USRE28850E - Process for preparing alternating copolymer of butadiene and α-olefine and novel alternating copolymer of butadiene and α-olefine containing cis-configuration butadiene unit - Google Patents

Process for preparing alternating copolymer of butadiene and α-olefine and novel alternating copolymer of butadiene and α-olefine containing cis-configuration butadiene unit Download PDF

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USRE28850E
USRE28850E US05/594,512 US59451275A USRE28850E US RE28850 E USRE28850 E US RE28850E US 59451275 A US59451275 A US 59451275A US RE28850 E USRE28850 E US RE28850E
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butadiene
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Akihiro Kawasaki
Isao Maruyama
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Maruzen Petrochemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers 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
    • C08F236/04Copolymers 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers 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
    • C08F236/04Copolymers 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
    • C08F236/06Butadiene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04Monomers containing three or four carbon atoms
    • C08F210/06Propene

Definitions

  • the present invention relates to a process for preparing an alternating copolymer of butadiene and ⁇ -olefine and a novel alternating copolymer obtained thereby.
  • the novel alternating copolymer of this invention contains considerable amounts of cis-configuration butadiene unit.
  • German Pat. 1,173,254 claims a process for preparing a copolymer of conjugated diene and mono-olefine using vanadium (V) oxychloride as the catalyst, but the examples do not show a copolymerization reaction of butadiene and propylene.
  • German Pat. 1,144,924 claims a process for preparing a copolymer of diene and ethylene or propylene by using a catalyst system consisting of a compound of Ti, Zr, Ce, V, Nb, Ta, Cr, Mo or W in which the metal is at least in part below a valency of 3.
  • This patent shows the copolymerization reaction of butadiene and ethylene by titanium tetrachloride-lithium-aluminum hydride, titanium, tetrachloride-phenylmagnesium bromide, titanium tetrachloride-sodium dispersion, zirconium, tetrachloride-tintetrabutyl and tetraoctyltitanate-phenylmagnesium bromide catalyst systems in its examples, but a process for preparing a copolymer of butadiene and propylene is not shown. Belgian Pat.
  • 625,657 also describes a process for preparing co- and terpolymers of butadiene with ethylene and (or) ⁇ -olefines by using a catalyst system containing a hydrocarbon-soluble vanadium compound and an organoaluminum compound containing more than one organic group having strong sterical hindrance, e.g. 3-methyl-butyl, cycloalkyl or cyclopentyl methyl, and it claims a process for preparing ethylene-propylene-butadiene terpolymer.
  • a catalyst system containing a hydrocarbon-soluble vanadium compound and an organoaluminum compound containing more than one organic group having strong sterical hindrance, e.g. 3-methyl-butyl, cycloalkyl or cyclopentyl methyl
  • British Pat. 1,108,630 shows a process for preparing a rubbery random copolymer of butadiene and propylene of high molecular weight with high content of propylene by using a three components catalyst system consisting of trialkylaluminum, iodine and a compound having the general formula of TiBr n Cl 4 -n wherein n is zero or an integer of 1 to 4.
  • the microstructure of butadiene unit and the content of propylene unit in the copolymer are shown in the patent. But there are shown no experimental results which support the assumption which the copolymer should be a random copolymer of butadiene and propylene.
  • a random copolymer of butadiene and propylene was also prepared by using a catalyst system consisting of triethylaluminum, titanium tetrachloride and polypropylene oxide.
  • Polypropylene oxide was used as a randomizer and therefore a copolymer of butadiene and propylene prepared by the catalyst system of triethylaluminum and titanium tetrachloride was shown to be blocktype.
  • 1,026,615 claims a process for preparing a random copolymer of butadiene and propylene by forming a catalyst system of triethylaluminum and titanium tetrachloride in the presence of propylene, and then adding butadiene to the catalyst system.
  • the propylene content of the copolymer was much higher than that of the copolymer prepared by the catalyst formed after the monomers were mixed. This result is inconsistent with the result described in the above paper.
  • a copolymerization reaction of butadiene and propylene was also carried out by using a catalyst system of triethylaluminum and titanium tetrachloride prepared in propylene and the product was confirmed, by fractional precipitation test, to be a copolymer of butadiene and propylene (Chemistry of High Polymers, The Society of Polymer Science, Japan, 20, 461 (1963)).
  • the content of this paper corresponds to that of the above British patent, but there is no description in it showing that the copolymer should be a random copolymer of butadiene and propylene.
  • the copolymer showed a characteristic infra-red absorption band at 11.95 microns. It was ascribed to trisubstituted ethylene structure. Therefore, the result does not support the assumption that the copolymer should be a random or alternating copolymer of butadiene and propylene.
  • the object of the present invention is to provide new catalytic systems giving high molecular weight alternating copolymer of butadiene and ⁇ -olefine in high yield.
  • the alternating copolymers of this invention are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.
  • the main components forming the catalyst systems were an organoaluminum compound and a vanadium compound.
  • the main components forming the catalyst systems of this invention are an organoaluminum compound and a titanium compound and moreover considerable amounts of cis 1.4-configuration and small amounts of 1.2-configuration are found in the butadiene unit of the alternating copolymer.
  • the structure of the alternating copolymer prepared by the catalyst system of an organoaluminum compound and a vanadim compound previously reported is different from that of the alternating copolymer prepared by the catalyst system of an organoaluminum compound and a titanium compound of this invention. Therefore the alternating copolymers of butadiene and ⁇ -olefine prepared by the process of this invention are new materials.
  • the carbonyl group containing compound which form the third component of the catalyst systems of this invention are carbon dioxide, aldehyde, keto-aldehyde, ketone, carboxylic acid, keto-carboxylic acid, oxy-carboxylic acid, carboxylic acid halide, keto-carboxylic acid halide, oxy-carboxylic acid halide, carboxylic acid anhydride, keto-carboxylic acid anhydride, oxy-carboxylic acid anhydride, salt of carboxylic acid, salt of keto-carboxylic acid, salt of oxy-carboxylic acid, ester of carboxylic acid, ester of keto-carboxylic acid, ester of oxy-carboxylic acid, carbonyl halide, carbonate, carbonic ester, lactone, ketene, quinone, acyl peroxide, metal complex involving carbonyl group, acid amide, acid imide, isocyanate, aminoacid, urein, ureide, salt
  • the halogen used as the other third component of the catalyst system of this invention is chlorine, bromine iodine or fluorine.
  • the halogen compounds which form the other third component of the catalyst system of this invention are the compounds having transition metal-X linkage (X is halogen) such as compounds having the general formulae VX 4 , VOX 3 , WX 6 , MoX 5 , CrO 2 X 2 , ZrX 4 , FeX 3 , OV(OR) n X 3 -n (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), Zr(OR) 2 X 2 , Ti(OR) n X 4 -n (n is a number from 1 to 3), Zr(OR) 3 X, OV(C 5 H 7 O 2 ) n X 3 -n (n is a number from 1 to 2), V(C 5 H
  • R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), VOX 3 , VX 4 , CrO 2 X 2 , NiX 2 , MoX 5 , ZrX 4 , PX 5 , SbX 5 , AlOX, WX 6 , MnX 2 , M g X 2 , and the like.
  • Lewis base such as ether, pyridine, amine, phosphine, derivatives of these compounds, etc.
  • the halogen compounds which form the fourth component of the catalyst system of this invention are the ones showing Lewis acid property such as compounds of the general formulae VX 4 (wherein X is halogen, hereinafter the same), VOX 3 , WX 6 , MoX 5 , CrO 2 X 2 , ZrX 4 , FeX 3 , BX 3 , PX 5 , SnX 4 , SbX 5 , AlOX, AlX 3 , AlR n X 3 -n (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical and n is a number from 1 to 2), WX 6 , CuX, MnX 2 , MgX 2 , ZnX 2 , HgX 2 , BiX 3 , NiX 2 , etc.; Lewis base complex compounds of the above mentioned halogen
  • the metal oxide or metalloid oxide which forms the other fourth component of the catalyst system of the present invention are magnesium oxide, zinc oxide, aluminum oxide, titanium dioxide, vanadium pentoxide, silicon dioxide, silica-alumina, zeolite, boron trioxide, etc.
  • the molar ratio of organoaluminum compound which forms the first component of the catalyst system of the present invention to titanium tetrahalide which forms the second component of the catalyst system should be higher than (1.5 Al/Ti>1.5).
  • the preparation of the alternating copolymer of butadiene and ⁇ -olefine is carried out by contacting butadiene with ⁇ -olefine in liquid phase in the presence of the catalyst system described above.
  • the copolymerization reaction is generally carried out in the presence of a liquid organic diluent.
  • a suitable diluent that can be used for the copolymerization reaction is a hydrocarbon compound, such as heptane, octane, isooctane, benzene or toluene.
  • the temperature of the copolymerization reaction may be varied from -100° C. to 50° C. and sufficient pressure is employed to keep the monomers in liquid phase.
  • the molar ratio of butadiene to ⁇ -olefine in the initial monomer composition may be from 20:80 to 80:20 and more preferably is 50:50.
  • the product is precipitated and deashed by using a methanol-hydrochloric acid mixture.
  • the precipitated product is washed with methanol for several times and dried under vacuum. Thereafter the product is extracted with methyl ethyl ketone and diethyl ether successively.
  • the methyl ethyl ketone soluble fraction is a low molecular weight alternating copolymer and methyl ethyl ketone insoluble and diethyl ether soluble fraction is a high molecular weight alternating copolymer.
  • FIG. 2 shows the nuclear magnetic resonance spectrum of the copolymer
  • FIG. 3 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and 4-methyl pentene-1 prepared by the process of this invention
  • FIG. 5 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and pentene-1 prepared by the process of this invention
  • FIG. 7 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and butene-1 prepared by the process of this invention
  • FIG. 9 shows the infra-red spectrum of the alternating copolymer of butadiene and styrene prepared by the process of this invention.
  • FIG. 10 shows the nuclear magnetic resonance spectrum of the copolymer.
  • composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for 1:1 copolymer of butadiene and propylene.
  • Copolymer compositions were determined by measuring the ratio of peak area at 4.65 ⁇ of butadiene unit to that of doublet at 9.11 ⁇ and 9.20 ⁇ of propylene unit.
  • the usual, dry, air-free technique was employed and 3.5 milliliters toluene, 0.12 milliliter isobutyric acid and 0.5 millimole titanium tetraiodide were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 5.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, were put successively into the bottle also employing the usual, dry, air-free technique.
  • FIG. 1 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene prepared by the process of Exp. No. 3.
  • FIG. 2 shows the nuclear magnetic resonance spectrum of the copolymer.
  • the product obtained by the vulcanization had the following values:
  • the microstructure of butadiene unit of the copolymer was as follows:
  • the copolymer is an alternating copolymer of butadiene and 4-methyl pentene-1.
  • composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and 4-methyl pentene-1.
  • FIG. 3 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and 4-methyl-pentene-1 prepared by the process of Exp. No. 4.
  • FIG. 4 shows the nuclear magnetic resonance spectrum of the copolymer.
  • the copolymer is an alternating copolymer of butadiene and pentene-1.
  • composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and pentene-1.
  • FIG. 5 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and pentene-1 prepared by the process of Exp. No. 5.
  • FIG. 6 shows the nuclear magnetic resonance spectrum of the copolymer.
  • the copolymer is an alternating copolymer of butadiene and butene-1.
  • composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and butene-1.
  • FIG. 7 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and butene-1 prepared by the process of Exp. No. 4.
  • FIG. 8 shows the nuclear magnetic resonance spectrum of the copolymer.
  • the copolymer is an alternating copolymer of butadiene and styrene.
  • composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and styrene.
  • FIG. 9 shows the infra-red spectrum of the alternating copolymer of butadiene and styrene prepared by the process of Exp. No. 8.
  • FIG. 10 shows the nuclear magnetic resonance spectrum of the copolymer.
  • the yield of the high molecular weight alternating copolymer of butadiene and propylene was increased by adding halogen or halogen compound to the three components catalyst system of organoaluminum compound, titanium tetrachloride and carbonyl compound.
  • 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.2 millimole boron trifluoride diethyl ester complex were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 100° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the conventional, dry, air-free technique.
  • the conventional, dry, air-free technique was employed and 5.0 milliliters toluene, 1.0 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 1.2 millimoles chromium (VI) oxychloride were put successively in a 25 milliliter glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.5 milliliters triisobutylaluminum solution in toluene (1 molar solution), 3 milliliters styrene and 2 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The yield of alternating copolymer of butadiene and styrene was 0.53 g.

Abstract

A process for preparing alternating copolymer of butadiene and α-olefine which comprises contacting butadiene and the α-olefine in liquid phase with a catalyst system comprising the first component of AIR3 wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical in which at least one R is selected from the group consisting of alkyl having at least 3 carbon atoms per one molecule, aryl and cycloalkyl radical and the second component of TiX'4 wherein X' is selected from the group consisting of chlorine, bromine and iodine, or a catalyst system comprising the first component of AlR3 wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical, and the second component of TiX'4 wherein X' is the same as that defined above and the third component of a carbonyl group-containing compound. An alternating copolymer of butadiene and α-olefine, the microstructure of butadiene unit of the alternating copolymer contains cis-configuration. The alternating copolymers are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.

Description

RELATED APPLICATIONS
This application is related to application Ser. Nos. 884,479 and 884,871, filed Dec. 12 and 15, 1969, respectively, and now U.S. Pat. Nos. 3,652,519 and 3,652,518, each of Mar. 28, 1972.
This is a division of application Ser. No. 35,637, filed May 8, 1970, now U.S. Pat. No. 3,714,133.
BACKGROUND OF THE INVENTION (1) Field of the Invention
The present invention relates to a process for preparing an alternating copolymer of butadiene and α-olefine and a novel alternating copolymer obtained thereby. The novel alternating copolymer of this invention contains considerable amounts of cis-configuration butadiene unit.
(2) Description of the Prior Art
Because of its chipping and cutting properites and its low skid resistance, the demand for cis-1.4 polybutadiene in the field of automobile tires is not so large as was expected at first. The defects have been ascribed to its unbranched straight-chain structure. In order to overcome these defects, many attempts have been made to produce alternating copolymers of butadiene and α-olefine, for example, butadiene and propylene, butadiene and 1-butene, etc. However, in general, it is not easy to produce even a random copolymer of butadiene and α-olefine by an ionic catalyst.
For instance, German Pat. 1,173,254 claims a process for preparing a copolymer of conjugated diene and mono-olefine using vanadium (V) oxychloride as the catalyst, but the examples do not show a copolymerization reaction of butadiene and propylene. German Pat. 1,144,924 claims a process for preparing a copolymer of diene and ethylene or propylene by using a catalyst system consisting of a compound of Ti, Zr, Ce, V, Nb, Ta, Cr, Mo or W in which the metal is at least in part below a valency of 3. This patent shows the copolymerization reaction of butadiene and ethylene by titanium tetrachloride-lithium-aluminum hydride, titanium, tetrachloride-phenylmagnesium bromide, titanium tetrachloride-sodium dispersion, zirconium, tetrachloride-tintetrabutyl and tetraoctyltitanate-phenylmagnesium bromide catalyst systems in its examples, but a process for preparing a copolymer of butadiene and propylene is not shown. Belgian Pat. 625,657 also describes a process for preparing co- and terpolymers of butadiene with ethylene and (or) α-olefines by using a catalyst system containing a hydrocarbon-soluble vanadium compound and an organoaluminum compound containing more than one organic group having strong sterical hindrance, e.g. 3-methyl-butyl, cycloalkyl or cyclopentyl methyl, and it claims a process for preparing ethylene-propylene-butadiene terpolymer. However, no example of butadiene-propylene copolymer is shown in it.
On the other hand, British Pat. 1,108,630 shows a process for preparing a rubbery random copolymer of butadiene and propylene of high molecular weight with high content of propylene by using a three components catalyst system consisting of trialkylaluminum, iodine and a compound having the general formula of TiBrn Cl4 -n wherein n is zero or an integer of 1 to 4. The microstructure of butadiene unit and the content of propylene unit in the copolymer are shown in the patent. But there are shown no experimental results which support the assumption which the copolymer should be a random copolymer of butadiene and propylene. A random copolymer of butadiene and propylene was also prepared by using a catalyst system consisting of triethylaluminum, titanium tetrachloride and polypropylene oxide. Polypropylene oxide was used as a randomizer and therefore a copolymer of butadiene and propylene prepared by the catalyst system of triethylaluminum and titanium tetrachloride was shown to be blocktype. The molar ratio of triethylaluminum to titanium tetrachloride was 1.08 (Al/Ti=1.08) (paper presented at 2nd Symposium on Polymer Synthesis, Tokyo, Oct. 5, 1968, the Society of Polymer Science, Japan). British Pat. 1,026,615 claims a process for preparing a random copolymer of butadiene and propylene by forming a catalyst system of triethylaluminum and titanium tetrachloride in the presence of propylene, and then adding butadiene to the catalyst system. According to the patent, the propylene content of the copolymer was much higher than that of the copolymer prepared by the catalyst formed after the monomers were mixed. This result is inconsistent with the result described in the above paper. A copolymerization reaction of butadiene and propylene was also carried out by using a catalyst system of triethylaluminum and titanium tetrachloride prepared in propylene and the product was confirmed, by fractional precipitation test, to be a copolymer of butadiene and propylene (Chemistry of High Polymers, The Society of Polymer Science, Japan, 20, 461 (1963)). The molar ratio of triethylaluminum to titanium tetrachloride of the above catalyst system was 1.5 (Al/Ti=1.5). The content of this paper corresponds to that of the above British patent, but there is no description in it showing that the copolymer should be a random copolymer of butadiene and propylene.
According to the methods of British Patent 982,708, a mixture containing 80-95 mole percent butadiene, the rest being 4-methyl-1-pentene, is polymerized at a temperature in the range 0° to 30° C. by a catalyst system which is the reaction product of vanadium (V) oxychloride with triisobutylaluminum, an aluminum-dialkyl monochloride or an aluminum sesquialkyl chloride. The microstructure of the copolymer is not shown in the patent. British Patent 924,654 describes a process for preparing a copolymer of butadiene and propylene by using an "Alfin" catalyst. The copolymer showed a characteristic infra-red absorption band at 11.95 microns. It was ascribed to trisubstituted ethylene structure. Therefore, the result does not support the assumption that the copolymer should be a random or alternating copolymer of butadiene and propylene.
Recently, Furukawa et al. also reported the process of preparing alternating copolymers of butadiene and α-olefine by using vanadyl (V) chloride-diethylaluminum monochloride-triethylaluminum catalyst system (22nd Annual Meeting of Japan Chemical Society, Tokyo, Mar. 31, 1969). However, the molecular weight of the copolymer was very low and its intrinsic viscosity did not exceed 0.1 dl./g.
Consequently, as far as the inventors know, with the exception of the methods of Furukawa et al. described above, there is no prior art in connection with alternating copolymers of butadiene and α-olefine nor of a process for their preparation.
SUMMARY OF THE INVENTION
The object of the present invention is to provide new catalytic systems giving high molecular weight alternating copolymer of butadiene and α-olefine in high yield.
In accordance with this invention, we have found that by using the catalyst system composed of the first component of an organoaluminum compound having the general formula of AlR3 where R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radicals and at least one R is selected from the group consisting of an alkyl radical having at least 3 carbon atoms, aryl radical and cycloalkyl radical and the second component of titanium tetrahalide having the general formula of TiX'4 (wherein X' represents chlorine, bromine or iodine, hereinafter the same) or by using the catalyst system composed of the first component of AlR3 wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radicals, the second component of TiX'4 (wherein X' is the same as that defined above) and the third component of a carbonyl group-containing compound, high molecular weight alternating copolymers of butadiene and α-olefine can be produced in high yield. We have also found that by adding halogen (fluorine inclusive), halogen (fluorine inclusive) containing compound, metal oxide or metalloid oxide to the above mentioned catalyst systems, the catalytic properties of the above mentioned catalysts can be further improved.
The alternating copolymers of this invention are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.
The microstructure of butadiene unit of the alternating copolymer of butadiene and α-olefine prepared by the methods of Furukawa et al. described above was trans 1.4-configuration. The main components forming the catalyst systems were an organoaluminum compound and a vanadium compound. On the other hand the main components forming the catalyst systems of this invention are an organoaluminum compound and a titanium compound and moreover considerable amounts of cis 1.4-configuration and small amounts of 1.2-configuration are found in the butadiene unit of the alternating copolymer. In other words the structure of the alternating copolymer prepared by the catalyst system of an organoaluminum compound and a vanadim compound previously reported is different from that of the alternating copolymer prepared by the catalyst system of an organoaluminum compound and a titanium compound of this invention. Therefore the alternating copolymers of butadiene and α-olefine prepared by the process of this invention are new materials.
The carbonyl group containing compound which form the third component of the catalyst systems of this invention are carbon dioxide, aldehyde, keto-aldehyde, ketone, carboxylic acid, keto-carboxylic acid, oxy-carboxylic acid, carboxylic acid halide, keto-carboxylic acid halide, oxy-carboxylic acid halide, carboxylic acid anhydride, keto-carboxylic acid anhydride, oxy-carboxylic acid anhydride, salt of carboxylic acid, salt of keto-carboxylic acid, salt of oxy-carboxylic acid, ester of carboxylic acid, ester of keto-carboxylic acid, ester of oxy-carboxylic acid, carbonyl halide, carbonate, carbonic ester, lactone, ketene, quinone, acyl peroxide, metal complex involving carbonyl group, acid amide, acid imide, isocyanate, aminoacid, urein, ureide, salt of carbamic acid, ester of carbamic acid, ureide acid, etc.
The halogen used as the other third component of the catalyst system of this invention is chlorine, bromine iodine or fluorine. The halogen compounds which form the other third component of the catalyst system of this invention are the compounds having transition metal-X linkage (X is halogen) such as compounds having the general formulae VX4, VOX3, WX6, MoX5, CrO2 X2, ZrX4, FeX3, OV(OR)n X3 -n (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), Zr(OR)2 X2, Ti(OR)n X4 -n (n is a number from 1 to 3), Zr(OR)3 X, OV(C5 H7 O2)n X3 -n (n is a number from 1 to 2), V(C5 H5)n X4 -n (n is a number from 1 to 2, V(C5 H5)2 X, OV(C5 H5)X2, Ti(C5 H5)2 X, Ti(C5 H5)X3, Ti(C5 H5)2 X2, (C5 H5)Ti(OR)X2, (C5 H5)2 CrX, (C5 H5)Mo(CO)3 X, (C5 H5)2 IrX3, etc.; and alkane compounds having C-X linkage wherein X is halogen such as tert-butyl chloride, tert-butyl bromide, tert-butyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, etc.; Lewis acid-base complex compounds which formed from halogen compounds showing Lewis acid property such as compounds of the general formulae Hg X2 (wherein X is halogen, hereinafter the same). CuX, ZnX2, BiX3, FeX3, SnX4, BX3, AlX3, AlRn X3 -n (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), VOX3, VX4, CrO2 X2, NiX2, MoX5, ZrX4, PX5, SbX5, AlOX, WX6, MnX2, Mg X2, and the like. Lewis base such as ether, pyridine, amine, phosphine, derivatives of these compounds, etc., are also employed. The halogen compounds which form the fourth component of the catalyst system of this invention are the ones showing Lewis acid property such as compounds of the general formulae VX4 (wherein X is halogen, hereinafter the same), VOX3, WX6, MoX5, CrO2 X2, ZrX4, FeX3, BX3, PX5, SnX4, SbX5, AlOX, AlX3, AlRn X3 -n (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical and n is a number from 1 to 2), WX6, CuX, MnX2, MgX2, ZnX2, HgX2, BiX3, NiX2, etc.; Lewis base complex compounds of the above mentioned halogen compounds showing Lewis acid property such as compounds of the general formulae AlX3 -O(C2 H5)2, BX3 -O(C2 H5)2, ZnX2 -Py (wherein Py represents pyridine, hereinafter the same), VOCl3 -O(C2 H5)2, NiX2 -Py, FeX3 -O(C2 H5)2, HgX2 -Py, etc.; organoaluminum compounds having Al-X linkage such as compounds of Al(OR)n X3 -n (n is a number from 1 to 2), etc., organotransition metal compounds having transition metal-X linkage such as compounds of the general formulae OV(OR)n X3 -n (n is a number from 1 to 2), Ti(OR)n X4 -n (n is a number from 1 to 3), Zr(OR)2 X2, Zr(OR)3 X, OV(C5 H7 O2)n X3 -n (n is a number from 1 to 2), V(C5 H5)n X4 -n (n is a number from 1 to 2), V(C5 H5)2 X, OV(C5 H5)X2, Ti(C5 H5)2 X, Ti(C5 H5)X3, Ti(C5 H5).sub. 2 X2, (C5 H5)Ti(OR)X2, (C5 H5)2 CrX, (C5 H5)Mo(CO)3 X, (C5 H5)2 IrX3, etc.; halogenated alkane compounds such as tert-butyl halide, sec-butyl halide, carbon tetrahalide. The metal oxide or metalloid oxide which forms the other fourth component of the catalyst system of the present invention are magnesium oxide, zinc oxide, aluminum oxide, titanium dioxide, vanadium pentoxide, silicon dioxide, silica-alumina, zeolite, boron trioxide, etc.
In the preferred embodiment, the molar ratio of organoaluminum compound which forms the first component of the catalyst system of the present invention to titanium tetrahalide which forms the second component of the catalyst system should be higher than (1.5 Al/Ti>1.5).
The olefine should be one having the general formula:
CH.sub.2 =CHR'
(in this formula, R' may be a normal chain or branched chain lower alkyl group or a phenyl group).
The preparation of the alternating copolymer of butadiene and α-olefine is carried out by contacting butadiene with α-olefine in liquid phase in the presence of the catalyst system described above. The copolymerization reaction is generally carried out in the presence of a liquid organic diluent. A suitable diluent that can be used for the copolymerization reaction is a hydrocarbon compound, such as heptane, octane, isooctane, benzene or toluene. The temperature of the copolymerization reaction may be varied from -100° C. to 50° C. and sufficient pressure is employed to keep the monomers in liquid phase. The molar ratio of butadiene to α-olefine in the initial monomer composition may be from 20:80 to 80:20 and more preferably is 50:50.
At the completion of the copolymerization reaction, the product is precipitated and deashed by using a methanol-hydrochloric acid mixture. The precipitated product is washed with methanol for several times and dried under vacuum. Thereafter the product is extracted with methyl ethyl ketone and diethyl ether successively. The methyl ethyl ketone soluble fraction is a low molecular weight alternating copolymer and methyl ethyl ketone insoluble and diethyl ether soluble fraction is a high molecular weight alternating copolymer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene prepared by the process of this invention;
FIG. 2 shows the nuclear magnetic resonance spectrum of the copolymer;
FIG. 3 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and 4-methyl pentene-1 prepared by the process of this invention;
FIG. 4 shows the nuclear magnetic resonance spectrum of the copolymer;
FIG. 5 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and pentene-1 prepared by the process of this invention;
FIG. 6 shows the nuclear magnetic resonance spectrum of the copolymer;
FIG. 7 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and butene-1 prepared by the process of this invention;
FIG. 8 shows the nuclear magnetic resonance spectrum of the copolymer;
FIG. 9 shows the infra-red spectrum of the alternating copolymer of butadiene and styrene prepared by the process of this invention; and
FIG. 10 shows the nuclear magnetic resonance spectrum of the copolymer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention will be illustrated with reference to the following examples.
Example 1
The usual, dry, air-free technique was employed and 6.5 milliliters toluene, 0.50 millimole carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 1. As can be seen in Table 1, the yield of high molecular weight alternating copolymer increased by using three components catalyst system.
The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and propylene.
(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for 1:1 copolymer of butadiene and propylene. Copolymer compositions were determined by measuring the ratio of peak area at 4.65τ of butadiene unit to that of doublet at 9.11τ and 9.20τ of propylene unit.
(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.
(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.
(4) The 1155 cm.- 1 band of propylene homopolymer is not shown in its infra-red spectrum. This means at least that the length of the propylene-propylene repeating unit of the copolymer is not so long as to be detected by its infra-red spectrum.
                                  TABLE 1                                 
__________________________________________________________________________
                                  Alternating copolymer                   
                                       MEK insoluble, diethyl ether       
                                       soluble                            
                                       fraction                           
Catalysts                         MEK       Microstructure of butadiene   
                                  soluble                                 
                                       unit (percent)                     
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4           fraction                                
                                       Yield                              
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                              Mmol                                        
                                  (g.) (g.) Trans-                        
                                                 Cis- 1,2-                
__________________________________________________________________________
1     2.0    0.2  1-chloroethyl benzoate                                  
                             0.50 0.05 0.05                               
2     2.0    0.2  Benzophenone                                            
                             0.50 0.23 0.57 57   36   7                   
3     2.0    0.2  Isobutylaldehyde                                        
                             0.50 0.20 0.57                               
4     2.0    0.2  Benzoyl chloride                                        
                             0.50 0.25 0.23                               
5     2.0    0.2  Isobutyric acid                                         
                             0.50 0.12 1.39 69   26   5                   
6     2.0    0.2  Benzoic acid                                            
                             0.50 0.14 0.61                               
7     2.0    0.2  Monochloroacetic acid                                   
                             0.50 0.17 0.29                               
8     2.0    0.2  Maleic acid anhydride                                   
                             0.50 0.16 0.82 70   24   6                   
Reference                                                                 
      2.0    0.2                       0.03                               
__________________________________________________________________________
Example 2
The usual, dry, air-free technique was employed and 6.5 milliliters toluene, 0.50 millimole carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -15° C. for 16 hours. The results are summarized in Table 2.
                                  TABLE 2                                 
__________________________________________________________________________
                                  Alternating copolymer                   
                                       MEK insoluble diethyl ether        
                                       soluble                            
                                       fraction                           
Catalysts                         MEK       Microstructure of butadiene   
                                  soluble   unit (percent)                
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4           fraction                                
                                       Yield                              
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                              Mmol                                        
                                  (g.) (g.) Trans-                        
                                                 Cis- 1,2-                
__________________________________________________________________________
1     2.0    0.2  Diethyl malonate                                        
                              0.50                                        
                                  0.35 0.12 74   21   5                   
2     2.0    0.2  Ethyl acetate                                           
                              0.50                                        
                                  0.30 0.56 60   28   12                  
3     2.0    0.2  Acetone     0.50                                        
                                  0.62 0.42 65   28   7                   
4     2.0    0.2  Benzaldehyde                                            
                              0.50                                        
                                  0.21 0.18 57   35   8                   
5     2.0    0.2  Acetic acid anhydride                                   
                              0.50                                        
                                  0.17 1.85 64   30   6                   
Reference                                                                 
      2.0    0.2                       0.07                               
__________________________________________________________________________
Example 3
The usual, dry, air-free technique was employed and 6.5 milliliters toluene, varying amounts of carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triethylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 3.
                                  TABLE 3                                 
__________________________________________________________________________
                            Alternating copolymer                         
                                         MEK insoluble, diethyl ether     
                                         soluble                          
                                         fraction                         
Catalysts                           MEK       Microstructure of           
                                              butadiene                   
                                    soluble   unit (percent)              
Experiment                                                                
      AlEt.sub.3                                                          
           TiCl.sub.4               fraction                              
                                         Yield                            
No.   (mmol)                                                              
           (mmol)                                                         
                Carbonyl compound   (g.) (g.) Trans-                      
                                                   Cis-  1,2-             
__________________________________________________________________________
1     2.0  0.2  Maleic acid anhydride                                     
                            0.05 (g.)                                     
                                    0.11 0.11 57   30    13               
2     2.0  0.2  Propionic acid                                            
                            0.037 (ml.)                                   
                                    0.21 0.21 70   25    5                
Reference                                                                 
      2.0  0.2                      0    0                                
__________________________________________________________________________
Example 4
The usual, dry, air-free technique was employed and 3.5 milliliters toluene, 0.12 milliliter acetic acid anhydride and 0.5 millimole titanium tetrabromide were put in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 5.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 14 hours. Yield of the methyl ethyl ketone soluble alternating copolymer of butadiene and propylene was 0.13 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene was 1.67 g. When the two components catalyst system consisting of 0.5 millimole titanium tetrabromide and 5.0 millimoles triisobutylaluminum was used and the other copolymerization conditions were the same as the example, yield of the methyl ethyl ketone soluble fraction was 0.07 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble fraction was 0.03 g.
Example 5
The usual, dry, air-free technique was employed and 3.5 milliliters toluene, 0.12 milliliter isobutyric acid and 0.5 millimole titanium tetraiodide were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 5.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 14 hours. Yield of the alternating copolymer was 0.10 g. When the two components catalyst system consisting of 0.5 millimole titanium tetraiodide and 5.0 millimoles triisobutylaluminum was used and the other copolymerization conditions were the same as the example, yield of the alternating copolymer was 0.01 g.
Example 6
The usual, dry, air-free technique was employed and varying amounts of carbonyl group containing compound, 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 6.5 milliliters toluene were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solutions) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 4.
                                  TABLE 4                                 
__________________________________________________________________________
                                   Alternating copolymer                  
                                        MEK Insoluble diethyl ether       
                                        soluble                           
                                        fraction                          
Catalysts                          MEK       Microstructure of butadiene  
                                   soluble   unit (percent)               
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4            fraction                               
                                        Yield                             
No.   (mmol) (mmol)                                                       
                  Carbonyi compound                                       
                               Gram                                       
                                   (g.) (g.) Trans-                       
                                                   Cls-  1,2-             
__________________________________________________________________________
1     2.0    0.2  Sodium oleate                                           
                               0.152                                      
                                   0.01 0.20                              
2     2.0    0.2  Aluminum stearate                                       
                               0.438                                      
                                   0.50 1.30 63    30    7                
3     2.0    0.2  Aluminum acetate                                        
                               0.102                                      
                                   0.01 0.20 75    20    5                
4     2.0    0.2  Tin (II) oxalate                                        
                               0.103                                      
                                   0.05 0.15 74    21    5                
5     2.0    0.2  Aluminum acetylacetonate                                
                               0.162                                      
                                   0.05 0.22 82    15    3                
6     2.0    0.2  Hexacarbonyl molybdenum                                 
                               0.132                                      
                                   0.05 0.15 83    14    3                
Reference                                                                 
      2.0    0.2                        0.03                              
__________________________________________________________________________
Example 7
The usual, dry, air-free technique was employed and 6.5 milliliters toluene, varying amounts of carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 5. In the table, η means the intrinsic viscosity measured in chloroform at 30° C. FIG. 1 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene prepared by the process of Exp. No. 3. FIG. 2 shows the nuclear magnetic resonance spectrum of the copolymer.
                                  TABLE 5                                 
__________________________________________________________________________
                                   Alternating copolymer                  
                                        MEK insoluble, diethyl ether      
                                        soluble fraction                  
Catalysts                          MEK          Microstructure of         
                                                butadiene                 
                                   soluble      unit (percent)            
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4            fraction                               
                                        Yield                             
                                            [η]                       
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                              Mmol (g.) (g.)                              
                                            (dl./g.)                      
                                                Trans-                    
                                                     Cis- 1,2             
__________________________________________________________________________
1     2.0    0.2  Acetic acid 0.025                                       
                                   0.19 0.08    55   38   7               
2     2.0    0.2  Acetic acid 0.100                                       
                                   0.28 0.21    67   24   9               
3     2.0    0.2  Acetic acid 0.500                                       
                                   0.36 0.79    66   29   5               
4     2.0    0.2  Acetic acid 0.750                                       
                                   0.13 0.19    66   28   6               
5     2.0    0.2  Isobutyl aldehyde                                       
                              0.250                                       
                                   0.26 0.23    72   22   6               
6     2.0    0.2  Isobutyl aldehyde                                       
                              0.750                                       
                                   0.17 0.44                              
                                            0.56                          
                                                65   26   9               
7     2.0    0.2  Isobutyl aldehyde                                       
                              1.000                                       
                                   0.03 0.20    60   32   8               
8     2.0    0.2  Acetone     0.750                                       
                                   0.16 0.24    69   25   6               
9     2.0    0.2  Benzoyl peroxide                                        
                              0.500                                       
                                   0.11 0.20                              
                                            1.40                          
                                                50   38   12              
10    2.0    0.2  Diphenyl acetic acid                                    
                              0.500                                       
                                   0.21 1.69                              
                                            0.45                          
                                                70   24   6               
11    2.0    0.2  α-chloropropionic acid                            
                              0.500                                       
                                   0.14 0.94                              
                                            0.36                          
                                                62   28   10              
12    2.0    0.2  Caproic acid                                            
                              0.500                                       
                                   0.52 0.69                              
                                            0.33                          
                                                59   33   8               
13    2.0    0.2  Phthalic acid anhydride                                 
                              0.500                                       
                                   0.17 0.44                              
                                            0.90                          
                                                73   19   8               
__________________________________________________________________________
Example 8
The usual, dry, air-free technique was employed and 190 milliliters toluene, 0.8 milliliter propionic acid anhydride and 0.275 milliliter titanium tetrachloride were put successively in a 500 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 25 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 50 milliliters liquid propylene and 50 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 42 hours. 58.0 g. alternating copolymer of butadiene and propylene was obtained. Its intrinsic viscosity was 2.26 (dl./g.) in chloroform at 30° C.
The vulcanization was carried out in the following way:
                    Parts                                                 
______________________________________                                    
Copolymer             100                                                 
Oil furnace black (HAF)                                                   
                      50                                                  
Zinc oxide            5                                                   
Sulphur               2                                                   
Stearic acid          1                                                   
Phenyl-β-naphthyl amine                                              
                      1                                                   
Benzothiazyl disulfide                                                    
                      1                                                   
______________________________________                                    
were mixed on a roller and vulcanized within 60 minutes at 150° C.
The product obtained by the vulcanization had the following values:
Elongation at break at 25° C.: 330%
Tensile strength at 25° C.: 193 kg./cm.2
Modulus 300% at 25° C.: 182 kg./cm.2
The microstructure of butadiene unit of the copolymer was as follows:
trans: 68%
cis: 26%
1.2: 6%
Example 9
The usual, dry, air-free technique was employed and 6.5 milliliters toluene, varying amounts of carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 6.
                                  TABLE 6                                 
__________________________________________________________________________
                                    Alternating copolymer                 
                                         MEK Insoluble, diethyl ether     
                                         soluble                          
                                         fraction                         
Catalysts                           MEK       Microstructure of           
                                              butadiene                   
                                    soluble   unit (percent)              
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4             fraction                              
                                         Yield                            
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                              Gram  (g.) (g.) Trans-                      
                                                   Cis-  1,2-             
__________________________________________________________________________
1     2.0    0.2  Azodicarbonamide                                        
                              0.06  0.12 0.11                             
2     2.0    0.2  Chloroacetamide                                         
                              0.047 0.13 0.10 -3                          
                                              2.0  0.2   Phenylisocyanate 
                                                         .sup.1 0.054 0.19
                                                          0.05            
4     2.0    0.2  Phenylurethane                                          
                              0.083 0.24 0.35 61   34    5                
5     2.0    0.2  Benzohydroxamic acid                                    
                              0.07  0.09 0.10                             
Reference                                                                 
      2.0    0.2                         0.03                             
__________________________________________________________________________
 .sup.1 Milliliter.                                                       
Example 10
The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 21 hours. The results are summarized in Table 7.
                                  TABLE 7                                 
__________________________________________________________________________
                                   Alternating copolymer                  
        Catalysts                      Microstructure of butadiene        
                                       unit (percent)                     
Experiment                                                                
        Al(i-Bu).sub.3                                                    
               TiCl.sub.4          Yield                                  
No.     (mmol) (mmol)                                                     
                    Carbonyl compound                                     
                              Mmol (g.)                                   
                                       Trans-                             
                                            Cis- 1,2-                     
__________________________________________________________________________
1       1.0    0.1  Terephthaldehyde                                      
                              0.25 0.25                                   
2       1.0    0.1  Glycolic acid                                         
                              0.25 0.33                                   
3       0.5    0.1  Carbon dioxide                                        
                              0.25 0.15                                   
4       0.5    0.1  Acetophenone                                          
                              0.10 1.90                                   
                                       82   15   3                        
5       1.0    0.1  Benzil    0.25 0.25                                   
6       1.0    0.1  Polyvinylacetate                                      
                              .sup.1 0.01                                 
                                   0.17                                   
7       1.0    0.1  Tartaric acid                                         
                              0.25 0.15                                   
Reference 1                                                               
        1.0    0.1                 0.02                                   
Reference 2                                                               
        0.5    0.1                 0.04                                   
__________________________________________________________________________
 .sup.1 Gram.                                                             
Example 11
The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.1 millimole titanium tetrabromide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 21 hours. The results are summarized in Table 8.
                                  TABLE 8                                 
__________________________________________________________________________
                                     Alternating copolymer                
        Catalysts                        Microstructure of butadiene      
                                         unit (percent)                   
Experiment                                                                
        Al(i-Bu).sub.3                                                    
               TiBr.sub.4            Yield                                
No.     (mmol) (mmol)                                                     
                    Carbonyl compound                                     
                                Mmol (g.)                                 
                                         Trans-                           
                                              Cis- 1,2-                   
__________________________________________________________________________
1       1.0    0.1  Benzalacetophenone                                    
                                0.25 0.97                                 
2       1.0    0.1  Diketene    0.25 0.12                                 
3       0.5    0.1  p-Methoxybenzoic acid                                 
                                0.10 0.57                                 
4       0.5    0.1  p-Benzoquinone                                        
                                0.10 0.14                                 
                                         68   25   7                      
5       0.5    0.1  Polymethylmethacrylate                                
                                .sup.1 0.01                               
                                     0.20                                 
Reference 1                                                               
        1.0    0.1                   0.02                                 
Reference 2                                                               
        0.5    0.1                   0.04                                 
__________________________________________________________________________
 .sup.1 Gram.                                                             
Example 12
The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 1.0 milliliter triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 9.
                                  TABLE 9                                 
__________________________________________________________________________
                                      Alternating copolymer               
                                           MEK Insoluble, diethyl ether   
                                           soluble                        
                                           fraction                       
Catalysts                             MEK       Microstructure of         
                                                butadiene                 
                                      soluble   unit (percent)            
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4               fraction                            
                                           Yield                          
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                                  Mmol                                    
                                      (g.) (g.) Trans-                    
                                                     Cis- 1,2-            
__________________________________________________________________________
1     1.0    0.1  Phosgene        0.1 0.07 0.24 85   13   2               
2     1.0    0.1  Phosgene        0.2 0.10 0.17                           
3     1.0    0.1  Acetyl chloride 0.25                                    
                                      0.18 0.53                           
4     1.0    0.1  Titanium oxydiacetylacetonate                           
                                  .sup.1 0.05                             
                                      0.13 0.10                           
5     1.0    0.1  Zinc carbonate  .sup.1 0.05                             
                                      0.05 0.12                           
6     1.0    0.1  Sodium carbonate                                        
                                  .sup.1 0.05                             
                                      0.08 0.10                           
7     1.0    0.1  Dimethyl carbonate                                      
                                  0.1 0.22 0.34 76   19   5               
__________________________________________________________________________
 .sup.1 Gram.                                                             
Example 13
The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.2 milliliter titanium tetrachloride and 0.5 millimole carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 10.
                                  TABLE 10                                
__________________________________________________________________________
                                   Alternating copolymer                  
                                        MEK insoluble, diethyl ether      
                                        soluble                           
                                        fraction                          
Catalysts                          MEK       Microstructure of butadiene  
                                   soluble   unit (percent)               
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4            fraction                               
                                        Yield                             
No.   (mmol) (mmol)                                                       
                  Carbonyl compound                                       
                               Mmol                                       
                                   (g.) (g.) Trans-                       
                                                   Cis-  1,2-             
__________________________________________________________________________
1     2.0    0.2  Trimethyl acetic acid                                   
                               0.5 0.42 0.56                              
2     2.0    0.2  Crotonic acid                                           
                               0.5 0.20 0.35 68    28    4                
3     2.0    0.2  Trichloro acetic acid                                   
                               0.5 0.03 0.18                              
4     2.0    0.2  Isobutyric acid anhydride                               
                               0.5 0.14 1.29 65    29    6                
5     2.0    0.2  Crotonic acid anhydride                                 
                               0.5 0.04 0.57 72    23    5                
6     2.0    0.2  Benzoic acid anhydride                                  
                               0.5 0.10 0.80                              
7     2.0    0.2  n-Butyric acid                                          
                               0.5 0.62 0.80 66    29    7                
__________________________________________________________________________
Example 14
The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize for 16 hours at 0° C. or -55° C. The results are summarized in Table 11.
                                  TABLE 11                                
__________________________________________________________________________
                                      Alternating copolymer               
                                           MEK insoluble, diethyl ether   
                                           soluble fraction               
                                                Microstructure of         
    Catalysts                    Polymer-                                 
                                      MEK       butadiene unit            
Exper-                           ization                                  
                                      soluble                             
                                           (percent)                      
iment                                                                     
    Al(i-Bu).sub.3                                                        
           TiCl.sub.4            tempera-                                 
                                      fraction                            
                                           Yield                          
No. (mmol) (mmol)                                                         
                Carbonyl compound                                         
                             Mmol                                         
                                 ture (°C.)                        
                                      (g.) (g.) Trans-                    
                                                     Cis- 1,2             
__________________________________________________________________________
1   0.5    0.1  Acetophenone 0.1 -55  0.02 0.27 88   8    4               
2   0.5    0.1  Acetophenone 0.1 0    0.16 0.29 70   23   7               
3   0.5    0.1  Isobutyl aldehyde                                         
                             0.1 -55  0.01 0.29 76   20   4               
4   0.5    0.1  Isobutyl aldehyde                                         
                             0.1 0    0.14 0.20 62   28   10              
5   1.0    0.1  Propionic acid anhydride                                  
                             0.25                                         
                                 -55  0.01 0.13 81   16   3               
6   1.0    0.1  Propionic acid anhydride                                  
                             0.25                                         
                                 0    0.06 1.14 69   27   4               
__________________________________________________________________________
Example 15
The usual, dry, air-free technique was employed and varying amounts of carbonyl group containing compound, 6.5 milliliters toluene and varying amounts of titanium tetrachloride were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 12.
                                  TABLE 12                                
__________________________________________________________________________
                                Alternating copolymer                     
                                     MEK insoluble, diethyl ether         
                                     soluble fraction                     
                                          Microstructure of               
Catalysts                       MEK       butadiene unit                  
                                soluble   (percent)                       
Experi-                                                                   
     Al(i-Bu).sub.3                                                       
            TiCl.sub.4          fraction                                  
                                     Yield                                
ment No.                                                                  
     (mmol) (mmol)                                                        
                 Carbonyl compound*                                       
                            Mmol.                                         
                                (g.) (g.) Trans-                          
                                               Cis- 1,2-                  
__________________________________________________________________________
1    2.0    0.2  O          0.16                                          
                                0.18 0.06 66   28   6                     
                 ∥                                               
                 TiCl.sub.3 (OCCH.sub.3)                                  
2    2.0    0.5  O          0.20                                          
                                0.17 0.15                                 
                 ∥                                               
                 Ti(Oi--Pr).sub.2 (OCCH.sub.3).sub.3                      
3    2.0    0.5  O          0.20                                          
                                0.32 1.71 63   32   5                     
                 ∥                                               
                 O[Ti(OCCH.sub.3).sub.3 ].sub.3                           
__________________________________________________________________________
 *i-Pr=Isopropyl; i-Bu=Isobutyl.                                          
Example 16
The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 2 milliliters liquid butadiene and 3.1 milliliters liquid 4-methyl pentene-1 were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 13.
The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and 4-methyl pentene-1.
(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and 4-methyl pentene-1.
(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.
(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.
                                  TABLE 13                                
__________________________________________________________________________
                                       Alternating copolymer              
Catalysts                              MEK  MEK insolu-                   
      Organo-                          soluble                            
                                            ble, diethyl                  
Experiment                                                                
      aluminum   TiCl.sub.4            fraction                           
                                            ether soluble                 
No.   compound*                                                           
             Mmol                                                         
                 (mmol)                                                   
                      Carbonyl compound                                   
                                   Mmol                                   
                                       (g.) fraction (g.)                 
__________________________________________________________________________
1     AlEt.sub. 3                                                         
             0.5 0.1  Isobutyl aldehyde                                   
                                   0.10                                   
                                       0.02 0.03                          
2     AlEt.sub.3                                                          
             1.0 0.1  Propionic acid anhydride                            
                                   0.25                                   
                                       0.05 0.26                          
3     Al(i-Bu).sub.3                                                      
             1.0 0.1  Propionic acid anhydride                            
                                   0.25                                   
                                       0.03 0.87                          
4     Al(i-Bu).sub.3                                                      
             0.5 0.1  Acetophenone 0.10                                   
                                       0.06 1.05                          
5     Al(i-Bu).sub.3                                                      
             0.5 0.1  Acetone      0.10                                   
                                       0.05 0.31                          
6     Al(i-Bu).sub.3                                                      
             1.0 0.1  Acetic acid  0.25                                   
                                       0.11 0.32                          
7     Al(i-Bu).sub.3                                                      
             0.5 0.1                        0.02                          
Reference                                                                 
      AlEt.sub.3                                                          
             0.5 0.1                        0                             
__________________________________________________________________________
 *Et=Ethyl; i-Bu=Isobutyl.                                                
FIG. 3 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and 4-methyl-pentene-1 prepared by the process of Exp. No. 4. FIG. 4 shows the nuclear magnetic resonance spectrum of the copolymer.
Example 17
The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titanium tetrahalide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 2 milliliters liquid butadiene and 2.8 milliliters liquid pentene-1 were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 14.
The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and pentene-1.
(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and pentene-1.
(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.
(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.
                                  TABLE 14                                
__________________________________________________________________________
Catalysts                                    Alternating copolymer        
                                                  MEK                     
                                             MEK  insoluble,              
      Organo-                                soluble                      
                                                  diethyl ether           
Experiment                                                                
      aluminum   Titanium                    fraction                     
                                                  soluble                 
No.   compound*                                                           
             Mmol                                                         
                 tetrahalide                                              
                        Mmol                                              
                            Carbonyl compound                             
                                         Mmol                             
                                             (g.) fraction                
__________________________________________________________________________
                                                  (g.)                    
1     AlEt.sub.3                                                          
             0.5 TiCl.sub.4                                               
                        0.1 Acetophenone 0.10                             
                                             0.03 0.06                    
2     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1   "          0.10                             
                                             0.06 1.02                    
3     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1 Isobutylaldehyde                              
                                         0.10                             
                                             0.03 0.43                    
4     Al(i-Bu).sub.3                                                      
             0.5 TiBr.sub.4                                               
                        0.1   "          0.10                             
                                             0.01 0.13                    
5     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 Acetic acid  0.25                             
                                             0.08 0.49                    
6     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 O            0.02                             
                                             0.08 0.11                    
                            ∥                                    
                            TiCl.sub.3 (OCCH.sub.3)                       
7     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 Same as above                                 
                                         0.10                             
                                             0.17 0.84                    
8     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 Propionic acid anhydride                      
                                         0.25                             
                                             0.01 0.17                    
9     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 Isobutyric anhydride                          
                                         0.25                             
                                             0.02 0.19                    
10    Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub. 4                                              
                        0.1 Acetone      0.10                             
                                             0.02 0.76                    
11    Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1                       0.08                    
Reference                                                                 
      AlEt.sub.3                                                          
             0.5 TiCl.sub.4                                               
                        0.1                       0.02                    
__________________________________________________________________________
 *Et=Ethyl; i-Bu=Isobutyl.                                                
FIG. 5 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and pentene-1 prepared by the process of Exp. No. 5. FIG. 6 shows the nuclear magnetic resonance spectrum of the copolymer.
Example 18
The usual, dry, air-free technique was employed and 7.0 milliliters, 0.1 millimole titanium tetrahalide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts or organoaluminum compound in toluene (1 molar solution), 2 milliliters liquid butadiene and 2 milliliters liquid butene-1 were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 15.
The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and butene-1.
(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and butene-1.
(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.
(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.
                                  TABLE 15                                
__________________________________________________________________________
Catalysts                                 Alternating copolymer           
                                               MEK                        
                                          MEK  insoluble,                 
      Organo-                             soluble                         
                                               diethyl ether              
Experiment                                                                
      aluminum   Titanium                 fraction                        
                                               soluble                    
No.   compound*                                                           
             Mmol                                                         
                 tetrahalide                                              
                        Mmol                                              
                            Carbonyl compound                             
                                      Mmol                                
                                          (g.) fraction                   
__________________________________________________________________________
                                               (g.)                       
1     AlEt.sub.3                                                          
             0.5 TiCl.sub.4                                               
                        0.1 Acetophenone                                  
                                      0.10                                
                                          0.06 0.15                       
2     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1 Isobutyl aldehyde                             
                                      0.10                                
                                          0.06 0.26                       
3     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 Isoamyl acetate                               
                                      0.25                                
                                          0.04 0.14                       
4     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1 Benzophenone                                  
                                      0.10                                
                                          0.04 0.70                       
5     Al(i-Bu).sub.3                                                      
             1.0 TiBr.sub.4                                               
                        0.1 Acetic acid                                   
                                      0.25                                
                                          0.08 0.11                       
6     Al(i-Bu).sub.3                                                      
             1.0 TiBr.sub.4                                               
                        0.1 Acetone   0.25                                
                                          0.03 0.05                       
7     Al(i-Bu).sub.3                                                      
             0.5 TiBr.sub.4                                               
                        0.1 Acetophenone                                  
                                      0.10                                
                                          0.05 1.26                       
8     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1                    0.03                       
Reference                                                                 
      AlEt.sub. 3                                                         
             0.5 TiCl.sub.4                                               
                        0.1                      0                        
__________________________________________________________________________
 *Et=Ethyl; i-Bu=Isobutyl.                                                
FIG. 7 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and butene-1 prepared by the process of Exp. No. 4. FIG. 8 shows the nuclear magnetic resonance spectrum of the copolymer.
Example 19
The usual, dry, air-free technique was employed and 5.0 milliliters toluene, 0.1 millimole titanium tetrahalide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 3 milliliters styrene and 2 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 21 hours. The results are summarized in Table 16.
The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and styrene.
(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and styrene.
(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.
(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.
                                  TABLE 16                                
__________________________________________________________________________
Catalysts                                                                 
      Organo-                                Alternating                  
Experiment                                                                
      aluminum   Titanium                    copolymer                    
No.   compound*                                                           
             Mmol                                                         
                 tetrahalide                                              
                        Mmol                                              
                            Carbonyl compound                             
                                         Mmol                             
                                             (g.)                         
__________________________________________________________________________
1     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1                  0.03                         
2     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1 Acetic acid  0.10                             
                                             0.05                         
3     Al(i-Bu).sub.3                                                      
             0.5 TiCl.sub.4                                               
                        0.1 Propionic acid anhydride                      
                                         0.10                             
                                             0.05                         
4     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1   "          0.25                             
                                             0.25                         
5     Al(i-Bu).sub.3                                                      
             0.5 TiBr.sub.4                                               
                        0.1 p-Benzoquinone                                
                                         0.10                             
                                             0.07                         
6     Al(i-Bu).sub.3                                                      
             0.5 TiBr.sub.4                                               
                        0.1 Terephthal aldehyde                           
                                         0.10                             
                                             0.11                         
7     AlEt.sub. 3                                                         
             0.5 TiBr.sub.4                                               
                        0.1 Propionic acid anhydride                      
                                         0.10                             
                                             0.04                         
8     Al(i-Bu).sub.3                                                      
             1.0 TiCl.sub.4                                               
                        0.1 O            0.10                             
                                             0.38                         
                            ∥                                    
                            TiCl.sub.3 (OCCH.sub.3)                       
Reference                                                                 
      AlEt.sub.3                                                          
             0.5 TiCl.sub.4                                               
                        0.1                    0                          
__________________________________________________________________________
 *Et=Ethyl; i-Bu=Isobutyl.                                                
FIG. 9 shows the infra-red spectrum of the alternating copolymer of butadiene and styrene prepared by the process of Exp. No. 8. FIG. 10 shows the nuclear magnetic resonance spectrum of the copolymer.
Example 20
The usual, dry, air-free technique was employed and 4.0 milliliters toluene, 0.2 millimole titanium tetrachloride and 0.2 millimole carbonyl containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and 6 milliliters liquid B--B fraction were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 24 hours. Alternating copolymer of butadiene and butene-1 was obtained. The results are summarized in Table 17. The mole fraction of B--B fraction used was as follows:
               Mole percent                                               
______________________________________                                    
Propane          0.03                                                     
Propylene        0.05                                                     
Methyl acetylene 0.69                                                     
Isobutane        0.52                                                     
n-Butane         3.67                                                     
Isobutylene      26.22                                                    
Butene-1         14.18                                                    
Trans-butene-2   5.18                                                     
Cis-butene-2     4.12                                                     
1,3-butadiene    44.02                                                    
1,2-butadiene    0.52                                                     
Ethyl acetylene  0.16                                                     
Vinyl acetylene  0.64                                                     
______________________________________                                    
                                  TABLE 17                                
__________________________________________________________________________
                               Alternating copolymer                      
Catalysts                      MEK  MEK insolu-                           
                               soluble                                    
                                    ble, diethyl                          
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4                                                   
                  Carbonyl     fraction                                   
                                    ether soluble                         
No.   (mmol) (mmol)                                                       
                  compound Mmol                                           
                               (g.) fraction (g.)                         
__________________________________________________________________________
1     1.0    0.2  Acetophenone                                            
                           0.2 0.14 0.02                                  
2     2.0    0.2  O        0.2 0.16 0.56                                  
                  ∥                                              
                  TiCl.sub. 3  OCCH.sub.3                                 
__________________________________________________________________________
Example 21
The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 1.0 milliliter triisobutylaluminum solution in toluene (1 molar solution), 0.25 millimole propionic acid anhydride, 0.1 millimole titanium tetrachloride and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into a 25 milliliters glass bottle at -78° C. Then the bottle was sealed and allowed to copolymerize at -30° C. for 15 hours. The yield of the alternating copolymer of butadiene and propylene was 0.13 g.
Example 22
The usual, dry, air-free technique was employed and 1.0 millimole butadiene, 0.25 millimole propionic acid anhydride and 0.1 millimole titanium tetrachloride were put successively into a 25 milliliters glass bottle at 25° C. Then the bottle was held in a low temperature bath at -78° C. and 10 milliliters triisobutylaluminum solution in toluene (1 mole solution) and a mixture of 3 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 15 hours. The yield of the alternating copolymer of butadiene and propylene was 0.65 g. and the microstructure of butadiene unit of the copolymer was as follows:
trans: 70%
cis: 22%
1,2: 8%
Example 23
The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, 0.18 millimole titanium tetrachloride, 0.6 milliliter of triisobutylaluminum solution in toluene (1 molar solution) and 0.12 millimole acetophenone were put successively at intervals of 10 minutes into a 25 milliliters glass bottle at -78° C. Thereafter the bottle was sealed and allowed to copolymerize at -40° C. for 4.5 hours. The yield of the alternating copolymer of butadiene and propylene was 0.60 g. and the microstructure of butadiene unit of the copolymer was as follows:
trans: 92%
cis: 6%
1.2: 2%
Example 24
The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2-milliliters liquid butadiene and 2 milliliters toluene, 0.18 millimole titanium tetrachloride, 0.12 millimole acetophenone and 0.6 milliliter triisobutylaluminum solution in toluene (1 molar solution) were put successively at intervals of 10 minutes into a 25 milliliters glass bottle at -78° C. Thereafter the bottle was sealed and allowed to copolymerize at -40° C. for 4.5 hours. The yield of the alternating copolymer of butadiene and propylene was 1.05 g. and the microstructure of butadiene unit of the copolymer was as follows:
trans: 91%
cis: 7%
1.2: 2%
Example 25
The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, 0.6 milliliter triisobutylaluminum solution in toluene (1 molar solution), 0.12 millimole acetophenone and 0.18 millimole titanium tetrachloride were put successively at intervals of 10 minutes into a 25 milliliters glass bottle at -78° C. Thereafter the bottle was sealed and allowed to polymerize at -40° C. for 4.5 hours. The yield of the alternating copolymer of butadiene and propylene was 1.01 g.
Example 26
The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2 milliliters toluene, 0.12 millimole acetophenone, 0.18 millimole titanium tetrachloride and 0.6 milliliter triisobutylaluminum solution in toluene (1 molar solution) were put successively at intervals of 10 minutes into a 25 milliliters glass bottle at -78° C. Thereafter the bottle was sealed and allowed to copolymerize at -40° C. for 4.5 hours. The yield of the alternating copolymer of butadiene and propylene was 1.06 g.
Example 27
The usual, dry, air-free technique was employed and 0.05 g. metal oxide or metalloid oxide, 6.5 milliliters toluene, 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.5 millimole carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 18. As can be seen in Table 18, the yield of the high molecular weight alternating copolymer of butadiene and propylene increased by adding metal oxide or metalloid oxide to the three components catalyst system of organoaluminum compound, titanium tetrahalide and carbonyl compound.
                                  TABLE 18                                
__________________________________________________________________________
                                                  Alternating copolymer   
        Catalysts                                 MEK  MEK insolu-        
                                                  soluble                 
                                                       ble, diethyl       
Experiment                                                                
        Al(i-Bu).sub.3                                                    
               TiCl.sub.4           Metal oxide or                        
                                                  fraction                
                                                       ether soluble      
No.     (mmol) (mmol)                                                     
                    Carbonyl compound                                     
                                Mmol                                      
                                    metalloid oxide                       
                                              Gram                        
                                                  (g.) fraction           
__________________________________________________________________________
                                                       (g.)               
1       2.0    0.2  Monochloroacetic acid                                 
                                0.5 Titanium dioxide                      
                                              0.05                        
                                                  0.23 *0.82              
Reference 1                                                               
        2.0    0.2    "         0.5               0.17 0.20               
2       2.0    0.2  Ethyl acetate                                         
                                0.5 Alumina   0.05                        
                                                  0.17 0.48               
Reference 2                                                               
        2.0    0.2    "         0.5               0.09 0.14               
3       2.0    0.2    "         0.5 Vanadium pentoxide                    
                                              0.05                        
                                                  0.23 0.56               
4       2.0    0.2  Diethyl malonate                                      
                                0.5 Silica    0.05                        
                                                  0.22 0.15               
Reference 3                                                               
        2.0    0.2    "         0.5               0.08 0.04               
5       2.0    0.2  Benzophenone                                          
                                0.5 Zirconium dioxide                     
                                              0.05                        
                                                  1.48 0.67               
Reference 4                                                               
        2.0    0.2    "         0.5               0.23 0.47               
6       2.0    0.2  Acetone     0.5 Titanium dioxide                      
                                              0.05                        
                                                  0.24 0.22               
Reference 5                                                               
        2.0    0.2    "         0.5               0.24 0.13               
7       2.0    0.2  Acetic acid anhydride                                 
                                0.5 Magnesia  0.05                        
                                                  0.12 0.93               
Reference 6                                                               
        2.0    0.2    "         0.5               0.13 0.83               
__________________________________________________________________________
 *Butadiene microstructure: Trans=73%, Cis=12%; 1.2=5%.                   
Example 28
The usual, dry, air-free technique was employed and 6.0 milliliters toluene, 0.5 millimole carbonyl group containing compound, 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.2 millimole halogen or halogen compound were put successviely in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter, the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 19.
As can be seen in Table 19, the yield of the high molecular weight alternating copolymer of butadiene and propylene was increased by adding halogen or halogen compound to the three components catalyst system of organoaluminum compound, titanium tetrachloride and carbonyl compound.
                                  TABLE 19                                
__________________________________________________________________________
Catalysts                                        Alternating copolymer    
                                                 MEK  MEK insoluble,      
                                                 soluble                  
                                                      diethyl ether       
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4                                                   
                  Carbonyl      Halogen or halogen com-                   
                                                 fraction                 
                                                      soluble frac-       
No.   (mmol) (mmol)                                                       
                  compound  Mmol                                          
                                pound        Mmol                         
                                                 (g.) tion                
__________________________________________________________________________
                                                      (g.)                
1     2.0    0.2  Benzophenone                                            
                            0.5 Stannic chloride                          
                                             0.2 0.16 0.79                
Reference 1                                                               
      2.0    0.2    "       0.5                  0.23 0.57                
2     2.0    0.2  Benzoyl peroxide                                        
                            0.5 tert-Butyl chloride                       
                                             0.2 0.12 0.25                
Reference 2                                                               
      2.0    0.2    "       0.5                  0.11 0.20                
3     2.0    0.2  Ethyl acetate                                           
                            0.5 Ethylaluminum dichlo-                     
                                             0.2 0.10 *0.54               
                                ride.                                     
Reference 3                                                               
      2.0    0.2    "       0.5                  0.09 0.14                
4     2.0    0.2  Diethyl malonate                                        
                            0.5 Aluminum bromide                          
                                             0.2 0.09 0.13                
Reference 4                                                               
      2.0    0.2    "       0.5                  0.08 0.04                
5     2.0    0.2  Acetone   0.5 AlCl.sub.3.O(C.sub.2 H.sub.5).sub.3       
                                             0.2 0.18 0.40                
Reference 5                                                               
      2.0    0.2    "       0.5                  0.24 0.13                
6     2.0    0.2  Benzophenone                                            
                            0.5 Iodine       0.2 0.15 0.67                
__________________________________________________________________________
 *Butadiene microstructure: Trans=67%; Cis=25%; 1.2=8%.                   
Example 29
The usual, dry, air-free technique was employed and 6.0 milliliters toluene, 0.5 millimole isobutyl aldehyde,
                                  TABLE 20                                
__________________________________________________________________________
                                               Alternating copolymer      
       Catalysts                               MEK MEK in-                
       Organo-                            Diluent                         
                                               soluble                    
                                                    soluble, diethyl      
Experiment                                                                
       aluminum   TiCl.sub.4              toluene                         
                                               fraction                   
                                                    ether soluble         
No.    compound                                                           
              Mmol                                                        
                  (mmol)                                                  
                       Halogen or halogen compound                        
                                      Mmol.                               
                                          (ml.)                           
                                               (g.) fraction              
__________________________________________________________________________
                                                    (g.)                  
1      Al(i-Bu).sub.3                                                     
              2.5 1.0                     5    0    0.09                  
2      Al(i-Bu).sub.3                                                     
              2.5 1.0  Chromium (VI) oxychloride                          
                                      1.2 5    0.40 1.00                  
3      Al(i-Bu).sub.3                                                     
              2.5 1.0  Vanadium (V) oxychloride                           
                                      1.0 4    0.89 0.58                  
4      Al(i-Bu).sub.3                                                     
              2.5 1.0  tert-Butyl chloride                                
                                      2.5 5    0.10 0.14                  
5      Al(i-Bu).sub.3                                                     
              2.5 1.0  Bromine        0.8 5    0.08 0.34                  
Reference 1                                                               
       Al(i-Bu).sub.3                                                     
              1.5 1.0                     5    0    0                     
Reference 2                                                               
       AlEt.sub.3                                                         
              2.5 1.0                     5    0    0                     
Reference 3                                                               
       AlEt.sub.3                                                         
              1.5 1.0                     5    0    0                     
__________________________________________________________________________
0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.2 millimole boron trifluoride diethyl ester complex were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 100° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the conventional, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The yield of methyl ethyl ketone soluble alternating copolymer of butadiene and propylene was 0.18 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble fraction, i.e. alternating copolymer of butadiene and propylene was 0.74 g. When the three components catalyst system consisting of triisobutylaluminum, titanium tetrachloride and isobutylaldehyde was used and the other copolymerization conditions were the same as those in this example, the yield of the high molecular weight alternating copolymer was 0.47 g.
Example 30
The usual, dry, air-free technique was employed and varying amounts of toluene, 1.0 milliliter titanium tetrachloride solution in toluene (1 molar solution) and varying amounts of halogen or halogen compound were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and varying amounts of organoaluminum compound in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 20. As can be seen in Table 20, by adding halogen or halogen compound to the two components catalyst system consisting of organoaluminum compound and titanium tetrahalide, the yield of the alternating copolymer increased, Ref. 1 also shows that when the mol ratio of triisobutylaluminum to titanium tetrachloride is 1.5 (Al/Ti=1.5) no alternating copolymer can be obtained.
Example 31
The conventional, dry, air-free technique was employed and 5.0 milliliters toluene, 1.0 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 1.2 millimoles chromium (VI) oxychloride were put successively in a 25 milliliter glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.5 milliliters triisobutylaluminum solution in toluene (1 molar solution), 3 milliliters styrene and 2 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The yield of alternating copolymer of butadiene and styrene was 0.53 g.
Example 32
The usual, dry, air-free technique was employed and 0.5 millimole halogen compound, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliter glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, milliliters liquid butadiene and 2 milliliters liquid toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The results are summarized in Table 21.
                                  TABLE 21                                
__________________________________________________________________________
Catalysts                    Alternating copolymer                        
                             MEK  MEK insoluble                           
                             soluble                                      
                                  diethyl ether                           
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4                                                   
                  Halogen    fraction                                     
                                  soluble fraction                        
No.   (mmol) (mmol)                                                       
                  compound*                                               
                         Mmol                                             
                             (g.) (g.)                                    
__________________________________________________________________________
1     2.0    0.2  BF.sub.3.OEt.sub.2                                      
                         0.5 0.12 0.28                                    
2     2.0    0.2  AlCl.sub.3.OEt.sub.2                                    
                         0.5 0.07 0.12                                    
3     2.0    0.2  ZnCl.sub.2.Py                                           
                         0.5 0.10 0.08                                    
4     2.0    0.2  VOCl.sub.3.OEt.sub.2                                    
                         0.5 0.50 0.60                                    
5     2.0    0.2  NH.sub.2.Py                                             
                         0.5 0.05 0.15                                    
6     2.0    0.2  FeCl.sub.3.OEt.sub.2                                    
                         0.5 0.11 0.21                                    
7     2.0    0.1  HgCl.sub.2.Py                                           
                         0.5 0.05 0.11                                    
8     2.0    0.1  Cu.sub.2 Cl.sub.2.Py                                    
                         0.5 0.04 0.12                                    
Reference                                                                 
      2.0    0.1               0  0.03                                    
__________________________________________________________________________
 *Et=Ethyl; Py=Pyridine.                                                  
Example 33
The usual, dry, air-free technique was employed and 0.5 millimole halogen compound, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliter glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 39 hours. The results are summarized in Table 22.
                                  TABLE 22                                
__________________________________________________________________________
Catalysts                    Alternating copolymer                        
                             MEK  MEK insoluble                           
Experiment                                                                
      Al(i-Bu).sub.3                                                      
             TiCl.sub.4                                                   
                  Halogen    soluble                                      
                                  diethyl ether                           
No.   (mmol) (mmol)                                                       
                  compound*                                               
                         Mmol                                             
                             fraction                                     
                                  soluble fraction                        
                                  (g.)                                    
__________________________________________________________________________
1     2      0.2  BiCl.sub.3.CEt.sub.3                                    
                         0.5 0.16 0.52                                    
2     2      0.2  SnCl.sub.4.OEt.sub.3                                    
                         0.5 0.02 0.15                                    
3     2      0.2  BCl.sub.3.OEt.sub.3                                     
                         0.5 0.02 0.10                                    
Reference                                                                 
      2      0.2               0  0.05                                    
__________________________________________________________________________
 *Et=Ethyl.                                                               
Example 34
The usual, dry air-free technique was employed and 0.5 millimole bismuth (III) chloride diethyl ether complex, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25° C. Then the bottle was left alone at 25° C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78° C. and 2.0 milliliters triethylaluminum solution in toluene and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30° C. for 16 hours. The yield of methyl ethyl ketone soluble alternating copolymer of butadiene and propylene was 0.05 g. and methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene was 0.11 g. By using two components catalyst system of triethylaluminum and titanium tetrachloride, no alternating copolymer of butadiene and propylene was obtained.

Claims (9)

What we claim is:
1. A process for preparing a 1:1 copolymer of butadiene and an alpha-olefin having alternating butadiene and alpha-olefin units, said alpha-olefin having the general formula of CH2 =CHR' wherein R' represents a phenyl radical or a C1 to C4 normal or branched chain alkyl radical, which comprises contacting butadiene and the alpha-olefin in liquid phase at a temperature of from -100° C. to 50° C. with a catalyst system comprising a first component of an organoaluminum compound having the general formula of AlR3 wherein R represents a hydrocarbon radical selected from the group consisting of an alkyl radical, an aryl radical and a cycloalkyl radical, a second component of titanium tetrahalide having the general formula TiX'4 wherein X' is selected from the group consisting of chlorine, bromine and iodine, and a third component of a carbonyl group-containing compound, wherein the molar ratio of said organoaluminum compound to said titanium tetrahalide is from greater than 1.5 to 20 and the molar ratio of butadiene to said alpha-olefin in the initial monomer composition is within a range of from 20:80 to 80:20.
2. A process as claimed in claim 1, wherein the catalyst system contains a material selected from the group consisting of a metal oxide, a metalloid oxide, a halogen and a halogen compound as a fourth component.
3. A process as claimed in claim 1, wherein the molar ratio of the organoaluminum compound to the titanium tetrahalide is approximately 1.5-10.
4. A process as claimed in claim 1, wherein said halogen compound is selected from the group consisting of a halogen compound having Lewis acid property, a Lewis acid-base complex of a halogen compound having Lewis acid property, an organoaluminum compound having an Al-X linkage, an organotransition-metal compound having a transition metal-X linkage and an alkane compound having a C-X linkage, wherein X represents halogen.
5. A process as claimed in claim 1 wherein the polymerization reaction is carried out in the presence of a hydrocarbon diluent.
6. A process as claimed in claim 1 wherein the molar ratio of butadiene to the alpha-olefin in the initial monomer composition is substantially 50:50.
7. A process as claimed in claim 1, wherein said α-olefin is styrene.
8. A process as claimed in claim 1, wherein said α-olefin is selected from the group consisting of propylene, butene-1, pentene-1 and hexene-1.
9. A process as claimed in claim 1, werein said α-olefin is 4-methyl pentene-1.
US05/594,512 1969-05-13 1975-07-09 Process for preparing alternating copolymer of butadiene and α-olefine and novel alternating copolymer of butadiene and α-olefine containing cis-configuration butadiene unit Expired - Lifetime USRE28850E (en)

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US27841672A 1972-08-07 1972-08-07
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US3210332A (en) * 1963-05-03 1965-10-05 Phillips Petroleum Co Production of solid olefin polymers
US3317496A (en) * 1955-03-18 1967-05-02 Montedison Spa Copolymers of diolefins and olefins and method of producing them
US3462406A (en) * 1965-04-07 1969-08-19 Montedison Spa Process for the polymerization of butadiene to polybutadiene having substantially 1,4 cis structure
US3466268A (en) * 1962-01-02 1969-09-09 Texas Us Chem Co Butadiene-isobutylene copolymers
US3470144A (en) * 1965-12-21 1969-09-30 Asahi Chemical Ind Process for producing copolymer
US3506632A (en) * 1965-01-12 1970-04-14 Goodyear Tire & Rubber Preparation of plastics
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
US3803106A (en) * 1970-03-19 1974-04-09 Maruzen Petrochem Co Ltd Process for preparing a copolymer of ethylene and a conjugated diene

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3317496A (en) * 1955-03-18 1967-05-02 Montedison Spa Copolymers of diolefins and olefins and method of producing them
US3466268A (en) * 1962-01-02 1969-09-09 Texas Us Chem Co Butadiene-isobutylene copolymers
US3210332A (en) * 1963-05-03 1965-10-05 Phillips Petroleum Co Production of solid olefin polymers
US3506632A (en) * 1965-01-12 1970-04-14 Goodyear Tire & Rubber Preparation of plastics
US3462406A (en) * 1965-04-07 1969-08-19 Montedison Spa Process for the polymerization of butadiene to polybutadiene having substantially 1,4 cis structure
US3470144A (en) * 1965-12-21 1969-09-30 Asahi Chemical Ind Process for producing copolymer
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
US3803106A (en) * 1970-03-19 1974-04-09 Maruzen Petrochem Co Ltd Process for preparing a copolymer of ethylene and a conjugated diene

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