JP3478350B2 - Method for producing hydrogenated ring-opened polymer - Google Patents

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 a hydrogenated product of a ring-opening polymer of a norbornene-based monomer, and more specifically to the opening of a norbornene-based monomer which is excellent in reaction solution stability and advantageous in process control. The present invention relates to a method for producing a ring polymer hydrogenated product.

[0002]

2. Description of the Related Art It is known that a ring-opening polymer of a norbornene-based monomer and a hydrogenated product thereof have excellent properties as an optical material and the like.

Of these, the unhydrogenated ring-opening polymer has a double bond in the main chain structure, so that it may be deteriorated by oxidization and the like, and has weather resistance, heat resistance deterioration, light resistance resistance and the like. There are difficulties. Therefore, it is common to use a double bond in the main chain as a hydrogenated product that is saturated by hydrogenation.

To obtain a hydrogenated product of a norbornene ring-opening polymer, it is common to contact the ring-opening polymer with hydrogen in a solvent in the presence of a hydrogenation catalyst. It is possible to hydrogenate an unsaturated hydrocarbon solvent such as toluene as a solvent, but when such a solvent is used, the solvent is also hydrogenated, which causes a problem that the hydrogenation efficiency is lowered. Therefore, a saturated hydrocarbon solvent such as cyclohexane, methylcyclohexane, n-hexane, cycloheptane, or methylcycloheptane is usually used.

However, depending on the type of norbornene-based monomer, the ring-opening polymer may not be sufficiently dissolved in a saturated hydrocarbon solvent and often precipitates. From the standpoint of preventing precipitation, the hydrogenation reaction has to be rushed, which makes it difficult to control the process. Especially the general formula 1

[Chemical 3] (In the formula, 1 represents 0 or 1, and R ¹ is -O- or -N.
R ⁹ — or —CR ¹⁰ R ¹¹ — is represented, and R ^{2 to} R ¹³ are hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, polar groups such as halogen, alkoxy groups, cyano groups, or polar groups thereof. This represents a major problem when the ring-opening polymerization of a norbornene-based monomer represented by (representing a hydrocarbon group having 1 to 4 carbon atoms substituted with) is performed. Further, many hydrogenated products of the ring-opening polymer are sufficiently dissolved in a saturated hydrocarbon solvent, but a ring-opening polymer of a norbornene-based monomer having an aromatic ring structure as represented by the general formula 1 is used. When the main chain structure of is hydrogenated and the aromatic ring structure is left without being selectively hydrogenated, the resulting selectively hydrogenated product is not sufficiently dissolved in a saturated hydrocarbon solvent and is easily precipitated, It was an administrative problem.

[0006]

The inventors of the present invention have conducted intensive studies on a method for producing a hydrogenated product of a norbornene ring-opening polymer whose process control is easy. As a result, the inventors have found that a solvent having a specific chemical structure is used. It was found that the solvent contained is capable of sufficiently dissolving the ring-opening polymer of norbornene-based monomer and its hydrogenated product, and that these resin solutions are stable without precipitating these resins, Came to complete.

[0007]

Thus, according to the present invention, a ring-opened polymer of a norbornene-based monomer is used in a solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure as at least a part of the solvent. To provide hydrogenation in the presence of a hydrogenation catalyst.

(Norbornene type monomer) The norbornene type monomer used in the present invention is disclosed in JP-A-2-227424,
JP-A-2-276842, JP-A-3-14882,
Known monomers such as JP-A-3-122137, for example, norbornene, its alkyl, alkylidene, aromatic substituted derivatives and halogens, hydroxyl groups, ester groups, alkoxy groups of these substituted or unsubstituted olefins,
Polar group substituents such as cyano group, amide group, imide group, silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, etc .; norbornene having one or more cyclopentadiene Added monomers, derivatives and substitutions similar to the above, for example,
1,4: 5,8-dimethano-1,2,3,4,4a,
5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8-dimethano-1,4
4a, 5,6,7,8,8a-octahydronaphthalene and the like; and the like.

Among them, the general formula 1

[Chemical 4] (In the formula, 1 represents 0 or 1, and R ¹ is -O- or -N.
R ⁹ — or —CR ¹⁰ R ¹¹ — is represented, and R ^{2 to} R ¹³ are hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, polar groups such as halogen, alkoxy groups, cyano groups, or polar groups thereof. A norbornene-based monomer having a structure represented by a C 1 -C 4 hydrocarbon group substituted with) is preferred because of its large improvement effect by the present invention. Examples of such norbornene-based monomers include 1,4-methano-1,4,4a, 9b-
Tetrahydrofluorene, 1,4-methano-1,4,4
a, 9b-tetrahydrodibenzofuran, 1,4-methano-1,4,4a, 9b-tetrahydrocarbazole,
1,4-methano-1,4,4a, 10b-tetrahydrofluoranthene, 1,4-methano-1,4,4a, 4
b, 5,6,7,10b-octahydrofluoranthene, 1,4-methano-1,4-dihydrophenanthrene, 1,4-methano-1,4,4a, 5,6,10-hexahydrophenanthrene Examples thereof include alkyl, alkylidene, alkenyl, aromatic substituted derivatives, and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, silyl groups and other polar substituents.

Further, within the range that does not impair the effects of the present invention,
A copolymerizable monomer may be copolymerized. The most preferable monomer composition used for copolymerization is a norbornene-based monomer having a structure represented by the general formula 1. Next, it is preferable to use a norbornene-based monomer having the structure represented by the general formula 1 and a norbornene-based monomer other than that, and further, a norbornene-based monomer and a norbornene having the structure represented by the general formula 1 Those composed of non-system monomers, those composed only of norbornene-based monomers having structures other than those represented by general formula 1, norbornene-based monomers and norbornenes having structures other than those represented by general formula 1 The order is that of non-system monomers.

(Metathesis Polymerization Catalyst) The metathesis polymerization catalyst used to obtain the ring-opening polymer used in the present invention is a known catalyst (for example, Japanese Patent Publication No. 41-2).
0111, JP-A-46-14910, JP-B-57-17883, JP-A-57-61044, JP-A-54-86600, and JP-A-58-1.
No. 27728, Japanese Patent Laid-Open No. 1-240517, etc.), and usually consists essentially of (a) a transition metal compound catalyst component and (b) a metal compound promoter component.

The (a) transition metal compound catalyst component used in the metathesis polymerization catalyst is a Deming periodic table IVB, V
Compounds of B, VIB, VIIB, or VIII group transition metals, including halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates of these transition metals.
Carbonyl complex, acetonitrile complex, hydride complex,
These derivatives, P (C of these or these derivatives
₆ H ₅ ) _{5 and} other complexing agents may be mentioned. Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , and WB.
r ₃ , WBr ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ ,
WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , Mo
Br ₂ , MoBr ₃ , MoCl ₅ , MoF ₄ , MoOC
l ₄ , WO ₂ , H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (N
_{H 4) 2 WO 4, CaWO} 4, CuWO 4, MgWO 4, (C
O) ₅ WC (OCH ₃ ) (CH ₃ ), tridecyl ammonium molybdate, tridecyl ammonium tungstate, and the like. Practically, a compound of W, Mo, Ti, or V is preferable from the viewpoint of polymerization activity and the like, and a halide, an oxyhalide, or an alkoxyhalide thereof is particularly preferable.

The metal compound promoter component (b) used in the metathesis polymerization catalyst is a Deming Periodic Table IA, II.
A compound of group A, IIB, IIIA, or IVA having at least one metal element-carbon bond or metal element-hydrogen bond, such as Al, Sn,
Examples thereof include organic compounds such as Li, Na, Mg, Zn, Cd, and B. Specifically, organic aluminum compounds such as trimethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, methylaluminum sesquichloride, ethylaluminum dichloride; tetramethyltin. , Organic compounds such as diethyldimethyltin, tetrabutyltin, tetraphenyltin, triethyltin fluoride, diethyltin diiodide and ethyltin trichloride; organic lithium compounds such as n-butyllithium; organic compounds such as n-pentyl sodium Sodium compound; methylmagnesium iodide,
Organic magnesium compounds such as n-propyl magnesium chloride; Organic zinc compounds such as diethyl zinc; Organic cadmium compounds such as diethyl cadmium; Organic boron compounds such as trimethylboron, triethylboron, tri-n-butylboron; .

The metathesis polymerization activity can be increased by adding a third component in addition to the components (a) and (b). As such a third component, aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether,
Examples thereof include peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. Among them, aliphatic or aromatic tertiary amines are preferable, and specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine,
α-picoline and the like can be mentioned. In addition, alcohol such as 0
The compound containing the H group functions as an inactivating agent that inhibits the metathesis polymerization activity when added in excess of the stoichiometric amount, so it is preferable to add the compound in the stoichiometric amount or less. The stoichiometric amount here means the product of the number of moles of component (a) and the oxidation number of the transition metal contained in component (a), OH per molecule of the compound containing an OH group.
It refers to the number of moles represented by the number divided by the number of groups.

The quantitative relationship between these components is (a) component:
The component (b) is a metal element in a molar ratio of 1: 1 to 1: 100,
The molar ratio of component (a): third component is preferably 1: 0.005 to 1:10, preferably 1: 0.05 to 1: 3, preferably 1: 2 to 1:50. . When the amount of the component (b) is too small relative to the amount of the component (a), sufficient activity cannot be obtained with respect to the amount of the component (a), and when the amount is too large, the excess amount of the component (b) is exceeded.
It becomes difficult to remove the component and the cost becomes high.
If the amount of the third component is too small with respect to the amount of the component (a), the effect of adding the third component is small, and if it is too large, it becomes difficult to remove an excessive amount of the third component or the cost increases.

(Polymerization reaction solution) The solvent used in the polymerization reaction of the ring-opening polymer used in the present invention is a solvent which can sufficiently dissolve the norbornene-based monomer and the ring-opening polymer. There is no particular limitation. The details will be described later because the polymer is not precipitated even after the polymerization reaction and can be stored for a long period of time, and the hydrogenation reaction can be performed without precipitating the polymer and changing the solvent. It is preferable to use the solvent used in the method for producing a hydrogenated product of the present invention.

In the polymerization reaction liquid, a solvent is generally used in a weight ratio of 2 to 100 times, preferably 3 to 50 times, particularly preferably 4 to 20 times the weight of the monomer represented by the general formula 1. . Further, the metathesis polymerization catalyst is composed of the component (a) and the component (b).
Although an appropriate amount varies depending on the combination of components, the ratio of each component, the type of monomer, etc., usually 0.000001 to 1 mol of the component (a), preferably 0.
0001 to 0.5 mol is added. If the amount of the solvent is too small, it cannot be sufficiently dispersed, and the monomer or polymer is likely to precipitate, and the viscosity of the polymerization reaction liquid increases as the reaction progresses, so that it is difficult to obtain a high molecular weight product. When the amount of the solvent is too large, the reaction efficiency is poor, the reaction takes time, and it is difficult to obtain a high molecular weight one. If the amount of the polymerization catalyst is too large, it becomes difficult to remove the metathesis polymerization catalyst from the polymer or its hydrogenated product, and the metathesis polymerization catalyst becomes useless, resulting in poor production efficiency. If the amount of the polymerization catalyst is too small, the reaction efficiency will be poor and the reaction will take time.

Further, compounds having at least a carbon-carbon double bond or a carbon-carbon triple bond in the molecule such as α-olefins, α, ω-diolefins and acetylene, or allyl chloride, allyl acetate, etc. The molecular weight of the obtained metathesis polymer can be adjusted by adding the polar allyl compound (1) to the reaction solution. The addition amount is determined according to the target molecular weight and the type of compound used.

(Polymerization reaction conditions) The temperature conditions for carrying out the polymerization reaction are not particularly limited, but the polymerization is usually carried out at -20 to 100 ° C, preferably 10 to 50 ° C. If the temperature is too low, the reaction rate decreases, and if it is too high, it becomes difficult to control the reaction.
High energy costs. The pressure condition is not particularly limited, and the polymerization is usually performed at 1 to 50 kg / cm ² .

In order to prevent the resulting ring-opening polymer from being deteriorated by oxidation and being colored, the reaction atmosphere is often replaced with nitrogen.

(Polymerization reaction liquid after polymerization reaction) When polymerization is carried out using the solvent used in the hydrogenation reaction of the present invention, the polymerization reaction liquid does not cause precipitation of the polymer even after the completion of the polymerization for a long period of 10 days or more. It can be stored for a long time.

(Polymer) The above-mentioned ring-opening polymer has the general formula 2

[Chemical 5] (In the formula, 1 represents 0 or 1, and R ¹ is -O- or -N.
R ⁹ — or —CR ¹⁰ R ¹¹ — is represented, and R ^{2 to} R ¹³ are hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, polar groups such as halogen, alkoxy groups, cyano groups, or polar groups thereof. Represents a hydrocarbon group having 1 to 4 carbon atoms substituted with) 30% by weight or more of all repeating units,
It preferably has 50% by weight, more preferably 70% by weight, and particularly preferably 80% by weight or more, and the number average molecular weight is generally 1 in terms of polystyrene by gel permeation chromatography using toluene as a solvent. 0
00 to 1,000,000, preferably 5,000 to 2
0,000, more preferably 8,000 to 10
50,000, the glass transition temperature is usually 50 to 200
℃, preferably 70 ~ 180 ℃, more preferably 90 ~
It is 170 ° C.

In the present invention, the polymer may be recovered from the polymerization reaction solution, if necessary. The method is not particularly limited, but for example, the polymerization reaction liquid may be added to a large amount of a poor solvent such as alcohol to precipitate and coagulate the polymer. However, when the solvent used for the hydrogenation reaction in the present invention is used as the solvent for the polymerization reaction solution, the polymer is not recovered from the polymerization reaction solution, and a hydrogenation catalyst or the like is added to the solvent for the hydrogenation reaction. This is good, and the production efficiency can be improved by doing so.

(Hydrogenating Solvent) The solvent used for hydrogenation in the present invention contains, as at least a part thereof, a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure. As the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure, a polycyclic saturated hydrocarbon in which all carbon atoms form a ring structure is preferable, particularly a norbornane structure, from the viewpoint of excellent solubility of the ring-opening polymer. A polycyclic saturated hydrocarbon having 3 to 5 carbon atoms other than one or one cyclohexane ring structure, and all carbon atoms constitute a ring structure is preferable. Examples of such polycyclic saturated hydrocarbons include decalin, octahydroindene, tricyclodecane, and 2-methano-octahydronaphthalene. Among these, from the viewpoint of solution stability, they have a norbornane ring structure. Preferred are those with tricyclodecane being particularly preferred.

The solvent used for hydrogenation in the present invention is
A compound other than a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure may be mixed as long as the effect of the present invention is not impaired. The solvent to be mixed is not particularly limited, and a solvent having an unsaturated portion such as toluene can also be used, but saturated hydrocarbons are preferable from the viewpoint of hydrogenation efficiency, and particularly those having 4 to 8 carbon atoms from the viewpoint of resin solubility. Saturated hydrocarbons are preferred. For example, cyclopentane or an alkyl-substituted cyclopentane, specifically, cyclopentane, methylcyclopentane, ethylcyclopentane, 1,2-dimethylcyclopentane, etc .; cyclohexane or an alkyl-substituted cyclohexane. , Specifically, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3
-Dimethylcyclohexane, 1,4-dimethylcyclohexane, etc .; cycloheptanes; cyclooctanes;
These isomers such as n-hexane, n-heptane, n-octane or isohexane; and the like. Among these, those having a ring structure are preferable, those having a cyclohexane structure are more preferable, and cyclohexane, methylcyclohexane and the like are particularly preferable.

The saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure in the hydrogenation solvent is 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more. Among saturated hydrocarbons having a norbornane ring structure or a cyclohexane ring structure, there are some such as tricyclodecane which are not suitable for use as a solvent because they have a high melting point as a simple substance and solidify at room temperature. When such a solvent is used, a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is 40 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 85% by weight, and another solvent, preferably Is a saturated solvent having a cyclohexane structure, particularly preferably cyclohexane, methylcyclohexane, etc.
A mixed solvent composed of wt%, more preferably 50 to 10 wt%, and particularly preferably 40 to 15 wt% may be used as the hydrogenation solvent.

(Hydrogenation catalyst) The hydrogenation catalyst used in the present invention may be a homogeneous catalyst composed of (c) a transition metal compound and (d) a reducing metal compound, or a heterogeneous catalyst. Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so the addition amount may be small, and since they have activity even without applying high temperature and pressure, polymer decomposition and gelation do not occur, low cost and stable quality It is also possible to obtain a resin having excellent properties and having a high refractive index by selecting a combination of each component as described below. On the other hand, the heterogeneous catalyst becomes highly active by applying high temperature and high pressure, can be hydrogenated in a short time, and is easy to remove, and is excellent in production efficiency.

Homogeneous catalysts are disclosed in JP-A-58-43412, JP-A-60-26024, and JP-A-64-2.
It is known in Japanese Patent Laid-Open No. 4826 and Japanese Patent Laid-Open No. 1-138257. Examples of the transition metal compound (c) include groups I or groups IV to VII of the Deming Periodic Table.
Compounds of transition metals belonging to any of the group I, for example
V, Ti, Cr, Mo, Zr, Fe, Mn, Co, N
halides of transition metals such as i, Pd, Ru, alkoxides, acetylacetonates, sulfanates, carboxylates, naphthenates, trifluoroacetates,
Stearate and the like, and specific compounds include:
Tetraisopropoxy titanate, tetrabutoxy titanate, titanocene dichloride, zirconocene dichloride, vanadocene dichloride, triethylvanadate, tributylvanadate, chromium (III) acetylacetonate, manganese (III) acetylacetonate, iron (III) acetylacetonate , Cobalt (III)
Acetylacetonate, bis- (triphenylphosphine) -cobalt dichloride, nickel (II) acetylacetonate, bis- (tributylphosphine) -palladium and the like can be mentioned. Further, (d) the reducing metal compound includes Deming's Periodic Table IA, IIA, II
A compound of Group B, IIIA, or IVA metal, wherein
At least one metal element-having a carbon bond or a metal element-hydrogen bond, for example, an Al compound,
Examples thereof include Li compounds, Zn compounds, Mg compounds, and the like. Specific examples include trimethyl aluminum, triphenyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, diethyl aluminum hydride, methyl lithium, n-propyl lithium, sec-
Examples thereof include butyl lithium, p-tolyl lithium, xylyl lithium, diphenyl zinc, bis (cyclopentadienyl) zinc, dimethyl magnesium, methyl magnesium bromide, lithium aluminum hydride and the like.

Specific examples of the combination of the components (c) and (d) include V, Ti, Mn and F as the component (c).
e, Co, or Ni organometallic compound, halide, alkoxide, acetylacetonate, sulfonate, or naphthenate, and (d) component Al, L
A catalyst in which an organic compound such as i, Zn, or Mg, or a hydride is combined is highly active, and the influence of impurities on reaction inhibition / activity reduction is small, which is preferable. As the component (c), Ti, Fe, Co, or Ni organometallic compound, halide, alkoxide, or acetylacetonate, as component (d), alkylaluminum,
Alternatively, a catalyst in which an alkyl lithium is combined is particularly highly active, and the influence of impurities on reaction inhibition / activity reduction is particularly small, so that it is more preferable.

The quantitative relationship of these components depends on the kind of each component, but generally 0.5 to 50 mol, preferably 0.5 to 50 mol, of the metal element of the component (d) to 1 mol of the metal element of the component (c). It is 1 to 10 mol. If the amount is too large or too small, the activity of the hydrogenation reaction is insufficient. If too much, gelation or side reaction may occur.

With these hydrogenation catalysts, unsaturated bonds in the main chain structure of the polymer are hydrogenated and saturated, and normally, unsaturated bonds other than the main chain structure are also hydrogenated and saturated. However, for example, a hydrogenation catalyst in which bis (cyclopentadienyl) titanium dichloride is used as the component (c) and alkyllithium is used as the component (d) (Japanese Patent Publication No. 63-4841), and dialkyl-bis is used as the component (c). (Cyclopentadienyl) titanium and (d)
Hydrogenation catalyst in which a reducing magnesium compound is combined as a component (JP-A-61-28507), (c)
Dialkyl-bis (cyclopentadienyl) as a component
In the case where the polymer has an aromatic ring by using a selective hydrogenation catalyst such as a hydrogenation catalyst in which titanium and alkoxylithium as the component (d) are combined (JP-A-1-275605). The unsaturated structure of the aromatic ring can be left as an unsaturated structure without being saturated by hydrogenation. The resin whose main chain is saturated in this way is less susceptible to the effects of oxidation, so the heat deterioration resistance, weather deterioration resistance, and light deterioration resistance are improved compared to before saturation, and the unsaturated ring in the aromatic ring structure is also improved. By bonding, a resin having a high refractive index can be obtained.

The heterogeneous catalyst used in the hydrogenation reaction is also known, and examples thereof include those in which a hydrogenation catalytic metal such as Ni or Pd is supported on a carrier. In particular, when it is preferable that the hydrogenated substance is mixed with less impurities such as medical use, it is preferable to use an adsorbent such as alumina or diatomaceous earth as a carrier, and a pore volume of 0.5 cm ³ / g or more. , preferably 0.7 cm ³ / g or more, preferably to be used preferably has a specific surface area of 250 cm ² / g or more aluminas. When such a carrier is used, a transition metal atom derived from the polymer catalyst or the like can be adsorbed, and a resin with few impurities can be obtained.
When the hydrogenation reaction is carried out using a heterogeneous catalyst,
The reactivity can be increased by adding a small amount of alcohols such as isopropyl alcohol. In that case, the added amount of alcohols is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the reaction solution.

(Hydrogenation reaction liquid) In the present invention, when the mixed solvent used in the hydrogenation reaction of the present invention is used as the solvent of the polymerization reaction liquid, hydrogen is obtained after precipitation and solidification of the polymer as described above. It is not necessary to prepare an addition reaction liquid, and a hydrogenation catalyst can be added to the polymerization reaction liquid after the polymerization reaction to obtain a hydrogenation reaction liquid. In this case, it is necessary to add a deactivating agent for the metathesis polymerization catalyst, for example, a compound having an OH group such as water or alcohol to the polymerization reaction liquid after the polymerization reaction to precipitate the metathesis polymerization catalyst and remove it. Absent. In particular, when a homogeneous catalyst is used as the hydrogenation catalyst, it is preferable not to add the deactivator to the polymerization reaction solution because the deactivator of the metathesis polymerization catalyst has a significantly reduced hydrogenation catalyst activity.

The amount of the solvent with respect to the ring-opening polymer in the solution used in the hydrogenation reaction of the present invention is preferably 1-by weight.
100 times, more preferably 2 to 50 times, particularly preferably 3 times.
~ 20 times. If the amount of the solvent is too small, the polymer hydrogenated product tends to precipitate, and if the amount of the solvent is too large, the hydrogenation reaction is difficult to proceed.

The amount of the hydrogenation catalyst used in the hydrogenation reaction varies depending on the type and combination of each component in the case of a homogeneous catalyst, but usually, the transition metal compound of the component (c) is a metal per 1 kg of the polymer. Element 0.01 mmol-10
mol, preferably 1 mmol to 1 mol.

Also in the case of a heterogeneous catalyst, the amount of the hydrogenation catalyst used in the hydrogenation reaction varies depending on the type of the catalyst metal and the state of being supported on the carrier.
The amount of catalytic metal is 1 to 200 g, preferably 1
It is 0 to 150 g. If the hydrogenation catalyst is excessively added to the hydrogenation reaction solution, it will be costly and post-treatment such as removal of the hydrogenation catalyst will be difficult, and if it is too small, the reaction efficiency will be deteriorated.

(Hydrogenation Reaction Conditions) The hydrogenation reaction is carried out by introducing hydrogen into the hydrogenation reaction solution,
For example, a method in which the hydrogen introduced under stirring is brought into sufficient contact with the polymer is preferable. The hydrogen pressure is usually 0.1 to
100 kg / cm ^2, preferably reacted in 2~40kg / cm ^2. If the hydrogen pressure is too low, the hydrogenation reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and side reactions or gelation may occur.

The hydrogenation reaction is usually 0 to 250 ° C., preferably 20 to 100 ° C. when using a homogeneous catalyst.
When using a heterogeneous catalyst, preferably 200 to 24
It is carried out at 0 ° C., particularly preferably 210-230 ° C. If the temperature is too low, the reaction rate will be slow, and if it is too high, the decomposition of the polymer or hydrogenated product or gelation will occur easily, and the energy cost will increase.

For the purpose of hydrogenation, the higher the hydrogenation rate, the more preferable. Generally, the hydrogenation rate of the unsaturated bond of the main chain structure is 50% or more, preferably 90% or more, particularly preferably 99% or more. Hydrogenate. Unsaturated bonds other than the main chain structure are also generally hydrogenated at the same ratio as the unsaturated bonds of the main chain, but by using a specific homogeneous catalyst as described above, selective aromatic ring structure is achieved. It is possible to saturate the unsaturated bonds of the main chain structure without saturating it. The unsaturated bond of the aromatic ring and the other unsaturated bond can be distinguished from each other by the infrared absorption spectrum, and the hydrogenation rate of each can be measured.

The hydrogenation reaction solution after the hydrogenation reaction is at room temperature (3 to 30) without precipitating the hydrogenated product of the ring-opening polymer.
It can be stored for 10 days or longer at (° C).

The method for recovering the ring-opening polymer hydrogenated product from the hydrogenation reaction liquid is not particularly limited. For example, the hydrogenation reaction liquid is added with a large amount of a poor solvent such as alcohol, and the ring-opening polymer hydrogenated product is added. May be precipitated and solidified.

(Additives) If necessary, various additives may be added to the hydrogenated product of the ring-opening polymer obtained by the production method of the present invention. As the additive used, for example,
Antioxidants such as phenols and phosphorus; Antistatic agents;
UV absorbers; Light stabilizers; Lubricants; Flame retardants; Pigments; Dyes; Anti-blocking agents; Rubber polymers such as polybutadiene, polyisoprene, styrene-butadiene-styrene block polymers; Thermoplastic resins such as petroleum resins, polyethylene, polypropylene Fibrous fillers such as glass fibers and carbon fibers; particulate fillers such as silica, alumina and talc; tetrakis [2- (3,5-di-t-butyl-4-hydroxyphenyl) ethylpropionate] Antioxidants such as methane and 2,6-di-t-butyl-4-methylphenol;
Fluorine-based nonionic surfactants, special acrylic resin-based leveling agents, silicone-based leveling agents; and the like.

The hydrogenated product of the ring-opening polymer obtained by the production method of the present invention is, if necessary, a polycarbonate,
Blending with other resins such as polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polyarylate, polysulfone, polyethersulfone, and polyetherimide can also be performed.

In order to avoid elution from the ring-opening polymer hydrogenated product molded product obtained by the production method of the present invention, it is preferable that these additives and resins have a large molecular weight, and the addition amount and the mixing amount are large. The less is preferable.

(Molding) The hydrogenated product of the ring-opening polymer obtained by the production method of the present invention can be prepared by a known method such as injection molding,
Extrusion molding, cast molding, inflation molding,
It can be molded by blow molding, vacuum molding, press molding, compression molding, rotational molding, calender molding, rolling molding, cutting molding and the like.

(Use) The hydrogenated product of the ring-opening polymer obtained by the production method of the present invention is useful in various fields such as optical materials and various molded articles. For example, optical disc, optical lens, prism, light diffusion plate, optical card,
Optical materials such as optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films, etc .; liquid medicine containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags, press-through packages. , Liquid medicines such as solid medicine containers and eye drops containers, or containers for solid medicines, food containers, sampling test tubes for blood tests, caps for medicine containers, blood collection tubes, sampling containers such as specimen containers, medical devices such as syringes Instrument, scalpel,
Sterile containers for medical instruments such as forceps, gauze and contact lenses, experimental / analytical instruments such as beakers, petri dishes, flasks, test tubes, centrifuge tubes, medical optical parts such as plastic lenses for medical inspection, medical infusion tubes, Plumbing materials such as pipes, joints and valves, medical equipment such as denture bases, artificial hearts, artificial roots and artificial organs, and parts thereof; tanks, trays, carriers, cases, etc. for processing or transfer containers,
Protective materials such as carrier tapes, separation films, pipes, tubes, valves, sipper flowmeters, filters, pipes such as pumps, sampling containers, bottles, liquid containers such as ampoule bags, and other electronic component processing equipment; OA for electric wire, coating material for cables, consumer / industrial electronic devices, copying machines, computers, printers, etc.
General insulating materials for equipment, instruments, etc .; rigid printed circuit boards,
Circuit boards such as flexible printed boards and multilayer printed wiring boards, especially high frequency circuit boards for satellite communication equipment that requires high frequency characteristics; transparent conductive materials such as liquid crystal boards, optical memories, surface heating elements such as defrosters of automobiles and aircraft. Base material of conductive film, electric / conductor encapsulant and parts such as transistor, IC, LSI, LED, etc., encapsulant of electric / electronic part such as motor, condenser, switch and sensor, body material such as TV and video camera. , Parabolic antennas, flat antennas, electric insulating materials such as radar dome structural members, and the like.

(Aspect) The aspect of the present invention is as follows: A ring-opening polymer of a norbornene-based monomer is characterized by being hydrogenated in the presence of a hydrogenation catalyst in a solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure as at least a part of the solvent. 1. A method for producing a hydrogenated product of a ring-opening polymer, 2. The method for producing a hydrogenated product of a ring-opening polymer according to 1 above, wherein the norbornene-based monomer is represented by the general formula 1. The method for producing a hydrogenated ring-opening polymer according to the above 1 or 2, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is a polycyclic saturated hydrocarbon having all carbon atoms constituting a ring structure, 4. A saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has 3 to 5 carbon atoms other than one norbornane structure or one cyclohexane ring structure, and all the carbon atoms form a ring structure. 4. The method for producing a hydrogenated product of a ring-opening polymer as described in 1 to 3 above, which is a polycyclic saturated hydrocarbon. The saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is decalin, octahydroindene, tricyclodecane, or 2-methano-octahydronaphthalene. 6. 6. The method for producing a hydrogenated product of a ring-opening polymer according to the above 4 to 5, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has a norbornane ring structure. 7. The method for producing a hydrogenated product according to 1 to 6 above, wherein the ring-opening polymer has a repeating structural unit derived from the norbornene-based monomer represented by the general formula 1 in all repeating units of 30% by weight or more. The ring-opening polymer has a number average molecular weight of 1,000 to 1,000,000 in terms of polystyrene by gel permeation chromatography using toluene as a solvent.
8. The method for producing a hydrogenated product according to 1 to 7 above, 10. The method for producing a hydrogenated product according to 1 to 8 above, wherein the ring-opening polymer has a glass transition temperature of 50 to 200 ° C. The method for producing a hydrogenated product according to 1 to 9, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure in a solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is 40% by weight or more, 11. 1 to 10, wherein the solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is composed of a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure and a saturated hydrocarbon having 4 to 8 carbon atoms. 11. A method for producing a hydrogenated product according to 12. Process for producing a hydrogenated product of the 1 to 11 wherein performing a hydrogen pressure of 0.1~100kg / cm ^2, a manufacturing method of a hydrogenated product of the above 1 to 12, wherein performing at from 13.0 to 250 ° C., 14. 14. The method for producing a hydrogenated product according to 1 to 13 above, which uses a hydrogenation catalyst composed of a transition metal compound and a reducing metal compound. 1 above, wherein the hydrogenation catalyst is a selective hydrogenation catalyst
15. The method for producing a hydrogenated product according to 4. The selective hydrogenation catalyst is a combination of bis (cyclopentadienyl) titanium dichloride and alkyl lithium, a combination of dialkyl-bis (cyclopentadienyl) titanium and a reducing magnesium compound, or a dialkyl-bis (cyclo) 16. The method for producing a hydrogenated product according to the above 15, which is a combination of pentadienyl) titanium and alkoxylithium. 17. The method for producing a hydrogenated product according to the above 14 to 16, which uses a hydrogenation catalyst in which the metal element of the reducing metal compound is 0.5 to 50 moles relative to 1 mole of the metal element of the transition metal compound. The method for producing a hydrogenated product according to the above 14 to 17, wherein the metal element of the transition metal compound is 0.01 mmol to 10 mols per 1 kg of the polymer, and the hydrogen according to the above 14 to 18 performed at 19.20 to 100 ° C. 20. A method for producing an additive, 20. The method for producing a hydrogenated product according to 1 to 13 above, which uses a hydrogenation catalyst in which a hydrogenation catalyst metal is supported on a carrier. 21. The method for producing a hydrogenated product according to the above 20, wherein the carrier is an adsorbent. 23. The method for producing a hydrogenated product according to the above 21, wherein the adsorbent is alumina having a pore volume of 0.5 cm ³ / g or more. 23. The method for producing a hydrogenated product according to 21 to 22 above, wherein the adsorbent is alumina having a specific surface area of 250 cm ² / g or more. Alcohols were added in an amount of 0.
25. A method for producing a hydrogenated product according to the above 20 to 23, which is added by 5 to 5 parts by weight. 1 to 200 g of catalyst metal per 1 kg of polymer
20. The method for producing a hydrogenated product according to the above 20 to 24, 26. The method for producing a hydrogenated product according to the above 20 to 25 performed at 26 to 200 to 240 ° C. 27. 27. The method for producing a hydrogenated product according to 1 to 26 above, wherein the hydrogenation rate of the unsaturated bond of the main chain structure is 50% or more. 29. The method for producing a hydrogenated product according to claim 27, wherein the unsaturated bond of the aromatic ring structure is not hydrogenated. The norbornene-based monomer is subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst in a solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure as at least a part of the solvent, and further in the presence of a hydrogenation catalyst. 30. A method for producing a hydrogenated product of a ring-opening polymer, characterized in that 31. The method for producing a hydrogenated product of a ring-opening polymer as described in 29 above, wherein the norbornene-based monomer is represented by the general formula 1. 31. The method for producing a ring-opening polymer hydrogenated product according to 29 to 30, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is a polycyclic saturated hydrocarbon in which all carbon atoms form a ring structure. 32. A saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has 3 to 5 carbon atoms other than one norbornane structure or one cyclohexane ring structure.
33. A method for producing a ring-opening polymer hydrogenated product according to the above 29 to 31, which is a polycyclic saturated hydrocarbon having one ring and all carbon atoms constituting a ring structure. 33. The method for producing a hydrogenated ring-opening polymer according to 29 to 32, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is decalin, octahydroindene, tricyclodecane, or 2-methano-octahydronaphthalene. 34. 34. The method for producing a hydrogenated product of a ring-opening polymer according to the above 32 to 33, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has a norbornane ring structure. 35. The method for producing a hydrogenated product according to 29 to 34 above, wherein the ring-opening polymer has a repeating structural unit derived from the norbornene-based monomer represented by the general formula 1 in all repeating units in an amount of 30% by weight or more. The ring-opening polymer has a number average molecular weight of 1,000 to 1,000,000 in terms of polystyrene by gel permeation chromatography using toluene as a solvent.
37. A method for producing a hydrogenated product according to the above 29 to 35, which is 0. The ring-opening polymer has a glass transition temperature of 50 to 200 ° C.
38. A method for producing a hydrogenated product according to 29 to 36 above, which is 38. The method for producing a hydrogenated product according to 29 to 37, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure in a solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is 40% by weight or more, 39. The above-mentioned 29 to 38, wherein the solvent containing a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is composed of a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure and a saturated hydrocarbon having 4 to 8 carbon atoms. 40. A method for producing a hydrogenated product according to 40. 29-wherein the metathesis polymerization catalyst comprises a transition metal compound catalyst component and a metal compound promoter component
39. Method for producing hydrogenated product according to 39. 42. The method for producing a hydrogenated product according to the above 40, wherein the transition metal compound catalyst component and the metal compound co-catalyst component are in a molar ratio of metal elements of 1: 1 to 1: 100. Aliphatic tertiary amine, along with metathesis polymerization catalyst
Aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, or molecular iodine 43. The method for producing a hydrogenated product according to 29 to 41, wherein ring-opening polymerization is carried out in the presence of 43. 44. The method for producing a hydrogenated product according to the above 40 to 42, wherein the transition metal compound catalyst component is 0.000001 to 1 mol per 1 mol of the monomer. 29 to 4 above, wherein ring-opening polymerization is carried out at -20 to 100 ° C.
45. The method for producing a hydrogenated product according to 3 above, 45. The method for producing a hydrogenated product according to 29 to 44 above, which comprises ring-opening polymerization under a pressure of 4 to 50 kg / cm ² . 47. The method for producing a hydrogenated product according to the above 29 to 45, wherein ring-opening polymerization is performed in a nitrogen atmosphere. 29. The method for producing a hydrogenated product according to 29 to 46, wherein hydrogenation is carried out at a hydrogen pressure of 0.1 to 100 kg / cm ² , and the method for producing a hydrogenated product according to 29 to 47, wherein hydrogenation is performed at 48.0 to 250 ° C. Method, 49. 50. The method for producing a hydrogenated product according to the above 29 to 48, wherein the hydrogenation catalyst comprises a transition metal compound and a reducing metal compound. The above 4 in which the hydrogenation catalyst is a selective hydrogenation catalyst
51. A method for producing a hydrogenated product according to 9, The selective hydrogenation catalyst is a combination of bis (cyclopentadienyl) titanium dichloride and alkyl lithium, a combination of dialkyl-bis (cyclopentadienyl) titanium and a reducing magnesium compound, or a dialkyl-bis (cyclo) 52. The method for producing a hydrogenated product according to the above 50, which is a combination of pentadienyl) titanium and alkoxylithium. 53. The method for producing a hydrogenated product according to the above 29 to 51, wherein the hydrogenation catalyst has 0.5 to 50 mol of the metal element of the reducing metal compound with respect to 1 mol of the metal element of the transition metal compound, 53. 49. The method for producing a hydrogenated product according to 49 to 52 above, wherein the metal element of the transition metal compound is 0.01 mmol to 10 mol per 1 kg of the polymer, and 49 to 53 above where hydrogenation is carried out at 54.20 to 100 ° C.
55. Method for producing hydrogenated product described above, 55. The method for producing a hydrogenated product according to the above 29 to 54, wherein the hydrogenation catalyst has a hydrogenation catalyst metal supported on a carrier. 57. The method for producing a hydrogenated product according to the above item 55, wherein the carrier is an adsorbent. 57. The method for producing a hydrogenated product according to the above 56, wherein the adsorbent is alumina having a pore volume of 0.5 cm ³ / g or more. 59. The method for producing a hydrogenated product according to the above 56 to 57, wherein the adsorbent is alumina having a specific surface area of 250 cm ² / g or more. Alcohols were added in an amount of 0.
60. A method for producing a hydrogenated product according to the above 55 to 58, which is added by 5 to 5 parts by weight. 1 to 200 g of catalyst metal per 1 kg of polymer
55. The method for producing a hydrogenated product according to the above 55 to 59, wherein the hydrogenation is performed at 61.200 to 240 [deg.] C.
62. Method for producing hydrogenated product according to 0. 63. The method for producing a hydrogenated product according to the above 29 to 61, wherein the hydrogenation rate of the unsaturated bond of the main chain structure is 50% or more. 63. The method for producing a hydrogenated product according to claims 29 to 62, wherein the unsaturated bond of the aromatic ring structure is not hydrogenated.

[0048]

[Examples] Hereinafter, reference examples, examples, and comparative examples will be described.
The present invention will be specifically described. The glass transition temperature is
It was measured by the DSC method. The number average molecular weight was measured as a polystyrene conversion value by gel permeation chromatography using toluene or cyclohexane as a solvent. The hydrogenation rate was measured by ¹ H-NMR.

Reference Example 1 60 parts by weight of 1,4-methano-1,4,4a, 9b-tetrahydrofluorene, 0.9 part by weight of 1-hexene, 0.1 part by weight of tetrabutyltin, and 0.
8 parts by weight of an 8% by weight cyclohexane solution was added to a mixed solvent of 144 parts by weight of tricyclodecane and 25 parts by weight of cyclohexane, and polymerization was carried out at 60 ° C. and normal pressure for 1 hour.

A part of the obtained polymerization reaction liquid was poured into a mixed solvent of acetone and isopropyl alcohol (weight ratio of 1: 1) to recover the polymer, and the number average molecular weight measured with toluene was 28,000. It has a glass transition temperature of 185 ° C. and by ¹ H-NMR, 1,4-methano-1,4,4.
It was confirmed to be a ring-opening polymer of 4a, 9b-tetrahydrofluorene, and the polymer concentration in the polymerization reaction solution was about 30% by weight.

The reaction solution was sealed so that the solvent would not volatilize, and allowed to stand at room temperature (minimum 5 ° C., maximum 18 ° C.) for 10 days, but no precipitation or precipitation was observed.

Example 1 240 parts by weight of the polymerization reaction solution obtained in Reference Example 1 was mixed with an alumina-supported nickel catalyst (0.35 part by weight of nickel, 0.2 part by weight of nickel oxide, and 0. 8 cm
6 parts by weight of ³ / g, specific surface area 300 cm ² / cm) and 5 parts by weight of isopropyl alcohol were added, and the mixture was reacted in an autoclave at 230 ° C. and hydrogen pressure of 45 kg / cm ² for 3 hours.

This hydrogenation reaction solution was treated in the same manner as in Reference Example 1
After leaving for 0 days, neither precipitation nor precipitation was observed.

The reaction solution was poured into this hydrogenation reaction solution while stirring a mixed solution of 250 parts by weight of acetone and 250 parts by weight of isopropyl alcohol to precipitate a resin, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, 100% in a vacuum dryer depressurized to 1 mmHg or less
It was dried at ℃ for 24 hours to obtain 57 parts by weight.

This resin has a number average molecular weight of 32,000 measured with cyclohexane and a glass transition temperature of 135.
C., and as a result of ¹ H-NMR analysis, it was a hydrogenation product of a ring-opening polymer of 1,4-methano-1,4,4a, 9b-tetrahydrofluorene, and the hydrogenation rate was 99.9% or more. I knew it was.

Example 2 240 parts by weight of the polymerization reaction solution obtained in Reference Example 1 was charged with 1 part by weight of cobalt (III) acetylcetonate in an autoclave equipped with a stirrer. After replacing the gas in the autoclave with hydrogen, triisobutylaluminum
A autoclave was charged with 6.7 parts by weight of a 5% by weight cyclohexane solution, hydrogen pressure was 10 kg / cm ² , and temperature was 80 ° C.
And reacted for 1 hour.

This hydrogenation reaction liquid was used in the same manner as in Reference Example 1
After leaving for 0 days, neither precipitation nor precipitation was observed.

Thereafter, this hydrogenation reaction solution was added with acetone 2
While stirring a mixed solution of 50 parts by weight and 250 parts by weight of isopropyl alcohol, the reaction solution was poured to precipitate a resin, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, it was dried at 100 ° C. for 24 hours in a vacuum dryer depressurized to 1 mmHg or less to obtain 58 parts by weight.

[0059] This resin had a number-average molecular weight 31,000 was measured using toluene, a glass transition temperature of 139 ° C., result of analysis by ¹ H-NMR, 1,4-methano -
It was found to be a hydrogenated product of a ring-opening polymer of 1,4,4a, 9b-tetrahydrofluorene, and the hydrogenation rate was 99.9% or more for the main chain structure and 0% for the aromatic ring structure. .

Reference Example 2 Polymerization was carried out in the same manner as in Reference Example 1 except that phenylnorbornene was used instead of 1,4-methano-1,4,4a, 9b-tetrahydrofluorene.

A part of the obtained polymerization reaction liquid was poured into a mixed solvent of acetone and isopropyl alcohol (weight ratio of 1: 1) to recover the polymer, and the number average molecular weight measured with toluene was 25,000. The glass transition temperature was 95 ° C., and it was confirmed by ¹ H-NMR that it was a ring-opening polymer of phenylnorbornene, and the polymer concentration in the polymerization reaction liquid was about 30% by weight.

This reaction solution was allowed to stand as in Reference Example 1, but no precipitation or precipitation was observed.

Example 3 A hydrogenation reaction solution was obtained in the same manner as in Example 1 except that the polymerization reaction solution obtained in Reference Example 2 was used in place of the polymerization reaction solution obtained in Reference Example 1.

This hydrogenation reaction solution was treated in the same manner as in Reference Example 1
After leaving for 0 days, neither precipitation nor precipitation was observed.

The hydrogenation reaction solution was poured into the reaction solution while stirring a mixed solution of 250 parts by weight of acetone and 250 parts by weight of isopropyl alcohol, to precipitate a resin, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, 100% in a vacuum dryer depressurized to 1 mmHg or less
It was dried at ℃ for 24 hours to obtain 56 parts by weight.

This resin has a number average molecular weight of 28,000 measured with cyclohexane and a glass transition temperature of 71 ° C.
As a result of ¹ H-NMR analysis, it was a hydrogenated product of a ring-opening polymer of phenylnorbornene, and the hydrogenation rate was 9
It was found to be 9.9% or more.

Reference Example 3 1,4-Methano-1,4,4a, 9b-tetrahydrofluorene Instead of 60 parts by weight of 1,4-methano-1,
Polymerization was carried out in the same manner as in Reference Example 1 except that 48 parts by weight of 4,4a, 9b-tetrahydrofluorene and 12 parts by weight of dicyclopentadiene were used.

A part of the obtained polymerization reaction solution was poured into a mixed solvent of acetone and isoprene (weight ratio of 1: 1) to recover the polymer, and the number average molecular weight measured with toluene was 26,000. The transition temperature is 175 ° C., and ¹ H-
1,4-methano-1,4,4a, 9b- by NMR
A ring-opening copolymer composed of about 80% by weight of a repeating structural unit derived from tetrahydrofluorenephenylnorbornene and about 20% by weight of a repeating structural unit derived from dicyclopentadiene, and having a copolymer concentration of about 30% by weight in a polymerization reaction solution.
Was confirmed.

The reaction solution was allowed to stand as in Reference Example 1, but no precipitation or precipitation was observed.

Example 4 A hydrogenation reaction solution was obtained in the same manner as in Example 1 except that the polymerization reaction solution obtained in Reference Example 3 was used in place of the polymerization reaction solution obtained in Reference Example 1.

This hydrogenation reaction solution was treated in the same manner as in Reference Example 1
After leaving for 0 days, neither precipitation nor precipitation was observed.

The hydrogenation reaction solution was poured into the reaction solution while stirring a mixed solution of 250 parts by weight of acetone and 250 parts by weight of isopropyl alcohol to precipitate a resin, which was collected by filtration. Further, after washing with 200 parts by weight of acetone, 100% in a vacuum dryer depressurized to 1 mmHg or less
It was dried at ℃ for 24 hours to obtain 57 parts by weight.

This resin has a number average molecular weight of 29,000 and a glass transition temperature of 127 measured using cyclohexane.
C, and the result of ¹ H-NMR analysis is a hydrogenated product of a ring-opening copolymer of 1,4-methano-1,4,4a, 9b-tetrahydrofluorene and dicyclopentadiene,
It was found that the hydrogenation rate was 99.9% or more.

Reference Example 4 Polymerization was carried out in the same manner as in Reference Example 1 except that 170 parts by weight of octahydroindene was used instead of the mixed solvent consisting of 144 parts by weight of tricyclodecane and 25 parts by weight of cyclohexane.

A part of the obtained polymerization reaction liquid was poured into a mixed solvent of acetone and isoprene (weight ratio of 1: 1) to recover the polymer, and the number average molecular weight measured with toluene was 29,000. It was

This reaction solution was allowed to stand in the same manner as in Reference Example 1, but no precipitation or precipitation was observed.

Example 5 A hydrogenation reaction solution was obtained in the same manner as in Example 1 except that the polymerization reaction solution obtained in Reference Example 4 was used in place of the polymerization reaction solution obtained in Reference Example 1.

This hydrogenation reaction solution was treated in the same manner as in Reference Example 1
After leaving for 0 days, neither precipitation nor precipitation was observed.

The hydrogenation reaction liquid was poured into the reaction solution while stirring a mixed solution of 250 parts by weight of acetone and 250 parts by weight of isopropyl alcohol, to precipitate the resin, and the resin was collected by filtration. Further, after washing with 200 parts by weight of acetone, 100% in a vacuum dryer depressurized to 1 mmHg or less
It was dried at ℃ for 24 hours to obtain 58 parts by weight.

This resin had a number average molecular weight of 32,000 measured using cyclohexane, and as a result of ¹ H-NMR analysis, 1,4-methano-1,4,4a, 9b- was obtained.
It was found to be a hydrogenated product of a ring-opening polymer of tetrahydrofluorene, and the hydrogenation rate was found to be 99.9% or more.

Comparative Example 1 The polymerization reaction solution obtained in Reference Example 1 was mixed with isopropyl alcohol 6
After pouring into 000 parts by weight to precipitate the polymer, 30 parts by weight of the recovered polymer was dissolved in 70 parts by weight of cyclohexane to obtain a polymer solution.

When this polymer solution was allowed to stand in the same manner as the polymer solution of Reference Example 1, the polymer was deposited and precipitated on the third day.

COMPARATIVE EXAMPLE 2 Immediately after obtaining a polymer solution in the same manner as in Comparative Example 1, the procedure of Example 1 was repeated except that this polymer solution was used in place of the polymer reaction solution obtained in Reference Example 2. A hydrogenation reaction solution was obtained.

When this hydrogenation reaction solution was allowed to stand in the same manner as the polymer solution of Reference Example 1, a polymer hydrogenated product was deposited and precipitated on the second day.

[0085]

When the norbornene-based monomer is subjected to ring-opening polymerization by the production method of the present invention, immediately after the polymerization, the polymer is not recovered or subjected to hydrogenation reaction and stored as a polymerization reaction solution. Even in this case, the polymer does not precipitate, which is advantageous in terms of process control and the like. Further, by adding the hydrogenation catalyst without removing the solvent and satisfying the reaction conditions, hydrogenation is performed, so that workability is excellent. Furthermore, it is not necessary to recover the hydrogenated product immediately after the hydrogenation reaction, and the hydrogenation reaction liquid can be stored, which is advantageous in terms of process control and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Io Natsuume Io 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center (56) Reference JP-A-2-133413 (JP, A) ) JP-A-5-301915 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8/50 C08G 61/00-61/12

Claims (6)

(57) [Claims] 1. A ring-opening polymer of a norbornene-based monomer,
Having a norbornane ring structure or a cyclohexane ring structure
Other than norbornane ring structure or cyclohexane
All carbons with 3 to 5 carbon atoms in addition to one ring structure
A method for producing a hydrogenated product of a ring-opening polymer, which comprises hydrogenating in the presence of a hydrogenation catalyst in a solvent containing a polycyclic saturated hydrocarbon having atoms constituting a ring structure . 2. A norbornene-based monomer is represented by the general formula 1 (In the formula, 1 represents 0 or 1, and R ¹ is -O- or -N.
R ⁹ — or —CR ¹⁰ R ¹¹ — is represented, and R ^{2 to} R ¹³ are hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, polar groups such as halogen, alkoxy groups, cyano groups, or polar groups thereof. (Representing a hydrocarbon group having 1 to 4 carbon atoms, which is substituted with), the method for producing a hydrogenated product of a ring-opening polymer according to claim 1. 3. A norbornane ring structure or cyclohexa
Has a ring structure other than one norbornane ring structure or
Has 3 to 5 carbon atoms in addition to one hexane ring structure
The polycyclic saturated hydrocarbon having all carbon atoms constituting a ring structure is tricyclodecane.
A method for producing the hydrogenated product described. The 4. A norbornene-based monomer, norbornane
Having a ring structure or cyclohexane ring structure, norborna
Ring structure other than 1 or cyclohexane ring structure other than 1
Has 3 to 5 carbon atoms, and all carbon atoms have a ring structure.
A ring-opening polymer hydrogenated product characterized by being subjected to ring-opening polymerization in the presence of a metathesis polymerization catalyst in a solvent containing a polycyclic saturated hydrocarbon, and then hydrogenated in the presence of a hydrogenation catalyst. Manufacturing method. 5. The norbornene-based monomer is represented by the general formula 1: (In the formula, 1 represents 0 or 1, and R ¹ is -O- or -N.
R ⁹ — or —CR ¹⁰ R ¹¹ — is represented, and R ^{2 to} R ¹³ are hydrogen atoms, hydrocarbon groups having 1 to 4 carbon atoms, polar groups such as halogen, alkoxy groups, cyano groups, or polar groups thereof. (Representing a hydrocarbon group having 1 to 4 carbon atoms, which is substituted with), the method for producing a hydrogenated product of a ring-opening polymer according to claim 4. 6. A norbornane ring structure or cyclohexa
Has a ring structure other than one norbornane ring structure or
Has 3 to 5 carbon atoms in addition to one hexane ring structure
The polycyclic saturated hydrocarbon in which all carbon atoms form a ring structure is tricyclodecane.
A method for producing the hydrogenated product described.