer of claim 13 wherein said vanadium chelate comprises a member selected from the group consisting of V(acetyleacetonate).sub.3, V(benzoylacetylacetonate).sub.3, and V(dibenzoylmethane).sub.3.
- 15. The block copolymer of claim 13 wherein said organoaluminum compound comprises a member selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride.
- 16. The block copolymer according to claim 12 wherein said vanadium chelate is used in an amount of from 1.times.10.sup.-4 to 0.01 mol per 1 mol of said ethylene and propylene and wherein said organoaluminum compound is used in an amount of from about 1.times.10.sup.-3 to 0.1 mol per 1 mol of said ethylene and propylene.
- 17. The block copolymer according to claim 16 wherein said step (a) polymerization temperature is -65.degree. C. or below.
- 18. The block copolymer according to claim 17 wherein said organoaluminum compound is used in an amount of from 5 to 25 mol per 1 mol of said vanadium chelate.
- 19. The block copolymer according to claim 12 wherein said step (a) polymerization is performed in an inert solvent, said methacrylate ester is added to the product of step (a) while maintaining said temperature at below -50.degree. C., and thereafter the temperature of the resulting mixture of said methacrylate ester and said ethylene-propylene random copolymer is raised to from 0.degree. to 30.degree. C. to effect said polymerization step (b).
- 20. The block copolymer according to claim 19 wherein said polymer segment (B) has a number average molecular weight of about 500 to 20,000.
- 21. The block copolymer according to claim 20 wherein said polymerization step (a) is performed at a temperature of -65.degree. C. or below to provide a living ethylene-propylene random copolymer having a M.sub.w /M.sub.n, of from 1.05 to 1.40, wherein M.sub.w is the weight-average molecular weight of said copolymer, and wherein said polymerization step (a) is conducted in the presence of from about 0.1 to 2 moles of a reaction accelerator per 1 mol of said vanadium compound, said reaction accelerator comprising a member selected from the group consisting of anisole, water, oxygen, methanol, ethanol, isopropanol, ethylbenzolate, and ethylacetate.
- 22. A process for producing a block copolymer having a number-average molecular weight of about 1,000 to about 600,000 and a molecular weight distribution of 1.05 to 1.40 in which a random copolymer segment (A) is bonded to a polymer segment (B), with the ratio of (A) to (B) being 15/85 to 97/3 by weight, said random copolymer segment (A) being composed of the constitutional units represented by the formulas I and II below ##STR14## wherein the amount of I in said segment (A) is from 30 to 80 wt% and the amount in II in said segment (A) is from 70 to 20 wt.%, and said polymer segment (B) being composed of the constitutional units represented by the formula ##STR15## wherein R is hydrocarbyl of from 1 to 20 carbon atoms, said process comprising the steps of:
- (a) performing living polymerization of ethylene and propylene at a temperature of less than -50.degree. C. in the presence of a catalyst comprising (i) a beta-diketone vanadium chelate of the formula ##STR16## wherein R.sup.1 and R.sup.2 are the same or different and are each alkyl or aryl, and (ii) an organoaluminum compound of the formula R.sub.2 AlX, wherein R is an alkyl group of 1 to 8 carbon atoms and X is a halogen atom, to provide a living ethylene-propylene random copolymer having an ethylene-to-propylene ratio of from 30/70 to 80/20 by weight, said vanadium chelate being used in an amount of from 1.times.10.sup.-4 to 0.01 mol per 1 mol of said ethylene and propylene, said organoaluminum compound being used in an amount from about 1.times.10.sup.-3 to 0.1 mol per 1 mol of said ethylene and propylene, and said organoaluminum compound being used in an amount of from 5 to 25 mol per 1 mol of said vanadium chelate; and
- (b) polymerizing the product of step (a) with a methacrylate ester of the formula ##STR17## wherein R is as defined above, to form said block copolymer.
- 23. The process of claim 22 wherein said vanadium chelate comprises a member selected from the group consisting of V(acetylacetonate).sub.3, V(benzoylacetylacetonate).sub.3, and V(dibenzoylmethanate).sub.3.
- 24. The process of claim 23 wherein said organoaluminum compound comprises a member selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride.
- 25. The process according to claim 23 wherein said step (a) polymerization temperature is at -65.degree. C. or below.
- 26. The process according to claim 23 wherein said step (a) polymerization is performed in an inert solvent, said methacrylate ester is added to the product of step (a) while maintaining a temperature of said step (a) product at below -50.degree. C., and thereafter the temperature of the resulting mixture of said methacrylate ester and said ethylene-propylene random copolymer is raised to from 0.degree. to 30.degree. C. to effect said polymerization step (b).
- 27. The process according to claim 26 wherein said polymer segment (B) has a number-average molecular weight of about 500 to 20,000.
- 28. The process according to claim 27 wherein said polymerization step (a) is performed at a temperature of -65.degree. C. or below to provide a living-propylene random copolymer having a M.sub.w /M.sub.n of from 1.05 to 1.40, wherein M.sub.w is the weight-average molecular weight of said copolymer and M.sub.n is the number-average molecular weight of said copolymer, and wherein said polymerization step (a) is conducted in the presence of from about 0.1 to 2 moles of a reaction accelerator per 1 mol of said vanadium compound, said reaction accelerator comprising a number selected from the group consisting of anisole, water, oxygen, methanol, ethanol, isopropanol, ethylbenzolate, and ethylacetate.
Priority Claims (1)
Number |
Date |
Country |
Kind |
59-107617 |
May 1984 |
JPX |
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Parent Case Info
Based On: Rule 60 Continuation of Ser. No. 061,116, filed June 12, 1987, now abandoned which is a Rule 60 Divisional of Ser. No. 738,069, filed May 24, 1985 U.S. Pat. No. 4,704,433.
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Entry |
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Divisions (1)
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Number |
Date |
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Parent |
738069 |
May 1985 |
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Continuations (1)
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Number |
Date |
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Parent |
61116 |
Jun 1987 |
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