JPH0859799A - Production of hydrogenated ring-opening polymer - Google Patents

Abstract

PURPOSE: To enable continuous production of hydrogenated ring-opening polymer which is useful as a transparent resin with excellent optical properties and heat resistance efficiently in high yield by hydrogenation of a specific ring- opening polymer in a tank-type reactor provided with a stirrer followed by hydrogenation in a piston-flow type reactor. CONSTITUTION: A monomer comprising one or more norbornene derivatives of the formula (R<1> -R<12> are each H, a halogen, a monofunctional organic group; R<9> and R<10> , R<11> and R<12> are incorporated to form a difunctional hydrocarbon; R<9> or R<10> and R<11> or R<12> link to each other to form a ring structure; m is 0-2) such as 8-methyl-tetracyclo[4.4.0.1<2> ,<5> .1<7> ,<10> ]-3-dodecene or a combination thereof with other monomers copolymerizable with these monomers are subjected to ring-opening polymerization. The resultant ring-opening polymer is hydrogenated in a tank type reactor provided with a stirrer, followed by hydrogenation in a piston-flow type reactor to give this hydrogenated ring-opening polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a ring-opening polymer hydride.

2. Description of the Related Art A hydride of a ring-opening polymer of a norbornene derivative (including a ring-opening copolymer; the same applies below) is
It is useful as a transparent resin having excellent optical properties and heat resistance, and various ring-opening polymer hydrides and methods for producing the same have been proposed. As such ring-opening polymer hydride, for example 8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene and W, Mo, Re, transition metal compounds such as Ti A polymerization catalyst selected from the above, or the above transition metal, Li,
A ring-opening polymer hydride obtained by further hydrogenating a ring-opening polymer obtained by performing a ring-opening polymerization reaction in the presence of a polymerization catalyst formed by combining an organometallic compound such as Mg, Al, or Sn is known. ing. On the other hand, as a method for hydrogenating a polymer having a carbon-carbon double bond, a specific ruthenium compound is used as a hydrogenation catalyst and hydrogenated as disclosed in, for example, JP-A-4-202404. A method of converting to hydrogen is known, and such a hydrogenation reaction is generally carried out by a batch reactor under hydrogen pressure. However, since this hydrogenation reaction is usually carried out under conditions of high temperature and high pressure, when the reaction is carried out in a batch reactor, operations other than the actual reaction such as temperature raising, cooling and pressurizing, and pressure releasing operations are carried out. Since it takes a lot of time, it is necessary to design the reactor capacity to be large in consideration of these times in order to obtain a predetermined production amount.
Furthermore, in batch reactions, variations in product quality for each reaction are often greater than in continuous reactions, and it also takes time and labor to supply the chemical solution to the reactor and withdraw the reaction solution.
When considering the industrialization of the production of hydrides of ring-opening polymers, it was never an advantageous method.

The hydrogenation reaction of the ring-opening polymer needs to be carried out under high pressure, but when this reaction is carried out in a batch reaction, as described above, other than the actual reaction, Since the process requires time, it is inevitable to increase the capacity of the reactor in order to obtain a predetermined production amount. Increasing the capacity of expensive high pressure reactors
Since this leads to an increase in plant cost, it has been desired to reduce the capacity of the reactor by shortening the time required for the reactions other than the batch reaction. On the other hand, in the case of batch reaction, even if the reaction is carried out by the catalyst disclosed in JP-A-4-202404, there is variation in the hydrogenation rate of each reaction. Considering industrialization, the variation is reduced,
It was desired to stabilize the quality. Furthermore, in the batch reaction, since the room temperature before the reaction and the normal pressure, the high temperature during the reaction, the temperature rise to the high pressure state, the pressurizing operation, conversely the cooling after the reaction is completed, the pressure releasing operation is required for each reaction. It is conceivable that the reactor, the mechanical seal, and the like will be subjected to stress due to changes in temperature and pressure, increasing the risk of leaking the contents. In this hydrogenation reaction, since high temperature and high pressure hydrogen is held in the reactor during the reaction,
If this leaks out, it could cause serious safety problems. As described above, when the hydrogenation reaction of a ring-opening polymer is carried out in a batch reaction, there are problems in manufacturing cost, stability of quality, and safety, and when industrially producing a hydride of a ring-opening polymer. , Was easily predicted to be at a disadvantage.

[0002]

The object of the present invention is to carry out the reaction in a continuous reaction in order to solve the above-mentioned drawbacks when the hydrogenation reaction of a specific ring-opening polymer is carried out in a batch reaction. It is an object of the present invention to provide a method for producing a hydrogenated ring-opening polymer. The present invention provides a monomer comprising at least one norbornene derivative represented by the following general formula (I),
Alternatively, the ring-opening polymerization intermediate obtained by ring-opening polymerization of this monomer and a copolymerizable monomer copolymerizable therewith is hydrogenated in a tank reactor equipped with a stirrer, and then the piston The present invention provides a method for producing a ring-opening polymer hydride, which comprises hydrogenating in a flow reactor.

[0003]

Embedded image

(In the general formula (I), R ^{1 to} R ¹² are each a hydrogen atom, a halogen atom or a monovalent organic group, and may be the same or different.
⁹ and R ¹⁰ or R ¹¹ and R ¹² may combine to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² are bonded to each other to form a cyclic structure. It may be formed. m is an integer of 0-2. ) Hereinafter, the present invention will be specifically described.

In the present invention, when a ring-opening polymer obtained by ring-opening polymerization of a specific monomer with a metathesis catalyst is further hydrogenated, the hydrogenation reaction is continuously conducted by two specific reactors. To do. <Specific monomer> The specific monomer used as a raw material for obtaining the ring-opening polymer to be hydrogenated in the present invention is a compound having a norbornene structure represented by the above general formula (I). R ^{1 to} R ¹² in the general formula (I) are each a hydrogen atom, a halogen atom such as chlorine or bromine, or a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group. Or an alkoxy group such as a methoxy group or an ethoxy group, a carboxyalkyl group such as a carboxymethyl group or a carboxyethyl group, or another monovalent organic group, which may be the same or different. Also, R ⁹ and R ¹⁰ or R ¹¹ and R ¹²
May combine with each other to form a divalent hydrocarbon group, or may be bonded to a carbon atom constituting the norbornene ring by an unsaturated bond. Examples of the divalent hydrocarbon group integrally formed include alkylidene groups such as ethylidene group and propylidene group. Further, R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may be bonded to each other to form a cyclic structure. The ring thus formed may have any of a monocyclic structure, a condensed polycyclic structure, a polycyclic structure having a bridge, and a cyclic structure having an unsaturated bond. Specific examples of such a cyclic structure include those shown in Chemical formulas 6 to 10 below, and these cyclic structures may have a substituent such as a methyl group. In the general formula (I), specific examples of the norbornene derivative in which the value of m is 0 include 5-carboxymethylbicyclo [2.2.1] -2-heptene, 5
-Methyl-5-carboxymethylbicyclo [2.2.
1] -2-heptene, bicyclo [2.2.1] -2-heptene, 5-vinylbicyclo [2.2.1] -2-heptene, 5-ethylidenebicyclo [2.2.1] -2- Heptene etc. can be mentioned. In the above general formula (I), a specific example of the norbornene derivative in which the value of m is 1 is 8-methyltetracyclo [4.4.0.1].
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Propyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Butylpropyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Vinyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 5-methyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 7-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-Dimethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5,10-Dimethyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 11,12-dimethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,7,9-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-Ethylidene-9-ethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 9,11,12-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Methyl-9-propyltetracyclo [4.4.0.1
^2,5 . ^1,7,10 ] -3-dodecene, and further 8-methyl-
8-Carboxymethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxyethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-methyl-8-carboxyn
-Propyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxy n-butyl tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxy sec-butyl tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-methyl-8-carboxycyclohexyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8-methyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxy t-butyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-carboxyisopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like can be mentioned. In the above general formula (I), specific examples of the norbornene derivative in which the value of m is 2 include hexacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ]-
4-heptadecene, 11-vinylhexacyclo [6.
6.1 ^1,8 . 1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^{9, 14} ] -4
- heptadecene, 11-methyl-11-carboxymethyl hexa cyclo [6.6.1 ^1,8. 1 ^3,6 . 1 ^10,13 .
0 ^2,7 . 0 ^9,14] -4-heptadecene, and the like. The above-mentioned specific monomers are not necessarily used alone, and ring-opening copolymerization can be performed using two or more kinds.

<Copolymerizable Monomer> The ring-opening polymer may be a ring-opening polymer of the above-mentioned specific monomer alone, but it may be a copolymerizable monomer with the specific monomer. It may be a compound obtained by ring-opening copolymerization with the body. Specific examples of the copolymerizable monomer used in this case include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and tricyclo [5,2,1,0 ^2.6 ] -3-decene. it can. Furthermore polybutadiene,
In the presence of unsaturated hydrocarbon-based polymers containing carbon-carbon double bonds in the main chain such as polyisoprene, styrene-butadiene copolymer, ethylene-propylene-non-conjugated diene copolymer, polynorbornene, etc. The monomer may be subjected to ring-opening polymerization. The hydride of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance. <Ring-Opening Polymerization Catalyst> The ring-opening polymerization reaction is carried out in the presence of a platinum group compound such as ruthenium, rhodium, palladium, iridium and platinum. (A) W, Mo and Re
At least one selected from the compounds of (b) Deming's periodic table, Group IA elements (eg, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, etc.)
Pb) or a group IVB element (for example, Ti, Zr, etc.) compound and a catalyst comprising a combination with at least one selected from those having at least one element-carbon bond or element-hydrogen bond. In addition, in order to enhance the activity of the catalyst in this case, the additive (c) described below may be added. Representative examples of W, Mo or Re compounds suitable as the component (a) include WCl ₆ , MoCl ₅ and ReO.
Examples thereof include compounds described in Japanese Patent Application No. 1-240517, such as Cl ₃ . (B) Specific examples of the _{component, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H
₅ ) ₂ AlCl, LiH, and other compounds described in Japanese Patent Application No. 1-240517 can be mentioned. As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, and further, the compounds shown in JP-A-1-240517 are used. be able to. The ratio of the component (a) to the component (b) is such that the metal atom ratio (a) :( b) is in the range of 1: 1 to 1:20, preferably 1: 2 to 1:10. The molar ratio of the component (a) to the component (c) is such that (c) :( a) is in the range of 0.005: 1 to 10: 1, preferably 0.05: 1 to 2: 1. It

<Solvent for ring-opening polymerization reaction> Examples of the solvent used in the ring-opening polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane, cycloheptane, cyclooctane, decalin, norbornane and the like. Cycloalkanes,
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorbutane, bromhexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene,
Compounds such as aryl, ethyl acetate, n-butyl acetate,
Examples thereof include saturated carboxylic acid esters such as iso-butyl acetate and methyl propionate, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. Of these, aromatic hydrocarbons are preferred. <Molecular Weight of Ring-Opening Polymer> The ring-opening polymer to be subjected to the hydrogenation reaction in the present invention has a molecular weight in a range of 0.2 to 5.0 in intrinsic viscosity (η _inh ). It is suitable. Generally, it becomes difficult to obtain a high hydrogenation rate as the molecular weight increases, but according to the present invention, a high hydrogenation rate can be relatively easily obtained even for a polymer having a high molecular weight. The molecular weight of the ring-opening polymer can be adjusted by the polymerization temperature, the type of catalyst and the type of solvent, but more preferably α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene. It is preferable to adjust by coexisting with the reaction system and changing the amount thereof. <Hydrogenation catalyst> The hydrogenation catalyst used in the hydrogenation reaction of the ring-opening (co) polymer includes organic acid salts or acetylacetone salts of titanium, cobalt, nickel and the like, and organic acids of lithium, magnesium, aluminum, tin and the like. Combined with a metal compound, so-called Ziegler type homogeneous catalyst, palladium, platinum, ruthenium, noble metals such as rhodium, carbon, alumina, silica alumina, silica magnesia, supported noble metal catalyst supported on a carrier such as diatomaceous earth, Examples thereof include noble metal complex catalysts such as rhodium, rhenium and ruthenium. Among the Ziegler type homogeneous catalysts, the catalysts composed of nickel compounds and cobalt compounds have high hydrogenation activity. Such nickel compounds include nickel naphthenate, nickel carboxylates such as nickel octoate, nickel acetylacetonate, nickel chloride,
Examples thereof include nickel carbonyl and nickelocene, and examples of the cobalt compound include cobalt naphthenate, cobalt acetylacetonate, cobalt chloride and cobalt carbonyl. Among the supported noble metal-based catalysts, the catalyst in which palladium is supported on the silica-alumina carrier or the silica-magnesia carrier has high hydrogenation activity. After the completion of the hydrogenation reaction, the supported noble metal-based catalyst is easily separated from the reaction solution by a known means such as filtration, sedimentation separation, and centrifugation. Among the noble metal complex catalysts, the catalyst composed of a ruthenium complex has high hydrogenation activity, and the ruthenium complex includes RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₅ and R.
uCl ₂ [P (C ₆ H ₅ ) ₂ ] ₅ , RuH ₂ (CO)
[P (C ₆ H ₅ ) ₃ ] ₃ , Ru (CO) ₃ [P (C ₆ H
₅ ) ₃ ] _{2 and the} like. <Hydrogenation Reaction Solvent> The hydrogenation reaction solvent is not particularly limited as long as it is a good solvent for the (co) polymer to be hydrogenated and is not itself hydrogenated. Specifically, the same solvent as the polymerization reaction solvent can be used. Ring opening (co) in polymer solution used for hydrogenation reaction
The concentration of the polymer is usually 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight. If the concentration of the ring-opening (co) polymer is too high, a large reaction rate cannot be obtained, while if it is too low, it is economically disadvantageous. <Hydrogenation reaction> The temperature of the hydrogenation reaction is usually 20 to 200.
C., preferably 50 to 180.degree. If this temperature is too low, a large reaction rate cannot be obtained, while
If the temperature is too high, the catalyst may be deactivated, which is not preferable. The pressure of the reaction system is usually 1 to 200 kg / cm
² , preferably ² to 150 kg / cm ² , and more preferably 5 to 120 kg / cm ² . If the pressure is too low, a large reaction rate cannot be obtained. On the other hand, if the pressure is increased, a large reaction rate can be obtained, but an expensive high-pressure device is required, which is economically disadvantageous. The time required for the reaction is related to the concentration of the ring-opening (co) polymer and the pressure, but is usually 30
It is selected in the range of minutes to 100 hours, preferably in the range of 1 to 30 hours.

In the present invention, the reactor for carrying out the hydrogenation reaction first (hereinafter also referred to as "first reactor") is a tank equipped with a stirrer for the purpose of improving the contact between hydrogen and the ring-opening polymer solution. Type reactors are preferred. In the present invention, the polymer solution used for the hydrogenation reaction is continuously supplied to the first reactor.
The type of the stirrer is such that the ring-opening polymer solution and the hydrogenation catalyst continuously supplied to the reactor are mixed with the polymer solution in the reactor to promote contact between hydrogen and the polymer solution. If there is no particular limitation as long as it exists, specific examples thereof include a disk turbine type agitator, a fan turbine type agitator, a propeller type agitator, a ribbon type agitator, and the like. In the initial stage of the hydrogenation reaction of the present invention, the diffusion rate of hydrogen into the polymer solution may be the rate-determining factor of the hydrogenation reaction, and the diffusion rate of hydrogen is increased by stirring with a stirrer as described above. , The reaction rate can be increased. The hydrogenation rate in the first reactor may be 70 to 95%. When the hydrogenation rate in the first reactor is lower than 70%, a high hydrogenation rate of 99% or more is finally obtained even if the hydrogenation reaction is performed in the piston flow type reactor described later after the first reactor. Becomes difficult. If the hydrogenation rate in the first reactor is higher than 95%, the capacity of the first reactor becomes large, which is economically disadvantageous. The ring-opening polymer solution hydrogenated to a hydrogenation rate of 70 to 95% in the first reactor is continuously withdrawn from the first reactor and retained in hydrogen in a piston flow reactor (hereinafter referred to as " It is continuously supplied to the second reactor). Here, the piston flow type reactor means that substances move at a uniform velocity in the flow direction in the reactor, and mixing in the flow direction,
A tubular reactor in which the degree of diffusion is so small that it can be ignored and the concentration distribution of the substance in the direction perpendicular to the flow direction is substantially uniform.

FIG. 1A is an explanatory view showing a partial structure of an example of a piston flow type reactor used in the present invention, and FIG. 1B is a piston shown in FIG. It is an explanatory view showing a part of composition when a flow type reactor is seen from the lower part of the figure. In this piston flow type reactor, a flow path is formed by alternately connecting a first element 21 and a second element 22 in a straight tubular reactor body 10 shown by being broken in an axial direction in the drawing. Board 20
Are inserted and arranged along the axial direction of the reactor body 10. In the reactor main body 10, the ratio of the axial length to the inner diameter (axial length / inner diameter) of 5 or more, particularly 10 or more, may improve the mixing performance (flow of substances in the reactor). It is preferable in that it can approach the ideal piston flow. As shown in FIG. 2A, the first element 21 constituting the flow path forming plate 20 has a state in which, for example, a rectangular plate-shaped body is twisted by 180 degrees about its longitudinal direction as an axis. It has a similar shape, and one end 23a and the other end 23b thereof are parallel to each other. The first element 21 is arranged in the reactor main body 10 in a state where one side portion 24a and the other side portion 24b are in contact with the inner peripheral surface of the reactor main body 10. on the other hand,
As shown in FIG. 2B, the second element 22 that constitutes the flow path forming plate 20 is, for example, a rectangular plate-like body that forms the first element 21 and has its longitudinal direction axis. Has a shape similar to that when a twist of 180 degrees is applied in the opposite direction to the first element 21, and its one end 25a and the other end 25b are parallel to each other. The second element 22 is arranged in the reactor main body 10 in a state where one side portion 26a and the other side portion 26b are in contact with the inner peripheral surface of the reactor main body 10. The flow path forming plate 20 is configured by alternately connecting the first element 21 and the second element 22 so that their ends intersect at right angles, for example. In such a piston flow type reactor, as shown in FIG. 3, the reaction raw material supplied into the reactor body 10 is composed of two walls formed by the inner wall of the reactor body 10 and the first element 21. It is divided into flow paths, and passes through the first element 21 while flowing in a spiral, for example, clockwise. Then, the first element 21 and the second
At the boundary with the element 22 of FIG. 1, the reaction raw material is divided into two flow paths formed by the inner wall of the reactor main body 10 and the second element 22, and the reaction raw materials divided in the first element 21 join again. And then mixed, and this time passing through the second element 22 while being spirally flowed counterclockwise. Such an operation is repeated every time the first element 21 and the second element 22 are passed, and as a result, the concentration distribution of the reaction raw material in the direction (radial direction) perpendicular to the axial direction of the reactor body 10 becomes uniform. On the other hand, in the axial direction of the reactor main body 10, the reaction raw materials flow almost uniformly, so that the degree of mixing and diffusion is small, whereby the piston flow is achieved in the reactor main body 10. It Commercially available products of the above piston flow type reactor include "Static Mixer" manufactured by Noritake Company, "Sulzer Mixer" manufactured by Sumitomo Heavy Industries, Ltd., "Sukeya Mixer" manufactured by Sakura Seisakusho Co., Ltd., etc. Is mentioned.

The present invention is not limited to the piston flow type reactor having the above construction, and various types can be used. For example, the flow path forming plate inserted and arranged in the reactor body may have another structure. In addition, the ratio of the axial length to the inner diameter of the reactor body (axial length /
If the inner diameter) is 20 or more, a tubular reactor having no flow path forming plate may be used. Unlike the reaction in the first reactor, the reaction in the second reactor is a reaction at a high hydrogenation rate, so the reaction rate becomes slower, and the reaction rate becomes rate-determining than the diffusion rate of hydrogen gas. From, stirring,
It is not necessary to promote the diffusion of hydrogen by sucking hydrogen gas into the reaction solution. For the reaction, only hydrogen already dissolved in the reaction solution is sufficient, and an operation such as stirring will disturb the state of the piston flow, so that it is rather the opposite effect in many cases.

[0012]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these. In the following, the value of the hydrogenation rate is δ = in the nuclear magnetic resonance absorption spectrum (NMR) measured at 100 MHz.
It is calculated on the basis of the size at which the peak attributed to the carbon-carbon double bond at 4.5 to 6.0 ppm is reduced by the hydrogenation reaction. <Production of ring-opening polymer> Synthesis Example 1 to substituted reaction vessel made of SUS316 with a nitrogen gas as a specific monomer 8-methyl-8-carboxymethyl tetracyclo [4,4,0,1 ^2.5, 1 ^7.10 ] -3-dodecene 200 kg, toluene 680 liters, molecular weight regulator 1-hexene 33 kg, ring-opening polymerization catalyst WCl ₆ concentration 0.05 M / liter chlorobenzene solution 3.4 liters and diethyl Aluminium chloride concentration of 0.8 M / liter of toluene solution of 4.4 liters was added, and ring-opening polymerization reaction was carried out at 80 ° C. for 3 hours to obtain a concentration of 24% by weight polymer solution. The polymer solution of Example 1 Synthesis Example 1 "INORGANIC SYSNTHESIS VOL.1
Ruthenium compound RuHCl (C
O) [P (C ₆ H ₅ ) ₃ ] ₃ was added as a hydrogenation catalyst so that the weight of the polymer was 0.05%. A jacket having a disk turbine type agitator, in which the polymer solution was maintained at a pressure of 100 kg / cm ² with hydrogen, was continuously supplied to a reactor (first reactor, content 20 liters), and the reaction was carried out. The liquid level in the reactor was adjusted so that the residence time in the reactor was 2 hours, and the reaction was carried out at 165 ° C. The polymer solution was continuously withdrawn from the bottom of the first reactor, and the withdrawn polymer solution was maintained at a pressure of 98 kg / cm ² with hydrogen gas. A piston flow type reactor having the structure shown in FIG. 1 (second reactor, inner diameter 49.5 mm, length 5 m,
It was fed to the bottom of an inner volume of 8.5 liters), reacted at 165 ° C., and the polymer solution was cooled from the top with a cooler and then continuously withdrawn. The feed rate to the first reactor was adjusted so that the residence time in the second reactor was 2 hours. The reaction was continued for 40 hours under the above conditions to obtain 150 liters of polymer hydride. Table 1 shows the results of measuring the hydrogenation rate of the polymer at the outlets of the first reactor and the second reactor every 4 hours. As is clear from Table 1, a polymer hydride having a high hydrogenation rate of 99% or more could be stably obtained.

[0013]

[Table 1]

Comparative Example 1 The same RuHCl (CO) [P (C ₆ H ₅ ) as in Example 1 was used.
₃ ] A polymer solution containing 0.05% by weight of ₃ was supplied to the same reactor as the first reactor of Example 1 so that the volume during the reaction was 17 liters, and batch reaction was carried out. The pressure was adjusted to 100 kg / cm ² with hydrogen gas, and the temperature was 16
After reaching 5 ° C, the reaction was carried out at 165 ° C for 3 hours. 1
The reaction time at 65 ° C was 3 hours, but it took time for charging and withdrawing the polymer solution, leak test of the apparatus, temperature increase, pressurization operation, etc., and the average time required for one batch reaction was 11 hours. Met. This batch reaction under the same conditions
Table 2 shows the results of measuring the hydrogenation rate of each of the tests performed 0 times.
Shown in

[0015]

[Table 2]

As is clear from the comparison between Table 1 and Table 2, the batch reaction has a larger variation in the hydrogenation rate than the continuous reaction.
It can be seen that the quality stability is inferior. On the other hand, regarding the production amount, the retention amount of the polymerization solution in the reactor of Example 1 and Comparative Example 1 was the same, but in Example 1, 150 liters of the polymer solution was obtained by continuous operation for 40 hours. In contrast,
In Comparative Example 2, 11 to obtain 150 liters of polymer
Since the calculation takes 0 hours, it can be seen that the continuous reaction is more advantageous in terms of productivity.

[0017]

As described above, according to the present invention, the ring-opening polymer solution is hydrogenated by a tank reactor equipped with a stirrer and a piston flow reactor connected to the tank reactor, A ring-opening polymer hydride can be efficiently and continuously produced.

[0018]

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a part of the configuration of an example of a piston flow reactor used in the method of the present invention.

FIG. 2 is an explanatory diagram showing an example of a first element and a second element that form a flow path forming plate.

FIG. 3 is an explanatory diagram showing a flow of substances in a reactor body of the piston flow type reactor having the configuration of FIG. 1.

[Explanation of symbols]

10 Reactor Main Body 20 Flow Forming Plate 21 First Element 22 Second Element 23a One End 23b Other End 24a One Side 24b Other Side 25a One End 25b Other End 26a One Side 26b Other Side

Claims (1)

[Claims] 1. A monomer comprising at least one norbornene derivative represented by the following general formula (I), or this monomer and a copolymerizable monomer copolymerizable therewith are subjected to ring-opening polymerization. A method for producing a ring-opening polymer hydride, comprising hydrogenating the obtained ring-opening polymer in a tank reactor equipped with a stirrer, and then hydrogenating in a piston flow reactor. Embedded image (In Chemical formula ¹ , R ^{1 to} R ¹² are each a hydrogen atom, a halogen atom or a monovalent organic group, and may be the same or different. R ⁹ and R ¹⁰ or R ¹¹ and R ¹² May combine with each other to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may bond to each other to form a cyclic structure. Is 0
Is an integer of ˜2. )