JP2000063425A - PREPARATION OF HYDROGENATED alpha-OLEFIN-DICYCLOPENTADIENE COPOLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively remove tetrahydrodicyclopentadiene, by employing a high-boiling-point medium from the beginning of steps of addition-polymerizing an α-olefin and dicyclopentadiene in a medium, hydrogenating the copolymeric soln. thus formed, and then removing tetrahydrodicyclopentadiene formed through the hydrogenation, or by adding a high-boiling-point medium at the later stage. SOLUTION: The high-boiling-point medium for use at least contains a hydrocarbon medium having a b.p. of 195-300 deg.C at normal pressure and an ignition point of >=260 deg.C. A preferable α-olefin is ethylene or propylene, in view of the polymerization activities and mol.wts. of the polymers. Propylene is esp. preferable. As a cyclic olefin, dicyclopentadiene is employed. This way, it is possible to remove, effectively and safely, tetrahydrodicyclopentadiene having a low ignition temp., which is formed as a byproduct of the hydrogenation, or prevent its formation. This copolymer is suitable as a material for optical use since it is highly pure, substantially without tetrahydrodicyclopentadiene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improved method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer useful as an optical material. More specifically, the hydrogenated copolymer is subjected to addition copolymerization of α-olefin and dicyclopentadiene and then hydrogenated to produce a polymer which does not substantially contain tetrahydrodicyclopentadiene which is a by-product in the process of production. The present invention relates to a method for manufacturing a united body.

[0002]

2. Description of the Prior Art An α-olefin-cyclic olefin copolymer obtained by addition copolymerization of α-olefin and a cyclic olefin is transparent, heat resistant, weather resistant, chemical resistant, solvent resistant, dielectric property, and It is a synthetic resin excellent in various mechanical properties and is widely used in various fields.

These α-olefin-cyclic olefin copolymers are generally used in the presence of an addition polymerization catalyst in a hydrocarbon solvent such as toluene, cyclohexane or hexane to form α-olefins.
-It is produced by addition-copolymerizing an olefin and a cyclic olefin.

When a copolymer of α-olefin and a cyclic olefin containing two or more carbon-carbon double bonds, that is, a cyclic polyene, is used as a resin, in order to improve heat resistance, weather resistance and light resistance. The carbon-carbon double bond contained in the copolymer needs to be saturated by hydrogenation. Hydrogenation of the polymer is usually accomplished by reacting the copolymer with hydrogen in the presence of a heterogeneous or homogeneous hydrogenation catalyst.

Among the α-olefin-cyclic polyene copolymers, the present inventors have found that the α-olefin-dicyclopentadiene copolymer obtained by using dicyclopentadiene as the cyclic polyene is a dicyclopentadiene copolymer. Chemically high homogeneity without containing a chain, further hydrogenated α-olefin-dicyclopentadiene copolymer is particularly excellent in optical homogeneity, transparency,
The inventors have found that they are suitable for optical materials such as optical disk substrate materials, and have previously proposed (International Publication No. WO98 / 3).
No. 3830).

The hydrogenated α-olefin-dicyclopentadiene copolymer is generally obtained by a step of polymerizing α-olefin and dicyclopentadiene in a hydrocarbon solvent, and the obtained α-olefin-dicyclopentadiene copolymer. It is manufactured through a step of hydrogenating, a step of removing a catalyst, and a step of removing a volatile component. In the polymerization reaction step, in order to obtain a copolymer with high chemical homogeneity, α
-It is very important to keep the olefin and dicyclopentadiene above a certain ratio. As a result, unreacted dicyclopentadiene inevitably remains in the solution after polymerization. In the subsequent hydrogenation step, the residual dicyclopentadiene is hydrogenated together with the copolymer to form tetrahydrodicyclopentadiene, and finally separated from the hydrogenated copolymer together with the solvent in the volatile component removing step.

By the way, the ignition point of by-produced tetrahydrodicyclopentadiene is 235 ° C., which is extremely lower than the ignition points (toluene: 480 ° C., cyclohexane: 260 ° C.) of commonly used solvents. Therefore, from the viewpoint of danger prevention, it is not preferable to keep the polymer solution containing tetrahydrodicyclopentadiene at 235 ° C. or higher in ordinary equipment even in an inert atmosphere. This problem can be solved if equipment with perfect airtightness can be used, but it is extremely difficult in industrial implementation because the equipment is heavily burdened.

Now, in JP-A-64-54011, JP-A-5-17527, and JP-A-8-239415, a solvent in a copolymerization reaction of an α-olefin and dicyclopentadiene is disclosed. Sho 63-24310
No. 3 discloses a solvent for the hydrogenation reaction of an ethylene-dicyclopentadiene copolymer, but most of these are boiling points of tetrahydrodicyclopentadiene (760
It is a compound showing a boiling point lower than 194 ° C. in mmHg. When such a solvent having a low boiling point is used, the solvent is first distilled off in the volatile component removing step, and then tetrahydrodicyclopentadiene is distilled off. However, when the solvent is distilled off almost completely, the hydrogenated copolymer becomes a solid state at a temperature below the ignition point of tetrahydrodicyclopentadiene, and it is extremely difficult to distill off tetrahydrodicyclopentadiene completely. become. Further, some of the compounds having a boiling point higher than that of tetrahydrodicyclopentadiene are also exemplified, but all have a high melting point and are not suitable for a polymerization reaction, and have an ignition point of 250.
There were many problems such as a low temperature of around ℃ or low solubility of the polymer, and it could not be used for actual production.

As described above, it has been impossible to remove tetrahydrodicyclopentadiene from the copolymer solution safely and efficiently by the conventionally known method.

Further, when a hydrocarbon solvent such as toluene or cyclohexane which is usually used is used, there is another big problem in the volatile component removing step. The boiling point of these hydrocarbon solvents is 1 when compared to the melting temperature of the polymer.
Since the temperature is lower than 00 ° C., the polymer once becomes a solid state once the solvent is completely distilled off, and the stirring becomes extremely difficult. It is possible to make the polymer in a molten state without going through the solid state by performing the volatile component removal operation with a pressure system and increasing the boiling point of the solvent, but it is extremely difficult to control the reaction, and the equipment side It will be a heavy burden. As described above, there is no method for easily converting a polymer from a solution state to a molten state directly, and its development has been desired.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art as described above, and is capable of safely and efficiently removing tetrahydrodicyclopentadiene, or of tetrahydrodicyclopentadiene. It is an object of the present invention to provide a method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer which does not substantially contain tetrahydrodicyclopentadiene by preventing the generation thereof.

[0012]

Means for Solving the Problems The present inventors have conducted a polymerization process of α-olefin and dicyclopentadiene in the presence of a polymerization catalyst, and an α-olefin-in the presence of a hydrogenation catalyst.
Diligent research on a method for removing by-produced tetrahydrodicyclopentadiene from a hydrogenated α-olefin-dicyclopentadiene copolymer solution produced through continuous hydrogenation process of dicyclopentadiene copolymer As a result, when the copolymer solution contained a hydrocarbon solvent having a boiling point higher than that of tetrahydrodicyclopentadiene and a high ignition point, tetrahydrodiene was easily obtained in a state where the solution viscosity of the copolymer solution was low. It has been found that cyclopentadiene can be removed. Further, when a hydrocarbon solvent having a high boiling point and a high ignition point is contained in the solution in the previous step of the hydrogenation step, dicyclopentadiene which has not reacted in the polymerization step can be easily distilled off, and tetrahydrodiene The inventors have also found that it is possible to prevent the generation of cyclopentadiene, and have completed the present invention.

That is, according to the present invention, (1) an α-olefin having 2 or more carbon atoms and a dicyclopentadiene are subjected to addition polymerization in a hydrocarbon solvent in the presence of a polymerization catalyst, and then the polymerization catalyst is removed if necessary, and A step of producing an α-olefin-dicyclopentadiene copolymer solution containing dicyclopentadiene in the reaction, (2) adding a hydrogenation catalyst to the copolymer solution produced in step (1), and subjecting it to a hydrogenation reaction. And hydrogenating the unsaturated double bond of the α-olefin-dicyclopentadiene copolymer to produce a mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer, and (3) in the preceding step A step of distilling off the tetrahydrodicyclopentadiene produced by the hydrogenation reaction of step (2) from the mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer produced. And at the end of the above step (3), at least 10 parts by weight of the high boiling hydrocarbon solvent is present per 100 parts by weight of the hydrogenated α-olefin-dicyclopentadiene copolymer, so that the following (i), ( i
i), (iii); (i) using a high boiling hydrocarbon solvent as at least a part of the hydrocarbon solvent in step (1), (ii) adding a high boiling hydrocarbon solvent in step (2), and ( iii) at least one operation of adding a high boiling hydrocarbon solvent in step (3) is carried out, wherein the high boiling hydrocarbon solvent is a hydrocarbon having a normal pressure boiling point of 195 to 300 ° C. and an ignition point of 260 ° C. or higher. A method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer (hereinafter sometimes referred to as the first production method of the present invention), which comprises at least a solvent.

Further, in the present invention, (1 ′) α-olefin having 2 or more carbon atoms and dicyclopentadiene are subjected to addition polymerization in a hydrocarbon solvent in the presence of a polymerization catalyst, and then the polymerization catalyst is removed if necessary. (2 ′) for producing an α-olefin-dicyclopentadiene copolymer solution containing unreacted dicyclopentadiene, α-olefin-dicyclo containing unreacted dicyclopentadiene produced in step (1 ′) Dicyclopentadiene was distilled off from the pentadiene copolymer solution, and α was substantially free of dicyclopentadiene.
A step of producing an olefin-dicyclopentadiene copolymer solution, and (3 ′) a hydrogenation catalyst was added to the α-olefin-dicyclopentadiene copolymer solution produced in the previous step and subjected to a hydrogenation reaction. Hydrogenating the unsaturated double bonds of the α-olefin-dicyclopentadiene copolymer to produce a mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer, and the above step (2 ′). At the end of at least 1 per 100 parts by weight of α-olefin-dicyclopentadiene copolymer.
High boiling point hydrocarbon solvent as at least a part of the hydrocarbon solvent in the following (i ′), (ii ′), and (i ′) step (1 ′) so that 0 part by weight of the high boiling point hydrocarbon solvent is present. And (ii) adding the high boiling hydrocarbon solvent in step (2 ′), wherein the high boiling hydrocarbon solvent has a normal pressure boiling point of 195 to 300 ° C. and an ignition point. A method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer, which comprises at least a hydrocarbon solvent at 260 ° C. or higher (hereinafter may be referred to as the second production method of the present invention). Is.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The first manufacturing method of the present invention will be described in detail below.

(Step (1)) Step (1) in the present invention
Is an addition-copolymerization of an α-olefin having 2 or more carbon atoms and dicyclopentadiene in a hydrocarbon solvent in the presence of a polymerization catalyst, after which the polymerization catalyst is removed as necessary to obtain an unreacted diamine. This is a step of obtaining an α-olefin-dicyclopentadiene copolymer containing cyclopentadiene.

Specific examples of the α-olefin having 2 or more carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-. C2-C20 alpha-olefins, such as octene and 1-decene, can be mentioned. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable, from the viewpoint of polymerization activity and the molecular weight of the polymer. These may be used alone or in combination of two or more.

In the present invention, dicyclopentadiene is used as the cyclic olefin. In consideration of the physical properties of the polymer, if necessary, a cyclic olefin represented by the following general formula (I) and / or (II) is preferably 10 mol% or less, more preferably 5 mol%, based on dicyclopentadiene. You may add below.

[0019]

[Chemical 1]

[In the formula (I), n is 0 or 1, m is 0 or a positive integer, and 0 or 1 is preferable. p is 0 or 1. R ^{1 to} R ²⁰ are the same or different and are a hydrogen atom,
A halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁷ and R ¹⁸ , or R ¹⁹ and R ²⁰
And may form an alkylidene group, and R ¹⁷
Alternatively, R ¹⁸ and R ¹⁹ or R ²⁰ may form a ring, and the ring may have a double bond or an aromatic ring. ]

[0021]

[Chemical 2]

[In the formula (II), q is an integer of 2-8. ] The following compounds can be illustrated as a cyclic olefin represented by the said Formula (I).

Bicyclo [2.2.1] hept-2-ene (norbornene), 1-methylbicyclo [2.2.1] hept-2-
Ene, 6-methylbicyclo [2.2.1] hept-2-ene,
6-ethylbicyclo [2.2.1] hept-2-ene, 6-n
-Propylbicyclo [2.2.1] hept-2-ene, 6-isopropylbicyclo [2.2.1] hept-2-ene, 6-n
-Butylbicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 6-ethylidenebicyclo [2.2.1] hept-2-ene, 6-propylidenebicyclo [ 2.2.1] Hept-2-ene, 6-isopropylidenebicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene and other bicyclo [2.
2.1] Hept-2-ene derivative, tricyclo [4.3.0.1 ^2.5 ]
-3-decene, 2-methyltricyclo [4.3.0.1 ^2.5 ] -3
- decene, 5-methyl-tricyclo [4.3.0.1 ^2.5] -3- decene, 10-methyl tricyclo [4.3.0.1 ^2.5] -3- tricyclo such decene [4.3.0.1 ^2.5] -3- decene derivatives,
Tricyclo [4.4.0.1 ^{2.5]-3-undecene,} 2-methyltricyclo [4.4.0.1 ^{2.5]-3-undecene,} 5-methyl-tricyclo [4.4.0.1 ^{2.5]-3-undecene,} 11-methyltricyclo [ 4.4.0.1 ^2.5 ] -3-undecene, tricyclo [4.4.0.1 ^2.5 ] -3-undecene derivative, tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-
Ethyl tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-n-propyl tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ]
-3-Dodecene, 8-isopropyltetracyclo [4.4.
0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-n-butyltetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene ,
8-Ethylidene tetracyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-
Dodecene, 8-n-propylidene tetracyclo [4.4.0.1
^2.5 .1 ^7.10] -3-dodecene, 8-isopropylidene-tetracyclo [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene tetracyclo such [4.4.0.1 ^2.5 .1 ^7.10] -3-dodecene derivatives, pentacyclo [6.5 .1.1 ^3.6 .0 ^2.7 .0 ^9.13] -4-pentadecene, pentacyclo ^{[6.5.1.1 3.6 .0 2.7 .0 9.13]} -4,10-
Pentadecadiene.

Further, examples of the compound represented by the formula (II) include the following. Cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene.

The hydrocarbon solvent used in the present invention is not particularly limited as long as it is a hydrocarbon in which the polymerization catalyst, the homogeneous hydrogenation catalyst and the copolymer produced can be dissolved. it can. Butane, isobutane, pentane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, isooctane, 2,2,3-trimethylpentane,
Nonane, 2,2,5-trimethylhexane, aliphatic hydrocarbons such as decane, cyclopentane, methylcyclopentane, ethylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, butylcyclohexane, pentylcyclohexane, hexylcyclohexane, Dicyclohexyl, heptylcyclohexane, octylcyclohexane, methylisopropylcyclohexane, dimethylcyclohexane, diethylcyclohexane, dipropylcyclohexane, dibutylcyclohexane, dipentylcyclohexane, trimethylcyclohexane, triethylcyclohexane, tetramethylcyclohexane, cyclooctane,
Alicyclic hydrocarbons such as decahydronaphthalene, benzene,
Toluene, ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, biphenyl, cyclohexylbenzene, cumene, xylene, diethylbenzene, dipropylbenzene, dibutylbenzene, dipentylbenzene, mesitylene, triethylbenzene, tetramethyl Aromatic hydrocarbons such as benzene, naphthalene, methylnaphthalene, ethylnaphthalene, dimethylnaphthalene, and tetrahydronaphthalene. These may be used alone or in combination of two or more. Among these, aromatic hydrocarbons and alicyclic hydrocarbons are preferable because of high solubility of the catalyst and the copolymer. Further, in the next step (2), when the hydrocarbon solvent is subjected to hydrogenation together with the polymer, alicyclic hydrocarbon is preferable.

The polymerization catalyst used in the present invention is α-
The catalyst is not particularly limited as long as it is a catalyst capable of copolymerizing an olefin and dicyclopentadiene, but a metallocene catalyst or a Ziegler catalyst can be preferably exemplified.

The metallocene catalyst is composed of metallocene and a cocatalyst. As the metallocene, those represented by the following general formula (III) are preferably used.

[0028]

[Chemical 3]

[In the formula (III), M is a metal selected from Group IV, R ²⁴ and R ²⁵ are the same or different, and are a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms. , An alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, R ²² and R ²³
Are the same or different and are monocyclic or polycyclic hydrocarbon groups capable of forming a sandwich structure with the central metal M, and R ²¹ is a bridge connecting the R ²² group and the R ²³ group,

[0030]

[Chemical 4]

Wherein R ^{26 to} R ²⁹ are the same or different and each is a hydrogen atom, a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carbon number. It may be a 6-12 aryloxy group, or R ²⁶ and R ²⁷ or R ²⁸ and R ²⁹ may form a ring. ]

In the metallocene represented by the above formula (III), the central metal M is most preferably zirconium from the viewpoint of catalytic activity. R ²⁴ and R ²⁵ may be the same or different, but are preferably an alkyl group having 1 to 6 carbon atoms or a halogen atom (especially chlorine atom). R ²² and R
Examples of the desirable cyclic hydrocarbon group for ²³ include a cyclopentadienyl group, an indenyl group, and a fluorenyl group. These may be substituted with a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, an isopropyl group or a tert-butyl group, or a phenyl group or a benzyl group. R ^{26 to} R ²⁹ are hydrogen atoms and have 1 carbon atom
Alkyl groups or phenyl groups of 6 to 6 are preferred, and R ²¹ is a lower alkylene group such as methylene group, ethylene group, propylene group, alkylidene group such as isopropylidene, substituted alkylene group such as diphenylmethylene, silylene group or dimethylsilylene. And substituted silylene groups such as diphenylsilylene can be preferably exemplified.

As the metallocene in which the central metal M is zirconium, the following compounds can be exemplified. Dimethylsilylene-bis (1-indenyl) zirconium dichloride, diphenylsilylene-bis (1-indenyl) zirconium dichloride, dibenzylsilylene-bis (1-indenyl) zirconium dichloride, methylene-bis (1-indenyl) zirconium dichloride,
Ethylene-bis (1-indenyl) zirconium dichloride, diphenylmethylene-bis (1-indenyl) zirconium dichloride, isopropylidene-bis (1-
Indenyl) zirconium dichloride, phenylmethylsilylene-bis (1-indenyl) zirconium dichloride, dimethylsilylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, diphenylsilylene-bis [1- (2,4) , 7-Trimethyl) indenyl] zirconium dichloride, dibenzylsilylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, methylene-bis [1.
-(2,4,7-trimethyl) indenyl] zirconium dichloride,

Ethylene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, diphenylmethylene-bis [1- (2,4,7-trimethyl)
Indenyl] zirconium dichloride, isopropylidene-bis [1- (2,4,7-trimethyl) indenyl] zirconium dichloride, phenylmethylsilylene-bis [1- (2,4,7-trimethyl) indenyl]
Zirconium dichloride, dimethylsilylene-bis [1
-(2,4-Dimethyl) indenyl] zirconium dichloride, diphenylsilylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, dibenzylsilylene-bis [1- (2,4-dimethyl) indenyl] zirconium Dichloride, methylene-bis [1-
(2,4-Dimethyl) indenyl] zirconium dichloride, ethylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, diphenylmethylene-bis [1- (2,4-dimethyl) indenyl] zirconium dichloride, isopropyl Reden-bis [1-
(2,4-Dimethyl) indenyl] zirconium dichloride, phenylmethylsilylene-bis [1- (2,4-
Dimethyl) indenyl] zirconium dichloride, dimethylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, diphenylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] Zirconium dichloride, dibenzylsilylene-bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, methylene-
Bis [1- (4,5,6,7-tetrahydro) indenyl] zirconium dichloride, ethylene-bis [1-
(4,5,6,7-Tetrahydro) indenyl] zirconium dichloride, diphenylmethylene-bis [1-
(4,5,6,7-Tetrahydro) indenyl] zirconium dichloride,

Isopropylidene-bis [1- (4,5,
6,7-Tetrahydro) indenyl] zirconium dichloride, phenylmethylsilylene-bis [1- (4,
5,6,7-Tetrahydro) indenyl] zirconium dichloride, dimethylsilylene- (9-fluorenyl)
(Cyclopentadienyl) zirconium dichloride, diphenylsilylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, dibenzylsilylene- (9-fluorenyl) (cyclopentadienyl)
Zirconium dichloride, methylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, ethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium Dichloride, isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- (9-fluorenyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene- (9-fluorenyl) [1- (3-t
ertbutyl) cyclopentadienyl] zirconium dichloride, diphenylsilylene- (9-fluorenyl)
[1- (3-tert-butyl) cyclopentadienyl]
Zirconium dichloride, dibenzyl silylene- (9-
Fluorenyl) [1- (3-tert-butyl) cyclopentadienyl] zirconium dichloride, methylene-
(9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, ethylene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,
Diphenylmethylene- (9-fluorenyl) [1- (3
-Tertbutyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,

Phenylmethylsilylene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride, dimethylsilylene-
(9-Fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, diphenylsilylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, dibenzylsilylene- ( 9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride,
Methylene- (9-fluorenyl) [1- (3-methyl)
Cyclopentadienyl] zirconium dichloride, ethylene- (9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, diphenylmethylene- (9-fluorenyl) [1- (3-methyl) cyclopentadiene [Enyl] zirconium dichloride,
Isopropylidene- (9-fluorenyl) [1- (3-
Methyl) cyclopentadienyl] zirconium dichloride, phenylmethylsilylene- (9-fluorenyl)
[1- (3-Methyl) cyclopentadienyl] zirconium dichloride, dimethylsilylene- [9- (2,7-
Di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, diphenylsilylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, dibenzylsilylene- [9- (2,7-di-ter
t-butyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, methylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, ethylene- [9-
(2,7-Di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, diphenylmethylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, isopropylidene -[9- (2,7-di-t
ertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- [9- (2,7-di-tertbutyl) fluorenyl] (cyclopentadienyl) zirconium dichloride, dimethylsilylene- (1-indenyl) (Cyclopentadienyl) zirconium dichloride,

Diphenylsilylene- (1-indenyl)
(Cyclopentadienyl) zirconium dichloride, dibenzylsilylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, methylene- (1-
Indenyl) (cyclopentadienyl) zirconium dichloride, ethylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene- (1- Indenyl) (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene- (1-indenyl)
(Cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, diphenylsilylene-bis (cyclopentadienyl) zirconium dichloride, dibenzylsilylene-bis (cyclopentadienyl) zirconium dichloride, methylene -Bis (cyclopentadienyl)
Zirconium dichloride, ethylene-bis (cyclopentadienyl) zirconium dichloride, diphenylmethylene-bis (cyclopentadienyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) zirconium dichloride, phenylmethylsilylene-bis (cyclopentadiene) (Enyl) zirconium dichloride, isopropylidene- (1-indenyl) [1- (3
-Tertbutyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-isopropyl) cyclopentadienyl] zirconium dichloride, isopropylidene- [1
-(2,4,7-Trimethyl) indenyl] (cyclopentadienyl) zirconium dichloride, ethylene-
(Cyclopentadienyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,
Ethylene- (cyclopentadienyl) [1- (3-phenyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dibromide, dimethylsilylene-bis (1-indenyl) ) Zirconium dibromide, ethylene-bis (1-indenyl) methyl zirconium monochloride.

In the present invention, particularly preferred metallocenes are isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethylene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride and isopropylidene-
(9-fluorenyl) [1- (3-methyl) cyclopentadienyl] zirconium dichloride, isopropylidene- (9-fluorenyl) [1- (3-tertbutyl) cyclopentadienyl] zirconium dichloride,
Isopropylidene- (1-indenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (1-indenyl) zirconium dichloride, ethylene-bis (1-indenyl) zirconium dichloride, isopropylidene-bis (1-indenyl) zirconium An example is dichloride.

The concentration of such a metallocene may be determined according to its polymerization activity, but based on the dicyclopentadiene added to the polymerization reaction system, dicyclopentadiene 1
10 ^-6 to 10 ^-2 mol, preferably 10
Used at a concentration of ^-5 to 10 ^-3 mol.

As the cocatalyst, aluminoxane which is an organic aluminum oxy compound is preferably used. The aluminoxane can be exemplified by the following general formula (IV) for the linear structure and the following general formula (V) for the cyclic structure.

[0041]

[Chemical 5]

[In the formulas (IV) and (V), R ³⁰
R ^{35 s} are the same or different, and are an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group;
Phenyl group or benzyl group, preferably methyl group, ethyl group, particularly preferably methyl group. m is 2
It is an integer of the above or more, preferably an integer of 5 to 100. ]

However, the exact structure of aluminoxane is unknown. Aluminoxanes are compounds containing adsorbed water or salts containing water of crystallization (eg copper sulfate hydrate).
And an organoaluminum compound such as trialkylaluminum in an inert solvent (for example, toluene). The aluminoxane may contain a small amount of organoaluminum compound derived from the production method.

The aluminoxane has a function of alkylating metallocene and further converting the metallocene into a cation, whereby polymerization activity is obtained. The metallocene is activated in a solution, but it is preferable to dissolve the metallocene in a solution of aluminoxane. As the solvent used in such activation, an aliphatic hydrocarbon,
Alicyclic hydrocarbons or aromatic hydrocarbons are preferable, and among them, the same solvent as that used for the polymerization reaction is most preferable. Activation of metallocenes by aluminoxanes is usually
It is carried out before use in the polymerization reaction, and the time spent for activation is 1 minute to 10 hours, preferably 3 minutes to 1 hour. The activation is performed in the temperature range of -40 to 110 ° C, preferably 0 to 80 ° C.

The concentration of the aluminoxane solution is not particularly limited from 1% by weight to the concentration limit, but 5 to 30% by weight is preferably used. The ratio of aluminoxane to metallocene is 3 mol of aluminoxane to 1 mol of metallocene.
0-20,000 mol, preferably 100-5,000
0 mol is used. If the amount of aluminoxane to the metallocene is too small, sufficient polymerization activity cannot be obtained, which is not preferable. Conversely, if the amount of aluminoxane is too large,
Although it has a high polymerization activity, it is not preferable because it uses a large amount of expensive aluminoxane, which is not economical and further makes purification after polymerization difficult.

Ion boron compounds and alkylating agents can be cited as cocatalysts which are preferably used in addition to aluminoxane.

The ionic boron compound is specifically a compound represented by the following general formulas (VI) to (IX).

[0048]

[Number 1] _{^{[R 36 3 C] + [}} BR 37 4] - ··· (VI) [R 36 x NH 4-x] + [BR 37 4] - ··· (VII) [R 36 x PH _{^{4-x] + [BR 37}} 4] - ··· (IIX) Li + [BR 37 4] - in ··· (IX) [wherein (VI) ~ (IX), R 36 are identical or different, carbon Aliphatic hydrocarbon group having 1 to 8 or 6 to 1 carbon atoms
8 is an aromatic hydrocarbon group. R ³⁷ is the same or different and is an aromatic hydrocarbon group having 6 to 18 carbon atoms. x is 1, 2,
3 or 4. ]

In the ionic boron compounds represented by the above formulas (VI) to (IX), R ³⁶ is an alkyl group such as methyl group, ethyl group, propyl group or butyl group or aryl group such as phenyl group. It can be preferably exemplified. R
It is preferable that ³⁷ are the same, a fluorinated or partially fluorinated aromatic hydrocarbon group is preferable, and a pentafluorophenyl group is particularly preferable. x is preferably 3. As specific compounds, N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, trityl-tetrakis (pentafluorophenyl) borate, and lithium-tetrakis (pentafluorophenyl) borate are illustrated. You can

The alkylating agent is preferably an alkyllithium compound or an alkylaluminum compound, and specific examples thereof include methyllithium, butyllithium, trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-butylaluminum. Can be done.

The ionic boron compound has a function of converting metallocene to a cation, and the alkylating agent has a function of alkylating metallocene. By combining both of them, polymerization activity can be obtained.

The ratio of the ionic boron compound to the metallocene is 0.5 to 10 mol, preferably 0.8 to 3 m, of the ionic boron compound to 1 mol of the metallocene.
ol, more preferably 0.9 to 1.5 mol is used. Alkylating agent is 2-5 for 1 mol of metallocene
00 mol is used. Compared with the case of using aluminoxane as a cocatalyst, the amount of the ionic boron compound required for the metallocene is significantly smaller, and the catalytic activity tends to be higher. Therefore, the amounts of the metallocene and the cocatalyst can be reduced, and there are great advantages economically and in terms of purification after polymerization.

These cocatalysts are usually used as they are, or they are handled as a solution of a hydrocarbon solvent as described above, but they can be supported on a carrier and used. Suitable carriers are inorganic compounds such as silica gel and alumina, or finely divided polyolefin powder such as polyethylene and polypropylene.

Another suitable polymerization catalyst used in the present invention is a Ziegler-based catalyst. The Ziegler-based catalyst in the present invention is a catalyst composed of a vanadium compound and an organic aluminum compound. As a vanadium compound,
Specifically, vanadium compounds represented by the following general formulas (X) to (XI), or electron donor adducts thereof are used.

[0055]

## EQU2 ## VO (OR ³⁸ ) _a R ³⁹ _b ... (X) V (OR ³⁸ ) _c R ³⁹ _d ... (XI) [In the formulas (X) to (XI), R ³⁸ is the same or different. Differently, an aliphatic hydrocarbon group having 1 to 8 carbon atoms or 6 to 1 carbon atoms
8 is an aromatic hydrocarbon group. R ³⁹ is a halogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. a, b, c and d are 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
It satisfies ≦ 4 and 3 ≦ c + d ≦ 4. ]

More specifically, vanadium (oxy) trichloride, vanadium (oxy) (ethoxy) dichloride, vanadium (oxy) (propoxy) dichloride,
Vanadium (oxy) (propoxy) dichloride, vanadium (oxy) (isopropoxy) dichloride, vanadium (oxy) (butoxy) dichloride, vanadium (oxy) (isobutoxy) dichloride, vanadium (oxy) (diethoxy) chloride, vanadium (oxy) (Diisopropoxy) chloride, vanadium (oxy) (dibutoxy) chloride, vanadium (oxy)
(Diisobutoxy) chloride, vanadium (oxy) triethoxide, vanadium (oxy) tripropoxide, vanadium (oxy) triisopropoxide, vanadium (oxy) tributoxide, vanadium (oxy) triisobutoxide, vanadium trichloride, vanadium tribromide , Vanadium tetrachloride can be exemplified. Further, as the electron donor used when adjusting the electron donor adduct of the vanadium compound, alcohols, phenols, ketones, aldehydes,
Carboxylic acids, acid esters, acid amides, acid anhydrides, ethers, oxygen-containing electron donors such as alkoxysilanes, amines,
Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

The concentration of the vanadium compound or its electron-donor adduct may be determined according to its polymerization activity. When the dicyclopentadiene added to the polymerization reaction system is used as a reference, it is based on 1 mol of dicyclopentadiene. 10 ^-6
It is used at a concentration of -10 ^-2 mol, preferably 10 ^-5 -10 ^-3 mol.

The organoaluminum compound used in the Ziegler type catalyst is a compound having at least one aluminum-carbon bond in the molecule. Specifically, triethylaluminum, trialkylaluminum compounds such as triisobutylaluminum, diethylaluminum ethoxide, diisobutylaluminum butoxide, organic aluminum alkoxide compounds such as ethylaluminum sesquiethoxide, methylaluminoxane, organoaluminum oxy compounds such as ethylaluminoxane, Organic aluminum halide compounds such as diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like can be exemplified, and organic aluminum halide compounds are particularly preferable.

The organoaluminum compound has a function of alkylating a vanadium compound or an electron donor adduct thereof, whereby a polymerization activity is obtained. As the solvent used for such activation, an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon is preferable, and among them, the same solvent as the solvent used for the polymerization reaction is most preferable.

The ratio of the organoaluminum compound to the vanadium compound or its electron donor adduct is 2 to 500 mol, preferably 2 to 50 mol, more preferably 1 to 50 mol of the vanadium compound or its electron donor adduct. 3 to 30 mol is used. If the amount of the organoaluminum compound is too small, high activity cannot be obtained, and if it is too large, the polymer may gel, which is not preferable.

The non-additive copolymerization is -20 ° C or higher and 150 ° C or lower,
The temperature is preferably -10 ° C or higher and 120 ° C or lower, and more preferably 0 ° C or higher and 100 ° C or lower. If the polymerization temperature is too low, the polymerization reaction is difficult to proceed, and if it is too high, the catalyst is deactivated, which is not preferable. Further, the polymerization temperature is preferably as constant as possible in order to obtain a homogeneous polymer.

Further, in order to obtain a copolymer having high chemical homogeneity, it is preferable to keep the ratio of α-olefin and dicyclopentadiene at a certain level or more. As a result, the copolymer solution after the step (1) inevitably contains unreacted dicyclopentadiene. It is preferable to control the reaction conditions so that the residual amount of unreacted dicyclopentadiene is 50% or less, preferably 30% or less, more preferably 20% or less with respect to the total amount of added dicyclopentadiene.

The copolymer solution produced by the polymerization reaction is subsequently subjected to a hydrogenation reaction in the presence of a hydrogenation reaction catalyst, and the polymerization catalyst contained in the copolymer solution is May inhibit activity. In such a case, the polymerization catalyst may be optionally removed from the copolymer solution before the hydrogenation reaction.

The method of removing the polymerization catalyst is not particularly limited, but a method of adding an active hydrogen-containing compound to the copolymerization solution to precipitate the catalyst component and removing it by filtration is preferable.
A method in which the copolymer solution is washed with water and the catalyst component is extracted into an aqueous phase can be mentioned. Examples of the active hydrogen-containing compound include alcohols such as water, methanol, ethanol and 1-butanol, phenols such as phenol, cresol, xylenol and catechol. Rus, formic acid, acetic acid,
Carboxylic acids such as lactic acid, ammonia, ethylamine, n
Examples thereof include amines such as propylamine, ethylenediamine, and monoethanolamine.

The solution after catalyst removal may be further purified by contacting it with an adsorbent. As the adsorbent, activated clay, silica gel, alumina, silica alumina, and zeolite are preferable.

(Step (2)) The α-olefin-dicyclopentadiene copolymer solution produced in step (1) is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst in step (2), The unsaturated double bond contained in the copolymer is hydrogenated to produce a hydrogenated α-olefin-dicyclopentadiene copolymer.

The hydrogenation catalyst used in the present invention is not particularly limited as long as it is a catalyst generally used in the hydrogenation reaction of an olefin compound, but a preferable one is a combination of a transition metal compound and an alkylating agent. Examples of such catalysts include homogeneous noble metal catalysts and heterogeneous catalysts.

The transition metal compound in the catalyst comprising a combination of a transition metal compound and an alkylating agent is, for example, a halide of a transition metal such as titanium, vanadium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel or palladium. , Acetylacetonate complex, carboxylate complex, naphthate complex, trifluoroacetate complex, stearate complex and the like,
Specifically, bis (cyclopentadienyl) titanium dichloride, triethylvanadate, tris (acetylacetonate) chromium, tris (acetylacetonate) manganese, cobalt acetate, tris (acetylacetonate). )
Examples thereof include cobalt, cobalt octenoate, and bis (acetylacetonato) nickel. Examples of the alkylating agent include lithium, magnesium, aluminum, and zinc compounds, and specific examples include butyllithium, dimethylmagnesium, triethylaluminum, triisobutylaluminum, methylaluminoxane, diethylzinc, and the like. Among these, from the viewpoint of catalytic activity, a combination of a titanium compound, a cobalt compound, a nickel compound and an alkylaluminum compound or an alkyllithium compound is preferable, and bis (cyclopentadienyl) titanium dichloride and butyllithium, tris (acetylacetonate). A combination of cobalt or bis (acetylacetonate) nickel and an alkylaluminum compound such as triethylaluminum, triisobutylaluminum or methylaluminoxane is particularly preferable.

Regarding the quantitative relationship between the transition metal compound and the alkylating agent, the metal component of the alkyl metal compound is 1 mol or more to 50 mol per 1 mol of the metal of the transition metal compound.
1 or less, preferably 10 mol or less.

The transition metal compound is converted into an alkylated transition metal compound by an alkylating agent and has a hydrogenation catalytic ability.

The homogeneous noble metal catalyst is a catalyst that does not necessarily require an alkylating agent, and specifically, carbonyl (chloro) (hydride) tris (triphenylphosphine) ruthenium, di (hydrido) (carbonyl) tris (tri). Phenylphosphine) ruthenium, di (hydrido) tetrakis (triphenylphosphine) ruthenium, tetra (hydrido) tris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, hydrido (carboni) tris (triphenylphosphine) rhodium, etc. It can be illustrated.

The heterogeneous catalyst is a solvent-insoluble solid catalyst in which a metal is supported on a carrier. Specifically, as metals, iron, ruthenium, cobalt, rhodium, iridium,
Examples of the carrier include nickel, palladium, platinum, and the like, and examples of the carrier include carbon, silica, alumina, silica-alumina, diatomaceous earth, and the like.

The concentration of the transition metal compound of these hydrogenation catalysts may be determined according to the polymerization activity thereof.
On the other hand, it is usually 10 ^-6 to 10 ^-1 mol, preferably 10 ^-5.
Used at a concentration of -10 ^-1 molar.

The temperature, hydrogen pressure and reaction time of the hydrogenation reaction of the copolymer may be determined according to the type of monomer used for the addition copolymerization and the type of hydrogenation catalyst. Usually, the temperature is 0 ° C or higher and 200 ° C or lower, preferably 20 ° C or higher and 1
80 ° C or less, hydrogen pressure is 0.1 kgf / cm ² or more, 2
00kgf / cm ² or less, preferably 1 kgf / cm ² or more, 150 kgf / cm ² or less, the reaction time is 0.1 hours or more and 20 hours or less. Under low temperature and low hydrogen pressure, the hydrogenation reaction hardly proceeds, which is not preferable, and under high temperature and high hydrogen pressure, the catalyst becomes inactive and a large facility burden is imposed, which is not preferable.

The hydrogenation rate (hydrogenation rate of carbon-carbon double bonds) of such a copolymer is preferably 99% or more, more preferably 99.5% or more, and further preferably 99.9% or more. . If the hydrogenation rate is lower than 99%, the thermal stability is insufficient, and coloring or the like is likely to occur during melt molding, which is not preferable. In the case of a ring-opening polymer having a carbon-carbon double bond in the main chain, its glass transition temperature is significantly lowered by hydrogenation, but in the case of the copolymer of the present invention, the carbon-carbon double bond is Is located in the side chain, the glass transition temperature hardly changes before and after hydrogenation, which is preferable.

The unreacted dicyclopentadiene monomer contained in the α-olefin-dicyclopentadiene copolymer solution produced in the step (1) is obtained in the step (2).
Is hydrogenated by a hydrogenation catalyst and converted into tetrahydrodicyclopentadiene. Generally, monomers are more easily hydrogenated than polymers, so that the hydrogenation rate of the copolymer is 99%.
When it is at least%, the dicyclopentadiene monomer is completely hydrogenated. Therefore, tetrahydrocyclopentadiene is contained in the solution mixture containing the hydrogenated copolymer.

After carrying out the step (2) or (3) described later, the polymerization catalyst and / or the hydrogenation catalyst can be removed from the solution mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer. . This makes it possible to produce a mixture containing a hydrogenated α-olefin-dicyclopentadiene copolymer substantially free of a metal derived from a polymerization catalyst and a metal derived from a hydrogenation catalyst.

When the hydrogenation catalyst is a homogeneous catalyst, the method of removing the catalyst can be the same as the method of removing the polymerization catalyst in step (1). When the hydrogenated catalyst is a heterogeneous catalyst, the heterogeneous catalyst can be separated from the hydrogenated copolymer solution by filtration. When the hydrogenated copolymer from which the heterogeneous catalyst has been removed contains a polymerization catalyst, the polymerization catalyst can be removed by the same method as the method for removing the polymerization catalyst in step (1).

(Step (3)) In step (3), tetrahydrodicyclopentadiene is distilled off from the solution mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer.

In the present invention, at the end of the step (3), at least 10 parts by weight of the high boiling hydrocarbon solvent is present per 100 parts by weight of the hydrogenated α-olefin-dicyclopentadiene copolymer, so that the following ( i), (i
It is necessary to perform at least one operation of i) and (iii). (I) A high boiling hydrocarbon solvent is used as at least a part of the hydrocarbon solvent in step (1). (Ii) A high boiling hydrocarbon solvent is added in step (2).
And (iii) the high boiling hydrocarbon solvent is added in step (3).

Here, the high boiling hydrocarbon solvent has a boiling point of 1 at atmospheric pressure.
It is a hydrocarbon having a temperature of 95 to 300 ° C and an ignition point of 260 ° C or higher. When the boiling point is lower than 195 ° C., tetrahydrodicyclopentadiene cannot be efficiently removed, which is not preferable, and when it is higher than 300 ° C., energy cost for removal is too high, which is not preferable. Also, the ignition point is 260 ° C.
If it is lower than this, the hydrogenated copolymer cannot be heated until it is in a molten state, which is not preferable. The high boiling hydrocarbon solvent preferably has a melting point of 50 ° C. or lower because it facilitates the polymerization reaction to be carried out in a solution state.

Specific examples of the high boiling hydrocarbon solvent include pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, cyclohexylbenzene, dibutylbenzene, dipentylbenzene, 1,3,5-triethylbenzene, 1,2,3. Alkylbenzene compounds such as 1,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1,2-dimethylnaphthalene, Examples thereof include alkylnaphthalene compounds such as 1,4-dimethylnaphthalene and 1,6-dimethylnaphthalene, and tetrahydronaphthalene. Of these, 1-methylnaphthalene, 2-methylnaphthalene, and tetrahydronaphthalene are particularly preferable from the viewpoint of industrial ease of use. You may use these individually or in combination of 2 or more types.

The high boiling hydrocarbon solvent is preferably contained at the stage of the copolymer solution in the step (1) by carrying out the above operation (i) from the viewpoint of avoiding complicated steps in industrial implementation. It is also preferable that the hydrocarbon solvent consists only of the high boiling point hydrocarbon solvent. The high-boiling hydrocarbon solvent has no significant influence on the copolymerization reaction of α-olefin with dicyclopentadiene and the hydrogenation reaction of α-olefin-dicyclopentadiene copolymer. However, in the hydrogenation reaction step (2), when the high boiling hydrocarbon itself is hydrogenated, the high boiling point hydrocarbon is added to the solution after the hydrogenation reaction step (2) and before the tetrahydrodicyclopentadiene removal step (3). It is preferred to add a high boiling hydrocarbon solvent.

The high boiling hydrocarbon solvent is present in the above (i), (so that it is present in an amount of at least 10 parts by weight per 100 parts by weight of the hydrogenated α-olefin-dicyclopentadiene copolymer at the end of the step (3). At least one operation of ii) and (iii) is performed. At the end of the step (3), tetrahydrodicyclopentadiene is distilled off, and tetrahydrodicyclopentadiene is substantially absent in the solution mixture containing the hydrogenated copolymer. The hydrogenated α-olefin-dicyclopentadiene copolymer is contained by the presence of at least 10 parts by weight, preferably 30 parts by weight, of the high boiling hydrocarbon solvent per 100 parts by weight of the hydrogenated copolymer in the solution mixture. The viscosity of the solution mixture is low, which is convenient for the tetrahydrodicyclopentadiene to be distilled off. Specifically, for example, the high-boiling hydrocarbon solvent is at least 100 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the hydrogenated α-olefin-dicyclopentadiene copolymer at the beginning of the step (3). By employing a method in which 150 parts by weight to 10000 important parts are present and at least one operation of (i), (ii), and (iii) above is carried out, tetrahydrodicyclopentadiene is added at the end of step (3). It can be distilled off easily and efficiently.

The tetrahydrodicyclopentadiene is distilled off by subjecting the hydrogenated copolymer solution to the boiling point of tetrahydrodicyclopentadiene (194 ° C. under normal pressure) or more and the ignition point (2
This is achieved by heating at a temperature below 35 ° C. At this time, in order to efficiently distill off tetrahydrodicyclopentadiene, the pressure inside the apparatus may be reduced.

The boiling point of tetrahydrodicyclopentadiene is lower than that of the high boiling hydrocarbon solvent. Therefore, tetrahydrodicyclopentadiene is distilled off from the hydrogenated copolymer solution before the high boiling hydrocarbon solvent. On this occasion,
The solution viscosity of the hydrogenated copolymer solution is much lower than that of the system in which the high boiling hydrocarbon solvent is not present, and tetrahydrodicyclopentadiene can be distilled off extremely easily and efficiently. Thus, the hydrogenated α-olefin-dicyclopentadiene copolymer is produced as a solution in a high-boiling hydrocarbon solvent which does not substantially contain tetrahydrodicyclopentadiene.

Next, the second manufacturing method of the present invention will be described. Regarding the second manufacturing method, the first item is not described here.
It should be understood that the matters described in the manufacturing method are applied as they are or with modifications obvious to those skilled in the art.

Step (1 ') is the step in the first manufacturing method.
Same as (1). In the step (2 ′), the unreacted dicyclopentadiene is distilled off from the α-olefin-dicyclopentadiene copolymer solution containing the unreacted dicyclopentadiene produced in the step (1 ′), and the dicyclopentadiene is substantially converted. A pentadiene-free α-olefin-dicyclopentadiene copolymer solution is prepared.

Since the boiling point of dicyclopentadiene (170 ° C. under normal pressure) is lower than that of the high boiling hydrocarbon solvent, dicyclopentadiene is distilled off before the high boiling hydrocarbon solvent. At this time, the solution viscosity of the α-olefin-dicyclopentadiene copolymer solution is much lower than that of the system in which the high boiling hydrocarbon solvent does not exist, and the unreacted dicyclopentadiene is extremely easily and efficiently removed. Can be distilled off.

When dicyclopentadiene is heated to 160 ° C., it undergoes a reverse Diels-Alder reaction and a Diels-Alder reaction.
A reaction occurs and it changes to a cyclopentadiene monomer or oligomer. Cyclopentadiene oligomer has a high boiling point and is extremely difficult to remove. Therefore, when dicyclopentadiene is distilled off, the pressure is preferably set to 600 mmHg or less in order to prevent generation of cyclopentadiene oligomer.

After carrying out the step (2 ′), a step of removing the polymerization catalyst from the α-olefin-dicyclopentadiene copolymer solution can be carried out.

Then, in the step (3 '), a hydrogenation catalyst is added to the α-olefin-dicyclopentadiene copolymer solution produced in the previous step, and the hydrogenation reaction is carried out to remove the impurities contained in the copolymer. The saturated double bond is hydrogenated to obtain a mixture containing a hydrogenated α-olefin-dicyclopentadiene copolymer solution. The step (3 ′) is performed in the same manner as the step (2) described above. Since unreacted dicyclopentadiene is substantially removed in the step (2 ′), the hydrogenation α
The mixture containing the -olefin-dicyclopentadiene copolymer is substantially free of tetrahydrodicyclopentadiene.

After carrying out the step (3 ′), the metal and hydrogen derived from the polymerization catalyst are removed by removing the polymerization catalyst and / or the hydrogenation catalyst from the mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer. A hydrogenated α-olefin-dicyclopentadiene copolymer solution containing substantially no metal derived from the added catalyst is obtained.

In the second production method, at the end of the step (2 ′), at least 10 parts by weight of the high boiling hydrocarbon solvent is present per 100 parts by weight of the α-olefin-dicyclopentadiene copolymer, so that the following ( i '), (i
i ');(i') using a high boiling hydrocarbon solvent as at least a portion of the hydrocarbon solvent of step (1 '), and (ii) adding a high boiling hydrocarbon solvent in step (2'), Perform at least one operation.

The hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained by the first and second production methods of the present invention is preferably further subjected to solvent removal to recover the polymer. The solvent is removed, for example, by a device such as a heated vacuum concentrator and an extruder with a vent. Since the copolymer solution does not substantially contain tetrahydrodicyclopentadiene, it can be heated to a temperature as high as 235 ° C. or higher and lower than the ignition point of the solvent.

Another major feature of the present invention is that
The solvent removal process is simple. Generally, when removing a solvent from a polymer solution, the temperature of the solution does not rise above the boiling point of the solvent used until the solvent is substantially completely removed.
When the boiling point of the solvent used is as low as about 100 ° C., it is not possible to expect a decrease in solution viscosity and an increase in solubility due to heating, the viscosity increases as the solvent is removed, and further, the concentration distribution of the solution occurs, and the polymer becomes It deposits on the wall as a solid. In such a situation, stirring of the solution is extremely difficult, and efficient solvent removal cannot be expected. On the other hand, when a high boiling hydrocarbon solvent is used as in the present invention, the solution viscosity can be lowered and the solubility can be increased by heating the solution to a high temperature. As a result, the polymer can be directly brought into a molten state from a solution state without being made into a solid state, and the solvent can be removed extremely efficiently and substantially completely.

If desired, various additives such as antioxidants may be added to the hydrogenated α-olefin-dicyclopentadiene copolymer obtained according to the present invention. As an example of the antioxidant, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-phenol, 4-
t-Butylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-bis (2,6di-t-butylphenol), 2,2'-methylene-bis (4- Methyl 6-t-butylphenol), 4,4'-methylene-
Bis (2,6-di-t-butylphenol), 2,2 '
-Dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [2- (3,5-
Di-t-butyl-4-hydroxyphenyl) ethylpropionate] methane, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,3 5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris (3,5-di-t)
-Butyl-4-hydroxybenzyl) isocyanurate, octadecyl- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-thio-
Bis (4-methyl 6-t-butylphenol), 2,
2'-thio-diethylenebis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] and other phenolic antioxidants, tris (2,4, -di-t
-Butylphenyl) phosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritolol diphosphite, tris (nonylphenyl) phosphite, 3,5-di-t- Examples thereof include phosphorus-based antioxidants such as butyl-4-hydroxybenzylphosphonate diethyl ester. These may be used alone or in combination of two or more. Moreover, you may mix and use a phosphorus antioxidant with a phenol antioxidant.

Further, the hydrogenated α-olefin-dicyclopentadiene copolymer obtained by the present invention is extremely high in purity and contains substantially no polymerization catalyst residue or tetrahydrodicyclopentadiene, and therefore has transparency and heat resistance. , Excellent in various properties such as weather resistance, dielectric properties, mechanical properties, etc.
It can be suitably used as an optical material such as a lens for a camera.

[0099]

According to the present invention, an α-olefin-cyclic olefin copolymer solution obtained by using a polymerization catalyst or a hydrogenated α-olefin-cyclic olefin copolymer solution obtained by using a hydrogenation catalyst By including a high boiling point hydrocarbon solvent in the solvent, tetrahydrodicyclopentadiene having a low ignition point can be efficiently and safely removed or prevented from being generated, and the co-polymer containing substantially no tetrahydrodicyclopentadiene can be prevented. A coalesced solution or copolymer can be obtained.

[0100]

EXAMPLES The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. Unless otherwise stated, the examples were carried out under an inert atmosphere of argon, nitrogen or the like.

Toluene, cyclohexane, tetrahydronaphthalene, and dicyclopentadiene were all distilled and purified by a conventional method and sufficiently dried. Metallocenes were prepared by adding isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride to
It was purchased from der Scientific, and used as it was. As the ionic boron compound, trityl-tetrakis (pentafluorophenyl) borate was purchased from Toso-Akzo Co., Ltd. and used as it was. As the aluminoxane, polymethylaluminoxane (PMAO) was purchased from Toso-Akzo Co., Ltd., and adjusted to a toluene solution having a concentration of 2M for use. Triisobutylaluminum was purchased from Toso Akzo Co., Ltd. and used as it was. Tris (acetylacetonato) cobalt was purchased from Wako Pure Chemical Industries, Ltd. and used as it was. Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010) was purchased from Tokyo Chemical Industry Co., Ltd. and used as it was. Nickel silica alumina was purchased from Aldorich.

The measurement items were measured by the following methods. Solution viscosity: Measured using a BH type viscometer manufactured by Tokyo Keiki. Glass transition temperature (Tg (° C)): TA Instrum
ents 2920 type DSC is used, and the heating rate is 2
It was measured at 0 ° C / min. Molecular weight: 30 ° C of a toluene solution having a concentration of 0.5 g / dL
The reduced viscosity η _sp / c (dL / g) was measured. Solution composition: The composition of the solution excluding the polymer was measured using a gas chromatograph GC-9A manufactured by Shimadzu Corporation. Hydrogenation rate: Quantified by ¹ H-NMR using a JEOL JNM-A-400 type nuclear magnetic resonance absorber.

Reference Example 1 Glass transition temperature is 148 ° C.
The temperature dependence and solution concentration dependence of the solution viscosity of the hydrogenated ethylene-dicyclopentadiene copolymer having a reduced viscosity of 0.40 dL / g were investigated. Toluene and tetrahydronaphthalene were used as the solvent. The results are shown in FIGS. 1 and 2, respectively. From this result, the relationship between the solution concentration and the solution viscosity of the hydrogenated ethylene-dicyclopentadiene copolymer toluene solution at 110 ° C and the tetrahydronaphthalene solution of the hydrogenated copolymer at 208 ° C was derived. The results are shown in Fig. 3.

Example 1 To 3 L of autoclave was added 343 g (2.6 mol) of dicyclopentadiene, 1320 g of tetrahydronaphthalene, and 36 g of triisobutylaluminum. The autoclave was pressurized with ethylene at 1.5 atm, and tetrahydronaphthalene solution containing 124 mg (0.29 mmol) of isopropylidene- (9-fluorenyl) (cyclopentadienyl) zirconium dichloride and 3 g of triisobutylaluminum, and further trityl-tetrakis. A solution of 250 mg (0.27 mmol) of (pentafluorophenyl) borate in tetrahydronaphthalene was added, and polymerization was carried out at 30 ° C. During the polymerization, 1.5 atm of ethylene was constantly supplied, and when 2.34 mol of ethylene was consumed, the supply of ethylene was stopped to obtain a polymer solution. The ethylene-dicyclopentadiene copolymer obtained here has a Tg of 153 ° C.,
The reduced viscosity was 0.77 dL / g, and the molar fraction of the dicyclopentadiene copolymer was 46%.

The copolymer solution was transferred to a 5 l autoclave, and tris (acetylacetonate) cobalt 3.0 was added.
A tetrahydronaphthalene solution containing g (8.4 mmol) and 4.8 g of triisobutylaluminum was added. The autoclave was pressurized with 40 atmospheres of hydrogen,
Hydrogenation reaction was carried out at 3 ° C. for 3 hours to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution. The hydrogenated copolymer thus obtained had a Tg of 153 ° C. and a reduced viscosity of 0.47 dL /
g, the hydrogenation rate was 99.9% or more.

21 g of lactic acid and 2.7 g of water were added to the hydrogenated copolymer solution and reacted at 95 ° C. for 2 hours to deposit a polymerization catalyst and a hydrogenation catalyst. The solution mixture was filtered through Celite to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution containing substantially no catalyst residue. The solution composition is such that tetrahydronaphthalene is 430 parts by weight and tetrahydrodicyclopentadiene is 2 parts with respect to 100 parts by weight of the hydrogenated ethylene-dicyclopentadiene copolymer.
It was 8 parts by weight. The following copolymer or hydrogenated copolymer 1
The part by weight of the volatile component relative to 00 parts by weight is expressed as phr.

Of the obtained hydrogenated copolymer solution, 250
g in a 500 mL flask, 125 mg of Irganox 1010 which is an antioxidant is further added, and under normal pressure,
The volatile components were removed. Solution temperature is 205-208
It was ℃. On the way, when the composition of the solution was analyzed, tetrahydrodicyclopentadiene became undetectable when the content of tetrahydronaphthalene reached 56 phr. The change in the composition of this solution is shown in FIG. The solution viscosity at this point was estimated to be 1000 cps from FIG. Volatile components were further removed while raising the solution temperature to 300 ° C. to obtain the hydrogenated copolymer in a molten state.
During the process, the solid hydrogenated copolymer did not precipitate from the solution.

Comparative Example 1 Toluene was used as a solvent,
Polymerization reaction, hydrogenation reaction, catalyst precipitation reaction and catalyst removal operation were performed in the same manner as in Example 1 except that ethylene was pressurized at 1 atm to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution. The Tg of the copolymer before hydrogenation is 150 ° C., ηsp /
C was 0.67, and the molar fraction of the dicyclopentadiene copolymer was 45%. The Tg of the hydrogenated copolymer is 14
The temperature was 7 ° C., the reduced viscosity was 0.43, and the hydrogenation rate was 99.9% or more. The solution composition was 430 phr for toluene and 28 phr for tetrahydrodicyclopentadiene.

250 g of the obtained hydrogenated copolymer solution
Was placed in a 500 mL flask and the antioxidant Irg was added.
125 mg of anox1010 was added, and volatile components were removed under normal pressure. The solution temperature was 110 to 115 ° C until the toluene was almost exhausted. The solution composition was analyzed on the way. The change in composition is shown in FIG. Toluene was distilled off first and most of the tetrahydrodicyclopentadiene was distilled off later. As the concentration of the copolymer increases, the solution viscosity rapidly increases, and the copolymer concentration increases to 70%.
The copolymer began to precipitate as a solid on the wall surface of the flask from around the point where the percentage exceeded. The solution viscosity at this point is shown in FIG.
Estimated to be 25,000 cps, and tetrahydrodicyclopentadiene is still 20 ph
r was left. When the heating was further continued, toluene was almost eliminated, and the temperature of the copolymer was increased at the same time when the copolymer was precipitated.
The temperature was raised to 225 ° C. and tetrahydrodicyclopentadiene was distilled off for 2 hours, but the copolymer was not yet melted and tetrahydrodicyclopentadiene could not be distilled off completely. 10 phr of tetrahydrodicyclopentadiene remained in the copolymer.

Example 2 The same polymerization reaction as in Example 1 was carried out except that cyclohexane was used as a solvent and ethylene was pressurized at 2 atm. The Tg of the copolymer is 147 ° C., η
The sp / C was 0.64, and the molar fraction of the dicyclopentadiene copolymer was 46%. Lactic acid 1 was added to the obtained polymerization solution.
1 g and 1.4 g of water were added and reacted for 2 hours to deposit a polymerization catalyst. Further, the obtained polymerization solution mixture was filtered using Celite, and the filtrate was transferred to a 5 L autoclave. To the autoclave, 30 g of nickel silica alumina as a hydrogenation catalyst was added, and hydrogen was pressurized at 100 atm to 150
The hydrogenation reaction was carried out at ℃. The hydrogenation catalyst was removed from the obtained hydrogenated copolymer solution mixture with Celite to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution. The Tg of the hydrogenated copolymer was 144 ° C., the reduced viscosity was 0.41, and the hydrogenation rate was 99.9% or more. The solution composition was 420 phr for cyclohexane and 26 phr for tetrahydrodicyclopentadiene.

250 g of the obtained hydrogenated copolymer solution
In a 1 L flask, and tetrahydronaphthalene 69 g
(150 phr with respect to the hydrogenated copolymer) and 125 mg of Irganox 1010 which is an antioxidant were added, and volatile components were removed under normal pressure. Solution temperature is 90-2
It was carried out at 10 ° C., and the solution composition was analyzed on the way. The change in composition is shown in FIG. When the concentration of tetrahydronaphthalene reached 45 phr of the hydrogenated copolymer, tetrahydrodicyclopentadiene was no longer detected in the solution. The solution viscosity at this point was estimated to be 2000 cps from FIG. Volatile components were further removed while raising the solution temperature to 300 ° C. to obtain the hydrogenated copolymer in a molten state. During the process, the solid hydrogenated copolymer did not precipitate from the solution.

Example 3 All the scales were reduced to 1/7 and the polymerization reaction was carried out in the same manner as in Example 1 using a flask to obtain an ethylene-dicyclopentadiene copolymer solution. Tg of the copolymer is 143 ° C., ηsp / C is 0.5
9, the molar fraction of the dicyclopentadiene copolymer is 43
%was. The solution composition was 400 phr of tetrahydronaphthalene and 30 phr of dicyclopentadiene. The flask was depressurized to 50 mmHg and volatile components were removed at 70 ° C. When the composition of the solution was analyzed on the way, dicyclopentadiene was not detected in the solution when tetrahydronaphthalene reached 270 phr. The change in solution composition is shown in FIG. The solution viscosity at this point was estimated from Figure 2 to be 300 cps.

To the obtained copolymer solution, 60 g of tetrahydronaphthalene was added, and the mixture was transferred to a 1 l autoclave and 0.4 g of tris (acetylacetonate) cobalt (1.
1 mmol) and a tetrahydronaphthalene solution containing 0.7 g of triisobutylaluminum were added. The autoclave was pressurized with 40 atm of hydrogen and hydrogenated at 110 ° C. for 3 hours to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution. Tg of hydrogenated copolymer obtained here
Was 143 ° C. and the reduced viscosity was 0.42 dL / g.

Lactic acid (3 g) and water (0.4 g) were added to the hydrogenated copolymer solution, and the mixture was reacted at 95 ° C. for 2 hours to precipitate a polymerization catalyst and a hydrogenation catalyst. The solution mixture was filtered through Celite to obtain a hydrogenated ethylene-dicyclopentadiene copolymer solution which was substantially free of tetrahydrodicyclopentadiene and catalyst residues.

The hydrogenated copolymer solution was placed in a 500 mL flask, and Irganox 1010 which was an antioxidant was added.
Was added 125 mg, and the volatile components were further removed under normal pressure while raising the solution temperature to 300 ° C. to obtain the hydrogenated copolymer in a molten state. During the process, the solid hydrogenated copolymer did not precipitate from the solution.

[Brief description of drawings]

FIG. 1 shows the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer obtained in Reference Example 1 in toluene and the temperature T (K) with the solution concentration as a parameter.

FIG. 2 shows the relationship between the solution viscosity and the temperature T (K) of the hydrogenated α-olefin-dicyclopentadiene copolymer in tetrahydronaphthalene obtained in Reference Example 1 using the solution concentration as a parameter.

FIG. 3 shows the relationship between the solution viscosity and the solution concentration of the hydrogenated α-olefin-dicyclopentadiene copolymer obtained in Reference Example 1 in toluene at 110 ° C. (line J), and the solution viscosity in tetrahydronaphthalene at 208 ° C. And the solution concentration (straight line K).

FIG. 4 shows the time-dependent change in the solution composition in the step of removing volatile components from the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 1.

FIG. 5 shows a change with time of a solution composition in a step of removing a volatile component from a hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Comparative Example 1.

FIG. 6 shows the change over time in the solution composition in the step of removing volatile components from the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 2.

FIG. 7 shows the change over time in the solution composition in the step of removing volatile components from the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 3.

[Explanation of symbols]

A: A straight line showing the relationship between the solution viscosity and the temperature of a 17% by weight hydrogenated α-olefin-dicyclopentadiene copolymer toluene solution. White symbols are measured values, black symbols are 1.
It is an extrapolated value at 10 ° C. B: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 30% by weight toluene solution and temperature. White symbols are measured values, black symbols are 1.
It is an extrapolated value at 10 ° C. C: A straight line showing the relationship between the solution viscosity of a 40% by weight hydrogenated α-olefin-dicyclopentadiene copolymer toluene solution and the temperature. White symbols are measured values, black symbols are 1.
It is an extrapolated value at 10 ° C. D: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 50 wt% toluene solution and temperature. White symbols are measured values, black symbols are 1.
It is an extrapolated value at 10 ° C. E: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 17% by weight tetrahydronaphthalene solution and the temperature. The white symbols are the measured values,
Black symbols are extrapolated values at 208 ° C. F: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 30% by weight tetrahydronaphthalene solution and the temperature. The white symbols are the measured values,
Black symbols are extrapolated values at 208 ° C. G: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 40% by weight tetrahydronaphthalene solution and the temperature. The white symbols are the measured values,
Black symbols are extrapolated values at 208 ° C. H: a straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 60 wt% tetrahydronaphthalene solution and the temperature. The white symbols are the measured values,
Black symbols are extrapolated values at 208 ° C. I: A straight line showing the relationship between the solution viscosity of a hydrogenated α-olefin-dicyclopentadiene copolymer 80% by weight tetrahydronaphthalene solution and the temperature. The white symbols are the measured values,
Black symbols are extrapolated values at 208 ° C. J: A straight line showing the relationship between the solution viscosity at 110 ° C. and the solution concentration of the hydrogenated α-olefin-dicyclopentadiene copolymer toluene solution obtained from FIG. 1. K: 208 of hydrogenated α-olefin-dicyclopentadiene copolymer tetrahydronaphthalene solution obtained from FIG.
A straight line showing the relationship between solution viscosity and solution concentration at ° C. L: The point where solids start to precipitate from the hydrogenated α-olefin-dicyclopentadiene copolymer toluene solution at 110 ° C. M: A curve showing the change with time of the concentration of tetrahydrodicyclopentadiene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 1. N: A curve showing the change with time of the concentration of tetrahydronaphthalene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 1. O: a curve showing the change with time of the concentration of tetrahydrodicyclopentadiene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Comparative Example 1. P: A curve showing the change with time of the concentration of toluene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Comparative Example 1. Q: A curve showing the change with time of the concentration of tetrahydrodicyclopentadiene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 2. R: A curve showing the change with time of the concentration of cyclohexane contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 2. S: A curve showing the change with time of the concentration of tetrahydronaphthalene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 2. T: A curve showing the change with time of the concentration of dicyclopentadiene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 3. U: A curve showing the change with time of the concentration of tetrahydronaphthalene contained in the hydrogenated α-olefin-dicyclopentadiene copolymer solution obtained in Example 3.

Claims (28)

[Claims] (1) An α-olefin having 2 or more carbon atoms and dicyclopentadiene are subjected to addition polymerization in a hydrocarbon solvent in the presence of a polymerization catalyst, and then the polymerization catalyst is removed as necessary to unreact. A step of producing an α-olefin-dicyclopentadiene copolymer solution containing dicyclopentadiene, (2) adding a hydrogenation catalyst to the copolymer solution produced in step (1), and subjecting it to a hydrogenation reaction The step of hydrogenating the unsaturated double bond of the α-olefin-dicyclopentadiene copolymer to produce a mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer, and (3) the step of producing Distilling off the tetrahydrodicyclopentadiene produced in the hydrogenation reaction of step (2) from the mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer, and At the end of the step (3), at least 10 parts by weight of the high boiling hydrocarbon solvent is present per 100 parts by weight of the hydrogenated α-olefin-dicyclopentadiene copolymer, so that the following (i), (ii), ( i
ii); (i) using a high boiling hydrocarbon solvent as at least a part of the hydrocarbon solvent in step (1), (ii) adding the high boiling hydrocarbon solvent in step (2), and (iii) step ( At least one operation of adding a high-boiling point hydrocarbon solvent in 3), wherein the high-boiling point hydrocarbon solvent contains at least a hydrocarbon solvent having a normal pressure boiling point of 195 to 300 ° C. and an ignition point of 260 ° C. or higher. The method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer, characterized in that 2. After carrying out step (2) or step (3), the polymerization catalyst and / or the hydrogenation catalyst is removed from the mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer produced in each step. The method of claim 1, further comprising the step of: 3. The method according to claim 1 or 2, wherein the hydrocarbon solvent in step (1) is mainly composed of a high boiling hydrocarbon solvent. 4. The method according to claim 1, wherein only the operation (i) is performed.
4. The method according to any one of 3 to 3. 5. The method according to claim 1, wherein only the operation (ii) is carried out. 6. The method according to claim 1, wherein the high boiling hydrocarbon solvent has a melting point of 50 ° C. or lower. 7. The method according to claim 1, wherein the high-boiling hydrocarbon solvent is at least one solvent selected from the group consisting of 1-methylnaphthalene, 2-methylnaphthalene and tetrahydronaphthalene. 8. The method according to claim 1, wherein the polymerization catalyst is a metallocene catalyst. 9. The method according to claim 8, wherein the metallocene catalyst is a catalyst comprising a group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and a cocatalyst. 10. The method of claim 9 wherein the transition metal in the metallocene-based catalyst is zirconium and the cocatalyst is aluminoxane. 11. The method of claim 9, wherein the transition metal in the metallocene-based catalyst is zirconium and the cocatalyst is an ionic boron compound and an alkylating agent. 12. The method according to claim 1, wherein the polymerization catalyst is a Ziegler type catalyst. 13. The method according to claim 1, wherein the α-olefin is ethylene. 14. The method according to claim 1, wherein the hydrogenated α-olefin-dicyclopentadiene copolymer is obtained as a solution of a high boiling hydrocarbon solvent. 15. (1 ′) α-Olefin having 2 or more carbon atoms and dicyclopentadiene are subjected to addition polymerization in a hydrocarbon solvent in the presence of a polymerization catalyst, and then the polymerization catalyst is removed as necessary to unreact. Α-Olefin-dicyclopentadiene copolymerization containing unreacted dicyclopentadiene produced in step (1 ′) of producing (α′-olefin-dicyclopentadiene copolymer solution containing dicyclopentadiene) The unreacted dicyclopentadiene was distilled off from the combined solution to obtain α containing substantially no dicyclopentadiene.
A step of producing an olefin-dicyclopentadiene copolymer solution, and (3 ′) a hydrogenation catalyst was added to the α-olefin-dicyclopentadiene copolymer solution produced in the previous step and subjected to a hydrogenation reaction. Hydrogenating the unsaturated double bonds of the α-olefin-dicyclopentadiene copolymer to produce a mixture containing the hydrogenated α-olefin-dicyclopentadiene copolymer, and the above step (2 ′). At the end of at least 1 per 100 parts by weight of α-olefin-dicyclopentadiene copolymer.
A high-boiling point hydrocarbon solvent is used as at least a part of the following (i ′), (ii ′); (i ′) step (1 ′) hydrocarbon solvent so that 0 part by weight of the high-boiling point hydrocarbon solvent is present. At least one of using, and (ii) adding a high boiling hydrocarbon solvent in step (2 ′), wherein the high boiling hydrocarbon solvent has a normal pressure boiling point of 195 to 300 ° C. and an ignition point of 260. A method for producing a hydrogenated α-olefin-dicyclopentadiene copolymer, which comprises at least a hydrocarbon solvent having a temperature of ℃ or more. 16. The method according to claim 15, further comprising the step of removing the polymerization catalyst from the α-olefin-dicyclopentadiene copolymer solution after carrying out step (2 ′). 17. After the step (3 ′) has been carried out, hydrogenation α
The method according to claim 15 or 16, further comprising the step of removing a polymerization catalyst and / or a hydrogenation catalyst from a mixture containing an -olefin-dicyclopentadiene copolymer. 18. The method according to claim 15, wherein the hydrocarbon solvent in step (1 ′) is mainly composed of a high boiling hydrocarbon solvent. 19. The method according to claim 15, wherein only the operation (i ′) is performed. 20. The method according to claim 15, wherein the high boiling hydrocarbon solvent has a melting point of 50 ° C. or lower. 21. The method according to claim 15, wherein the high-boiling hydrocarbon solvent is at least one solvent selected from the group consisting of 1-methylnaphthalene, 2-methylnaphthalene and tetrahydronaphthalene. 22. The method according to claim 15, wherein the polymerization catalyst is a metallocene catalyst. 23. The method according to claim 22, wherein the metallocene catalyst is a catalyst comprising a group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and a cocatalyst. 24. The method of claim 23, wherein the transition metal in the metallocene-based catalyst is zirconium and the cocatalyst is aluminoxane. 25. The method of claim 23, wherein the transition metal in the metallocene-based catalyst is zirconium and the cocatalyst is an ionic boron compound and an alkylating agent. 26. The method according to claim 15, wherein the polymerization catalyst is a Ziegler type catalyst. 27. The method according to claim 15, wherein the α-olefin is ethylene. 28. The method according to claim 15, wherein the hydrogenated α-olefin-dicyclopentadiene copolymer is obtained as a solution of a high boiling hydrocarbon solvent.