JP2000026580A - Production of hydrogenated product of ring-opened norbornene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial process for producing a hydrogenated product of a ring-opened norbornene polymer in high productivity and hydrogenation ratio in a short hydrogenation reaction time. SOLUTION: The objective hydrogenated product of a ring-opened norbornene polymer is produced by carrying out the ring-opening polymerization of a norbornene monomer using a polymerization catalyst and the hydrogenation of the produced ring-opened norbornene polymer using a hydrogenation catalyst. In the above process, a catalyst produced by carrying a transition metal on an inorganic carrier is used as the hydrogenation catalyst, a solid component containing the hydrogenation catalyst is separated and recovered from the solution containing the hydrogenated ring-opened norbornene polymer after the hydrogenation reaction and the recovered solid component containing the hydrogenation catalyst is used in the subsequent hydrogenation treatment.

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 hydrogenated norbornene ring-opening polymer, and more particularly, to a hydrogenated norbornene ring-opening polymer having a high hydrogenation rate, in which the hydrogenation reaction time can be reduced. And a method for industrially producing the product with high productivity.

[0002]

2. Description of the Related Art A norbornene ring-opening polymer can be used as a molding material as it is, but when it is not hydrogenated, it has a double bond in its main chain structure, so it may be deteriorated by oxidation or the like. There is. Therefore, it is common practice to saturate the double bond of the main chain by hydrogenation to use it as a hydrogenated product (see, for example, JP-A-1-190726). In order to produce such a hydrogenated product, a polymer hydrogenation step is performed after the polymerization step, and the hydrogenation step is carried out in the presence of a hydrogenation catalyst in a solvent for the norbornene-based polymer in the solvent of the polymer. It is common to contact the ring polymer with hydrogen.

As a technique relating to hydrogenation of a norbornene-based ring-opening polymer, a method of adding a polymerization catalyst deactivator to a polymer solution to remove a residue of the polymerization catalyst, and then performing hydrogenation (Japanese Patent Laid-Open No. 161421), a method of adding an acid scavenger after polymerization to hydrogenate (Japanese Patent Laid-Open No. 7-1020)
No. 42) is known.

[0004]

However, when hydrogenating a conventional norbornene-based ring-opening polymer, a hydrogenated product of the norbornene-based ring-opening polymer having a high hydrogenation rate is industrially produced with high efficiency with a small amount of a hydrogenation catalyst. There was a problem about manufacturing with the nature.

In the hydrogenated norbornene ring-opening polymer, its hydrogenation rate (the number of unsaturated bonds after the polymerization step,
The ratio between the number of unsaturated bonds after the hydrogenation step and the number of unsaturated bonds) is an important characteristic that determines the resistance to oxidation deterioration, and the higher the hydrogenation rate (the closer to 100%), the more preferable. Means for increasing the hydrogenation rate in the hydrogenation step include increasing the hydrogenation reaction time and increasing the amount of the hydrogenation catalyst used, but the former requires a longer time for the hydrogenation step. In the latter case, a large amount of the residue of the hydrogenation catalyst is generated, which causes a problem of disposal.

The present invention has been made in view of the above situation, and has a hydrogenation reaction time which is shorter than that of conventional hydrogenation products. It is an object to provide a method for manufacturing with.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, in the hydrogenation step of the norbornene ring-opening polymer, the hydrogenation catalyst was once used due to poisoning of the hydrogenation catalyst. It was expected that the hydrogenation catalyst could not be reused.However, if a specific hydrogenation catalyst was used, it could be separated and recovered without substantially reducing the activity of the hydrogenation catalyst, and it could be reused. I found something.

As a result, by reusing the separated and recovered hydrogenation catalyst in the next hydrogenation treatment, the amount of the hydrogenation catalyst used as a whole can be reduced, and the waste derived from the hydrogenation catalyst can be reduced. They have found that they can do this and have completed the present invention.

That is, in the method of the present invention, a norbornene-based monomer is subjected to ring-opening polymerization using a polymerization catalyst to form a norbornene-based ring-opened polymer, and then subjected to a hydrogenation treatment using a hydrogenation catalyst to obtain a norbornene-based polymer. In the method for producing a ring polymer hydrogenated product, as the hydrogenation catalyst, using a hydrogenation catalyst having a transition metal supported on an inorganic carrier, after the hydrogenation reaction containing the norbornene-based ring-opened polymer hydrogenated product The solid content containing the hydrogenation catalyst is separated and collected from the solution, and the collected solid content containing the hydrogenation catalyst is used for the next hydrogenation treatment.

According to the method of the present invention, the hydrogenation catalyst once used is separated and recovered from the polymer and used in the next hydrogenation step, so that the consumption of the hydrogenation catalyst is reduced and the hydrogenation of the polymer is reduced. The production cost can be kept low, waste can be reduced at the same time, and a hydrogenated norbornene ring-opening polymer having a high hydrogenation rate can be industrially produced with high productivity.

The hydrogenation catalyst used in the present invention is one in which a transition metal is supported on an inorganic carrier.

The transition metals are Cu, Ni, Fe, Pd, P
It is not particularly limited as long as it is used for a hydrogenation catalyst such as t or Ru, but it is preferably at least one selected from Ni, Pd and Ru. By selecting these, the hydrogenation efficiency when used in the hydrogenation step of the norbornene ring-opening polymer is good, and the hydrogenation catalyst after hydrogenation without removing the polymerization catalyst before hydrogenation Even when the polymerization catalyst and the polymerization catalyst are collected together, the catalyst activity can be maintained enough to withstand the re-hydrogenation and can be used for the next hydrogenation treatment. Therefore, the amount of newly added hydrogenation catalyst can be reduced,
The target hydrogenated norbornene-based ring-opening polymer can be produced with high productivity.

The inorganic carrier is an inorganic porous material such as diatomaceous earth, magnesia, alumina, silica-magnesia, silica-zirconia, diatomaceous earth-zirconia, alumina-zirconia, and synthetic zeolite.

The amount of the hydrogenation catalyst to be added to the norbornene ring-opening polymer is not particularly limited, but is preferably larger than usual. By adding a large amount of the hydrogenation catalyst, a hydrogenated norbornene-based ring-opening polymer having a target hydrogenation rate can be obtained in a short reaction time. Therefore, a hydrogenated norbornene ring-opening polymer can be industrially produced with high productivity. In addition, the hydrogenation catalyst once used is in a highly active reducing state, and can be advantageously used in the next hydrogenation reaction, and as a result, hydrogenated norbornene-based ring-opening polymers can be industrially produced with high productivity. It is advantageous to manufacture with.

The specific amount of the hydrogenation catalyst added is such that the amount of the transition metal as the catalyst metal is 100 parts by weight of the polymer.
Preferably, the amount is 0.5 to 20 parts by weight, more preferably 1.0 to 15 parts by weight, and most preferably 1.5 to 10 parts by weight. This is because if the amount of the hydrogenation catalyst added to the norbornene ring-opening polymer is small, the hydrogenation efficiency is reduced, and if it is too large, the separation efficiency between the hydrogenation catalyst and the polymer solution is reduced, which is not economical.

[0016] It is preferable to add an acid scavenger before the hydrogenation step, since the number of repeated use of the hydrogenation catalyst can be increased and the consumption of the hydrogenation catalyst can be reduced.
It is also preferable to separate and remove the polymerization catalyst used in the polymerization step in advance. If the process proceeds to the hydrogenation step while containing the polymerization catalyst, the activity of the hydrogenation catalyst may be reduced, and further, the polymerization catalyst may be included in the hydrogenation catalyst recovered after the hydrogenation step, and the subsequent hydrogenation catalyst This may decrease the catalytic activity of the catalyst. For example, when a transition metal halide is used as a polymerization catalyst, the hydrogenation catalyst is poisoned and the activity tends to decrease, but by adding an acid scavenger before hydrogenation, the activity decrease can be suppressed, and It can be advantageously used in the next hydrogenation treatment without lowering the activity of the hydrogenation catalyst. In addition, the polymerization catalyst may be separated and removed before hydrogenation, and the hydrogenation catalyst once used can be used for the next hydrogenation treatment while maintaining the activity higher.

In order to simplify the process and not reduce the overall productivity, in the method of the present invention, it is not always necessary to separate and remove the polymerization catalyst before the hydrogenation process.

The recovered hydrogenation catalyst is at least twice,
It can be reused preferably 3 times or more, more preferably 5 times or more, and still more preferably 10 times or more. Each time the recovered hydrogenation catalyst is reused, a new hydrogenation catalyst can be added each time.

Industrially, a method of discarding a part of the recovered hydrogenation catalyst, replenishing it by adding a new hydrogenation catalyst, and repeatedly using the same is preferably used. Such partial disposal is particularly preferable when the polymerization catalyst is not separated and removed before hydrogenation. Every time it is reused, part of it is discarded,
By adding a new hydrogenation catalyst, a hydrogenated norbornene-based ring-opening polymer having a high hydrogenation rate can be stably produced with high productivity in a constant reaction time. Because.

The proportion of the new hydrogenation catalyst is not particularly limited, but the new hydrogenation catalyst is preferably 0.1 to 50%, more preferably 1 to 50% of the total amount of the hydrogenation catalyst.
４０40%, most preferably 2-30%. By setting the content in this range, the activity of the entire catalyst can be continuously maintained, and the amount of the discarded catalyst can be reduced.

[0021]

Embodiments of the present invention will be described below.

The method for producing a hydrogenated norbornene ring-opening polymer according to the present invention comprises at least a polymerization step and a hydrogenation step.

Polymerization Step In the present invention, the norbornene-based ring-opening polymer comprises 30% by weight or more, preferably 50% by weight or more, more preferably 30% by weight or more of the total repeating structural units obtained by ring-opening polymerization of the norbornene-based monomer. It contains 70% by weight or more.

The norbornene-based ring-opening polymer is not particularly limited as long as it is polymerized by a ring-opening polymerization catalyst, and may be a homopolymer or a copolymer, and may be a random copolymer or a random copolymer. A block copolymer may be used. Further, (co) polymers obtained by graft-modifying these may be used.

[0025](1) Norbornene monomer As the norbornene monomer used in the polymerization step,
For example, but not limited to, bicyclo [2.2.1]
Pt-2-ene (common name norbornene), 5-methyl-
Bicyclo [2.2.1] hepta-2-ene, 5,5-di
Methyl-bicyclo [2.2.1] hept-2-ene, 5
-Ethyl-bicyclo [2.2.1] hept-2-ene,
5-butyl-bicyclo [2.2.1] hepta-2-e
, 5-ethylidene-bicyclo [2.2.1] -hepta
2-ene, 5- (4'-cyclohexenyl) -bicyclo
[2.2.1] Hept-2-ene, 5-vinyl-bisic
B [2.2.1] hepta-2-ene, 5-propenylbi
Cyclo [2.2.1] hept-2-ene, 5-methoxy
Carbonyl-bicyclo [2.2.1] hepta-2-e
5-cyanobicyclo [2.2.1] hepta-2-e
, 5-methyl 5-methoxycarbonyl-bicyclo
[2.2.1] bicyclo such as hepta-2-ene;
[2.2.1] hept-2-enes; tricyclo [4.
3.0.1.^2,5] Deca-3,7-diene (common name di
Cyclopentadiene), tricyclo [4.3.0.1
^2,5] Dec-3-ene; tricyclo [4.4.0.
1^2,5] Undeca-3,7-diene or trici
Black [4.4.0.1^2,5] Undeca-3,8-di
Ene or their partially hydrogenated (or cyclopentene)
Tricyclo which is an adduct of tadiene and cyclohexene)
[4.4.0.1^2,5] Undec-3-ene; 5-
Cyclohexenylbicyclo [2.2.1] hept-2-
Ene; tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodec-3-ene (simply tetracyclodode
8-methyltetracyclo [4.4.
0.1^2,5. 1^7,10] -Dodeca-3-ene, 8
-Ethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-methylidenetetra
Cyclo [4.4.0.1^2,5. 1^7,10]-Dode
Car-3-ene, 8-ethylidenetetracyclo [4.4.
0.1^2,5. 1^7,10] -Dodeca-3-ene, 8
-Vinyltetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-methoxycarboni
Letetracyclo [4.4.0.1^2,5.
1^7,10] -Dodeca-3-ene, 8-methyl-8-me
Toxicarbonyltetracyclo [4.4.0.1
^2,5. 1^7,10Tet such as -dodec-3-ene
Lacyclo [4.4.0.1^2,5. 1^7,10] -Do
Deca-3-enes; tetracyclo [7.4.0.1
^10,13. 0^2,7] Trideca-2,4,6,1
1-tetraene (1,4-methano-1,4,4a, 9a
-Tetrahydrofluorene), tetracyclo
[8.4.0.1^11,14. 0^3,8 ] Tetradeca
-3,5,7,12-tetraene (1,4-methano-
1,4,4a, 5,10,10a-hexahydroant
Pentacyclo [6.5.1.1].
^3,6. 0^2,7. 0^9,13] Pentadeca-3,
10-diene, pentacyclo [7.4.0.
1^3,6. 1^10,13. 0^2,7] Pentadeca
-4,11-diene; tetramer of cyclopentadiene;
And the like.

The norbornene-based monomer has a cycloalkyl group or an aryl group, or has a polar group such as a halogen atom, an ester residue, an ether residue, a cyano group or a pyridyl group. You may. These norbornene monomers can be used alone or in combination of two or more.

(2) Copolymerization other than norbornene-based monomer
Possible monomers The norbornene-based ring-opening polymer used in the present invention is a polycyclic cycloolefin other than the norbornene-based monomer, as long as the effects of the present invention are not substantially impaired; cyclobutene;
Monocyclic cycloolefins such as 1-methylcyclobutene, cyclopentene and cyclododecene; acetylenes which are substituted acetylenes such as acetylene and propyne and 1-butyne; dienes having double bonds at both ends such as 1,6-heptadiene And the like may be copolymerized.

(3) Ring-Opening Polymerization Catalyst Ring-opening polymerization of a norbornene-based monomer is usually performed using a metathesis ring-opening polymerization catalyst. Such a polymerization catalyst is not particularly limited.
No. 20111, JP-A-46-14910, JP-B-57-17883, JP-B-57-61044.
JP-A-54-86600, JP-A-58-86600
Known ring-opening polymerization catalysts of norbornene-based monomers as disclosed in, for example, JP-A-127728 and JP-A-1-240517 can be exemplified. Usually, a metathesis ring-opening polymerization catalyst essentially comprising a transition metal compound catalyst component (hereinafter, also referred to as component a) and a metal compound co-catalyst component (hereinafter, also referred to as component b) is used.

Transition Metal Compound Catalyst Component The transition metal compound catalyst component is described in Deming Periodic Table IV.
Group B, VB, VIB, VIIB, or VIII transition
Compounds of metals and halogenation of these transition metals
Compounds, oxyhalides, alkoxy halides,
Lucoxide, carboxylate, (oxy) acetylacetate
Nate, carbonyl complex, acetonitrile complex, hydrido
Complexes, their derivatives, these or their derivatives
P (C₆H ₅)₅Complexed products with complexing agents such as
You.

As a specific example, TiCl₄, TiB
r₄, VOCl₃, VOBr₃, WBr ₄, WBr₆,
WCl₂, WCl₄, WCl₅, WCl₆, WF₄, W
I₂, WOBr₄, WOCl₄, WOF₄, MoB
r₂, MoBr₃, MoBr₄, MoCl₄, MoCl
₅, MoF₄, MoOCl₄, MoOF₄, WO₂, H
₂WO ₄, NaWO₄, K₂WO₄, (NH₄)₂WO
₄, CaWO₄, CuWO₄, MgWO₄, (CO)₅
WC (OCH₃) (CH₃), (CO)₅WC (OC₂
H₅) (CH₃), (CO)₅WC (OC₂H₅) (C
₄H₅), (CO)₅MoC (OC₂H₅) (C
H₃), (CO)₅Mo = C (C₂H₅), (N (C₂
H₅)₂), Tridecylammonium molybdate,
Tridecyl ammonium tungstate and the like.
You.

In order to recover and reuse the hydrogenation catalyst, a compound containing no halogen is preferable. However, practically, a compound of W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and particularly, these halogens are preferable. Preferred are halides, oxyhalides, or alkoxy halides.

Metal Compound Co-catalyst Component The metal compound co-catalyst component is represented by Deming's Periodic Table IA,
Group IIA, IIB, IIIA or IVA metal compounds having at least one metal element-carbon bond or metal element-hydrogen bond, for example, Al,
Organic compounds such as Sn, Li, Na, Mg, Zn, Cd, and B can be exemplified.

Specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminummonochloride,
Di-n-propylaluminum monochloride, di-isobutylaluminum monochloride, di-n-butylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, di-n-propylaluminum monohydride , Diisobutyl aluminum monohydride, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, isobutyl aluminum sesquibromide, ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum diiodide, etc. Organoaluminum compounds: tetramethyltin, diethyldimethyltin, tet Ethyltin, dibutyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltin chloride, triethyltin bromide, triethyltin iodide, diethyltin difluoride, diethyltin diiodide, ethyltin trifluoride Organic tin compounds such as lido, ethyltin trichloride, ethyltin tribromide, and ethyltin triiodide; organic lithium compounds such as n-butyl lithium; organic sodium compounds such as n-pentyl sodium; methyl magnesium iodide;
Organic magnesium compounds such as ethyl magnesium bromide, methyl magnesium bromide, n-propyl magnesium chloride, t-butyl magnesium chloride, allyl magnesium chloride; organic zinc compounds such as diethyl zinc; organic cadmium compounds such as diethyl cadmium; trimethyl boron, triethyl boron , Bird
organic boron compounds such as n-butyl-boron; and the like.

Third component In addition to the above components (a) and (b), a third component is added,
Polymerization activity and selectivity of ring-opening polymerization can be improved.

As the third component, an aliphatic tertiary amine,
Aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, etc. Of Lewis acids and the like. Among them, aliphatic or aromatic tertiary amines are preferable, and specific examples thereof include triethylamine,
Examples include dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like. Further, a compound containing an OH group, such as an alcohol, functions as a deactivator that inhibits the polymerization activity when added in excess of the stoichiometric amount, so it is necessary to add the compound in a stoichiometric amount or less.

The stoichiometric amount as used herein means (b)
The product of the number of moles of the component and the oxidation number of the transition metal contained in the component (b) is divided by the number of OH groups per molecule of the compound containing an OH group, and the number of moles is represented by the following formula: Say.

Quantitative Relationship of Various Components The quantitative relationship of these components is as follows: component (a): component (b) is a metal element in a molar ratio of 1: 1 to 1: 100, preferably 1: 2 to 1: 50, and usually a molar ratio of component (a): third component of 1: 0.005 to 1:10, preferably 1:
It is used in the range of 0.05 to 1: 3. When the amount of the component (b) is too small relative to the component (a), sufficient activity cannot be obtained with respect to the amount of the component (a). When the amount is too large, removal of the excessive component (b) becomes difficult. , The cost will be higher. (A)
If the amount of the third component is too small relative to the component, the effect of adding the third component is small. If the amount is too large, removal of the excessive third component may become difficult or the cost may increase.

(4) Polymerization Method The ring-opening polymerization of the norbornene-based monomer can be performed by using a solvent.
Although it is possible without using it, when it is used, it is not particularly limited as long as it can sufficiently dissolve the norbornene-based monomer and its ring-opening polymer. Preferably, the polymerization is performed in an inert organic solvent.

The inert organic solvent is not particularly limited, but is preferably a hydrocarbon solvent, and among them, a cyclic hydrocarbon solvent which is excellent in the solubility of the norbornene ring-opening polymer to be formed is particularly preferable. Specific examples include benzene,
Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as m-pentane and hexane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane and decalin; methylene dichloride, dichloroethane, dichloroethane Hydrocarbon solvents such as chloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene and the like; ethers such as diethyl ether; and the like, and hydrocarbon solvents such as a mixture of two or more thereof can be used. Is also good.

When a solvent is used for the ring-opening polymerization, the amount of the solvent is not particularly limited. However, in order to reduce the solution viscosity, improve the stirring, and control the reaction in a uniform solution, the amount of the solvent may be large. Although desirable, it is desired that the amount of the solvent is small in order to enhance the productivity. Therefore, the weight ratio is usually 1 to 100 times, preferably 1.5 times to the weight of the norbornene monomer.
It is desirably 20 times, more preferably 2 to 10 times. This is because a polymer having a high degree of polymerization can be efficiently obtained when it is in this range.

The amount of the polymerization catalyst to be added is not particularly limited, but is usually 0.000001 times to 0.01 times, preferably 0.00001 times, the molar ratio of the component (a) to the norbornene monomer. It is desirable that the ratio be in the range of 2 times to 0.005 times, more preferably 0.00005 times to 0.001 times. If the amount of the component (a) is too small relative to the norbornene-based monomer, the monomer and the catalyst will not easily come into contact with each other, so that the reaction rate will be slow and the efficiency will be poor. If the amount of the component (a) is too large, it becomes difficult to increase the molecular weight of the polymer to a desired molecular weight. That is, the amount of the component (a) with respect to the norbornene monomer is 0.000001 to
By adjusting the ratio to 0.01 times, the polymerization efficiency can be improved and a polymer having a desired molecular weight can be obtained.

Compounds having at least a carbon-carbon double bond in the molecule, such as α-olefins and α, ω-diolefins, or polar allyl compounds such as allyl chloride, allyl acetate, and trimethylallyloxylan With respect to the norbornene monomer in a molar ratio of 0.0005 to 1
The molecular weight of the norbornene-based ring-opened polymer can be adjusted by adding the reaction solution to the reaction solution in an amount of from 0.001 to 0.1 times, more preferably from 0.002 to 0.05 times. it can.

The temperature conditions for the ring-opening polymerization are not particularly limited, but are usually -20 ° C to 100 ° C, preferably 0 ° C.
The temperature is preferably in the range of 100 to 100 ° C, more preferably 10 to 80 ° C, most preferably 10 to 50 ° C. If the temperature is too low, the reaction rate decreases, and if it is too high, control of the reaction becomes difficult, and energy costs increase. That is, the temperature condition is -20 ° C to 100 ° C.
By adjusting to the range, the reaction can be easily controlled, the energy cost can be kept low, and the polymerization can be advanced at an appropriate reaction rate.

The pressure condition of the ring-opening polymerization is not particularly limited, but is usually 0 to 50 kg / cm ² , preferably normal pressure to 1 kg / cm ² .
0 kg / cm ² , more preferably normal pressure to 5 kg / cm
Desirably, the range is ^two .

The ring-opening polymerization is sometimes carried out in an atmosphere of an inert gas such as nitrogen or argon in order to prevent the resulting polymer from being deteriorated by oxidization or colored.

To control the molecular weight of the polymer,
It is preferable to add an α-olefin to the polymerization system. As the α-olefin, 1-hexene,
Examples thereof include 1-octene and 4-vinylcyclohexene. The amount used is selected according to the desired molecular weight. Usually, the weight ratio is 0.0001 to 0.1 times the monomer.

(5) The polymerization proceeds to a molecular weight or conversion according to the purpose of terminating the polymerization ,
When almost no monomer is left, the polymerization is terminated. afterwards,
The polymerization catalyst is deactivated in order to prevent the polymerization reaction solution from gelling, and then the polymerization catalyst is removed as required.

The method for inactivating the polymerization catalyst is not particularly limited. For example, a catalyst deactivator may be added to the polymerization reaction solution.

The catalyst deactivator is not particularly restricted but preferably includes compounds having a hydroxyl group such as water, alcohols, carboxylic acids and phenols.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, 2-ethyl-1-hexanol and 2-propene-1.
-Ol, 1,2-ethanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, pentaerythritol, 2-ethoxyethanol, 2,2-dichloro-1-ethanol ,
Examples thereof include aliphatic, alicyclic, and aromatic mono-, di-, and polyalcohols such as 2-bromo-1-ethanol and 2-phenyl-1-ethanol.

The carboxylic acids include formic acid, acetic acid, trichloroacetic acid, acrylic acid, oxalic acid, maleic acid, propanetricarboxylic acid, tartaric acid, citric acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid,
Examples thereof include aliphatic, alicyclic, and aromatic mono-, di-, and polycarboxylic acids such as phthalic acid and pyromellitic acid.

Examples of phenols include phenol, cresol, xylenol and the like. These catalyst deactivators can be used alone or in combination of two or more.

Of these compounds having a hydroxyl group, water or a water-soluble compound (for example, a compound having 4 or less carbon atoms) is preferable because it has low solubility in a polymer solution and hardly remains in the polymer. . Among them, water or lower alcohols are preferred, but particularly when water and alcohol are used at the same time, the catalyst deactivation efficiency is better than when water is used alone, and when alcohol is used alone. This is preferable because precipitation of the catalyst residue becomes easier as compared with The preferred usage ratio of water to alcohol is 0.1 to 5 parts by weight, especially 0.2 to 2% by weight of alcohols per 1 part by weight of water.

The amount of the deactivator may be an amount sufficient to inactivate the polymerization catalyst, and can be easily determined by experiment. For example, when the catalyst deactivator is a compound having a hydroxyl group, the hydroxyl group-containing compound is calculated based on the total value of the product of the metal oxide and the number of moles of the metal compound promoter component, which is a ring-opening polymerization catalyst. Is used in such a range that the total value of the equivalents of the hydroxyl groups is 0.5 to 10 times.

Further, when a polymerization catalyst is precipitated as a result of adding a catalyst deactivator to the polymer solution, activated clay, talc, diatomaceous earth, bentonite may be used as a coagulation nucleus or coagulation aid for the insoluble component to be precipitated. , Synthetic zeolite, silica gel powder, alumina powder and the like may be added. The range of the addition amount is arbitrary, but preferably about 0.1 to
The range is 10 times.

The catalyst deactivator may be added to the polymer solution at any temperature between -50 ° C. and 100 ° C., preferably between 0 ° C. and 80 ° C. and at any pressure between 0 and 50 kg / cm ² .
Usually, normal pressure to 10 kg / cm ² , preferably normal pressure to 5
The reaction is performed at 0.5 kg / cm ² , and the reaction is performed under the conditions for 0.5 to 10 hours, preferably 1 to 3 hours to inactivate.
Insoluble products can be removed from the polymer solution by filtration or centrifugation. Filtration is carried out, for example, using a pressure filter, usually at a pressure of about 0.5 to ¹⁰ kg / cm ² , using a filter layer or filter paper, and optionally using a filter aid such as diatomaceous earth or perlite. By using it, insoluble products can be removed. Insoluble products can be removed by centrifugation at, for example, 10 to 500 G for about 1 hour.

The molecular weight of the norbornene-based ring-opening polymer is not particularly limited, but polyisoprene (toluene solution in toluene solution) measured by gel permeation chromatography of a cyclohexane solution (toluene solution when the polymer resin does not dissolve). (Polystyrene) in terms of weight average molecular weight, 5,000 to 1,000,000, preferably 6,
000-500,000, more preferably 8,000-
200,000, particularly preferably 10,000 to 10
It is in the range of 0000.

(6) Addition of acid scavenger When a transition metal halide is used as the polymerization catalyst, hydrogen halide is generated by the addition of the polymerization catalyst deactivator, and the hydrogenation catalyst is easily poisoned. It is preferable to add an acid scavenger in advance after the polymerization has progressed to the molecular weight or conversion according to the purpose and before the polymerization catalyst deactivator is added. Further, it is preferable to additionally add an acid scavenger after the addition of the polymerization catalyst deactivator and before the start of the hydrogenation reaction. This is because the conditions such as temperature are different between the polymerization catalyst inactivation reaction and the hydrogenation reaction, so that a suitable acid scavenger may be different.

Examples of the acid scavenger include metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; metal oxides such as calcium oxide and magnesium oxide;
Metals such as aluminum, magnesium, zinc, iron, etc .;
Calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ C
O ₃ .4H ₂ O), salts such as sodium acetate and magnesium acetate; epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, butyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, 4-vinylcyclohexene oxide, and styrene oxide And the like.

Salts having an acid scavenging effect are salts showing alkalinity, and salts of strong acids and weak alkalis are preferred. Among these acid scavengers, as the acid scavenger used before the addition of the polymerization catalyst deactivator, an epoxy compound, a salt, and a combination thereof are preferable because of their excellent acid scavenging effect. As an acid scavenger to be added at the time of hydrogenation,
Salts are preferred. This is because corrosion of the reactor can be effectively suppressed under the temperature conditions during the hydrogenation reaction.

The amount of the acid scavenger used in the present invention is at least 0.5 equivalent to the maximum amount of hydrogen halide which can be generated by hydrolysis of the metathesis polymerization catalyst used, that is, at least 0.5 equivalent, preferably 1 to 100 equivalents, more preferably 2
10 to 10 equivalents. For example, when a metathesis polymerization catalyst composed of tungsten hexachloride and triethylaluminum is used, no hydrogen halide is generated from triethylaluminum, but up to 6 mol of hydrogen chloride can be generated per 1 mol of tungsten hexachloride. In the case of using aluminum powder that becomes trivalent metal ions as the acid scavenger, the amount of the acid scavenger used is 1 mol or more (6 mol０．５3 × 0.5) per mol of tungsten hexachloride.

When the hydrogenation catalyst contains a halide, it is 0.5 equivalent or more, preferably 1 to 10 equivalents to the maximum amount of hydrogen halide that can be generated from the hydrogenation catalyst.
100 equivalents, more preferably 2 to 10 equivalents, are further added.

The addition of the acid scavenger is carried out at -50 ° C to 100 ° C.
C at any temperature, preferably 0 ° C to 80 ° C, 0 to 5
Any pressure of 0 kg / cm ² , usually normal pressure to 10 kg
/ Cm ² , preferably at normal pressure to 5 kg / cm ² . The subsequent addition and reaction of the polymerization catalyst deactivator are the same as described above.

When an acid scavenger is added, the polymerization catalyst is not removed prior to the hydrogenation step, and the effect of maintaining the activity of the hydrogenation catalyst even in the presence of the polymerization catalyst residue is preferable, which is preferable.

Hydrogenation Step In the present invention, the norbornene-based ring-opened polymer is partially or wholly substituted with olefinically unsaturated groups (such as a main chain double bond and an unsaturated ring double bond) in the molecule. To obtain a hydrogenated product of a norbornene-based ring-opened polymer.

By hydrogenating the norbornene-based ring-opening polymer, the heat-induced deterioration resistance of the norbornene-based ring-opening polymer can be improved.
The light deterioration resistance can be further improved.

The hydrogenation rate theoretically ranges from 0 to 100%, assuming that all double bonds of the ring-opened polymer are saturated by hydrogenation as 100%. It can be adjusted arbitrarily by changing the type and amount, hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc., but higher is preferable to improve heat resistance and light resistance, 90% or more, preferably 99% or more, and particularly preferably 99.% or more of the unsaturated bonds in the structure.
It is desirable that 5% or more be hydrogenated.

Incidentally, unsaturated bonds other than the main chain structure may also be
At the same time as unsaturated bonds in the main chain structure
Be added. For aromatic rings, select a hydrogenation catalyst.
This allows the unsaturated bond to remain without selective hydrogenation.
It is also possible to leave it. Unsaturated bond of aromatic ring
And other unsaturated bonds are in the infrared absorption spectrum or ¹H
-Hydrogenation rate measured by nuclear magnetic resonance spectrum
It is possible to

(1) Hydrogenation Catalyst In the present invention, an inorganic carrier-supported transition metal catalyst is particularly used as the hydrogenation catalyst. Transition metal catalyst supported on inorganic carrier,
The desired hydrogenation can be performed in a short time while maintaining high activity, but when used in the hydrogenation step of the norbornene-based ring-opening polymer, it can be recovered and reused.
Further, the catalyst can be easily removed, and the residue of the polymerization catalyst can be adsorbed. As a result, a hydrogenated norbornene-based ring-opening polymer having few impurities can be obtained.

The transition metal catalyst supported on an inorganic carrier is obtained by supporting a transition metal on an inorganic carrier.

The transition metal is not particularly limited.
For example, Cu, Ni, Fe, Pd, Pt, Ru and the like can be exemplified, and among them, it is preferable to use at least one or more selected from Ni, Pd, and Ru.

As the inorganic carrier, diatomaceous earth, magnesia, alumina, synthetic zeolite, silica-zirconia,
Diatomaceous earth-zirconia, pumice, activated carbon, silica gel,
Silica-magnesia and the like can be exemplified, and among them, those using at least one of diatomaceous earth, magnesia, alumina and synthetic zeolite as a carrier are preferable. Further, it is preferable to use one having a specific surface area of 250 cm ² / g or more.

The transition metal catalyst supported on an inorganic carrier has a particle size of 1
It is preferable to use those having a particle size of at least μm (substantially not containing particles having a particle size of less than 1 μm), because separation and recovery to be performed later are easy. If the particle size is too small, for example, it is easy to leak during filtration, and it is difficult to separate and recover even if you try to centrifuge, and if you filter using a filter with a small pore size so as not to leak, it is easy to cause clogging, This is because the working efficiency is deteriorated in any case.
In other words, the use of a material having substantially no particle diameter of less than 1 μm makes it possible to easily and efficiently separate and recover the hydrogenation catalyst.

When the hydrogenation reaction is carried out using a heterogeneous catalyst, the reactivity can be increased by adding a small amount of alcohol such as isopropyl alcohol. In this case, the amount of the alcohol to be added is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight per 100 parts by weight of the reaction solution.

(2) Hydrogenation Reaction The hydrogenation reaction of the norbornene-based ring-opening polymer is carried out by introducing hydrogen into the hydrogenation reaction solution. For example, the hydrogen introduced under stirring is sufficiently weighted. The method of contacting with coalescence is preferred.

The pressure of the introduced hydrogen is usually 1 to 100.
kg / cm ^2, preferably 2~40kg / cm ^2. This is because when it is within this range, the reactivity of the hydrogenation reaction is good and the reaction can be easily controlled.

The reaction temperature is generally 0 to 250 ° C., preferably 50 to 240 ° C., particularly preferably 100 to 23 ° C.
Performed at 0 ° C. This is because, when it is in this range, the hydrogenation rate is appropriate, the decomposition of the polymer or hydrogenated product or gelation hardly occurs, and the energy cost is also in the appropriate range.

The reaction time varies depending on the amount of the hydrogenation catalyst, the H ₂ pressure, the concentration of the polymer and the like.
0 hours, preferably 1 to 5 hours.

The solvent in the hydrogenation is not particularly limited, and a solvent common to the solvent used in the polymerization step can be used. However, in order to efficiently carry out the intended hydrogenation rate, a saturated hydrocarbon solvent is used. It is desirable to use
The amount of the solvent with respect to the ring-opening polymer in the solution used for hydrogenation is preferably 1 to 100 times, more preferably 1.5 to 20 times, particularly preferably 2 to 10 times by weight. When in this range, the viscosity of the polymer solution becomes appropriate,
This is because the reactivity of the hydrogenation reaction becomes good and the hydrogenation can be performed efficiently.

The hydrogenation reaction can be stopped by stopping the supply of hydrogen.

(3) Separation and Recovery of the Hydrogenation Catalyst
Similar to the method for separating and removing the polymerization catalyst, the method is not particularly limited. For example, the polymerization catalyst can be separated and recovered from the solution after the hydrogenation reaction by filtration or centrifugation.

The filtration is performed by using a suitable filter, preferably by applying a pressure difference between the in side and the out side of the reaction solution by pressurization or decompression.

Examples of the filter include a paper filter, a synthetic resin filter, a fiber (cloth) filter, and a metal filter. A cloth filter is preferable because of its strength and reusability.

As a method of applying a differential pressure, a method of pressurizing the inside side, a method of reducing the pressure of the outside side, or a combination thereof can be considered. However, a method of pressurizing the inside side is preferable because of its simple structure.

As a method of pressurizing, a method of pressurizing the reaction solution itself with a pump or the like and sending the solution through a filter, putting the reaction solution in a pressurized vessel, and using a pressurized gas such as compressed air or compressed nitrogen. There is a method of pressing.

[0086] The pressure to be applied is not particularly limited, but is usually 0.1 to 20 kg / kg for efficiency of filtration and simplicity of the apparatus.
cm ² , preferably 0.2 to 15 kg / cm ² , particularly preferably 0.5 to 10 kg / cm ² . When the hydrogenation catalyst to be separated during filtration is one that easily causes clogging of the filter, it is also preferable to previously deposit a filter aid on the in side of the filter.

As filter aids, diatomaceous earth, silica,
Inert and solvent-insoluble powders such as synthetic zeolites, perlites and radiolites are suitable.

The thickness to be deposited is preferably 1 to 20 m
m, particularly preferably 3 to 10 mm, and is preferably filtered with a filter even if the reaction solution passes by making it wet with the same solvent as that used in the reaction solution after hydrogenation. It is preferable that the agent is not suspended.

The centrifugation is carried out, for example, by using a so-called solid-liquid separation centrifuge, preferably by continuously feeding the reaction solution. The conditions are, for example, 1000-9000G
By performing the reaction for about 0.01 to 0.2 hours, the hydrogenation catalyst can be separated and recovered.

From the simplicity of the apparatus and the efficiency of the separation, of the filtration and centrifugation, the filtration method is preferred.

The separated hydrogenation catalyst, if possible,
It may be collected by scraping, or, if necessary, may be washed out of a filter or a centrifugal separator using an appropriate solvent or the like to form a slurry, and then flow and collected. As such a solvent, a solvent that does not inhibit the hydrogenation reaction, particularly the same solvent as that used in the hydrogenation reaction, is preferable. The hydrogenation catalyst recovered by scraping or slurrying often contains a residue of the polymerization catalyst, a filter aid, a solvent, and the like. Therefore, the effective hydrogenation catalyst ( Alternatively, it is preferable to analyze and quantify the (transition metal) component by an appropriate method. In an actual process, if the process becomes steady, it is not always necessary to perform this analysis every time.

The recovered hydrogenation catalyst is washed with a solvent (similar to a slurrying solvent) if necessary, dried if necessary, and used again for hydrogenation. The above operation of separation / recovery is preferably performed in an atmosphere of an inert gas such as nitrogen without bringing the hydrogenation catalyst into contact with oxygen in order to maintain high activity.

In the method of the present invention, after a predetermined amount of a hydrogenated product is produced, a hydrogenation catalyst and a hydrogenated product are once separated and recovered, and the next norbornene-based ring-opening polymer is newly polymerized to form a hydrogenated product. It is suitable for batch type (individual type) production such as addition.

(4) The solution obtained in the step of recovering and drying hydrogenated hydrogen is subjected to removal of volatile components in a closed system so as to prevent foreign matter from entering from the external environment, and pelletized for use. Can be.

As a method for removing the solvent and other volatile components, known methods such as a coagulation method and a direct drying method can be employed.

The coagulation method is a method of precipitating a resin component by mixing a solution with a poor solvent of a norbornene-based ring-opening polymer. The type of the poor solvent varies depending on the type of the norbornene-based ring-opening polymer. Examples thereof include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and i-propyl alcohol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate.

The component containing the resin in the form of powder obtained by coagulation is dried by heating, for example, in a vacuum or in nitrogen or air, and if necessary, extruded from a melt extruder to be used in the form of pellets. Is preferred.

The direct drying method is described in, for example,
No. 425, etc., in which the solution is heated under reduced pressure to remove the solvent. This method can be performed using a known device such as a centrifugal thin film continuous evaporator, a scratch surface heat exchange type continuous reactor dryer, or a high-viscosity reactor. The degree of vacuum and temperature are appropriately selected depending on the device, and are not limited.

The molecular weight of the hydrogenated hydrogenated norbornene ring-opening polymer is not particularly limited, but the polyisoprene (polyisoprene) measured by gel permeation chromatography of a cyclohexane solution (a toluene solution when the polymer resin does not dissolve) is used. 5,000 to 1,000,000, preferably 5,000 to 500,000, and more preferably 8,5 in terms of weight average molecular weight in terms of polystyrene in a toluene solution).
000 to 200,000, particularly preferably 10,000
It is in the range of ~ 100,000.

The glass transition temperature (Tg) of the hydrogenated norbornene ring-opening polymer is usually from 50 ° C. to 250 ° C.
C, preferably in the range of 70C to 220C, more preferably in the range of 80C to 200C.

The hydrogenated norbornene-based ring-opening polymer,
JIS-K- at 280 ° C and 2.16kgf load
The melt flow rate measured by 6719 is usually
1 to 100 g / 10 min. , Preferably 2 to 50 g /
10 min. , More preferably 3 to 40 g / 10 mi.
n. Range.

Additives To the hydrogenated ring-opening polymer obtained by the method of the present invention, other polymers, various compounding agents and fillers may be used alone or in combination of two or more, if necessary.

(1) Other Polymers Other polymers include elastomers such as polybutadiene, polyisoprene, SBS, SIS and SEBS; polystyrene, poly (meth) acrylate, polycarbonate, polyester, polyether, polyamide, polyimide, polysulfone, etc. Resin; and the like. These other polymers can be used alone or in combination of two or more.

(2) Compounding Agent The compounding agent is not particularly limited as long as it is generally used in a thermoplastic resin material. Examples thereof include an antioxidant, an ultraviolet absorber, a light stabilizer, and a near-infrared absorbing agent. Additives, coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, optical brighteners, flame retardants, antiblocking agents, leveling agents, and other compounding agents.

Above all, it is preferable to add an antioxidant. Examples of such an antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

As the phenolic antioxidant, those conventionally known can be used. For example, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-
t-Amyl-6- (1- (3,5-di-t-amyl-2)
-Hydroxyphenyl) ethyl) phenyl acrylate and the like.
Acrylate compounds described in 68643;
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-t-butylphenol),
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenylpropionate) methane [namely, pentaerythrimethyl-tetrakis (3- (3,5 -Di-t
-Butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3- (3-t-
Alkyl-substituted phenolic compounds such as butyl-4-hydroxy-5-methylphenyl) propionate);
-(4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1,3,5-triazine, 2-octylthio -4,6-bis- (3,5-di-
triazine group-containing phenolic compounds such as t-butyl-4-oxyanilino) -1,3,5-triazine;

The phosphorus-based antioxidant and the sulfur-based antioxidant may be used alone, in combination, or in combination with the above-mentioned phenolic antioxidant.

(3) Filler As the organic or inorganic filler, for example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, domite, calcium oxide, carbonate Minerals such as calcium, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos;
Fibers such as glass fiber, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber and polyamide fiber; glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide,
And the like.

These fillers can be added alone or in combination of two or more. The compounding ratio of the filler can be appropriately determined according to each function and purpose of use as long as the object of the present invention is not impaired.

In order to avoid elution from the hydrogenated product of the ring-opened polymer obtained by the production method of the present invention, the larger the molecular weight of these additives and resins, the more preferable. The smaller the number, the more preferable.

Molding The hydrogenated norbornene ring-opening polymer obtained by the method of the present invention is kneaded in a molten state using a twin-screw extruder or the like after production, and
It can be used as pellets. And well-known methods, for example, injection molding, extrusion molding, cast molding,
It can be formed by inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, rolling molding, cutting molding, or the like.

Use The hydrogenated norbornene ring-opening polymer obtained by the method of the present invention is useful in a wide range of fields as various molded articles including optical materials.

For example, an optical disk, an optical lens, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror,
Optical materials such as liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquid medicine containers for injections, ampules, vials, prefilled syringes, bags for infusions,
Liquid, powder or solid medicine containers such as sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, food containers, blood test sampling test tubes, medicine container caps, blood collection tubes, specimen containers, etc. Sampling containers, medical instruments such as syringes, sterile containers such as scalpels, forceps, gauze, contact lenses and other medical instruments, experiment and analysis instruments such as beakers, petri dishes, flasks, test tubes, centrifuge tubes,
Medical optical components such as plastic lenses for medical examination, medical infusion tubes, piping materials such as pipes, joints, valves, etc., medical equipment such as artificial organs such as denture bases, artificial hearts, artificial roots and their parts; tanks, Trays, carriers, containers for processing or transfer such as cases, carrier tapes, protective materials such as separation films, pipes, tubes, valves, pipes such as sipper flow meters, filters, pumps, sampling containers, bottles, ampoule bags Equipment for processing electronic components such as liquid containers, etc .; Covering materials for electric wires and cables; OA equipment such as consumer / industrial electronic equipment, copying machines, computers, printers, etc .; Board, flexible printed circuit board,
Circuit boards such as multilayer printed wiring boards, especially high-frequency circuit boards for satellite communication equipment that require high-frequency characteristics; bases for transparent conductive films such as liquid crystal substrates, optical memories, and surface heating elements such as automobile and aircraft defrosters Material, transistor, I
Sealing materials and parts for electric and conductors such as C, LSI, LED, etc., sealing materials for electric and electronic parts such as motors, capacitors, switches and sensors, body materials such as TVs and video cameras, parabolic antennas, flat antennas, radar Electrical insulating materials such as dome structural members; and the like.

[0114]

EXAMPLES Reference Examples, Examples and Comparative Examples will be given below.
The present invention will be specifically described. In the following Reference Examples, Examples and Comparative Examples, methods for measuring various physical properties are as follows.

(1) Main chain hydrogenation rate and aromatic ring hydrogenation rate (nuclear hydrogenation rate) were measured by ¹ H-NMR.

(2) The glass transition temperature is JIS-K71
21 (DSC method).

(3) The weight average molecular weight is determined by gel permeation chromatography (GPC) using cyclohexane as a solvent in terms of polyisoprene, or
It was measured as a polystyrene conversion value by GPC using toluene as a solvent.

(4) The specific gravity was measured based on JIS-K7112-A method.

(5) The melt flow rate is JIS-K
Based on 6719, it was measured at 280 ° C. under a load of 2.16 kgf.

(6) Transparency was measured using a spectrophotometer (manufactured by JASCO Corporation; U-3
0), the light transmittance (%) was measured while continuously changing the wavelength in the wavelength range of 400 to 800 nm, and the minimum transmittance was measured as the light transmittance. The higher the light transmittance, the better the transparency.

Reference Example 1 (Polymerization) Under a nitrogen atmosphere, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] dodeca-3-
Ethene (MTD) 10 parts by weight was dissolved in cyclohexane 300 parts by weight, and 1-hexene 0.30
Parts by weight were added.

To this solution, 1.1 parts by weight of a 10% by weight solution of triisobutylaluminum in cyclohexane, and
A mixture of 0.043 parts by weight of isobutyl alcohol was added.

While maintaining this solution at 40 ° C., the MTD
90 parts by weight and 11 parts by weight of a 0.6% by weight solution of tungsten hexachloride in cyclohexane were continuously added over 2 hours to carry out polymerization. 0.067 parts by weight of butyl glycidyl ether and 0.20 parts by weight of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst.

The polymerization conversion was 100%, and the weight average molecular weight of the polymer measured by GPC (cyclohexane solvent) was 16,000.

Reference Example 2 (Polymerization) Tricyclo [4.3.0.1] was added under a nitrogen atmosphere.
^2,5 ] dec-3-ene (DCP) 8.5 parts by weight and tetracyclo [4.4.0.1 ^2,5 .
1.5 parts by weight of [ ^17,10 ] dodec-3-ene (TCD) were dissolved in 300 parts by weight of cyclohexane, and 0.37 parts by weight of 1-hexene was added as a molecular weight regulator.

To this solution, 1.5 parts by weight of a 10% by weight solution of triisobutylaluminum in cyclohexane, and
A mixture of 0.055 parts by weight of isobutyl alcohol was added.

While maintaining this solution at 40 ° C., DCP7
A mixture of 6.5 parts by weight and 13.5 parts by weight of TCD and 15 parts by weight of a 0.6% by weight solution of tungsten hexachloride in cyclohexane were continuously added over 2 hours to carry out polymerization. 0.048 parts by weight of butylene oxide and 0.26 parts by weight of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst.

The polymerization conversion was 100%, and the weight average molecular weight of the polymer measured by GPC (cyclohexane solvent) was 15,000.

Example 1 (First hydrogenation) Polymerization reaction solution 1 obtained in Reference Example 1
To 00 parts by weight, 0.24 part by weight of hydrotalcite powder (manufactured by Kyowa Chemical Industry Co., Ltd., synthetic hydrotalcite) and a nickel catalyst supported on diatomaceous earth (manufactured by Nissan Gardler Co .;
G-96D, nickel loading 58% by weight) and 1.2 parts by weight of cyclohexane, and 10 parts by weight of cyclohexane were added thereto, and the mixture was placed in a pressure-resistant reactor at 170 ° C. and a hydrogen pressure of 45 kgf / cm ² for 2 hours.
A hydrogenation reaction was performed.

The solution was filtered with a pressure filter (leaf filter, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.) equipped with a filter cloth made of polypropylene to separate the catalyst. The obtained reaction solution containing the hydrogenated polymer was poured into 400 parts by weight of isopropyl alcohol with stirring to precipitate the hydrogenated product, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, it was dried at 100 ° C. for 24 hours in a vacuum dryer reduced to 1 mmHg or less to obtain 23 parts by weight of a hydrogenated norbornene ring-opening polymer.

The weight average molecular weight of the obtained hydrogenated product is as follows:
33,300 (polyisoprene exchange in cyclohexane
Calculation), the glass transition temperature is 150 ° C, and the transmittance is 98%.
, ¹As a result of H-NMR, the ring opening of the norbornene monomer
It is a hydrogenated product of a polymer, and the hydrogenation rate is 99.9% or less.
Was on.

The diatomaceous earth-supported nickel catalyst containing the polymerization catalyst separated by filtration was discharged from the filter under nitrogen and introduced into 10 parts by weight of cyclohexane.
The solid content of the cyclohexane slurry containing the recovered catalyst was 1.
The content was 42 parts by weight, and the Ni content in the solid content by an atomic absorption method was 47% by weight. From this, it was found that the recovered amount of the hydrogenation catalyst was 1.15 parts by weight (recovery rate 96%).

(Second Hydrogenation) A cyclohexane slurry containing 1.15 parts by weight of the recovered diatomaceous earth-supported nickel catalyst was added to 100 parts by weight of the next polymerization reaction solution (Reference Example 1), and hydrotalcite was newly added. 0.12 parts by weight of the powder and 0.05 parts by weight of the same diatomaceous earth-supported nickel catalyst were added, and hydrogenation was carried out in the same manner under the same conditions.
The hydrogenated product and the catalyst were separated in the same manner as in the first test.

The weight average molecular weight of the obtained hydrogenated product was:
33,300 (polyisoprene exchange in cyclohexane
Calculation), the glass transition temperature is 150 ° C, and the transmittance is 98%.
, ¹As a result of H-NMR, the hydrogenation rate was 99.9% or more.
Met.

The solid content of the cyclohexane slurry containing the recovered catalyst was 1.57 parts by weight, and the recovered amount of the hydrogenation catalyst was 1.16 parts by weight (recovered) from the Ni content of 43% by weight in the solid content by the atomic absorption method. 97%).

(Third Hydrogenation) A cyclohexane slurry containing 1.16 parts by weight of the recovered diatomaceous earth-supported nickel catalyst was added to 100 parts by weight of the next polymerization reaction solution (Reference Example 1), and hydrotalcite was newly added. 0.12 parts by weight of the powder and 0.04 parts by weight of the same diatomaceous earth-supported nickel catalyst were added, and hydrogenation was carried out in the same manner under the same conditions.
The hydrogenated product and the catalyst were separated in the same manner as in the first test.

The weight average molecular weight of the obtained hydrogenated product was:
33,300 (polyisoprene exchange in cyclohexane
Calculation), the glass transition temperature is 150 ° C, and the transmittance is 98%.
, ¹As a result of H-NMR, the hydrogenation rate was 99.9% or more.
Met.

The solid content of the cyclohexane slurry containing the recovered catalyst was 1.69 parts by weight, and the recovered amount of the hydrogenation catalyst was 1.16 parts by weight (recovered from the Ni content of 40% by weight in the solid content by the atomic absorption method). 97%).

(Repeated hydrogenation) A cyclohexane slurry containing a diatomaceous earth-supported nickel catalyst recovered in the same manner as in the second and third times was added to 100 parts by weight of the following polymerization reaction solution (Reference Example 1), and hydrotalcite was newly added. 0.12 parts by weight of the powder and the same diatomaceous earth-supported nickel catalyst were added so that the hydrogenation catalyst became 1.2 parts by weight, and hydrogenation was carried out under the same conditions and in the same manner.

When the hydrogenation was repeated 10 times, the hydrogenation reaction could be carried out to the desired hydrogenation rate in 2 hours in any case, and the hydrogenation rate of each of the obtained hydrogenated products was 99. 9% or more. In this example, the amount of the polymerization catalyst used was 5 parts by weight with respect to 100 parts by weight of the polymer per one hydrogenation reaction, but was repeated 10 times by adding only the shortage of the unrecovered hydrogenation catalyst. Because of its use, the consumption of the hydrogenation catalyst per 100 parts by weight of the polymer was 0.52 parts by weight.

Example 2 An alumina-supported palladium catalyst (manufactured by Nissan Gardler Co., G-58B, palladium support rate 0.05
% By weight) except that hydrogenation was performed in the same manner as in Example 1.
When the recovery of the hydrogenation catalyst and the re-hydrogenation were repeated five times, each hydrogenation reaction was possible to a desired hydrogenation rate in 1.5 hours, and the hydrogenation reaction could be performed in a short time. . In addition, a hydrogenated product having a hydrogenation ratio of 99.9% or more was obtained, and hydrogenation could be performed without any problem even if the hydrogenation catalyst used once was repeatedly used.

Example 3 Hydrogenation, recovery of a hydrogenation catalyst and re-hydrogenation were repeated 10 times in the same manner as in Example 1 except that the polymer of Reference Example 2 was used as the polymer. The addition reaction is
The desired hydrogenation rate was possible in 2 hours, and the hydrogenation reaction was able to be performed in a short time. The hydrogenation rate is 9
A hydrogenated product of 9.9% or more was obtained, and hydrogenation could be performed without any problem even if the hydrogenation catalyst used once was repeatedly used. The Tg of the hydrogenated polymer is 10
7 ° C.

Examples 4 and 5 Prior to hydrogenation in Examples 1 and 3, the residue of the polymerization catalyst in the polymerization reaction solution was removed in advance. That is, 1 part by weight of water was added to 100 parts by weight of the polymer solution, the mixture was treated at 70 ° C. for 2 hours, and 2 parts by weight of magnesium sulfate was added and cooled to 30 ° C. The solution was removed by filtration using the pressure filter used in Example 1.

Then, hydrogenation was carried out in the same manner as in Example 1.
When the recovery of the hydrogenation catalyst and the re-hydrogenation were repeated 10 times, each hydrogenation reaction was possible to a desired hydrogenation rate in 1.5 hours, and the hydrogenation reaction was able to be performed in a short time. . In addition, a hydrogenated product having a hydrogenation ratio of 99.9% or more was obtained, and hydrogenation could be performed without any problem even if the hydrogenation catalyst used once was repeatedly used.

Examples 6 and 7 Each time hydrogenation is repeated, 1.2 parts by weight of a hydrogenation catalyst to be recovered and reused with respect to 100 parts by weight of a polymer solution without newly adding a hydrogenation catalyst. The hydrogenation was repeated 10 times in the same manner as in Examples 4 and 5 except that the hydrogenation was performed as described above, and each hydrogenation reaction was able to reach the desired hydrogenation rate in 1.5 hours. The hydrogenation reaction could be performed in a short time. The hydrogenation rate was 99.9.
% Or more of the hydrogenated product was obtained. Even if the hydrogenation catalyst used once was repeatedly used, hydrogenation could be performed without any problem.

Example 8 A polymer solution was prepared in the same manner as in Reference Example 2 except that butylene oxide was not added after the polymerization.

(First Hydrogenation) This polymer solution 1
To 00 parts by weight, 2.4 parts by weight of the same diatomaceous earth-supported nickel catalyst as in Example 1 and 10 parts by weight of cyclohexane were added,
170 ° C., hydrogen pressure 45 kgf / cm as in Example 1.
^A hydrogenation reaction was carried out at ² . The reaction time was one hour, and the hydrogenation was completed. The hydrogenated product and the catalyst were separated in the same manner as in Example 1. The hydrogenation rate of the obtained hydrogenated product was 99.
9% or more. The recovered amount of the hydrogenation catalyst was 2.30 parts by weight (recovery rate 96%).

(Second hydrogenation) A cyclohexane slurry containing 2.30 parts by weight of the recovered diatomaceous earth-supported nickel catalyst was mixed with the following polymerization reaction solution (prepared in this example).
It was added to 96 parts by weight, and hydrogenation was performed under the same conditions as the first time.

The second hydrogenation reaction did not end in one hour (hydrogenation rate: 98.4%), but when the reaction was completed in two hours, the hydrogenation rate of the hydrogenated product was 99.
Above 9%, the desired hydrogenation rate was achieved.

Comparative Example 1 The same nickel catalyst as in Example 1 was added to 100 parts by weight of the polymerization reaction solution of Reference Example 1, except that 0.52 parts by weight of the hydrogenation catalyst used in Example 1 was added. A norbornene-based ring-opening polymer hydrogenated product was produced in the same manner as in Example 1. After 2 hours, the hydrogenation rate of the obtained hydrogenated product was 23%.

Example 9 (First hydrogenation) The same procedure was carried out except that the polymer solution prepared in Example 8 was used, and 1.2 parts by weight of the same diatomaceous earth-supported nickel catalyst was used in 100 parts by weight of the polymer solution. A hydrogenation reaction was carried out in the same manner as in Example 8. The hydrogenation rate in 2 hours during the hydrogenation reaction was 98.6%, and the reaction was completed in 4 hours. The hydrogenated product and the catalyst were separated in the same manner as in Example 8. The hydrogenation rate of the obtained hydrogenated product was 99.9% or more. The recovered amount of the hydrogenation catalyst was 1.15 parts by weight (recovery rate: 96%).

(Second hydrogenation) The cyclohexane slurry containing 1.15 parts by weight of the recovered diatomaceous earth-supported nickel catalyst was mixed with the following polymerization reaction solution (prepared in Example 8).
It was added to 96 parts by weight, and hydrogenation was performed under the same conditions as the first time. When the reaction was completed in 4 hours, the hydrogenation rate was 93.6%.

Table 1 summarizes the results of Examples 1 to 9 and Comparative Example 1.

[0154]

[Table 1]

[0155]

According to the method of the present invention, a hydrogenation catalyst can be repeatedly used, and a process for producing a hydrogenated norbornene-based ring-opening polymer having low waste and excellent productivity can be performed.

When a large amount of hydrogenation catalyst is used for hydrogenation in combination with an additive for capturing poisoning substances of the hydrogenation catalyst, the activity of the entire catalyst after hydrogenation is not affected, and Can be used for the next hydrogenation treatment without performing an activation treatment, and a hydrogenated norbornene-based ring-opening polymer having a high hydrogenation rate can be industrially produced with high productivity.

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Claims (4)

[Claims] 1. A norbornene-based ring-opening polymer is obtained by subjecting a norbornene-based monomer to ring-opening polymerization using a polymerization catalyst to form a norbornene-based ring-opened polymer, and then hydrogenating using a hydrogenation catalyst. In the method for producing a product, a hydrogenation catalyst having a transition metal supported on an inorganic carrier is used as the hydrogenation catalyst, and the hydrogenation reaction solution containing the norbornene-based ring-opening polymer hydrogenated product is used as the hydrogenation catalyst. A method for producing a hydrogenated norbornene-based ring-opening polymer, comprising separating and recovering a solid content containing an added catalyst, and using the recovered solid content containing a hydrogenation catalyst in the next hydrogenation treatment. . 2. The method for producing a hydrogenated norbornene ring-opening polymer according to claim 1, further comprising a step of adding an acid scavenger after completion of the polymerization reaction and before the hydrogenation reaction. . 3. The hydrogenated norbornene ring-opening polymer according to claim 1, further comprising a step of separating and removing the polymerization catalyst after the completion of the polymerization reaction and before the hydrogenation reaction. Production method. 4. The norbornene-based system according to claim 1, wherein a new hydrogenation catalyst is added when the recovered solid content containing the hydrogenation catalyst is reused. A method for producing a hydrogenated ring-opening polymer.