JP2016069642A - Method for preparing raw material liquid for hydrogenation reaction, method for producing hydrogenated product of polymer, and hydrogenated product of polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a raw material liquid for hydrogenation reaction, in which the raw material liquid that is to be provided for the hydrogenation reaction of the polymer having a carbon-carbon double bond in a molecule causes the hydrogenation reaction to proceed to a sufficient degree without excessively using a hydrogenation catalyst and suppresses an isomerization reaction of the polymer, to provide a method for producing a hydrogenated product of the polymer, in which the polymer is subjected to the hydrogenation reaction by using the raw material liquid for hydrogenation reaction obtained by the preparation method, and to provide the hydrogenated product of the polymer obtained by the producing method.SOLUTION: There is provided a method for preparing a raw material liquid that is to be provided for hydrogenation reaction of a polymer having a carbon-carbon double bond in a molecule. There is also provided a method for preparing a raw material liquid for hydrogenation reaction including the steps of: adding an adsorbent comprising zero-valent nickel to a mixture including a solvent, a metal component, and the polymer to adsorb the metal component to the adsorbent; and separating the adsorbent that adsorbs the metal component by filtration. There are provided a method for producing a hydrogenated product of the polymer, in which the polymer is subjected to hydrogenation reaction by using the raw material liquid for hydrogenation reaction obtained by the preparation method, and the hydrogenated product of the polymer obtained by the producing method.SELECTED DRAWING: None

Description

  The present invention relates to a method for preparing a hydrogenation reaction raw material liquid used for the hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule, and using the hydrogenation reaction raw material liquid obtained by this method, The present invention relates to a method for producing a polymer hydride that performs a hydrogenation reaction, and a polymer hydride obtained by this method.

  Conventionally, hydrogenation of this polymer has been carried out in order to improve the oxidation resistance, thermal stability, transparency and the like of the polymer having a carbon-carbon double bond in the molecule.

For example, Patent Document 1 includes a step of solution polymerization of a norbornene monomer to obtain a ring-opening polymer, and a step of hydrogenating a main chain double bond of the ring-opening polymer. A method for producing a ring-opening polymer hydride is described.
In the example of Patent Document 1, a ring-opening polymerization reaction is performed using a predetermined monomer to obtain a polymerization reaction solution, and then a large amount of a poor solvent is added to the polymerization reaction solution to precipitate a ring-opening polymer. The ring-opened polymer obtained by filtration is redissolved in a solvent, and a solution obtained by adding a hydrogenation catalyst to this solution is subjected to a hydrogenation reaction of the ring-opened polymer. Manufactures combined hydrides.

  Patent Document 2 discloses that a norbornene-based ring-opening copolymer hydrogen obtained by hydrogenating a norbornene-based ring-opening copolymer obtained by ring-opening polymerization of a monocyclic non-conjugated polyene and a norbornene-based monomer. The compounds are described. In the examples of Patent Document 2, a ring-opening polymerization reaction is performed using a predetermined monomer to obtain a polymerization reaction solution, and then a hydrogenation catalyst is added to the polymerization reaction solution. By subjecting it to a hydrogenation reaction, the desired polymer hydride is produced.

Unlike the method of the example of Patent Document 1, the method of the example of Patent Document 2 does not have a step of isolating the ring-opened polymer obtained by the polymerization reaction before the hydrogenation reaction, and thus more efficiently. Polymer hydrides can be produced.
However, when the hydrogenation reaction is carried out in a state where the metal component derived from the polymerization catalyst or the like is present in the system as in this method, the hydrogenation catalyst is used in order to sufficiently advance the hydrogenation reaction of the polymer. It may be necessary to use excessively, or depending on the reaction conditions, the isomerization reaction (side reaction) of the polymer may proceed.

JP 2006-52333 A JP 2012-92284 A

  The present invention has been made under such circumstances, and is a hydrogenation reaction raw material liquid used for the hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule, and an excess of the hydrogenation catalyst. A method for preparing a hydrogenation reaction raw material solution that can sufficiently proceed a hydrogenation reaction without being used and is less likely to cause a polymer isomerization reaction (side reaction), and a hydrogenation reaction obtained by this method. It aims at providing the manufacturing method of the polymer hydride which performs the hydrogenation reaction of the said polymer using a raw material liquid, and the polymer hydride obtained by this method.

  In order to solve the above problems, the present inventors have intensively studied a hydrogenation reaction raw material liquid used for a hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule, and as a result, a solvent, a metal component, and By adding an adsorbent containing zero-valent nickel to the mixed solution containing the dissolved polymer, adsorbing the metal component to the adsorbent, and then filtering the adsorbent adsorbing the metal component, The present inventors have found that the metal component can be efficiently removed and the target hydrogenation reaction raw material liquid can be efficiently obtained, and the present invention has been completed.

Thus, according to the present invention, there are provided the following hydrogenation reaction raw material preparation methods [1] to [9], a polymer hydride production method [10], and a polymer hydride [11]. .
[1] A method for preparing a hydrogenation reaction raw material solution for use in a hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule, the solvent, a metal component, and a mixed solution containing the polymer A method for preparing a hydrogenation reaction raw material liquid, comprising adding an adsorbent containing zero-valent nickel, adsorbing the metal component to the adsorbent, and then removing the adsorbent adsorbing the metal component.
[2] The method for preparing a hydrogenation reaction raw material liquid according to [1], wherein the metal component includes a metal element of Group 3 to Group 14 of the periodic table.
[3] The method for preparing a hydrogenation reaction raw material liquid according to [1] or [2], wherein the metal component is derived from a polymerization catalyst used in a polymerization reaction for producing the polymer.
[4] The method for preparing a hydrogenation reaction raw material liquid according to any one of [1] to [3], wherein the metal component is dissolved in the mixed liquid.
[5] The mixed liquid according to any one of [1] to [4], wherein the mixed liquid is a polymerization reaction liquid obtained by ring-opening polymerization of a cyclic olefin monomer in a solvent in the presence of a metathesis polymerization catalyst. Of preparing a hydrogenation reaction raw material liquid.
[6] The addition amount of the adsorbent containing zero-valent nickel is the molar ratio of the metal atom contained in the mixed solution to the nickel atom contained in the adsorbent (metal atom contained in the mixed solution: contained in the adsorbent. The method for preparing a hydrogenation reaction raw material liquid according to any one of [1] to [5], which is a nickel atom) of 1: 0.08 to 1: 200.
[7] The method for preparing a hydrogenation reaction raw material liquid according to any one of [1] to [6], wherein the temperature of the mixed liquid when adsorbing the metal component to the adsorbent is 30 to 150 ° C.
[8] The method for preparing a hydrogenation reaction raw material liquid according to any one of [1] to [7], wherein the operation of adsorbing the metal component to the adsorbent is performed in an inert atmosphere.
[9] A heavy hydrogenation catalyst is added to the hydrogenation reaction raw material liquid obtained by any one of the methods [1] to [8], and the hydrogenation reaction of the polymer is performed. A method for producing a combined hydride.
[10] A polymer hydride obtained by the method according to [9].

The hydrogenation reaction raw material liquid obtained by the method of the present invention is one in which the metal component in the mixed liquid has been efficiently removed. Therefore, by using this hydrogenation reaction raw material liquid, it is possible to obtain a polymer hydride with a small amount of metal components.
Further, in the hydrogenation reaction using the hydrogenation reaction raw material liquid, the hydrogenation reaction can be sufficiently advanced without adding excessive hydrogenation catalyst. (B) The removal operation of the hydrogenation catalyst can be efficiently performed, (c) the isomerization reaction (side reaction) of the polymer is suppressed, and the target polymer hydride is produced with high quality and It can be obtained in high yield.

  Hereinafter, the present invention will be described in detail by dividing into 1) a method for preparing a hydrogenation reaction raw material liquid, 2) a method for producing a polymer hydride, and 3) a polymer hydride.

1) Method for Preparing Hydrogenation Reaction Raw Material Solution The method of the present invention is used for a hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule (hereinafter sometimes referred to as “polymer (α)”). A method for preparing a hydrogenation reaction raw material liquid to be provided, wherein an adsorbent containing zerovalent nickel is added to a mixed liquid containing a solvent, a metal component, and a polymer (α), and the metal component is used as the adsorbent. After the adsorption, the adsorbent that has adsorbed the metal component is removed.

〔Mixture〕
The mixed solution used in the present invention contains a solvent, a metal component, and a polymer (α).
The solvent contained in the mixed solution is not particularly limited as long as it can dissolve the polymer (α). As a solvent to be used, aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; cyclopentane, cyclohexane, cyclooctane, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, Aliphatic hydrocarbon solvents such as hexahydroindene; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Halogen-containing aliphatic hydrocarbon solvents such as dichloromethane, chloroform and 1,2-dichloroethane; And halogen-containing aromatic hydrocarbon solvents such as chlorobenzene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran;

The metal component contained in the mixed solution is an object to be removed in the method of the present invention.
Examples of the metal component include those containing a metal element of Group 3 to Group 14 of the periodic table.
Examples of the metal elements include group 3 metal elements such as scandium and yttrium; group 4 metal elements such as titanium, zirconium and hafnium; group 5 metal elements such as vanadium, niobium and tantalum; chromium, molybdenum, Group 6 metal elements such as tungsten; Group 7 metal elements such as manganese; Group 8 metal elements such as iron, ruthenium and osmium; Group 9 metal elements such as cobalt, rhodium and iridium; Nickel, Group 10 metal elements such as palladium and platinum; Group 11 metal elements such as copper, silver and gold; Group 12 metal elements such as zinc; Group 13 metal elements such as aluminum; Tin and lead Group 14 metal elements; and the like.

  Examples of the metal component include those derived from the polymerization catalyst used in the polymerization reaction for producing the polymer (α) [that is, a polymerization catalyst (including a cocatalyst, etc.) or a decomposition product thereof].

  The metal component may or may not be dissolved in the mixed solution. For example, the metal component may exist in a dispersed state in the mixed solution, or may be included as a precipitate. The method of the present invention is preferably used when at least a part of the metal component is dissolved in the mixed solution.

  The amount of the metal component contained in the mixed liquid is not particularly limited, but is usually 1,000 ppm or less, preferably 100 to 500 ppm, based on the content of the polymer (α).

The polymer (α) contained in the mixed solution is a polymer having a carbon-carbon double bond in the molecule, and is a precursor of a polymer hydride.
A polymer ((alpha)) will not be specifically limited if it can melt | dissolve in a liquid mixture.

  Examples of the polymer (α) include a cyclic olefin ring-opening polymer obtained by ring-opening polymerization of a cyclic olefin monomer described later; a cyclic olefin addition weight obtained by addition polymerization of a cyclic olefin monomer described later. Polybutadiene, butadiene / styrene copolymer, butadiene / isoprene copolymer, butadiene / 1,3-pentadiene copolymer, ethylene / butadiene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, Polyisoprene, polychloroprene, butadiene / acrylonitrile copolymer, butadiene / methacrylonitrile copolymer, butadiene / methyl acrylate copolymer, conjugated diene compound addition polymer such as butadiene / methyl methacrylate copolymer, etc. Is mentioned.

  Among them, the cyclic olefin ring-opening polymer is often used for applications that require a reduction in the amount of mixed metal components, and is also required to perform a hydrogenation reaction efficiently. The method of the present invention is preferably used when the combination (α) is a cyclic olefin ring-opening polymer.

Although the number average molecular weight (Mn) of a polymer ((alpha)) is not specifically limited, Usually, 5,000-100,000, Preferably it is 6,000-70,000, More preferably, it is 7,000-60, 000.
The weight average molecular weight (Mw) of the polymer (α) is not particularly limited, but is usually 10,000 to 350,000, preferably 12,000 to 245,000, more preferably 14,000 to 210,000. is there.
Although molecular weight distribution (Mw / Mn) of a polymer ((alpha)) is not specifically limited, Preferably it is 1-5, More preferably, it is the range of 1-4.
These can be obtained, for example, as standard polystyrene equivalent values by performing gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

  The content of the polymer (α) dissolved in the mixed solution is not particularly limited, but is usually a weight ratio of the mixed solution and the dissolved polymer (α) [mixed solution: polymer (α)]. 100: 5 to 100: 70, preferably 100: 10 to 100: 60, more preferably 100: 15 to 100: 50.

  The mixed liquid used in the present invention includes, for example, an addition polymerization reaction or ring-opening polymerization using a catalyst containing a metal in a solution obtained by dissolving a polymer containing a metal component as an impurity in a solvent, or in a solvent. Polymerization reaction liquid obtained by carrying out the reaction (in the present invention, “polymerization reaction liquid” includes, in addition to the liquid at the end of the polymerization reaction, concentrated liquid or diluted liquid obtained by concentrating or diluting it ).

  Among them, as a mixed liquid to be used, a polymerization reaction liquid obtained by ring-opening polymerization of a cyclic olefin monomer in a solvent in the presence of a metathesis polymerization catalyst (hereinafter referred to as “ring-opening polymerization reaction liquid (I)”). May be preferred).

There is no limitation in particular as a metathesis polymerization catalyst used for preparation of ring-opening polymerization reaction liquid (I), A well-known thing is used. For example, a catalyst system comprising a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent, etc .; selected from titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a metal halide or acetylacetone compound and a co-catalyst organoaluminum compound; J. Pat. Appln. KOKAI Publication No. 7-179575; Am. Chem. Soc. , 108, 733 (1986); Am. Chem. Soc. 115, 9858 (1993); Am. Chem. Soc. , 118, 100 (1996), etc., known Schrock-type and Grubbs-type living ring-opening metathesis catalysts;
These catalysts can be used alone or in combination of two or more.

  The amount of the catalyst used can be appropriately selected depending on the polymerization conditions and the like, but is usually 1:10 to 1: 1,000,000, preferably in terms of the molar ratio of the catalyst to the monomer (catalyst: monomer). Is from 1: 100 to 1: 100,000.

  The cyclic olefin monomer used for the preparation of the ring-opening polymerization reaction solution (I) has a ring structure formed of carbon atoms, and has one polymerizable carbon-carbon double bond in the ring structure. A compound. In the present specification, “polymerizable carbon-carbon double bond” means a carbon-carbon double bond capable of ring-opening polymerization. There are various types of ring-opening polymerization such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it usually means metathesis ring-opening polymerization.

  Examples of the ring structure of the cyclic olefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combinations thereof. Although there is no limitation in particular in carbon number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.

Specific examples of the cyclic olefin monomer include monocyclic compounds such as cyclobutene, cyclopentene, and cyclooctene; bicyclic compounds such as 2-norbornene and norbornadiene; dicyclopentadiene (DCPD: cyclopentadiene dimer), 1,2 -Tricyclics such as dihydrodicyclopentadiene; tetracyclo [6.2.1.1 ^3,6 . Tetracycles such as 0 ^2,7 ] dodec-4-ene (tetracyclododecene, TCD), 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (MTF); cyclopentadiene trimer, etc. And the like.

These cyclic olefin monomers include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups having 2 to 10 carbon atoms such as vinyl group and allyl group; An alkylidene group having 2 to 10 carbon atoms such as a group; an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group; an acryloyl group; a methacryloyl group; .
A cyclic olefin monomer can be used individually by 1 type or in combination of 2 or more types.

When ring-opening polymerization of a cyclic olefin monomer, a linear α-olefin may be used as a molecular weight regulator. Examples of the linear α-olefin include those having 4 to 40 carbon atoms such as 1-butene, 1-hexene and 1-decene.
When a molecular weight regulator is used, the amount added is the molar ratio of monomer to molecular weight regulator (monomer: molecular weight regulator), usually 100: 0.1 to 100: 3, preferably 100: 0. .3 to 100: 2, more preferably 100: 0.5 to 100: 1.5.

The polymerization temperature at the time of ring-opening polymerization of the cyclic olefin monomer is usually in the range of −50 ° C. to + 250 ° C., preferably −30 ° C. to + 200 ° C., more preferably −20 ° C. to + 150 ° C. The polymerization pressure is usually in the range of 0 to 50 kg / cm ² , preferably 0 to 20 kg / cm ² . The polymerization time is appropriately selected depending on the polymerization conditions, but is usually in the range of 30 minutes to 20 hours, preferably 1 to 10 hours.

[Method of preparing hydrogenation reaction raw material liquid]
In the method of the present invention, an adsorbent containing zero-valent nickel (hereinafter sometimes referred to as “Ni-containing adsorbent”) is added to the mixed solution, and the metal component is adsorbed on the adsorbent. The adsorbent that has adsorbed the metal component is removed.

Examples of the Ni-containing adsorbent include those in which nickel metal is supported on a carrier, such as those conventionally used as hydrogenation catalysts. Examples of the carrier include carbon, silica / alumina, alumina, diatomaceous earth and the like.
In the method of the present invention, the metal component contained in the mixed liquid can be efficiently adsorbed and removed by using the Ni-containing adsorbent.

The content of nickel in the Ni-containing adsorbent is not particularly limited, but is usually 5 to 60% by weight, more preferably 10 to 40% by weight based on the Ni-containing adsorbent.
By using the Ni-containing adsorbent having a nickel content in the above range, the metal component contained in the mixed solution can be adsorbed and removed more efficiently.

The addition amount of the Ni-containing adsorbent is not particularly limited, but the molar ratio of the metal atom contained in the mixed solution and the nickel atom contained in the adsorbent (metal atom contained in the mixed solution: nickel atom contained in the adsorbent) And preferably 1: 0.08 to 1: 200, more preferably 1: 0.8 to 1: 100, and still more preferably 1: 8 to 1:45.
When the addition amount of the Ni-containing adsorbent is within the above range, the metal component contained in the mixed solution can be more efficiently adsorbed and removed. In particular, by preventing a large amount of nickel atoms from being contained in the system, it is possible to suppress the extraction reaction of hydrogen atoms from the polymer and the subsequent isomerization reaction.

The Ni-containing adsorbent may be activated by contacting it with hydrogen gas at a high temperature before adding it to the mixture. By performing this activation process, the metal component may be more efficiently adsorbed and removed.
The conditions for the activation treatment are not particularly limited, but the heating temperature is usually 100 to 300 ° C, preferably 120 to 250 ° C. The heating time is usually 10 minutes to 24 hours, preferably 30 minutes to 12 hours.

  The method for adsorbing the metal component on the Ni-containing adsorbent is not particularly limited. For example, after adding the Ni-containing adsorbent to the mixed solution, the metal component can be adsorbed on the Ni-containing adsorbent by stirring the mixed solution and bringing the Ni-containing adsorbent into contact with the metal component.

The temperature of the mixed solution when the metal component is adsorbed on the Ni-containing adsorbent is preferably 30 to 150 ° C., more preferably 50 to 120 ° C., and further preferably 70 to 100 ° C. The temperature of the mixed solution is within the above range. By being inside, the metal component contained in a liquid mixture can be adsorbed and removed more efficiently. In particular, by preventing the temperature from being too high, it is possible to suppress a hydrogen atom extraction reaction from the polymer and a subsequent isomerization reaction.
The time for adsorbing the metal component to the Ni-containing adsorbent is not particularly limited, but is usually 10 minutes to 24 hours, preferably 30 minutes to 12 hours, and more preferably 1 to 6 hours.

  The operation of adsorbing the metal component on the Ni-containing adsorbent is preferably performed in an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere. By performing the adsorption under an inert atmosphere, deterioration of the hydrogenation reaction raw material liquid can be suppressed. Moreover, by avoiding the hydrogenation atmosphere, an unintended hydrogenation reaction can be suppressed.

  Examples of the method for removing the adsorbent that has adsorbed the metal component include a method of separating the adsorbent. The filtration method is not particularly limited, and methods such as natural filtration, pressure filtration, and vacuum filtration can be appropriately used.

According to the method of the present invention, it is possible to obtain a hydrogenation reaction raw material liquid in which the content of the metal component in the mixed liquid is reduced.
By using the hydrogenation reaction raw material liquid obtained by the method of the present invention, it is possible to obtain a polymer hydride with a small amount of metal components.
Further, in the hydrogenation reaction using this hydrogenation reaction raw material liquid, the hydrogenation reaction can be sufficiently advanced without adding an excessive hydrogenation catalyst. Therefore, the cost for the hydrogenation catalyst can be reduced, the removal operation of the hydrogenation catalyst can be efficiently performed, the isomerization reaction (side reaction) of the polymer is suppressed, and the target polymer hydride can be obtained. High quality and high yield can be obtained.

2) Method for Producing Polymer Hydride The method for producing a polymer hydride according to the present invention comprises adding a hydrogenation catalyst to the hydrogenation reaction raw material liquid obtained by the method according to the present invention, and hydrogenating the polymer (α). It is characterized by performing a chemical reaction.

A conventionally known hydrogenation catalyst can be used as the hydrogenation catalyst used in the present invention.
The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec- Combinations of butyl lithium, tetrabutoxy titanate / dimethyl magnesium and the like can be mentioned. Further examples include noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium.

  As the heterogeneous catalyst, nickel, palladium, platinum, rhodium, ruthenium, or a solid catalyst in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, titanium oxide, for example, nickel / silica, nickel / Examples of the catalyst system include diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

  The hydrogenation catalyst used may be selected according to the solubility of the resulting polymer hydride in the solvent. That is, if the polymer hydride is dissolved in the reaction solution, the polymer hydride and the hydrogenation catalyst can be easily separated by selecting a heterogeneous catalyst. In addition, if the polymer hydride is precipitated from the reaction solution, the polymer hydride and the hydrogenation catalyst can be easily separated by selecting a homogeneous catalyst.

  Although the addition amount of a hydrogenation catalyst is not specifically limited, Usually, it is 0.001-0.5 weight part with respect to 100 weight part of polymers ((alpha)), Preferably it is 0.005-0.1 weight part.

  The reaction conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst system to be used, but the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. If the reaction temperature is too low, the reaction rate may be slow, and if it is too high, side reactions may occur. The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be slow, and if it is too high, a high pressure reactor is required. Although reaction time will not be specifically limited if a desired hydrogenation rate can be achieved, Usually, it is 0.1 to 10 hours.

  After completion of the hydrogenation reaction, the polymer hydride and the catalyst can be separated according to conventional methods such as centrifugation and filtration.

  In the method for producing a polymer hydride according to the present invention, since the hydrogenation reaction can sufficiently proceed without adding an excessive amount of the hydrogenation catalyst, the cost for the hydrogenation catalyst can be suppressed. The removal operation of the hydrogenation catalyst can be performed efficiently.

3) Polymer hydride The polymer hydride of the present invention is obtained by the method for producing a polymer hydride of the present invention.
Therefore, the polymer hydride of the present invention has a very small amount of impurities due to the metal component and the isomerization reaction of the polymer.
The amount of the metal component contained in the polymer hydride of the present invention is preferably less than 80 ppm, more preferably less than 50 ppm. The lower limit is not particularly limited and is preferably as small as possible, but is usually 1 ppm or more.
Since it has the said characteristic, the polymer hydride of this invention is preferably used as manufacturing raw materials, such as an optical member and a pharmaceutical container.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The evaluation method of each characteristic is as follows.

(1) Molecular weight (weight average molecular weight and number average molecular weight) of cyclic olefin ring-opening polymer
Gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent (apparatus: manufactured by Tosoh Corporation, HLC-8320, column: manufactured by Tosoh Corporation, H type column) is carried out at 40 ° C. The molecular weight of the olefin ring-opening polymer was determined.

(2) Residual metal amount The obtained cyclic olefin ring-opening polymer hydride was put in a glass container and weighed, and then wet decomposition was performed using sulfuric acid and nitric acid. The obtained decomposition product was diluted with ultrapure water, and the volume was adjusted to 10 mL to prepare a test solution. Using ICP-AES (manufactured by SIS Nanotechnology, product name “SPS-5100”), the amount of metal in this test solution was quantified to determine the amount of residual metal in the cyclic olefin ring-opening polymer hydride.

(3) Hydrogenation rate About the obtained cyclic olefin ring-opening polymer hydride, a mixed solvent (mixing ratio: 2/1) of 1,2,4-trichlorobenzene-d ³ / orthodichlorobenzene-d ⁴ was used as a solvent ¹ H-NMR measurement was performed at 200 ° C. to determine the hydrogenation rate.

(4) Melting | fusing point About the obtained cyclic olefin ring-opening polymer hydride, the glass transition temperature and melting | fusing point were calculated | required using the differential scanning calorimeter, respectively. The measurement was performed by heating the sample to 300 ° C. in a nitrogen atmosphere, then rapidly cooling with liquid nitrogen, and again raising the temperature at 10 ° C./min.

[Production Example 1] Synthesis of dicyclopentadiene ring-opening polymer solution (1) After drying, 90.4 parts of cyclohexane and dicyclopentadiene (with an end-body content of 99% or more) were placed in a metal pressure-resistant reaction vessel whose inside was substituted with nitrogen. 71.4 parts of a 70% cyclohexane solution (containing 50 parts as dicyclopentadiene) and 2.48 parts of 1-hexene were added, and the whole volume was heated to 50 ° C. To this, 0.12 part of diethylaluminum ethoxide in n-hexane (concentration 19%) was added and stirred for 10 minutes. Further, a toluene solution of tetrachlorotungsten (VI) phenylimide (tetrahydrofuran) complex (concentration 2). %) 1.39 parts was added, and a ring-opening polymerization reaction was carried out at 50 ° C. for 3 hours. Subsequently, after adding 0.3 part of isopropyl alcohol to the obtained polymerization reaction liquid, the whole volume was stirred for 30 minutes and the dicyclopentadiene ring-opening polymer solution (1) was obtained.
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer in the dicyclopentadiene ring-opening polymer solution (1) are 9,570 and 28,700, respectively, and the molecular weight distribution (Mw / Mn) was 3.00.
In addition, the tungsten content based on the dicyclopentadiene ring-opening polymer in the dicyclopentadiene ring-opening polymer solution (1) is about 200 ppm.

[Production Example 2] Synthesis of dicyclopentadiene ring-opening polymer solution (2) After drying, 90.4 parts of cyclohexane and dicyclopentadiene (99% or more of the end product content) were added to a metal pressure-resistant reaction vessel whose inside was substituted with nitrogen. 71.4 parts of a 70% cyclohexane solution (containing 50 parts as dicyclopentadiene) and 0.95 part of 1-hexene were added, and the whole volume was heated to 50 ° C. To this, 2.8 parts of a toluene solution (concentration 2%) of 2,6-diisopropylphenylimido neophylidene molybdenium (VI) bis (hexafluoro-t-butoxide) complex was added, and at 50 ° C. for 3 hours, A ring-opening polymerization reaction was performed. Subsequently, after adding 0.3 part of isopropyl alcohol to the obtained polymerization reaction liquid, the whole volume was stirred for 30 minutes and the dicyclopentadiene ring-opening polymer solution (2) was obtained.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer in the dicyclopentadiene ring-opening polymer solution (2) are 9,640 and 26,900, respectively, and the molecular weight distribution (Mw / Mn) was 2.79.
In addition, the molybdenum content in the dicyclopentadiene ring-opening polymer solution (2) based on the dicyclopentadiene ring-opening polymer is about 200 ppm.

[Example 1]
Add 2.5 parts of diatomaceous earth-supported nickel compound (product name: T8400RL, nickel support rate 58%, diluted diatomaceous earth 50%) and 166 parts of cyclohexane to the pressure-resistant reaction vessel, and introduce hydrogen gas. The pressure was increased to 0.2 MPa, and the entire volume was heated to 140 ° C. to activate nickel. Subsequently, after cooling the whole volume to room temperature (25 degreeC) and returning the pressure in a pressure-resistant reaction container to a normal pressure (atmospheric pressure), nitrogen substitution of the gas phase part was performed.
Next, 167 parts of the dicyclopentadiene ring-opening polymer solution (1) obtained in Production Example 1 (containing 50 parts of dicyclopentadiene ring-opening polymer) is placed in the pressure-resistant reaction vessel, and the whole volume is 100 ° C. After stirring for 2 hours to adsorb the metal component to the diatomaceous earth-supported nickel compound, the diatomaceous earth-supported nickel compound was separated by filtration to obtain a hydrogenation reaction raw material liquid (1).

In a pressure-resistant reaction vessel, 200 parts of the obtained hydrogenation reaction raw material liquid (1) (containing 30 parts of dicyclopentadiene ring-opening polymer), 100 parts of cyclohexane, and 0.0108 parts of chlorohydridocarbonyltris (triphenylphosphine) ruthenium. Then, hydrogen gas was introduced and the pressure was increased to 4 MPa. Subsequently, the whole volume was heated and hydrogenation reaction was performed at 180 degreeC for 5 hours.
After cooling the reaction solution, a large amount of isopropyl alcohol was added thereto to precipitate a reaction product, which was collected by filtration. The obtained precipitate was dried under reduced pressure at 60 ° C. for 24 hours to obtain 27.2 parts of a crystalline dicyclopentadiene ring-opening polymer hydride (1).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (1) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

[Example 2]
In Example 1, except having changed the usage-amount of the diatomaceous earth carrying | support nickel compound from 2.5 parts to 1 part, it carried out similarly to Example 1, and obtained the hydrogenation reaction raw material liquid (2), and using this Dicyclopentadiene ring-opening polymer hydride (2) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (2) was 99.5%, and the melting point was 264 ° C. The amount of residual tungsten was 9 ppm, and the amount of residual aluminum was 4 ppm.

Example 3
In Example 2, a hydrogenation reaction raw material liquid (3) was obtained in the same manner as in Example 2 except that the temperature at which the metal component was adsorbed was changed to 50 ° C., and this was used to open dicyclopentadiene. A ring polymer hydride (3) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (3) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was 25 ppm, and the amount of residual aluminum was 13 ppm.

Example 4
In Example 1, a hydrogenation reaction raw material liquid (4) was obtained in the same manner as in Example 1, except that the amount of nickel compound supported on diatomaceous earth was changed from 2.5 parts to 0.5 parts. To obtain a hydrogenated dicyclopentadiene ring-opening polymer (4).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (4) was 99.6%, and the melting point was 266 ° C. The amount of residual tungsten was 16 ppm, and the amount of residual aluminum was 7 ppm.

Example 5
In Example 4, a hydrogenation reaction raw material liquid (5) was obtained in the same manner as in Example 4 except that the temperature at which the metal component was adsorbed was changed to 150 ° C., and this was used to open dicyclopentadiene. A ring polymer hydride (5) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (5) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 6
In Example 1, the amount of nickel compound supported on diatomaceous earth was changed from 2.5 parts to 10 parts, and the temperature at the time of adsorbing the metal content was changed to 30 ° C., as in Example 1. Thus, a hydrogenation reaction raw material liquid (6) was obtained, and a dicyclopentadiene ring-opening polymer hydride (6) was obtained using this.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (6) was 99.6%, and the melting point was 265 ° C. The residual tungsten amount was 34 ppm, and the residual aluminum amount was 15 ppm.

Example 7
In Example 1, except that the amount of nickel compound supported on diatomaceous earth was changed from 2.5 parts to 0.05 parts, and the temperature at which the metal component was adsorbed was changed to 150 ° C. Similarly, a hydrogenation reaction raw material liquid (7) was obtained, and a dicyclopentadiene ring-opening polymer hydride (7) was obtained using this.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (7) was 99.5%, and the melting point was 264 ° C. The amount of residual tungsten was 48 ppm and the amount of residual aluminum was 28 ppm.

Example 8
In Example 1, a hydrogenation reaction raw material liquid (8) was obtained in the same manner as in Example 1 except that the temperature at which the metal component was adsorbed was changed to 120 ° C., and this was used to open dicyclopentadiene. A ring polymer hydride (8) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (8) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 9
In Example 1, the amount of nickel compound supported on diatomaceous earth was changed from 2.5 parts to 5 parts, and the temperature at the time of adsorbing the metal content was changed to 70 ° C., as in Example 1. Thus, a hydrogenation reaction raw material liquid (9) was obtained, and a dicyclopentadiene ring-opening polymer hydride (9) was obtained using this.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (9) was 99.6%, and the melting point was 266 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 10
To the pressure-resistant reaction vessel, 10 parts of diatomaceous earth-supported nickel compound (manufactured by Clariant Catalysts, product name: T8400RL, nickel support rate 58%, diluted diatomaceous earth 50%) and 166 parts of cyclohexane were added. 167 parts of dicyclopentadiene ring-opening polymer solution (1) (containing 50 parts of dicyclopentadiene ring-opening polymer) was added, and the gas layer part was substituted with nitrogen. The whole volume was stirred at 150 ° C. for 6 hours to adsorb the metal component to the diatomaceous earth-supported nickel compound, and then the diatomaceous earth-supported nickel compound was separated by filtration to obtain a hydrogenation reaction raw material liquid (10).

In a pressure resistant reactor, 200 parts of the resulting hydrogenation reaction raw material liquid (10) (containing 30 parts of dicyclopentadiene ring-opening polymer), 100 parts of cyclohexane, and 0.0108 parts of chlorohydridocarbonyltris (triphenylphosphine) ruthenium. Then, hydrogen gas was introduced and the pressure was increased to 4 MPa. Subsequently, the whole volume was heated and hydrogenation reaction was performed at 180 degreeC for 5 hours.
After cooling the reaction solution, a large amount of isopropyl alcohol was added thereto to precipitate a reaction product, which was collected by filtration. The obtained precipitate was dried under reduced pressure at 60 ° C. for 24 hours to obtain 27.2 parts of a crystalline dicyclopentadiene ring-opening polymer hydride (10).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (10) was 99.5%, and the melting point was 264 ° C. The amount of residual tungsten was 35 ppm, and the amount of residual aluminum was 13 ppm.

Example 11
In Example 1, it replaced with the diatomaceous earth carrying | support nickel compound, and carried out similarly to Example 1 except having used 2 parts of alumina carrying | support nickel compounds (The product made from JGC Catalysts and Chemicals, product name: N163A, nickel carrying | support rate 37%). The hydrogenation reaction raw material liquid (11) was obtained, and 27.2 parts of a dicyclopentadiene ring-opening polymer hydride (11) was obtained using this.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (11) was 99.5%, and the melting point was 266 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 12
In Example 1, instead of 167 parts of dicyclopentadiene ring-opening polymer solution (1) obtained in Production Example 1 (50 parts of dicyclopentadiene ring-opening polymer), dicyclopentadiene obtained in Production Example 2 was used. A hydrogenation reaction raw material liquid (12) was obtained in the same manner as in Example 1 except that 167 parts of the ring-opening polymer solution (2) (50 parts of dicyclopentadiene ring-opening polymer) were used. As a result, 27.1 parts of dicyclopentadiene ring-opening polymer hydride (12) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (12) was 99.5%, and the melting point was 251 ° C. The amount of residual molybdenum was less than 1 ppm.

Example 13
To a pressure-resistant reaction vessel, 2.5 parts of a nickel compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name: Raney nickel, nickel 40%, water slurry) and 1.25 parts of anhydrous magnesium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added. 167 parts of dicyclopentadiene ring-opening polymer solution (1) obtained in Production Example 1 (containing 50 parts of dicyclopentadiene ring-opening polymer) was added, and the air layer part was substituted with nitrogen. The whole volume was stirred at 100 ° C. for 2 hours to adsorb the metal component to the nickel compound, and then the nickel compound and magnesium sulfate were separated by filtration to obtain a hydrogenation reaction raw material liquid (13). In the same manner as in Example 1, 27.8 parts of dicyclopentadiene ring-opening polymer hydride (13) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (13) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 14
In a pressure-resistant reaction vessel, 5 parts of a nickel compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name: Raney nickel, nickel 40%, water slurry) and 5 parts of anhydrous magnesium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added. 167 parts of the obtained dicyclopentadiene ring-opening polymer solution (1) (containing 50 parts of dicyclopentadiene ring-opening polymer) was added, and the gas layer part was substituted with nitrogen. The whole volume was stirred at 100 ° C. for 2 hours to adsorb the metal component to the nickel compound, and then the nickel compound and magnesium sulfate were separated by filtration to obtain a hydrogenation reaction raw material liquid (14). In the same manner as in Example 1, 26.9 parts of a dicyclopentadiene ring-opening polymer hydride (14) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (14) was 99.6%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

Example 15
To the pressure-resistant reaction vessel, 0.5 part of a nickel compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name: Raney nickel, nickel 40%, water slurry) and 1 part of anhydrous magnesium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added. 167 parts of dicyclopentadiene ring-opening polymer solution (1) obtained in 1 (containing 50 parts of dicyclopentadiene ring-opening polymer) was added, and the air layer part was substituted with nitrogen. The whole volume was stirred at 100 ° C. for 2 hours to adsorb the metal component to the nickel compound, and then the nickel compound and magnesium sulfate were separated by filtration to obtain a hydrogenation reaction raw material liquid (15). 1, 27.5 parts of dicyclopentadiene ring-opening polymer hydride (15) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (15) was 99.5%, and the melting point was 265 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

[Comparative Example 1]
In Example 5, a hydrogenation reaction raw material liquid (13) was obtained in the same manner as in Example 5 except that 12.25 parts of nickel (II) oxide was used instead of the diatomaceous earth-supported nickel compound. Was used to obtain 26.2 parts of dicyclopentadiene ring-opening polymer hydride (16).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (16) was 99.1%, and the melting point was 261 ° C. The amount of residual tungsten was 197 ppm and the amount of residual aluminum was 90 ppm.

[Comparative Example 2]
In Example 5, the hydrogenation reaction raw material liquid (14) was used in the same manner as in Example 5 except that 10 parts of activated alumina (D2-Y, manufactured by Mizusawa Chemical Co., Ltd.) was used instead of the diatomaceous earth supported nickel compound. Using this, a dicyclopentadiene ring-opening polymer hydride (17) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (17) was 99.2%, and the melting point was 262 ° C. The amount of residual tungsten was 194 ppm and the amount of residual aluminum was 96 ppm.

[Comparative Example 3]
In Example 5, hydrogenation reaction raw material liquid (18) was used in the same manner as in Example 5 except that 10 parts of synthetic zeolite (manufactured by Union Showa Co., Ltd., MS-13X) was used in place of the diatomaceous earth-supported nickel compound. Using this, a dicyclopentadiene ring-opening polymer hydride (15) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (18) was 99.1%, and the melting point was 260 ° C. The amount of residual tungsten was 199 ppm, and the amount of residual aluminum was 95 ppm.

[Comparative Example 4]
In Example 5, it replaced with the diatomaceous earth carrying | support nickel compound, and obtained hydrogenation reaction raw material liquid (19) like Example 5 except having used 10 parts of activated carbon (the Kuraray Chemical company make, Pw), This was used to obtain a dicyclopentadiene ring-opened polymer hydride (16).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (19) was 99.2%, and the melting point was 262 ° C. The residual tungsten amount was 190 ppm and the residual aluminum amount was 88 ppm.

[Comparative Example 5]
In a pressure-resistant reaction vessel, 100 parts of the dicyclopentadiene ring-opening polymer solution (1) obtained in Production Example 1 (30 parts of dicyclopentadiene ring-opening polymer), 200 parts of cyclohexane, chlorohydridocarbonyltris (triphenylphosphine) 0.0108 part of ruthenium was added, and hydrogen gas was further introduced to pressurize to 4 MPa. Subsequently, the whole volume was heated and hydrogenation reaction was performed at 180 degreeC for 5 hours.
After cooling the reaction solution, a large amount of isopropyl alcohol was added thereto to precipitate a reaction product, which was collected by filtration. The obtained precipitate was dried under reduced pressure at 60 ° C. for 24 hours to obtain 26.2 parts of a crystalline dicyclopentadiene ring-opening polymer hydride (20).
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (20) was 99.1%, and the melting point was 261 ° C. The amount of residual tungsten was 198 ppm and the amount of residual aluminum was 90 ppm.

[Comparative Example 6]
In a pressure-resistant reaction vessel, 100 parts of the dicyclopentadiene ring-opening polymer solution (1) obtained in Production Example 1 (30 parts of dicyclopentadiene ring-opening polymer), 200 parts of cyclohexane, a diatomaceous earth-supported nickel compound (manufactured by Clariant Catalyst) , Product name: T8400RL, nickel loading rate 58%, diatomaceous earth 50% diluted product) 6 parts, hydrogen gas is introduced to make hydrogen pressure 0.2 MPa, the whole volume is stirred at 150 ° C. for 2 hours, The minute was adsorbed on a diatomaceous earth-supported nickel compound. Subsequently, hydrogen gas was further introduced to bring the hydrogen pressure to 4 MPa, the whole volume was heated, and a hydrogenation reaction was performed at 180 ° C. for 5 hours.
After cooling the reaction solution, a large amount of isopropyl alcohol was added thereto to precipitate a reaction product, which was collected by filtration. The obtained precipitate was dried under reduced pressure at 60 ° C. for 24 hours to obtain 26.8 parts of a dicyclopentadiene ring-opening polymer hydride (21) having crystallinity.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (21) was 99.5%, the melting point was not observed, and the glass transition temperature was 99 ° C. The amount of residual tungsten was less than 1 ppm, and the amount of residual aluminum was less than 2 ppm.

[Comparative Example 7]
To the pressure-resistant reaction vessel, 2.5 parts of a nickel compound (manufactured by Tokyo Chemical Industry Co., Ltd., product name: Raney nickel, nickel 40%, water slurry) was added, and the dicyclopentadiene ring-opening polymer solution obtained in Production Example 1 was further added. (1) 167 parts (50 parts of dicyclopentadiene ring-opening polymer) were added, and the air layer part was substituted with nitrogen. The whole volume was stirred at 100 ° C. for 2 hours to adsorb the metal component to the nickel compound, and then the nickel compound was filtered off to obtain a hydrogenation reaction raw material liquid (22), which was used in the same manner as in Example 1. As a result, 27.4 parts of dicyclopentadiene ring-opening polymer hydride (22) was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride (22) was 99.3%, and the melting point was 263 ° C. The residual tungsten amount was 152 ppm, and the residual aluminum amount was 82 ppm.

  The types and amounts of dicyclopentadiene ring-opening polymers used in Examples 1 to 15 and Comparative Examples 1 to 7, the types and amounts of adsorbents, the amounts of dehydrating agents, the temperature of the adsorption reaction, (Ni / coating Adsorbed metal) molar ratio, presence or absence of adsorbent removal, residual tungsten (W) amount, residual molybdenum (Mo) amount, residual aluminum (Al) amount, hydrogenation rate, and the resulting ring-opening polymer hydride Tables 1 and 2 collectively show the melting points.

Tables 1 and 2 show the following.
In Examples 1-15, the dicyclopentadiene ring-opening polymer hydride with little residual metal amount was obtained.
On the other hand, in Comparative Examples 1 to 5 and 7, almost no metal component could be removed.
In Comparative Example 6, since the melting point of the obtained dicyclopentadiene ring-opening polymer hydride was not observed, it is considered that the isomerization reaction proceeded as a side reaction.

Claims (10)

A method for preparing a hydrogenation reaction raw material solution for use in a hydrogenation reaction of a polymer having a carbon-carbon double bond in the molecule,
An adsorbent containing zero-valent nickel is added to a mixed solution containing a solvent, a metal component, and the polymer, and the adsorbent that has adsorbed the metal component is removed after the metal component is adsorbed to the adsorbent. A method for preparing a hydrogenation reaction raw material liquid.   The method for preparing a hydrogenation reaction raw material liquid according to claim 1, wherein the metal component contains a metal element belonging to Groups 3 to 14 of the periodic table.   The method for preparing a hydrogenation reaction raw material liquid according to claim 1 or 2, wherein the metal component is derived from a polymerization catalyst used in a polymerization reaction for producing the polymer.   The method for preparing a hydrogenation reaction raw material liquid according to claim 1, wherein the metal component is dissolved in the mixed liquid.   The hydrogenation reaction raw material according to any one of claims 1 to 4, wherein the mixed liquid is a polymerization reaction liquid obtained by ring-opening polymerization of a cyclic olefin monomer in a solvent in the presence of a metathesis polymerization catalyst. Liquid preparation method.   The amount of the adsorbent containing zerovalent nickel is the molar ratio of the metal atoms contained in the mixed solution and the nickel atoms contained in the adsorbent (metal atoms contained in the mixed solution: nickel atoms contained in the adsorbent). The method for preparing a hydrogenation reaction raw material liquid according to any one of claims 1 to 5, wherein the ratio is 1: 0.08 to 1: 200.   The method for preparing a hydrogenation reaction raw material liquid according to any one of claims 1 to 6, wherein the temperature of the mixed liquid when adsorbing the metal component on the adsorbent is 30 to 150 ° C.   The method for preparing a hydrogenation reaction raw material liquid according to any one of claims 1 to 7, wherein the operation of adsorbing the metal component to the adsorbent is performed in an inert atmosphere.   A method for producing a polymer hydride, comprising adding a hydrogenation catalyst to the hydrogenation reaction raw material liquid obtained by the method according to any one of claims 1 to 8, and performing a hydrogenation reaction of the polymer. .   A polymer hydride obtained by the method according to claim 9.