JPH03234716A - Production of random cycloolefin copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer of excellent randomness and a narrow molecular weight distribution in an excellent polymerization activity by copolymerizing an alpha-olefin with a cycloolefin in the presence of a catalyst comprising a specified transition metal compound and an organoaluminumoxy compound. CONSTITUTION:The purpose copolymer is obtained by copolymerizing an alpha-olefin with a cycloolefin in the presence of a catalyst comprising a transition metal compound (A) having as a ligand a polydentate compound composed of at least two conjugated cycloalkadienyl groups or substitution products thereof bonded through a silylene group or a substituted silylene group and an organoaluminumoxy compound (B).

Description

[Detailed description of the invention]

Edan Ritcho Vsei 1 Present invention hawk a- in the presence of a novel highly active polymerization catalyst
The present invention relates to a method for producing a cyclic olefin random copolymer by copolymerizing an olefin and a cyclic olefin. More specifically, the present invention relates to a method for producing a cyclic olefin random copolymer by copolymerizing an a-olefin and a cyclic olefin in the presence of a catalyst comprising a specific transition metal compound and an organoaluminumoxy compound. . As a method for producing a cyclic olefin random copolymer by copolymerizing an a-olefin such as ethylene and a cyclic olefin, a titanium-based copolymer consisting of a titanium compound and an organoaluminum compound or a vanadium compound and a titanium-based copolymer are used. A method using a vanadium-based catalyst comprising an organoaluminum compound is known. Among these methods, in copolymerization using a titanium-based catalyst, cyclic olefins have poor reactivity and low copolymerization efficiency compared to a-olefins such as ethylene. Therefore, in order to expect a copolymer with α-olefin, 1) it is necessary to add a large amount of cyclic olefin to the polymerization system. However, when a large amount of cyclic olefin is added, the catalytic activity is impaired and it also causes a decrease in the molecular weight of the copolymer, making it difficult to obtain a high molecular weight copolymer. Furthermore, side reactions such as ring-opening polymerization reactions of monocyclic olefins are likely to occur.
There is a problem that the resulting polymer has a wide molecular weight distribution. On the other hand, copolymerization using vanadium-based catalysts has a higher copolymerization efficiency of cyclic olefins than titanium-based catalysts, and the resulting copolymer has a narrow molecular weight distribution. There is a problem that the polymerization activity decreases and the copolymerization efficiency also decreases.In addition, in the polymerization method of olefins, a catalyst method consisting of a transition metal compound and an aluminoxane is proposed as a new highly active polymerization catalyst. Japanese Patent Application Publication No. 5
9-95292 Public/Private JP 60-35005 Public/Private JP 60-35006 Public/Private JP 60-350
No. 07 Public/Private This has been proposed in Japanese Patent Application Laid-Open No. 60-35008. Among these prior art, JP-A-58-19309, Public and Private JP-A-60-35005, JP-A-60-3,
5006 Public/Private Public/Private JP-A No. 60-35007 Public/Private JP-A-60-35008

It is stated that the catalyst system is applicable to the copolymerization of ethylene and a-olefins. In addition, regarding the method for producing a cyclic olefin random copolymer, 14 JP-A-61-22120
Publication No. 6 describes the copolymerization of an a-olefin and a cyclic olefin using a catalyst consisting of a transition metal compound and an aluminoxane. The C1 polymerization activity is low and the copolymer can be obtained in an excellent yield. Sara&; JP-A No. 64-106 describes (L) In the presence of a catalyst consisting of a transition metal compound and an aluminoxane,
- Copolymerization of olefins and cyclic olefins has been described. 8. Therefore, in the field of producing cyclic olefin random copolymers, there is a problem that it is difficult to obtain copolymers with a high cyclic olefin content; Improved copolymerizability of cyclic olefins and improved polymerization activity. Emergence of a method for producing cyclic olefin random copolymers that can efficiently produce cyclic olefin random copolymers with a narrow molecular weight distribution. is strongly requested. The present inventors 1 also recognized that the prior art in the field of producing cyclic olefin-based random copolymers was in the above-mentioned situation, and achieved excellent copolymerizability of cyclic olefins even at high polymerization temperatures, and excellent polymerization activity. A method for producing a cyclic olefin-based random copolymer with a narrow molecular weight distribution was studied.A transition metal compound of the rvB group of the periodic table and an organoaluminum oxy with a specific polydentate compound as a ligand. It has been discovered that the above object can be achieved by copolymerizing an a-olefin and a cyclic olefin in the presence of a catalyst consisting of a compound, and the present invention has been completed. This was developed in view of the above, and by copolymerizing an a-olefin and a cyclic olefin in the presence of a catalyst consisting of a specific transition metal compound and an organoaluminumoxy compound, it is possible to achieve copolymerizability even at high polymerization temperatures. The object of the present invention is to provide a method for producing a cyclic olefin random copolymer which has excellent polymerization activity and narrow molecular weight distribution. Misatotachihana 1 According to the present invention (A) a polydentate compound in which at least two conjugated cycloalkagenyl groups or substituents thereof are bonded via a silylene group or a substituted silylene group is used as a ligand. Provided is a method for producing a cyclic olefin-based random copolymer, which comprises copolymerizing an olefin and a cyclic olefin in the presence of a catalyst formed from a transition metal compound and (B) an organoaluminumoxy compound. The method for producing a cyclic olefin random copolymer according to the present invention will be specifically explained below. When copolymerizing a 14 a-olefin and a cyclic olefin in the present invention, As the catalyst, (A) a transition metal compound and (B) an organoaluminumoxy compound are used. A) GL is a transition metal compound having as a ligand a polydentate compound in which at least two cycloalkagenyl groups or substituted products thereof are bonded via a silylene group or a substituted silylene group.Such a transition Metal compound (A) an alkadienyl group or a substituted product thereof, R3 and R4
is cycloalkagenyl group aryl group alkyl group
Aralkyl group Cycloalkyl group Halogen, waterfish O
R-, S Rb, N R2O or PR2-, R-, Rb, RO and Ra are alkyl groups, cycloalkyl groups, aryl groups, hydrocarbon groups such as aralkyl groups, or silyl groups, and two R- and R4 can also be linked to form a ring. ] It is a compound represented by In the above formula, Me is a transition metal, but specifically I
L Zirconium, titanium, nofnium, chromium, and vanadium are preferable, and among these, zirconium and hafnium are particularly preferable. Examples of the substituted silylene group include substituted silylene groups such as dimethylsilylene group, diethylsilylene group, methylethylsilylene group, jetoxysilylene group, and diphenylsilylene group. Examples of cycloalkagenyl groups include 1L cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, indenyl group, tetrahydroindenyl group Examples include fluorenyl groups. As an alkyl group, hawk (formula methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group,
Examples of octyl groups include 2-ethylhexyl pentadecyl, oleyl groups, etc., examples of aryl groups include phenyl pentatolyl groups, and examples of aralkyl groups such as (!, benzyl Shiki opyl group, etc.) Examples of the cycloalkyl group include cyclopentyl group, cyclohexyl group, cyclooctylpenta-norbonyl group, bicyclononyl group, and alkyl substituents of these groups.Also, R3 and RA GL Vinyl group Allyl group Propenyl group Group Isopropenyl group It may be an unsaturated aliphatic group such as a 1-butenyl group or an unsaturated alicyclic group such as a cyclohexenyl group. Examples of the halogen include flat fish, salt fish, and bromine. Specific examples of transition metal compounds in which Me is zirconium are listed below.Dimethylsilylenebis(cyclopentagenyl)zirconium monochloride monohydride, dimethylsilylenebis(cyclopentagenyl>zirconium dichloride, dimethylsilylenebis) (cyclopentagenyl)methylzirconium monochloride, dimethylsilylenebis(cyclopentagenyl)dimethylzirconium, dimethylsilylenebis(cyclopentagenyl)diphenylzirconium, silylenebis(cyclopentagenyl)zirconium dichloride, silylenebis(cyclopentagenyl)diphenylzirconium ) dimethylzirconium, diethylsilylenebis(cyclopentagenyl)zirconium dichloride, diethylsilylenebis(cyclopentagenyl)dimethylzirconium, dimethylsilylenebis(methylcyclopentagenyl)
Zirconium silylene bis(
Dimethylsilylenebis(indenyl)zirconium dichloride, Dimethylsilylenebis(indenyl)zirconium monochloride monohydride, Dimethylsilylenebis(indenyl)ethoxyzirconium chloride, Dimethylsilylenebis(indenyl)dimethylzirconium, Dimethylsilylenebis(indenyl)diethylzirconium, Dimethylsilylenebis(indenyl)diethylzirconium, Dimethylsilylenebis(indenyl)diethylzirconium indenyl) diphenylzirconium, dimethylsilylenebis(indenyl)dibenzylzirconium, dimethylsilylenebis(indenyl)methylzirconium monopromide, dimethylsilylenebis(indenyl)ethylzirconium monochloride, dimethylsilylenebis(indenyl)benzylzirconium monochloride, dimethylsilylenebis(indenyl)benzylzirconium monochloride silylenebis(indenyl)methylzirconium monochloride, dimethylsilylenebis(indenyl)zirconium dibromide, dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium, dimethylsilylenebis(4,5,6 ,7-tetrahydro-1-indenyl)ethylzirconium ethoxide, dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, dimethylsilylenebis(
4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, dimethylsilylenebis(4-methyl-1-indenyl)zirconium dichloride, dimethylsilylenebis(5-methyl-1-indenyl)
Zirconium dichloride, dimethylsilylenebis(6-methyl-1-indenyl)
Zirconium dichloride, dimethylsilylene bis(7-methyl-1-indenyl)
Zirconium dichloride, Dimethylsilylenebis(5-methoxy-1-indenyl)zirconium dichloride, Dimethylsilylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, Dimethylsilylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride , Dimethylsilylenebis(4,7-Simethoxy1-indenyl)zirconium dichloride, Dimethylsilylenebis(indenyl)zirconium dimethoxide, Dimethylsilylenebis(indenyl)zirconium jetoxide, Dimethylsilylenebis(indenyl)methoxyzirconium chloride, Dimethylsilylenebis(indenyl)methoxyzirconium dichloride (indenyl)ethoxyzirconium chloride, dimethylsilylenebis(indenyl)methylzirconium ethoxide, dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide, dimethylsilylenebis(4,5,6, 7-tetrahydro-1-
indenyl) zirconium jetoxide, dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium chloride, dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride, Dimethylsilylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium ethoxide, Diethylsilylenebis(indenyl)zirconium dichloride, Diethylsilylenebis(indenyl)dimethylzirconium, Diethylsilylenebis(4,5,6) ,7-tetrahydro-1-indenyl)zirconium dichloride, dimethylsilylenebis(fluorenyl)zirconium dichloride, dimethylsilylenebis(fluorenyl)dimethylzirconium, dimethylsilylenebis(fluorenyl)diphenylzirconium, dimethylsilylenebis(fluorenyl)zirconium dichloride, dimethylsilylenebis(fluorenyl)zirconium dichloride Bis(fluorenyl)dimethylzirconium, dimethylsilylenebis(fluorenyl)zirconium dichloride. Among these transition metal compounds, transition metal compounds having as a ligand a bidentate compound in which two cyclopentadienyl groups are bonded via a silylene group or a substituted silylene group are preferably used. The organoaluminumoxy compound [B] used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminumoxy compound discovered by the present inventors. Aluminoxane (L) as described above can be produced, for example, by the following method: (1) A compound containing adsorbed water or a salty gas containing water of crystallization, such as magnesium chloride hydrate and sulfuric acid steel hydrate; Hydrocarbon medium suspensions such as aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which organic aluminum compounds such as trialkylaluminum are added and reacted, and recovered as a hydrocarbon solution. Circle (2) In a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran, organic aluminum compounds such as trialkylaluminum are directly treated with water, ice, or steam to recover the hydrocarbon solution. Nooxane 14 May contain a small amount of organometallic component.Also, after removing the solvent or unreacted organoaluminum compound by distillation from the recovered aluminoxane solution, it may be redissolved in the solvent. Specific examples of organoaluminum compounds used in producing aluminoxane solutions include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum,
tri-n-butylaluminum, tri-isobutylaluminum, tri-5ec-butylaluminum, tri-t
Trialkylaluminum such as ert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminium, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum Examples include dialkyl aluminum halides such as chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum alkoxides such as diethyl aluminum phenoxide. Among these, trialkylaluminum is particularly preferred. Moreover, isoprenyl aluminum represented by the general formula %) can also be used as an organoaluminum compound. The above organoaluminum compounds may be used alone or in combination. Solvents used in aluminoxane solutions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, cyclopentane, Alicyclic hydrocarbonized aquatic fish gasoline such as cyclohexane, cyclooctane, and methylcyclopentane, petroleum distillates such as gas oil, or the above-mentioned aromatic hydrocarbonized aquatic fish Aliphatic hydrocarbonized aquatic fish Halogenated alicyclic hydrocarbons, especially chlorinated and brominated ones Examples include hydrocarbon solvents such as. The image Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred. In addition, the benzene-insoluble organic aluminum oxy compound used in the present invention is AQ, which is soluble in benzene at 1460°C
It is 10% or less, preferably 5% or less, particularly preferably 2% or less, and is insoluble or sparingly soluble in benzene, in terms of AQ atoms. The solubility of such an organoaluminumoxy compound in benzene is such that the organoaluminumoxy compound corresponding to 100 milligram atoms of AQ is suspended in 100ml of benzene, mixed at 60°C for 6 hours with stirring, and then heated with a jacket. Using a G-5 glass filter, 6
Perform hot filtration at 0°C, wash the solid portion separated on the filter 4 times with 50ml of benzene at 60°C, and then measure the amount of Ag atoms present in the total filtrate (X mmol). (X%). Furthermore, when the above-mentioned benzene-insoluble organoaluminumoxy compound is analyzed by infrared spectroscopy (IR),
1220c, absorbance near -1 (D + a
2.) and the absorbance near S 1260 (to)-1 (
Date@) ratio (DI2611/DI221)
+40.09 or less, preferably 0.08 or less, particularly preferably in the range of 0.04 to 0.07. Infrared spectroscopic analysis of organoaluminumoxy compounds iL
Do it as follows. First, in a nitrogen box, the organoaluminumoxy compound and Nujol are ground into a paste using an agate needle. Next, the paste-like sample was placed between KBr plates, and the IR spectrum was measured using IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere. I of the organoaluminumoxy compound used in the present invention
The R spectrum is shown in FIG. From the IR spectrum obtained in this way, D126
@／ The power to seek J22@・ This D 126 @
/ D 122 @ value is determined as follows. (a) Connect the maximum points near 1280c, -1 and 1240cm-1, and define this as the baseline L1. (b) Transmittance of absorption minimum point near 1260 cm-+ (T
%), draw a perpendicular line from this minimum point to the wavenumber axis (horizontal axis), and calculate the transmittance (
Ts%) and calculate the absorbance around 1260cs-' (D+zs@=10g To/T). (c) Similarly, around 1280cm-1 and 1180cm-1
Connect nearby maximum points and use this as the baseline L2. (d) Transmittance of absorption minimum point near 1220c, -1 (T
-%), draw a perpendicular line from this minimum point to the wavenumber axis (horizontal axis), read the transmittance (T=.%) at the intersection of this perpendicular line and baseline L2, and read the absorbance (T=.%) near 1220C11-1. Calculate D+22s=lOg T'o/T°). (e) From these values, calculate 28°/D122@. Incidentally, an IR spectrum of a conventionally known benzene-soluble organoaluminumoxy compound is shown in FIG. As can be seen from this Figure 3, benzene-soluble organoaluminumoxy compound +L DI26/DI22- value τ
, is between 0.10 and 0.13, and the benzene-insoluble organoaluminumoxy compound used in the present invention +
4 Conventionally known benzene-soluble organoaluminumoxy compound and D126@/D, 22. There is a clear difference in value. It is estimated that the benzene-insoluble organoaluminumoxy compound has an alkyloxydialuminum unit represented by the above formula [wherein R1 is a hydrocarbon group having 1 to 12 carbon atoms]. In the above alkyl oxydialuminum unit, RI
Specific examples of i4 include 1-inversion methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, five decyl group, cyclohexyl group, and the like. Among these, methyl group and ethyl group are preferred, and methyl group is particularly preferred. This benzene-insoluble organoaluminumoxy compound contains an alkyloxyaluminum unit represented by the formula +OAg+ and an oxydialuminum unit represented by the formula +OAQ+ [where R1 is the same as above, and R2i4 has a carbon number of 1 to 12]. hydrocarbon group of
Alkoxy group having 1 to 12 carbon atoms Aryloxy group having 6 to 20 carbon atoms Hydroxyl group Halogen or hydrogen, R1
and R2 represent mutually different groups]. In that case, an organoaluminumoxy compound having an alkyloxydialuminum unit containing 14 alkyloxydialuminum units -+0AQ-)- in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. is preferred. Next, a method for producing the benzene-insoluble organoaluminumoxy compound as described above will be specifically explained. This benzene-insoluble organoaluminumoxy compound:
(ix) Obtained by contacting a solution of aluminoxane with water or an active hydrogen-containing compound. As active hydrogen-containing compounds, GL, alcohols such as methanol, ethanol, n-propanol and isoprobal, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid are used. Among these, alcohol melon diols are preferred, and alcohols are particularly preferred. Water or an active hydrogen-containing compound + 4 in contact with a solution of aluminoxane; Hydrocarbon solvents such as benzene, toluene, hexane; Ether dissolution such as tetrahydrofuran; Dissolved or dispersed in amine solvents such as triethylamine; Steam or solid. It can be used in the following conditions. Also, as water, magnesium chloride, magnesium sulfate,
Aluminum sulfate, sulfuric acid, crystalline water of salts such as nickel sulfate, iron sulfate, and cerous chloride, or adsorbed water adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide, can also be used. A catalytic reaction between a solution of aluminoxane and water or an active hydrogen-containing compound (circle) is usually carried out in a hydrocarbon solvent, such as a hydrocarbon solvent. Aromatic hydrocarbonized fish Aliphatic hydrocarbonized fish such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane Alicyclic hydrocarbonized waterfish such as cyclopentane, cyclohexane, cyclooctane, and methylcyclohexane Gasoline, good fishing Petroleum such as gas oil Hydrocarbon solvents such as distillates or the above-mentioned aromatic hydrocarbon water milk aliphatic hydrocarbon water gourd Halogenated alicyclic hydrocarbons, especially halogenated hydrocarbons such as chlorides and brominates Ethers such as ethyl ether and tetrahydrofuran are used. Among these media, aromatic hydrocarbons are particularly preferred.
It is used in an amount of ~5 mol, preferably 0.2-3 mol. The concentration in the reaction system is usually LX 10-” to 5 g atoms/g, preferably 1xl, in terms of aluminum atoms.
The concentration of water in the reaction system is preferably in the range of O-2 to 3 gram atoms/9, and the concentration of water in the reaction system [L] is usually 2X10" to 5 mol 151, preferably 2X10-3 to 3 mol/$1. It is desirable that the solution of aluminoxane is brought into contact with water or a compound containing active hydrogen. Block (2) where the compound is brought into contact with a hydrocarbon solvent (2) Solution number of aluminoxane Block (3) where the aluminoxane and steam are brought into contact by blowing in water or vapor of an active hydrogen-containing compound, etc. (4) Direct contact between an aluminoxane solution and water or ice or an active hydrogen-containing compound A method of contacting aluminoxane with adsorbed water or water of crystallization by mixing the compound with a hydrocarbon suspension of the adsorbed compound. Other components may be included as long as they do not adversely affect the reaction with water or an active hydrogen-containing compound. Contact reaction between an aluminoxane solution and water or an active hydrogen-containing compound 1 thick Usually -50 to 150 It is preferably carried out at a temperature of 0 to 120°C, more preferably 20 to 100°C.Although the reaction time varies greatly depending on the reaction temperature, it is usually 0.5 to 300 hours, preferably 1 to 15 hours.
It takes about 0 hours. Furthermore, a benzene-insoluble organoaluminumoxy compound can also be directly obtained by bringing the above organoaluminum into contact with water. In this case, 1 water (conversion) is added.Organoaluminum atoms dissolved in the reaction system are 2
It is used in an amount that is 0% or less. It can be used by contacting with an organoaluminum compound, dissolved or dispersed in filtered water, a hydrocarbon solution such as benzene, toluene or hexane, an ether latent arc such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of water vapor or ice. In addition, as water, crystallization water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, iron sulfate, nickel sulfate, iron sulfate, and cerous chloride, or adsorption adsorbed on inorganic compounds or polymers such as silica, alumina, and aluminum hydroxide. Water etc. can also be used. Contact reaction between organoaluminum compounds and water 1 Usually carried out in a hydrocarbon solvent. Hydrocarbon solvents used at this time include: Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; Cyclopentane, cyclohexane; , cyclooctane, methylcyclohexane, etc. Gasoline, good fishing Petroleum distillates such as gas oil or the above aromatic hydrocarbons Aliphatic hydrocarbon aquatic fish Halogenation of alicyclic hydrocarbons, especially chlorides, bromides, etc. Examples include hydrocarbon solvents. Ethers such as ethyl ether tetrahydrofuran can also be used. Among these media, aromatic hydrocarbons are particularly preferred. In terms of normal IX 10-3 to 5 gram atoms/Q, preferably IX 10-2 to 3 gram atoms/1
The concentration of water in the reaction system is preferably in the range of 1 & usually 1 x 10-2 to 5 mol/Q, preferably 1 x 10-2 to 3 mol/9. At this time, it is desirable that the content of the organic aluminum atoms dissolved in the reaction system be 20% or less, preferably 10% or less, and more preferably 0 to 5%, based on the total organic aluminum atoms dissolved in the reaction system. +1 for contacting organoaluminum compounds with water
Specifically, it may be done as follows. (1) A method of bringing a hydrocarbon solution of an organoaluminum into contact with a hydrocarbon solvent containing water. (2) A method of bringing an organoaluminum into contact with water vapor, such as by blowing water vapor into the hydrocarbon solution of an organoaluminium. Arashi (3) A cube in which a hydrocarbon solution of organoaluminum and a hydrocarbon suspension of an adsorbed water-containing compound or a crystal water-containing compound are mixed, and the organoaluminum and adsorbed water or crystal water are brought into contact with each other (4) Organic Those who contact ice with a hydrocarbon solution of aluminum may also contact a hydrocarbon solution of organoaluminum (as described above).
Other components may be included as long as they do not adversely affect the reaction between organic aluminum and water. Contact reaction between organoaluminum compounds and water 1 Taijo-10
It is carried out at a temperature of 0 to 150°C, preferably -70 to 100°C, more preferably -50 to 80°C. In addition, the reaction time varies greatly depending on the reaction temperature. Usually 1~
200 hours, preferably about 2 to 100 hours. The above-mentioned transition metal compound (A) and organoaluminumoxy compound (B) IL may be used as they are or supported on a carrier. Examples of carriers include inorganic compounds such as silica and alumina, and organic polymer compounds such as polyethylene and polypropylene. In the present invention, the a-olefin supplied to the polymerization reaction is +4, specifically ethylene, propylene, 1
-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,
2 to 2 carbon atoms, such as 1-tetradecene, 1-hexadecene, 1-octadecene, l-engine, 1'cosene, etc.
0 α-olefin can be exemplified. Among these, ethylene is particularly preferred. In addition, in the present invention, as the cyclic olefin supplied to the polymerization reaction, +1 specifically iL cyclopropene,
Cyclobutene, cyclopentene, cyclohexene, 3-
Monocycloalkenes such as methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,
5-isobutyl-2-norbornene, 5.6-dimethyl-2-norbornene, 5.5.6-)trimethyl-2-
Bicycloalkenes such as norbornene and 2-bornene,
2.3.3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5.6.7a-tetrahydro! :+ Tricycloalkene such as -4,7-methano-IH-indene, 1°4,5.8-dimethano-1,2
, 3,4,4a, 5.8.8a-In addition to octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5.8.8a- Octahydronaphthalene, 2ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5.8.8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5.8.8a- Octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5.8゜8a-octahydronaphthalene, 2-stearyl-1,4゜5.8 -dimethano-1,2,3,4,4a, 5.8.8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,
8-dimethano-1,2゜3,4.4a, 5.8.8a
-octahydronaphthalene, 2-methyl-3-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5.8゜8a-octahydronaphthalene, 2-chloro-
1,4,5,8-dimethano-1,2,3,4,4a,
5.8.8a-Octahydronaphthalene, 2-bromo-
1,4,5,8-dimethano-1,2,3,4,4a5,
8.8a-octahydronaphthalene, 2-fluoro-1
゜4,5.8-dimethano-1,2,3,4,4a, 5
．． 8.8a-octahydronaphthalene, 2.3-dichloro-1,4,5,8-dimethano-1°2, 3.4.4a
, 5.8.8a-Tetracycloalkenes such as octahydronaphthalene, hexacyclo(6,6,1°13.
6J+11.13. Q2・7.09・14] Hebutandecene Pentacyclo [8, 8, 12, 9, 14, ? ,
111.111. Q, QlllQ12・17] Henikosen 1 Octacyclo (8,8°12.9,14.?,
111. +11,113. +6. Q, Ql#, Q12.
+7) Cyclic monoenes such as polycycloalkenes such as tococene-5, dicyclopentadiene, 5-methylene-
2-norbornene, 5-ethylidene-2-norbornene, 5-norbornene, 1,5-cyclooctadiene, 5
, 8-endomethylene hexahydronaphthalene, and alkylidene tetrahydroindene. To specifically illustrate the cyclic olefins preferably used below, such cyclic olefin +i, the following formula [r] ・ [E] (wherein, n is O or 1, m is ○ or a positive integer, , R1~Rl River 1 each independently &; hydrogen atom, halogen atom or hydrocarbon group, R15~Rl @
+ and L may be combined with each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. Furthermore, RI5 and RIB or R17 and R18 may form an alkylidene group). The cyclic olefin represented by the above formula [r] can be easily produced by condensing cyclopentadiene and the corresponding olefin milk or cyclic olefin by Diels-Alder reaction. The cyclic olefin represented by the above formula [rl used in the present invention is 1-turn bicyclo[2,2,11hept-2-ene-derived tetracyclo[4,4,0,12, S, 1te, +@]-3
-Dodecene derived image hexacyclo[5,5,1,1111,11113,Q
2. ? ,Q...14]-4-heptadensene derivative octacyclo[8,8,Q,12,@,14
, ? , 111, 1・113.16911, Q
I217]-5-tocosene derivative, pentacyclo[6,
6, 1, 1! , 1,02.7,0,14-hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-5-heneicosene derivative, tricyclo[4,3,0,12,5-3-decene derivative, tricyclo[ 4,3,0,125-3-undecene derivative pentacyclo[6,5,1,13,6,Q2. ? , Qi13
Co-4-Pentadecene Derivative Pentacyclopentadecadiene Derivative Pentacyclo[4,7,0,12,S,0'',
+ 3, 19, + 21-3-pentadecene derived bed pentacyclo[7,8,Q, 13. e, Q2. ? ,
11@, +? , QI1. l8112, Is]-4-eicosene derived bed and nonasif0 [9,10,1,1,4,7,03,1'
,02.11,012.21113・2@,QIA・+
Examples include s, 1+s·18co-5-bentacocene derivatives. Specific examples of such compounds are shown below. Bicyclo[2,2,1]hept-2-ene derivatives such as 1-methylbicyclo[2 and 7-methylbicyclo[2; CH. 5.10-dimethyltetraCH. 2,7.9-)limethylteCH. 9-isobutyl-11,12 5,8,9,10-tetramethyC,,H,. 8-methyltetrasif 8-ethyltetrasif 1-]-]3-dodecene i @]-3-dodecene, +5l-3-dodecene 8-methyl-9-ethylte 8-chlorotetrasif 3-dodecene 8-bromo Tetrashift 8-Fluorotetrano1@Co-3-dodecene] e2-3-dodecene 5.17・1s Co-3-dodecene! 11]-3-dodecene-3-dodecene II] 3-dodecene, 12.5.17 +l! 1-3-dodecene 8-ethylidene-9-ethyne 8-ethylidene-9-iso-dodecene, 12 5.1, +@1-3-dodecene 5.17.111-3-dodecene 8-n-propylidene- 9-dodecene8-n-propylidene-9 [4,4,0,12・5.17・I@1-3-dodecenecro[4,4,0,12・5 7 1]-3-dodecene8- n-Propylidene-9 [4,4,0,12 5,17'']-3-dodecene 8-isopropylidene-dodecene 8-isopropylidene-dodecene 1e-3-dodecene CH. [4,4,0,12 s , 1v, ti3-3 -dodecene and other tetracyclo[4,4,0,125,17,le
Coco-dodecene derivative; (blank below) + 4]-4-heptadecenedecenedeceneheptadecene+S, Q2.7. Q. Hexacyclo[6,6,1,138,11@,+
3. Q2. ? , Q.1' ]-]4-heptadecene derivative; 3, + 6
, (p ・, 012 1〒] −5− tococene 1 @, 13. + 6. Ql ・ Ql 2・1] −5‐tococene 2・+v] −5‐tococene and other octacyclo[8, 8, 0, 12s, 14.?,
111 1@, 11 16.03 @, QI2
*, +4]-4-hexadecene derivatives; heptacyclo[8,7,0 Heptacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-heneicosene derivatives; CH. Tricyclo[4,3,0,12S]-3-decene derivatives such as 2-methyltricyclo; Tricyclo[4,4,0,126]3-undecene derivatives such as 10-methyl-tricif; 1.3 -dimethyl-penta1,6-dimethylbenta14,15-dimethylben and other pentacyclo[6,5,1,138, Q2. T,
Q9 +3-4-pentadecene derivatives: diene compounds such as; pentacyclo[4,7,0,12・S,Q・13.111 12-3-pentadecene derivatives; cosene2.1S]-4-eicosene Hebutacyclo[7,8,0,13,8,02 7,1111 +7. Q 111, l12. ls] -4-eicosene derivative: 21.1!3.2・,O12,+9,11118co5
-bentacocene 3.2@, QIJ, i, lIs, IJ -5-bentacocene etc. nonacyclo[9,IQ,l,14.7. Q3. l
l, Q2. l, QI221.113.2・0+a,+s
, 1+s, +J -5-hentacocene derivatives. (Left below) And then there's sleep. (Left space below) In the method of the present invention, the raw material olefin (gas) supplied to the polymerization reaction system is a mixture consisting of the a-olefin and cyclic olefin as described above.The a-olefin iL in the polymerization raw material olefin is usually 1 ~90 mol%,
The cyclic olefin (9) is preferably used in an amount of 2 to 80 mol%, usually 10 to 99 mol%, preferably 20
It is used in an amount of ~98 mol%. In the present invention, the copolymerization reaction of alpha-olefin and cyclic olefin is usually carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as 4-butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane; Alicyclic hydrocarbon aquatic fish, aromatic hydrocarbons such as benzene, toluene, and xylene, and olefins, which are paper raw materials used in petroleum distillates such as gasoline and gas oil, are also hydrocarbon media. Among them, aromatic hydrocarbons are preferred.In the present invention, tit, copolymerization reaction 1 turn usually -50 to 1
It is carried out at a temperature of 50°C, preferably -30 to 100°C. When carrying out the above copolymerization reaction by liquid phase polymerization, the concentration of transition metal atoms in the polymerization reaction system is usually 10-8 to 10-2 gram atoms/transition metal compound (A) + L. Q1 is preferably used in an amount of 10-7 to 10-3 gram atom/Q.Also, the concentration of aluminum atoms in the polymerization reaction system of the organoaluminumoxy compound is usually 10-4 to 10-1 gram atom/Q. Q,
Preferably 10-3 to 5X 10-2 gram atoms/
It is desirable that the ratio of aluminum atoms to transition metal atoms in the polymerization reaction system is usually 4 to 107, preferably 10 to 106. The molecular weight of the copolymer can be controlled by making hydrogen exist in the conversion reaction system or by changing the polymerization temperature. In the present invention, the polymerization reaction mixture in which the polymerization reaction has been completed is
A cyclic olefin random copolymer can be obtained by processing in a conventional manner. In such a cyclic olefin random copolymer, the structural unit derived from a converted α-olefin is usually 10 to 99.9 mol%, preferably 20
It is desirable that the structural unit derived from the cyclic olefin is present in an amount of ~99.5 mol%, and usually in an amount of 0.1-90 mol%, preferably 0.5-80 mol%. In addition, the temperature of the cyclic olefin random copolymer at 135°C
Intrinsic viscosity measured in decalin solvent [wa] 1 circle usually 0.005-20a, preferably 0.01-10a
1/g, and the molecular weight distribution measured by gel permeation chromatography (GPC) is usually 4 or less, preferably 3 or less. By the method of the present invention, it is possible to efficiently produce a cyclic olefin-based random copolymer with a narrow molecular weight distribution, which has superior copolymerizability even at high polymerization temperatures, and superior polymerization activity. [Example] Next, the method of the present invention will be specifically explained by Examples.The present invention is not limited to these Examples. [Preparation] A112 (S○,) 3.
Charge 1 g of 14H2037 and 133 ml of toluene, and after cooling to -5°C, add 47.9 ml of trimethylaluminum diluted with 152 ml of toluene dropwise over 1 hour.Then, react at 0 to -5°C for 1 hour, and then 3 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the filtrate to obtain a white solid benzene-soluble organic aluminum oxy compound. 9. The benzene-soluble organoaluminumoxy compound obtained above was redissolved in toluene (A11 = 2.57 mol/1
2)1. ) toluene 90.5ml
After charging 25 g of a Teflon cylinder (1.2 am x Z fin φ) into a 400 ml flask and cooling the temperature inside the round system to -5°C, 1.08 ml of water was gradually added dropwise over 20 minutes. After the completion of the dropwise addition, the temperature was raised to 80°C over 30 minutes, and the reaction was carried out at 80°C for 3 hours.Then, the Teflon cylinder was removed using a 32-mesh sieve. A benzene-insoluble organoaluminumoxy compound was obtained, which has a solubility in benzene of 0.4% by weight at °C and a ratio of D12@@/D122@ measured by IR of 0.053. ) Preparation of zirconium dichloride] In a 200 ml glass flask that was sufficiently purged with nitrogen, 4.7 g of zirconium tetrachloride was slurried with 10 ml of benzene and 10 ml of tetrahydrofuran, and cooled to 0°C. Add 20 mmol of lithium salt of bis(cyclopentadienyl)dimethylsilane dissolved in 50 ml of tetrahydrofuran, and add 20 mmol of lithium salt at room temperature.
After stirring for a while, the solvent was distilled off, and the catalyst component was extracted with 150 ml of chloroform. After some chloroform was distilled off from the extract, it was cooled to obtain a solid. The solid was filtered and dried under reduced pressure to obtain 1.5 g of dimethylsilylenebis(cyclopentadienyl)zirconium dichloride [Polymerization] In a 500 ml glass autoclave that was sufficiently purged with nitrogen, 250 ml of purified toluene and tetra cyclododecene 1
After charging 5 g of ethylene gas, ethylene gas was passed through at a rate of 1041/h and held at 80°C for 10 minutes. .5×10
Polymerization was started by charging dimethylsilylenebis(cyclopentagenyl)zirconium dichloride dissolved in toluene equivalent to -2 milligram atoms f, and after polymerization was carried out at 80°C for 1 hour at normal pressure, Polymerization was stopped at Polymerization (circle) Proceeding in a uniform solution state, polymerization 1
Ethylene absorption was observed even after several hours. After the reaction, the polymer solution was added to a large amount of methanol to precipitate the polymer, which was dried under reduced pressure at 130°C overnight. The polymer yield after drying was 6.4 g, unit The activity per zirconium was 14260 g polymer/milligram atom Zr -hr. Furthermore, the ethylene content of this polymer, [ηL
Mw/Mn are 63 mol% and 0. l 5d
llA2.33 and Yutaka Kuri 1 Polymerization in the same manner as in Example 1 except that bis(cyclopentagenyl)zirconium dichloride was used instead of dimethylsilylenebis(cyclopentagenyl)zirconium dichloride in the polymerization of Example 1 As a result, the ethylene content, [wa], and My/Mn were each 9.
2 mol %, 1.46 dll/i2.13 of the polymer was obtained, and the activity 1f per round unit zirconium was obtained.
, 130 g polymer/milligram atom Zr-hr, 250 ml purified toluene and tetracyclododecene 7
．． After charging 5 g, ethylene gas was passed through at 1011/h, held at 60°C for 10 minutes, and tied in a circle. .5X1
Polymerization was started by charging 0-2 milligram atoms of dimethylsilylenebis(cyclopentagenyl)zirconium dichloride dissolved in toluene and heating at 60 °C for 10 min.
After polymerization was carried out at normal pressure for 1 minute, the polymerization was stopped using an inproper tool and the polymerization proceeded in a uniform solution state.
Ethylene absorption was observed even after 10 minutes of polymerization. After the reaction was complete, the polymer solution was added to a large amount of methanol to precipitate the polymer, which was then dried under reduced pressure at 130°C overnight. The polymer yield after drying was 0.71 g. , activity per unit zirconium (Ll 70g polymer/milligram atom Zr
-hr, the ethylene content of this polymer,
[W], My/Mnl & 66 mol%, 0.
[Preparation of dimethylsilylenebis(methylcyclopentagenyl)zirconium dichloride] In a 200 ml glass flask that was sufficiently purged with nitrogen, 4.7 g of zirconium tetrachloride was mixed with 10 ml of benzene. Tetrahydrofuran 10
Make a slurry with ml and cool to 0°C, add 20 mmol of lithium salt of bis(methylcyclopentadienyl)dimethylsilane dissolved in 50 ml of tetrahydrofuran, and gently reflux for 2 hours.Then, the solvent is distilled off. After that, the catalyst component was extracted with 150 ml of chloroform. After partially distilling off the chloroform from the extract, it was cooled to obtain a solid. The solid was filtered.
After drying under reduced pressure, 1.4 g of dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride was obtained. [Polymerization] 250 ml of purified toluene and tetracyclododecene were placed in a 500 ml glass autoclave that was sufficiently purged with nitrogen. 7
．． After charging 5 g, ethylene gas was passed at 10 Q/h and nitrogen gas was passed at 40 Q/h, and the temperature was maintained at 60°C for 10 minutes. Dimethylsilylene bis(
After charging zirconium dichloride (methylcyclopentadienyl) and starting polymerization, polymerization was carried out at 60℃ for 1 hour at normal pressure, and then the polymerization was stopped using an inproper tool and the polymerization proceeded in a homogeneous solution state. Ethylene absorption was observed even after 1 hour of polymerization. After the reaction, the polymer solution was added to a large amount of methanol to precipitate the polymer, which was then dried under reduced pressure at 130°C overnight. The yield of polymer after drying was 5.5 g. and the activity per unit zirconium is 1122
0g polymer/milligram atom Zr-hr. Of course, the ethylene content of this polymer, [η], My/M
ni & 73 mol% and 0.41 dQ respectively 2.
In a 500 ml glass autoclave that was sufficiently purged with nitrogen, 250 ml of purified toluene and 7 ml of tetracyclododecene were placed.
．． After charging, propylene gas was introduced at a rate of 50Q/h and held at 20°C for 10 minutes.Subsequently, the organoaluminum oxy prepared in Example 1, which corresponds to 2.5 milligram atoms in terms of aluminum atoms, was added. The compound, dimethylsilylenebis(cyclopentagenyl)zirconium dichloride prepared in Example 1 dissolved in toluene corresponding to 2.5xlO-2 milligram atoms in terms of zirconium atoms, was charged to start polymerization, and 7'Ql, 20 After polymerization was carried out at normal pressure for 2 hours at ℃, the polymerization was stopped using an inproper tool.9 Polymerization+4 Proceeded in a homogeneous solution state, and absorption of propylene was observed even after 2 hours of polymerization.After the reaction was completed,
The polymer solution was added to a large amount of methanol, the polymer was precipitated, and dried overnight at 130°C under reduced pressure. r = The yield of the polymer after drying was 0.37 g, and the activity per unit zirconium + 415 g polymer/milligram atom Zr - hr
The glass transition temperature of the obtained copolymer measured by a differential scanning calorimeter was 78°C, and the intrinsic viscosity was 0.09 an/g.

[Brief explanation of drawings]

Figure 19 is an explanatory diagram of the catalyst for olefin polymerization according to the present invention, Figure 2 (9) is an IR spectrum of a benzene-insoluble aluminum oxy compound, and Figure 3 (L is an IR spectrum of a benzene-soluble aluminum oxy compound). be.

Claims (1)

[Claims] (1) (A) A transition metal compound having as a ligand a polydentate compound in which at least two conjugated cycloalkadienyl groups or substituted products thereof are bonded via a silylene group or a substituted silylene group, and ( B) A method for producing a cyclic olefin random copolymer, which comprises copolymerizing an α-olefin and a cyclic olefin in the presence of a catalyst formed from an organoaluminumoxy compound.