US3883493A - Method for producing copolymers of 1-olefins with conjugated dienes - Google Patents

Method for producing copolymers of 1-olefins with conjugated dienes Download PDF

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US3883493A
US3883493A US359069A US35906973A US3883493A US 3883493 A US3883493 A US 3883493A US 359069 A US359069 A US 359069A US 35906973 A US35906973 A US 35906973A US 3883493 A US3883493 A US 3883493A
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aluminum
dithiocarbamate
vanadium
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vanadate
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Takashi Yamao
Shujiro Shiga
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

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  • ABSTRACT A method for preparing copolymers of l-olefins with conjugated dienes, such as an alternating copolymer of ethylene with butadiene, which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a novel catalyst composition comprising (A) at least one dithiocarbamate-containing organoaluminum compound such as or a mixture thereof with at least one organoaluminum compound such as triisobutyl aluminum or diethyl aluminum chloride and (B) at least one transition metal compound selected from vanadium compounds and titanium compounds.
  • a novel catalyst composition comprising (A) at least one dithiocarbamate-containing organoaluminum compound such as or a mixture thereof with at least one organoaluminum compound such as triisobutyl aluminum or diethyl aluminum chloride and (B) at least one transition metal compound selected from vanadium compounds and titanium compounds.
  • This invention relates to a method for preparing copolymers of l-olefins and conjugated dienes using a novel catalyst composition comprising an organoaluminum compound and a transition metal compound.
  • a method for preparing copolymers of l-olefins with conjugated dienes which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a catalyst composition comprising:
  • B at least one transition metal compound selected from the group consisting of vanadium compounds and titanium compounds.
  • the dithiocarbamate-containing organoaluminum compound, which constitutes component (A) in the catalyst composition is represented by various methods.
  • compounds expressed by the formula u c" AlR or R 2 x 5-x n cs AlR x 2 m n 5(n+m) wherein x is more than 0 but less than 3, and n and m are the same as defined above is prepared by exchange reaction between a compound of (Eli; N
  • component (A) a compound of AIR; or AIR,,X wherein R is an organic group containing l to 20 carbon atoms, X is a halogen atom and y is more than 0 but less than 3, respectively.
  • R is an organic group containing l to 20 carbon atoms
  • X is a halogen atom
  • y is more than 0 but less than 3, respectively.
  • component (A) A greater diversity of organoaluminum compounds containing dithiocarbamate groups are synthesized by reacting the resulting compounds with compounds of formula AlR,,X or AlR in proper proportions. These reaction products can also be used effectively as component (A).
  • dithiocarbamate group of the compound represented by the general formula examples include dimethyl dithiocarbamate, diethyl dithiocarbamate, methyl ethyl dithiocarbamate, dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate, and diphenyl dithiocarbamate.
  • the compound represented by the general formula AlR may, for example, be trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum, or triphenyl aluminum.
  • Examples of the compound represented by the general formula AlR,,x are dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide, dihexyl aluminum chloride, diphenyl aluminum chloride, and dicyclohexyl aluminum chloride, of which chlorine or bromine may be replaced by fluorine or iodine.
  • the alkyl group content (represented by n) in the dithiocarbamate-containing organoaluminum compound is less than 0.5, the compound cannot function substantially as an organoaluminum compound.
  • the vanadium compound and the titanium compound used as component (B) of the catalyst composition may. for example, be halides. alcoholates, acetylacetonates, salicylates, or cyclopentadienyl comaounds of these metals.
  • vanadyl trichloride vanadium tetrachloride, vandyl-chlorodio- :lytatonate dichloro, vanadyl monoacetylacetonate, iicyclopentadienyl vanadium dichloride, di-n-propyl nonochloro-ortho-vanadate, ethyl dichloro-rotho Janadate, ethyl dibromo-ortho-vanadate, vanadium Letrabromide, vanadium salicylate dichloride, t-butyl iichloro-ortho-vanadate, phenyl dichloro-orthovana- :late, vanadyl acetylacetonate, vanadyl naphthenate, vanadyl acetate, titanium tetrachloride, butoxy trizhlorotitanium, tributoxy chlorotitanium, tribu
  • the preparation of the catalyst composition may be performed by various methods known in the art. For example, it may be prepared in the presence of monomers to be copolymerized.
  • l-olefins used in this invention are ethylene, propylene, l-butene, l-pentene, lhexene, styrene, and mixtures thereof. Of these, ethylene is especially preferred.
  • the conjugated dienes may be those containing 4 to carbon atoms. Typical examples are butadiene-1,3, isoprene, pentadienel,3, hexadiene l,3, 2,3-dimethylbutadiene-l,3, 2- phenylbutadiene-l ,3, phenylbutadiene-l ,3 or mixtures thereof. Of these, butadiene-l ,3, isoprene, and pentadiene-1,3 are preferred.
  • the copolymerization reaction may be performed in bulk in the substantial absence of a diluent, although it is possible to use a diluent that does not interfere with the copolymerization.
  • a diluent may be an aliphatic hydrocarbon. alicyclic hydrocarbon, aromatic hydrocarbon, or a halogenated product of any one of these hydrocarbons. Typical examples are pentane, hexane, heptane, cyclohexane, benzene. toluene, pe troleum ether, ethylene tetrachloride, dichloroethane, chlorobenzene, and mixtures thereof. Pentane, hexane, petroleum ether, and cyclohexane are especially preferred. As a matter of course, one of the monomers may be used in a greater quantity to make it function as a diluent.
  • the proportion of the diluent to the monomers may be determined arbitrarily.
  • the copolymerization may be carried out at a temperature of lOOC to +500C,
  • the polymerization pressure may usually be from atmospheric pressure to lOO atmospheres.
  • the copolymerization is carried out in an atmosphere which does not interfere with the reaction, namely in an inert gaseous atmosphere such as nitrogen or argon.
  • l-Olefins and conjugated dienes can be copolymerized using the catalyst composition described above. Some examples of the copolymerization will be given below,
  • an amorphous ethylene/isoprene copolymer can be obtained using the catalyst composition described above.
  • the copolymerization of ethylene with isoprene resulted in a crystalline polymer consisting predominantly of ethylene units and only a small proportion of isoprene units, or a polymer consisting predominantly of isoprene units and only a small proportion of ethylene units.
  • ethylene/isoprene amorphous copolymer obtained with the catalyst composition of this invention offers a new material as a synthetic rubber.
  • a copolymer having an intrinsic viscosity [1 of 2 and consisting of 30 mol% of ethylene units and mol% of isoprene units has a glass transition temperature of as low as 62C, and when vulcanized, shows sufficient tensile strength as rubber, and superior permanent compression strain and permanent elongation to those of natural rubber. From the infrared spectrum and the nuclear magnetic resonance spectrum of the product, it was identified as a true copolymer. The uniformity of the proportions of both of these monomers with respect to molecular weight distribution was extremely good.
  • FIG. 1 is an infrared spectrum of the copolymer obtained in Example 1 to be given below;
  • FIG. 2 is a nuclear magnetic resonance spectrum of the same copolymer;
  • FIG. 3 is an infrared spectrum of the ethylenebutadiene alternating copolymer obtained in Example 3.
  • the catalyst composition can be prepared at low temperatures.
  • the catalyst composition is prepared at C, it gives an ethylene/- butadiene alternating copolymer in a very high yield, and it is very easy to produce a copolymer having a mo' lecular weight of greater than 0.4 in terms of [1
  • Another feature of this invention is that when the mol ratio between the organoaluminum compound and the transition metal compound is varied, the resulting product may either be a powdery copolymer or a rubbery copolymer depending upon the mol ratio.
  • the powdery polymer can be formed into a film by hot press, and the rubbery copolymer can be used as a synthetic rubber after vulcanization.
  • EXAMPLE 1 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of isoprene, 1.5 millimols of tri-isobutyl aluminum and l millimol of and cooled to 0C. Furthermore, 1 mol of vanadyl trichloride was added, and immediately then, ethylene was added, and the mixture was stirred for 30 minutes. There was obtained 27.8 g of a polymer. The infrared spectrum of the polymer is shown in FIG. 1 by a thick solid line. For comparison, the infrared spectrum of polyisoprene (thin solid line) and that of polyethylene (broken line) are shown also in FIG. 1.
  • the nuclear magnetic resonance spectrum of the copolymer obtained above is shown in FIG. 2 by a thick solid line.
  • the spectrum (thin solid line) of polyisoprene is shown also in FIG. 2.
  • the copolymer thus obtained was a rubbery elastomeric polymer having an intrinsic viscosity [1 of [.76
  • the permanent compression strain and permanent elongation of the vulcanized ethylene/isoprene copolymer rubber were measured, and compared with those of natural rubber.
  • the permanent compression strain of natural rubber was 39, whereas the ethylene/isoprene copolymer as vulcanized had a permanent compression strain of 34.
  • the permanent elongation of natural rubber was 13, whereas that of the ethylene/ism prene copolymer as vulcanized was 8. In either case, the ethylene/isoprene copolymer obtained in this Example showed superior properties to natural rubber.
  • EXAMPLE 2 A 300 ml autoclave was charged with ml of cyclohexane, 50 ml of isoprene, 2 mmols of Al(iBu) Cl and l mmol of and the contents were cooled to l0C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added, and the mixture was stirred for 30 minutes.
  • EXAMPLE 4 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of butadiene, 4 mmols of A1(i-Bu) and 1 mmol of and the contents were cooled to 5C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. In minutes, 21.4 g of a polymer was obtained. The infrared spectrum and nuclear magnetic resonance spectrum of this polymer showed that it was an alternating copolymer. This polymer had rubbery elasticity, and when vulcanized, became a rubber of good repulsive elasticity.
  • This catalyst composition made it possible for the first time to provide a new material, that is, an ethylene/butadiene alternating copolymer rubber.
  • EXAMPLE 5 A 300 ml autoclave was charged with ml of nhexane, 50 ml of butadiene, 4 mmols of Al(l-lex) and 1 mmol of and the contents were cooled to -10C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, ethylene was added. There was obtained 17.4 g of a polymer, which was identified as a copolymer by its infrared spectrum and nuclear magnetic resonance spectrum.
  • EXAMPLE 7 A 300 ml of autoclave was charged with 70 ml of cyclohexane, 50 ml of isoprene, 1.5 mmols of A1(i-Bu); and 1 mmol of and the contents were cooled to OC. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then, ethylene was added. In 30 minutes, 25.3 g of a polymer was obtained, which had an intrinsic viscosity of 1.10 (dl/g) and a glass transition temperature of 6 1 .5C. It was identified as a copolymer by its infrared spectrum.
  • EXAMPLE 8 A 300 m1 of autoclave was charged with 70 ml of benzene, 50 ml of butadiene, 1.5 mmols of Al(iBu) and 1 mmol of EXAMPLE 9 A 300 ml of autoclave was charged with 70 ml of nhexane, 50 ml of isoprene, 1,5 mmols of Al(i-Bu) and 1 mmol of N saying-Bu) and the contents were cooled to C. Furthermore, 1 mmol of vanadyl trichloride was added, and immediately then, propylene was added. The mixture was stirred for 30 minutes to give 11.7 g of a copolymer.
  • EXAMPLE 10 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of butadiene, 8 mmols of Al(i-Bu) and 2 mmols of and the contents were cooled to -5C. Furthermore, 2 mmols of titanium tetrachloride was added, and immediately then, ethylene was added. The mixture was stirred for 30 minutes to give 1.3 g of a copolymer.
  • EXAMPLE 11 A 300 ml autoclave was charged with 70 ml of cyclohexane, ml of butadiene, 40 ml of isoprene, 5 mmols of Al(C,H and 1 mmol of C-H 2:11 Cu )Al(C E9) and the contents were cooled to 5C. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then ethylene was added. The mixture was stirred for 30 minutes to form 29.3 g of a terpolymer.
  • EXAMPLE 12 A 300 ml autoclave was charged with 70 ml of nhexane, 50 ml of 1,3-pentadiene, 4 mmols of Al(C H and 1 mmol of CH 5 n and the contents were cooled to 5C. Furthermore, 1 mmol of vanadium tetrachloride was added, and immediately then, ethylene was added. The mixture was stirred for 30 minutes to give 27.1 g of a copolymer.
  • a method for preparing copolymers of l-olefins with conjugated dienes which comprises copolymerizing at least one l-olefin with at least one conjugated diene using a catalyst composition comprising:
  • B at least one transition metal compound selected from the group consisting of vanadium or titanium halides, alcoholates, acetyl acetonates, salicylates and cyclopentadienyl compounds.
  • dithiocarbamate group is selected from the group consisting of di methyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate, dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.
  • organoaluminum compound of the formula AIR is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributy] aluminum, triisobutyl aluminum, tripentyl aluminum. trihexyl alumi num, triheptyl aluminum and triphenyl aluminum.
  • organoaluminum compound of the formula AIR X is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide,
  • diethyl aluminum chloride ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, and these compounds with their chlorine or bromine replaced by fluorine or iodine.
  • vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochloro-orthovanadate, ethyl dichloro-ortho'vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-orthovanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium, ethoxy t
  • vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate and mixtures thereof.
  • said l-olefin is selected from the group consisting of ethylene, propylene, l-butene, l-pentene, l-hexene, styrene or mixtures thereof, and said conjugated diene is butadiene- [,3, isoprene, pentadiene-l ,3, hexadiene-l ,3, 2,3-dimethylbutadienel ,3, Z-phenylbutadiened ,3 and mixtures thereof.
  • said l-olefin is selected from the group consisting of ethylene, and said conjugated diene is butadiene-l,3, isoprene and pentadienel ,3.
  • said diluent is selected from the group consisting of pentane, hexane, petroleum ether and cyclohexane.
  • a catalyst composition for use in copolymerizing l-olefins with conjugated dienes comprising:
  • A at least one dithiocarbamate-containing organoaluminum compound represented by the following formula wherein each of R, R" and R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, m is not less than 0.05, n is not less than 0.5, and n+ m is not more than 3, or a mixture thereof with at least one organoaluminum compound represented by the following formula wherein R is an organic group containing 1 to 20 carbon atoms, X is a halogen atom, and y is more than 0 but less than 3, and b. at least one transition metal compound selected from the group consisting of vanadium or titanium halides, alcoholates, acetyl acetonates, salicylates and cyclopentadienyl compounds.
  • composition of claim 14 wherein said dithiocarbamate group is selected from the group consisting of dimethyl dithiocarbamate, diethyl dithiocarbamate, methylethyl dithiocarbamate dipropyl dithiocarbamate, dibutyl dithiocarbamate, phenylethyl dithiocarbamate, tolylethyl dithiocarbamate and diphenyl dithiocarbamate.
  • composition of claim 14 wherein said organoaluminum compound of the formula AlR is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, trisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum and triphenyl aluminum.
  • composition of claim 14 wherein said organoaluminum compound of the formula AlR X is selected from the group consisting of dimethyl aluminum chloride, methyl aluminum dichloride, dimethyl aluminum bromide, methyl aluminum dibromide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, diisobutyl aluminum chloride, isobutyl aluminum dichloride, isobutyl aluminum sesquibromide, dihexyl aluminum chloride, diphenyl aluminum chloride, dicyclohexyl aluminum chloride, or these compounds with their chlorine or bromine replaced by fluorine and iodine.
  • vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, vanadyl chloro-acetylacetonate vanadyl dichloro-monoacetylacetonate, dicyclopentadienyl vanadium dichloride, di-n-propyl monochlormorthovanadate, ethyl dichloro-ortho-vanadate, ethyl dibromo-ortho-vanadate, vanadium tetrabromide, vanadium salicylate dichloride, t-butyl dichloro-orthovanadate, phenyl dichloro-ortho-vanadate, vanadyl acetylacetonate, titanium tetrachloride, butoxy trichlorotitanium, tributoxy chlorotitanium,-ethoxy trichlor
  • vanadium and titanium compounds are selected from the group consisting of vanadyl trichloride, vanadium tetrachloride, ethyl dichloro-ortho-vanadate, dicyclopentadienyl vanadium dichloride, titanium tetrachloride, diethyl chloro-ortho-vanadate, and mixtures thereof.

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4378456A (en) * 1980-09-19 1983-03-29 Bayer Aktiengesellschaft Terpolymers of ethylene, butadiene and isoprene and a process for their preparation
US4378455A (en) * 1979-02-19 1983-03-29 Maruzen Petrochemical Co., Ltd. Process for bulk alternating copolymerization of propylene and butadiene
US5364916A (en) * 1991-09-11 1994-11-15 Dsm N.V. Catalyst and process for the preparation of an olefin polymer
US6288191B1 (en) * 1998-03-06 2001-09-11 Sumitomo Chemical Company, Limited Ethylene-isoprene random copolymer
US6465383B2 (en) 2000-01-12 2002-10-15 Eastman Chemical Company Procatalysts, catalyst systems, and use in olefin polymerization
US6677410B2 (en) 2000-01-12 2004-01-13 Eastman Chemical Company Procatalysts, catalyst systems, and use in olefin polymerization
US6696380B2 (en) 2000-01-12 2004-02-24 Darryl Stephen Williams Procatalysts, catalyst systems, and use in olefin polymerization

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US3318858A (en) * 1962-08-06 1967-05-09 Sumitomo Chemical Co Method for polymerizing olefins in the presence of a coordination catalyst modified b the presence of a sulfur containing compound
US3542693A (en) * 1967-12-13 1970-11-24 Avisun Corp Catalytic system containing disubstituted carbamates
US3652519A (en) * 1968-12-21 1972-03-28 Maruzen Petrochem Co Ltd Alternating copolymers of butadiene and alpha-olefine and a process for their preparation
US3652518A (en) * 1968-12-26 1972-03-28 Maruzen Petrochem Co Ltd Process for preparing alternating copolymers of butadiene and alpha-olefine and high molecular weight alternating copolymers
US3700638A (en) * 1969-04-25 1972-10-24 Maruzen Petrochem Co Ltd Process for preparing alternating copolymer of butadiene and alpha-olefine
US3714133A (en) * 1969-05-13 1973-01-30 Maruzen Petrochem Co Ltd PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND alpha -OLEFINE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND alpha -OLEFINE CONTAINING CIS-CONFIGURATION BUTADIENE UNIT
US3737416A (en) * 1970-03-17 1973-06-05 Maruzen Petrochem Co Ltd Process for preparing an alternating copolymer of an alpha-olefin and butadiene
US3737417A (en) * 1970-05-07 1973-06-05 Maruzen Petrochem Co Ltd Process for preparing an alternating copolymer of an alpha-olefin and a conjugated diene
US3766153A (en) * 1969-05-13 1973-10-16 Maruzen Petrochem Co Ltd Process for preparing alternating copolymer of butadiene and alphaolefine and novel alternating copolymer of butadiene and alphaolefine containing cis configuration butadiene unit

Patent Citations (9)

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Publication number Priority date Publication date Assignee Title
US3318858A (en) * 1962-08-06 1967-05-09 Sumitomo Chemical Co Method for polymerizing olefins in the presence of a coordination catalyst modified b the presence of a sulfur containing compound
US3542693A (en) * 1967-12-13 1970-11-24 Avisun Corp Catalytic system containing disubstituted carbamates
US3652519A (en) * 1968-12-21 1972-03-28 Maruzen Petrochem Co Ltd Alternating copolymers of butadiene and alpha-olefine and a process for their preparation
US3652518A (en) * 1968-12-26 1972-03-28 Maruzen Petrochem Co Ltd Process for preparing alternating copolymers of butadiene and alpha-olefine and high molecular weight alternating copolymers
US3700638A (en) * 1969-04-25 1972-10-24 Maruzen Petrochem Co Ltd Process for preparing alternating copolymer of butadiene and alpha-olefine
US3714133A (en) * 1969-05-13 1973-01-30 Maruzen Petrochem Co Ltd PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND alpha -OLEFINE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND alpha -OLEFINE CONTAINING CIS-CONFIGURATION BUTADIENE UNIT
US3766153A (en) * 1969-05-13 1973-10-16 Maruzen Petrochem Co Ltd Process for preparing alternating copolymer of butadiene and alphaolefine and novel alternating copolymer of butadiene and alphaolefine containing cis configuration butadiene unit
US3737416A (en) * 1970-03-17 1973-06-05 Maruzen Petrochem Co Ltd Process for preparing an alternating copolymer of an alpha-olefin and butadiene
US3737417A (en) * 1970-05-07 1973-06-05 Maruzen Petrochem Co Ltd Process for preparing an alternating copolymer of an alpha-olefin and a conjugated diene

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4378455A (en) * 1979-02-19 1983-03-29 Maruzen Petrochemical Co., Ltd. Process for bulk alternating copolymerization of propylene and butadiene
US4378456A (en) * 1980-09-19 1983-03-29 Bayer Aktiengesellschaft Terpolymers of ethylene, butadiene and isoprene and a process for their preparation
US5364916A (en) * 1991-09-11 1994-11-15 Dsm N.V. Catalyst and process for the preparation of an olefin polymer
US6288191B1 (en) * 1998-03-06 2001-09-11 Sumitomo Chemical Company, Limited Ethylene-isoprene random copolymer
US6465383B2 (en) 2000-01-12 2002-10-15 Eastman Chemical Company Procatalysts, catalyst systems, and use in olefin polymerization
US6677410B2 (en) 2000-01-12 2004-01-13 Eastman Chemical Company Procatalysts, catalyst systems, and use in olefin polymerization
US6696380B2 (en) 2000-01-12 2004-02-24 Darryl Stephen Williams Procatalysts, catalyst systems, and use in olefin polymerization

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GB1406928A (en) 1975-09-17
JPS497395A (de) 1974-01-23
DE2323740C3 (de) 1978-05-24
DE2323740A1 (de) 1973-11-29
JPS554762B2 (de) 1980-01-31
DE2323740B2 (de) 1977-09-29
FR2184087A1 (de) 1973-12-21
FR2184087B1 (de) 1976-04-23

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