JPH0261962B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for copolymerizing ethylene and α-olefin with good randomness using a highly active Ziegler catalyst. Olefin polymerization catalysts have made great progress since the discovery of Ziegler's catalyst, and highly active catalysts have been discovered, which have led to the industrialization of polyethylene and polypropylene production processes that do not require a decatalyst step. On the other hand, copolymer rubbers of ethylene and α-olefin, particularly propylene, are produced using panadium compounds-organoaluminum compounds. Although the catalyst has good random copolymerizability, the catalyst activity decreases at high temperatures, resulting in a significant decrease in productivity.
Therefore, it is necessary to carry out the polymerization reaction at a relatively low temperature.
Excessive energy is required to remove the heat of polymerization reaction. Further, if the panadium metal remains in the rubber, the rubber becomes susceptible to aging, so it is necessary to sufficiently remove the catalyst. Against this technical background, a patent has recently been filed for copolymerizing ethylene and α-olefin with high activity at a relatively high temperature using a titanium compound (Japanese Unexamined Patent Publication No. 104687/1983, Japanese Unexamined Patent Publication 1973-
148093), the former is aimed at modifying polypropylene resin, the latter is aimed at modifying polyethylene resin, and neither is aimed at rubber-like random copolymers. It is extremely difficult to obtain ethylene and α-olefin with high activity and good randomness using a titanium compound as a catalyst, and this cannot be inferred from the production technology of resins such as polyethylene and polypropylene. The present inventors have been intensively researching a method for producing a rubbery olefin copolymer with high randomness using a highly active solid catalyst. As a result, when using a catalyst consisting of a finely powdered solid containing Ti, Mg, and P and an organoaluminum compound modified with alcohol, ethylene and α-
It was discovered that an olefin copolymer rubber can be obtained, and the present invention was accomplished based on this finding. That is, the present invention provides (A) a powder obtained by contacting a homogeneous solution 1 containing a chlorine-containing magnesium compound and a phosphorus compound having a P=O bond with a titanium compound 2, preferably the homogeneous solution 1 and the titanium compound 2; ethylene and α-olefin or The present invention provides a method for producing a rubbery olefin copolymer, which is characterized by copolymerizing ethylene, α-olefin, and a nonconjugated diene with good randomness. The present invention will be explained in detail below. First, the catalyst component (A) used in the present invention will be explained.
No. 65490, patent application No. 1983-65491, patent application No. 1983-65492
It can be prepared by the method described in Japanese Patent Application No. 57-92131 and Japanese Patent Application No. 57-99955. Specifically, the chlorine-containing magnesium compound is MgCl ₂
Alternatively, Mg(OH)Cl is preferably anhydrous, and MgCl ₂ that has been subjected to a modification treatment such as ball milling, vibration milling, or complexing treatment can also be used. Moreover, Mg(OH)Cl can be obtained by heating MgCl ₂ .6H ₂ O 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. So m+n=3, j is 1
Or 2, k, l are integers from 0 to 2, and j+k+l=3
). Specifically, 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, trioleyl 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, triisopropylphosphine oxide, tri-n-butylphosphine oxide, triisobutylphosphine oxide, tri-
n-octylphosphine oxide, tri-2-ethylhexylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, tritolylphosphine oxide,
Trixylylphosphine oxide, monohydroxydiethoxyphosphine oxide, monohydroxydipropoxyphosphine oxide, monohydroxydi-n-butoxyphosphine oxide, monohydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t- Butoxyphosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, monohydroxydi-n-
Octyloxyphosphine oxide, 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-ethylhexyloxyphosphine oxide, monohydroxybutylphosphine oxide, monohydroxydi-2-ethylhexylphosphine oxide,
dihydroxymonobutoxyphosphine oxide,
Examples include dihydroxymono-n-octyloxyphosphine oxide, dihydroxymono-2-ethylhexyloxyphosphine oxide, dihydroxymono-n-dodecyloxyphosphine oxide, dihydroxybutyloxyphosphine oxide, dihydroxy 2-ethylhexylphosphine oxide, and the like. When preparing the homogeneous solution 1 containing the chlorine-containing magnesium compound and the phosphorus compound, the solution may be prepared in a large amount of the phosphorus compound or in the presence of a hydrocarbon or halogenated hydrocarbon solvent.
When the phosphorus compound is solid or waxy, it is necessary to carry out the reaction in the presence of these solvents. 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. Two or more of these solvents can be used in combination. The chlorine-containing magnesium compound is prepared by adding 1 to 30 moles, preferably 2 to 10 moles, of the above-mentioned phosphorus compound to 1 mole of chlorine-containing magnesium in the presence or absence of the above-mentioned solvent, and heating at -30° to 120°C. , preferably at a temperature of 0 to 60°C for 2 minutes to 20 hours, preferably 5 minutes to
A homogeneous solution of the chlorine-containing magnesium compound can be obtained by stirring for 5 hours. Furthermore, titanium tetrachloride was added to the solution containing the above chlorine-containing magnesium compound and phosphorus compound.
It is desirable to add it in an atomic ratio of 0.2 to 2.0, preferably 0.1 to 1.5. Further, the solution containing the chlorine-containing magnesium compound and the phosphorus compound can also be prepared in a large amount of a titanium tetrachloride compound. That is, a homogeneous solution can be obtained by adding a chlorine-containing magnesium compound and a phosphorus compound to a large excess of titanium tetrachloride. However, in this case, dissolution becomes difficult if hydrocarbons or halogenated hydrocarbons coexist. Therefore, it is desirable not to allow these solvents to coexist. The method for preparing a liquid material containing a chlorine-containing magnesium compound, a phosphorus compound, and titanium tetrachloride is not particularly limited, but the following method may be mentioned. (1) In the presence or absence of a hydrocarbon or halogenated hydrocarbon solvent, add and dissolve 1 to 30 moles of a phosphorus compound to 1 mole of a chlorine-containing magnesium compound, and then add 0.2 to 2 moles of titanium tetrachloride. (2) 1 mole of chlorine-containing magnesium compound and 0.2 to 2 moles of titanium tetrachloride are co-pulverized using a vibration mill, a ball mill, etc., and 1 to 30 moles of the phosphorus compound are added and dissolved, and if necessary, the above-mentioned (3) A method in which 1 mole of a chlorine-containing magnesium compound, 0.2 to 2 moles of titanium tetrachloride, 1 to 30 moles of a phosphorus compound, and the above-mentioned solvent added if necessary, are wet-pulverized and dissolved in a vibration mill, ball mill, etc. , (4) Add 5 to 1000 moles of titanium tetrachloride to 1 mole of chlorine-containing magnesium compound, suspend it, and suspend the phosphorus compound 2.
A method of adding ~10 mol and dissolving it in a large amount of titanium tetrachloride. Titanium compound 2 of the present invention has the general formula Ti(OR)
nX _4-o (where R is a hydrocarbon group, X is a halogen,
n=0 to 4. ), such as TiCl ₄ , TiBr ₄ , TiI ₄ , Ti(OC ₂ H ₅ )
_Cl3 , Ti _{( OC6H5} ) _Cl3 , Ti _{( OC2H7} ) _{2Cl2 ,} Ti
(OC ₆ H ₅ ) Cl ₂ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti(OC ₂ H ₅ ) ₄ ,
Ti(OC ₆ H ₁₁ ) ₄ , TiCl ₃ , Ti(OC ₂ H ₅ ) ₃ , Ti(on−
Examples include C ₄ H ₉ ) ₃ . Among these, titanium trichloride (TiCl ₃ ) or titanium tetrachloride (TiCl ₄ ) is particularly preferred. When using titanium trichloride as the titanium compound 2, it is preferable to prepare a homogeneous solution containing titanium trichloride. -octenyl) ether, anisole, diphenyl ether, or the above-mentioned phosphorus compound having a P=O bond. The amount of ether or phosphorus compound used at this time is in the range of ether or phosphorus compound/Ti=1.5 to 20, preferably 2.0 to 10, expressed as a molar ratio to the titanium compound. In addition, titanium trichloride is
56-53113, 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 mixing amount of the homogeneous solution containing the titanium compound and the homogeneous solution containing the chlorine-containing magnesium compound is expressed by the molar ratio of Mg and Ti, and Mg/Ti = 0.1 to
10000, preferably 1-1000. The temperature at which the powder which is the catalyst component (A) is precipitated is 0 to 200°C, preferably 20 to 150°C. Examples of the precipitating agent include organometallic compounds of metals from groups 1 to 3 of the periodic table, and halogen-containing compounds such as titanium, panadium, boron, sulfur, tin, and germanium. For example TiCl ₄ , TiCl ₃
(OC ₂ H ₅ ), TiCl ₃ (on-C ₄ H ₉ ), Al (C ₅ H ₅ )
Examples include Cl ₂ , Al ₂ (CaH ₅ ) ₃ Cl ₃ . Preferably titanium halides and organic aluminum compounds, particularly preferably TiCl ₄ and Al(C ₂ H ₅ )
Cl ₂ , Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ . The amount of precipitating agent used is 1.0 to 1.0 to 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 200 times the molar amount, preferably 1.0 to 100 times the molar amount. The precipitation treatment of the powder that is the catalyst component (A) 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, zeolite, and magnesia. The amount of the inorganic solid carrier used is 0.5 to 200 g, preferably 1 g per 1 g of chlorine-containing magnesium used.
~100g. The catalyst component (A) powder prepared as described above is preferably washed thoroughly 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 powder was measured by the KBr tablet method, characteristic absorption of phosphorus compounds was observed. Further, after decomposing a suspension solution of the solvent containing the powder with water, a 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 in the powder = 0.5 to 100 (mole ratio), preferably 0.5 to 50 (mole ratio), phosphorus compound/Ti = 0.01
2 (molar ratio), preferably 0.05 to 2 (molar ratio). Next, the catalyst component (B) will be explained. The organoaluminum compound used for the catalyst component (B) has the general formula AlRmX _3-n (R has 1 to 12 carbon atoms)
Preferred are organoaluminum compounds represented by a hydrocarbon residue, X is a halogen, and m is 1 to 3). For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium, tri-n-dodecylaluminum, diethylaluminum chloride, diethylaluminium Bromide, G-n
- dialkylaluminum halides such as butylaluminum chloride, di-n-octylaluminum chloride, di-n-octylaluminium bromide, ethylaluminum sesquichloride,
Examples include alkylaluminum sesquihalides such as isobutylaluminum sesquichloride, monoalkylaluminum dihalides such as ethylaluminum dichloride, n-butylaluminum dichloride, and ethylaluminum dipromide, and trialkylaluminum is preferred. The denaturing alcohol used in the catalyst component (B) includes methyl alcohol, ethyl alcohol,
Alcohols having 1 to 20 carbon atoms such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, dodecyl alcohol, nonyl phenyl alcohol, and stearyl alcohol can be used. Next, a method for preparing the catalyst component (B) will be explained. The solvent used when preparing the catalyst component (B) is
The same solvents (described above) used when preparing the catalyst component (A) can be used. Modification of organoaluminum compounds is generally −10 to
It is carried out at a temperature of 50°C, preferably from 0 to 30°C.
Denaturation time is 0.1-2.0 hours, preferably 0.5-1.0 hours. The amount of alcohol used as a denaturing agent is 0.05 to 0.5 mol per 1 mol of the organoaluminum compound.
Preferably it is 0.1 to 0.3 mol. In addition, the catalyst component
The ratio between (A) and catalyst component (B) is such that the organoaluminum compound in catalyst component (B) is 1.5 to 200 moles, preferably 2 to 100 moles, per 1 mole of Ti in catalyst component (A). Next, the monomers used in the present invention are ethylene,
α-olefin and non-conjugated diene, α-
olefins and non-conjugated dienes, examples of α-olefins include propylene, butene-1,
Pentene-1, 4-methylpentene-1, hexene-1, heptene-1, 4-methylhexene-
1, octene-1, etc. As non-conjugated dienes, all non-conjugated dienes which are used in copolymerizations of this type to make the copolymers vulcanizable can be used, for example 1,4-hexadiene, dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbonadiene,
Examples include 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, and tetrahydroindene. These non-conjugated dienes are added to the polymerization reactor in a necessary amount so that the iodine value in the copolymer is 2 to 50, preferably 3 to 40. At this time, two or more types of non-conjugated dienes can also be used in combination. Polymerization temperature is usually 10 to 150°C, preferably 30° to
The temperature is 120℃. Polymerization pressure usually ranges from normal pressure to 100Kg/
It is in the range of cm ² G. Copolymerization can be solution polymerization or suspension polymerization. That is, copolymerization can be carried out in the form of suspension polymerization using propylene as a solvent, suspension polymerization using a solvent in which the produced polymer has a low solubility, and solution polymerization using a solvent in which the produced polymer has a high solubility. Specific examples of polymerization solvents include, in addition to the monomer propyne, hydrocarbon solvents include hexane, heptane, octane, kerosene, benzene, toluene, xylene, and cyclohexane, and halogenated hydrocarbon solvents include , methylene chloride, monochloroethane, 1,1-dichloroethane, 1,
2-dichloroethane, 1,2-dichloropropane, monochlorobutane, monochlorobenzene, etc. can be used. These solvents can be used in combination of two or more in order to adjust the solubility parameter. The molecular weight of the copolymer can be arbitrarily adjusted by using hydrogen as necessary. Next, the present invention will be explained in more detail with reference to Examples. In addition, in the physical property values of the copolymer in the examples, Mooney viscosity was determined by preheating for 1 minute, measurement was performed for 4 minutes, and at a temperature of 100°C, propylene content was determined by infrared absorption spectrum, and iodine value was determined by titration method. The amount of heat is the value determined by a differential calorimeter (DSC). In addition, the titanium content in the catalyst can be determined by colorimetric method.
Mg was analyzed by chelate titration, and phosphorus compounds were analyzed by colorimetry. The amount of heat absorbed by DSC indicates the amount of heat absorbed due to melting of the crystalline portion in the rubbery copolymer. Therefore, a small amount of endotherm indicates a small content of crystalline parts,
In other words, this shows that the copolymer has good randomness. Example 1 Combination of catalyst components (A), (a) and (B) (1) Preparation of catalyst components (A) and (a) In a 300 ml flask purged with nitrogen, 1 g of dry palladium carbon powder and 1,2 - 200 ml of dichloroethane and 100 mmol of titanium tetrachloride were charged, and 200 mmol of n-butyl ether was added under stirring. Next, when hydrogen was supplied at a rate of 0.3 I/min for 6 hours at 20°C or lower, a yellow-black solution was obtained. This solution was filtered to remove palladium on carbon to obtain a yellow-black homogeneous solution. The reduction rate of titanium tetrachloride was almost 100%. Next, adjust the concentration of titanium trichloride to 0.4mol/1,2-dichloroethane.
It was prepared to l. On the other hand, put 25 g (0.262 mol) of anhydrous magnesium chloride into a 1000 ml flask that has been purged with nitrogen.
2-Ethylhexyl (di-2-ethylhexyloxy)phosphine oxide 361.5ml
(0.787 mol) was added and dissolved. After dissolving, n-hexane was added to bring the total volume to 524 ml. Next, put 20 ml of the above magnesium chloride solution into a 200 ml flask, add 20 ml of the above titanium trichloride solution, and finally add 145 ml of n-hexane.
ml, a green homogeneous solution was obtained. 10 ml of titanium tetrachloride was gradually added dropwise to this solution while stirring. After the addition was completed, stirring was continued for 3 hours and then left to stand, resulting in separation into a black, uniform supernatant liquid and a finely powdered solid. Remove the supernatant and
200 ml of n-hexane was added to wash the powder solid. Repeat this washing operation 4 times for a total volume of 200ml.
It was prepared as follows. The final state was a suspension of a slightly yellow, finely powdered solid in n-hexane. The Ti concentration was 0.011 mol/l, the Mg/Ti ratio was 4.5 molar ratio, and the phosphorus compound/Ti ratio was 0.23 molar ratio. (2) Preparation of catalyst component (B) A thoroughly dried 500 ml flask was purged with dry nitrogen, and 200 ml of n-hexane was charged. Next, 18.8ml of triisobutyl aluminum
(0.0747 mol) was added under stirring and stirring was continued for 10 minutes after addition. Meanwhile, replace the 100ml flask with dry nitrogen.
50 ml of n-hexane was charged, and 4.6 ml (0.050 mol) of n-butyl alcohol was added under stirring. Next, a 200 ml flask was purged with nitrogen, 100 ml of the above n-hexane solution of triisobutylaluminum was charged, and an n-hexane solution of n-butyl alcohol was added under stirring and nitrogen blowing.
3.8 ml was gradually added dropwise (n-butyl alcohol/triisobutyl aluminum = 0.10 molar ratio). The temperature was maintained at 20°C during the dropwise addition. After the addition was completed, stirring and nitrogen bubbling were continued for 1 hour at 20°C. The obtained solution was a colorless and transparent homogeneous solution. (3) Copolymerization operation A 3I autoclave equipped with a stirrer was purged with nitrogen, charged with 800g of liquid propylene, and heated at 50°C.
The temperature rose to Next, ethylene is supplied at a pressure of 32.0Kg/
It was supplied to the autoclave while keeping the cm ² G constant. After the autoclave pressure became constant at 32.0 kg/cm ² G, 15 g of 5-ethylidene-2-norbornene was added. Next, each of the catalyst components (A), (a) and (B)
0.0388 mmol (in terms of Ti) and 1.552 mmol (in terms of Al) were supplied in 30 minutes. It was observed that polymerization started simultaneously with the start of supply of this catalyst component. During the polymerization, the polymerization temperature was maintained at 55±1°C with cooling water. In addition, for ethylene, the polymerization pressure is 32.0Kg/cm ²
G was continuously supplied to keep it constant. Forty minutes after the start of polymerization, the supply of ethylene was stopped, and 50 ml of methanol was supplied to the autoclave, followed by stirring for 10 minutes to remove unreacted gas and obtain a rubbery copolymer. After drying this rubbery copolymer, it was left at 150℃ for 6 hours, and then heated to 20℃.
It was left to cool for 20 hours. The yield, Mooney viscosity, propylene content, iodine value, and heat of crystal fusion of the rubbery copolymer thus treated were measured. The results are summarized in Table 1. Example 2 Catalyst component (A), combination of (a) and (B) (1) Preparation of catalyst component (A), (a) The catalyst component prepared in Example 1 was used. Preparation of catalyst component (B) In the same manner as in Example 1, triisobutylaluminum and n-butyl alcohol were
- A hexane solution was prepared. Next, the 200ml flask was purged with nitrogen, and a solution of triisobutylaluminum in n-hexane was added.
A solution of 18.9 ml of n-butyl alcohol in n-hexane was gradually added dropwise thereto while stirring and bubbling nitrogen (n-butyl alcohol/triisobutyl aluminum = 0.50 molar ratio). After completing the dropping, perform the same operation as in Example 1,
A colorless and transparent homogeneous solution was obtained. (3) Copolymerization operation Copolymerization, heat treatment, and measurement were performed under the same conditions as in Example 1. The results are summarized in Table 1. Example 3 Combination of catalyst components (A), (b) and (B) (1) Preparation of catalyst components (A) and (b) 1.0 g (10.5 mmol) of anhydrous magnesium chloride was placed in a 200 ml flask purged with nitrogen. Prepare
2-ethylhexyl (di-2-
ethylhexyloxy)phosphine oxide
14.5 ml (31.5 mmol) was added, and the magnesium chloride was dissolved while stirring at 80°C to form a homogeneous solution. Meanwhile, a 100 ml flask was purged with nitrogen, and 20 ml of dried n-hexane and 1.44 ml of titanium tetrachloride were added.
(13.125 mmol) and 3.5 ml of monohydroxydi-2-ethylhexyloxyphosphine oxide
(10.49 mmol) was added, and the mixture was reacted at about 70°C, and the mixture was heated and stirred for 3 hours until no hydrogen chloride was generated. The solution was a deep yellow homogeneous solution. The entire volume of this deep yellow homogeneous solution was added to the above magnesium chloride solution, and further n-hexane was added to bring the total volume to 100 ml. The solution containing magnesium chloride and titanium tetrachloride thus obtained was kept at about 60° C., and 10 ml of titanium tetrachloride was gradually added dropwise while stirring to precipitate a yellow fine powder solid. After the addition of titanium tetrachloride, the mixture was kept at 60° C. for 1 hour, stirring was stopped, and the mixture was left standing to precipitate a finely powdered solid, and the supernatant liquid was removed. 80 ml of n-hexane was newly added for washing, left to stand, and the supernatant liquid was removed. After performing this washing operation six times, n-hexane was added to bring the total volume to 100 ml. The solution is a suspension of pale yellow fine powder solid in n-hexane, the Ti concentration is 0.004 mol/l, and the Mg/Ti ratio is 25.
The molar ratio and phosphorus compound/Ti ratio were 0.85 molar ratio. (2) Preparation of catalyst component (B) In the same manner as in Example 1, n-hexane solutions of triethylaluminum and 2-ethylhexyl alcohol were prepared, respectively. Next, replace the 200ml flask with nitrogen, and add 100ml of triethylaluminum n-hexane solution.
(triethylaluminum 0.04mol),
Further, a solution of 2-ethylhexyl alcohol in n-hexane was added while bubbling nitrogen under stirring.
24.3ml (2-ethylhexyl alcohol
0.012mol) was gradually added (2-ethylhexyl alcohol/triethylaluminum=
0.30 molar ratio). After the addition, the same operation as in Example 1 was performed to obtain a colorless and transparent homogeneous solution. (3) Copolymerization operation Copolymerization was carried out using the same 3I autoclave as in Example 1. The polymerization pressure was 30.5 Kg/cm ² G, therefore the ethylene supply pressure was 30.5 Kg/cm ² G, and the other conditions were the same as in Example 1. In addition, catalyst components (A), (b) and (B) are respectively
0.0505mmol (Ti equivalent) and 2.02mmol (Al equivalent)
was fed in the same manner as in Example 1. polymerization termination,
Heat treatment and measurements were performed in the same manner as in Example 1. The results are summarized in Table 1. Comparative Example 1 Using an unmodified organoaluminium compound as the catalyst (B) component (1) Preparation of catalyst components (A) and (a) The catalyst components prepared in Example 1 were used. (2) Copolymerization operation Using the same 3I autoclave as in Example 1, copolymerization was carried out at a pressure of 32.0 Kg/cm ² G and a temperature of 55°C. The amount of catalyst added is 0.0388 mmol of component (A) and (a).
(in terms of Ti), 1.552 mmol of unmodified triisobutylaluminum as an organic aluminum compound was supplied in the same manner as in Example 1. All other polymerization conditions were the same as in Example 1. Termination of polymerization, heat treatment, and measurement were also carried out in the same manner as in Example 1. The results are summarized in Table 1. Comparative Example 2 Using an unmodified organoaluminum compound as catalyst component (B) (1) Preparation of catalyst components (A) and (b) The catalyst prepared in Example 3 was used. (2) Copolymerization operation Copolymerization was carried out in the same manner as in Example 3 at a pressure of 30.5 Kg/cm ² G and a temperature of 55°C. 0.0505 mmol of catalyst components (A) and (b) (in terms of Ti), 2.02 mmol of triethylaluminum as an organoaluminum compound (not subjected to modification treatment)
was fed in the same manner as in Example 3. other conditions,
All measurement methods were the same as in Example 3. The results are summarized in Table 1. Comparative Example 3 Example of increasing the amount of alcohol in catalyst component (B) (1) Preparation of catalyst components (A) and (a) The catalyst prepared in Example 1 was used. (2) Preparation of catalyst component (B) In the same manner as in Example 1, the n of triisobutylaluminum and n-butyl alcohol were
A -hexane solution was prepared and reacted in the same manner as in Example 1, with the n-butyl alcohol/triisobutylaluminum ratio being 1.0 molar, to obtain a colorless and transparent homogeneous solution. (3) Copolymerization operation Copolymerization, heat treatment, and measurement were performed in the same manner as in Example 1. The results are summarized in Table 1. Comparative Example 4 Example of increasing the amount of alcohol in catalyst component (B) (1) Preparation of catalyst components (A) and (b) The catalyst components prepared in Example 3 were used. (2) Preparation of catalyst component (B) In the same manner as in Example 3, n-hexane solutions of triethylaluminum and 2-ethylhexyl alcohol were prepared, and the 2-ethylhexyl alcohol/triethylaluminum ratio was adjusted in the same manner as in Example 3. The reaction was carried out at a molar ratio of 1.0 to obtain a colorless and transparent homogeneous solution. (3) Copolymerization operation Copolymerization, heat treatment, and measurement were performed in the same manner as in Example 3. The results are summarized in Table 1. Comparative Example 5 Example using alkyl aluminum alkoxide as catalyst component (B) (1) Preparation of catalyst components (A) and (a) The catalyst components prepared in Example 1 were used. (2) Preparation of alkyl aluminum alkoxide A thoroughly dried 200 ml flask was purged with nitrogen, and 100 ml of n-hexane was charged. Diisobutylaluminum monobutoxide is added to this.
34.5 mmol was added and dissolved under stirring to obtain a homogeneous solution. (3) Copolymerization operation Copolymerization was carried out using the same 3I autoclave as in Example 1. Polymerization pressure is 32.0Kg/cm ² G,
The polymerization temperature was 55° C., and the other conditions were the same as in Example 1. The amount of catalyst supplied is 0.0388 mmol of components (A) and (a).
(in terms of Ti), 1.552 mmol of diisobutylaluminum monobutoxide was supplied in the same manner as in Example 1, and copolymerization was carried out. The treatment method and measurement method for the obtained copolymer were the same as in Example 1. The results are summarized in Table 1. Comparative Example 6 Example using alkyl aluminum alkoxide as catalyst component (B) (1) Preparation of catalyst components (A) and (b) The catalyst prepared in Example 3 was subjected to polymerization. (2) Preparation of alkylaluminum alkoxide In the same manner as in Comparative Example 5, diethylaluminum 2
- A solution of ethylhexoxide in n-hexane was prepared. (3) Copolymerization operation Using the same 3I autoclave as in Example 3, the pressure was 30.5 Kg/cm ² G, the temperature was 55°C, and the amount of catalyst supplied was 0.0505 mmol of components (A) and (b) (in terms of Ti). , diethylaluminum 2-ethylhexoxide
Copolymerization was carried out in the same manner as in Example 3 using 2.02 mmol. The treatment method and measurement method for the obtained copolymer were the same as in Example 3. The results are summarized in Table 1. 【table】

[Brief explanation of the drawing]

FIG. 1 shows a flowchart representing the catalyst preparation process of the present invention.

Claims (1)

[Claims] 1. (A) 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 alcohol-denatured organic powder. A rubber-like product characterized by copolymerizing ethylene and α-olefin or ethylene, α-olefin, and a non-conjugated diene with good randomness using a catalyst consisting of an aluminum compound (molar ratio of the former to the latter 0.05 to 0.5). A method for producing an olefin copolymer. 2. The manufacturing method according to claim 1, wherein the component (A) is a powder obtained by adding a precipitating agent to a homogeneous solution obtained by contacting a homogeneous solution with a titanium compound to precipitate it.