JP3478351B2 - Process for producing hydrogenated dicyclopentadiene ring-opening 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 dicyclopentadiene monomer, more specifically, a dicyclopentadiene monomer having a stable reaction solution and being advantageous in process control. The present invention relates to a method for producing a polymer open polymer hydrogenated product.

[0002]

2. Description of the Related Art It is known that a ring-opening polymer of a dicyclopentadiene monomer and its hydrogenated product have excellent properties as optical materials 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.

In order to obtain a hydrogenated product of a dicyclopentadiene 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.

The dicyclopentadiene ring-opening polymer dissolves well in these saturated hydrocarbon solvents, but often precipitates when hydrogenated. Therefore, in order to prevent precipitation, it is necessary to rush the treatment after the hydrogenation reaction, and there is a problem that the process is difficult to control.

[0006]

Accordingly, the present inventors have earnestly studied about a method for producing a hydrogenated product of a dicyclopentadiene ring-opening polymer whose process control is easy, and as a result,
A solvent containing a compound having a specific chemical structure can sufficiently dissolve a dicyclopentadiene ring-opening polymer and its hydrogenated product, and these resin solutions are stable and do not precipitate these resins. As a result, they came to complete the present invention.

[0007]

Thus, according to the present invention, a ring-opening polymer of a dicyclopentadiene monomer contains, as at least a part of a solvent, a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure. A method for producing a hydrogenated product of a ring-opening polymer, which comprises hydrogenating in a solvent in the presence of a hydrogenation catalyst, and a norbornane ring structure or a cyclohexane ring containing dicyclopentadiene-based monomer as at least a part of the solvent. A ring-opening polymer characterized by carrying out ring-opening polymerization in the presence of a metathesis polymerization catalyst in a solvent containing a saturated hydrocarbon having a structure, and further adding a hydrogenation catalyst to carry out hydrogenation without removing the solvent. A method of making a combined hydrogenated product is provided.

(Dicyclopentadiene-Based Monomer) The dicyclopentadiene-based monomer used in the present invention is dicyclopentadiene or a substituted product thereof, and specific examples of the substituted product include alkyl and alkylidene. , Aromatic substituted derivatives and halogens, hydroxyl groups, ester groups, alkoxy groups of these substituted or unsubstituted olefins, and specifically, polar group substituted derivatives such as cyano group, amide group, imide group and silyl group. . Specifically, dicyclopentadiene, 2-methyldicyclopentadiene, 2-
Ethyldicyclopentadiene, 5-methyldicyclopentadiene, 5,5-dimethyldicyclopentadiene,
2,3-dihydrodicyclopentadiene and the like are exemplified. Particularly preferred are the cyclopentadiene, alkyl, alkylidene, aromatic substituted derivatives thereof, and substituted or unsubstituted polar group-substituted derivatives thereof, among which dicyclopentadiene is preferable, among which dicyclopentadiene is preferable.

The dicyclopentadiene ring-opening polymer used in the present invention contains, as a comonomer, a monomer other than the dicyclopentadiene monomer which is copolymerizable within a range that does not essentially impair the effects of the present invention. It may be a copolymer. Examples of such comonomers include norbornene-based monomers other than dicyclopentadiene-based monomers, for example, norbornene, its alkyl, alkylidene, aromatic substituted derivatives and halogens, hydroxyl groups, ester groups of these substituted or unsubstituted olefins. , Alkoxy groups, cyano groups, amide groups, imide groups, silyl groups and other polar group substituents, such as 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene and the like;
A monomer in which one or more cyclopentadiene is added to norbornene, a derivative or substituent 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; an adduct of dicyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4 , 4a, 4b, 5, 8, 8
a, 9a-octahydrofluorene; and the like, cyclobutene, 1-methylcyclobutene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclo Monocyclic cycloolefins such as octene, 5-methylcyclooctene, cyclooctatetraene, 1,5-methylcyclooctdiene, and cyclododecene; acetylene, propyne, acetylene which is a substituted acetylene such as 1-butyne; Dienes having double bonds at both ends such as 6-heptadiene; and the like. Among these, norbornene-based monomers are preferable.

(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 transition metal compound catalyst component (a) 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 co-catalyst component (b) used in the metathesis polymerization catalyst is the 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; .

A metathesis polymerization activity can be enhanced 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 an H group functions as an inactivating agent that inhibits the metathesis polymerization activity when added in excess of the stoichiometric amount, so it is necessary to add the compound in the stoichiometric amount or less. The stoichiometric amount here means the product of the number of moles of the component (a) and the oxidation number of the transition metal contained in the component (a), the OH group per molecule of the compound containing the OH group. It refers to the number of moles represented by the number divided by the number.

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 liquid) The solvent used in the polymerization reaction of the ring-opening polymer used in the present invention should be one which can sufficiently dissolve the dicyclopentadiene-based monomer as a monomer and the ring-opening polymer. However, it is not particularly limited. 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 with respect to the dicyclopentadiene monomer.
Times, preferably 3 to 50 times, particularly preferably 4 to 20 times. Further, the metathesis polymerization catalyst has an appropriate amount depending on the combination of the components (a) and (b), the ratio of each component, the kind of the monomer, etc. The component is added 0.000001 to 1 mol, preferably 0.0001 to 0.5 mol. 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.

(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 also not particularly limited, and the polymerization is performed at 1 to 50 kg / cm ² .

In order to prevent deterioration and coloration of the resulting polymer due to oxidation, the reaction atmosphere is often replaced with nitrogen.

(Polymerization reaction liquid after the polymerization reaction) When the dicyclopentadiene-based monomer is polymerized using the solvent used in the method for producing a hydrogenated product of the present invention, the polymerization reaction liquid remains even after the completion of the polymerization. It can be stored for a long period of one week or longer without causing the polymer to precipitate.

(Polymer) In the dicyclopentadiene ring-opening polymer used in the present invention, the repeating unit obtained by ring-opening polymerization of the dicyclopentadiene monomer is 50% by weight or more, preferably 60% of all repeating structural units. The content is preferably at least 70% by weight, particularly preferably at least 70% by weight. The number average molecular weight is determined by gel permeation
It is usually 1,000 to 1,000,000, preferably 5, in terms of polystyrene by the chromatography method.
000 to 200,000, more preferably 8.0
00 to 100,000, glass transition temperature is usually 50
-200 degreeC, Preferably it is 70-180 degreeC, More preferably, it is 90-170 degreeC.

If necessary, the dicyclopentadiene ring-opening polymer is recovered from the polymerization reaction solution. 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. In the polymerization reaction, when the mixed solvent used in the method for producing a hydrogenated product of the present invention is used as the solvent, it is not necessary to recover the ring-opened polymer.

(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 constitute a ring structure is preferable from the viewpoint of excellent solubility of the ring-opening polymer, and particularly, A polycyclic saturated hydrocarbon having 3 to 5 carbon atoms other than one norbornane structure or one cyclohexane ring structure, and all carbon atoms form a ring structure is preferable. Examples of such polycyclic saturated hydrocarbons include decalin, octahydroindene, tricyclodecane, 2-methano-octahydronaphthalene, and the like. Among these, those having a norbornane ring structure from the stability of the solution are listed. Preferred is tricyclodecane, and particularly preferred is tricyclodecane.

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 has excellent properties. 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.

The homogeneous catalyst used in the hydrogenation reaction is
JP-A-58-43412, JP-A-60-2602
4, JP-A-64-24826, JP-A-1-
It is known in Japanese Patent No. 138257. Examples of the transition metal compound (c) include compounds of transition metals belonging to any one of Group I or Groups IV to VIII of the Deming Periodic Table, for example, V, Ti, Cr, Mo, Zr,
Examples thereof include halides of transition metals such as Fe, Mn, Co, Ni, Pd and Ru, alkoxides, acetylacetonates, sulfanates, carboxylates, naphthenates, trifluoroacetates and stearates, and specific compounds include: Tetraisopropoxy titanate, titanocene dichloride, zirconocene dichloride,
Triethylvanadate, chromium (III) acetylacetonate, manganese (III) acetylacetonate,
Examples thereof include bis- (triphenylphosphine) -cobalt dichloride. Examples of the reducing metal compound (d) include Deming's periodic table IA, IIA, IIB, and I.
A compound of Group IIA or IVA metal having at least one metal element-carbon bond or metal element-hydrogen bond, and examples thereof include Al compounds, Li compounds, Zn compounds, Mg compounds and the like. Specific examples include trimethyl aluminum, triphenyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, p-tolyl lithium, diphenyl zinc, bis (cyclopentadienyl) zinc, dimethyl magnesium, 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 of the metal element of the component (d), preferably 1 to 1 mol of the metal element of the component (c), preferably 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.

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 Solution) In the present invention, the polymerization reaction and the hydrogenation reaction can be carried out using a common solvent. In that case, 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 liquid because the deactivator of the metathesis polymerization catalyst significantly reduces the activity of the hydrogenation catalyst.

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 to
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 loading 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 a homogeneous catalyst is used.
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 generally hydrogenated in the same proportion as the unsaturated bonds in the main chain.

The hydrogenation reaction solution after the hydrogenation reaction is at room temperature (3 to 30%) without depositing the ring-opening polymer hydrogenated product.
It is possible to store at (° C) for a long term of 1 week or more.

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 to give the ring-opening polymer hydrogenated product. 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.

Further, 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 ring-opening polymer obtained by the production method of the present invention is useful in a wide variety of fields as various molded articles including optical materials. 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: It is possible to hydrogenate a ring-opening polymer of a dicyclopentadiene-based monomer 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 characterized dicyclopentadiene ring-opening polymer, 2. The method for producing a hydrogenated product of a ring-opening polymer according to 1 above, 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. 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. 3. A method for producing a hydrogenated product of a ring-opening polymer as described in 1 to 2 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. 5. 5. The method for producing a hydrogenated product of a ring-opening polymer according to the above 3 to 4, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has a norbornane ring structure. 1 above, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is tricyclodecane
6. A method for producing a hydrogenated product of a ring-opening polymer according to 5; The hydrogenated product according to any one of 1 to 6 above, wherein the dicyclopentadiene-based monomer is selected from dicyclopentadiene, its alkyl, alkylidene, aromatic substituted derivatives, and substituted or unsubstituted polar group substituted derivatives thereof. Manufacturing method, 8. 9. The method for producing a hydrogenated product according to 1 to 7, wherein the ring-opening polymer of the dicyclopentadiene-based monomer has 50% by weight or more of the repeating units derived from the dicyclopentadiene-based monomer in all the repeating units. ． The ring-opening polymer of a dicyclopentadiene-based monomer 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. ~
10. The method for producing a hydrogenated product according to 8. Ring-opening polymer of dicyclopentadiene-based monomer,
The above 1 to 1 having a glass transition temperature of 50 to 200 ° C.
10. The method for producing a hydrogenated product according to 9. 11. The method for producing a hydrogenated product according to 1 to 10, wherein the solvent contains 40% by weight or more of a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure. 12. The method for producing a hydrogenated product according to the above 11, wherein the solvent is a saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure and a saturated hydrocarbon. The above 1 in which the saturated hydrocarbon has 4 to 8 carbon atoms
14. The hydrogenated product according to 2. 15. The method for producing a hydrogenated product according to 1 to 13 above, which 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 1 to 14 above, which is carried out at 15.0 to 250 ° C. 15. The method for producing a hydrogenated product according to 1 to 15 above, which uses a hydrogenation catalyst comprising a transition metal compound and a reducing metal compound. 17. The method for producing a hydrogenated product according to the above 16, which uses a hydrogenation catalyst in which the metal element of the reducing metal compound is 0.5 to 50 moles with respect to 1 mole of the metal element of the transition metal compound. The method for producing a hydrogenated product according to the above items 16 to 17, wherein the metal element of the transition metal compound is 0.01 mmol to 10 mol per 1 kg of the polymer, and the hydrogen according to the above items 15 to 18, carried out 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 15 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
27. 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 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. A dicyclopentadiene-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, without removing the solvent. 29. A method for producing a hydrogenated product of a ring-opening polymer, which further comprises adding a hydrogenation catalyst for hydrogenation. 29. The method for producing a ring-opened polymer hydrogenated product according to the above 28, 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. 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.
32. A method for producing a hydrogenated ring-opening polymer according to the above 28 to 29, which is a polycyclic saturated hydrocarbon having one ring and all carbon atoms constituting a ring structure. 28. The method for producing a hydrogenated polymer of the hall polymer according to 28 to 30, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure is decalin, octahydroindene, tricyclodecane, or 2-methano-octahydronaphthalene. 32. 33. The method for producing a hydrogenated product of a ring-opening polymer according to the above items 30 to 31, wherein the saturated hydrocarbon having a norbornane ring structure or a cyclohexane ring structure has a norbornane structure. 28. The metathesis polymerization catalyst comprises a transition metal compound catalyst component and a metal compound promoter component
34. A method for producing a hydrogenated product according to 32. 34. The method for producing a hydrogenated product according to 33 above, wherein the transition metal compound catalyst component and the metal compound promoter 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 35. The method for producing a hydrogenated product according to the above 28 to 34, which comprises ring-opening polymerization in the presence of 36. 37. The method for producing a hydrogenated product according to the above 33 to 35, wherein the transition metal compound catalyst component is 0.000001 to 1 mol per 1 mol of the monomer. 28 to 3 above in which ring-opening polymerization is performed at -20 to 100 ° C
38. The method for producing a hydrogenated product according to 6 above, 38. The method for producing a hydrogenated product according to 28 to 37 above, wherein ring-opening polymerization is carried out under a pressure of ^{3 to} 50 kg / cm ² . The method for producing a hydrogenated product according to the above 28 to 38, which performs ring-opening polymerization in a nitrogen atmosphere, and the like are exemplified.

[0046]

[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 dicyclopentadiene and 1.3 of 1-hexene
Parts, tetrabutyltin 0.14 parts by weight, tungsten hexachloride 0.8% by weight cyclohexane solution 11 parts by weight, tricyclodecane 270 parts by weight and cyclohexane 59.
Add to a mixed solvent consisting of parts by weight, and add 1 at 60 ° C and atmospheric pressure.
The polymerization reaction was carried out for a time.

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 17,000, and the glass was used. It has a transition temperature of 185 ° C. and ¹ H-
As a result of NMR, it was confirmed to be a ring-opening polymer of dicyclopentadiene and the polymer concentration was 30% by weight.

The reaction solution was sealed so that the solvent would not volatilize, and the solution was kept at room temperature (minimum temperature 5 ° C, maximum temperature 18 ° C) at 1
After being left for a week, neither precipitation nor 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 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 58 parts by weight.

The number average molecular weight of this resin measured using cyclohexane was 32,000 and the glass transition temperature was 93 ° C. As a result of ¹ H-NMR, it was a hydrogenated product of a ring-opening polymer of dicyclopentadiene and hydrogen. Addition rate is 99.9%
That was all.

Example 2 To 240 parts by weight of the polymerization reaction solution obtained in Reference Example 1 was added 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 solution was treated with 1 as in Reference Example 1.
After leaving for 0 days, neither precipitation nor precipitation was observed.

The reaction solution was poured into the 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 had a number average molecular weight of 32,000 measured using cyclohexane and a glass transition temperature of 94 ° C. As a result of ¹ H-NMR, it was a hydrogenated product of a ring-opening polymer of dicyclopentadiene and hydrogen. Addition rate is 99.9%
That was all.

Reference Example 2 Octahydroindene 3 was used instead of a mixed solvent consisting of 270 parts by weight of tricyclodecane and 59 parts by weight of cyclohexane.
A polymerization reaction was performed in the same manner as in Reference Example 1 except that 40 parts by weight was used.

This polymerization reaction solution was left for 1 week in the same manner as in Reference Example 1, but no precipitation or precipitation was observed.

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 17,000, ¹ As a result of 1 H-NMR, it was confirmed that the polymer was a ring-opening polymer of dicyclopentadiene and the polymer concentration was 30% by weight.

Example 3 Hydrogenation was carried out in the same manner as in Example 1 except that the polymerization reaction solution obtained in Reference Example 2 was used instead of the polymerization reaction solution obtained in Reference Example 1.

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.

The reaction solution was poured into the 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.

The number average molecular weight of this resin measured with cyclohexane was 31,000. As a result of ¹ H-NMR, it was a hydrogenated product of a ring-opening polymer of dicyclopentadiene, and the hydrogenation rate was 99.9. % Or more.

Example 4 Hydrogenation was carried out in the same manner as in Example 2 except that the polymerization reaction solution obtained in Reference Example 2 was used instead of the polymerization reaction solution obtained in Reference Example 1.

This hydrogenation reaction solution was used 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.

The number average molecular weight of this resin measured using cyclohexane was 32,000. As a result of ¹ H-NMR, it was a hydrogenated product of a ring-opening polymer of dicyclopentadiene, and the hydrogenation rate was 99.9. % Or more.

Comparative Example 1 The polymerization reaction liquid obtained in Reference Example 1 was mixed with isopropyl alcohol 6
It poured into 000 parts by weight, then to precipitate a polymer, a 30-fold amount portion of the recovered polymer was dissolved in 70 parts by weight of cyclohexane, to obtain a polymer solution.

Hydrogenation was carried out in the same manner as in Example 1 except that this polymer solution was used instead of the polymer reaction solution obtained in Reference Example 1, but the polymer hydrogenated product was deposited on the second day after the reaction. .

[0071]

Industrial Applicability When the dicyclopentadiene ring-opening polymer is hydrogenated by the production method of the present invention, it is stable after the hydrogenation reaction and does not precipitate even if left alone, and is industrially Excellent operability.

─────────────────────────────────────────────────── ─── 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) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 8/00-8/50 C08G 61/00-61/12

Claims (4)

(57) [Claims] 1. A ring-opening polymer of a dicyclopentadiene-based monomer having a norbornane ring structure or a cyclohexane ring structure.
Structure other than one norbornane ring structure or cyclo
It has 3 to 5 carbon atoms in addition to one xane ring structure,
Of hydrogenated dicyclopentadiene ring-opening polymer characterized by hydrogenation in the presence of hydrogenation catalyst in a solvent containing polycyclic saturated hydrocarbon in which the carbon atoms of the ring constitute a ring structure Method. 2. 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 method for producing a hydrogenated product according to claim 1, wherein the polycyclic saturated hydrocarbon in which all carbon atoms form a ring structure is tricyclodecane . 3. A dicyclopentadiene-based monomer is used as a norm.
Has a bornane ring structure or a cyclohexane ring structure,
Rubornane ring structure other than one or cyclohexane ring structure
It has 3 to 5 carbon atoms in addition to one, and all carbon atoms
Ring- opening polymerization is performed in the presence of a metathesis polymerization catalyst in a solvent containing a polycyclic saturated hydrocarbon constituting a ring structure , and hydrogenation can be performed by further adding a hydrogenation catalyst without removing the solvent. A method for producing a hydrogenated product of a ring-opening polymer. 4. 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 method for producing a hydrogenated product according to claim 3 , wherein the polycyclic saturated hydrocarbon in which all carbon atoms constitute a ring structure is tricyclodecane .