JP7310136B2 - Polymer production method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymer.

Polymer production methods generally utilize chemical reactions using metal catalysts containing simple metals or metal compounds. For example, when performing a polymerization reaction to polymerize various monomers to form a polymer, a metal catalyst is used as the polymerization catalyst. In addition, when performing a hydrogenation reaction for further hydrogenating the formed polymer, a metal catalyst is used as the hydrogenation catalyst.

More specifically, in ring-opening polymerization reactions in which cyclic olefin monomers such as norbornene and dicyclopentadiene are ring-opening polymerized to form ring-opening polymers, metals such as chromium, molybdenum, and tungsten are used as ring-opening polymerization catalysts. In the hydrogenation reaction in which a metal catalyst containing is used and the formed ring-opening polymer is further hydrogenated, a metal catalyst containing metals such as nickel, palladium, platinum, rhodium, and ruthenium is used as the hydrogenation catalyst ( See Patent Documents 1 and 2).

Here, the polymer obtained by the reaction using the metal catalyst may contain a residue derived from the metal catalyst (hereinafter sometimes referred to as "metal catalyst residue").
If the polymer contains a large amount of metal catalyst residue, the amount of residual metal in the polymer increases, which can cause problems such as deterioration of the color of the polymer.
Therefore, it is possible to obtain a polymer with a reduced amount of residual metal by removing the metal catalyst residue from a polymer containing such a metal catalyst residue (hereinafter sometimes referred to as a "crude polymer"). Desired.

For example, in Patent Document 3, production of a polymer including a step of contacting a crude polymer solution in which a crude polymer is dissolved in a solvent with an aprotic polar solvent such as dimethylsulfoxide capable of liquid-liquid separation from the solvent. It is disclosed that the method can remove the metal catalyst residue from the crude polymer to obtain a polymer solution with reduced residual metal content.

JP 2014-162811 A JP 2015-54885 A JP 2012-92258 A

However, in the above-described conventional polymer production methods, there is still room for improvement in reducing the amount of residual metal in the polymer. In particular, from the viewpoint of suppressing yellowing of the polymer (that is, increasing the yellowing resistance of the polymer), it has been desired to reduce the amount of residual ruthenium (Ru) in the polymer.

Accordingly, an object of the present invention is to provide a method for producing a polymer capable of producing a polymer with a reduced amount of residual Ru.

The inventor of the present invention has made intensive studies with the aim of solving the above problems. Then, the present inventors brought a crude polymer containing a polymer and a metal catalyst residue containing ruthenium into contact with a polar organic compound at a temperature equal to or higher than a predetermined temperature to remove the metal catalyst residue from the crude polymer, and remove the metal catalyst residue from the crude polymer. The inventors have found that a polymer with a reduced amount of residual Ru can be produced by cooling a crude polymer from which catalyst residues have been removed, and have completed the present invention.

That is, the object of the present invention is to advantageously solve the above-mentioned problems, and the method for producing a polymer of the present invention comprises purifying a crude polymer containing a polymer and a metal catalyst residue containing ruthenium. A method for producing a polymer to obtain a polymer, wherein the crude polymer is brought into contact with a polar organic compound at a temperature equal to or higher than the glass transition temperature of the polymer to remove the metal catalyst residue from the crude polymer. and a cooling step of cooling the crude polymer from which the metal catalyst residue has been removed. In this way, the crude polymer containing the polymer and the metal catalyst residue containing ruthenium is brought into contact with the polar organic compound at a temperature equal to or higher than the predetermined temperature to remove the metal catalyst residue from the crude polymer and remove the metal catalyst. By cooling the crude polymer from which the residue has been removed, a polymer with a reduced amount of residual Ru can be produced.
Incidentally, the glass transition temperature of the polymer can be measured by the method described in the examples of the present specification.

Here, in the method for producing a polymer of the present invention, the polar organic compound preferably contains a compound containing at least one atom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus. In this way, if the polar organic compound contains a compound containing the above-mentioned predetermined atom, it is possible to produce a polymer with a further reduced amount of residual Ru.

Further, in the method for producing a polymer of the present invention, the polar organic compound is amines, quaternary ammonium salts, amides, nitriles, pyridines, alcohols, ethers, phenols, carboxylic acids, carboxylic acid esters. thiols, sulfoxides, sulfides, sulfonic acids, phosphonic acids, trialkylphosphines, and triarylphosphines. Thus, if the polar organic compound contains the above-mentioned predetermined compound, a polymer with a further reduced amount of residual Ru can be produced.

Furthermore, in the method for producing a polymer of the present invention, the metal catalyst residue preferably further contains at least one metal other than ruthenium selected from group 4 to group 13 metals in the periodic table. . Thus, if the metal catalyst residue further contains a metal other than the above-specified ruthenium, a polymer with a reduced amount of residual metal can be produced.

In the method for producing a polymer of the present invention, the metal other than ruthenium is preferably at least one metal selected from the group consisting of tungsten, titanium, nickel, cobalt and aluminum. Thus, if the metal catalyst residue further contains the predetermined metal, it is possible to produce a polymer with a further reduced amount of residual metal.

Furthermore, in the method for producing a polymer of the present invention, the metal catalyst residue is preferably derived from a ring-opening polymerization catalyst and/or a hydrogenation catalyst.

In addition, in the method for producing a polymer of the present invention, the polymer preferably contains a cyclic olefin polymer.

Furthermore, in the method for producing a polymer of the present invention, the polymer is preferably crystalline.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polymer which can manufacture the polymer with which the amount of residual Ru was reduced can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

(Method for producing polymer)
The method for producing a polymer of the present invention is a method for producing a polymer to obtain a purified polymer from a crude polymer containing a polymer and a predetermined metal catalyst residue, and comprises a predetermined removing step and a predetermined cooling step. and optionally further including any other steps.

According to the method for producing a polymer of the present invention, the residue of the metal catalyst can be sufficiently removed from the crude polymer described above, so that a polymer with a reduced amount of residual Ru can be produced. By reducing the amount of residual Ru in the polymer, a polymer with excellent yellowing resistance can be obtained.

Moreover, according to the production method of the present invention, the metal catalyst residue can be sufficiently removed from the crude polymer described above, so that a polymer with a reduced amount of residual metal can be produced. Here, the “residual metal amount” refers to the amount of metal remaining in the polymer, and the metal remaining in the polymer includes either ruthenium (Ru) or metals other than Ru. good too. Therefore, "reducing the amount of residual metal" can also include "reducing the amount of residual Ru".

<Removal process>
In the removing step, the crude polymer and the polar organic compound are brought into contact at a temperature equal to or higher than the glass transition temperature of the polymer to remove the metal catalyst residue from the crude polymer. This is because the metal catalyst residue contained in the crude polymer is adsorbed by the polar organic compound.

Here, in the removing step, "removing the metal catalyst residue from the crude polymer" means removing at least part of the metal catalyst residue contained in the crude polymer.

In this specification, a state in which the crude polymer and the polar organic compound obtained in the removal step are brought into contact with each other at a temperature equal to or higher than the predetermined temperature is sometimes referred to as a "contact system".

<<Contact>>
The contact between the crude polymer and the polar organic compound is not particularly limited as long as the crude polymer and the polar organic compound are brought into contact at a temperature equal to or higher than a predetermined temperature. Mixing to obtain a mixture as a contact system is preferred. By mixing and contacting the crude polymer and the polar organic compound, a polymer with a further reduced amount of residual metal can be produced. The mixture may contain a non-polar organic solvent, which will be described later.

-Contact temperature-
In the removal step, the temperature at which the crude polymer and the polar organic compound are brought into contact (contact temperature) must be at least the glass transition temperature of the polymer contained in the crude polymer (the glass transition temperature of the polymer +50 ° C.) or more, more preferably (glass transition temperature of the polymer + 75 ° C.) or more, further preferably (glass transition temperature of the polymer + 100 ° C.) or more, (the weight It is preferably (the glass transition temperature of the polymer + 250 ° C.) or less, more preferably (the glass transition temperature of the polymer + 200 ° C.) or less, and is (the glass transition temperature of the polymer + 180) ° C. or less. More preferred. If the temperature at which the crude polymer is brought into contact with the polar organic compound is equal to or higher than the above lower limit, a polymer with a reduced amount of residual Ru can be produced. On the other hand, if the temperature at which the crude polymer is brought into contact with the polar organic compound is equal to or lower than the above upper limit, the metal catalyst residue and the polar organic compound contained in the crude polymer can be more strongly adsorbed. Further reduced polymers can be produced.

-Contact time-
The time for which the crude polymer and the polar organic compound are brought into contact at the predetermined contact temperature can be appropriately adjusted according to the manner and scale of contact between the crude polymer and the polar organic compound.
For example, when the removal step is performed by mixing the crude polymer, the polar organic compound, and an arbitrary non-polar organic solvent by a method such as stirring, the contact time between the crude polymer and the polar organic compound is 10 minutes or longer. preferably 30 minutes or longer, more preferably 1 hour or longer, preferably 30 hours or shorter, more preferably 20 hours or shorter, and 10 hours or shorter. More preferred. If the contact time between the crude polymer and the polar organic compound is at least the above lower limit, it is possible to produce a polymer with a further reduced amount of residual metal.

-others-
The removal step is preferably performed in the presence of an inert gas such as nitrogen and argon. For example, when a crude polymer and a polar organic compound are placed in a heat-resistant reactor and the contacting operation is performed, it is preferable to replace the inside of the heat-resistant reactor with the inert gas.

At the time of contact, the polymer contained in the crude polymer may be dissolved in the polar organic compound, dispersed in the polar organic compound, or mixed with the polar organic compound. They may be separated.

Further, when a non-polar organic solvent is used in the contact operation in the removal step, the polymer contained in the crude polymer may be dissolved in the non-polar organic solvent or dispersed in the non-polar organic solvent. It may be separated from the non-polar organic solvent without being mixed.

<<crude polymer>>
Crude polymer comprises polymer and metal catalyst residues. The crude polymer may contain components other than the polymer and metal catalyst residue described above. Other components include residues other than metal catalyst residues that may be generated during the preparation of the crude polymer.

-Polymer-
The polymer contained in the crude polymer is not particularly limited, and for example, a polymer obtained by polymerizing various monomers in the presence of a metal catalyst as a polymerization catalyst can be used.

Furthermore, the polymer contained in the crude polymer may be hydrogenated. That is, the polymer contained in the crude polymer may be a hydrogenated polymer. A hydride of a polymer is obtained, for example, by hydrogenating a polymer in the presence of a metal catalyst as a hydrogenation catalyst.

In this specification, "hydrogenating" a polymer refers to reducing the unsaturated bond of the polymer. Here, the unsaturated bond includes a carbon-carbon unsaturated bond, a carbon-nitrogen unsaturated bond, a carbon-oxygen unsaturated bond, etc., preferably a carbon-carbon unsaturated bond, more preferably a carbon-carbon It is a double bond. The carbon-carbon unsaturated bond includes an unsaturated bond that constitutes an aromatic ring.

As the metal catalyst such as the above-described polymerization catalyst and/or hydrogenation catalyst, a known one can be used, and for example, a metal catalyst derived from the metal catalyst residue described later can be used.

The weight average molecular weight (Mw) of the polymer contained in the crude polymer is not particularly limited, but is preferably 500 or more, more preferably 5000 or more, still more preferably 10000 or more, and 1000000 or less. preferably 500,000 or less, and even more preferably 200,000 or less. If the weight-average molecular weight (Mw) of the polymer is at least the above lower limit, the adsorption efficiency between the polar organic compound and the metal catalyst residue can be increased, and a polymer with a further reduced amount of residual metal can be produced. On the other hand, if the weight average molecular weight (Mw) of the polymer is equal to or less than the above upper limit, it is possible to produce a polymer with a further reduced amount of residual metal.
In addition, the weight average molecular weight (Mw) of the polymer can be measured by the method described in the examples of the present specification.

The glass transition temperature of the polymer contained in the crude polymer is not particularly limited, and varies depending on the type of polymer, but is preferably −10° C. or higher, more preferably 30° C. or higher, and 50° C. or higher. °C or higher, preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.

The melting point of the polymer contained in the crude polymer is not particularly limited, but is preferably 50° C. or higher, more preferably 100° C. or higher, still more preferably 130° C. or higher, and 400° C. or lower. , more preferably 350° C. or lower, and even more preferably 300° C. or lower. When the melting point of the polymer is at least the above lower limit, the produced polymer is excellent in heat deformation resistance when actually used. On the other hand, if the melting point of the polymer is equal to or less than the above upper limit, the produced polymer has sufficient fluidity when melted and is excellent in moldability.
The melting point of the polymer can be measured by the method described in the examples of this specification.

Although the polymer contained in the crude polymer is not particularly limited, it is preferable to use a cyclic olefin polymer.

In addition, in this specification, a "cyclic olefin polymer" refers to the polymer obtained by superposing|polymerizing a cyclic olefin monomer, and/or its hydride. Here, when the cyclic olefin monomer is polymerized to obtain the cyclic olefin polymer, only the cyclic olefin monomer may be polymerized, or the cyclic olefin monomer and other substances other than the cyclic olefin monomer may be polymerized. You may copolymerize with a monomer.

As the cyclic olefin polymer, for example, a polymer obtained by addition polymerization of a cyclic olefin monomer (cyclic olefin addition polymer) may be used. It is more preferable to use a polymer obtained by ring polymerization (cyclic olefin ring-opening polymer) and its hydride, and it is even more preferable to use a cyclic olefin ring-opening polymer hydride. The cis content of the cyclic olefin ring-opening polymer subjected to the hydrogenation reaction measured by ¹ H-NMR is preferably higher than 50%, more preferably higher than 70%, and particularly preferably higher than 90%. .

Specific examples of the cyclic olefin monomer include, but are not limited to, monocyclic (monocyclic) cyclic olefins such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, and 1,3-cyclohexadiene, and substituents on the ring. derivatives of these having

bicyclo[2.2.1]hept-2-ene (common name: norbornene, hereinafter sometimes abbreviated as "NB"), 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-ethylidene-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-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl- bicyclic cyclic olefins such as bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene and derivatives thereof having a substituent on the ring;

tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopentadiene, hereinafter sometimes abbreviated as “DCP”), tricyclo[5.2.1. 0 ^2,6 ]dec-3-ene, tricyclo[6.2.1.0 ^2,7 ]undeca-3,9-diene, tricyclo[6.2.1.0 ^2,7 ]undeca-4,9 -diene, tricyclo[6.2.1.0 ^2,7 ]undec-9-ene, 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2. Tricyclic olefins such as 1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene and derivatives thereof having substituents on the ring;

Tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene (also simply referred to as “tetracyclododecene”; hereinafter sometimes abbreviated as “TCD”), 9-methyltetracyclo[6.2.1.1 ^{3, 6} . 0 ^2,7 ]dodeca-4-ene, 9-ethyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene (hereinafter sometimes abbreviated as “ETD”), 9-methylidenetetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethylidenetetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-vinyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, tetracyclo[9.2.1.0 ^2,10 . 0 ^3,8 ]tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a,9a-tetrahydrofluorene; hereinafter sometimes abbreviated as “MTF”), Tetracyclo[10.2.1.0 ^2,11 . 0 ^4,9 ]Pentadeca-4,6,8,13-tetraene (also known as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene) and other four-ring cyclic olefins and ring Derivatives thereof having a substituent at;

9-Cyclopentyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-cyclohexyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-cyclohexenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, pentacyclo[6.6.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 ^2,7 . 1 ^{3, 6} . 1 ^10,13 ]-4-pentadecene, 9-phenyl-cyclopentyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, heptacyclo[8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} . 0 ^{3, 8} . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0.1 ^2,9 . 0 ^3,8 . 1 ^{4, 7} . 0 ^{12, 17} . 1 ^13,16 ]-14-eicosene and other cyclic olefins having five or more rings, and derivatives thereof having substituents on the rings;
The ratio of the amount of dicyclopentadiene used to the total amount of cyclic olefin monomers used for preparing the cyclic olefin ring-opening polymer is preferably 50% by mass or more, more preferably 80% by mass or more. , 100% by mass.

The substituents that the above derivatives have on the ring are not particularly limited, and examples thereof include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group.

Further, other monomers other than the cyclic olefin monomers are not particularly limited as long as they are copolymerizable with the cyclic olefin monomers. The monomers include ethylene, propylene, 1-butene, 1-pentene, and α-olefins having 2 to 20 carbon atoms such as 1-hexene and their derivatives; 1,4-hexadiene, 4-methyl-1 ,4-hexadiene, 5-methyl-1,4-hexadiene, and non-conjugated dienes such as 1,7-octadiene;

Here, when obtaining a cyclic olefin polymer by polymerizing a cyclic olefin monomer and other monomers other than the cyclic olefin monomer, The mass ratio of the amount used (other monomer/cyclic olefin monomer) is not particularly limited, but is preferably 30/70 or less, more preferably 20/80 or less, and 10/90 or less. is more preferable, and 0/100 is particularly preferable.

The above-mentioned cyclic olefin ring-opening polymer is, for example, a method using a metathesis reaction catalyst (ring-opening polymerization catalyst) such as a ruthenium carbene complex catalyst described in WO 2010/110323, and JP-A-2015-54885. can be produced by a method using a ring-opening polymerization catalyst such as a tungsten (phenylimide) tetrachloride/tetrahydrofuran complex described in 1.

Furthermore, as a method of hydrogenating a cyclic olefin ring-opened polymer to produce a cyclic olefin ring-opened polymer hydride, for example, a method using a hydrogenation catalyst described in International Publication No. 2010/110323 and the like can be mentioned. Further, for example, after producing a cyclic olefin polymer using the ruthenium carbene complex catalyst described above as a ring-opening polymerization catalyst, the ruthenium carbene catalyst is used as it is as a hydrogenation catalyst, and the cyclic olefin ring-opening polymer is hydrogenated. It is also possible to produce a hydrogenated cyclic olefin ring-opening polymer by hydrogenation.

The hydrogenation rate of the hydrogenated cyclic olefin ring-opening polymer is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. When the hydrogenation rate of the hydrogenated cyclic olefin ring-opening polymer is at least the predetermined value, the weather resistance and heat resistance can be improved.
The hydrogenation rate of the hydrogenated cyclic olefin ring-opening polymer can be measured by the method described in the Examples of the present specification.

Moreover, the polymer contained in the crude polymer is preferably crystalline. If the polymer contained in the crude polymer is crystalline, a purified polymer with a reduced amount of residual metal can be obtained in high yield.
Furthermore, when the polymer contained in the crude polymer is a hydrogenated cyclic olefin ring-opening polymer, the hydrogenated cyclic olefin ring-opening polymer preferably has syndiotactic stereoregularity. If the cyclic olefin ring-opening polymer hydride is syndiotactic, physical properties such as heat resistance, mechanical strength, and solvent resistance of the produced polymer can be enhanced. Here, the proportion of syndiotactic is not particularly limited, but from the viewpoint of improving the crystallinity of the hydrogenated cyclic olefin ring-opening polymer and particularly improving the heat resistance, the proportion of syndiotactic is preferably higher. is preferred. More specifically, the proportion of racemo dyads in repeating units obtained by ring-opening polymerization of a cyclic olefin monomer followed by hydrogenation is preferably 51% or more, and preferably 60% or more. is more preferable, and 70% or more is particularly preferable. The higher the ratio of racemo diads, that is, the higher the syndiotactic ratio, the higher the melting point of the dicyclopentadiene ring-opening polymer hydride. The ratio of racemo dyads can be measured and quantified by 13C-NMR spectrum analysis. As a specific quantification method, ortho-dichlorobenzene-d4 is used as a solvent, 13C-NMR measurement is performed by applying the inverse-gated decoupling method at 150 ° C., and the 127.5 ppm peak of ortho-dichlorobenzene-d4 is used as a reference. The shift is a method of determining the ratio of racemo dyads from the meso/racemo ratio calculated from the intensity ratio of the 43.35 ppm signal derived from the meso dyads and the 43.43 ppm signal derived from the racemo dyads. be able to.
Here, the "crystallinity" refers to the property of being able to observe the melting point by differential scanning calorimetry (DSC) by optimizing the measurement conditions, etc., and is a property determined by the stereoregularity of the polymer chain. be.

-Metal catalyst residue-
The metal catalyst residue may contain at least ruthenium, and optionally at least one ruthenium selected from group 4 to group 13 metals in the periodic table such as tungsten, titanium, nickel, cobalt, and aluminum. You may further contain metals other than.

Here, the metal catalyst residue is a component derived from the metal catalyst, and may be a component having at least a part of the chemical structure of the metal catalyst. , a component having a chemical structure in which other components other than the metal catalyst are further bonded. And the metal catalyst residue usually contains the metal contained in the metal catalyst.

--metal catalyst--
The metal catalyst from which the ruthenium-containing metal catalyst residue is derived comprises at least a ruthenium-containing metal catalyst A and optionally further comprises a ruthenium-free metal catalyst B.

[Metal catalyst A]
Metal catalyst A is a metal catalyst containing ruthenium.

The metal catalyst A is not particularly limited as long as it contains ruthenium and can be used for preparing a crude polymer. For example, it may be a polymerization catalyst or a hydrogenation catalyst. , may contain both a polymerization catalyst and a hydrogenation catalyst.

Here, the polymerization catalyst that can be used as the metal catalyst A is not particularly limited. Examples include carbene complex catalysts. The ruthenium carbene complex catalyst can also be used as a hydrogenation catalyst. The polymerization catalysts that can be used as the metal catalyst A may be used singly or in combination of two or more.

Further, the hydrogenation catalyst that can be used as the metal catalyst A is not particularly limited. Those containing ruthenium can be used. In addition, the hydrogenation catalyst which can be used as the metal catalyst A may be used individually by 1 type, and may be used in mixture of 2 or more types.

[Metal catalyst B]
Metal catalyst B is a metal catalyst containing no ruthenium and containing a metal other than ruthenium. If the metal catalyst from which the metal catalyst residue is derived contains, in addition to the above-described ruthenium-containing metal catalyst A, a metal catalyst B that does not contain ruthenium and contains a metal other than ruthenium, the residual Polymers with reduced metal content can be produced.

The metal catalyst B is not particularly limited, but from the viewpoint of producing a polymer with a further reduced amount of residual metal, at least one selected from metals of groups 4 to 13 in the periodic table other than ruthenium more preferably at least one metal selected from the group consisting of tungsten, titanium, nickel, cobalt, and aluminum, and still more preferably tungsten.
In addition, the "periodic table" in the above refers to the long periodic table.

The metal catalyst B containing a metal other than ruthenium is not particularly limited as long as it can be used for preparing a crude polymer. For example, it may be a polymerization catalyst or a hydrogenation catalyst. Alternatively, it may contain both a polymerization catalyst and a hydrogenation catalyst.

Here, the polymerization catalyst that can be used as the metal catalyst B is not particularly limited. A polymerization catalyst can be used. The polymerization catalysts that can be used as the metal catalyst B may be used singly or in combination of two or more.

In addition, the hydrogenation catalyst that can be used as the metal catalyst B is not particularly limited. can be used. In addition, the hydrogenation catalyst which can be used as the metal catalyst B may be used individually by 1 type, and may be used in mixture of 2 or more types.

-Method for preparing crude polymer-
The method for preparing the above-mentioned crude polymer is not particularly limited, and a method of performing a reaction using a metal catalyst containing the above-described predetermined metal catalyst, that is, metal catalyst A containing ruthenium is usually used. can be done. Here, the above reaction may be a polymerization reaction, a hydrogenation reaction, or both a polymerization reaction and a hydrogenation reaction catalyst.

For example, the crude polymer is subjected to a polymerization reaction in the presence of a polymerization catalyst to polymerize various monomers to form a polymer, and then to a hydrogenation reaction in the presence of a hydrogenation catalyst to form a polymer. It can be prepared by further hydrogenating the coalescence. Here, as various monomers, for example, the cyclic olefin monomers described above in the "polymer" section can be used. As the polymerization catalyst and the hydrogenation catalyst, the metal catalysts described above in the section "Metal catalyst residue" can be used. The metal catalyst A containing ruthenium may be contained in the polymerization catalyst, may be contained in the hydrogenation catalyst, or may be contained in both the polymerization catalyst and the hydrogenation catalyst. and Further, when the metal catalyst contains a metal catalyst B that does not contain ruthenium, the metal catalyst B may be contained in the polymerization catalyst, may be contained in the hydrogenation catalyst, or may be contained in the polymerization catalyst and the hydrogenation catalyst. may be included in both

Although the method for preparing the crude polymer in which both the polymerization reaction and the hydrogenation reaction are carried out has been described above in detail, the method for preparing the crude polymer is not limited to this, and only the polymerization reaction may be carried out. However, only the hydrogenation reaction may be carried out.

In the method of preparing a crude polymer when only the polymerization reaction is performed, for example, the polymerization reaction is performed in the presence of a polymerization catalyst containing a metal catalyst A containing ruthenium, and various monomers are polymerized to form a polymer. Thus, a crude polymer can be obtained.

In addition, in the method for preparing a crude polymer when only the hydrogenation reaction is performed, for example, the hydrogenation reaction is performed in the presence of a hydrogenation catalyst containing a metal catalyst A containing ruthenium, and a commercially available heavy polymer is prepared. A crude polymer can be obtained by hydrogenating the coalescence.

The properties of the crude polymer obtained by the method for preparing the crude polymer described above are not particularly limited, and may be solid or liquid.

Moreover, in the method for preparing the crude polymer described above, the crude polymer may be prepared in a state of being dissolved or dispersed in an organic solvent. Here, the organic solvent is the one used during the polymerization reaction and/or the hydrogenation reaction during the preparation of the crude polymer. Although the organic solvent is not particularly limited, for example, a non-polar organic solvent, which will be described later, can be used.

Since the crude polymer contains the metal catalyst residue derived from the metal catalyst described above, the metal contained in the metal catalyst, which is the origin of the metal catalyst residue, remains in the crude polymer.

The kind of metal remaining in the crude polymer is not particularly limited. For example, when the metal catalyst from which the metal catalyst residue is derived contains multiple types of metals, at least some of the multiple types of metals remain in the crude polymer. Since the crude polymer contains metal catalyst residues containing ruthenium, it is assumed that ruthenium usually remains in the crude polymer.

Here, the amount of residual metal in the crude polymer is not particularly limited as long as it is within the range where the desired effects of the present invention can be obtained, and varies depending on the type of metal remaining in the crude polymer.
For example, from the viewpoint of producing a polymer with a reduced residual ruthenium (Ru) content, the residual Ru content in the crude polymer is preferably 5 ppm or more and 50 ppm or less.
Moreover, from the viewpoint of producing a polymer with a reduced amount of residual tungsten (W), the amount of residual tungsten (W) in the crude polymer is preferably 10 ppm or more and 100 ppm or less.

- Polar organic compounds -
The polar organic compound used in the removal step is a component capable of adsorbing the metal catalyst residue contained in the crude polymer by contacting it with the crude polymer at a predetermined contact temperature.

Here, the number of carbon atoms in the polar organic compound is preferably 10 or more, more preferably 15 or more, even more preferably 18 or more, and preferably 10,000 or less. If the number of carbon atoms in the polar organic compound is at least the above lower limit, it is possible to produce a polymer with a further reduced amount of residual metal.

From the viewpoint of producing a polymer with a further reduced amount of residual metal, the polar organic compound preferably has a hydrocarbon group. The hydrocarbon group that the polar organic compound may have is not particularly limited, and examples thereof include linear or branched chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

The molecular weight of the polar organic compound is preferably 70 or more, more preferably 300 or more, even more preferably 500 or more, and preferably 500,000 or less. If the molecular weight of the polar organic compound is at least the above lower limit, it is possible to produce a polymer with a further reduced amount of residual metal.

Furthermore, the boiling point of the polar organic compound is preferably 60° C. or higher, more preferably 100° C. or higher, and even more preferably 200° C. or higher. If the boiling point of the polar organic compound is at least the above lower limit, it is possible to produce a polymer with a further reduced amount of residual metal.

The polar organic compound is not particularly limited, but from the viewpoint of producing a polymer with a further reduced amount of residual Ru, a compound containing at least one atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus. It preferably contains amines, quaternary ammonium salts, amides, nitriles, pyridines, alcohols, ethers, phenols, carboxylic acids, carboxylic acid esters, thiols, sulfoxides, sulfides, sulfones More preferably, it contains at least one compound selected from the group consisting of acids, phosphonic acids, trialkylphosphines, and triarylphosphines.

Here, as the amines, any of primary amines, secondary amines and tertiary amines may be used. A primary amine is preferably used, and a primary amine is more preferably used.

As the amines, either alkylamines or arylamines may be used, but alkylamines are preferably used from the viewpoint of producing a polymer with a further reduced amount of residual metal.
As the amines, it is more preferable to use amines having 2 to 1000 carbon atoms, such as propylamine, hexylamine, and hexadecylamine, from the viewpoint of producing a polymer with a further reduced amount of residual metal. It is more preferable to use amines having 5 to 500 carbon atoms such as amines and hexadecylamine, and it is particularly preferable to use amines having 10 to 100 carbon atoms such as hexadecylamine.

Dimer acid-type diamines can also be used as amines.
Here, the dimer acid-type diamine means that two terminal carboxylic acid groups (—COOH) of the dimer acid are replaced by a primary aminomethyl group (—CH ₂ —NH ₂ ) or a diamine substituted with an amino group (—NH ₂ ). A dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid, and is obtained, for example, by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms in the presence of a clay catalyst or the like. Incidentally, industrially obtained dimer acid is mainly composed of dibasic acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, but the degree of purification Depending on the requirements, any amount of monomeric acids (18 carbon atoms), trimer acids (54 carbon atoms), other polymerized fatty acids of 20 to 54 carbon atoms may be included. In addition, double bonds remain in the dimer acid obtained by the intermolecular polymerization reaction of unsaturated fatty acids. and For example, obtained by further hydrogenating a dibasic acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, apparently dimerized stearic acid A dibasic acid having 36 carbon atoms is also included in the dimer acid.
As the dimer acid type diamine, a commercial product can be used, for example, "Priamine 1075" manufactured by CRODA can be used.

As quaternary ammonium salts, for example, stearylamine hydrochloride and the like can be used.

As amides, for example, N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidone and the like can be used.

Examples of nitriles that can be used include decanenitrile and butyronitrile.

As pyridines, for example, pyridine, 2,2'-bipyridyl and the like can be used.

As the alcohol, either a monohydric alcohol or a polyhydric alcohol can be used, but from the viewpoint of producing a polymer with a further reduced amount of residual Ru, it is preferable to use a polyhydric alcohol.
The polyhydric alcohol is not particularly limited, but for example, 1,2-ethanediol (ethylene glycol), 1,2,6-hexanetriol and the like can be used.

As ethers, for example, dibutyl ether can be used.

As phenols, for example, butylhydroxytoluene or the like can be used.

Examples of carboxylic acids that can be used include butyric acid and decanoic acid.

Examples of carboxylic acid esters that can be used include n-octyl acetate.

As thiols, for example, decyl mercaptan and the like can be used.

Examples of sulfoxides that can be used include dimethylsulfoxide (DMSO) and dibutylsulfoxide.

As sulfides, for example, dodecylmethyl sulfide and the like can be used.

As sulfonic acids, for example, benzenesulfonic acid or the like can be used.

As phosphonic acids, for example, diethyl methylphosphonate and the like can be used.

Examples of trialkylphosphines that can be used include trioctylphosphine and tributylphosphine.

As triarylphosphines, for example, triphenylphosphine and the like can be used.

These polar organic compounds may be used singly or in combination of two or more as long as the desired effects of the present invention can be obtained.

The mass ratio of the amount of the polar organic compound used to the amount of the crude polymer used in the removal step (polar organic compound/crude polymer) is preferably 1/10000 or more, more preferably 1/5000 or more. , more preferably 1/1000 or more, and preferably 10000/1 or less. If the mass ratio of the amount of the polar organic compound used to the amount of the crude polymer used (polar organic compound/crude polymer) is at least the above lower limit, a polymer with a further reduced amount of residual metal can be produced.

-Nonpolar organic solvent-
The removal step may be performed in the presence of a non-polar organic solvent. That is, in the removing step, the crude polymer and the polar organic compound may be brought into contact with each other in the presence of a non-polar organic solvent at a temperature equal to or higher than the predetermined temperature.
Examples of nonpolar organic solvents that can be used include alicyclic hydrocarbons such as cyclohexane and decalin (decahydronaphthalene); aromatic hydrocarbons such as toluene; and the like.

When a crude polymer dissolved or dispersed in a nonpolar organic solvent is used as the crude polymer, the nonpolar organic solvent, which is the solvent or dispersion medium of the crude polymer, may be used as it is in the removal step. good.

The mass ratio of the amount of non-polar organic solvent used to the amount of crude polymer used in the removal step (non-polar organic solvent/crude polymer) is preferably 1/2 or more, more preferably 1/1 or more. , more preferably 2/1 or more, and preferably 100000/1 or less. If the mass ratio of the amount of non-polar organic solvent used to the amount of crude polymer used (non-polar organic solvent/crude polymer) is equal to or higher than the above lower limit, the crude polymer dissolves in the non-polar organic solvent during the removal step, By increasing the adsorption efficiency between the polar organic compound and the metal catalyst residue, it is possible to produce a polymer with a further reduced amount of residual metal.

<Cooling process>
In the cooling step, the crude polymer from which the metal catalyst residue has been removed is cooled. As a result, the crude polymer from which the metal catalyst residue has been removed is easily separated from other components in the contact system such as the polar organic compound and the non-polar organic solvent that adsorb the metal catalyst residue, and is separated and obtained as a purified polymer. be able to.

In the cooling step, the temperature for cooling the crude polymer from which the metal catalyst residue has been removed is not particularly limited as long as it is lower than the contact temperature described above, but is preferably (the glass transition temperature of the polymer + 50 ° C.) or less, (Glass transition temperature of the polymer + 10 ° C.) or less, more preferably less than the glass transition temperature of the polymer, preferably (glass transition temperature of the polymer - 10) ° C. or higher, It is more preferably (the glass transition temperature of the polymer −30° C.) or higher, and still more preferably (the glass transition temperature of the polymer −50° C.) or higher. When the temperature for cooling the crude polymer from which the metal catalyst residue has been removed is equal to or lower than the upper limit and equal to or higher than the lower limit, the yield of the purified polymer can be increased.

The method for cooling the crude polymer from which the metal catalyst has been removed is not particularly limited, and the crude polymer from which the metal catalyst has been removed may be cooled alone, or the crude polymer from which the metal catalyst has been removed is The entire contact system may be cooled. Further, for example, when a mixture is obtained as a contact system by mixing a crude polymer, a polar organic compound, and a non-polar organic solvent at a temperature equal to or higher than a predetermined temperature in the removal step, the entire mixture may be cooled as it is. Then, the mixture is heated to a temperature equal to or higher than the glass transition temperature of the polymer and allowed to stand, and a non-polar organic solvent phase in which the crude polymer from which the metal catalyst residue has been removed is dissolved or dispersed and the metal catalyst residue is adsorbed. After separation into the polar organic compound phase, only the non-polar organic solvent phase may be taken out and cooled.

Further, in the cooling step, the crude polymer from which the metal catalyst residue has been removed is usually cooled to solidify the crude polymer from which the metal catalyst residue has been removed to obtain a purified polymer. For example, by cooling the mixture as the contact system obtained in the removal step described above, the crude polymer from which the metal catalyst residue has been removed precipitates and/or precipitates, and polymer precipitates and/or precipitates are formed. Occur. Then, the precipitate and/or sediment of the generated polymer can be separated by a known solid-liquid separation method such as filtration to obtain a purified polymer.

In addition, the obtained purified polymer may be washed with an organic solvent such as toluene, cyclohexane, or acetone. Furthermore, the organic solvent mixed in the purified polymer can be removed by heating the purified polymer washed with the organic solvent in the presence of an inert gas such as nitrogen and argon.

<<Purified polymer>>
The purified polymer obtained by the removing step and the cooling step described above has a reduced amount of residual Ru, and is therefore excellent in yellowing resistance.
Therefore, the purified polymer can be suitably used for applications such as optical members such as optical lenses, prisms, and light guides.

Here, the purified polymer obtained by the removing step and the cooling step may be used as it is for the above applications as a polymer produced by the method for producing a polymer of the present invention, or may be After further passing through other steps, it may be used for the above purpose.

The amount of residual metal in the purified polymer is not particularly limited and varies depending on the type of metal remaining in the purified polymer, but it is usually less than the amount of residual metal in the crude polymer.
For example, from the viewpoint of producing a polymer with a reduced amount of residual ruthenium (Ru), the amount of residual Ru in the purified polymer is preferably 6.0 ppm or less, more preferably 5.0 ppm or less. , is more preferably 4.0 ppm or less, and even more preferably 2.5 ppm or less.
Further, from the viewpoint of producing a polymer with a reduced amount of residual tungsten (W), the amount of residual tungsten (W) in the purified polymer is preferably 19.0 ppm or less, more preferably 10.0 ppm or less. is more preferably 2.5 ppm or less, and even more preferably 2.0 ppm or less.

<Other processes>
The method for producing the polymer of the present invention may optionally include steps other than the removal step and cooling step described above.
Such other steps are not particularly limited, and include, for example, a crude polymer preparation step of preparing a crude polymer. In addition, in the crude polymer preparation step, as a method for preparing a crude polymer, the method for preparing a crude polymer described above in the “removal step” section can be used.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these. "Parts" in the examples are based on mass unless otherwise specified.
Various measurements and evaluations in Examples and Comparative Examples were carried out according to the following methods.

<Measurement of molecular weight>
The weight-average molecular weight (Mw) of the ring-opening polymer was obtained as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent. GPC was measured at 40°C. In addition, as a measuring device, "System HLC-8320" manufactured by Tosoh Corporation was used, and as a measurement column, "H type column" manufactured by Tosoh Corporation was used.

<Measurement of cis/trans ratio of carbon-carbon double bond in main chain of ring-opening polymer>
Based on ¹ H-NMR measurement, the cis/trans ratio of carbon-carbon double bonds in the main chain of the ring-opened polymer was determined.

<Measurement of hydrogenation rate of ring-opening polymer hydride>
Based on ¹ H-NMR measurement, the degree of hydrogenation of unsaturated bonds in the hydrogenated ring-opening polymer was determined.

<Measurement of meso/racemo ratio of ring-opening polymer hydride>
Using ortho-dichlorobenzene-d ₄ as a solvent, ¹³ C-NMR measurement was performed by applying the inverse-gated decoupling method at 150 ° C., and the peak of ortho-dichlorobenzene-d ₄ at 127.5 ppm was used as a reference shift, and Based on the intensity ratio between the 43.35 ppm signal derived from the racemo diad and the 43.43 ppm signal derived from the racemo dyad, the meso/racemo ratio of the hydrogenated ring-opening polymer was determined.

<Measurement of glass transition temperature of ring-opening polymer hydride>
Using a differential scanning calorimeter (DSC, X-DSC7000 manufactured by Hitachi High-Tech Science), the glass transition temperature (Tg) was measured under the condition that the temperature was raised from 20°C to 320°C at a rate of 10°C/min.

<Measurement of melting point of ring-opening polymer hydride>
Crystals of a crude polymer containing a ring-opening polymer hydride as a sample were completely melted by heating in a differential scanning calorimeter, cooled to room temperature at a rate of 10°C/min, and then The temperature at the endothermic maximum of the crystalline melting peak when differential scanning calorimetry was performed up to 320° C. under the condition of increasing the temperature at 10° C./min was taken as the melting point of the sample. As a differential scanning calorimeter, a high-sensitivity differential scanning calorimeter "EXSTAR X-DSC7000" manufactured by Hitachi High-Tech Science Co., Ltd. was used. Differential scanning calorimetry was calibrated using indium, tin, and lead as standard substances for temperature and calorific value.

<Measurement of residual metal content>
About 0.3 g to about 0.5 g of each of the crude polymer and the purified polymer obtained in each example and comparative example was used as a measurement sample, wet-decomposed using sulfuric acid and nitric acid, and added to 10 mL with ultrapure water. After constant volume, measurement was performed by ICP-AES (“SPS5100” manufactured by SII Nano Technology) to measure the amount of residual ruthenium (Ru) and the amount of residual tungsten (W) as residual metal amounts.

<Yellowness>
A film-like test piece (thickness: 3 mm) was produced by hot press molding using the purified polymer obtained in each example and comparative example.
Then, in accordance with JISK7373, using a color difference meter ("SE-2000" manufactured by Nippon Denshoku Industries Co., Ltd.), the yellowness index (YI: yellow index) of the test piece is measured four times in transmission mode with an optical path length of 3 mm. Then, the average value was calculated, and the yellowness index YI of the test piece before the heat resistance test was ₀ .
Furthermore, a heat resistance test was performed by leaving the test piece still under conditions of an oxygen concentration of 21% by volume and a temperature of 125° C. for 1000 hours. Using the film after the heat resistance test, the yellowness index was measured four times in the same manner as above, and the average value was taken as the yellowness index YI ₁ of the test piece after the heat resistance test.
The yellowness index of the blank (air) was measured four times in the same manner as above, and the average value was taken as the yellowness index _YIB of the blank (air).
Then, using the values of YI ₀ , YI ₁ and YI _B obtained above, the degree of yellowing (ΔδYI) was determined according to the following formula (I). The smaller the yellowing index (ΔδYI) value, the better the yellowing resistance of the polymer.
ΔδYI=δYI ₁ −δYI ₀ (I)
Here, in formula (I), δYI ₁ represents the difference (YI ₁ -YI _B ) between the yellowness (YI ₁ ) of the test piece after the heat resistance test and the yellowness (YI _B ) of the blank (air). , δYI ₀ represents the difference (YI ₀ −YI _B ) between the yellowness (YI ₀ ) of the test piece before the heat resistance test and the yellowness (YI _B ) of the blank (air).

(Example 1)
<Crude polymer preparation step>
A solution prepared by dissolving 0.060 parts of a tungsten (phenylimide) tetrachloride/tetrahydrofuran complex as a ring-opening polymerization catalyst in 1.0 parts of cyclohexane was added to a glass reactor equipped with a stirrer. Further, a solution prepared by dissolving 0.047 parts of diethylaluminum ethoxide as an organometallic reducing agent in 0.50 parts of hexane was added and reacted at room temperature for 30 minutes. To the resulting mixture were added 7.5 parts of dicyclopentadiene as a cyclic olefin monomer, 27.0 parts of cyclohexane and 5.0 parts of 1-octene as a solvent, and a polymerization reaction was carried out at 50°C. After initiation of the polymerization reaction, the viscosity of the solution gradually increased. After the polymerization reaction was carried out for 3 hours, a large amount of isopropyl alcohol was poured into the polymerization reaction liquid to coagulate the precipitate, which was washed by filtration and dried under reduced pressure at 40° C. for 24 hours. The yield of the obtained dicyclopentadiene ring-opening polymer was 7.4 parts, and its weight average molecular weight (Mw) was 29,700. Also, the cis/trans ratio of the carbon-carbon double bond in the main chain of the dicyclopentadiene ring-opening polymer was 93/7.
Next, 3.0 g of the resulting dicyclopentadiene ring-opening polymer and 47 g of cyclohexane as a solvent were added to an autoclave equipped with a stirrer. Then, 0.00165 g of chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium as a hydrogenation catalyst dispersed in 10 ml of cyclohexane was further added, and a hydrogenation reaction was carried out at a hydrogen pressure of 4.0 MPa and 160° C. for 8 hours. . This hydrogenation reaction solution is poured into a large amount of acetone to completely precipitate the crude polymer, filtered and washed, and dried under reduced pressure at 40° C. for 24 hours to obtain a crude polymer containing a hydrogenated dicyclopentadiene ring-opening polymer. got
The hydrogenation rate of the hydrogenated dicyclopentadiene ring-opening polymer in the obtained crude polymer was 99% or more. In addition, since the meso/racemo ratio of the hydrogenated dicyclopentadiene ring-opening polymer in the crude polymer is 10/90 (ratio of racemo diad is 90%), the hydrogenated dicyclopentadiene ring-opening polymer is syndiotac It had tick stereoregularity. After drying the crude polymer under reduced pressure, the glass transition temperature and melting point of the hydrogenated dicyclopentadiene ring-opening polymer in the crude polymer were measured.
Then, the amount of residual metal in the obtained crude polymer was measured. Table 1 shows the results.

<Removal process>
31.5 g of decalin as a nonpolar organic solvent, 7.875 g of dimethyl sulfoxide (DMSO, molecular weight: 78.13, boiling point: 189° C.) as a polar organic compound, and the dicyclo obtained above were placed in a 500 ml pressure-resistant reactor. 3.5 g of crude polymer containing pentadiene ring-opening polymer hydride was added to each. After that, the heat-resistant reactor was set in a TVS-N2 type portable reactor (manufactured by Pressure Glass Industry Co., Ltd.), and the atmosphere was replaced with nitrogen. Furthermore, the pressure-resistant reactor was stirred while being heated at 215° C. for 3 hours to obtain a mixture as a contact system.
<Cooling process>
The mixture obtained above was then cooled to normal temperature (23° C.). Then, it was confirmed that precipitates were generated in the mixture after cooling. The precipitate was separated and obtained by filtering the mixture. The resulting precipitate is washed with toluene, cyclohexane, and acetone in this order, and then heated in the presence of nitrogen gas to remove these organic solvents, yielding a crystalline dicyclopentadiene ring-opening polymer. A purified polymer of the hydride was obtained.
The amount of residual metal in the purified polymer was measured. Table 1 shows the results.
In addition, based on the residual Ru amount in the crude polymer and the residual Ru amount in the purified polymer obtained above, the total amount of residual Ru contained in the crude polymer was reduced to polar organic compounds in the removal step and the cooling step. The ratio of the amount of Ru removed by adsorption was calculated as the Ru removal rate (% by mass). Table 1 shows the results.
Similarly, based on the amount of residual W in the crude polymer and the amount of residual W in the purified polymer obtained above, of the total amount of residual W contained in the crude polymer, the polar organic The ratio of the amount of W removed by adsorption to the compound was calculated as the W removal rate (% by mass). Table 1 shows the results.
Furthermore, the degree of yellowing (ΔδYI) of a film-like test piece obtained by hot-press molding the purified polymer was measured. Table 1 shows the results.

(Example 2)
Same as Example 1 except that in the removal step of Example 1, the polar organic compound was changed from 7.875 g of dimethyl sulfoxide (DMSO) to 7.875 g of decanenitrile (molecular weight: 153.27, boiling point: 237° C.). Then, a purified polymer of the hydrogenated dicyclopentadiene ring-opening polymer was obtained. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.

(Example 3)
In the removal step of Example 1, except that the polar organic compound was changed from dimethyl sulfoxide (DMSO) 7.875 g to N,N-dimethylformamide (DMF, molecular weight: 73.09, boiling point: 153 ° C.) 7.875 g , in the same manner as in Example 1, to obtain a purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.

(Example 4)
In the removal step of Example 1, except that the polar organic compound was changed from 7.875 g of dimethyl sulfoxide (DMSO) to 7.875 g of trioctylphosphine (molecular weight: 370.65, boiling point: 234°C). Similarly, a purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer was obtained. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.

(Example 5)
In the removal step of Example 1, except that the polar organic compound was changed from dimethyl sulfoxide (DMSO) 7.875 g to pyridine (molecular weight: 79.10, boiling point: 115.2 ° C.) 7.875 g. Similarly, a purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer was obtained. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.

(Example 6)
In the removal step of Example 1, the polar organic compound was removed from 7.875 g of dimethyl sulfoxide (DMSO) by CRODA's "Priamine 1075" (amines containing dimer acid type diamines having 36 carbon atoms, etc., hereinafter referred to as "priamine"). A) A purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer was obtained in the same manner as in Example 1, except that the weight was changed to 7.875 g. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.

(Comparative example 1)
A purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer was obtained in the same manner as in Example 1, except that the following liquid-liquid separation step was performed instead of the cooling step. Then, the same measurements and calculations as in Example 1 were performed. Table 1 shows the results.
<Liquid-liquid separation process>
The mixture as the contact system obtained in the removal step was heated to 150° C. and allowed to stand still to separate into a decalin phase in which the hydrogenated dicyclopentadiene ring-opening polymer and the like were dissolved, and a DMSO phase. The DMSO phase was then removed from the mixture as the contact system. DMSO heated to 150° C. was added to the remaining decalin phase, mixed by stirring, allowed to stand, and then the operation of removing the separated DMSO phase (decantation) was repeated twice. The decalin solution of the hydrogenated dicyclopentadiene ring-opening polymer obtained by the above operation was mixed with acetone to precipitate the hydrogenated dicyclopentadiene ring-opening polymer. The resulting precipitate was washed with acetone to obtain a purified polymer of the hydrogenated dicyclopentadiene ring-opening polymer having crystallinity.

(Comparative example 2)
A purified polymer of dicyclopentadiene ring-opening polymer hydride was obtained in the same manner as in Example 2, except that the following liquid-liquid separation step was performed instead of the cooling step. Then, the same measurements and calculations as in Example 2 were performed. Table 1 shows the results.
<Liquid-liquid separation process>
The mixture as the contact system obtained in the removal step was heated to 150° C. and allowed to stand still to separate into a decalin phase in which the hydrogenated dicyclopentadiene ring-opening polymer and the like were dissolved, and a decanenitrile phase. . Then, the decanenitrile phase was removed from the mixture as the contact system. Then, decanenitrile heated to 150° C. is added to the remaining decalin phase, mixed by stirring, allowed to stand, and then the operation of removing the separated decanenitrile phase (decantation) is repeated twice. rice field. The decalin solution of the hydrogenated dicyclopentadiene ring-opening polymer obtained by the above operation was mixed with acetone to precipitate the hydrogenated dicyclopentadiene ring-opening polymer. The resulting precipitate was washed with acetone to obtain a purified polymer of the hydrogenated dicyclopentadiene ring-opening polymer having crystallinity.

(Comparative Example 3)
A purified polymer of a hydrogenated dicyclopentadiene ring-opening polymer was obtained in the same manner as in Example 3, except that the following liquid-liquid separation step was performed instead of the cooling step. Then, the same measurements and calculations as in Example 3 were performed. Table 1 shows the results.
<Liquid-liquid separation process>
The mixture as the contact system obtained in the removal step was heated to 150° C. and allowed to stand still to separate into a decalin phase in which hydrogenated dicyclopentadiene ring-opening polymer and the like were dissolved, and a DMF phase. The DMF phase was then removed from the mixture as the contact system. Furthermore, the operation (decantation) of adding DMF heated to 150° C. to the remaining decalin phase, stirring and mixing, leaving the mixture to stand, and then removing the separated DMF phase was repeated twice. The decalin solution of the hydrogenated dicyclopentadiene ring-opening polymer obtained by the above operation was mixed with acetone to precipitate the hydrogenated dicyclopentadiene ring-opening polymer. The resulting precipitate was washed with acetone to obtain a purified polymer of the hydrogenated dicyclopentadiene ring-opening polymer having crystallinity.

(Comparative Example 4)
In Example 4, the mixture obtained in the removal step was heated to 150° C. and allowed to stand still without performing the cooling step. Trioctylphosphine could not be removed from the contact system by a liquid-liquid extraction process similar to Examples 1-3, and a purified polymer could not be obtained.

(Comparative Example 5)
In Example 5, the mixture obtained in the removal step was heated to 150° C. and allowed to stand without performing the cooling step. Pyridine could not be removed from the contact system by the same liquid-liquid extraction process as in 1 to 3, and a purified polymer could not be obtained.

(Comparative Example 6)
In Example 6, the mixture obtained in the removal step was heated to 150° C. and allowed to stand still without performing the cooling step. Puramine could not be removed from the contact system by the same liquid-liquid extraction process as in 1 to 3, and a purified polymer could not be obtained.

From Table 1, a crude polymer containing a polymer and a metal catalyst residue containing ruthenium is brought into contact with a polar organic compound at a temperature equal to or higher than a predetermined temperature to remove the metal catalyst residue from the crude polymer. It can be seen that by cooling the removed crude polymer (Examples 1 to 6), a polymer with a reduced amount of residual Ru can be produced.

On the other hand, a crude polymer containing a polymer and a metal catalyst residue containing ruthenium is brought into contact with a polar organic compound at a temperature equal to or higher than a predetermined temperature to remove the metal catalyst residue from the crude polymer, thereby removing the metal catalyst residue. It can be seen that because the crude polymer was not cooled (Comparative Examples 1 to 6), a polymer with a reduced amount of residual Ru could not be produced.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polymer which can manufacture the polymer with which the amount of residual Ru was reduced can be provided.

Claims (7)

A method for producing a polymer to obtain a purified polymer by removing 43% by mass or more of ruthenium from a crude polymer containing a polymer and a metal catalyst residue containing ruthenium,
The metal catalyst residue further contains at least one metal other than ruthenium selected from group 4 to group 13 metals in the periodic table,
a removal step of contacting the crude polymer with a polar organic compound at a temperature equal to or higher than the glass transition temperature of the polymer to remove the metal catalyst residue from the crude polymer;
and a cooling step of cooling the crude polymer from which the metal catalyst residue has been removed and separating and obtaining the purified polymer as the purified polymer. 2. The method for producing a polymer according to claim 1, wherein the polar organic compound comprises a compound containing at least one atom selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus. The polar organic compound includes amines, quaternary ammonium salts, amides, nitriles, pyridines, alcohols, ethers, phenols, carboxylic acids, carboxylic acid esters, thiols, sulfoxides, sulfides, and sulfones. 3. The method for producing a polymer according to claim 1, wherein at least one compound selected from the group consisting of acids, phosphonic acids, trialkylphosphines, and triarylphosphines is included. 2. The method for producing a polymer according to claim 1, wherein said metal other than ruthenium is at least one metal selected from the group consisting of tungsten, titanium, nickel, cobalt and aluminum. The method for producing a polymer according to any one of claims 1 to 4, wherein the metal catalyst residue is derived from a ring-opening polymerization catalyst and/or a hydrogenation catalyst. The method for producing a polymer according to any one of claims 1 to 5, wherein the polymer comprises a cyclic olefin polymer. The method for producing a polymer according to any one of claims 1 to 6, wherein the polymer is crystalline.