JP2001316455A - Method for manufacturing polymer containing alicyclic structure and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a polymer containing an alicyclic structure suitable as an optical material and the like, which permits efficient removal of a volatile component from a reaction solution containing a polymer and moreover inhibition of lowering of the molecular weight of the polymer obtained. SOLUTION: The manufacturing method comprises a preliminary condensation process where a part of a volatile components of the polymer solution containing a polymer containing an alicyclic structure is removed to give a polymer concentration of 30-95 wt.%, and a drying process where the rest of the volatile components of the polymer solution containing an alicyclic structure containing polymer and having a polymer concentration of 30-95 wt.% is removed to give a content of the volatile components of 1 wt.% or less. According to the method, the volatile components can be efficiently decreased and the obtained polymer has hardly undergone shear stress and therefore scission of the polymer chain is reduced, thus resulting in inhibition of lowering of the molecular weight of the polymer obtained. Moreover, a molded product molded from the polymer has high strength and is reduced in discoloration and molding defects such as silver streak and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alicyclic structure-containing polymer, and more particularly to a method for producing an alicyclic structure-containing polymer suitable as a material for an optical molded product having excellent color tone and the like. About.

[0002]

2. Description of the Related Art An alicyclic structure-containing polymer such as a norbornene-based polymer has excellent transparency and is a material suitable for optical materials and the like. Such a norbornene-based polymer can be produced by solution polymerization using an organic solvent.However, in order to use the polymer as an optical material, a molded product is formed by removing the solvent from the solution after the reaction, and then heating and molding. Need to be

In order to avoid the use of foreign materials such as optical materials, the solvent is removed from the reaction solution by heating the reaction solution without using a coagulation method using a poor solvent or steam. The direct drying method in which the solvent is gradually removed by reducing the pressure is effective, and several methods have been proposed.

For example, Japanese Patent Application Laid-Open No. 4-161444 discloses a technique in which a reaction solution containing a norbornene-based polymer is heated under reduced pressure to remove volatile components such as a solvent and unreacted monomers in the reaction solution. Is disclosed,
Specific examples include a centrifugal thin-film continuous evaporator dryer, a scraped surface heat exchange continuous reactor dryer, and a high-viscosity reactor device.

In Japanese Patent Application Laid-Open No. H11-134711, the solvent (cyclohexane) in a reaction solution containing a norbornene-based polymer is removed using a cylindrical concentrating dryer.
It is disclosed to be performed in stages.

[0006] However, if the volatile components are not completely removed from the reaction solution, silver streaks, voids, and the like are generated in a molded article formed by using the obtained polymer, resulting in poor molding.

[0007] On the other hand, in the case of using a means such as a thin film dryer such as a cylindrical concentrating dryer which has a high ability to remove volatile components but applies a shear stress to the polymer, the conditions must be optimized. Breakage of the polymer chain occurs,
Problems such as coloring of a molded article obtained by molding the obtained polymer and reduction in the strength of the molded article due to a decrease in molecular weight may occur.

[0008]

An object of the present invention is to efficiently remove volatile components from a reaction solution containing a polymer,
In addition, an object of the present invention is to provide a method for producing an alicyclic structure-containing polymer suitable as an optical material or the like, which can suppress a decrease in the molecular weight of the obtained polymer. Another object of the present invention is to provide a molded article having high strength, no coloring, and free from molding defects such as silver streaks and voids.

[0009]

Means for Solving the Problems The present inventors have found that volatile components such as a solvent and unreacted monomers are removed from a polymer solution containing a polymer having an alicyclic structure (hereinafter, also referred to as a reaction solution) at once. Instead, first remove some of the volatile components in the reaction solution to a predetermined polymer concentration, and then remove the remainder of the volatile components in the reaction solution to reduce the molecular weight of the resulting polymer. The present inventors have found that volatile components can be efficiently reduced while suppressing, and that not only the strength of a molded article molded using the obtained polymer can be reduced, but also coloring and molding defects such as silver streaks can be prevented. The invention has been completed.

That is, the process for producing an alicyclic structure-containing polymer according to the present invention comprises the steps of: polymerizing an alicyclic structure-containing monomer; and, if necessary, hydrogenating a solution containing the polymer. In the step of removing the components and recovering the polymer,
(1) A part of the volatile component of the polymer solution containing the alicyclic structure-containing polymer is removed by evaporation in the container to reduce the polymer concentration to 30 to
After the preconcentration step of 95% by weight, (2) the polymer solution after the preconcentration is formed into a thin film, and the remaining volatile components are removed by heating and / or reducing the pressure to remove volatile components. Characterized by having a drying step of reducing the content by 1% by weight or less.

Preferably, the pre-concentration step is performed using a solvent removing device capable of reducing pressure, and the drying step is performed using a thin film dryer.

Preferably, the solvent removing device is provided with a heating means.

Preferably, before the pre-concentration step, the polymer solution containing the alicyclic structure-containing polymer is pre-heated.

Preferably, at least one of the preconcentration step and the drying step is performed in a low oxygen concentration atmosphere.

The molded article according to the present invention is characterized by comprising an alicyclic structure-containing polymer obtained by the above production method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing an alicyclic structure-containing polymer according to the present invention comprises a polymerization step of polymerizing an alicyclic structure-containing monomer in the presence of a polymerization catalyst, and if necessary, the polymerization step. A hydrogenation step of hydrogenating the polymer obtained by the above in the presence of a hydrogenation catalyst, and a volatile component removing step of removing volatile components of the reaction solution obtained by the polymerization step or the hydrogenation step. Hereinafter, the present invention will be described along each step.

Polymerization Step The polymerization step of the alicyclic structure-containing monomer in the present invention is usually carried out in the presence of a polymerization catalyst in an inert solvent.

The alicyclic structure-containing monomer used in the polymerization step has an alicyclic structure in its molecular structure, and includes, for example, a norbornene monomer, a monocyclic cycloolefin monomer, and a cyclic olefin monomer. Examples thereof include a conjugated diene-based monomer and a vinyl alicyclic hydrocarbon-based monomer. From the viewpoint of the transparency and heat resistance of the obtained polymer, a norbornene-based monomer is preferable.

Examples of the norbornene monomer include, for example,
Bicyclo [2.2.1] -hept-2-ene (common name:
Norbornene), 5-methyl-bicyclo [2.2.1]
-Hept-2-ene, 5,5-dimethyl-bicyclo
[2.2.1] -Hept-2-ene, 5-ethyl-bishi
Black [2.2.1] -hept-2-ene, 5-butyl-
Bicyclo [2.2.1] -hept-2-ene, 5-hex
Sil-bicyclo [2.2.1] -hept-2-ene, 5
-Octyl-bicyclo [2.2.1] -hept-2-e
5-octadecyl-bicyclo [2.2.1] -heptane
To-2-ene, 5-ethylidene-bicyclo [2.2.
1] -Hept-2-ene, 5-methylidene-bicyclo
[2.2.1] -Hept-2-ene, 5-vinyl-bishi
Black [2.2.1] -hept-2-ene, 5-propeni
Rubicyclo [2.2.1] -hept-2-ene, 5-
Methoxy-carbonyl-bicyclo [2.2.1] -hep
To-2-ene, 5-cyano-bicyclo [2.2.1]-
Hept-2-ene, 5-methyl-5-methoxycarboni
Rubicyclo [2.2.1] -hept-2-ene, 5-
Methoxycarbonyl-bicyclo [2.2.1] -hept
-2-ene, 5-ethoxycarbonyl-bicyclo [2.
2.1] -Hept-2-ene, 5-methyl-5-ethoxy
Cycarbonyl-bicyclo [2.2.1] -hept-2-
Ene, bicyclo [2.2.1] -hept-5-enyl-
2-methylpropionate, bicyclo [2.2.1]-
Hept-5-enyl-2-methyloctanatebicyclo
[2.2.1] -Hept-2-ene-5,6-dicarbo
Acid anhydride, 5-hydroxymethyl-bicyclo [2.
2.1] -Hept-2-ene, 5,6-di (hydroxy
Methyl) -bicyclo [2.2.1] -hept-2-e
5-hydroxy-i-propyl-bicyclo [2.
2.1] -Hept-2-ene, 5,6-dicarboxy-
Bicyclo [2.2.1] -hept-2-ene, bicyclo
[2.2.1] -Hept-2-ene-5,6-dicarbo
Acid imide, 5-cyclopentyl-bicyclo [2.2.
1] -Hept-2-ene, 5-cyclohexyl-bisic
B [2.2.1] -Hept-2-ene, 5-cyclohexyl
Senyl-bicyclo [2.2.1] -hept-2-ene,
5-phenyl-bicyclo [2.2.1] -hept-2-
Ene, tricyclo [4.3.0.1^2,5]-Deca-
3,7-diene (common name dicyclopentadiene), tri
Cyclo [4.3.0.1^2,5] -Dec-3-ene,
Tricyclo [4.4.0.1^2,5]-Undeca-
3,7-diene or tricyclo [4.4.0.1
^2,5] -Undeca-3,8-diene, and
Partially hydrogenated (or cyclopentadiene and cyclohexane
Tricyclo [4.4.0.1), which is an adduct of xen).
^2,5] -Undec-3-ene, tetracyclo [7.
4.0.0^2,7. 1^10,13] -Trideca-
2,4,6,11-tetraene (1,4-methano-1,
4,4a, 9a-tetrahydrofluorene),
Tetracyclo [8.4.0.0^3,8. 1
^11,14] -Tetradeca-3,5,7,12-tetra
Raen (1,4-methano-1,4,4a, 5,10,1
0a-hexahydroanthracene), tetracy
Black [4.4.0.1^2,5. 1^7,10]-Dodeca
-3-ene (also simply referred to as tetracyclododecene), 8
-Methyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-ethyl-tetracy
Black [4.4.0.1^2,5. 1^7,10]-Dodeca
-3-ene, 8-methylidene-tetracyclo [4.4.
0.1^2,5. 1^7,10] -Dodeca-3-ene, 8
-Ethylidene-tetracyclo [4.4.0.
1^2,5. 1^7,10] -Dodeca-3-ene, 8-bi
Nyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-propenyl-tet
Lacyclo [4.4.0.1^2,5 . 1^7,10]-Dode
Car-3-ene, 8-methoxycarbonyl-tetracyclo
[4.4.0.1^2,5. 1^7,10] -Dodeca-3
-Ene, 8-methyl-8-methoxycarbonyl-tetra
Cyclo [4.4.0.1^2,5. 1^7,10]-Dode
Car-3-ene, 8-hydroxymethyl-tetracyclo
[4.4.0.1^{2 , 5}. 1^7,10] -Dodeca-3
-Ene, 8-carboxy-tetracyclo [4.4.0.
1^2,5. 1^7,10] -Dodeca-3-ene, 8-si
Clopentyl-tetracyclo [4.4.0.1^2,5.
1^7,10] -Dodeca-3-ene, 8-cyclohexyl
-Tetracyclo [4.4.0.1^2,5.
1^7,10] -Dodeca-3-ene, 8-cyclohexene
Le-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-phenyl-tetra
Cyclo [4.4.0.1^2,5. 1^7,10]-Dode
Car-3-ene, pentacyclo [6.5.1.
1^3,6. 0^2,7. 0^9,13] -Pentadeca-
4,10-diene, pentacyclo [7.4.0.0
^2,7. 1^3,6. 1^10,13] -Pentadeca
-4,11-diene and the like are exemplified. These norbo
Runene monomers have a cycloalkyl group or an aryl group.
Or a halogen atom, ester type residue,
Polarity such as ether type residue, cyano group, pyridyl group, etc.
It may have a group.

The monocyclic cyclic olefin monomer includes:
For example, cyclohexene, cycloheptene, cyclooctene and the like are exemplified.

Examples of the cyclic conjugated diene monomer include cyclopentadiene and cyclohexadiene.

Examples of the vinyl cyclic hydrocarbon monomer include, for example, vinylcyclohexene and vinylcyclohexane.

These alicyclic structure-containing monomers can be used alone or in combination of two or more.

In addition to the alicyclic structure-containing monomer, a monomer (vinyl compound) copolymerizable therewith can be used. Examples of the vinyl compound include ethylene, propylene, 1-butene, 1-pentyne, 1-hexene,
3-methyl-1-butene, 8-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 4.4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-
Chain vinyl compounds such as ethylene or α-olefins having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; 1,4-hexadiene ,
4-methyl-1,4-hexadiene, 5-methyl-1,
Non-conjugated diene compounds such as 4-hexadiene and 1,71-octadiene; and the like.

The amount of the alicyclic structure-containing monomer is,
Usually, it is at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight.

The molecular weight of the alicyclic structure-containing polymer obtained in the polymerization step is appropriately selected according to the purpose of use.
From the viewpoint of the balance between mechanical strength and moldability, the weight average of polyisoprene (polystyrene in toluene solution) as measured by gel permeation chromatography of cyclohexane solution (toluene solution if the polymer does not dissolve) In molecular weight (Mw), it is usually 5000 or more, preferably 5000 to 500000, more preferably 3000 to 200000, and particularly preferably 10000.
１００100,000. If the molecular weight is excessively large, not only does the moldability deteriorate, but also in the case of performing hydrogenation described below, the progress of the hydrogenation reaction is slowed, and the hydrogenation rate is reduced. If the molecular weight is too low, the mechanical strength of the polymer will be low.

The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing polymer obtained in the polymerization step is usually 7 or less, preferably 5 or less, more preferably 3.5 or less. When the molecular weight distribution is in the above range, a molded article molded using the polymer is not colored, and molded articles such as silver streaks and voids do not occur.

The alicyclic structure-containing polymer obtained in the polymerization step may be a homopolymer or a copolymer, and the copolymer may be a random copolymer or a block copolymer. These were further graft-modified (co)
It may be a polymer.

The polymerization of norbornene-based monomers is described, for example, in JP-A-3-14882 and JP-A-3-122.
Polymerization can be carried out by a known method disclosed in, for example, JP-A-137-137, to give a ring-opened polymer, an addition polymer, an addition copolymer with a copolymerizable vinyl monomer, or the like. Among these, a ring-opened polymer of a norbornene-based monomer is preferable in order to highly balance the heat resistance, transparency, and light resistance of the resulting alicyclic structure-containing polymer.

The ring-opening polymerization comprises a norbornene-based monomer as a ring-opening polymerization catalyst, a metal halide such as ruthenium, rhodium, palladium, osmium, iridium or platinum, a nitrate or acetylacetone compound, and a reducing agent. Catalyst system, or titanium, vanadium,
In the presence of a catalyst system comprising a halide or acetylacetone compound of a metal such as zirconium, tungsten or molybdenum, and an organoaluminum compound, the polymerization temperature is usually -50 to 100C in an inert solvent, and 0 to 50.
The reaction can be performed at a polymerization pressure of kg / cm ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, other A third component such as a Lewis acid can be added to increase the polymerization activity and the selectivity of ring-opening polymerization.

The addition polymerization of a norbornene monomer or the addition copolymerization of a norbornene monomer and a vinyl compound is carried out, for example, by mixing a monomer component in a solvent with a titanium, zirconium, or vanadium compound and an organoaluminum. In the presence of a catalyst system comprising the compound, usually -50 to 1
It can be carried out by a method of copolymerizing at a polymerization temperature of 00 ° C. and a polymerization pressure of 0 to 50 kg / cm ² .

The polymerization of a monocyclic cyclic olefin monomer is carried out by
The addition polymerization can be carried out by a known method, for example, a method disclosed in JP-A-64-66216.

The polymerization of the cyclic conjugated diene monomer can be carried out by a known method, for example, a method disclosed in JP-A-6-13657 or JP-A-7-258318.
A polymer obtained by 2- or 1,4-addition polymerization can be obtained.

The polymerization of the vinyl alicyclic hydrocarbon monomer is carried out by
For example, the polymerization can be carried out by the method disclosed in JP-A-51-59989.

Polymerization Catalyst Removal Step In the present invention, when the hydrogenation step described below is not carried out,
It is preferable to include a step of removing the polymerization catalyst from the solution containing the polymer after the polymerization step. Note that, even when the hydrogenation step is performed, a polymerization catalyst removal step may be included after the polymerization step. The residual amount of the catalyst in the reaction solution after removing the catalyst is usually 10 ppm or less, preferably 1 pp, based on the weight of the (catalyst) metal element, based on the polymer in the reaction solution.
m, more preferably 0.1 ppm or less.

Hydrogenation Step In the present invention, the polymer having an alicyclic structure obtained by the above-mentioned polymerization step has a carbon-carbon unsaturated bond (a non-conjugated unsaturated bond and / or an aromatic bond) in a main chain and / or a side chain. Group-containing unsaturated bond), it is possible to obtain a hydride of the alicyclic structure-containing polymer by saturating a part or all of the unsaturated group. That is, in the present invention, a hydrogenation step may be included as necessary. Thus, when having a carbon-carbon unsaturated bond,
Hydrogenation of the unsaturated group can improve the heat deterioration resistance and light deterioration resistance of the alicyclic structure-containing polymer. Incidentally, when the carbon-carbon unsaturated bond is only an aromatic ring,
Whether or not to carry out hydrogenation is selected depending on the purpose of use of the alicyclic structure-containing polymer.

When the polymer to be subjected to the hydrogenation reaction has an aromatic ring, the residual ratio of the aromatic ring is generally 80% or less, preferably 50% or less, more preferably 30% or less from the viewpoint of light resistance and the like. It is. The hydrogenation rate of the non-conjugated unsaturated bond is usually at least 80%, preferably at least 90%, more preferably at least 95%. If the hydrogenation rate is low, oxidative deterioration and molecular breakage are likely to occur, resulting in poor tint, reduced transparency, and reduced mechanical strength.

When the alicyclic structure-containing polymer has a repeating unit having an aromatic ring, the aromatic ring structure can be left in the hydrogenation reaction, but it may be completely hydrogenated. . Note that, by ¹ H-NMR analysis, the unsaturated bond of the aromatic ring can be recognized and distinguished from other unsaturated bonds.

The hydrogenation reaction is carried out according to a conventional method by bringing the polymer into contact with hydrogen in the presence of a hydrogenation catalyst. Examples of the hydrogenation catalyst include JP-A-58-43412, JP-A-60-26024, and JP-A-64-24826.
JP, JP-A-1-138257, JP-A-7-4
Those described in, for example, JP-A No. 1550 can be used, and either a homogeneous catalyst or a heterogeneous catalyst may be used. Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so they need to be added in a small amount.Also, they are active even without high temperature and pressure, so they do not cause polymer decomposition or gelation, resulting in low cost and quality. Excellent stability etc. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are excellent in production efficiency such as being easily removed. Among them, a heterogeneous catalyst is preferable because it is easily removed.

As the homogeneous catalyst, for example, a so-called Wilkinson complex such as chlorotris (triphenylphosphine) rhodium (I); cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-
A catalyst comprising a combination of a transition metal compound such as butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium and an alkyl metal compound; and the like.

Examples of the heterogeneous catalyst include Ni, P
Examples include those in which a hydrogenation catalyst metal such as d, Pt, Ru, and Rh is supported on a carrier. In particular, when an adsorbent such as alumina or diatomaceous earth is used as the carrier, it is preferable because impurities are not mixed. These catalysts are used in an amount of ^{10-5 to} 0.5 parts by weight, preferably ^10-4 to 0.5 parts by weight, based on 1 part by weight of the polymer.
Used in the range of 0.3 parts by weight. The hydrogenation catalyst can be added to the polymerization reaction solution as it is, or added after removing the polymerization catalyst from the polymerization reaction solution to cause a reaction.

The hydrogenation reaction is usually carried out in an inert solvent. The inert solvent is not particularly limited as long as it is inert to the catalyst, and may be the same as the polymerization reaction solvent, or may be further added to the polymerization reaction solution. The amount of the inert solvent used for hydrogenation is usually 1 to 1 in weight ratio to the polymer in the polymerization reaction solution from the viewpoint of hydrogenation reaction efficiency.
100 times, preferably 1.5 to 20 times, more preferably 2 times
It is 10 times.

The hydrogenation reaction can be carried out according to a conventional method.
Although hydrogenation depends on the type of hydrogenation catalyst and reaction temperature
Rate can be changed, and the residual rate of aromatic ring can also be changed.
You. When the above hydrogenation catalyst is used, the aromatic ring is unsaturated.
In order to maintain a certain amount of bonds, lower the reaction temperature.
Decrease the hydrogen pressure, shorten the reaction time, etc.
May be performed. Complete aromatic ring structure in polymer
Non-conjugated unsaturation of the main chain while remaining without hydrogenation
In order to selectively increase the hydrogenation rate of the sum bond, hydrogen
Pressure is 0.1-50kg / cm², Preferably 0.5 to
40kg / cm ², More preferably 1 to 30 kg /
cm²And The reaction temperature of the hydrogenation
When used, it is usually −10 to 150 ° C., preferably 0 to 150 ° C.
To 130 ° C, more preferably 20 to 110 ° C.
When a heterogeneous catalyst is used, it is usually 0 to 300 ° C.
Preferably 100-250 ° C, more preferably 150-
Performed at 230 ° C.

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

The molecular weight of the hydride of the alicyclic structure-containing polymer obtained in the hydrogenation step is appropriately selected according to the purpose of use, but the gel permeation of a cyclohexane solution (a toluene solution when the polymer is not dissolved) is used. Weight average molecular weight (Mw) in terms of polyisoprene (polystyrene in a toluene solution) measured by the Aion Chromatography method,
Usually 5000 or more, preferably 5000 to 50,000
0, more preferably 8,000 to 200,000, particularly preferably 10,000 to 100,000.

The molecular weight distribution Mw / Mn of the hydride of the alicyclic structure-containing polymer obtained in the hydrogenation step is usually 7 or less, preferably 5 or less, more preferably 3.5 or less.

The glass transition temperature (Tg) of the hydride of the alicyclic structure-containing polymer obtained in the hydrogenation step is usually
The temperature is 50 to 250 ° C, preferably 70 to 220 ° C, more preferably 80 to 200 ° C.

Hydrogenation Catalyst Removal Step In the present invention, it is preferable to include a step of removing the hydrogenation catalyst from the solution containing the hydride of the polymer after the hydrogenation step. Incidentally, both the polymerization catalyst and the hydrogenation catalyst may be removed at once after the hydrogenation without performing the polymerization catalyst removal step. The removal method and the residual amount of the catalyst after the removal are performed in the same manner as in the polymerization catalyst removing step.

Inert solvent The inert solvent used in the above-mentioned polymerization reaction and hydrogenation reaction sufficiently dissolves an alicyclic structure-containing monomer, an alicyclic structure-containing polymer and a hydride of the alicyclic structure-containing polymer. Those which can be used and which do not inhibit the polymerization reaction or the hydrogenation reaction are used. Examples of the inert solvent include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, cycloheptane, cyclooctane, Cycloalkanes such as decalin, norbornane, methylnorbornane and ethylnorbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene;
Compounds such as halogenated alkanes and aryls such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibromide, chlorobenzene, chloroform, and tetrachloroethylene; among others, cycloalkanes and aromatic compounds from the viewpoint of solubility and the like; Hydrocarbons are preferred, and cycloalkanes are more preferred.

These inert solvents are each used alone.
Alternatively, two or more kinds can be used in combination.

The amount of the inert solvent to be used is not particularly limited, but is usually 40 to 2 parts per 100 parts by weight of the alicyclic structure-containing monomer in consideration of the balance between the stirring efficiency and the productivity.
000 parts by weight, preferably 100 to 1000 parts by weight, more preferably 250 to 600 parts by weight.

Volatile Component Removal Step In the process of the present invention, the step of removing the volatile component from the reaction solution containing the alicyclic structure-containing polymer or its hydride and recovering (drying) the polymer includes the steps of: 1) After a pre-concentration step in which a polymer solution containing an alicyclic structure-containing polymer is removed in a vessel and a part of volatile components is evaporated in the vessel to make the polymer concentration constant, (2) The method further comprises a drying step of forming the polymer solution after the preconcentration into a thin film, removing the remaining volatile components, and drying the polymer.

In the present invention, an inert solvent and other volatile components are removed from the reaction solution obtained in the polymerization step or the hydrogenation step by using a closed system so that foreign substances are not mixed in from the external environment. A ring structure-containing polymer (including a hydride) can be obtained. In addition, the evaporated solvent may be liquefied again by the condensing device and collected, and may be reused if necessary.

Preconcentration Step In the preconcentration step of the present invention, the concentration of the polymer contained in the reaction solution is 30 to 95% by weight, preferably 3% by removing a part of the volatile components contained in the reaction solution by evaporation.
This is a step of adjusting the content to 5 to 90% by weight, preferably 40 to 85% by weight. Immediately after the reaction, that is, even when the polymer concentration of the solution before the preconcentration is already higher than 30% by weight as described above, performing the preconcentration to a higher concentration within the above range may deteriorate the polymer. It is preferable for reduction.

The volatile components are removed by heating or reducing the pressure of the reaction solution while the reaction solution is stored in a container. In that case, it is preferable that a shear stress is not applied to the polymer in the solution.

If the preconcentration concentration of the reaction solution is too low, the effect obtained by providing the preconcentration step is hardly obtained. That is, when the concentrated liquid is fed into the thin film dryer used in the subsequent drying step, the amount of volatile components increases and the degree of reduced pressure does not increase, so that the volatile component content in the polymer after drying is reduced. Increase. If the content of volatile components after drying is too large, molding defects such as silver streaks, voids, and foaming occur in the molded product, which is not preferable.
In addition, a large amount of heat of vaporization causes a large decrease in the temperature of the concentrated liquid, which causes a sharp rise in viscosity and solidification in the dryer, which causes interruption of the drying process and damage to equipment. If the preconcentration concentration is too high, the polymer is liable to be unnecessarily sheared in the drying step described below, and the mechanical strength of a molded article molded using the obtained polymer decreases.

In the present invention, as an apparatus which can be suitably applied to the preconcentration step, the reaction solution can be concentrated by (1) an apparatus capable of reducing the pressure of an evaporator, and (2) a reaction solution pressurized. A device that feeds into an evaporator at normal pressure to remove (flash) the solvent instantaneously, (3) A device that can be concentrated by stirring and heating under atmospheric pressure in a vessel equipped with a stirring device and a heating device, etc. Examples of more specific devices include flash boxes, flash separators, and devices such as evaporators represented by hibiscus (manufactured by Mitsui Engineering & Shipbuilding Co., Ltd.).

In the preconcentration step, it is preferable that the reaction solution is not formed into a thin film in the form of a thin film and is not instantaneously increased in concentration while giving a sliding stress.

The above-mentioned solvent removing device is preferably provided with a heating means such as a heater from the viewpoint of preventing the temperature from being lowered by the heat of vaporization when evaporating the solvent and increasing the evaporation efficiency.

Examples of the heater include a jacket type heater. Examples of the solvent removing device provided with such a heater include the above-mentioned hibiscus evaporator (manufactured by Mitsui Engineering & Shipbuilding Co., Ltd.).

The preconcentration by the above-mentioned solvent removing device can be carried out either under normal pressure or under reduced pressure.

In the present invention, it is preferable that the reaction solution is preliminarily heated (hereinafter, abbreviated as preheating) before the preconcentration. By preheating the reaction solution before the preconcentration, the concentration efficiency of the polymer is improved. As the preheating method, (1) a method of heating a storage container for the reaction solution before concentration and / or a transfer pipe from the storage container to the solvent removing device with a jacket-type heating device, (2) a multi-tube method A method using a known heat exchanger such as a heat exchanger of the type or a plate fin type heat exchanger may be used. When a heat exchanger is used, it is not always necessary to install the heat exchanger outside the solvent removing device. If necessary, an integrated solvent removing device having a built-in heat exchanger may be used.

The temperature of the solution at the time of preheating is usually 50
To 400 ° C, preferably 70 to 350 ° C, more preferably 100 to 330 ° C. If the heating temperature is too low, the evaporation efficiency deteriorates, and in order to increase the degree of concentration, it is necessary to increase the residence time in the solvent removing device, which causes problems such as a decrease in productivity and thermal degradation of the polymer. If the preheating temperature is too high, the polymer is thermally degraded, which is not preferable.

In the present invention, the preconcentration step is preferably performed in a low oxygen concentration atmosphere. Performing the preconcentration step in a low oxygen concentration atmosphere can effectively prevent coloring of the finally recovered alicyclic structure-containing polymer (including hydride). The low oxygen concentration atmosphere preferably has an oxygen concentration of 10% by volume or less, more preferably 8% by volume.
Adjust so that it has the following atmosphere. By setting the working atmosphere to a lower oxygen concentration, oxidation of the polymer is prevented, and coloring of the obtained molded body is prevented. As a specific means for creating such a low oxygen concentration atmosphere, there is a method of setting the inside of an apparatus used for the preconcentration step to an atmosphere of an inert gas such as nitrogen or helium.

Drying Step In the drying step in the present invention, the volatile components contained in the polymer are removed by removing the remaining volatile components contained in the pre-concentrated reaction solution having a polymer concentration of 30 to 95% by weight. This is a step of reducing the content to 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less. If the content of the volatile components remaining after drying is too large, molding defects such as silver streaks, voids, foaming, and coloring occur in the molded product.

The method of removing volatile components in the drying step is to heat the high-concentration reaction solution after pre-concentration in a state where the surface area of the reaction solution in contact with gas is increased by forming the thin film into a thin film. And / or reducing pressure to remove volatile components in a short time. Specifically, in the present embodiment, the drying is performed using a thin film dryer. The thin film dryer used in the present embodiment is not particularly limited as long as it can efficiently remove volatile components by increasing the surface area by forming the reaction solution into a thin film in the dryer,
Known ones can be used. However, in order to more efficiently remove volatile components, means for reducing pressure and heating are provided, and the degree of reduced pressure in the dryer is increased to instantaneously evaporate the volatile components in the reaction solution. It is preferable that the solution has a high concentration, more preferably,
This is a form in which the high-concentration and high-viscosity solution can be made into a fluid state by heating to easily form a thin film. As such a thin film dryer, for example, a centrifugal thin film continuous evaporator type dryer, a scraping type continuous film evaporator type dryer, a cylindrical concentration dryer and the like, and a scratch surface heat exchange type continuous reactor type A dryer, a high-viscosity reactor device and the like can also be used.

As a method for forming the high-concentration solution into a thin film, a method utilizing centrifugal force due to rotation of the apparatus, etc.
A method in which a stirring blade is provided in a dryer and a method using a shearing force between the wall surface of the dryer and the stirring blade may be used.However, in order to further reduce volatile components, a method using a stirring blade is more preferable. preferable.

In the present invention, the internal pressure of the thin film dryer is usually 200 kPa or less, preferably 150 kPa or less, more preferably 100 kPa or less. If the internal pressure is too high, the evaporation efficiency of the solution will be poor and the content of volatile components in the polymer after drying will increase. The heating temperature of the solution is usually 50 to 300C, preferably 80 to 250C, more preferably 100 to 200C higher than the glass transition temperature of the polymer to be dried.

If the heating temperature is too low, the evaporation efficiency of the solution becomes poor, and the content of volatile components in the polymer after drying increases. Further, it is not preferable because the solution is damaged or the solidification of the solution increases the viscosity or solidifies the solution. If the heating temperature is too high, it is not preferable because the polymer is thermally degraded.

In the drying step of the present invention, two or more of the above-mentioned thin film dryers may be used, and in this case, the degree of reduced pressure and / or the heating temperature may be different for each of the thin film dryers.

In the present invention, the drying step is preferably performed in a low oxygen concentration atmosphere, and more preferably the preconcentration step is performed in a low oxygen concentration atmosphere together with the drying step.
By performing the drying step in a low oxygen concentration atmosphere, coloring of the finally recovered alicyclic structure-containing polymer (including hydride) can be effectively prevented. In particular, when both the preconcentration step and the drying step are performed in a low oxygen concentration atmosphere, the obtained effect becomes more remarkable. The means for creating the oxygen concentration and low oxygen concentration atmosphere is the same as in the preconcentration step described above.

Various Compounding Agents Various compounding agents can be added to the alicyclic structure-containing polymer (including hydrides) obtained by the method of the present invention, if necessary. The various compounding agents are not particularly limited as long as they are generally used in the resin industry. For example, phenol-based, phosphite-based, thioether-based antioxidants, and hindered phenol-based ultraviolet absorbers Release agents such as aliphatic alcohols, aliphatic esters, aromatic esters, triglycerides, fluorine-based surfactants and metal salts of higher fatty acids; other lubricants, antifoggants, plasticizers, pigments, near infrared absorption Agents, antistatic agents and the like. These compounding agents may be used alone or in combination of two or more. The amount of the compounding agent used is appropriately selected within a range that does not impair the scope of the present invention. An alicyclic structure-containing polymer to which various compounding agents are added (including hydrides)
Are used alone or in combination of two or more.

Molding The alicyclic structure-containing polymer (including a hydride) obtained by the method of the present invention can be kneaded in a molten state using a twin-screw extruder or the like after production, and used as pellets. And it can be formed by known methods, for example, injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, compression molding, rotational molding, calendar molding, rolling molding, cutting molding, and the like. it can.

Applications The alicyclic structure-containing polymer (including hydride) obtained by the method of the present invention is useful in a wide range of fields as various molded articles including optical materials.

For example, optical materials such as an optical disk, an optical lens, a prism, a light diffusion plate, an optical card, an optical fiber, an optical mirror, a liquid crystal display element substrate, a light guide plate, a polarizing film and a retardation film; a liquid chemical container, an ampule, and a vial , Prefilled syringe, infusion bag, sealed medicine bag, press-through package, solid medicine container, liquid medicine container such as ophthalmic medicine container, powder or solid medicine container, food container, sampling test tube for blood test, medicine container Sampling containers such as caps, blood collection tubes, specimen containers, medical instruments such as syringes, sterile containers such as scalpels, forceps, gauze, contact lenses, and other medical instruments, beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc. Analytical instruments,
Medical optical components such as plastic lenses for medical examinations,
Infusion tubes for medical use, piping materials such as pipes, fittings, valves, etc., medical equipment such as artificial organs such as denture bases, artificial hearts, artificial roots and their parts; tanks, trays, carriers,
Containers for processing or transport such as cases, carrier tapes, protective materials such as separation films, pipes,
Equipment for processing electronic components such as tubes, valves, pipes such as sipper flowmeters, filters, pumps, and liquid containers such as sampling containers, bottles, and ampoule bags;
General insulation materials for OA equipment such as electric wires and cables, consumer electronics and industrial electronic equipment, copying machines, computers, printers, and instruments; circuit boards such as rigid printed boards, flexible printed boards, and multilayer printed wiring boards In particular, high-frequency circuit boards for satellite communication equipment requiring high-frequency characteristics; transparent conductive film bases such as liquid crystal substrates, optical memories, surface heating elements such as automobile and aircraft defrosters, transistors, ICs, LSIs, Sealing materials and parts for electric and conductors such as LEDs, sealing materials for electric and electronic parts such as motors, capacitors, switches, and sensors; body materials such as televisions and video cameras; parabolic antennas, flat antennas, and structural members for radar dome Electrical insulating materials such as; Film such as packaging film and agricultural film; Chromatography (registered trademark) disk, information recording substrates, such as a magnetic hard disk and the like. Above all, it is preferable to apply to an optical material that does not like coloring of a molded article.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and can be implemented in various modes without departing from the gist of the present invention. Of course.

[0077]

EXAMPLES Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples. In the following examples, parts and percentages are by weight unless otherwise specified.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (in terms of polystyrene) using cyclohexane as a moving bed, unless otherwise specified. The hydrogenation rate of the main chain (unsaturated bond other than the aromatic ring) and the hydrogenation rate of the aromatic ring were measured by ¹ H-NMR.

Production Example 1 ( Production of reaction solution) In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane was added
Hexene 0.56 parts, dibutyl ether 0.11 parts,
0.22 parts of triisobutylaluminum was placed in a reactor at room temperature and mixed.
Tetracyclo [4.4.0.1 ^2,5 . ^17,10 ]
200 parts of dodeca-3-ene (ethyltetracyclododecene, hereinafter referred to as ETCD) and 30 parts of a 0.7% tungsten hexachloride toluene solution were continuously added over 2 hours to carry out polymerization. 0.78 parts of butyl glycidyl ether and 0.38 parts of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst and terminate the polymerization reaction.

The polymerization conversion of the obtained ETCD ring-opened polymer was almost 100%, Mn was 18,000, Mw was 36,200, and molecular weight distribution (Mw / Mn) was 2.01.

Next, cyclohexane 27 was added to 100 parts of the reaction solution containing the obtained ETCD ring-opening polymer.
0 parts, and 5 parts of a nickel-alumina catalyst (manufactured by Nikki Chemical Co., Ltd.) as a hydrogenation catalyst.
The mixture was heated to a temperature of 200 ° C. while being pressurized to g / cm ² and stirred, and then reacted for 4 hours to obtain a reaction solution containing 20% of a hydrogenated polymer of a ring-opening polymer.

Next, the obtained reaction solution containing the hydrogenated polymer was subjected to pressure filtration at a pressure of 2.5 kg / cm ² using a pressure filter (Funda filter, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.). A colorless and transparent solution (solution 1) was obtained. Radiolite # 500 was used for the filtration bed.

Example 1 Next, the obtained solution 1 (polymer concentration: 20%) was pre-concentrated using a flash separator (manufactured by Hitachi, Ltd.), and a concentrated solution (solution 2) having a polymer concentration of 45% was obtained. Obtained.
The concentration conditions were such that the feed rate of the solution was 250 kg / H
R, pressure is 330kPa, jacket temperature is 140 ℃
While heating at. Before feeding to the flash separator, the reaction solution was preheated to 200 ° C. by an external heat exchanger. The preconcentration step was performed in a low oxygen concentration atmosphere having an oxygen concentration of 0.1% by volume.

Next, the solution 2 was subjected to removal of volatile components using a cylindrical concentrator / dryer (manufactured by Hitachi, Ltd.) to obtain a hydrogenated ring-opening polymer 150 having a volatile component content of 0.05%. Got a part. The operating conditions of the cylindrical concentrating dryer were as follows: first step: temperature 270 ° C., pressure 20 kPa, second step: temperature 270 ° C., pressure 1 kPa or less, and the residence time of the solution was 5 hours.

The hydrogenated polymer obtained had Mn of 17,
000, Mw: 33,300, (Mw / Mn): 1.9
6. The hydrogenation rate was 99.9% or more.

In 100 parts of the obtained hydrogenated ring-opening polymer,
Anti-aging agent (Irganox 101 manufactured by Ciba-Geigy)
0) 0.2 part and a soft polymer (ToughTech H manufactured by Asahi Kasei Corporation)
1052) 0.2 parts were added, and a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., screw diameter 37 mm, L / D = 3)
2. Screw rotation speed 250 rpm, resin temperature 210
At a feed rate of 10 kg / hour) and extruded into pellets.

The above-mentioned pellets are injected into a side gate mold type injection molding apparatus (product number IS4 manufactured by Toshiba Machine Co., Ltd.).
50), the length is 280 mm and the width is 1 by injection molding.
A flat plate having a thickness of 90 mm and a thickness of 2 mm was formed. The molding conditions are
The mold temperature was 80 ° C, the cylinder temperature was 280 ° C, and the nozzle temperature was 260 ° C.

The degree of coloring, mechanical strength and moldability of the obtained flat plate were evaluated. As a result, the obtained flat plate was colorless and transparent without coloration, had high mechanical strength, and was good without observing molding defects such as silver streaks and voids. The results are shown in Table 1.

[0089]

[Table 1]

The degree of coloring of the plate was determined by the difference in yellowing index (ΔYI)
Was evaluated. ΔYI is a color difference meter (YI; Yellow Index) of a solution obtained by dissolving a part of a formed flat plate in a soluble solvent at a concentration of 15% by weight according to JIS-K7103. Color analyzer). The measurement optical path was measured at 10 mm, and the blank was measured as a solvent for dissolution.
The value obtained by subtracting the YI value of only the blank solvent from the I value was determined as the ΔYI value derived from the flat plate. The measurement was 3
The evaluation was performed using the average value. Also, whether the solution was completely dissolved was determined by filling the syringe into a syringe with a 0.5 μm PTFE filter attached to the tip, and discharging all the liquid from the filter tip without resistance when the piston was pressed. confirmed. “◎ (very good)” when ΔYI was less than 0.7, “○ (good)” when ΔYI was 0.7 or more and less than 1.0, and ΔYI was 1.0 or more and 1.5. When the value was less than △ (somewhat bad), and when △ YI was 1.5 or more, it was rated “x (bad)”.

The mechanical strength of the flat plate (in the present embodiment, the impact resistance by the drop test) is 3 at the same position of the ten prepared flat plates.
5/4 inch radius missile type weight (weight 10g)
The sample was dropped naturally from a height of 0 cm, and it was evaluated according to the following criteria by observing whether cracks or cracks were formed. 0 out of 10 with cracks and cracks "◎", 1 to 3 with cracks and cracks "○", 4 to 6 with cracks and cracks 7 or more out of 10 sheets having "△" and cracks or cracks were indicated as "x".

The moldability of the flat plate was evaluated according to the following criteria by visually judging the obtained flat plate. 10
No appearance failure such as sink marks, silver streaks, etc. in the first injection molding "◎", 10 or more injection moldings showing the above molding failure in 1 to 2 samples "○", 10 injection moldings in 3 injection moldings △ indicates that the molding failure was observed in 4 samples, and “X” indicates that the molding failure was observed in 5 or more samples after 10 injection moldings.

Example 2 The same procedure as in Example 1 was carried out except that the preheating before the preconcentration was not performed and the polymer concentration in the preconcentration was 35%.
A ring-opened polymer hydrogenated polymer having a volatile component content of 0.10% was obtained.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, the obtained flat plate had some silver streaks.
It was colorless and transparent without coloring, had high mechanical strength, and was good. The results are shown in Table 1.

Example 3 Example 1 was repeated except that the polymer concentration in the preconcentration was 70%.
A ring-opened polymer hydrogenated polymer having a volatile component content of 0.01% was obtained in the same manner as in 1.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets and evaluated. The results are shown in Table 1.

Comparative Example 1 Pre-concentration was performed without performing pre-heating and jacket heating to obtain a reaction solution 2 having a hydrogenated polymer concentration of 25%. 270
° C, pressure 30kPa, 2nd stage: temperature 270 ° C, pressure 5k
A ring-opened polymer hydrogenated polymer having a volatile component content of 1.5% was obtained in the same manner as in Example 1 except that the pressure was changed to Pa.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, although the obtained flat plate had high mechanical strength, it was colored (yellow) and had a silver streak. Was observed. Thereby, the superiority of Examples 1 to 3 was confirmed. The results are shown in Table 1.

Comparative Example 2 The operating conditions of the thin film dryer were changed to the first stage without preheating and preconcentration: temperature of 270 ° C., pressure of 35 kPa,
Step: A ring-opened polymer hydrogenated polymer having a volatile component content of 2.1% was obtained in the same manner as in Example 1, except that the drying step was performed at a temperature of 270 ° C and a pressure of 10 kPa.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, although the obtained flat plate had high mechanical strength, it was colored (yellow) and had a silver streak. Was observed. Thereby, the superiority of Examples 1 to 3 was confirmed. The results are shown in Table 1.

Comparative Example 3 The operating conditions of the thin film dryer were changed to the first stage without preheating and preconcentration: temperature: 300 ° C., pressure: 20 kPa,
Step: The volatile component content was 1. as in Example 1 except that the drying step was performed at a temperature of 300 ° C. and a pressure of 1 kPa or less, that is, the temperature was increased to increase the degree of pressure reduction.
A 1% hydrogenated ring-opened polymer was obtained.

Thereafter, pellets were produced in the same manner as in Example 1, and a flat plate was formed using the pellets. As a result, the obtained flat plate was colored (yellow, burnt with resin), had low mechanical strength, and had a low silver strength. Streaks were observed. Thereby, the superiority of Examples 1 to 3 was confirmed. Table 1 shows the results
It describes in.

Comparative Example 4 A volatile component was removed in the same manner as in Comparative Example 3, except that the residence time of the solution in the cylindrical concentrating dryer in the drying step was extended from 5 hours to 10 hours. 0.2
A 0% ring-opened polymer hydrogenated polymer was obtained. Thereafter, pellets and flat plates were manufactured and evaluated. As a result, the thermal history of the polymer was increased, the coloring of the flat plates was increased, and the mechanical strength was lowered.
The results are shown in Table 1.

[0104]

As described above, according to the present invention, as an optical material or the like, volatile components can be efficiently removed from a reaction solution containing a polymer, and a decrease in the molecular weight of the obtained polymer can be suppressed. A method for producing a suitable alicyclic structure-containing polymer can be provided.

Further, according to the present invention, it has high strength,
A molded article free from coloring and free from molding defects such as silver streaks and voids can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J032 CA34 CA36 CA38 CF05 CG02 4J100 AR03P AR05P AR09P AR11P AR17P AR18P AR22P AR25P AS15P AS25P BA03P BA05P BA12P BA16P BA40P BC04P BC43P BC55P BC66P CA01 CA31 GB02 GC03 GB03

Claims (6)

[Claims] In the step of recovering a polymer by removing a volatile component from a solution containing a polymer obtained by polymerizing an alicyclic structure-containing monomer and, if necessary, hydrogenating the polymer, (1) )
After the preconcentration step of evaporating and removing a part of the volatile components of the polymer solution containing the alicyclic structure-containing polymer in the vessel to make the polymer concentration 30 to 95% by weight, (2) the preconcentration A fat comprising a drying step of removing the remaining volatile components by heating and / or reducing the pressure of the resulting polymer solution into a thin film to reduce the volatile component content to 1% by weight or less. A method for producing a polymer having a ring structure. 2. The process for producing an alicyclic structure-containing polymer according to claim 1, wherein the preconcentration step is performed using a solvent removing device capable of reducing pressure, and the drying step is performed using a thin film dryer. Method. 3. The method for producing an alicyclic structure-containing polymer according to claim 2, wherein said solvent removing device is provided with a heating means. 4. The alicyclic structure-containing polymer according to claim 1, wherein a polymer solution containing the alicyclic structure-containing polymer is preheated before the preconcentration step. Manufacturing method. 5. The method for producing an alicyclic structure-containing polymer according to claim 1, wherein at least one of the preconcentration step and the drying step is performed in a low oxygen concentration atmosphere. 6. A molded article comprising an alicyclic structure-containing polymer obtained by the production method according to claim 1.