JP2002249515A - Hydrogenation method for cyclic-structure-containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenation method for a cyclic-structure-containing polymer whereby a high hydrogenation degree almost equal to that attained by using a conventional fluidized catalyst can be maintained, the removal of a catalyst used is not necessary, the amount of a side reaction product is small, and a hydrogenated polymer having good mechanical strengths, heat resistance, processibility, and clarity can be obtained. SOLUTION: A cyclic-structure-containing polymer having a wt. average mol.wt. (in terms of polystyrene, by gel permeation chromatography) of 10,000-1,000,000 is hydrogenated by causing a solution containing the polymer and hydrogen to pass at a linear velocity of 0.01-1.5 cm/sec through a fixed bed packed with a hydrogenation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydrogenating a polymer having a ring structure, and more particularly, to a method for hydrogenating a polymer having a ring structure by a fixed catalyst bed reaction method.

[0002]

2. Description of the Related Art Hydrogenation of a polymer containing a ring structure such as a thermoplastic norbornene-based polymer is carried out by using a slurry reactor.
Method for fluidizing catalyst particles by blowing hydrogen into a solution of a thermoplastic norbornene-based polymer in which a particulate hydrogenation catalyst is suspended, or by mechanically stirring or without blowing and blowing with hydrogen Has been done by This hydrogenation method using a fluidized catalyst has the advantage that the reaction rate per unit volume of the reactor is high and a high hydrogenation rate can be realized. On the other hand, (1) it takes a long time for the hydrogenation rate to reach a target value. Time response or multi-stage
(2) There is a problem that the removal of the catalyst particles by filtration is not easy and the cost is increased, and (3) a side reaction is likely to occur when the amount of the liquid with respect to the catalyst is large.

Hitherto, it has been known that a low-molecular-weight petroleum resin having high fluidity is hydrogenated using a fixed-bed reactor. The hydrogenation reaction using such a fixed-bed reactor is an effective method that can solve the above problems (2) and (3). JP-A-7-228873 and JP-A-10-151350 also disclose that a fixed-bed reactor may be used for hydrogenation of a thermoplastic norbornene-based polymer or a styrene-butadiene copolymer. However, when the molecular weight of the polymer is large and the fluidity of the solution is low, a high hydrogenation rate cannot always be achieved.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the need for removing the used hydrogenation catalyst, to reduce the amount of by-products during hydrogenation, and to obtain a good and balanced mechanical strength. A hydrogenated ring structure-containing polymer having heat resistance, processability, and transparency can be obtained, and a high hydrogenation rate that is almost comparable to that of a conventional hydrogenation method using a fluidized catalyst can be achieved. An object of the present invention is to provide a method for hydrogenating a structure-containing polymer.

[0005]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors filled a solution containing a polymer having a ring structure having a specific range of molecular weight and hydrogen with a hydrogenation catalyst. Hydrogenation by passing through a fixed bed at a specific range of linear velocity eliminates the need to remove the used catalyst, reduces the amount of by-products during hydrogenation, and provides a well-balanced mechanical A hydrogenated ring structure-containing polymer having strength, heat resistance, processability, and transparency can be obtained, and a high hydrogenation rate that is almost comparable to a conventional hydrogenation method using a fluidized catalyst can be achieved. Was found.

Thus, according to the present invention, the weight average molecular weight measured by gel permeation chromatography is from 10,000 to 1,000,000 in terms of polystyrene.
A solution containing the ring structure-containing polymer and hydrogen, which is 0, is applied to a fixed bed filled with a hydrogenation catalyst at a linear velocity of 0.01 to 1.5 cm.
/ Sec, and a method for hydrogenating a polymer containing a ring structure is provided.

[0007]

DETAILED DESCRIPTION OF THE INVENTION Ring Structure-Containing Polymers Ring structure-containing polymers which are hydrogenated in accordance with the present invention include carbon-containing polymers which are hydrogenated in and / or outside the ring structure.
A hydrocarbon polymer having a carbon-unsaturated bond, and when the polymer containing a ring structure having an unsaturated bond is hydrogenated, substantially all or a part of the unsaturated bond is hydrogenated to form an unsaturated bond. Is obtained. The ring structure of the hydrogenated ring structure-containing polymer may be present in any of the main chain and / or the side chain, but the mechanical strength, heat resistance, transparency, etc. of the obtained hydrogenated ring structure-containing polymer are obtained. In view of the above, a polymer containing a ring structure in the main chain is preferable.

The ring structure of the polymer containing a ring structure to be hydrogenated includes a cycloalkane structure, a cycloalkene structure, an aromatic ring structure, and the like. From the viewpoints of mechanical strength, heat resistance, transparency and the like, it is preferable that the compound has a cycloalkane structure.
The number of carbon atoms constituting the ring structure is usually 4 to 30, from the viewpoint of mechanical strength, heat resistance, transparency, and moldability.
It is preferably in the range of 5 to 20, more preferably 5 to 15.

The proportion of the repeating unit having a ring structure in the polymer containing a ring structure to be hydrogenated is appropriately selected according to the purpose of use, but is usually 50% by weight or more, and is preferably from the viewpoint of transparency and heat resistance. Therefore, it is preferably at least 70% by weight, more preferably at least 90% by weight. If the proportion of the repeating unit having a ring structure in the ring structure-containing polymer is excessively small, the transparency and heat resistance of the hydrogenated ring structure-containing polymer decrease. The remainder other than the repeating unit having a ring structure in the ring structure-containing polymer is not particularly limited, and is appropriately selected depending on the purpose of use.

[0010] Examples of the polymer containing a ring structure to be hydrogenated include:
For example, (1) a norbornene-based polymer which is a polymer of a norbornene-based monomer such as dicyclopentadiene or tetracyclododecene; and (2) a monocyclic cyclic olefin-based monomer such as cyclohexene or cyclopentene. (3) a cyclic conjugated diene-based polymer which is an addition polymer of a cyclic conjugated diene-based monomer such as cyclopentadiene and cyclohexadiene;
(4) the weight of a vinyl alicyclic hydrocarbon-based polymer which is a polymer of a vinyl alicyclic hydrocarbon-based monomer such as vinylcyclohexene; and (5) the weight of a vinyl-aromatic hydrocarbon-based monomer such as styrene. Examples thereof include a vinyl aromatic hydrocarbon-based polymer which is a coalesced polymer. Among these, a norbornene-based polymer, a vinyl alicyclic hydrocarbon-based polymer, a vinyl aromatic hydrocarbon-based polymer and a cyclic conjugated diene-based polymer are preferable, and in particular, the norbornene-based polymer has heat resistance and mechanical strength. , From the viewpoint of transparency.

The above (1) norbornene-based monomer,
(2) Monocyclic cyclic olefin monomer, (3) cyclic conjugated diene monomer, (4) vinyl alicyclic hydrocarbon monomer, and (5) vinyl aromatic hydrocarbon monomer The monomers giving a ring structure-containing polymer such as can be polymerized alone or in combination of two or more. Such copolymers include block copolymers, random copolymers, and the like. In the block copolymer,
Examples include diblock, triblock or higher multiblock copolymers, gradient block copolymers, and the like, but are not particularly limited.

(1) Norbornene-based polymer The norbornene-based polymer is disclosed in, for example, JP-A-3-1488.
No. 2 and JP-A-3-122137, specifically, ring-opening polymers of norbornene-based monomers, addition polymers of norbornene-based monomers, and norbornene-based polymers. Addition copolymers of other monomers copolymerizable with the system monomer are included.

Specific examples of the norbornene-based monomer include:
Bicyclo [2.2.1] -hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] -hept-2-ene, 5,5-dimethyl-bicyclo [2. 2.1]-
Hept-2-ene, 5-ethyl-bicyclo [2.2.1]-
Hept-2-ene, 5-butyl-bicyclo [2.2.1]-
Hept-2-ene, 5-hexyl-bicyclo [2.2.1]
-Hept-2-ene, 5-octyl-bicyclo [2.2.
1] -Hept-2-ene, 5-octadecyl-bicyclo
[2.2.1] -Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hept-2-ene, 5-methylidene-
Bicyclo [2.2.1] -hept-2-ene, 5-vinyl-
Bicyclo [2.2.1] -hept-2-ene, 5-propenyl-bicyclo [2.2.1] -hept-2-ene, 5-methoxy-carbonyl-bicyclo [2.2.1] -hept -2-
Ene, 5-cyano-bicyclo [2.2.1] -hept-2-
Ene, 5-methyl-5-methoxycarbonyl-bicyclo
[2.2.1] -Hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] -hept- 2-ene, 5-methyl-5-ethoxycarbonyl-bicyclo
[2.2.1] -Hept-2-ene, bicyclo [2.2.1]-
Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] -hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] -hept-2-ene-
5,6-dicarboxylic anhydride, 5-hydroxymethyl-
Bicyclo [2.2.1] -hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] -hept-
2-ene, 5-hydroxy-i-propyl-bicyclo
[2.2.1] -Hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] -hept-2-ene, bicyclo
[2.2.1] -Hept-2-ene-5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexyl-bicyclo [2.
2.1] -Hept-2-ene, 5-cyclohexenyl-bicyclo [2.2.1] -hept-2-ene, 5-phenyl-
Bicyclo [2.2.1] -hept-2-ene,

[0014] tricyclo [4.3.1 ^2,5 .0 ^1,6] - dec -
3,7-diene (common name dicyclopentadiene), tricyclo [4.3.1 ^2,5 .0 ^1,6] - dec-3-ene, tricyclo [4.4.1 ^2,5 .0 ^{1, 6]} - undec-3,7-diene or tricyclo [4.4.1 ^2,5 .0 ^1,6] - undec -3,
8- diene, tricyclo [4.4.1 ^2,5 .0 ^1,6] - undec-3-ene, tetracyclo [7.4.1 ^10,13 .0 ^1,9 .0
^2,7 ] -Trideca-2,4,6-11 -tetraene (also known as 1,
4-methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo [8.4.1 ^11,14 .0 ^1,10 .0 ^3,8] - tetradec -3,5,7,12-11- Tetraene (also known as 1,
Norbornene monomers having no norbornane ring, such as 4-methano-1,4,4a, 5,10,10a-hexahydroanthracene);

Tetracyclo [4.4.1]^2,5.1^7,10.0]-
Dodeca-3-ene (also known as tetracyclododecene), 8-
Methyl-tetracyclo [[4.4.1^2,5.1^7,10.0] -do
Dec-3-ene, 8-methyl-tetracyclo [4.4.1
^2,5.1^7,10.0] -Dodeca-3-ene, 8-ethyl-tet
Lacyclo [4.4.1]^2,5.1^7,10.0] -Dodeka-3-e
, 8-methylidene-tetracyclo [4.4.1^2,5.1
^7,100] -Dodeca-3-ene, 8-ethylidene-tetra
Cyclo [4.4.1^2,5.1^7,100] -dodec-3-ene,
8-vinyl-tetracyclo [4.4.1]^2,5.1^7,10.0]-
Dodeca-3-ene, 8-propenyl-tetracyclo [4.
4.1^2,5.1^7,10.0] -Dodeca-3-ene, 8-methoxy
Cycarbonyl-tetracyclo [4.4.1]^2,5.1^7,10.0]
-Dodeca-3-ene, 8-methyl-8-methoxycarbo
Nyl-tetracyclo [4.4.1^2,5.1^{7 ,Ten}.0] -Dodeka
-3-ene, 8-hydroxymethyl-tetracyclo [4.
4.1^{2, Five}.1^7,10.0] -Dodeca-3-ene, 8-carbo
Xy-tetracyclo [4.4.1^2,5.1^7,10.0] -Dodeka
-3-ene, 8-cyclopentyl-tetracyclo [4.
4.1 ^2,5.1^7,10.0] -Dodeca-3-ene, 8-cyclo
Hexyl-tetracyclo [4.4.1]^2,5.1^7,10.0] -do
Dec-3-ene, 8-cyclohexenyl-tetracyclo
[4.4.1^2,5.1^7,10.0] -Dodeka-3-ene, 8-fu
Phenyl-tetracyclo [4.4.1^2,5.1^7,10.0] -Dode
Car-3-ene, pentacyclo [6.5.1^1,8.1^3,6.
0 ^2,7.0^9,13] -Pentadeca-3,10-diene, penta
Cyclo [7.4.1^3,6.1^{Ten, 13}.0^1,9.0^2,7] -Pentade
A compound having a norbornane ring such as -4,11-diene
And rubornene-based monomers.

The ring-opening polymer of the norbornene-based monomer is formed from a metal halide such as ruthenium, rhodium, palladium, osmium, iridium or platinum, a nitrate or an acetylacetone compound as a ring-opening polymerization catalyst, and a reducing agent. Or a catalyst system comprising a metal halide or acetylacetone compound such as titanium, vanadium, zirconium, nickel, tungsten, molybdenum, and an organoaluminum compound, in a solvent or without a solvent, usually- 50 ° C-1
It can be obtained by a method in which ring-opening polymerization is performed at a polymerization temperature of 00 ° C. and a polymerization pressure of 0 to 50 kg / cm ² . The addition copolymer of a norbornene-based monomer, for example, a monomer component in a solvent or without solvent, titanium, nickel, palladium, zirconium and a metal selected from vanadium or a compound thereof and an organic aluminum compound and In the presence of a catalyst system consisting of the following, it can be usually obtained by a method of copolymerizing at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 50 kg / cm ² .

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cycloolefin polymer include monocyclic cycloolefin polymers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. An addition polymer of a cyclic olefin-based monomer can be used. (3) Cyclic conjugated diene-based polymer As the cyclic conjugated diene-based polymer, for example,
Polymers obtained by subjecting a cyclic conjugated diene-based monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization disclosed in JP-A-136057 and JP-A-7-258318.

(4) Vinyl alicyclic hydrocarbon-based polymer Examples of the vinyl alicyclic hydrocarbon-based polymer include vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. A polymer of an alicyclic hydrocarbon-based monomer is exemplified. A copolymer of a vinyl alicyclic hydrocarbon-based monomer and another copolymerizable monomer may be used, and such a copolymer includes a block copolymer and a random copolymer. Is included. The block copolymer includes, but is not particularly limited to, diblock, triblock or higher multiblock copolymers, and gradient block copolymers.

(5) Vinyl Aromatic Hydrocarbon Polymer Examples of the vinyl aromatic hydrocarbon polymer include, for example, JP-A-63-43910 and JP-A-64-1706.
And styrene, α-methylstyrene and other vinyl aromatic hydrocarbon monomers. A copolymer of a vinyl aromatic hydrocarbon-based monomer and another copolymerizable monomer may be used, and such a copolymer includes a block copolymer and a random copolymer. included. The block copolymer includes, but is not particularly limited to, diblock, triblock or higher multiblock copolymers, and gradient block copolymers.

The ring structure-containing polymer to be hydrogenated in the present invention is a copolymer of the above-mentioned monomer giving the ring structure-containing polymer and the monomer giving the polymer having substantially no ring structure. It may be a polymer. Examples of a monomer that gives a polymer having substantially no ring structure include, for example, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene , Cyclooctene, 3
a, 5,6,7a-tetrahydro-4,7-methano-1H-
Ring-opening polymerized cycloolefins such as indene; ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 3-methyl-1-butene, 3-methyl-1-
Pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
Α-olefin having 2 to 20 carbon atoms such as 1-eicosene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
Conjugated dienes such as 3-pendiene, 1,3-hexadiene; and 1,4-hexadiene, 4-methyl-1,4
-Hexadiene, 5-methyl-1,4-hexadiene,
Non-conjugated dienes such as 1,7-octadiene; and the like. The monomers to be copolymerized with the monomers giving the ring structure-containing polymer can be used alone or in combination of two or more. The proportion of the monomer that is copolymerized with the monomer that gives the polymer having a ring structure is preferably 30% by weight or less based on the total amount of the monomers.

The molecular weight of the polymer having a ring structure to be hydrogenated in the present invention is such that the weight average molecular weight measured by gel permeation chromatography is 10,000 in terms of polystyrene.
0 to 1,000,000. If the molecular weight is too small, the hydrogenation reaction proceeds irrespective of the linear velocity of the polymer solution, making it difficult to control the linear velocity, making it difficult to carry out the hydrogenation reaction efficiently. Conversely, if the molecular weight is too large, the viscosity of the polymer solution is too high, and it is difficult to pass through the catalyst layer. Preferred molecular weights are from 12,000 to 500,000, with 15,000 to 300,000 being particularly preferred. Also, from the viewpoint of the properties of the hydrogenated polymer, those having a molecular weight in this range are suitable because mechanical strength and moldability are highly balanced.

The molecular weight distribution is usually 5 or less, preferably 4 or less, more preferably 3 or less, as a ratio of weight average molecular weight / number average molecular weight (Mw / Mn).
Glass transition temperature (T of the ring structure-containing polymer to be hydrogenated
g) may be appropriately selected depending on the purpose of use, but is usually 50 to 300 ° C, preferably 60 to 280 ° C, more preferably 70 to 250 ° C.

When the ring structure-containing polymer to be hydrogenated has a repeating unit having an aromatic ring, the side chain aromatic ring structure is formed by the hydrogenation reaction of the carbon-carbon double bond in the main chain structure. Although it can be left, it may be completely hydrogenated including the aromatic ring structure of the side chain. Note that ¹ H-N
According to the analysis by MR, the carbon-carbon double bond in the main chain structure can be recognized and distinguished from the unsaturated bond in the aromatic ring structure.

In the hydrogenation reaction of the present invention, it is important to use a polymer having a ring structure having a specific range of molecular weight and to pass the reaction components through a fixed bed filled with a hydrogenation catalyst at a specific range of linear velocity. However, as other hydrogenation conditions and hydrogenation catalysts, commonly used hydrogenation conditions and hydrogenation catalysts can be employed. As the hydrogenation catalyst, a heterogeneous catalyst is used. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are excellent in production efficiency such as being easily removed.

Examples of the heterogeneous catalyst include a particulate catalyst in which a metal selected from the group consisting of nickel, ruthenium, rhenium, platinum, palladium and rhodium is supported on a carrier. The carrier is not particularly limited, and a carrier such as alumina or diatomaceous earth which has been conventionally used for supporting a hydrogenation catalyst metal can be used. The catalyst comprising the hydrogenation catalyst metal and the carrier is preferably in the form of particles having an average particle size of 0.5 to 10 mm. When the average particle size is too small, the reaction in the fixed bed becomes difficult. Conversely, if the average particle size is too large, the reaction rate per unit volume of the reactor will be low, and the hydrogenation efficiency will be poor. The shape of the catalyst particles may be any of a sphere, a column, a disk (tablet), a Raschig ring, a cylinder and the like.

In the hydrogenation method of the present invention, a solution containing a ring structure-containing polymer having the above specific molecular weight and hydrogen is brought into contact with a fixed catalyst layer to form a carbon-carbon double bond in the polymer. Hydrogenate. Although substantially all of the ring structure-containing polymer guided to the fixed catalyst layer is dissolved in the solution, the entire amount of hydrogen does not necessarily have to be dissolved in the solution. When the solution containing the ring structure and the solution containing hydrogen are brought into contact with the fixed catalyst layer, the linear velocity at which the solution containing the polymer and hydrogen passes through the catalyst layer is 0.01 cm / sec or more.
1.5 cm / sec. If the linear velocity is too low, the hydrogenation rate will decrease. Conversely, if the linear velocity is too high, the pressure loss will be large, and the catalyst will be broken or a powerful pump will be required. Also, from the viewpoint of the properties of the hydrogenated polymer, when the linear velocity is within this range, a hydrogenated polymer having a good balance between mechanical strength and moldability can be produced industrially advantageously. To perform the hydrogenation reaction more efficiently, the linear velocity is 0.05 c
m / sec to 1.4 cm / sec is preferred, and 0.10 c
m / sec to 1.3 cm / sec is more preferable, and 0.2 / m
0 cm / sec to 1.2 cm / sec is particularly preferred.

The longer the time for which the solution containing the ring structure-containing polymer and hydrogen is brought into contact with the catalyst layer, the more the hydrogenation reaction proceeds. In the present invention, when the contact time is fixed, hydrogenation is most efficiently performed when the catalyst is passed through the catalyst layer within the above-described range of the linear velocity. As a method of changing the linear velocity while keeping the contact time constant, it can be adjusted by the inner diameter and length of the fixed bed catalyst layer.

The hydrogenation method of the present invention can be carried out either in a continuous system or in a batch system. However, it is possible to easily control the linear velocity when a solution containing a polymer containing a ring structure and hydrogen passes through a catalyst layer. To the continuous type. The hydrogenation method is performed using a fixed-bed reactor, but the fixed-bed reactor may itself constitute a fixed bed filled with a hydrogenation catalyst, or may be packed with a hydrogenation catalyst. The fixed layer which was set may be inserted. Examples of the fixed bed reactor used in the hydrogenation method of the present invention include (a) a packed tower or a tray column reactor, (b) a fixed catalyst reactor, and (c) a wire mesh or thin-layer catalyst reactor. And the like.

In the packed column or tray column reactor (a),
The solution containing the ring structure-containing polymer and hydrogen flows through the column filled with the catalyst particles. For example, in the packed tower or tray column type reactor 4 shown in FIG. 1, a solution containing a ring structure-containing polymer and hydrogen is supplied to the top end of the reactor, and a plurality of trays 5 loaded with a catalyst are charged. Each of them flows down sequentially. The fixed catalyst reactor (b) can be divided into an isothermal type, a heat insulating type, a multi-stage heat insulating type, a self heat exchange type, an external heat exchange type, and the like.
Any type can be used in the hydrogenation reaction of the present invention.
A typical example of the fixed catalyst reactor (b) is JH Ga
ry and GE Handwerk: Petrolium Refining Technology and Economics (197
5) A reactor of the type described on page 74, ie, the bottom is filled with ceramic balls, the center of the reactor is filled with catalyst particles, and the ring structure-containing polymer and hydrogen are charged from the top of the reactor. Is supplied, and the reaction product is discharged from the lower end of the reactor.

The wire mesh or thin layer catalyst reactor (c) is a reactor in which several to several tens of wire meshes or granular catalysts are mounted as a catalyst as a thin layer. The method is divided into a radial flow type and a parallel flow type depending on the flow of the solution containing the ring structure-containing polymer and hydrogen, and any type may be used.
In the hydrogenation method of the present invention, when a solution containing a ring structure-containing polymer and hydrogen is passed through a fixed bed, it is preferable that the solution flow on the surface of the catalyst particles in a film form.

In order to carry out the hydrogenation process in batch mode, a reactor equipped with a fixed bed filled with catalyst particles is provided.
A solution containing a polymer and hydrogen is charged therein, and a bath of the solution is stirred to form a reactor configured such that the solution passes through the fixed catalyst-packed bed at a predetermined relative linear velocity. Can be used. An example of a typical reactor is the Journal of Chemical Engineering of Japan, 27
Vol. 3, No. (1994) p310, that is, a stainless steel cylindrical mesh basket filled with catalyst particles in a frame mounted on a rotating shaft is attached as a fixed layer, and a stirrer is further provided. It is a equipped reactor. A solution containing a polymer and hydrogen is charged into the reactor,
With the catalyst-filled basket immersed in the bath of the solution,
The catalyst-filled basket is rotated about an axis of rotation and the solution is agitated. Another example is that a cage filled with a catalyst is placed in a double cylinder of a double cylindrical mesh basket as a fixed layer with a slight gap from the inner wall of the reactor, and the center of the double cylinder is rotated. A reactor equipped with a stirring blade on the shaft is also used.

The polymer containing a ring structure is supplied to a reactor together with hydrogen as an organic solvent solution, and hydrogenated. The organic solvent is not particularly limited as long as it is inert to the catalyst. However, a hydrocarbon-based solvent is usually used because the resulting hydrogenated polymer has excellent solubility. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, and bicyclononane; Among them, cyclic alicyclic hydrocarbons are preferable. These organic solvents can be used alone or in combination of two or more. Usually, it may be the same as the polymerization reaction solvent.

The viscosity of the solution containing the ring structure-containing polymer and hydrogen is preferably 1,000 cp or less, more preferably 1 cp or less.
00 cp or less. The concentration of this solution is usually 5 to 40
% By weight, preferably 10 to 30% by weight. Before the solution containing the ring structure-containing polymer and hydrogen is supplied to a fixed-bed reactor or a reactor equipped with a catalyst-filled cage, catalyst poisons due to the polymerization catalyst used in the production of the polymer are removed. Is preferably passed through an adsorption device. In the adsorption device,
Activated clay, activated carbon, diatomaceous earth, perlite, alumina,
An adsorbent such as nickel, silica, and silica-alumina is filled. Filtration can be used in combination with adsorption.

The hydrogenation reaction can be carried out according to a conventional method. However, the hydrogenation rate varies depending on the type of the hydrogenation catalyst and the reaction temperature, and the aromatic ring remaining rate can also vary. In the case of using the above hydrogenation catalyst, in order to allow the unsaturated bond of the aromatic ring to remain to some extent or more, control such as lowering the reaction temperature, lowering the hydrogen pressure, or shortening the reaction time may be performed. Good. The solution containing the ring structure-containing polymer and hydrogen to be supplied to the fixed catalyst is prepared by blowing hydrogen into a solution in which the ring structure-containing polymer is dissolved.
The pressure of the hydrogen bubbling is generally 0.1 kg / cm ² or more,
It is preferably 0.5 kg / cm ² or more, and usually 10 kg / cm ² or more.
0 kg / cm ² or less, preferably 50 kg / cm ² or less.

The reaction temperature of the hydrogenation reaction is usually 0 ° C. or higher, preferably 100 ° C. or higher, more preferably 150 ° C. or higher.
℃ or more, usually 300 ℃ or less, preferably 250 ℃
° C or lower, more preferably 230 ° C or lower. In addition,
Under the conditions where the double bond in the main chain structure is hydrogenated, the non-conjugated double bond (for example, an alkylidene group) in the side chain is also hydrogenated. The slurry discharged from the fixed-bed reactor is introduced into a separator such as a flash separator 6 as shown in FIG. 1 to separate a hydrogenated solution of the ring-structure-containing polymer from unreacted hydrogen. It can be recycled to the hydrogenation reactor 4.

In the present invention, it is not necessary to remove the catalyst from the polymer after the completion of the hydrogenation reaction. However, in applications where residual transition metals may be harmful if the remaining transition metal elutes, such as medical equipment. Since it is preferable that substantially no transition metal remains, it is preferable to perform centrifugation, filtration and the like. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added. Further, in order to obtain such a polymer having a hydrogenated ring structure, adsorption of alumina or the like having a specific pore volume and a specific surface area as disclosed in JP-A-5-317411 or the like is required. It is preferable to use an agent or wash the hydrogenated polymer solution with acidic water and pure water. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used, and from the viewpoint of efficiency, it is preferable to use a filter aid such as diatomaceous earth and perlite.

FIG. 1 shows a flow diagram of an example of a process for carrying out the hydrogenation method of the present invention. The organic solvent solution of the ring structure-containing polymer raw material passes through the surging drum 2 and the adsorption tower 3 to remove residual catalyst and other catalyst poisons. Further, after being preheated by a combined heat exchanger (not shown) if necessary, hydrogen is blown in by a blower 9 and the solution is introduced to the top end of the fixed catalyst bed reactor 4 as a solution containing a polymer having a ring structure and hydrogen. I will The fixed catalyst bed reactor 4 is provided with a plurality of trays 5 filled with catalyst particles. The number of shelves, the amount of catalyst particles, the supply amount of the polymer solution and the supply amount of hydrogen are appropriately set according to the desired reaction rate, contact time, reaction rate and the like. The liquid discharged from the fixed catalyst bed reactor 4 is cooled in a heat exchanger, introduced into a flash separator 6, and separated into a hydrogenated solution of a ring structure-containing polymer and unreacted hydrogen. The ring-structure-containing polymer hydride 7 is recovered, and the separated unreacted hydrogen is circulated through the circulating gas discharge drum 8 to the polymer solution supply system, where the polymer
It is supplied to the hydrogenation reactor 4 as a hydrogen solution. In the illustrated process, the solution containing the polymer and hydrogen rises and is fed from the top of the hydrogenation reactor 4,
May be configured to be supplied from the top end.

[0038]

EXAMPLES Examples 1 to 4 and Comparative Examples 1 and 2 A thermoplastic norbornene ring-opening polymer (8-ethyltetracyclo [4. 4.0.1 ^{2,5.1 7,10} ] Dodeca-3-ene ring-opened polymer: weight average molecular weight Mw: 4.01 × 10 ⁴ , M
Hydrogenation was performed at a w / Mn ratio of 2.9). (I) Hydrogenation catalyst (a) Catalyst 1: 1.5 mm diameter spherical catalyst in which 1% by weight of platinum is supported on silica (SiO ₂ ) (specific surface area: 30 m ²
/ g, pore volume 1.05ml / g, average pore diameter 99.8n
m, bulk density 0.42 g / ml; E. FIG. Chemcat Co., Ltd.) (ii) Catalyst 2: palladium 1% by weight of alumina (Al ₂
1.5 mm diameter spherical catalyst supported on O ₃ ) (specific surface area 11 m ² / g, pore volume 0.33 ml / g, average pore diameter 107.4 nm, bulk density 0.98 g / ml; NE. Chemcat Corporation)

(Ii) Resin solution (solvent: cyclohexane, concentration: 5% by weight) (iii) Catalyst poison adsorbent: diatomaceous earth (filled in adsorption tower 3) (iv) Hydrogen / resin solution ratio: 23 Nl / l (V) Hydrogen pressure: 4.5 MPa (vi) Reaction temperature: 160 ° C. A reactor in which the diameter and length of the catalyst layer were changed by adjusting the inner diameter and length of the fixed catalyst bed reactor was prepared, and the LHSV (resin) was used. With the constant of the reciprocal of the time of contact of the solution with the catalyst), the linear velocity of the resin solution passing through the fixed hydrogenation catalyst layer was changed to flow out of the reactor 5 hours, 10 hours and 50 hours after the start of hydrogenation. The hydrogenation rate (determined from ¹ H-NMR spectrum) of the hydrogenated resin was measured. Table 1 shows the results.

[0040]

[Table 1]

Examples 5 to 8, Comparative Examples 3 and 4 The polymer to be hydrogenated was polystyrene (weight average molecular weight M
(W: 1.21 × 10 ⁵ , Mw / Mn ratio: 1.05), and a hydrogenation experiment was performed in the same manner as in Examples 1 to 4 and Comparative Examples 1 and 2. Table 2 shows the results.

[0042]

[Table 2]

[0043]

According to the method for hydrogenating a ring structure-containing polymer of the present invention, there is no need to remove the used hydrogenation catalyst.
The amount of by-products from the hydrogenation reaction is small, and a hydrogenated polymer having good and balanced mechanical strength, heat resistance, processability, and transparency can be obtained, and a conventional fluidized catalyst is used. It is possible to achieve a high hydrogenation rate almost equal to that of the hydrogenation method.

[Brief description of the drawings]

FIG. 1 is a flow diagram illustrating an example of a process for hydrogenating a ring structure-containing polymer using a fixed catalyst bed reactor according to the present invention. DESCRIPTION OF SYMBOLS: 2 Surge drum for feed ring structure-containing polymer raw material 3 Catalyst poison adsorption tower 4 Fixed catalyst bed reactor 5 Fixed catalyst bed reactor shelf 6 Flash separator 7 Hydrogenated ring structure containing polymer 8 Circulating gas Discharge drum 9 blower

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masafumi Miyamoto 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Within the Zeon Corporation General Development Center (72) Inventor Sadaji Ohara Yakko-ichi, Kawasaki-ku, Kawasaki-shi, Kanagawa No.2-1, Zeon Corporation Integrated Development Center (72) Inventor Teruhiko Suzuki 1-1-2, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-Terminology within Zeon Corporation Integrated Development Center 4J100 AR03P AR04P AR05P AR11P AS01P AS02P AU21P CA31 DA01 HA03 HB17

Claims (4)

[Claims] 1. The weight average molecular weight measured by gel permeation chromatography is 1 in terms of polystyrene.
A solution containing a polymer having a ring structure of from 0.001 to 1,000,000 and hydrogen is passed through a fixed bed filled with a hydrogenation catalyst at a linear velocity of from 0.01 to 1.5 cm / sec. For hydrogenating ring-containing polymers. 2. The fixed bed is a fixed bed reactor.
The described method. 3. A solution containing a ring structure-containing polymer and hydrogen is passed through a fixed bed charged in the reactor.
The described method. 4. A hydrogenation catalyst comprising nickel, ruthenium,
Rhenium, platinum, palladium and a compound containing a metal selected from the group consisting of rhodium supported on a carrier,
4. The method according to claim 1, which is in the form of particles having an average particle size of 0.5 to 10 mm.