JP5203305B2 - β-pinene-based graft copolymer and method for producing the same - Google Patents

Description

  The present invention relates to a novel β-pinene-based graft copolymer that has higher impact resistance and strength than the prior art, and is excellent in transparency and light resistance, and a molded product comprising the same, and a method for producing the same. In particular, optical films, lens sheets, optical substrate materials, transparent materials for lamps, optical moldings such as diffusers and light guide plates, transparent materials for building materials, and insulation for communication and electrical / electronic equipment The present invention relates to a polymer that can be advantageously used in producing molded articles, pharmaceutical-related equipment and the like.

  A hydrocarbon polymer having an alicyclic skeleton in the molecule (alicyclic hydrocarbon polymer) is excellent in relative dielectric constant, transparency, heat-resistant dimensional stability, solvent resistance, flatness, etc. Therefore, it is used as various industrial component materials. As such an alicyclic hydrocarbon polymer, conventionally produced by polymerizing or copolymerizing a petroleum-derived monomer, or adding hydrogen to the polymer obtained thereby. Cycloolefin polymers or copolymers are known. Since alicyclic hydrocarbon polymers are amorphous and have high transparency, they have been widely used as various optical materials such as lenses, films or sheets.

  On the other hand, in recent years, effective use of biomass derived from plants has attracted attention from the viewpoint of carbon neutral for the purpose of forming a recycling-oriented society and preventing global warming. For example, as one of the natural biomass that exists abundantly in nature, there are terpenes that are abundantly contained in rosin and citrus peel, and such terpenes are widely used as raw materials for pharmaceuticals and perfumes. .

  Here, some terpenes have an alicyclic vinyl monomer structure and have been known to be polymerizable for a long time. In Non-Patent Document 1, β-pinene is cationically polymerized. It is described that a β-pinene polymer having a relatively large molecular weight was obtained by adding 2,6-di-t-butyl-4-methylpyridine. The glass transition temperature of the pinene polymer was 65 ° C., which was not practically sufficient as a molded product.

  Under such circumstances, β-pinene, which is a plant-derived alicyclic terpene, is conventionally obtained by cationic polymerization or cationic copolymerization using a Lewis acid catalyst in the presence of a bifunctional vinyl compound. An alicyclic hydrocarbon polymer (β-pinene polymer) having a large molecular weight that cannot be produced has been reported (Patent Document 1, Non-Patent Document 2). However, although the β-pinene polymer disclosed therein has excellent characteristics such as heat resistance, low water absorption, and low specific gravity, for example, molding for communication equipment and electrical / electronic equipment. When used as a body, it is difficult to say that the impact resistance is sufficient.

  As an example in which the impact resistance is improved, Patent Document 2 proposes a polymer composition containing a β-pinene polymer and a predetermined soft polymer. Although such a polymer composition has good impact resistance, since two or more different polymers are physically mixed, a phase separation structure is formed and the transparency is insufficient, or the mixed state is It has the drawback that it is difficult to control and the physical properties tend to vary. Patent Document 3 proposes a polymer composition of a cyclic olefin polymer and an α-olefin / diene copolymer. In this case, since the α-olefin / diene copolymer is mixed while being cross-linked, a gel is generated in part, and the molded product has a flaw in the mold, or the mixed spots are partially generated, resulting in a decrease in transparency. End up.

International Publication No. 08/44640 Pamphlet JP 2008-208361 A Japanese Patent No. 2800057

B. Keszler et al., “Synthesis of High Moleculer Weight Poly (β-Pinene)”, Advances in Polymer Science, 100, 1-9, 1992 K. Satoh et al., “Biomass-derived heat-resistant alicyclic hydrocarbon polymers: poly (terpenes) and their hydrogenated derivatives”, Green Chemistry, Vol. 8, 878-882, 2006.

  Accordingly, an object of the present invention is to provide a β-pinene-based graft copolymer having excellent impact resistance and strength while maintaining high transparency, high heat resistance and light resistance, and low water absorption, and a molded article thereof. There is.

That is, the present invention
A β-pinene-based graft copolymer obtained by grafting a β-pinene-based polymer to a soft polymer having a glass transition temperature of 0 ° C. or less, wherein the soft polymer in the β -pinene-based graft copolymer A β-pinene-based graft copolymer having a proportion of 5 to 50% by mass and having at least 90 mol% of olefinic double bonds hydrogenated, and a molded body comprising the β-pinene-based graft copolymer is there.
The present invention also provides
The above β-pinene-based graft copolymer comprising a step of polymerizing at least a part of a monomer containing β-pinene in the presence of a soft polymer and a step of hydrogenating the obtained polymer. It is a manufacturing method.

  The β-pinene-based graft copolymer of the present invention has high impact resistance and strength while maintaining high transparency, and is excellent in light resistance. Therefore, it is an optical molding material, a transparent material for building materials, and a transparent material for electrical and electronic use. It is advantageously used for transparent materials for automobiles and medical equipment.

  The β-pinene-based graft copolymer of the present invention is a polymer obtained by grafting a polymer containing β-pinene as a structural unit to a soft polymer as a trunk as a branch and hydrogenating the graft copolymer. is there.

[I] Monomer / β-Pinene Used for Formation of β-Pinene Polymer As the β-pinene monomer used in the present invention, known monomers can be used. In other words, those collected from plants such as pine, β-pinene synthesized from other raw materials such as α-pinene, and the like can also be used.

-Other copolymerization monomer (beta) -pinene-type polymer may contain the unit which consists of another monomer copolymerizable with (beta) -pinene as a structural component. The copolymerizable monomer is not particularly limited, and specific examples include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinyl. Aromatic vinyls such as naphthalene and indene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid monomers such as glycidyl acid; maleic anhydride, maleic acid, fumaric acid, maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; ethylene , Propylene, isobutylene, butadiene, isoprene, norbol Olefins such as styrene; compounds containing double bonds derived from turpentine other than β-pinene such as limonene, α-pinene, myrcene, camphene, and kalen; vinyl esters such as vinyl acetate, vinyl pivalate, and vinyl benzoate; Examples thereof include styrene derivatives having a polar group, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. It is also possible to contain bifunctional monomers such as p-divinylbenzene, p-diisopropenylbenzene, ethylene glycol divinyl ether and the like. These may be used alone or in combination of two or more.

  When the copolymerizable monomer is copolymerized with β-pinene, the amount of copolymerization is preferably 20% by mass or less per total monomer unit of the polymer. If the amount of copolymerization is too large, polymerization may become difficult, and heat resistance often decreases.

  The form of copolymerization is not particularly limited, and for example, random, block or tapered copolymerization may be used. The copolymerization is particularly preferably random copolymerization.

[II] Soft polymer The soft polymer used in the present invention is not particularly limited as long as it has a glass transition temperature of 0 ° C. or lower and β-pinene can undergo graft polymerization. Examples thereof include a soft polymer having an olefinic double bond and a soft polymer in which a cation is generated in the polymer by contacting with a polymerization catalyst of β-pinene.

  Isoprene polymer, butadiene polymer, isoprene / butadiene copolymer, isobutylene / isoprene copolymer, styrene / isoprene copolymer, styrene / butadiene copolymer, acrylonitrile / butadiene as a soft polymer having an olefinic double bond Conjugated diene polymers such as copolymers, cyclic olefin ring-opening polymers such as cycloheptene, cyclooctene, cyclononene, and cyclooctadiene, (meta) such as allyl (meth) acrylate polymers and vinyl (meth) acrylate polymers ) Acrylic polymers, 4-allylstyrene polymers, aromatic polymers such as 4-allyl-α-methylstyrene polymers, and polysiloxanes such as polymethylallylsiloxane and polydiallylsiloxane. Among these, from the viewpoint of little influence on the cationic polymerization of β-pinene, conjugated diene-based polymers and cyclic olefin-based ring-opening polymers are preferable, and among them, the resistance of β-pinene-based graft copolymers obtained is preferred. Isoprene polymers, butadiene polymers, and isoprene / butadiene copolymers are preferred because of their good impact properties.

  Examples of the soft polymer in which a cation is generated in the polymer by being brought into contact with the polymerization catalyst of β-pinene include those having a structure in which a halogen, an alkoxy group, an acyloxy group, or a hydroxyl group is bonded to a tertiary carbon. Examples of such a soft polymer include chlorinated rubber and chlorinated polypropylene.

  The glass transition temperature of the soft polymer used in the present invention is 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −40 ° C. or lower. Generally, the lower the glass transition temperature, the higher the mobility of the main chain, and the impact resistance performance of the β-pinene-based graft copolymer can be expected.

  The number average molecular weight of the soft polymer used in the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000 from the viewpoint of mechanical properties and workability. preferable. If the number average molecular weight is too small, it cannot be called a polymer, and if it is too large, it becomes difficult to form a β-pinene-based graft copolymer. Here, the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.

  The amount of functional groups involved in the formation of olefinic double bonds and cations in the soft polymer used in the present invention is not particularly limited as long as it is one or more per soft polymer. 0.1 mol% or more and 100 mol% or less are preferable with respect to the monomer unit, and 10 mol% or more and 100 mol% or less are preferable.

[III] Graft copolymerization of β-pinene The β-pinene-based graft copolymer of the present invention is a process comprising a step of polymerizing at least a part of a monomer containing β-pinene in the presence of a soft polymer. It can be manufactured by a method.

  When the soft polymer is a soft polymer having an olefinic double bond, it is generated by the reaction of a proton liberated from an initiator or a polymer end or a Lewis acid with a protic compound during the cationic polymerization of β-pinene. By adding protons or the like to the olefinic double bond of the soft polymer, a cation is generated in the soft polymer, and graft polymerization of β-pinene proceeds therefrom.

  In the case of a soft polymer in which a cation is generated in the polymer by bringing the soft polymer into contact with the polymerization catalyst for β-pinene, graft polymerization of β-pinene proceeds from the cation generated by the polymerization catalyst for β-pinene.

  As a method for adding the soft polymer, a method of dissolving the β-pinene in the polymerization solution before starting the polymerization, a method of sequentially adding the soft polymer solution simultaneously with the β-pinene, and a predetermined amount of β-pinene. Examples include a method of adding a soft polymer solution when half-polymerized and polymerizing the remaining β-pinene.

As the mass fraction of the soft polymer is Ri 5% to 50% by mass in the β- pinene-based graft copolymer, more preferably from 7% to 30% by weight. If the amount added is too small, impact resistance and strength cannot be expected. Moreover, when there is too much addition amount, the heat resistance which is the characteristic of a beta-pinene-type polymer will fall.

-Polymerization reaction The monomer or monomer mixture containing β-pinene can be graft-polymerized by a cationic polymerization method. Cationic polymerization can be controlled by the solvent, the type and amount of the polymerization catalyst, the polymerization initiator, the electron donating compound, the reaction temperature, the reaction pressure, the reaction time, and the like.

-Cationic polymerization solvent Cationic polymerization used for this invention can be performed by the well-known method of a nonpatent literature 1 grade | etc.,. Specifically, for example, it is carried out by adding or contacting a polymerization catalyst in an inert organic solvent. The inert organic solvent can be used without particular limitation as long as it is an organic solvent in which β-pinene and aromatic monomers are dissolved and is inert to the polymerization catalyst. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, decalin; methyl chloride, methylene chloride Halogenated hydrocarbon solvents such as propane chloride, butane chloride, 1,2-dichloroethane, 1,1,2-trichloroethylene; oxygen-containing solvents such as esters and ethers can be used. In view of reactivity, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents and the like are preferable. These solvents may be used alone or in combination of two or more.

  When an inert organic solvent is used in cationic polymerization, the amount of the inert organic solvent used is not particularly limited, but is usually 100 to 10,000 parts by weight, preferably 100 parts by weight of β-pinene and aromatic monomers, preferably It is 150-5000 mass parts, More preferably, it is 200-3000 mass parts. If the amount of the inert solvent is small, the viscosity when the copolymer is formed becomes high and stirring becomes difficult, so that the reaction becomes non-uniform, and a uniform copolymer cannot be obtained or the control of the reaction becomes difficult. When the amount of the inert solvent is large, productivity is lowered.

-Polymerization catalyst An acidic compound can be used as a polymerization catalyst for cationic polymerization. The acidic compound is not particularly limited, and examples thereof include Lewis acid or Bronsted acid. _BF 3 in _{particular, BF 3 OEt 2, BBr 3} , BBr 3 OEt 2, AlCl 3, AlBr 3, AlI 3, TiCl 4, TiBr 4, TiI 4, FeCl 3, FeCl 2, SnCl 2, SnCl 4, Metal halides from Group IIIA to Group VIII of the periodic table such as WCl ₆ , MoCl ₅ , SbCl ₅ , TeCl ₂ , EtMgBr, Et ₃ Al, Et ₂ AlCl, EtAlCl ₂ , Et ₃ Al ₂ Cl ₃ , Bu ₃ SnCl Hydrogen acids such as HF, HCl, HBr; H ₂ SO ₄ , H ₃ BO ₃ , HClO ₄ , CH ₃ COOH, CH ₂ ClCOOH, CHCl ₂ COOH, CCl ₃ COOH, CF ₃ COOH, p-toluenesulfonic acid, CF _{3 SO 3 H, H 3 PO} 4, P 2 O 5 , etc. oxo acid, Contact Beauty polymer compounds such as ion-exchange resins having these groups; phosphomolybdic acid, heteropoly acids such as phosphotungstic _{acid; SiO 2, Al 2 O 3} , SiO 2 -Al 2 O 3, MgO-SiO 2, B 2 O 3 -Al ₂ O ₃ , WO ₃ -Al ₂ O ₃ , Zr ₂ O ₃ -SiO ₂ , sulfated zirconia, tungstate zirconia, zeolite exchanged with H ⁺ or rare earth elements, activated clay, acidic clay, γ-Al ₂ Examples thereof include solid acids such as solid phosphoric acid in which O ₃ and P ₂ O ₅ are supported on diatomaceous earth. These acidic compounds may be used in combination, or other compounds may be added. Other compounds etc. are compounds etc. which can improve the activity of an acidic compound, for example by adding it. Examples of compounds that improve the activity of the metal halide as an acidic compound include MeLi, EtLi, BuLi, Et ₂ Mg, (i-Bu) ₃ Al, Et ₂ Al (OEt), Me ₄ Sn, Et ₄ Sn. And metal alkyl compounds such as Bu ₄ Sn.

  The amount of the polymerization catalyst used in the cationic polymerization varies depending on the type of the polymerization catalyst, so it is difficult to generally define the amount used. However, in the case of a homogeneous catalyst, the amount used is β-pinene and 0.001-10 mass parts is preferable with respect to 100 mass parts of another copolymerizable monomer, 0.01-5 mass parts is more preferable, and 0.01-1 mass part is the most preferable. When a heterogeneous catalyst such as a solid acid or ion exchange resin is used as the polymerization catalyst, the amount used is preferably 0.1 to 10,000 parts by mass with respect to 100 parts by mass of β-pinene and other copolymerizable monomers. 1 to 1000 parts by mass is more preferable. If the amount of catalyst is small, the progress of cationic polymerization is slow, and if it is large, it is uneconomical.

  The polymerization initiator for performing cationic polymerization is not particularly limited as long as it is a compound that generates a cation with a polymerization catalyst, but an organic compound having at least one functional group represented by the following formula is preferably used. For example, t-butyl chloride, t-butyl methyl ether, t-butyl methyl ester, t-butanol, 2,5-dichloro-2,5-dimethylhexane, 2,5-dimethoxy-2,5-dimethylhexane, 2 , 5-dimethyl-2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol diacetate, cumyl chloride, cumyl methoxide, cumyl alcohol acetate, cumyl alcohol, p-dicumyl chloride, m- Examples include dicumyl chloride, p-dicumyl methoxide, p-dicumyl alcohol diacetate, p-dicumyl alcohol, 1,3,5-tricumyl chloride, 1,3,5-tricumyl methoxide. it can.

  Since the amount of the polymerization initiator used in the cationic polymerization varies depending on the molecular weight of the target polymer, it is difficult to generally define the amount used, but β-pinene and other copolymerizable monomers are 100 parts by mass. On the other hand, 0.001-10 mass parts is preferable, 0.001-5 mass parts is more preferable, and 0.01-1 mass part is the most preferable. When the amount of the polymerization initiator is small, the polymerization reaction rate becomes slow, or the polymerization starts from the impurities and is difficult to produce stably. When there are many polymerization initiators, the molecular weight of the polymer obtained will become small and a polymer will become weak.

  When performing cationic polymerization, it is possible to further control the polymerization reaction by adding an electron donating compound. Examples of such electron donating compounds include ether compounds such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and anisole, cyclic ether compounds having 2 to 10 carbon atoms, ester compounds such as ethyl acetate and butyl acetate, methanol, Alcohol compounds such as ethanol and butanol, nitrogen-containing compounds such as triethylamine, diethylamine, pyridine, 2-methylpyridine, 2,6-di-t-butylpyridine, 2,6-lutidine, N, N-dimethylacetamide, acetonitrile, Examples thereof include ammonium salts such as tetrabutylammonium chloride and tetrabutylammonium bromide.

  In the reaction system, the electron donating compound is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the polymerization catalyst. If the amount of the electron-donating compound is too small, side reactions tend to increase, and the strength of the polymer that can produce a large amount of low molecular weight products decreases. Conversely, when there are too many electron donors, the polymerization reaction rate is remarkably suppressed, and the cationic polymerization reaction takes a long time, and the productivity is lowered. Therefore, the more preferable amount of the electron donating compound is 0.1 to 100 parts by mass with respect to the polymerization catalyst.

  In the case of performing cationic polymerization, the reaction temperature is usually preferably -120 ° C to 60 ° C, more preferably -80 ° C to 0 ° C, and most preferably -40 ° C to 0 ° C. If the reaction temperature is too low, it is uneconomical, and if it is too high, it is difficult to control the reaction.

  The reaction pressure for performing cationic polymerization is not particularly limited, but is preferably 0.5 to 50 atm, and more preferably 0.7 to 10 atm. Usually, cationic polymerization is performed at around 1 atm.

  The reaction time for carrying out the cationic polymerization is not particularly limited, and the reaction time can be appropriately determined according to the type of aromatic monomer used, the amount thereof, the type and amount of the polymerization catalyst, the reaction temperature, the reaction pressure and the like. That's fine. Usually, it is 0.01 hours to 24 hours, preferably 0.1 hours to 10 hours.

  The polymer after cationic polymerization may be used for isolating the polymer from a solution, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. It can be separated and obtained from the reaction mixture by ordinary operations.

[IV] Hydrogenation The hydrogenated β-pinene-based graft copolymer according to the present invention can be obtained by a hydrogenation reaction, but the hydrogenation method is not particularly limited, and any known arbitrary Can take the way.

  The β-pinene-based graft copolymer of the present invention prevents olefinic double bonds derived from β-pinene and soft polymers before hydrogenation in order to prevent deterioration due to oxygen in the air and to suppress coloring of the molded product. It is hydrogenated by 90 mol% or more. The hydrogenation rate is preferably 95 mol% or more, and more preferably 97 mol% or more. When the residual amount of the olefinic double bond is large, there is a possibility that it is likely to deteriorate.

-Hydrogenation catalyst The catalyst of a hydrogenation reaction can use what can hydrogenate an olefin compound and an aromatic compound. Usually, a heterogeneous catalyst or a homogeneous catalyst is used.

The catalyst when the hydrogenation reaction is performed using a heterogeneous catalyst is not particularly limited, but specific examples include sponge metal catalysts such as sponge nickel, sponge cobalt and sponge copper; nickel silica, nickel alumina and nickel zeolite. , Nickel diatomaceous earth, palladium silica, palladium alumina, palladium zeolite, palladium diatomaceous earth, palladium carbon, palladium calcium carbonate, platinum silica, platinum alumina, platinum zeolite, platinum diatomaceous earth, platinum carbon, platinum calcium carbonate, ruthenium silica, ruthenium alumina, ruthenium zeolite , Ruthenium diatomaceous earth, ruthenium carbon, ruthenium calcium carbonate, iridium silica, iridium alumina, iridium zeolite, iridium diatomaceous earth, iridium carbon, Indium calcium carbonate, cobalt silica, cobalt alumina, cobalt zeolite, cobalt diatomaceous earth, cobalt carbon include supported metal catalysts such as cobalt calcium carbonate.
These catalysts may be modified with iron, molybdenum, magnesium or the like for the purpose of improving activity, improving selectivity and stability. Moreover, these catalysts may be used alone or in combination.
The catalyst when the hydrogenation reaction is performed using a homogeneous catalyst is not particularly limited, and specific examples include a catalyst composed of a transition metal compound and alkylaluminum or alkyllithium.

  When the hydrogenation reaction is performed, the β-pinene-based graft copolymer is subjected to a hydrogenation reaction, so that the reaction activity is generally low for low-molecular compounds. Accordingly, relatively high temperature and high pressure conditions are often preferred as reaction conditions, and it is preferable to carry out with a heterogeneous catalyst having high thermal stability. From the aspect of hydrogenation activity, nickel or palladium is preferably used as the metal having hydrogenation activity, and a palladium compound is more preferably used. Further, in order to suppress an undesirable side reaction that proceeds during hydrogenation, it is preferable to use calcium carbonate or a carbon support, and it is more preferable to use a carbon support.

-Solvent When performing a hydrogenation reaction, it is normally performed in an organic solvent, and the solvent used in the polymerization step can be used as it is, or a part of the solvent can be removed by a method such as distillation. Further, after completion of the polymerization step, the polymer may be once taken out by the above-mentioned method. When the non-hydrogenated polymer is introduced into the hydrogenation step by these methods, the solvent in the polymerization step can be used as it is or after being removed, and then diluted with a separate solvent.

-Reaction pressure When performing the hydrogenation reaction, the pressure of the hydrogenation reaction may vary depending on the catalyst used, and cannot always be specified, but usually the total pressure of the hydrogenation reaction is 0.1 MPa to 50 MPa, Preferably it is 0.5MPa-30MPa, More preferably, it is 1MPa-20MPa.

  The hydrogenation reaction is carried out under the condition where hydrogen gas is present. However, in addition to hydrogen gas, the hydrogenation reaction may be carried out by mixing with any gas as long as it is inert to the hydrogenation reaction. Specific examples of the inert gas include nitrogen, helium, argon, carbon dioxide and the like. Depending on the reaction conditions, the solvent used for the reaction may have a partial pressure at a significant ratio as a gas component, but there is no problem.

-Reaction temperature and reaction time When a hydrogenation reaction is carried out, the temperature of the hydrogenation reaction may vary depending on the catalyst used and cannot always be specified, but is usually 10 ° C to 300 ° C, preferably 60 ° C. It is -250 degreeC, More preferably, it is 70 degreeC-220 degreeC. In general, a heterogeneous catalyst may be used at a higher temperature than a homogeneous system. The hydrogenation reaction time varies depending on the type of catalyst used, the amount of catalyst, and the reaction temperature, and thus is not necessarily limited, but is usually 5 minutes to 20 hours, preferably 10 minutes to 15 hours. If the reaction time is too short, the desired hydrogenation rate cannot be obtained. Moreover, when reaction time is too long, the progress of the undesired side reaction will become remarkable and the hydrogenated polymer of the desired physical property may not be obtained.

-Reaction form When performing hydrogenation reaction, embodiment of hydrogenation reaction can take arbitrary well-known methods. Depending on the type of catalyst to be introduced, there may be an appropriate reaction form. For example, a batch reaction, a semi-continuous reaction, or a continuous reaction system can be adopted. In the continuous reaction format, a plug flow format (PFR) and a continuous flow stirring format (CSTR) can be used. Moreover, when using a heterogeneous catalyst, a fixed bed reaction tank can be used. When the reaction is carried out by positive mixing, a method of mixing by stirring, a method of circulating and mixing the hydrogenation reaction solution in a loop form, or the like can be employed. In this case, when a heterogeneous catalyst is used, it becomes a suspension bed reaction and becomes a gas-liquid-solid reaction field. Moreover, when using a homogeneous catalyst, it becomes a gas-liquid two-phase reaction field.
The extracted liquid after the hydrogenation reaction is partly divided and can be used again for the hydrogenation reaction. By using it again, there are cases in which the generation of heat generated by hydrogenation is avoided and the hydrogenation reaction rate is improved.
In any of these reaction formats, two or more reaction formats, which are the same or different, can be connected to carry out the hydrogenation reaction. When aiming for a higher hydrogenation reaction rate, it may be desirable to include a step of reacting in a plug flow format using a fixed bed.

  It is difficult to limit the amount of catalyst used depending on the type of hydrogenation catalyst used, the concentration of β-pinene-based graft copolymer, the reaction mode, etc. The amount of catalyst used per 100 parts by mass of the hydrogenation reaction liquid is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass. It is. When the amount used is small, the hydrogenation reaction requires a long time. When the amount used is large, a large amount of power for mixing the heterogeneous catalyst is required. Moreover, when using a fixed bed, it is difficult to prescribe | regulate the usage-amount of the catalyst per reaction solution, and arbitrary amounts can be used. When a homogeneous catalyst is used, the transition metal compound concentration in the hydrogenation reaction solution is 0.001 mmol / liter to 100 mmol / liter, more preferably 0.01 mmol / liter to 10 mmol / liter. is there.

  Olefinic double bonds in the soft polymer may remain after the graft copolymerization of β-pinene. In such a case, the olefinic double bond derived from the soft polymer is preferably hydrogenated together with the olefinic double bond derived from the β-pinene unit in order to suppress deterioration and coloring due to oxygen in the air.

The used hydrogenation catalyst can be separated from the β-pinene-based graft copolymer as necessary after completion of the hydrogenation reaction. The separation can be carried out by any known method, but when a heterogeneous catalyst is used, the separation can be carried out by continuous or batch filtration, centrifugal separation, or settling / decantation by standing.
When a homogeneous catalyst is used, it can be separated from the catalyst by using, for example, an aggregation precipitation method, an adsorption method, a washing method, an aqueous phase extraction method, or the like.
Even if the catalyst is separated by using these separation methods, a trace amount of metal component may remain in the β-pinene-based graft copolymer. Also in this case, since the metal component is dissolved, as described above, the remaining metal can be separated by using the coagulation precipitation method, the adsorption method, the washing method, the aqueous phase extraction method, and the like.
The catalyst recovered by the separation can be used again for the hydrogenation reaction after removing a part of the catalyst or adding a part of the new catalyst as necessary.

  The β-pinene-based graft copolymer after hydrogenation is, for example, β-pinene-based, such as reprecipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. The graft copolymer can be separated and obtained from the reaction mixture by a normal operation in isolating the graft copolymer from the solution.

[V] β-Pinene Graft Copolymer / Number Average Molecular Weight The number average molecular weight of the β-pinene graft copolymer of the present invention is not particularly limited, but is 1,000 to 1,000,000 from the viewpoint of mechanical properties and processability. Is preferably 10,000 to 500,000, more preferably 30,000 to 200,000, and most preferably 40,000 to 200,000. If the number average molecular weight is too small, it cannot be called a polymer, and if it is too large, molding becomes difficult. Here, the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.

・ Glass transition temperature (Tg)
The Tg of the β-pinene-based graft copolymer of the present invention cannot be generally defined by the type and ratio of the soft polymer and the type and ratio of the monomer copolymerized with β-pinene, but it is 70 ° C to 250 ° C. More preferably, 100 ° C to 230 ° C is more preferable. When Tg is low, heat resistance is insufficient, and when it is too high, the β-pinene-based graft copolymer becomes brittle. Tg can be measured by differential scanning calorimetry (DSC).

-Total light transmittance The β-pinene-based graft copolymer of the present invention preferably has a high total light transmittance particularly when used for transparent applications. The total light transmittance of the β-pinene-based graft copolymer is preferably 80% or more, and more preferably 85% or more. The total light transmittance is measured according to JIS-K7361-1-1997 “Plastics—Testing method of total light transmittance of transparent material—Part 1: Jingle beam method”.

Light resistance The β-pinene-based graft copolymer of the present invention preferably has higher light resistance and weather resistance. For example, an accelerated exposure test for 100 hours with UVB light is performed according to ASTM-G53, and the yellowing degree (ΔYI) before and after the test of YI (yellow index) measured according to JIS-K7373 is preferably 5 or less. 2 or less is more preferable, and 1 or less is more preferable.

  The β-pinene-based graft copolymer of the present invention can be used alone, or is not graft-bonded with a β-pinene-based polymer that is not graft-bonded to a soft polymer or a β-pinene-based polymer. Other polymers such as soft polymer, polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, styrene block copolymer, It can also be used as a composition contained as a product or additive. When used as a composition, stabilizers, lubricants, pigments, impact resistance improvers, processing aids, reinforcing agents, colorants, flame retardants, weather resistance improvers, UV absorbers, antioxidants, fungicides, Various additives such as antibacterial agents, light stabilizers, antistatic agents, silicone oils, antiblocking agents, mold release agents, foaming agents, fragrances; various fibers such as glass fibers and polyester fibers; talc, mica, montmorillonite, smectite, Fillers such as silica and wood powder; optional components such as various coupling agents can be blended as required.

[VI] Molded Product A molded product comprising the β-pinene-based graft copolymer of the present invention can be obtained according to a conventional method. As a molding method, a known method such as a method using an injection molding method, a hot press molding method, or an extrusion molding method is appropriately employed from the viewpoint of productivity.

Optical Material The β-pinene-based graft copolymer of the present invention can be used for various optical materials, and the range thereof is not particularly limited, but excellent heat resistance, low water absorption and high transparency are required. Suitable for optical materials. Examples of optical materials include lenses, aspheric lenses, Fresnel lenses, lenses for silver salt cameras, lenses for digital electronic cameras, lenses for video cameras, lenses for projectors, lenses for copying machines, camera lenses for mobile phones, and lenses for glasses. Aspheric pickup lens for digital optical disc device using blue light emitting diode, rod lens, rod lens array, micro lens, micro lens array, various lens arrays, step index type, gradient index type, single mode type, multi-core type, polarized Wavefront storage type, side emission type optical fiber, optical fiber connector, optical fiber adhesive, digital optical disc (compact disc, magneto-optical disc, digital disc, video disc, computer disc, light guide , Light diffusive molding, liquid crystal glass substrate substitute film, retardation film, antistatic layer, antireflection layer, hard coat layer, transparent conductive layer, antiglare layer and other functional thin films, for flat panel displays Anti-reflection film, touch panel substrate, transparent conductive film, anti-reflection film, anti-glare film, electronic paper substrate, organic electroluminescence substrate, plasma display front protection plate, plasma display electromagnetic wave prevention plate, field emission display front Protective plates, light guide plates that use a piezoelectric element to diffuse the light of a specific part in front, polarizers, prisms constituting analyzers, diffraction gratings, endoscopes, endoscopes that guide high-energy lasers, roof mirrors, etc. Representative camera mirrors or half mirrors (automobiles Transparent materials used in vehicle lamps (headlight lenses, automotive headlight reflectors, etc.), solar cell front protective plates, residential window glass, moving objects (automobiles, trains, ships, aircraft, spacecraft, space) Base glass, anti-reflection film for window glass, dust-proof film during semiconductor exposure, protective film for electrophotographic photosensitive material, semiconductor (EPROM, etc.) encapsulant that can be written or rewritten by ultraviolet light, light emission Diode sealing material, ultraviolet light emitting diode sealing material, white light emitting diode sealing material, SAW filter, optical bandpass filter, second harmonic generator, Kerr effect generator, optical switch, optical interconnection, light Isolators, optical waveguides, surface light emitters using organic electroluminescence, surface emission with dispersed semiconductor fine particles Examples thereof include a phosphor member and a phosphor in which a phosphor substance is dissolved or dispersed.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to said specific example. Further, the exemplified materials may be used alone or in combination unless otherwise specified.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Reference Example 1>
480 parts by mass of cyclohexane and 3.1 parts by mass of sec-butyllithium (1.3M cyclohexane solution) were added to a pressure vessel equipped with a stirrer purged with nitrogen, and heated to 40 ° C. 190 parts by mass of isoprene were sequentially added thereto at a rate of 1.4 parts by mass / minute, and after the addition was completed, the reaction was further continued at 40 ° C. for 60 minutes, and then 1 part by mass of methanol was added to complete the polymerization. The obtained polymerization solution was reprecipitated in 10,000 parts by mass of a mixed solvent of methanol / acetone (50/50 vol), and then sufficiently dried to obtain 187 parts by mass of an isoprene polymer. The obtained isoprene polymer had a weight average molecular weight of 62,700, a number average molecular weight of 50,600, and a glass transition temperature of −65 ° C. The structure of the isoprene unit in the obtained isoprene polymer was 93% for 1,4 structural units and 7% for 3,4 structural units.
<Reference Example 2>
An isoprene / butadiene copolymer was obtained in the same manner as in Reference Example 1 except that the solution was changed to 190 parts by mass of isoprene and changed to a solution in which isoprene / butadiene (106 parts by mass / 84 parts by mass) was mixed. The obtained isoprene / butadiene copolymer had a weight average molecular weight of 49,300, a number average molecular weight of 45,600, and a glass transition temperature of −75 ° C.

<Example 1>
(1) After thoroughly substituting the well-dried glass flask with a cock with nitrogen, add 153 parts by mass of dehydrated n-heptane, 262 parts by mass of dehydrated methylene chloride, 0.52 parts by mass of dehydrated diethyl ether, Cooled to 20 ° C. Further, 7.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at −20 ° C. Furthermore, when 2.5 parts by mass of a 0.1 mol / L heptane solution of p-dicumulyl chloride was added while being kept at −20 ° C., the color changed to red. Immediately after the distillation, 30 parts by mass of β-pinene was continuously added dropwise at a rate of 6 parts by mass / hr. While adding β-pinene at 2.5 hours from the start of dropping, 15 parts by mass of a solution obtained by dissolving 3.0 parts by mass of the isoprene polymer obtained in Reference Example 1 in 12 parts by mass of heptane was added over 1 minute. Added. After the addition of β-pinene, 6 parts by mass of methanol was added to complete the reaction. An aqueous solution in which 5 parts by mass of citric acid was added to 100 parts by mass of distilled water was added and stirred for 5 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the aluminum compound was removed. The obtained organic layer was reprecipitated in 5000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and then sufficiently dried to obtain 33 parts by mass of a β-pinene-based graft copolymer (A1). The obtained β-pinene-based graft copolymer (A1) had a weight average molecular weight of 177,000 and a number average molecular weight of 38,400.

(2) 120 mass parts of cyclohexane and 30 mass parts of β-pinene-based graft copolymer (A1) are accommodated in a pressure-resistant container equipped with a stirrer substituted with nitrogen, and β-pinene-based graft is stirred. The copolymer (A1) was completely dissolved. Thereafter, as a hydrogenation catalyst, 30 parts by mass of 5% palladium-supported carbon (product number: E1002R / W manufactured by Evonik Degussa Japan Co., Ltd.) was added, stirred, and sufficiently dispersed. The reaction was continued for 22 hours at 90 ° C. and a hydrogen pressure of 1 MPa with stirring, and then returned to normal pressure. The solution after the reaction was filtered through a 0.2 μm fluororesin filter to separate and remove the catalyst, and then reprecipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%). It dried and obtained 24 mass parts of (beta) -pinene type graft copolymer hydride (H1). When ¹ H-NMR of the thus obtained β-pinene-based graft copolymer hydride (H1) was measured, the remaining olefinic double bond was 2.8 mol%. The glass transition temperature was 109 ° C. The obtained β-pinene graft copolymer hydride (H1) had a weight average molecular weight of 171,100 and a number average molecular weight of 40,500. Table 1 shows the evaluation results of the hydrogenated β-pinene graft copolymer (H1).

In addition, about the material obtained at each above-mentioned process, and the material manufactured at the following process, the physical-property measurement was performed as follows.
○ Molding The obtained β-pinene copolymer was prepared as a test piece by press molding or injection molding. In press molding, a molded body of 50 mm × 50 mm × 3 mmt size was obtained at 180 ° C. Injection molding was performed using a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and a mold of 50 mm × 50 mm × 3 mmt.
○ Molecular weight Both the number average molecular weight and the weight average molecular weight are determined in terms of polystyrene based on measurement by gel permeation chromatography (GPC). Here, as the GPC apparatus, HLC-8020 (product number) manufactured by Tosoh Corporation was used, and as the column, two TSKgel / GMH-M manufactured by Tosoh Corporation and one G2000H were connected in series. .
○ Residual double bond rate: Measured 1000 times at room temperature using a 400 MHz magnet nuclear magnetic resonance apparatus manufactured by JEOL. The integrated value of 5.15-5.75 ppm of the obtained ¹ H-NMR spectrum (the proton of tetramethylsilane is 0 ppm) is defined as the olefinic double bond, and the remaining two from the ¹ H-NMR before and after hydrogenation. The double bond rate was calculated.
○ Glass transition temperature (Tg)
It measured by the differential scanning calorimetry (DSC) using the sample which fully dried and removed the solvent. Here, DSC30 (product number) manufactured by METTLER TOLEDO was used as the measuring apparatus.
-Total light transmittance It measured based on JIS-K7361-1 using HR-100 (product number) by Murakami Color Research Laboratory.

○ Light Resistance Test According to ASTM-G53, an accelerated exposure test for 100 hours was performed, and the yellowing degree (ΔYI) before and after the test of YI (yellow index) was measured. Here, an ultraviolet exposure tester (ATLAS-UVCON manufactured by Toyo Seiki Seisakusho) was used. YI was measured according to JIS-K7373. And it evaluated according to the following criteria.
ΔYI = (YI after 100 hours of UV exposure) − (YI before UV exposure)
○: ΔYI ≦ 10 Long-term light resistance is good ×: ΔYI> 10 Long-term light resistance is poor ○ Three-point bending test According to JIS-K7171, a molded product having a thickness of 3 mm is used as a test piece, 25
Maximum point stress was measured under the conditions of ° C and humidity: 40%. Here, Autograph AG-5000 (product number) manufactured by Shimadzu Corporation was used as a measuring device.
O Izod impact strength Based on JIS-K7110, it measured on 25 degreeC and humidity: 40% conditions, using a molded article (with type A notch) of thickness: 3mm as a test piece. Here, a digital impact tester DG-UB (product number) manufactured by Toyo Seiki Co., Ltd. was used as a measuring device.

<Example 2>
(1) After thoroughly substituting the well-dried glass flask with a cock with nitrogen, add 153 parts by mass of dehydrated n-heptane, 262 parts by mass of dehydrated methylene chloride, 0.52 parts by mass of dehydrated diethyl ether, Cooled to 20 ° C. Further, 7.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at −20 ° C. Furthermore, when 2.5 parts by mass of a 0.1 mol / L heptane solution of p-dicumulyl chloride was added while being kept at −20 ° C., the color changed to red. Immediately after the distillation, 30 parts by mass of β-pinene was continuously added dropwise at a rate of 6 parts by mass / hr. While continuing to drop β-pinene at the point of 20 minutes from the start of dropping, 15 parts by mass of a solution obtained by dissolving 3.0 parts by mass of the isoprene polymer obtained in Reference Example 1 in 12 parts by mass of heptane was added over 4 hours. Added. After the addition of β-pinene, 6 parts by mass of methanol was added to complete the reaction. An aqueous solution in which 5 parts by mass of citric acid was added to 100 parts by mass of distilled water was added and stirred for 5 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the aluminum compound was removed. The obtained organic layer was reprecipitated in 5000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and then sufficiently dried to obtain 33 parts by mass of β-pinene-based graft copolymer (A2). The resulting β-pinene graft copolymer (A2) had a weight average molecular weight of 210,000 and a number average molecular weight of 39,600.

(2) 120 parts by mass of cyclohexane and 30 parts by mass of β-pinene graft copolymer (A2) are accommodated in a pressure vessel equipped with a stirrer purged with nitrogen, and stirred to obtain a β-pinene graft. Copolymer (A2) was completely dissolved. Thereafter, as a hydrogenation catalyst, 30 parts by mass of 5% palladium-supported carbon (product number: E1002R / W manufactured by Evonik Degussa Japan Co., Ltd.) was added, stirred, and sufficiently dispersed. The reaction was continued for 22 hours at 90 ° C. and a hydrogen pressure of 1 MPa with stirring, and then returned to normal pressure. The solution after the reaction was filtered through a 0.2 μm fluororesin filter to separate and remove the catalyst, and then reprecipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%). It dried and obtained 24 mass parts of (beta) -pinene type graft copolymer hydride (H2). When ¹ H-NMR of the β-pinene graft copolymer hydride (H2) thus obtained was measured, the remaining olefinic double bond was 3.5 mol%. The glass transition temperature was 120 ° C. The obtained β-pinene-based graft copolymer hydride (H2) had a weight average molecular weight of 192,100 and a number average molecular weight of 44,600. Table 1 shows the evaluation results of the hydrogenated β-pinene graft copolymer (H2).

<Example 3>
(1) 30 parts by mass of a solution in which 6.0 parts by mass of isoprene polymer was dissolved in 24 parts by mass of heptane was changed to 15 parts by mass of 3.0 parts by mass of isoprene polymer dissolved in 12 parts by mass of heptane. 35 parts by mass of β-pinene-based graft copolymer (A3) was obtained in the same manner as in Example 1 (1) except that the addition was performed. The obtained β-pinene-based graft copolymer (A3) had a weight average molecular weight of 142,000 and a number average molecular weight of 42,000.

(2) 120 mass parts of cyclohexane and 30 mass parts of β-pinene-based graft copolymer (A3) are accommodated in a pressure vessel equipped with a stirrer purged with nitrogen, and β-pinene-based graft is stirred. The copolymer (A3) was completely dissolved. Thereafter, 30 parts by mass of 5% palladium-supported carbon (product number: E106O / W Evonik Degussa Japan Co., Ltd.) was added as a hydrogenation catalyst, stirred, and sufficiently dispersed. The reaction was continued at 100 ° C. and hydrogen pressure: 1 MPa for 22 hours with stirring, and then returned to normal pressure. The solution after the reaction was filtered through a 0.2 μm fluororesin filter to separate and remove the catalyst, and then reprecipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%). It dried and obtained 24 mass parts of (beta) -pinene type graft copolymer hydride (H3). When ¹ H-NMR of the β-pinene graft copolymer hydride (H3) thus obtained was measured, the remaining olefinic double bond was 9.3 mol%. The glass transition temperature was 100 ° C. The obtained β-pinene-based graft copolymer hydride (H3) had a weight average molecular weight of 309,200 and a number average molecular weight of 49,500. Table 1 shows the evaluation results of the hydrogenated β-pinene graft copolymer (H3).

<Example 4>
(1) Example 1 (1) except that 3.0 parts by mass of the isoprene / butadiene copolymer obtained in Reference Example 2 were used instead of 3.0 parts by mass of the isoprene polymer obtained in Reference Example 1. ), 33 parts by mass of β-pinene-based graft copolymer (A4) was obtained. The obtained β-pinene-based graft copolymer (A4) had a weight average molecular weight of 288,000 and a number average molecular weight of 38,500.

(2) 120 mass parts of cyclohexane and 30 mass parts of β-pinene-based graft copolymer (A4) are accommodated in a pressure-resistant vessel equipped with a stirrer substituted with nitrogen, and β-pinene-based graft is stirred. The copolymer (A4) was completely dissolved. Thereafter, 30 parts by mass of 5% palladium-supported carbon (product number: E106O / W Evonik Degussa Japan Co., Ltd.) was added as a hydrogenation catalyst, stirred, and sufficiently dispersed. The reaction was continued at 100 ° C. and hydrogen pressure: 1 MPa for 22 hours with stirring, and then returned to normal pressure. The solution after the reaction was filtered through a 0.2 μm fluororesin filter to separate and remove the catalyst, and then reprecipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%). It dried and obtained 24 mass parts of (beta) -pinene type graft copolymer hydride (H4). When ¹ H-NMR of the thus obtained β-pinene-based graft copolymer hydride (H4) was measured, the remaining olefinic double bond was 1.5 mol%. The glass transition temperature was 105 ° C. The obtained β-pinene-based graft copolymer hydride (H4) had a weight average molecular weight of 164,800 and a number average molecular weight of 41,200. Table 1 shows the evaluation results of the hydrogenated β-pinene graft copolymer (H4).

<Comparative Example 1>
(1) A β-pinene polymer (A5) was obtained in the same manner as in Example 1 (1) except that a heptane solution of an isoprene polymer was not added. The obtained β-pinene polymer (A5) had a weight average molecular weight of 88,100 and a number average molecular weight of 34,900.

(2) The β-pinene polymer (A5) obtained in the above (1) was hydrogenated in the same manner as in Example 1 (2) to obtain a β-pinene polymer hydride (H5). When the ¹ H-NMR of the thus obtained β-pinene polymer hydride (H5) was measured, the remaining olefinic double bond was 0.1 mol%. The glass transition temperature was 130 ° C. The obtained β-pinene polymer hydride (H5) had a weight average molecular weight of 90,000 and a number average molecular weight of 35,100. The evaluation results of the β-pinene polymer hydride (H5) are shown in Table 1.

<Comparative example 2>
(1) After thoroughly substituting the well-dried glass flask with a cock with nitrogen, add 153 parts by mass of dehydrated n-heptane, 262 parts by mass of dehydrated methylene chloride, 0.52 parts by mass of dehydrated diethyl ether, Cooled to 20 ° C. Further, 7.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at −20 ° C. Furthermore, when 2.5 parts by mass of a 0.1 mol / L heptane solution of p-dicumulyl chloride was added while being kept at −20 ° C., the color changed to red. Immediately after the distillation, 30 parts by mass of β-pinene was continuously added dropwise at a rate of 6 parts by mass / hr. After the addition of β-pinene, 15 parts by mass of a solution obtained by dissolving 3.0 parts by mass of the isoprene polymer obtained in Reference Example 1 in 12 parts by mass of heptane was added over 1 minute, followed by stirring at −20 ° C. for 1 hour. After that, 6 parts by mass of methanol was added to complete the reaction. An aqueous solution in which 5 parts by mass of citric acid was added to 100 parts by mass of distilled water was added and stirred for 5 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the aluminum compound was removed. The obtained organic layer was reprecipitated in 5000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and then sufficiently dried to obtain 33 parts by mass of a β-pinene copolymer (A6). The obtained β-pinene copolymer (A6) had a weight average molecular weight of 87,400 and a number average molecular weight of 28,100.

(2) The β-pinene copolymer (A6) obtained in (1) above was hydrogenated in the same manner as in Example 1 (2) to obtain a β-pinene copolymer hydride (H6). . When ¹ H-NMR of the thus obtained β-pinene copolymer hydride (H6) was measured, the remaining olefinic double bond was 0.1 mol%. Two glass transition temperatures were present at −65 ° C. and 130 ° C., suggesting no grafting. The obtained β-pinene copolymer hydride (H6) had a weight average molecular weight of 86,300 and a number average molecular weight of 29,100. Table 1 shows the evaluation results of the β-pinene polymer hydride (H6).

<Comparative Example 3>
(1) After thoroughly substituting the well-dried glass flask with a cock with nitrogen, add 153 parts by mass of dehydrated n-heptane, 262 parts by mass of dehydrated methylene chloride, 0.52 parts by mass of dehydrated diethyl ether, Cooled to 20 ° C. Further, 7.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at −20 ° C. Furthermore, when 2.5 parts by mass of a 0.1 mol / L heptane solution of p-dicumulyl chloride was added while being kept at −20 ° C., the color changed to red. Immediately thereafter, dropwise addition of a solution obtained by mixing 30 parts by mass of β-pinene purified by distillation and 3 parts by mass of isoprene was started at a rate of 6.6 parts by mass / hr. After completion of the addition, 6 parts by mass of methanol was added to complete the reaction. An aqueous solution in which 5 parts by mass of citric acid was added to 100 parts by mass of distilled water was added and stirred for 5 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the aluminum compound was removed. The obtained organic layer was reprecipitated in 5000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and then sufficiently dried to obtain 33 parts by mass of a β-pinene copolymer (A7). ^{When 1} H-NMR was measured, it was not a graft copolymer but a β-pinene / isoprene random copolymer. The obtained β-pinene copolymer (A7) had a weight average molecular weight of 42,500 and a number average molecular weight of 16,100.

(2) The β-pinene copolymer (A7) obtained in (1) above was hydrogenated in the same manner as in Example 1 (2) to obtain a β-pinene copolymer hydride (H7). . When the ¹ H-NMR of the thus obtained β-pinene copolymer hydride (H7) was measured, the remaining olefinic double bond was 0.1 mol%. The glass transition temperature was 112 ° C. The obtained β-pinene copolymer hydride (H7) had a weight average molecular weight of 42,000 and a number average molecular weight of 16,300. The β-pinene polymer hydride (H7) was very brittle and could not be molded.

<Comparative example 4>
A mixture of 91 parts by weight of the β-pinene polymer (A5) obtained in Comparative Example 1 (1) and 9 parts by weight of the isoprene polymer obtained in Reference Example 1 was designated as a β-pinene polymer mixture (B1). . This β-pinene copolymer (B1) was hydrogenated in the same manner as in Example 1 (2) to obtain a β-pinene copolymer hydride (H8). When the ¹ H-NMR of the thus obtained β-pinene copolymer hydride (H8) was measured, the remaining olefinic double bond was 0.1 mol%. Two glass transition temperatures were present at −65 ° C. and 130 ° C., suggesting no grafting. The obtained β-pinene copolymer hydride (H8) had a weight average molecular weight of 89,200 and a number average molecular weight of 36,400. The β-pinene polymer hydride (H8) was very brittle and could not be molded.

<Comparative Example 5>
The β-pinene-based graft copolymer (A1) obtained in Example 1 (1) was used as this comparative example without passing through the hydrogenation step (2). Table 1 shows the evaluation results of the β-pinene-based graft copolymer (A1).

Claims (6)

A β-pinene-based graft copolymer obtained by grafting a β-pinene-based polymer to a soft polymer having a glass transition temperature of 0 ° C. or less, wherein the soft polymer in the β -pinene-based graft copolymer A β-pinene-based graft copolymer having a proportion of 5 to 50% by mass and having at least 90 mol% of olefinic double bonds hydrogenated. The β-pinene-based graft copolymer according to claim 1, wherein the soft polymer is a polymer having an olefinic double bond. The β-pinene graft copolymer according to claim 1 or 2 , wherein the polymer having an olefinic double bond is a conjugated diene polymer. The β-pinene-based graft copolymer according to any one of claims 1 to 3 , wherein the β-pinene-based polymer contains 80% by mass or more of β-pinene units. The molded object which consists of a beta-pinene type graft copolymer of any one of Claims 1-4 . The method according to any one of claims 1 to 4 , comprising a step of polymerizing at least a part of the monomer containing β-pinene in the presence of a soft polymer, and a step of hydrogenating the obtained polymer. A process for producing the described β-pinene graft copolymer.