JPH0261487B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a highly active Ziegler catalyst to
This invention relates to a method for randomly copolymerizing ethylene and α-olefin with good yield. Olefin polymerization catalysts have made great progress since the discovery of Ziegler's catalyst. That is, highly active catalysts have been developed, and processes for producing polyethylene or polypropylene that do not require decatalyzing have been developed. On the other hand, catalysts for producing ethylene-propylene copolymer rubber have been produced using vanadium compound-organoaluminium compound catalysts that have good random copolymerizability of ethylene and propylene since they were developed. However, this catalyst has low polymerization activity at high temperatures, poor productivity, and the aging of rubber due to vanadium is large, so it is necessary to remove the catalyst sufficiently. Recently, patents have been filed for highly active catalysts for copolymerizing α-olefins using titanium-based catalysts (Japanese Patent Laid-Open Nos. 104687-1987 and 148093-1983), but rubber-like copolymerization It is not intended for polymers and does not fall outside the scope of modified polyolefin resins. In other words, JP-A-53-104687 aims at a polypropylene resin with a high propylene content in which the molar ratio of ethylene to propylene is 15/85 to 37/63 (propylene content 89.5 to 71.5 wt%), and it is rubber-like. Not a copolymer. Furthermore, JP-A-148093 specifies that the ethylene content in the copolymer of ethylene and α-olefin must be 90 mol% or more, and is aimed at polyethylene resins with high ethylene content. . Using a titanium-based highly active catalyst, ethylene and α
- It is very difficult to copolymerize olefins with good randomness to obtain a rubber-like copolymer, and it is difficult to make analogies to the production technology of polyolefins, which is the homopolymerization of olefins or the copolymerization of small amounts of other olefins. do not have. Conventionally, magnesium chloride was dissolved in alcohol (Japanese Patent Application Laid-Open No. 104907/1982), and dissolved in a hydrocarbon solvent in the presence of an electron donor (Japanese Patent Application Laid-Open No. 120992/1989).
Methods for doing so are known. It is also known that a catalyst in which titanium tetrachloride is supported on the solid surface of Mg(OH)Cl provides high activity as a catalyst for olefin polymerization (Japanese Unexamined Patent Publication No. 44273/1983). However, so far it has not been known to dissolve Mg(OH)Cl in organic compounds. The present inventors have discovered that a homogeneous solution can be obtained by contacting three components: Mg(OH)Cl, a phosphorus compound having an O═P bond, and titanium tetrahalide. If any one of these three components is missing, a homogeneous solution will not be obtained. Based on this knowledge, the present inventors have been conducting research on catalysts that produce olefin copolymer rubber. As a result, we established a method for obtaining a rubber-like copolymer with unprecedented high activity and good random copolymerizability, and achieved the present invention. That is, the present invention provides Mg in the presence or absence of (A) a hydrocarbon or a halogenated hydrocarbon.
(OH)Cl and phosphorus compound with O=P bond
A homogeneous solution consisting of TiCl ₄ was prepared, and using a fine powder solid composite precipitated from the homogeneous solution and (B) a catalyst consisting of an organoaluminum compound, ethylene and α-
This is a method for producing an olefin copolymer rubber characterized by copolymerizing olefin or ethylene, α-olefin, and a non-conjugated polyene. The present invention will be explained in detail below. Regarding the catalyst component (A) used in the present invention, Mg
(OH)Cl can be produced by heating MgCl ₂ .6H ₂ O at high temperatures. Mg(OH)Cl that has been subjected to ball mill crushing, vibration mill crushing, or modification treatment such as complexing treatment can also be used. As a phosphorus compound, the general formula O=P(R ¹ )m
It is a phosphorus compound represented by ( ^OR2 )n (where ^R1 and ^R2 are hydrocarbon residues having 1 to 20 carbon atoms, m=an integer of 0 to 3, and n=3-m). Specific examples thereof include the following compounds. 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 Eight, Tory-2
-Ethyl-hexyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trioleyl phosphate, triphenyl phosphate, tritolyl phosphate, tricylyl phosphate, octyl diphenyl phosphate, tolyldif enyl 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 The compounds include, but are not limited to, inoxide, tritolylphosphine oxide, tricylylphosphine oxide, and the like. Preferably R ¹ and R ² have 2 to 12 carbon atoms
It is a phosphorus compound that is an alkyl group. These compounds can also be used in combination of two or more. When preparing a solution containing Mg(OH)Cl, a phosphorus compound, and titanium tetrachloride, the solution may be prepared in 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,
Examples include methylene chloride, ethyl chloride, ethyl bromide, 1,2-dichloroethane, 1,1-dichloroethane, n-butyl chloride, n-octyl chloride, monochlorocyclohexane, monochlorobenzene, o-dichlorobenzene, etc. It is not limited to solvents.
Two or more of these solvents can be used in combination. Next, a method for preparing the catalyst component (A) will be described.
It is sufficient to bring three components, Mg(OH)Cl, a phosphorus compound, and titanium tetrachloride into contact, and although there is no particular limitation, a homogeneous solution will not be generated if any one of these three components is missing. Examples include the following methods. (1) Suspend Mg(OH)Cl in a phosphorus compound and gradually add titanium tetrachloride while stirring. (2) After suspending Mg(OH)Cl in the above solvent, a phosphorus compound is added while stirring, and titanium tetrachloride is gradually added. (3) Add a phosphorus compound to a solid powder obtained by co-pulverizing Mg(OH)Cl with titanium tetrachloride using a vibration mill, ball mill, etc. and dissolve it. Dilute with the above solvent as necessary. (4) Add the Mg(OH)Cl, titanium tetrachloride, phosphorus compound, and the above-mentioned solvent if necessary, and wet-pulverize and dissolve in a vibration mill, ball mill, etc. The melting temperature is 0~200℃, preferably 20~150℃,
The dissolution time is 10 minutes to 24 hours, preferably 30 minutes to 5 hours. The quantitative ratio (mole) of each component used at this time is:
Ti:Mg:P=0.75~3/1/2~50, preferably 0.9~2/1/2~25, more preferably 1~
It ranges from 1.5/1/2 to 20. Next, a method for precipitating a finely powdered solid composite from the above-mentioned homogeneous solution will be described. However, the method is not limited to these methods. The method for depositing the fine powder solid composite includes the following method. A finely powdered solid component can be effectively obtained by removing phosphorus compounds, concentrating, adding a poor solvent, or by combining these methods. Among these methods, the method of removing phosphorus compounds is preferred. A method for removing phosphorus compounds is to convert the reaction product of magnesium chloride, phosphorus compound, and titanium tetrachloride into a fine powder solid by reacting or coordinating the following compounds with the phosphorus compound. These are organometallic compounds of metals from Groups 1 to 3 of the Table of Contents, and halides of titanium, vanadium, silicon, sulfur, tin, germanium, etc. Particularly preferred are halogen-containing compounds such as titanium and silicon. The precipitation treatment of this finely powdered solid composite can be carried out in the presence of an inorganic solid carrier. The inorganic solid carrier has a surface area of 10 m ² /g or more, preferably 50 m ² /g or more, particularly preferably 60 m 2 /g or more.
m ² /g or more, an average particle size of 200 μm or less, preferably 150 μm or less, and an average pore size of 50 Å or more, preferably 60 Å or more, such as silica, alumina, zeolite, and magnesia.
The amount of the inorganic solid carrier used is Mg(OH)
The amount is 0.5 to 200 g, preferably 1 to 100 g per gram of Cl. The finely powdered solid composite prepared as described above is preferably washed thoroughly with a solvent such as pentane, hexane, heptane, toluene, etc., and then used as the catalyst component (A) in a suspended state in these solvents. As the catalyst component (B), an organic aluminum compound is used. General formula AlRmX _3-n (R is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen or alkoxy group,
m is an organoaluminum compound represented by 1 to 3). For example, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-dodecylaluminum, diethylaluminum chloride, diethylaluminium bromide, diethylaluminium iodine Do, G-n
-Butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, n
- Examples include, but are not limited to, octylaluminum sesquichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-octylaluminum dichloride, ethylaluminum dibromide, diethylaluminum monoethoxide, diethylaluminium monobutoxide, etc. It is not something that will be done. Moreover, two or more kinds of compounds can be used in combination. Preferred is a trialkylaluminum or a mixture of a trialkylaluminum and a halogen-containing organic aluminum. The amount of catalyst component (B) used is 1.5 to 200 times, preferably 2 to 100 times, per mole of Ti in catalyst component (A). As monomers for polymerization, ethylene and one or more types of α
- Olefin can be used. Specific examples of α-olefin include propylene, butene-1,
Examples include pentene-1, hexene-1, 4-methylpentene-1, octene-1, and the like. The ethylene content in the copolymer is preferably 30 to 75 wt%. To facilitate vulcanization of the copolymer rubber, monomers of non-conjugated polyenes can be copolymerized with the olefin monomers. Specific examples of non-conjugated polyenes include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-(1'-butenyl)
-2-norbornene, 5-(2'-butenyl)-2
-norbornene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9-tetrahydroindene, 2,2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-
Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,6
-Octadiene, 6-methyl-1,5-heptadiene, etc. These non-conjugated polyenes 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 polyenes can also be used in combination. Polymerization temperature is usually 10-150℃, preferably 30-120℃
It is ℃. Polymerization pressure usually ranges from normal pressure to 100Kg/cm ²
is within the range of Copolymerization can be solution polymerization or suspension polymerization. It 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. Solution polymerization is preferred. Specific examples of polymerization solvents are listed below. Hydrocarbon solvents include propylene, pentane, hexane, heptane, octane, kerosene, benzene, toluene, xylene, cyclohexane; halogenated hydrocarbon solvents include methylene chloride, monochloroethane, 1,1-dichloroethane, 1,2-dichloroethane, These include 1,2-dichloropropane, monochlorobutane, and monochlorobenzene. Two or more of these solvents can be used in combination to adjust the solvability 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, the measured values of the various physical properties of the copolymer in the examples were as follows: Mooney viscosity was preheated for 1 minute, measured for 4 minutes, and the temperature was 100°C.
The propylene content was determined by infrared absorption spectrum, and the iodine value was determined by titration.
100% modulus, tensile strength, elongation at break, and Shore A hardness are values determined by a measuring method according to JISK 6301. The titanium content was determined by a colorimetric method using hydrogen peroxide as a coloring agent after decomposition with phosphoric acid. Example 1 (1) Preparation of catalyst component (A) 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. In a 100ml flask that has been thoroughly dried and replaced with nitrogen,
A rotor and 1 g (13 mmol) of Mg(OH)Cl were added. 2-Ethylhexyl (di-2-ethylhexyloxy) dried over molecular sieves
36 mmol of phosphine oxide was added and heated to 130°C. Although Mg(OH)Cl does not dissolve in this state, 13 mmol of titanium tetrachloride is added to this flask.
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.
(poor solvent as precipitating agent) and titanium tetrachloride
13 mmol was added and kept at 60°C in a hot water bath. While vigorously stirring this solution, the above homogeneous solution containing magnesium, titanium, and phosphorus was slowly added dropwise. Immediately a yellow fine powder solid complex precipitated out. Stirring was continued for 2 hours at 60°C. Stirring was stopped, a yellow fine powder solid was precipitated, and the supernatant liquid was separated. Another 60 ml of dry n-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. n-
Hexane was added to bring the total volume to 50 ml. The titanium concentration in this fine powder solid composite slurry is
0.024mol/, Mg/Ti=10.5 (molar ratio)
It was hot. (2) Ethylene, propylene and 5-ethyldene-2
- Copolymerization of norbornene The separable flask in step 3 was equipped with a stirring blade, a three-way pot, a gas blowing tube, a thermometer, and a dropping funnel for adding 5-ethylidene-2-norbornene, and the flask was sufficiently purged with nitrogen. This flask was dried with molecular sieves and degassed.
Added 2 hexane. Dry ethylene 4/min, propylene 6/min through the gas blowing pipe
/min, hydrogen 0.2/min was bubbled into the flask temperature-controlled at 35℃ for 10 minutes, and 1 mol/min of triisobutylaluminum was added.
After adding 2 ml of n-hexane solution, 0.05 mmol of the n-hexane slurry of catalyst component (A) prepared in (1) above was added in terms of titanium atoms to initiate polymerization. Simultaneously with the start of polymerization, a mixed solution of 10 ml of 5-ethylidene-2-norbornene and 200 ml of n-hexane was added dropwise at a rate of 7 ml/min, and polymerization was carried out for 30 minutes. During the polymerization, a monomer mixed gas was passed through the reactor at the above flow rate. The polymerization temperature was controlled at 35°C by external cooling. Almost no gel formation was observed during copolymerization. After 30 minutes, 20 ml of methanol was added to stop the polymerization. After adding a small amount of anti-aging agent, steam stripping was performed to obtain a solid rubber. The yield, Mooney viscosity, and propylene content in the copolymer were measured. The results are summarized in Table 1. The raw rubber physical properties of the copolymer obtained in Example 1 were as follows. 100% modulus = 5 Kg/cm ² Tensile strength = 15 Kg/cm ² Elongation at break = 4000% Shore A hardness = 30 Example 2 (1) Preparation of catalyst component (A) The same operation as in Example 1 was performed, and the resultant product was yellowish white. An n-hexane slurry of a finely powdered solid composite was obtained. Add 10ml of titanium tetrachloride to this slurry,
The mixture was stirred at 60°C for 2 hours. After stopping stirring and separating the supernatant, the washing operation of Example 1 was repeated six times. N-hexane was added to bring the total volume to 50 ml.
The titanium concentration in this fine powder solid composite slurry is 0.025 mol/Mg/Ti=9.2 (molar ratio)
It was hot. (2) Copolymerization Copolymerization was carried out in the same manner as in (2) of Example 1. The results are summarized in Table 1. Example 3 The same operation as in Example 1 was repeated except that 36 mmol of tri-n-butyl phosphate and 20 ml of monochlorobenzene were used instead of the phosphorus compound used in Example 1. A light yellow fine powder solid composite was obtained. N-hexane was added to bring the total volume to 50 ml to form a slurry. The titanium concentration in the slurry is 0.01mol/,
Mg/Ti=26 (molar ratio). The copolymerization results are summarized in Table 1. Example 4 In place of the phosphorus compound used in Example 1, n-
Butyl (d-n-butoxy)phosphine oxide
The same operation as in Example 1 was repeated except that 36 mmol and 20 ml of monochlorobenzene were used. A light yellow fine powder solid composite was obtained. N-hexane was added to bring the total volume to 50 ml to form a slurry. The titanium concentration in the slurry is 0.028mol/,
Mg/Ti=8.7 (molar ratio). The copolymerization results are summarized in Table 1. Example 5 The same operation as in Example 1 was repeated except that 20 ml of Isoper-E (trade name, Esso, a hydrocarbon solvent whose main component is isooctane) was used as the solvent. A light yellow fine powder solid composite was obtained.
N-hexane was added to make a 50 ml slurry. The titanium concentration in the slurry was 0.022 mol/Mg/Ti=10.8 (molar ratio). The copolymerization results are summarized in Table 1. 【table】

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 A homogeneous solution consisting of Mg(OH)Cl, a phosphorus compound having an O=P bond, and TiCl ₄ was prepared in the presence or absence of a hydrocarbon or halogenated hydrocarbon solvent, and precipitated from the homogeneous solution. A method for producing an olefin copolymer rubber, which comprises copolymerizing ethylene and α-olefin or ethylene, α-olefin and non-conjugated polyene using a fine powder solid composite and (B) a catalyst consisting of an organoaluminum compound. .