JPH04161421A - Production of norbornene polymer and its hydrogenated product - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent transparency and suitable for colorless optical material, etc., by carrying out ring-opening polymerization in the presence of a metathesis catalyst, adding a catalyst-inactivation agent to effect the precipitation and separation of the residue and optionally hydrogenating the polymer. CONSTITUTION:The objective polymer can be produced by mixing (A) 100mol of a norbornene monomer such as 2-norbornene with (B) a metathesis catalyst comprising (i) preferably 0.005-5mol of a transition metal compound such as titanium chloride and (ii) preferably 0.1-10mol of an organic aluminum compound such as trimethyl aluminum, polymerizing the monomer e.g. at -20 to +100 deg.C, adding (C) a catalyst-inactivation agent such as water or alcohol to the obtained polymer to precipitate the catalyst and removing the catalyst e.g. by centrifugal separation.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a norbornene-based ring-opening polymer and its hydrogenated product, and more specifically relates to a method for producing a norbornene-based ring-opening polymer and its hydrogenated product, and more specifically, after ring-opening polymerization of a norbornene-based monomer, the ring-opening polymer is Production of norbornene-based ring-opening polymers and norbornene-based ring-opening polymer hydrogenated products, characterized by adding a catalyst inactivator to a solution to precipitate catalyst residues, and removing the catalyst residues by filtration or centrifugation. Regarding the method.

[Conventional technology]

In recent years, hydrogenated ring-opening polymers of norbornene monomers, such as tetracyclododecene, its alkyl-substituted products, and ester-type substituted products, have attracted attention as raw materials for optical materials and other molded products that require transparency. (For example, JP-A-60-262024, JP-A-63-317520,
JP-A No. 1-132626, etc.).

In the production of norbornene-based ring-opening polymers, it is necessary to remove catalyst residue after polymerization, and the conventional method for this is to add an alcohol-based compound to the polymerization solution and then treat it with a solution containing a chelating agent. Method (Unexamined Vi
49-430500), a method of treating with a triethanolamine aqueous solution (JP-A-54-99198), a method of treating a polymer solution after the polymerization reaction with an acidic aqueous solution of an organic acid (JP-A-2-24319) etc. are known.

However, with these methods, the aqueous solution containing the polymerization catalyst is finely dispersed in the polymer solution, making it difficult to separate the layers, and the separation operation is complicated, requiring multiple washings and separations to sufficiently remove the catalyst. In addition, there were problems such as a low recovery rate of the separated polymer solution.

After producing a ring-opening polymer, when hydrogenating individual polymers to produce a hydrogenated polymer, the polymerization solvent and the hydrogenation solvent are the same solvent, and the polymer solution after the polymerization reaction is JP-A-1-311120 discloses a method in which a hydrogenation reaction is carried out after the treatment, but the problems in production operations are the same as in the prior art.

[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing norbornene-based polymers that efficiently removes polymerization catalyst residues remaining in norbornene-based ring-opening polymers with simple operations. Another object of the present invention is to provide a method for efficiently producing a hydrogenated norbornene-based ring-opening polymer that is free from coloration and has excellent transparency by utilizing the above method.

1”!Means for Solving Problem 1] The first object of the present invention is to perform ring-opening polymerization of τ norbornene monomer using a metathesis catalyst, add a catalyst deactivating agent to the polymer solution obtained, and inactivate the catalyst. This is achieved by precipitating the residue, removing the catalyst residue by filtration or centrifugation, and then recovering the norbornene-based ring-opening polymer from the polymer solution.A second object of the present invention is to recover the norbornene-based ring-opening polymer from the polymer solution. This is achieved by adding a hydrogenation catalyst to the polymer solution from which the catalyst residue has been removed, hydrogenating the polymer in the presence of hydrogen, and then recovering the hydrogenated norbornene-based ring-opening polymer.

Hereinafter, the configuration of the present invention will be explained in detail.

(Norbornene Monomer) Specific examples of the norbornene monomer used in the present invention include 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, and 5-ethyl-2-norbornene.

5-butyl-2-norbornene, 5-ethylidene-2-
Bicyclic monomers such as norbornene, dicyclopentadiene, 2,3-dihydrodicyclopentadiene,
and cyclocyclic monomers such as alkyl substituted products of these such as methyl, ethyl, propyl, butyl, dimetanooctahydronaphthalene, 6-methyl-1,4: 5,
8-dimethano-1t4,4a,5,6,7,8,8a-
Octahydronaphthalene, 6-ethyl-1,4:5,8
-Dimethano-1,4,4a,5,6,7,8,8a-
Octahydronaphthalene, 6-nitylidene-1,4:5
．． 8-dimethano-1,4,4a, 5,6,7,8,8a
- Tetracyclics such as octahydronaphthalene - Tri-tetramers of cyclopentadiene, for example 4.9:5.
8-dimethano-3a, 4,4a, 5,8,8a, 9,9
a-octahydro-IH-benzoindene, 4,1
1:5, 10:6, 9-) Rimetano 3a, 4, 4a,
5.5a, 6,9,9a, 10,10a, 11,1la
-Dodecahydro-IH-cyclopentaanthracene and other polycyclic monomers having five or more rings are exemplified. Further, the norbornene monomer may have a cycloalkyl group or an aryl group, or a polar group such as a halogen atom, an ester residue, an ether residue, a cyano group, or a pyridyl group. These monomers may be used alone or in combination of two or more.

In addition, other cycloolefins, such as cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc., may be used as copolymerization components, depending on the properties of the resulting polymer. It can be used as long as it is suitable for the purpose.

Furthermore, an acyclic olefin, preferably an α-olefin, may be used as a molecular weight regulator, usually in a range of up to 10 mol%.

(Metathesis Polymerization Catalyst) The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it is a catalyst known for ring-opening polymerization of norbornene monomers. Usually, it consists essentially of a transition metal compound and an organometallic compound of metals from groups 1 to 2 of the periodic table.

The transition metal compounds used include titanium, vanadium,
Transition metal compounds such as tungsten and molybdenum are preferred. Examples include halides-oxyhalides, oxides, carbonyl compounds, and organic ammonium salts of these transition metals.

Specifically -TiGa, TiBr4, VOG3- VO
Br3, WBr2, WBr4, WBrs, WC
u2, WCGL4- WCQs-WOJa,
WF4- Wb, WL, WOBra, Police0α4,
-〇F4, AoBr2- MoBr:+, MoBr4,
A0α4, Moα5, MoF4, Mo0C
Qt, Mo0Fa, 1102゜H2WO4-N
aWO4, K2WOa, (NH4hWOa, CaWO4
, CuWO4, MgWOa, (Co)stjc(OCH
3) (CL), (Co)s
3), (CO)5Wc (OCJs) (CJs), (Co
)sMoC(OC2t(s)(CH3),(CO)5M
Examples include o=c(OC2Hs)(N(C2Hs)2), tridecylammonium molybdenum W1 salt, tridecylammonium tungstate, and the like.

In addition, examples of the organometallic compounds of group 1 to 2 metals that can be used include organoaluminum compounds, organotin compounds, lithium, sodium, magnesium, zinc,
Examples include compounds such as cadmium and boron. Specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminium monochloride, di-n-butylaluminum monochloride, diethylaluminum monopromide. , diethylaluminum monochloride, diethylaluminium monohydride, ethylaluminum sesquichloride, ethylaluminum dibromide, etc.; tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, triethyltin bromide, Toluethyltin chloride, triethyltin bromide, toluethyltin chloride, diethyltin sioside, diethyltin dichloride, diethyltin bromide, diethyltin sioside,
Organotin compounds such as ethyltin trichloride, ethyltin trichloride, ethyltin tripromide, ethyltin trichloride, etc. Others include n-butyllithium, n-pentyl sodium, methylmagnesium bromide, ethylmagnesium promide, etc. mido, methylmagnesium bromide, n-propylmagnesium chloride, t-butylmagnesium chloride, allylmagnesium chloride, cyatylzinc, diethylcadmium,
Examples include trimethylboron, triethylboron, tri-n-butyl-boron, and the like.

Furthermore, by adding other components in addition to transition metal compounds and organometallic compounds of metals from groups 1 to 2 of the periodic table,
It can be used as a metathesis polymerization catalyst with increased polymerization activity and improved selectivity in ring-opening polymerization. Examples of such ingredients include:

Molecular oxygen, alcohol, ether, peroxide, carboxylic acid, W! Examples include anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. Particularly preferred are aliphatic or aromatic tertiary amines, and specific examples include triethylamine, dimethylaniline, tri-n
-butylamine, pyridine, α-picoline, etc.

This metathesis polymerization catalyst consists of norbornene monomer 1
00 mole, the transition metal compound is o.
5-5 mol, 0.2-5 mol when adding other catalyst components
Ring-opening polymerization is carried out using 20 mol, preferably 1 to 10 mol.

(Polymerization method) The ring-opening polymerization of the norbornene monomer in the present invention is as follows:
Although it is possible to do this without a solvent, it is usually carried out in an inert organic solvent.

As the organic solvent, hydrocarbon solvents are preferable, and among them, cyclic hydrocarbon solvents are particularly preferable because they have excellent solubility for the norbornene ring-opening polymer to be produced, and specific examples include benzene, toluene, xylene, and ethylbenzene. Aromatic hydrocarbons; aliphatic hydrocarbons such as n-pentane, hexane, heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin; methylene dichloride, dichloroethane, dichloroethane, tetrachloroethane, Examples include halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and two or more of these can also be used as a mixture.

When a solvent is used, the amount of the solvent used is 1 to 20 parts by weight, preferably 2 to 101 parts by weight, per 1 part by weight of the norbornene monomer.

There are no particular restrictions on the temperature conditions for ring-opening polymerization, and -2
0℃~100℃1 Usually 0~100℃, preferably 10℃
Any temperature between ~80°C can be selected.

The polymerization pressure conditions are selected from the range of 0 to 50 kg/cm2, usually normal pressure to 10 kg/cm2, preferably 5 kg/cm2 or less. Further, ring-opening polymerization is generally performed in an inert gas atmosphere such as nitrogen or argon.

(Catalyst deactivator) In the present invention, a catalyst deactivator is added to the polymer solution obtained in this way, catalyst residue is precipitated, and the residue is selectively removed by mechanical means.

The catalyst deactivator is preferably a compound having a hydroxyl group, such as water, alcohol, carboxylic acid, phenols, and the like. Specifically, alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methyl-
1-butanol, 2-ethyl-1-hexanol, 2-
Propen-1-ol, 1,2-ethanediol, ■.

2-butanediol, 1,4-butanediol, 1,q
-hexanediol, glycerin, pentaerythritol, 2-ethoxyethanol, 2゜2-dichloro-1-
Examples include aliphatic, alicyclic, and aromatic di- or polyalcohols such as ethanol, 2-bromo-1-ethanol, and 2-phenyl-1-ethanol, and examples of carboxylic acids include formic acid, #acid, trichloroacetic acid, acrylic acid,
Oxalic acid, maleic acid, propanetricarboxylic acid, tartaric acid, citric acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, phthalic acid.

Aliphatic, alicyclic, and aromatic compounds such as pyromellitic acid
Examples include di- or polycarbonate am, and examples of phenols include phenol, cresol, xylenol, and the like.

These catalyst deactivators can be used alone or in combination of two or more.

Among these compounds having a hydroxyl group, water or water-soluble compounds (for example, compounds having 4 or less carbon atoms) are preferable because they have low solubility in a polymer solution and are unlikely to remain in the polymer. Among them, water or lower alcohols are preferred, but in particular, when water and alcohols are used simultaneously, the efficiency of catalyst inactivation is better than when water is used alone,
Further, catalyst residues can be easily precipitated compared to when alcohol is used alone. A preferred ratio of water to alcohol is 0.1 to 5 parts by weight, particularly 0.2 to 2% by weight of alcohol per 1 part by weight of water.

The amount of deactivating agent used in the present invention deactivates the catalyst,
And the amount is sufficient to selectively deposit the catalyst. This can be easily determined by experiment. For example, when the catalyst deactivator is a compound having a hydroxyl group, the product of the metal oxidation number and the number of moles of the organometallic compound of the group ■~■ metal that is the ring-opening polymerization catalyst, and the metal oxidation number of the transition metal compound. It is used in a range where the total value of the equivalents of hydroxyl groups of the hydroxyl group-containing compound is 0.5 to 10 times the total value of the product of the number and the number of moles. In particular, it is preferable to use the amount in the range of 1 to 3 times, since the polymerization catalyst is well insolubilized and hardly remains in the polymer.

Furthermore, activated clay, talc, diatomaceous earth, bentonite, synthetic zeolite, silica gel powder, alumina powder, etc. are added as coagulation nuclei or coagulation aids for insoluble components that precipitate as a result of adding a catalyst deactivator to the polymer solution. You may do so. Although the amount added is arbitrary, it is preferably about 0.1 to 10 times the amount of the polymerization catalyst.

In the present invention, the catalyst inactivator may be used within the range necessary for the catalyst residue to precipitate, and if it is added in excess, the precipitated catalyst residue will be redissolved in the excess amount of the catalyst inactivator. Prone to layer separation. However, even in that case,
Compared to conventional technology, the amount added is much smaller, so moisture can be removed by adding well-known dehydrating agents such as anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous calcium sulfate, etc. Residues can be efficiently removed in the catalyst residue removal step.

The catalyst deactivator is added to the polymer solution at any temperature between 0°C and 100°C, preferably between 30°C and 80°C.
℃ or below, any pressure between 0kg/70m" and 50k/am", usually normal pressure or above 10kg/am2
Hereinafter, preferably within a range of 5 kg/crn2 or less,
Under these conditions, the reaction is carried out for 0.5 hours or more and 10 hours or less, preferably 1 hour or more and 3 hours or less, to form an insoluble product. Undissolved products can be removed from the polymer solution by filtration or centrifugation. The filtration is
For example, using a pressure filter, it is usually 0.5 or more and 10 kg/
Insoluble products can be removed by applying a pressure of about cI112 or less, using a filter layer or passing paper, and if necessary using a filter aid such as diatomaceous earth. Centrifugation is
For example, undissolved products can be removed by applying a force of 100 to 500 G for about 1 hour.

When the desired product is an unhydrogenated polymer, the polymer is recovered from the polymer solution from which catalyst residues have been removed according to a conventional method. The method is not particularly limited, but - for boat fishing,
The method used is to coagulate the polymer by mixing it with isopropyl alcohol, acetone, etc., which are poor solvents for the polymer.

The amount of metal remaining in the ring-opened polymer polymerized and recovered in this manner is usually 50 ppm or less.

(Hydrogenation Reaction) When the target polymer is a hydrogenated product, the polymer solution from which the catalyst residue has been removed can be directly subjected to the hydrogenation step.

As the hydrogenation catalyst, any catalyst commonly used in the hydrogenation of olefin compounds can be used. For example, Wilkinson complex, cobalt acetate/triethylaluminum, nickel acetylacetonate/triisobutylaluminum, palladium-carbon, Ruthenium-carbon, nickel-diatomaceous earth, etc. can be used.

The hydrogenation reaction is carried out in a homogeneous or heterogeneous system depending on the type of catalyst, under a hydrogen pressure of 1 to 200 atmospheres, and at a temperature of 0 to 250°C.

The hydrogenation rate is +90% or more, preferably 95% or more, particularly preferably 99% or more from the viewpoint of heat deterioration resistance, light deterioration resistance, etc.

According to this method, since the unhydrogenated polymer is subjected to the hydrogenation step without being isolated, deterioration of the polymer can be prevented and the process can be extremely simplified. Furthermore, when alcohol is used as a catalyst deactivator, it has the advantage that even if it remains in the polymer solution, it does not inhibit the hydrogenation reaction, but rather promotes the reaction.

There are no particular limitations on the method for recovering the hydrogenated product from the reaction solution of the hydrogenation reaction. Generally, the hydrogenation catalyst is removed from the hydrogenation reaction solution, and the solution is brought into contact with the same amount or more, usually 2 to 3 times the amount of ketone or alcohol, to precipitate and isolate the hydrogenated norbornene-based ring-opening polymer. or,
A method is used in which the hydrogenated product is isolated by heating and evaporating volatile components from the reaction solution from which the catalyst has been removed under reduced pressure.

〔Effect of the invention〕

According to the method of the present invention, polymerization catalyst residues can be efficiently removed by simple operations from a polymer solution obtained by using a metathesis polymerization catalyst for norbornene monomers, and polymers from which catalyst residues have been removed in this way can be removed. By directly subjecting the solution to hydrogenation reaction, it is possible to efficiently obtain a hydrogenated polymer with excellent transparency and resistance to coloring through a simple process.

〔Example〕

EXAMPLES The present invention will be explained in more detail by giving Examples and Comparative Examples below. Note that parts are based on weight unless otherwise specified.

(Reference example) 6-ethyl-1,4:5.8-dimethano-1,4,4a
, 5,6°7.8,8a-octahydronaphthalene 60
1 part was dissolved in 200 parts of cyclohexane, and 1 part of 1-hexene was added as a molecular weight regulator. This solution was heated at 30°C.
Then, 10 parts (13 mmol) of 15% triethylaluminum/cyclohexane solution, 5 parts (50 mmol) of triethylamine, and 10 parts (11 m+++ol) of 20% titanium tetrachloride/cyclohexane solution were added as polymerization catalysts to initiate ring-opening polymerization. .

30 minutes after the start of polymerization, when the conversion rate was 85%, 10 parts of 0.5% tungsten hexachloride/cyclohexane solution (0.13
mmol) was added and stirred for an additional 30 minutes to obtain 296 parts of a dark brown, cloudy polymer solution.

As measured by high performance liquid chromatography, the conversion rate of monomer to polymer was 99%. The intrinsic viscosity of the obtained polymer was 0.4 ton/g at 25° C. in toluene.

(Example 1) To 100 parts of the ring-opened polymer solution obtained in Reference Example, 1.0 part (31 mmol) of methanol and 1 part of water were added as a catalyst inactivator.
．． 0 parts (56 m+mol) and 1.5 parts of diatomaceous earth (Radiolite! 1300, manufactured by Showa Kagaku) as a coagulation aid were added and stirred at 80°C for 1 hour.

After the reaction was completed, 3 parts of anhydrous magnesium sulfate was added to
The mixture was stirred for an additional hour at ℃. The solution was pale yellow with blackish brown side precipitates dispersed therein.

Upon standing, the precipitate settled out, and the solution became somewhat cloudy and pale yellow. When the ring-opened polymer solution in which the insolubilized catalyst was precipitated was centrifuged at 100 G for 1 hour, the precipitated insolubilized catalyst precipitated and 95 parts of a pale yellow transparent polymer solution was obtained. A portion of this solution was concentrated using a rotary evaporator at 70°C and 10 mmH1, and dried at 120°C and lmmHg to obtain 19 parts of a polymer. When a part of the obtained polymer was dissolved in cyclohexane and the amount of metals was measured by atomic absorption spectrometry, the amount of residual metals in the obtained polymer was 15 ppm of aluminum, 5 ppm of titanium, and no tungsten was detected. There wasn't.

(Example 2) 1.0 part of citric acid hydrate (4,8
The treatment was carried out in the same manner as in Example 1, except that 1.0 part (56 mmol) of water was used. The amount of residual metal in the polymer was 7 ppm of aluminum, and no titanium or tungsten was detected.

(Example 3) 1.0 part of isopropyl alcohol (17 m+aol) was added to 100 parts of the polymer solution obtained in Reference Example, and the mixture was stirred at room temperature for 10 minutes. Furthermore, add 1.0 part of distilled water (56 m
m.

1) It was added and stirred at 80°C for 1 hour. After the reaction is complete,
Add 3 parts of anhydrous magnesium sulfate, let the solution cool to room temperature, and use Radiolite #800 (manufactured by Showa Kagaku) as a filter layer to filter the solution containing insolubilized substances under pressure to 2.0 kg/cva2 to obtain a colorless and transparent solution. 94 parts of a polymer solution were obtained.

A portion of this solution was concentrated using a rotary evaporator at 70'C, 10 mmt (g, 120°C).

The mixture was dried at lmmHg to obtain 19 parts of a polymer.

When the obtained polymer was dissolved in cyclohexane and the amount of metal was measured by atomic absorption spectrometry, the amount of residual metal in the obtained polymer was 5 ppm of aluminum, and no titanium or tungsten was detected.

(Example 4) 1 part of palladium-carbon catalyst was added to 500 parts of the liquid containing the polymer obtained in Example 3, and the mixture was placed in an autoclave, and after stirring and mixing, the air inside was replaced with hydrogen. , while stirring at a hydrogen pressure of 70 kg/crn2 and a temperature of 30°C.
It was held for 0 minutes. Thereafter, the temperature was raised to 140°C and a reaction was carried out for 3 hours. After the reaction, the solution was allowed to cool to room temperature, and the solution containing the insolubilized material was filtered using Radiolite #300 as a filter layer.
．． After filtering under pressure of 0 kg 7 cm2 to remove the catalyst, the mixture was poured into 2000 parts of isopropyl alcohol with stirring to dry up the polymer hydrogenated product. The polymer hydrogenated product was collected by filtration through a 400-mesh stainless steel filter, washed with 500 parts of azetone, and then heated at a temperature of 10
It was dried under reduced pressure at 0° C. and a pressure of 1+a+iHg for 20 hours to obtain 93 parts of a solid hydrogenated polymer.

As a result of proton NMR spectrum analysis of this hydrogenated polymer, it was confirmed that the proton absorption due to double bonds had disappeared, and that it was hydrogenated by more than 99% (the hydrogenation rate was 99%). that's all).

The glass transition temperature determined by differential scanning calorimetry was 142°C.

(Example 5) Pentaerythritylcotetrakis (3-(3,
0.02 part of 5-di-t-butyl-4-hydroxyphenyl)propionate) was blended and extruded to 230
It was melt extruded at ℃ and cut with a pelletizer to obtain pellets for molding.

Using this pellet, an injection molding machine (DISK-5, manufactured by Sumitomo Heavy Industries, Ltd.) was used to mold the resin at a temperature of 330°C and a mold temperature of 11°C.
An optical disk substrate having a diameter of 13 cm and a thickness of 1.25 mm was molded at 0°C. The obtained optical disc substrate was colorless and transparent, and the light transmittances at 400 parts m and 700 parts m were 90.0% and 91.5%, indicating excellent transparency.

(Comparative Example 1) When the polymer solution obtained in the reference example was centrifuged at 500G for 1 hour, a light brown suspension solution was obtained. This solution was concentrated and dried in the same manner as in Example 1, and the amount of residual metal in the obtained polymer was measured.
00pp@-Titanium 1700pp, Tungsten 30
It was 0ppa+. Further, when this solution was hydrogenated in the same manner as in Example 4, the hydrogenation rate was about 45%. When pellets were prepared from this hydrogenated product in the same manner as in Example 1, the pellets were colored extremely yellow and were unsuitable as an optical material.

(Comparative Example 2) The polymer solution obtained in the reference example was allowed to cool to room temperature, and the solution containing insolubilized substances was filtered using Radiolite #800 as a filtration layer under pressure of 2-0 kg/crtr2. It became clogged and no fluid could be passed.

(Comparative Example 3) Citric w1 was added to 100 parts of the ring-opened polymer solution obtained in the reference example.
Add an aqueous solution of 2 parts dissolved in 100 parts of water, and stir for 1 hour.
Stir vigorously at 0°C. The emulsified mixed solution was heated to 50℃ for 5 minutes.
After standing for 1 day at room temperature, it separated into three layers: the upper layer was a colorless and transparent polymer cyclohexane solution layer, the middle layer was an emulsified polymer cyclohexane layer with an aqueous solution dispersed therein, and the lower layer was a colorless and transparent aqueous solution layer. did. The three layers were separated to obtain 92 parts of an aqueous solution, 70 parts of an emulsion, and 32 parts of a transparent polymer solution in cyclohexane. When the emulsion was centrifuged at 100 G for 1 hour, a clear solution was separated into an upper layer and an emulsion was formed into a lower layer. The upper layer was separated to obtain 49 parts of a transparent cyclohexane solution of the polymer. Cyclohexane solutions of transparent polymers recovered by static separation and centrifugation were mixed.

The polymer was recovered from the mixed solution in the same manner as in Example 1, and 1
6 parts of polymer were obtained.

This recovered amount was inferior to that in Example 1.

Patent applicant: Zeon Corporation

Claims (1)

[Claims] 1. A catalyst inactivator is added to a polymer solution obtained by ring-opening polymerization of a norbornene monomer using a metathesis catalyst to precipitate a catalyst residue, and the catalyst residue is filtered or A method for producing a norbornene-based ring-opening polymer, which comprises recovering the polymer from a polymer solution after removal by centrifugation. 2. A catalyst inactivator is added to a polymer solution obtained by ring-opening polymerization of a norbornene monomer using a metathesis catalyst to precipitate a catalyst residue, and the catalyst residue is removed by filtration or centrifugation. A method for producing a hydrogenated norbornene-based ring-opening polymer, which comprises adding a hydrogenation catalyst to a polymer solution, hydrogenating the polymer in the presence of hydrogen, and then recovering the hydrogenated product.