JPH0261961B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for copolymerizing an olefin and a conjugated diene in good yield using a highly active Ziegler catalyst. As a catalyst for ethylene/butadiene copolymerization, for example, a Ti(OBu) ₄ /AlEt ₃ catalyst was disclosed in Japanese Patent Publication No. 47-15696, and a TiCl ₄ /Al(i-
Bu) ₃ /carbonyl compound-based catalysts have been proposed, but in these catalyst systems the catalytic activity is limited to 1 Ti atom.
The amount of polymer per gram is very low, less than 100g.
Furthermore, Japanese Patent Publication No. 49-16784 describes a method for copolymerizing ethylene and butadiene using a fixed catalyst component obtained by heat-treating MgCl ₂ with titanium tetrachloride in the presence of an electron donor and a catalyst consisting of trialkylaluminium. is disclosed. This catalytic activity is
Although it is high at 30 kg/g-Ti.hr, the diene portion in the copolymer is very low at 2.3 mol% or less. As mentioned above, there are many research examples of methods for producing olefin/conjugated diene copolymers; however, (1) the polymerization temperature is relatively high (from -20 to
(150℃), (2) high catalytic activity, (3) ability to control the proportion of conjugated diene units in the copolymer, and (4) ability to prepare the catalyst at around room temperature. A method for producing an olefin/conjugated diene copolymer that is simultaneously satisfactory has not yet been found. The present inventors have conducted extensive research into methods for producing a copolymer that satisfies the above conditions, and as a result, have discovered the following production method and have arrived at the present invention. The process for preparing the polymerization catalyst used to carry out the method for producing the copolymer of the present invention can be carried out according to the flowchart shown in the attached FIG. 1. However, the flowchart in the figure is not intended to limit the scope of the present invention. According to the present invention, a titanium compound is obtained by contacting a homogeneous solution containing (A) a chlorine-containing magnesium compound and a phosphorus compound having a P=O bond prepared in the presence or absence of an organic solvent. Powder and (B) organoaluminum compound or general formula
It is characterized by copolymerizing an olefin and a conjugated diene using a catalyst made of an organoaluminum compound modified with an alcoholic compound represented by R ² OH (R ² is a hydrocarbon group having 1 to 20 carbon atoms). A method for producing an olefin-conjugated diene copolymer is provided. The present invention will be explained in detail below. First, to explain the catalyst component (A) used in the present invention, the chlorine-containing magnesium compound is specifically
MgCl ₂ or Mg(OH)Cl, MgCl ₂ is preferably anhydrous, and those subjected to modification treatments such as ball milling, vibration milling, and complexing treatment can also be used. is MgCl ₂ 6H ₂ O
obtained by heating at high temperature. Phosphorus compounds having a P=O bond have the general formula O=PR ¹ m(OR ² )n and/or O=P(OH) _j
(OR ³ _k ) A compound represented by R ⁴ _l is used (where R ¹ , R ² , R ³ , and R ⁴ are hydrocarbon groups having 1 to 20 carbon atoms, and m and n are integers of 0 to 3. m+n=3, j is 1 or 2, k, l are integers from 0 to 2, and j+k+l=
3). Specifically, the following can be mentioned. Trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-
Iso-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate,
Tri-t-butyl phosphate, tri-n-hexyl phosphate, tri-n-octyl phosphate, tri-2-ethyl-hexyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trio Leyl phosphate, triphenyl phosphate, tritolyl phosphate, trixyl phosphate, octyl diphenyl phosphate, tolyl diphenyl phosphate, xylyl diphenyl phosphate, ethyl (diethoxy) phosphine oxide, n-propyl (di -n-propyloxy)phosphine oxide, n-butyl(di-n
-butoxy)phosphine oxide, n-octyl (di-n-octyloxy)phosphine oxide,
2-Ethylhexyl(di-2-ethylhexyloxy)phosphine oxide, diethyl(ethoxy)phosphine oxide, di-n-butyl(n-
butoxy)phosphine oxide, diisobutyl(isobutoxy)phosphine oxide, di-n-
Octyl(n-octyloxy)phosphine oxide, di-2-ethylhexyl(2-ethylhexyloxy)phosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, tri-isopropylphosphine oxide, tri-n- Butylphosphine oxide, triisobutylphosphine oxide, tri-n-octylphosphine oxide, tri-2-ethylhexylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, tritolylphosphine oxide, trixylphosphine oxide monooxide, monohydroxydiethoxyphosphine oxide, monohydroxydipropoxyphosphine oxide, monohydroxydipropoxyphosphine oxide,
n-butoxyphosphine oxide, monohydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t-butoxyphosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, monohydroxydi-n-octyloxyphosphine oxide monooxide, monohydroxydi-2-ethylhexyloxyphosphine oxide, monohydroxydi-n-decyloxyphosphine oxide, monohydroxydi-n-dodecylphosphine oxide, monohydroxy(n-butyl)n-butoxyphosphine oxide, monohydroxy (n-hexyl) n-hexyloxyphosphine oxide, monohydroxy (n-octyl) n-octyloxyphosphine oxide, monohydroxy (2-ethylhexyl) 2-ethylhexylphosphine oxide, monohydroxybutylphosphine oxide inoxide, monohydroxydi-2
-Ethylhexylphosphine oxide, dihydroxymonobutoxyphosphine oxide, dihydroxymono-n-octyloxyphosphine oxide, dihydroxymono-2-ethylhexyloxyphosphine oxide, dihydroxymono-n-
Dodecyloxyphosphine oxide, dihydroxybutylphosphine oxide, dihydroxy 2-
Examples include ethylhexylphosphine oxide. A homogeneous solution containing a chlorine-containing magnesium compound and a phosphorus compound can be prepared using a large amount of the above-mentioned liquid phosphorus compound, or when the phosphorus compound is solid or waxy, it can be prepared in the presence of an organic solvent. It can be prepared with As the organic solvent, one or more hydrocarbons or halogenated hydrocarbons are used. Specific examples of these solvents include n-pentane,
n-hexane, n-heptane, n-octane, isooctane, n-decane, petroleum ether, ligroin, kerosene, kerosene, benzene, toluene, xylene, cyclohexane, methylcyclohexane, methylene chloride, ethyl chloride, ethyl bromide, 1,2- Examples include dichloroethane, 1,1-dichloroethane, n-butyl chloride, n-octyl chloride, monochlorocyclohexane, monochlorobenzene, o-dichlorobenzene, etc., but are not limited to these solvents. 1 to 30 moles of phosphorus compound per mole of chlorine-containing magnesium compound in the presence or absence of a solvent,
A homogeneous solution can be obtained by adding preferably 2 to 10 mol and stirring at a temperature of -30° to 120°C, preferably 0 to 60°C, for 2 minutes to 20 hours, preferably 5 minutes to 5 hours. Furthermore, it is desirable to add titanium tetrachloride to the solution containing the chlorine-containing magnesium compound and the phosphorus compound at a Ti/Mg atomic ratio in the range of 0.2 to 2.0, preferably 0.1 to 1.5. A homogeneous solution can also be prepared by adding a chlorine-containing magnesium compound and a phosphorus compound to a large amount of titanium tetrachloride. However, in this case, if the above-mentioned solvents are allowed to coexist, dissolution becomes difficult, so it is desirable not to coexist these solvents. The method for preparing a homogeneous solution is not particularly limited, but examples include the following methods: (1) In the presence or absence of a hydrocarbon or halogenated hydrocarbon solvent, 1 to 30% of the chlorine-containing magnesium compound is added to 1 mole of the compound. A method in which 0.2 to 2 moles of titanium tetrachloride is added after adding and dissolving 1 mole of a phosphorus compound, (2) Co-pulverization of 1 mole of a chlorine-containing magnesium compound and 0.2 to 2 moles of titanium tetrachloride using a vibration mill, ball mill, etc. A method of adding 1 to 30 moles of a phosphorus compound to the co-pulverized product, dissolving it, and diluting it with the above solvent if necessary, (3) 1 mole of a chlorine-containing magnesium compound, 0.2 to 2 moles of titanium tetrachloride, and 1 to 30 moles of a phosphorus compound. (4) 5 to 1,000 moles of titanium tetrachloride are added to 1 mole of the chlorine-containing magnesium compound and suspended, and the phosphorus compound 2 is dissolved.
A method of adding ~10 mol and dissolving it in a large amount of titanium tetrachloride. The titanium compound to be brought into contact with the homogeneous solution is represented by the general formula _Ti (OR)oX4 _-o (where R is a _C1-12 hydrocarbon, titanium compounds such as TiCl ₄ , TiBr ₄ ,
_TiI4 , _{Ti ( OC2H5} ) _Cl3 , Ti( _OC6H5 ) _Cl3 , Ti
(OC ₂ H ₇ ) ₂ Cl ₂ , Ti (OC ₆ H ₅ )Cl ₂ , Ti
( _OC2H5 ) _{3Cl ,} Ti _{( OC2H5} ) ₄ , Ti _{( OC6H11} ) ₄ ,
Examples include _TiCl3 , Ti( _OC2H5 ) ₃ , Ti( _{Oo - C4H9} ) _{3 ,} and the like. Among these, titanium trichloride (TiCl ₃ ) or titanium tetrachloride (TiCl ₄ ) is particularly preferred. When titanium trichloride is used as the titanium compound, it is preferable to prepare a homogeneous solution containing titanium trichloride, and such a solution may be prepared using diethyl ether,
Prepared by dissolving titanium trichloride in an ether such as di-n-propyl ether, di-n-butyl ether, bis(1-octenyl) ether, anisole, diphenyl ether, or the above-mentioned phosphorus compound having a P=O bond. be done. At this time, the amount of ether or phosphorus compound used is preferably ether or phosphorus compound/Ti=1.5 to 20 when expressed in molar ratio with the titanium compound.
It ranges from 2.0 to 10. In addition, titanium trichloride is disclosed in JP-A-56-53112 and JP-A-56-53112.
53113, 56-59816, 56-59813, 56-
Homogeneous solutions prepared by the methods described in Publications No. 59814, No. 56-59815, and No. 56-155021 can be used. The means for precipitating the powder of the catalyst component (A) is, for example,
A method may be mentioned in which a large excess of titanium tetrachloride is dropped into the above homogeneous solution. The temperature during precipitation is 0 to 200℃,
Preferably it is 20-150°C. The precipitating agent is an organometallic compound of a group metal to group metal of the periodic table, or a halogen-containing compound such as titanium, panadium, boron, sulfur, tin, or germanium. For example TiCl ₄ , TiCl ₃
(OC ₂ H ₅ ), TiCl ₃ (O-n-C ₄ H ₉ ), Al (C ₅ H ₅ )
Examples include Cl ₂ , Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ . Preferred are titanium halides, organic aluminum compounds, and particularly preferred are TiCl ₄ . The amount of precipitating agent used is 1.0 to 200 per the sum of the moles of ether and phosphorus compound contained in a homogeneous solution containing a titanium compound and a chlorine-containing magnesium compound.
It is twice the molar amount, preferably 1.0 to 100 times the molar amount. This precipitation treatment of the catalyst component (A) powder can be carried out in the presence of an inorganic solid carrier. The inorganic solid carrier has a surface area of 50 m ² /g or more, preferably 60 m ² /g or more, and an average particle size of 200 μ or less,
Preferably 150 μ or less, average pore diameter 50 Å or more,
Preferably an inorganic solid with a diameter of 60 Å or more, such as silica,
Examples include alumina, theolite, and magnesia. The amount of the inorganic solid carrier used is 0.5 to 200 g, preferably 1 to 100 g, per 1 g of the chlorine-containing magnesium compound used. The powder of catalyst component (A) prepared as described above is preferably washed sufficiently with pentane, hexane, heptane, benzene, toluene, etc., and then used as a polymerization catalyst in a suspended state in these solvents. When the infrared absorption spectrum of the thoroughly washed catalyst component (A) was measured by the KBr tablet method, characteristic absorption of phosphorus compounds was observed. Further, after decomposing the suspension solution of the solvent containing the catalyst component (A) with water, the gas chromatogram of the solvent layer was measured, and the amount of the phosphorus compound present could be determined. The titanium content was determined by a colorimetric method, and the magnesium content was determined by an atomic absorption method. Mg/Ti of catalyst component (A) = 0.5 to 100 (molar ratio), preferably 0.5 to 50 (molar ratio), phosphorus compound/Ti =
0.01-2 (molar ratio), preferably 0.05-2 (molar ratio)
is within the range of As the catalyst component (B), an organoaluminum compound or a modified product consisting of an organoaluminum compound and an alcohol is used. _The organoaluminum compound has ^the general formula AlR ¹ _n
It is expressed as For example, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium, tri-n-dodecylaluminum, diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n
-octylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride,
Examples include n-octylaluminum sesquichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-octylaluminum dichloride, ethylaluminum dipromide, diethylaluminum monoethoxide, diethylaluminum monobutoxide, etc. It is not limited. Moreover, two or more kinds of compounds can also be used as a mixture. Alternatively, as the catalyst component (B), the organic aluminum modified with an alcoholic compound represented by the general formula R ² OH (R ² is a hydrocarbon group having 1 to 20 carbon atoms) may also be used. Examples of alcoholic compounds include methanol, ethanol, n-butanol, sec-butanol, t-butanol, phenol, 2-phenylpropanol, phenylethyl alcohol, 2-methylbutanol, neopentyl alcohol, 4-heptanol, -Ethylhexanol, cyclohexanol, etc. The mixed ratio (mole ratio) of the modified product of an organoaluminum compound and an alcoholic compound is 1:0.01 to 1:2, preferably 1:0.1 to 1:1.
Two or more of each type can be optionally diluted with an inert solvent and used. Among the monomers for polymerization, examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In addition, the conjugated diene is 1,3-butadiene,
Examples include isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like.
These olefins and conjugated dienes can each be any 2
More than one type of olefin can be mixed and used in any ratio, but ethylene and/or propylene is preferably used as the olefin, and butadiene is preferably used as the conjugated diene. The polymerization temperature is usually -20°C to 150°C, preferably 0° to 120°C.
Polymerization pressure usually ranges from normal pressure to 100 kg/cm ² . The copolymerization method may be solution polymerization, suspension polymerization, or bulk polymerization. Hydrocarbon solvents such as hexane, heptane, octane, kerosene, benzene, toluene, xylene, and cyclohexane are used as polymerization solvents, and methylene chloride, monochloroethane, 1,1-dichloroethane, 1,2 as halogenated hydrocarbon solvents.
-dichloroethane, 1,2-dichloropropane,
Examples include monochlorobutane and monochlorobenzene. These can be used alone or in combination of two or more. The molecular weight of the copolymer can be arbitrarily adjusted by using hydrogen, if necessary. According to the method of the present invention, polymerization can be performed at relatively high temperatures;
It has the advantage that the diene units in the copolymer can be controlled arbitrarily. Next, the present invention will be explained in more detail with reference to Examples. The monomer composition and the microstructure of the diene moiety in the copolymers of ethylene, propylene, butadiene, isoprene, etc. in the Examples were determined by ¹³ C-NMR spectroscopy. Example 1 (1) Preparation of catalyst component A-1: A rotor and 1.0 g of anhydrous magnesium chloride were placed in a 100 ml Schlenk that had been thoroughly dried and purged with nitrogen.
(10.5 mmol). Further dried 2-
Add 13.2 g (31.5 mmol) of ethylhexyl (di-2-ethylhexyl) phosphine oxide,
Upon heating, a clear and colorless solution is obtained. 40ml of this
19.9 g of titanium tetrachloride diluted with n-hexane
(105 mmol) was added dropwise to produce a yellow fine powder. After aging this overnight, the supernatant liquid was removed and further washed with 80 ml of n-hexane. Do this operation 6
After repeating this process several times, n-hexane was added to prepare 50 ml of slurry solution, which was used as a polymerization catalyst. (2) Copolymerization of ethylene and butadiene: A stainless steel autoclave containing a rotor was connected to a vacuum line, thoroughly dried at 10 ^-3 Torr for 30 minutes, and returned to normal pressure with nitrogen. Thereafter, 20 ml of n-hexane was added under a nitrogen stream, and 0.032 mmol of the n-hexane slurry of the catalyst component (A) prepared in (1) above was added in terms of titanium atoms.
0.128 mmol was added. This reaction vessel was cooled and degassed under liquid nitrogen temperature, and then 6.9 g (164 mmol) of butadiene and 4.6 g of ethylene were added.
g (164 mmol) was introduced, and the mixture was left stirring at 50° C. for 1 hour. After the reaction, return to normal pressure, add a large amount of methanol containing anti-aging agent, and wash thoroughly.
After drying under reduced pressure, 6.3 g of a white powdery polymer was obtained.
The catalyst activity was 4.1 Kg/g·Ti·hr. The ¹³ C-NMR spectrum of the obtained polymer revealed that the ethylene content was 81 mol percent, and the microstructure of the butadiene moiety was trans-
The composition was 68% 1.4 structure, 16% cis-1.4 structure, and 16% vinyl structure. Example 2 Ethylene and butadiene were polymerized in the same manner as in Example 1 except that 1.28 mmol of triisobutylaluminum was used, and 5.7 g of a white powder polymer was obtained.
The catalyst activity was 3.7 Kg/g・Ti・hr. Also, the ethylene content was 45 mole percent. Example 3 Diisobutylaluminum chloride 0.128m instead of triisobutylaluminum in Example 1
Ethylene and butadiene were copolymerized in the same manner as in Example 1 except that mol was used, and 3.8 g of a white powder polymer was obtained. The catalyst activity was 2.5Kg/g・Ti・hr. The ethylene content was 72 mol%. Example 4 Propylene 6.9g instead of ethylene in Example 2
Propylene and butadiene were polymerized in the same manner as in Example 2 except that (164 mmol) was used. As a result, 3.5 g of a white rubbery polymer was obtained. The catalyst activity was 2.3 Kg/g·Ti·hr. The ¹³ C-NMR spectrum of this polymer revealed that the propylene content was 43 mol percent, and the microstructure of the butadiene moiety was 78 percent trans-1.4 structure, 8 percent cis-1.4 structure, and 14 vinyl structure.
It was a percentage. Example 5 6.9g of propylene instead of ethylene in Example 1
(164 mmol), 1.28 m of diisobutyl aluminum chloride instead of triisobutyl aluminum
Propylene and butadiene were polymerized in the same manner as in Example 1, except that mol was used and the polymerization temperature was 90°C. As a result, 5.4 g of white polymer was obtained. The catalyst activity was 3.5Kg/g・Ti・hr. Also, the propylene content was 32 mole percent. Example 6 1.28m of diisobutylaluminum chloride instead of triisobutylaluminum in Example 1
mol, polymerization temperature 90℃, butadiene as monomer
4.4g (82mmol), ethylene 2.3g (82mmol),
Polymerization was carried out in the same manner as in Example 1 except that 6.9 g (164 mmol) of propylene was used to obtain 5.4 g of a white rubbery polymer. The catalyst activity was 3.5Kg/g・Ti・hr. The compositions of ethylene, propylene, and butadiene in the copolymer were 43 mole percent, 34 mole percent, and 23 mole percent, respectively. The microstructure of the butadiene moiety in the copolymer is trans-1.4
35% structure, 52% cis-1.4 structure,
The vinyl structure was 13%. According to GPC analysis, the number average molecular weight was 42,000 and the weight average molecular weight was 354,000. Example 7 The polymerization temperature of Example 6 was 50°, the polymerization time was 15 minutes,
Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 6, except that the amount of toluene was changed to 40 ml, and 5.9 g of a white rubbery polymer was obtained. Catalytic activity is 15.4
It was Kg/g・Ti・hr. The compositions of ethylene, propylene, and butadiene in the copolymer are 37 mol percent, 41 mol percent, and 22 mol percent, and the microstructure of the butadiene part includes 32 percent trans-1.4 structure, 59 percent cis-1.4 structure, and 9 vinyl structure. It was a percentage. According to GPC analysis, the number average molecular weight was 25,000 and the weight average molecular weight was 213,000. Example 8 Catalyst component (A) was prepared in the same manner as in Example 1. Catalyst component (B) was prepared by the method shown below. After thoroughly drying Schülenk, the atmosphere was replaced with nitrogen, 1.2 mmol of diisobutylaluminum chloride was added, and 0.24 mmol of t-butanol was added dropwise to remove the catalyst component.
(B). 0.03 mmol of catalyst component (A) was collected in terms of titanium, and the entire amount of catalyst component (B) prepared by the above method was added dropwise. Furthermore, these catalyst components (A) and catalyst components (B) were placed in a stainless steel autoclave and cooled and degassed under liquid nitrogen temperature, yielding 4.6 g (164 mmol) of ethylene.
and 8.8 g (164 mmol) of butadiene were introduced,
The mixture was left stirring at 50°C for 15 minutes to obtain 5.0 g of a white polymer.
The catalyst activity was 13.9 Kg/g·Ti·hr. The composition of ethylene and butadiene in the copolymer was 82 mole percent and 18 mole percent. Example 9 Ethylene 2.3 as a monomer under the conditions of Example 8
g (84 mmol), propylene 6.9 g (164 mmol),
Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 8 except that 4.4 g (84 mmol) of butadiene was used. As a result, 5.4 g of a white rubbery polymer was obtained. The catalyst activity was 15.0 Kg/g・Ti・hr. The molar ratio of ethylene/propylene/butadiene in the copolymer is
It was 28/33/39. According to DSC analysis, Tg is −
At 58°C, Tm showed a broad peak ranging from about 40° to about 100°C. Example 10 Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 8 except that the amount of t-butanol was changed to 0.36 mmol. As a result, 4.1 g of a white rubbery copolymer was obtained. The catalyst activity was 11.4 Kg/g・Ti・hr. The molar ratio of ethylene/propylene/butadiene in the copolymer was 27/39/34. DSC analysis showed a broad peak with a Tg of -58°C and a Tm of about 40-100°C. Example 11 Ethylene, propylene, and isoprene were polymerized in the same manner as in Example 8 except that isoprene was used instead of butadiene. As a result, 2.2 g of a white rubbery polymer was obtained. The catalytic activity is 6.1Kg/g・Ti・hr. Example 12 (1) Preparation of catalyst component A-2 100 g of magnesium chloride hexahydrate was placed in a 300 ml flask under a nitrogen stream and heated to 300°C. Once a homogeneous solution was obtained, a white solid formed upon further heating. After grinding under a nitrogen stream, it was heated at 300°C for 10 hours under reduced pressure to produce Mg.
(OH)Cl powder was obtained. A rotor and 1 g (13 mmol) of Mg(OH)Cl were placed in a thoroughly dried 100 ml flask that had been purged with nitrogen. Add 36 mmol of 2-ethylhexyl (di-2-ethylhexyloxy)phosphine oxide dried with molecular sieves,
heated to ℃. Although Mg(OH)Cl does not dissolve in this state, 13 m of titanium tetrachloride is added to this flask.
Upon addition of mol, a brown homogeneous solution was obtained. This homogeneous solution was further heated at 130°C for 2 hours. Add 60 ml of n-hexane to another 100 ml flask that has been thoroughly dried and purged with nitrogen.
Add 13 mmol of titanium tetrachloride and heat at 60℃ in a hot water bath.
I kept it. While vigorously stirring this solution, the above homogeneous solution containing magnesium, titanium, and phosphorus was slowly added dropwise. A yellow finely powdered solid complex was immediately formed. Stirring was continued for 2 hours at 60°C. Stirring was stopped to precipitate a yellow fine powder solid, and the supernatant liquid was separated. Freshly dried n-
60 ml of hexane was added and stirred for 30 minutes for washing. This washing operation was repeated six times. A yellowish white finely powdered solid was obtained. Add n-hexane and bring the total volume to 50ml
I made it. The titanium concentration in this fine powder solid composite slurry is 0.024 mol/Mg/Ti=
The molar ratio was 10.5. (2) Copolymerization of ethylene, propylene and butadiene: 0.03 m of the above catalyst component A-2 in terms of titanium.
Mol fractions were collected, and ethylene, propylene, and butadiene were copolymerized in the same manner as in Example 9 to obtain 2.8 g of a rubbery polymer. Catalytic activity is 7.8Kg/
It was g・ti・hr. Examples 13 to 15 (1) Preparation of catalyst components A-3, A-4, and A-5: A rotor and 1 g (10.5
mmol). A predetermined amount of the solvent shown in Table 1 dried with molecular sieves and 21 mmol of the phosphorus compound shown in Table 1 were added, and the mixture was stirred at room temperature for 20 minutes. Magnesium chloride was completely dissolved to obtain a colorless and transparent homogeneous solution. Add 1.16ml (10.5ml) of titanium tetrachloride to this homogeneous solution.
mol) was added and left to stand for 30 minutes. It became a yellow transparent homogeneous solution. 12 ml of titanium tetrachloride was gradually added to this solution while stirring, producing a yellow fine powder. After continued stirring for 2 hours, a yellow fine powder solid complex was precipitated and the supernatant was separated. 80 ml of freshly dried n-hexane was added and stirred for 30 minutes for washing. This washing operation was repeated six times. A yellow-white finely powdered solid composite was obtained. N-hexane was added to make a 50 ml slurry.

[Table] (2) Polymer yield obtained by copolymerizing ethylene, propylene, and butadiene in the same manner as in Example 9 except that catalyst components A-3 to A-5 prepared by the above method were used. are shown in Table 1. Example 16 (1) Preparation of catalyst component A-6: In a thoroughly dried 300 ml flask that was purged with nitrogen, 1 g of dried palladium carbon powder (palladium content 5%), 200 ml of dried 1,2-dichloroethane, and Titanium chloride 11ml (100m
mol), and then 34 ml (200 mmol) of n-butyl ether was added while stirring [ether/Ti=2.0 (mole ratio)]. The flask was kept at 20°C, and hydrogen was bubbled in at a rate of 0.2/mm for 8 hours. A yellow-black solution formed. The solution was filtered under nitrogen to separate the powdered palladium on carbon. The liquid was a homogeneous yellow-black solution.
When this homogeneous solution was analyzed by redox titration method, the reduction rate of titanium tetrachloride was found to be almost 100%.
It was hot. It was diluted by adding 1,2-dichloroethane. Concentration of titanium trichloride produced
The amount was adjusted to 0.4 mol/. In addition, 25 g of anhydrous powdered magnesium chloride was placed in a 1000 ml flask that had been thoroughly dried and purged with nitrogen.
(0.262 mol) and 360 ml (0.787 mol) of di(2-ethyl-hexyloxy)(2-ethylhexyl)phosphine oxide were added and dissolved under stirring. Add n-hexane to bring the total volume to 524ml
(0.50 mol/MgCl ₂ ). A 300 ml flask was charged with 20 ml of the homogeneous solution containing magnesium chloride (10 mmol in MgCl ₂ ). Next, 25 ml (10 m
mol) was added. Furthermore, 145 ml of n-hexane was added. A green homogeneous solution was obtained. When 10 ml of titanium tetrachloride as a precipitating agent was slowly added dropwise to the homogeneous solution thus produced while stirring, a dark green fine powder solid was produced. After stirring for 1 hour, a finely powdered solid was precipitated. The supernatant was a black homogeneous solution. Separate the supernatant and create a new n
- 200 ml of hexane was added to wash the finely powdered solid. This operation was repeated six times. N-hexane was added to bring the total volume to 200 ml to obtain an n-hexane suspension of a slightly yellow-green fine powder solid. The Ti concentration was determined by colorimetric analysis and was 0.011mol/
It was hot. Mg/Ti (molar ratio) was 4.5. (2) Copolymerization of ethylene, propylene, and butadiene: 0.03 m of the above catalyst component A-6 in terms of titanium.
Copolymerization of ethylene, propylene, and butadiene was carried out in the same manner as in Example 9, except that the mol fraction was used as a catalyst, and 6.2 g of a rubbery polymer was obtained.
The catalyst activity was 17.3 Kg/g·Ti·hr.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a polymerization catalyst used to carry out the production method of the present invention.

Claims (1)

[Claims] 1. Prepared in the presence or absence of an organic solvent
(A) Powder obtained by contacting a titanium compound with a homogeneous solution containing a chlorine-containing magnesium compound and a phosphorus compound having a P=O bond, and (B) an organoaluminum compound or a compound with the general formula R ² OH (R ² is carbon An olefin-conjugated diene copolymer characterized in that an olefin and a conjugated diene are copolymerized using a catalyst made of an organoaluminum compound modified with an alcoholic compound represented by a hydrocarbon group of numbers 1 to 20. Production method. 2. The manufacturing method according to claim 1, wherein the olefin is ethylene and/or propylene and the conjugated diene is butadiene.