JP2003026718A - Method for producing cyclohexene addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cyclohexane addition polymer with a small dimer content from a cyclohexene monomer in good productivity. SOLUTION: There is provided a method for producing a cyclohexene addition polymer by polymerizing a cyclohexene monomer by using a catalyst comprising a specified transition metal compound, a specified alkylaluminoxane, and a specified boron compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cyclohexene addition polymer from a cyclohexene monomer with good productivity by using a catalyst composed of a transition metal compound, an alkylaluminoxane and a boron compound.

[0002]

BACKGROUND OF THE INVENTION Olefinic low polymers are ethylene, α
-Synthesized from various monomers such as olefins and conjugated dienes by various addition polymerization methods, for various purposes, for example, lubricants,
It is used in a wide range of applications such as heat media, plasticizers for polymer materials, printing inks, paints and adhesives. In particular, a low polymer obtained by reacting a monomer having an aliphatic or alicyclic structure with a transition metal complex as a catalyst is widely used because it is industrially manufactured at low cost.

As the olefinic low polymer, there is a low polymer using ethylene, propylene, n-butene, isobutene, n-pentene, n-hexene, diene or the like as a monomer raw material, and the melt viscosity of the obtained low polymer. , The melting point, the volatilization temperature, etc. are used for various purposes. However, since an aliphatic low polymer generally has a low melting point and a low volatilization temperature, for example, when it is used as a plasticizer for a polymer material, the aliphatic low polymer is compounded with the polymer material and melt-processed at a low aliphatic weight. Part of the coalesced component volatilizes, causing problems such as mold deposits. In addition, there is a limit to the use as a plasticizer for engineering plastics and super engineering plastics that require a high processing temperature, and a plasticizer having a higher volatilization temperature is desired.

The aliphatic low polymer can be used without any problem in plasticizing performance during processing for a resin having a low processing temperature.
However, since the aliphatic low-polymer has a low melting point, it has high mobility at around room temperature, and during use as a resin molded product, there is a problem of bleeding out on the resin surface depending on the use environment, A cyclic olefin-based addition polymer capable of solving these problems is strongly desired. Conventionally, many addition polymers of cyclic olefins have been reported. For example, it is already known that a low polymer can be obtained from a monomer such as cyclobutene, cyclopentene, cyclooctene or norbornene by using a Ziegler-Natta type catalyst composed of a titanium compound as an organoaluminum as a catalyst. However, when these catalysts are used, there is a problem in that a ring-opening reaction partially occurs. Further, it is known that a cycloaddition polymer can be obtained from cyclobutene, cyclopentene, cyclooctene, norbornene or the like by using a Kaminsky catalyst composed of metallocene and alkylaluminoxane.

When the catalyst disclosed in JP-A-1-66216 is used, a cycloaddition polymer can be obtained from cyclohexene without causing a ring-opening reaction. However, the obtained cycloaddition polymer contains a high proportion of the dimer, and therefore, when it is used for the above-mentioned applications, there is a problem in that it cannot express sufficiently satisfactory performance. It was necessary to reduce the proportion of dimers. C. Tsonis et al. Reported a method for polymerizing cyclohexene using a catalyst composed of a rhenium compound and organoaluminum (J. Polym. Sc.
i. Polym Chem Ed, 17, 185 (19
79)). Japanese Unexamined Patent Publication No. 8-104716 discloses a method of prepolymerizing other cyclic olefins such as norbornene using a catalyst system consisting of a transition metal compound of a rhenium compound, a tungsten compound, a molybdenum compound or a lanthanum compound and an organoaluminum. A method of polymerizing cyclohexene is disclosed.

However, in the cyclohexene addition polymers obtained by these methods, side reactions frequently occur during the reaction, and the obtained cyclohexene addition polymers can only obtain a polymer which has already turned brown. Further, the heat resistance of the obtained addition polymer is very poor even when judged from the discoloration rate of the addition polymer at the time of use, and it is at a level that can be used satisfactorily as compared with conventional aliphatic low polymers. Had not reached.

[0007]

DISCLOSURE OF THE INVENTION The present invention includes 2
It is an object of the present invention to provide a method for producing a cyclohexene addition polymer having a low proportion of a monomer with high productivity.

[0008]

In view of the above problems, the present inventors have earnestly studied about a method for producing a cyclohexene addition polymer, and as a result, by using a complex catalyst composed of specific components, The inventors have found what is achieved and have completed the present invention. That is, the present invention is
It is as follows. (1) a cyclohexene monomer, a transition metal compound represented by the formula (1), an alkylaluminoxane represented by the formula (2), and a boron compound represented by the formula (3) and / or the formula (4) A method for producing a cyclohexene addition polymer, which comprises polymerizing using a catalyst comprising

[0009]

[Chemical 6]

(In the formula, M is Ti, Zr or Hf, and v is 1
To an integer of 4, Z is a cross-linking structural unit that connects two indenyl skeletons, p is 1 or 2, m is an integer of 1 to 4, a plurality of groups R ¹ and R ² are the same or different. It may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, X ¹ and X ^2. May be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

[0011]

[Chemical 7]

(In the formula, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer)

[0013]

[Chemical 8]

(In the formula, B is a boron atom, s is an integer of 1 to 5, a plurality of groups R ⁴ may be the same or different from each other, a hydrogen atom, a halogen atom, and a carbon number of 1 to 20. A hydrocarbon group or a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms)

[0015]

[Chemical 9]

(Wherein A is a cation, B is a boron atom,
t is an integer of 1 to 5, plural groups R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or fluorine having 1 to 20 carbon atoms. Containing Hydrocarbon Group (2) In the formula (1), M is Zr or Hf, v is 1 or 2, and Z is a methylene group which may have a hydrocarbon group having 1 to 20 carbon atoms as a substituent, or Silylene group, p is 2,
R ¹ is H, The method for producing a cyclohexene addition polymer as described in (1) above. (3) The method for producing a cyclohexene addition polymer as described in (1), which comprises polymerizing under a pressure of 20,000 to 10,000,000 kPa. (4) The cyclohexene addition polymer is represented by the formula (5),
The weight average molecular weight thereof is 100 or more and 3000 or less, and the proportion of the dimer contained is 50% by mass or less, and the method for producing a cyclohexene addition polymer described in (1).

[0017]

[Chemical 10]

(Where u is a positive integer) The present invention will be described in detail below. In the present invention, the transition metal compound used as the catalyst component is represented by the formula (1).

[0019]

[Chemical 11]

In the formula (1), the central metal represented by M is V
It is Ti, Zr or Hf which is a transition metal of the group. v is 1
Is an integer from 4 to 4, Z represents a cross-linking structural unit that connects two indenyl skeletons. Preferably, v is 1 or 2, Z
Is a methylene group or a silylene group. The methylene group or silylene group may have a hydrocarbon group having 1 to 20 carbon atoms as a substituent. In this case, the substituents on the methylene group or silylene group may be the same or different. When v is 2 to 4, the substituents of each methylene group or silylene group may be the same or different. Specific examples of (Z) _v include alkylene groups such as methylene and 1,2-ethylene, arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene, methylsilylene,
Examples include alkylsilylene groups such as dimethylsilylene and diethylsilylene groups, (alkyl) (aryl) silylene groups such as methylphenylsilylene and methyltolylsilylene, arylsilylene groups such as diphenylsilylene, and oligosilylene groups such as tetramethyldisilene group. Can be mentioned.

In the formula (1), a plurality of groups R ¹ and R ² may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 1 carbon atom. 20
Is a hydrocarbon group containing silicon or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the halogen atom include:
Fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-
Examples thereof include alkyl groups such as propyl, n-butyl, i-butyl and t-butyl, alkenyl groups such as vinyl and propenyl, arylalkyl groups such as benzyl and phenylethyl, and alkyl groups such as phenyl, tolyl and 1-naphthyl. . Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trimethylsilyl, triethylsilyl, t
Examples thereof include trialkylsilyl groups such as butyldimethylsilyl, triarylsilyl groups such as triphenylsilyl, (alkyl) (aryl) silyl groups such as dimethylphenylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl.

In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogenated hydrocarbon group is a compound in which a halogen atom is substituted at any position of the above hydrocarbon group. Specific examples include a fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl group and the like.

In the formula (1), p is 1 or 2, m is an integer of 1 to 4, X ¹ and X ² may be the same or different from each other, and a hydrogen atom, a halogen atom or a carbon atom 1 ~ 20
Shows a hydrocarbon group of. Specific examples of the halogen atom include:
Examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl, alkenyl groups such as vinyl and propenyl. , Benzyl,
Examples thereof include an arylalkyl group such as phenylethyl, and an alkyl group such as phenyl, tolyl, and 1-naphthyl.

In the present invention, the aluminoxane represented by the formula (2) is used as a cocatalyst.

[0025]

[Chemical 12]

R ³ in the formula (2) is a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl. n is an integer, preferably an integer of 2-40. The terminal structure in formula (2) is not particularly limited. Specific examples thereof include linear aluminoxane represented by an alkylaluminum group having 1 to 20 carbon atoms, cyclic aluminoxane, or a mixture thereof.

The boron compound used in the present invention is a Lewis acid and / or ionic compound having a structure represented by the formula (3) and / or (4).

[0028]

[Chemical 13]

[0029]

[Chemical 14]

In the formulas (3) and (4), B represents a boron atom, and s and t are integers of 1-5. A plurality of groups R ⁴ and R ⁵ may be the same or different from each other,
It is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl, alkenyl groups such as vinyl and propenyl. , Benzyl,
Examples thereof include an arylalkyl group such as phenylethyl, and an alkyl group such as phenyl, tolyl, and 1-naphthyl. The fluorine-containing hydrocarbon group having 1 to 20 carbon atoms is a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group.
Examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl groups and the like.

A is a cation, which is a cation composed of a metal of Group I or II (for example, Li, Na, K, Be, Mg, Ca) or a cation composed of a hydrocarbon having 1 to 30 carbon atoms. , A cation composed of a hydrocarbon having 1 to 30 carbon atoms and a nitrogen atom. As the cation composed of a hydrocarbon having 1 to 30 carbon atoms, an alkylmethane cation,
Examples thereof include (alkyl) (aryl) methane cations and (aryl) methane cations, with triarylmethane cations being preferred. Examples of the cation composed of a hydrocarbon having 1 to 30 carbon atoms and a nitrogen atom include an alkylammonium cation, an alkylanilinium cation, and an arylanilinium cation. Specific examples of the boron compound include, for example, tris (perfluorophenyl) borane as a Lewis acid, and examples of the ionic compound include lithium (perfluorophenyl) borate, trityltetra (perfluorophenyl) borate, N. , N-dimethylanilinium tetra (perfluorophenyl) borate and the like.

The composition of the catalyst used in the present invention is such that the aluminum of the aluminoxane represented by the formula (2) and the boron compound represented by the formula (3) and / or (4) per 1 mol of the transition metal catalyst represented by the formula (1) are used. [Transition metal complex catalyst]: [aluminoxane]: [boron compound] is preferably [1]: [10 to 500 when expressed as a ratio of the number of moles.
0]: [0.5 to 20], and more preferably
[1]: [50-2000]: [1-10]. When the number of moles of the aluminoxane and / or the boron compound is lower than this range with respect to the transition metal catalyst, the polymerization activity tends to decrease. Further, when the number of moles of the aluminoxane and / or the boron compound is higher than this range, the reaction rate may be high, and it may be difficult to control the reaction.

The amount of the catalyst used in the present invention is usually preferably 0.0001 to 0.1, and more preferably a molar ratio of the transition metal catalyst to 1 mol of cyclohexene.
It is 0.0002 to 0.02. As the amount of catalyst decreases, the polymerization rate may easily decrease, while
As the amount increases, the productivity in the deashing process may decrease. The cyclohexene addition polymer produced by the method of the present invention has a structure represented by formula (5).

[0034]

[Chemical 15]

In the formula, u is an integer, and the terminal structure and the binding mode are arbitrary. The weight average molecular weight of the cyclohexane addition polymer is preferably 100 or more and 3000 or less, and the proportion of the dimer contained in the polymer is preferably 50% by mass or less. The olefin low polymer may be required to have fluidity when used as a lubricant or a plasticizer for polymer materials. Due to its structure, the alicyclic low polymer has a lower molecular mobility than that of the aliphatic low polymer, and therefore the fluidity thereof generally tends to deteriorate. The fluidity of the aliphatic low polymer can be controlled by the molecular weight. In the case of the cyclohexene addition polymer, the weight average molecular weight is preferably 100 or more and 3000 or less, and more preferably 1 in order to exhibit good fluidity.
30 or more and 2800 or less, most preferably 150 or more and 25
It is 00 or less. When a high molecular weight cyclohexene addition polymer having a weight average molecular weight of more than 3000 is used, the fluidity tends to deteriorate. When a cyclohexene addition polymer having a weight average molecular weight of less than 100 is used as a plasticizer for a polymeric material, it may partially volatilize during compounding with the polymeric material or during melt molding, causing problems such as mold deposits. Even when a cyclohexene addition polymer having a dimer content of more than 50% by mass is used as a plasticizer for a polymer material, it partially volatilizes during compounding with the polymer material or during melt molding, and mold deposit It may cause problems such as.

In the present invention, cyclohexene can be usually subjected to solution polymerization, suspension polymerization, and further gas phase polymerization depending on the polymerization temperature. The solvent used in solution polymerization and suspension polymerization is not particularly limited as long as it does not deactivate the catalyst or inhibits the polymerization reaction, for example,
Aliphatic hydrocarbon solvents such as pentane, n-hexane, heptane, cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, diethyl ether, diisopropyl ether, dibutyl ether,
Ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbon solvents such as dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, and mixed solvents thereof. Can be used. Of these, preferably used are aliphatic hydrocarbon solvents such as pentane, n-hexane, heptane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene.

The polymerization temperature in the present invention is usually from 0 ° C to
It is 150 ° C, preferably 20 ° C to 120 ° C. Outside this temperature range, the reaction rate of cyclohexene decreases. The concentration of cyclohexene used for the polymerization is not particularly limited, but a high concentration is preferable. In the present invention, when the polymerization reaction system is carried out at a high pressure, the pressure of the polymerization reaction system is usually 20,000 to 10,000,000 k.
Pa, preferably 35,000 to 7,000,000,
More preferably 50,000 to 5,000,000 k
Pa. When the cyclohexene addition polymer is produced under high pressure, the medium for pressurization deactivates the catalyst,
There is no particular limitation as long as it does not inhibit the polymerization reaction, and it may be any of gas, liquid, solid, and a mixture thereof.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. A. Compound (1) Cyclohexene Monomer Used in Examples: Cyclohexene monomer manufactured by Asahi Kasei Co., Ltd. was distilled once under CaH ₂ , degassed, and molecular sieves were put therein, and the mixture was sealed under dry nitrogen. . (2) Ethylbenzene: A special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was distilled under reduced pressure once under CaH ₂ , and after degassing, molecular sieves were put and sealed under dry nitrogen. (3) Toluene: An anhydrous toluene of 99.8% purity manufactured by Aldrich and sealed under dry nitrogen was put in a molecular sieve and sealed under dry nitrogen. (4) Methanol and 25% ammonium aqueous solution: Special grade reagents manufactured by Wako Pure Chemical Industries, Ltd., respectively.

(5) Polymerization terminator: A mixture of the methanol of (4) and a 25% aqueous ammonia solution at 20/80 (vol). (6) Racemic-ethylene bisindenyl zirconium dichloride [Et (Ind) ₂ ZrCl ₂ ], bis (cyclopentadienyl) zirconium dichloride [Cp ₂
ZrCl ₂ ], bis (pentamethylcyclopentadienyl) zirconium dichloride [Cp ^* ₂ ZrCl ₂ ],
Bis (indenyl) zirconium dichloride [(In
d) ₂ ZrCl ₂ ] (above, manufactured by Aldrich). (7) Racemic-dimethylsilylbis (indenyl) zirconium dichloride [Me ₂ Si (Ind) ₂ ZrCl
₂ ], [dimethylbis (cyclopentadienyl) silyl] zirconium dichloride [Me ₂ Si (Cp) ₂ Z
rCl _2] (Strem Chemical, manufactured by Inc Co., Ltd.). (8) Racemic-ethylenebis (indenyl) hafnium dichloride [Et (Ind) ₂ HfCl ₂ ]: J. A
m. Chem. Soc. , 190, 6544, (198
It was synthesized and purified with reference to the synthesis method quoted from 7). (9) Modified methylaluminoxane [MMAO
-3A]: Methylaluminoxane partially having an isobutyl group in the alkyl group manufactured by Tosoh Finechem. Toluene solution, molecular weight about 1000-2000. (10) Tris (perfluorophenyl) borane [FA
B] (manufactured by Aldrich). (11) Trityl tetra (perfluorophenyl) borate [TRI-FABA] (manufactured by Tosoh Finechem Co., Ltd.).

B. Measurement of number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) It was measured using gel permeation chromatography (GPC), and the cyclohexene conversion was determined by measuring the unreacted cyclohexene monomer. It is measured by gas chromatography (GC), and the polymerization rate (conversion rate) is calculated by the following formula. Conversion rate (%) = ([concentration of charged cyclohexene monomer])
-[Unreacted cyclohexene monomer concentration]) / (charged cyclohexene monomer concentration) x 100 The ratio of the dimer is calculated according to the following formula using the area area of the peak obtained from GPC. Ratio of dimer (% by mass) = (area of dimer area) /
(Sum of area areas of all peaks) × 100 These measuring instruments and measuring conditions are shown below. [GC conditions] Measuring instrument: Shimadzu gas chromatography:
GC14B type column: Shinwa Kako Co., Ltd. GC column: ULBON
HR-20M Detector: FID Carrier gas: Helium Column temperature: Hold at 40 ° C for 8 minutes, then 35 ° C /
Temperature rise to 220 ° C in min, injection and detector temperature: 230 ° C. Internal standard reagent: Ethylbenzene [GPC condition] Measuring instrument: Tosoh Corporation GPC: HLC-8220 Column: Tosoh Corporation column TSKgel-Su
2 pieces of per (registered trademark) H1000, TSKgel-
Two Super (registered trademark) H2000, TSKge
One l-Super (registered trademark) H3000 is used Column temperature: 40 ° C. Developing solvent: chloroform, flow rate 0.4 ml / min Sample concentration: 0.1 to 0.5 wt / v% Molecular weight calculation: standard polystyrene molecular weight and elution A calibration curve is created and calculated using the time relationship as a cubic regression curve.

C. Polymerization Method Unless otherwise specified in the description of the following examples and comparative examples, all polymerizations were carried out by the following procedures. [Polymerization method] A monomer, a reagent, a solvent, etc., a dry glass container heated to 120 ° C, and a syringe were put in a nitrogen glove. As the nitrogen glove, a nitrogen glove VDB-SA-Q type manufactured by Eikosho Co., Ltd. was used. The inside of the nitrogen glove was dehydrated and dried with molecular sieves, and was placed in an environment sufficiently replaced with nitrogen in which oxygen was sufficiently removed using GC-RX, a deoxidizing column manufactured by Nikka Seiko Co., Ltd. 30 ~
A catalyst, a monomer and a solvent were put in predetermined amounts in a 50 ml pressure resistant glass tube. At this time, a syringe was used as needed. When polymerization was performed using a pressure resistant glass tube, after the completion of charging,
The pressure-resistant glass tube was stoppered with nitrile rubber, then taken out from the nitrogen glove and capped with a metal crown.

The pressure-resistant glass tube was placed in an oil bath at a predetermined temperature, the time of insertion was set to 0 hours, and after the predetermined time had elapsed, the pressure-resistant glass tube was taken out of the oil bath and immediately cooled in an ice bath. After cooling, a terminating agent was added and stirred rapidly to uniformly disperse the terminating agent to terminate the polymerization reaction.
Then, the polymerization solution was diluted with toluene, GC measurement was performed, and the cyclohexene conversion rate was measured. The polymerization solution was diluted with chloroform and GPC measurement was performed to calculate the molecular weight of the product (cyclohexene addition polymer).

[High Pressure Polymerization Method] As a high pressure polymerization apparatus, an apparatus (M
acromolecules 2000, 33, 75
4) was used. This apparatus uses a Teflon (registered trademark) polymerization reaction tube as a polymerization reaction tube, and the reaction tube is submerged in a pressure vessel filled with a liquid pressure medium (castor oil),
It is a device that makes the pressure inside the reaction tube extremely high by applying pressure with a piston.

As the polymerization operation, the Schlenk technique was used. A 25 ml Teflon container was placed in a large Schlenk, and after evacuating, a nitrogen filling operation was performed three times or more to perform nitrogen substitution. The monomer, solvent and catalyst solution were prepared in advance with a nitrogen glove, and the solution was transferred to a Teflon container with a syringe. The Teflon container was tightly closed with a screw-type lid so as to prevent gas from entering and the polymerization solution from being deactivated. The Teflon container was immersed in the pressure medium in the high-pressure polymerization apparatus to raise the pressure and temperature. After the lapse of the predetermined time and the predetermined time of 0 hours, the pressure was returned to normal pressure and the polymerization reaction was stopped by adding a stopping agent. The analysis after the polymerization reaction was performed by the same operation as the experiment at normal pressure ([Polymerization operation method] described above).

[0045]

Example 1 A racemic-ethylene bis (indenyl) zirconium dichloride [Et (Ind) ₂ ZrCl ₂ ] was placed in a pressure-resistant glass reaction tube having an internal volume of 50 ml which had been sufficiently replaced with nitrogen.
(0.044g: 0.10mmol), and
Cyclohexene monomer / toluene solution (volume ratio 9/1,
11 ml as cyclohexene monomer: 0.10 mo
l) was added. Subsequently, an MMAO / toluene solution (aluminum / zirconium ratio of 100/1) was added, and tris (perfluorophenyl) borane [FAB] (0.267 g: 0.52 mmo) as a boron compound was further added.
l) was added and stirred. Then, the reaction was performed at 60 ° C. for 8 hours. Then, a polymerization terminator was added to terminate the polymerization reaction.

The conversion of cyclohexene in this polymerization reaction was 84%, the number average molecular weight of the obtained cyclohexene addition polymer was 185, and the weight average molecular weight was 210.
The molecular weight distribution was 1.14. The proportion of the produced dimer was 36% by mass. The above results are shown in Table 1.

[0047]

[Examples 2 and 3] In Example 2, racemic catalyst was used.
Dimethylsilylbis (indenyl) zirconium dichloride [Me ₂ Si (Ind) ₂ ZrCl ₂ ] was used, and in Example 3, racemic-ethylenebis (indenyl) hafnium dichloride [Et (Ind) ₂ Hf was used as the catalyst.
Cl ₂ ] was used for the polymerization. The experimental procedure and experimental conditions were the same as in Example 1.

Cyclohexene conversion rate 5 in Example 2
3%, the obtained cyclohexene addition polymer had a number average molecular weight of 166, a weight average molecular weight of 184, a molecular weight distribution of 1.10, and the proportion of the produced dimer was 45% by mass. The cyclohexene conversion rate in Example 3 was 15
%, The number average molecular weight of the obtained cyclohexene addition polymer was 271, the weight average molecular weight was 395, the molecular weight distribution was 1.46, and the ratio of the produced dimer was 11% by mass.
The above results are shown in Table 1.

[0049]

Example 4 Polymerization was carried out using trityl tetra (perfluorophenyl) borate [TRI-FABA] as a boron compound. The complex catalyst, the polymerization conditions and the polymerization operation were the same as in Example 1. As a result of the polymerization, the conversion of cyclohexene was 70%, and the obtained cyclohexene addition polymer had a number average molecular weight of 164 and a weight average molecular weight of 18.
1, the molecular weight distribution is 1.10, the ratio of the dimer produced is 4
It was 3% by mass. The above results are shown in Table 1.

[0050]

[Example 5] High-pressure polymerization method ([high-pressure polymerization method] described above)
Was used under the pressure of 506 and 500 kPa, and the same polymerization catalyst as in Example 1 was used to carry out a reaction at 60 ° C. for 2 hours. As a result of the polymerization, the conversion of cyclohexene was 96%, the number average molecular weight of the cyclohexane addition polymer was 237, the weight average molecular weight was 296, and the molecular weight distribution was 1.25.
The proportion of the produced dimer was 16% by mass. The above results are shown in Table 1.

[0051]

[Comparative Example 1] Et (Ind) ₂ ZrCl ₂ (0.027
1 g: 0.0648 mmol) and cyclohexene / toluene solution (volume ratio 9/1, cyclohexene (6.7 ml: 0.065 mol)). Subsequently, an alkylaluminoxane / toluene solution (aluminum / zirconium ratio of 1000/1) was added and stirred. Then, the reaction was performed at 60 ° C. for 8 hours. Then, an ammonia / methanol solution was added to stop the reaction.

The conversion rate of cyclohexene of the obtained reaction solution was measured by GC to be 41%, which was only about 1/2 of the conversion rate of Example 1. The number average molecule of the obtained cyclohexene addition polymer was 169, the weight average molecular weight was 188, and the molecular weight distribution was 1.10. The proportion of the produced dimer was 56% by mass. The above results are shown in Table 1.

[0053]

Comparative Examples 2 and 3 As Comparative Example 2, the catalyst was Me ₂ Si.
Polymerization was performed using (Ind) ₂ ZrCl ₂ and, as Comparative Example 3, using Et (Ind) ₂ HfCl ₂ as a catalyst. The experiment operation and the experiment conditions were the same as in Comparative Example 1. In Comparative Example 2, the conversion of cyclohexene was 37%,
The number average molecular weight of the obtained cyclohexene addition polymer was 1
62, weight average molecular weight 179, molecular weight distribution 1.09
Met. In Comparative Example 3, the conversion of cyclohexene was 6
%, And the obtained cyclohexene addition polymer had a number average molecular weight of 194, a weight average molecular weight of 229, and a molecular weight distribution of 1.18. Comparing the conversion rates of Comparative Examples 2 and 3 with those of Examples 2 and 3, both showed only about 1/2 conversion rate. The proportion of the produced dimer was 59% by mass in Comparative Example 2 and 34% by mass in Comparative Example 3, which were higher than those in Examples 2 and 3, respectively. The above results are shown in Table 1.

[0054]

[Comparative Examples 4 to 7] As a catalyst, in Comparative Example 4, bis (cyclopentadienyl) zirconium dichloride [Cp
₂ ZrCl ₂ ] was used for the polymerization. In Comparative Example 5, bis (pentamethylcyclopentadienyl) zirconium dichloride [Cp ^* ₂ ZrCl ₂ ], and in Comparative Example 6, bis (indenyl) zirconium dichloride [(Ind) ₂
ZrCl ₂ ], in Comparative Example 7, [dimethylbis (cyclopentadienyl) silyl] zirconium dichloride [M
Polymerization was carried out using e ₂ Si (Cp) ₂ ZrCl ₂ ]. However, the polymerization conditions and the polymerization operation were the same as in Example 1. As a result of the polymerization, in all the catalysts, the conversion of cyclohexene was 0 to 5%, and the polymerization activity was not shown. From GPC measurement, it was found that a cyclohexene addition polymer was not formed. The above results are shown in Table 1.

[0055]

[Table 1]

[0056]

By using the catalyst of the present invention, it is possible to produce a cyclohexene addition polymer containing a small amount of a dimer from a cyclohexane monomer with high productivity.

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Claims (4)

[Claims] 1. A cyclohexene monomer is represented by a transition metal compound represented by formula (1), an alkylaluminoxane represented by formula (2), and a formula (3) and / or formula (4). A method for producing a cyclohexene addition polymer, which comprises polymerizing using a catalyst composed of a boron compound. [Chemical 1] (In the formula, M is Ti, Zr or Hf, v is an integer of 1 to 4,
Z is a bridging structural unit that connects two indenyl skeletons, p
Is 1 or 2, m is an integer of 1 to 4, a plurality of groups R ¹ and R
² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 2 carbon atoms.
0 halogenated hydrocarbon group, X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (In the formula, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer.) (In the formula, B is a boron atom, s is an integer of 1 to 5, a plurality of groups R ⁴ may be the same or different, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms. Or a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms) (In the formula, A is a cation, B is a boron atom, t is an integer of 1 to 5, a plurality of groups R ⁵ may be the same or different from each other, and is a hydrogen atom, a halogen atom, or a carbon number of 1 to 1. 20 hydrocarbon groups, or fluorine-containing hydrocarbon groups having 1 to 20 carbon atoms) 2. In the formula (1), M is Zr or Hf,
v is 1 or 2, Z is a methylene group or silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms as a substituent, p
Is 2 and R ¹ is H, The method for producing a cyclohexene addition polymer according to claim 1, wherein 3. 20,000 to 10,000,000 k
The method for producing a cyclohexene addition polymer according to claim 1, wherein the polymerization is performed under a pressure of Pa. 4. The cyclohexene addition polymer is represented by the formula (5), its weight average molecular weight is 100 or more and 3000 or less, and the proportion of the dimer contained is 50% by mass or less. 1. The method for producing a cyclohexene addition polymer according to 1. [Chemical 5] (Where u is a positive integer)