JPWO2009125784A1 - β-pinene copolymer and process for producing the same - Google Patents

Abstract

The present invention provides a β-pinene copolymer having excellent heat resistance and light resistance, low water absorption and high transparency, and a molded product thereof. 30-80% by mass of β-pinene units and α- It is composed of 70 to 20% by mass of an aromatic monomer unit such as methylstyrene, and has an olefinic double bond of 80 mol% or more, more preferably 50 mol% or more of an aromatic ring derived from an aromatic monomer. And a β-pinene copolymer formed by adding the same, and a molded body comprising the β-pinene copolymer.

Description

  The present invention relates to a novel β-pinene copolymer having higher heat resistance and higher light resistance than conventional ones, a molded article comprising the same, and a method for producing the same.

  In recent years, the demand for optical resins has been increasing, and there has been a demand for resins having excellent heat resistance and light resistance, low water absorption, and high transparency. However, conventional optical resins do not have these required performances in a well-balanced manner and have various drawbacks as optical resins.

  For example, polymethyl methacrylate, polycarbonate and the like have been conventionally used as optical resins with high transparency. Polymethylmethacrylate is excellent in optical properties such as high transparency and low birefringence, but has the disadvantages that its dimensions are easily changed due to its large water absorption, and its heat resistance is also low. Polycarbonate, on the other hand, has a high glass transition temperature (Tg) and excellent heat resistance, but has a disadvantage that it has a slightly high water absorption and is easily hydrolyzed by alkali.

  As an optical resin having high heat resistance, low water absorption, and excellent transparency, a ring-opening polymer hydrogenated product of a norbornene monomer and an addition copolymer of a norbornene monomer and ethylene are known. (Patent Documents 1 to 4). However, the tetracyclododecene polycyclic monomer used as the norbornene-based monomer is not always easy to produce, and it is necessary to use rare metals such as molybdenum and tungsten chloride as the polymerization catalyst.

  A β-pinene-based polymer has been proposed as an optical resin that has improved the above problems (Patent Document 5, Non-Patent Documents 1 and 2). The β-pinene polymer is a material having high heat resistance and low water absorption. It has also attracted attention as a carbon neutral material that suppresses the emission of carbon dioxide, which has become a problem in recent years. However, there has been no β-pinene polymer that has both higher heat resistance and light resistance. That is, the copolymer of β-pinene and indene described in Patent Document 5 (Examples 7 to 12) has high heat resistance, but olefinic double bonds derived from β-pinene and aromatic rings derived from indene remain. In addition, since it is easily oxidized and deteriorated, it has a problem that it is easily colored by light or heat. Moreover, although the β-pinene-based polymer described in Non-Patent Document 1 has an example of high light resistance, in that case, the heat resistance is insufficient.

JP-A 64-24826 JP 60-168708 A Japanese Patent Laid-Open No. 61-115912 JP 61-120816 A JP 2002-121231 A

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

  Accordingly, an object of the present invention is to provide a β-pinene copolymer having excellent heat resistance and light resistance, low water absorption and high transparency, and a molded product thereof.

That is, the present invention
a β-pinene copolymer comprising 30 to 80% by mass of β-pinene units and 70 to 20% by mass of aromatic monomer units, wherein 80 mol% or more of olefinic double bonds are hydrogenated, and It is a molded body made of the β-pinene copolymer.

The present invention also provides
It is characterized in that an olefinic double bond and an aromatic ring are hydrogenated in the presence of a palladium catalyst in which a copolymer obtained by copolymerizing β-pinene and an aromatic monomer is fixed to carbon. This is a method for producing the β-pinene copolymer.

  Since the β-pinene copolymer of the present invention is excellent in heat resistance and light resistance, has low water absorption and high transparency, it is particularly suitable for optical applications.

[I] Copolymer Composed of β-Pinene and Aromatic Monomer The β-pinene copolymer of the present invention is a copolymer containing β-pinene units and aromatic monomer units as structural units. This is a polymer obtained by hydrogenating the coalescence. The copolymer used for hydrogenation is obtained by copolymerizing monomers including β-pinene and an aromatic monomer.

.Beta.-Pinene Any known beta-pinene for use in the present invention 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.

-Aromatic monomer The aromatic monomer used in the present invention is not particularly limited as long as it is a polymerizable monomer having an aromatic group. For example, styrene, α-methylstyrene, 3 -Methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene, indene and the like can be mentioned. From the viewpoint of availability and easy copolymerization with β-pinene, styrene, α-methylstyrene, and indene are preferable. These aromatic monomers may be used alone or in combination of two or more.

  The copolymer used in the present invention is a copolymer obtained by polymerizing the above β-pinene and an aromatic monomer in combination at a predetermined copolymerization ratio. Specific examples of the copolymer include β-pinene / styrene copolymer, β-pinene / α-methylstyrene copolymer, β-pinene / 3-methylstyrene copolymer, β-pinene / 4-methylstyrene copolymer. Polymer, β-pinene / 4-ethylstyrene copolymer, β-pinene / 4-t-butylstyrene copolymer, β-pinene / 1-vinylnaphthalene copolymer, β-pinene / indene copolymer, etc. Is mentioned.

  The structure of the copolymer is not particularly limited, and any of random, block and tapered copolymers may be used. The copolymer is particularly preferably a random copolymer from the viewpoint of heat resistance.

  The mass ratio (β-pinene / aromatic monomer) of β-pinene units and aromatic monomer units in the copolymer used in the present invention is the heat resistance of the copolymer obtained after the hydrogenation reaction. From the viewpoint of property and mechanical strength, a range of 30/70 to 80/20 is preferable, and a range of 40/60 to 80/20 is more preferable. If the amount of β-pinene is too small, the heat resistance of the copolymer obtained after hydrogenation becomes low, and if the amount of β-pinene is too large, the copolymer obtained after hydrogenation becomes brittle.

-Other copolymerization monomer The copolymer of this invention may contain the other monomer unit copolymerizable with (beta) -pinene and an aromatic monomer as a structural unit. The copolymerizable monomer is not particularly limited as long as it is a vinyl monomer. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic monomers such as butyl, 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate; maleic anhydride, maleic acid, fumaric acid, maleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, and norbornene; Oil-derived double bond-containing compounds; vinyl acetate, piva Examples thereof include vinyl phosphate, 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 and an aromatic monomer, the copolymerization amount is preferably 0.001 to 20 mol% per all monomer units in the polymer, 10 mol% is more preferable. If the amount of copolymerization is too large, polymerization may become difficult, and heat resistance often decreases.

-Number average molecular weight The number average molecular weight of the copolymer containing β-pinene and aromatic monomer used in the present invention is not particularly limited, but mechanical properties and processability of the copolymer obtained after hydrogenation. In view of the above, about 10,000 to 1,000,000 g / mol is preferable. If the number average molecular weight is too small, the mechanical strength is insufficient, 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.

-Hydride The copolymer used for hydrogenation has an olefinic double bond of a cyclohexene ring derived from a β-pinene unit and an aromatic ring derived from an aromatic monomer.

The hydrogenated copolymer of the present invention preferably has an olefinic double bond derived from β-pinene at 20 mol% based on β-pinene units in the copolymer in order to prevent deterioration due to oxygen in the air. Below, more preferably 10 mol% or less, still more preferably 1 mol% or less, and most preferably 0.5 mol% or less. The β-pinene-based copolymer of the present invention is not generally defined by the copolymerization ratio, but it is 4.5 to 6 ppm in its ¹ H-NMR spectrum [the proton of tetramethylsilane (TMS) is 0 ppm]. The ratio of the integral value of protons to the integral value of all protons (4.5-6 ppm proton integral value / total proton integral value) is preferably 1.1 × 10 ⁻² or less, more preferably 5 .6 × 10 ⁻³ or less. When the said ratio is large, the quantity of an olefinic double bond may increase and may deteriorate easily.

The hydrogenated copolymer of the present invention preferably has an aromatic ring derived from an aromatic monomer in the aromatic monomer unit in the copolymer in order to improve heat resistance and transmittance. It is 50 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and most preferably 1 mol% or less. The β-pinene-based copolymer of the present invention is not generally determined by the copolymerization ratio, but its ¹ H-NMR spectrum [tetramethylsilane (TMS) proton is 0 ppm] in 6-8 ppm proton The ratio of the integral value of all protons to the integral value of all protons (6-8 ppm proton integral value / total proton integral value) is preferably 4.3 × 10 ⁻² or less, more preferably 2.2 × 10. ^-2 or less.

・ Glass transition temperature (Tg)
The β-pinene copolymer of the present invention is characterized in that Tg is remarkably increased as compared with a hydride of a β-pinene homopolymer and compared with a copolymer before hydrogenation. Tg can be measured by differential scanning calorimetry (DSC).

  Tg cannot be generally defined by the type and content of the aromatic monomer used, the hydrogenation rate of the olefinic double bond, and the hydrogenation rate of the aromatic ring, but is preferably 135 ° C to 250 ° C, more preferably 140 ° C -240 degreeC is further more preferable. When Tg is low, heat resistance is insufficient, and when it is too high, the β-pinene copolymer becomes brittle.

-Total light transmittance The β-pinene copolymer of the present invention preferably has a high total light transmittance particularly when used in an optical material. The total light transmittance of the β-pinene copolymer is preferably 80% or more, more preferably 85% or more. The total light transmittance is measured according to JIS-K-7361-1-1997 “Plastics—Test method for total light transmittance of transparent material—Part 1: Jingle beam method”.

-Light resistance The β-pinene copolymer of the present invention preferably has higher light resistance and weather resistance. For example, an accelerated exposure test for 100 hours of 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-K-7373 is 10 or less. Is preferable, 5 or less is more preferable, and 2 or less is most preferable.

-Heat resistance According to the present invention, a copolymer having a high 5% mass reduction temperature can be obtained. The 5% mass reduction temperature of the β-pinene copolymer of the present invention is preferably 300 ° C. or higher, and more preferably 320 ° C. or higher. The 5% mass reduction temperature means a temperature at which the mass is reduced by 5% as measured by a thermobalance (TGA) according to JIS-K-7120-1987 “Thermo mass measurement method of plastics”.

[II] Production Method / Polymerization Reaction of β-Pinene Copolymer A copolymer containing β-pinene and an aromatic monomer as a structural unit is a cationic polymerization, radical polymerization method, coordination polymerization method, etc. It can be obtained by a known method. From the viewpoint that it can be easily carried out industrially and a high molecular weight product can be obtained, a cationic polymerization method is particularly preferred.

Cationic polymerization The 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 can be performed by the well-known method of a nonpatent literature 1, a nonpatent literature 2, 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 aromatic monomers, 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 10000 parts by mass with respect to 100 parts by mass of β-pinene and aromatic monomers. -1000 mass parts 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.

-Initiator The polymerization initiator for performing cationic polymerization is not particularly limited as long as it is a compound that generates more cations as 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.

-C (-R < ¹ >) (-R < ² >)-X

In the formula, R ¹ represents hydrogen, an alkyl group, or an aryl group, R ² represents hydrogen, an alkyl group, or an aryl group, and X represents a halogen, an alkoxy group, an acyloxy group, or a hydroxyl group.

  Since the amount of the polymerization initiator used in the cationic polymerization varies depending on the molecular weight of the target copolymer, it is difficult to generally define the amount used, but the amount of β-pinene and aromatic monomer is 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 copolymer obtained will become small and a copolymer will become weak.

-Electron-donating compound In the present invention, when cationic polymerization is performed, the polymerization reaction can be further controlled 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 copolymer that can produce a large amount of low molecular weight compounds is lowered. 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 present invention, the reaction temperature in the case of performing cationic polymerization is usually preferably from -120 ° C to 60 ° C, more preferably from -80 ° C to 0 ° C, and most preferably from -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.

  In the present invention, the reaction pressure for carrying out 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 copolymer after the cationic polymerization is isolated from the solution by, 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.

[III] Hydrogenation The hydrogenated β-pinene copolymer according to the present invention can be obtained by a hydrogenation reaction, but the hydrogenation method is not particularly limited, and any known method can be used. Can be taken.

-Hydrogenation catalyst In this invention, what can hydrogenate an olefin compound and an aromatic compound can be used for the catalyst in the case of performing hydrogenation reaction. Usually, a heterogeneous catalyst or a homogeneous catalyst is used.

-Heterogeneous catalyst In the present invention, 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 nickel, nickel alumina, 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 Examples thereof include supported metal catalysts such as diatomaceous earth, iridium carbon, iridium calcium carbonate, cobalt silica, cobalt alumina, cobalt zeolite, cobalt diatomaceous earth, cobalt carbon, and 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.

-Homogeneous catalyst In the present invention, the catalyst when the hydrogenation reaction is carried out using a homogeneous catalyst is not particularly limited, but specific examples include a catalyst comprising a transition metal compound and alkylaluminum or alkyllithium. It is done. Specific examples of transition metal compounds include nickel salts such as nickel acetate, nickel octylate and nickel acetylacetonate, cobalt salts such as cobalt acetate, cobalt octylate and cobalt acetylacetonate, titanocene dichloride, zirconocene dichloride and the like. It is done. Specific examples of alkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum and the like. Specific examples of the alkyl lithium include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium and the like.
The homogeneous catalyst may be used alone or in combination. Moreover, you may mix and use a heterogeneous catalyst.
When the hydrogenation reaction is carried out in the present invention, the copolymer is hydrogenated, so that the reaction activity is generally low for low molecular weight 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 hydrogenation reaction in this invention, it is normally performed in an organic solvent. Although the solvent which can be used for this invention is not specifically limited, What dissolves a copolymer easily is preferable. Since the solvent differs depending on the comonomer, it is difficult to limit, but specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene; pentane, hexane, heptane, octane, Aliphatic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, tricyclodecane; halogens such as methyl chloride, methylene chloride, propane chloride, butane chloride, 1,2-dichloroethane, 1,1,2-trichloroethylene Hydrocarbon solvents; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether and dibutyl ether, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol Alcohol The solvent or the like can be used.

  When the hydrogenation reaction is carried out in the present invention, 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.

  When performing hydrogenation reaction in this invention, the usage-amount of an organic solvent is the quantity used as the density | concentration of a copolymer from 1 mass% or more and 30 mass% or less. When it is carried out at less than 1% by mass, the productivity is remarkably reduced, and when it is 30% by mass or more, the solution viscosity is remarkably increased and the mixing efficiency is lowered.

-Reaction pressure When performing the hydrogenation reaction in the present invention, the pressure of the hydrogenation reaction may vary depending on the catalyst used and cannot necessarily be specified, but usually the total pressure of the hydrogenation reaction is 0.1 MPa. -30 MPa, preferably 0.5 MPa to 20 MPa, more preferably 1 MPa to 15 MPa. In general, the higher the hydrogen gas partial pressure is, the more advantageous it is for hydrogenation. However, when the pressure is 30 MPa or more, the cost for the equipment for boosting pressure and the equipment having a pressure-resistant structure increases, which is not desirable.
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 performing a hydrogenation reaction in the present invention, the temperature of the hydrogenation reaction may vary depending on the catalyst used and cannot always be specified, but is usually 10 to 300 ° C, preferably Is 60 ° C to 250 ° C, more preferably 70 ° C to 220 ° C. 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.

-Embodiment When performing hydrogenation reaction in this invention, 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.

  Depending on the type of hydrogenation catalyst used, copolymer concentration, reaction type, etc., the amount of catalyst used is difficult to limit because it varies, but generally when using a heterogeneous catalyst in a suspended bed, 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. 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.

The used hydrogenation catalyst can be separated from the 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 using these separation methods, a trace amount of metal components may remain in the 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 hydrogenated β-pinene copolymer can be prepared by, for example, re-precipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. The product can be separated and obtained from the reaction mixture by a normal operation for isolation from the reaction mixture.

  The β-pinene copolymer of the present invention may be used alone, or may be polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, It can also be used as a composition blended with other polymers such as polystyrene and styrenic block copolymers. 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.

[IV] Molded Product A molded product of the β-pinene copolymer of the present invention can be obtained according to a conventional method. As the molding method, a known method such as an injection molding method, a hot press molding method, an extrusion molding method, a cutting method, or a method using an active energy ray-curable resin is appropriately employed. Among these, from the viewpoint of productivity, an injection molding method, a hot press molding method, and an extrusion molding method are preferably used.

-Optical material The β-pinene copolymer of the present invention can be used for various optical materials, and its range is not particularly limited, but it is excellent in heat resistance, and is required to have low water absorption and high transparency. Suitable for material. 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.

-Light guide The light guide can be formed in various known shapes, for example, various forms such as a plate shape, a block shape, a rod shape, a bent shape, and a curved shape, and at least on one side. The ones with dots printed by screen printing, or linear patterns such as V-grooves, hemispherical lens-like irregularities, and textured patterns formed on the surface of the light guide are also targeted.

-Light diffusible molded body The light diffusible molded body is a mixture of the above-mentioned β-pinene copolymer and further containing a light diffusing agent similar to the conventional one, and the obtained light diffusibility. A molded body having a predetermined shape such as a plate shape or a block shape is formed using the composition.
Functional thin film A functional thin film formed by coating on at least one surface of a substrate using a β-pinene copolymer is not particularly limited, but preferably an antistatic layer, an antireflection layer, a hard It is a thin film having functionality such as a coat layer, a transparent conductive layer, and an antiglare layer.

Optical film An optical film using a β-pinene-based copolymer is particularly suitable for a polarizing plate protective film. The method for forming such an optical film is not particularly limited, and various conventionally known methods such as a solution casting method and a melt extrusion method can be employed. Among these, the melt extrusion method that does not use a solvent is preferably employed from the viewpoints of the global environment, work environment, and manufacturing cost. Further, in order to particularly improve optical performance such as phase difference, a solution casting method is also advantageously used.

Lens sheet A lens sheet is a lens unit composed of a lens group formed of one or a plurality of lens shapes formed on at least one of the sheet main surfaces, and changes the direction of light rays irradiated to the sheet. It refers to those having functions such as condensing, refraction, reflection, and dispersion. Such lens sheets generally include what are called prism sheets, Fresnel lens sheets, lenticular lens sheets, microlens array sheets, and the like.

-Plastic lens The plastic lens means a plastic molded product having a lens function, and is not particularly limited, but includes a spectacle lens, a camera lens, a binocular lens, a microscope lens, a projector lens, an fθ lens, a pickup lens, and the like. Various lenses are applicable.

・ Vehicle lamps “Lamps” for vehicle lamps are used as having at least a light source and a lamp cover, and “vehicles” are two-wheeled vehicles, three-wheeled vehicles, four-wheeled vehicles, and other vehicles. It is used to mean vehicles in a broad sense such as railway vehicles, forklifts and other industrial vehicles. “Vehicle lamp” means a lamp for illumination, identification, or signage mounted on such various vehicles, and is not particularly limited, but includes a headlamp, a taillamp, a brake. A lamp (stop lamp), a direction indicator lamp (so-called blinker), a vehicle width lamp, a reverse lamp, and the like are applicable.

-Medical equipment Examples of medical equipment include liquid chemical containers for injection, ampoules, prefilled syringes, infusion bags, solid chemical containers, eye drops containers, instillation containers, etc., liquid or powder, solid chemical containers Sample containers such as sampling tubes for blood tests, blood collection tubes and specimen containers; sterilization containers such as scalpels, chestnuts (forceps), gauze and contact lenses; medical instruments such as syringes; beakers, petri dishes, Medical laboratory instruments such as flasks; optical parts such as plastic lenses for medical examinations; medical infusion tubes, piping, fittings, piping materials such as valves; artificial organs such as denture bases, artificial hearts, artificial tooth roots, and parts thereof Is exemplified.

  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
After fully replacing the well-dried glass flask with a cock with nitrogen, 1100 parts by mass of dehydrated N-hexane, 1100 parts by mass of dehydrated methylene chloride, and 23 parts by mass of distilled and purified β-pinene. Part, 20 parts by mass of α-methylstyrene and 4.5 parts by mass of dehydrated triethylamine were added and cooled to a temperature of −78 ° C. Furthermore, 70 mass parts of 1.0 mol / L hexane solution of ethylaluminum dichloride was added while stirring at −78 ° C. to initiate polymerization. After polymerization for 10 minutes, 10 parts by mass of methanol was added to terminate the polymerization. Then, after reducing the pressure at room temperature to remove methylene chloride, an aqueous solution obtained by adding 20 parts by mass of citric acid to 800 parts by mass of distilled water was added and stirred for 30 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the catalyst was removed. The methylcyclohexane layer thus obtained was reprecipitated in 10000 parts by mass of a mixed solvent of methanol / acetone (60/30 vol%), and then sufficiently dried to obtain a β-pinene / α-methylstyrene copolymer (A1). 39 parts by mass were obtained. The obtained β-pinene / α-methylstyrene copolymer (A1) has a weight average molecular weight of 33,000, a number average molecular weight of 20,000, and β-pinene / α-methylstyrene determined from ¹ H-NMR. The mass ratio of the units was 51/49.

Reference example 2
After thoroughly substituting the well-dried glass flask with a cock with nitrogen, 1100 parts by mass of dehydrated N-hexane, 1100 parts by mass of dehydrated methylene chloride, and 37 parts by mass of distilled and purified β-pinene. Part, 8 parts by mass of α-methylstyrene, and 4.5 parts by mass of dehydrated triethylamine were added and cooled to a temperature of −78 ° C. Furthermore, 70 mass parts of 1.0 mol / L hexane solution of ethylaluminum dichloride was added while stirring at −78 ° C. to initiate polymerization. After polymerization for 10 minutes, 10 parts by mass of methanol was added to terminate the polymerization. Then, after reducing the pressure at room temperature to remove methylene chloride, an aqueous solution obtained by adding 20 parts by mass of citric acid to 800 parts by mass of distilled water was added and stirred for 30 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the catalyst was removed. The methylcyclohexane layer thus obtained was reprecipitated in 10000 parts by mass of a mixed solvent of methanol / acetone (60/30 vol%), and then sufficiently dried to obtain a β-pinene / α-methylstyrene copolymer (A2). 39 parts by mass were obtained. The obtained β-pinene / α-methylstyrene copolymer (A2) has a weight average molecular weight of 38,000, a number average molecular weight of 22,000, and β-pinene / α-methylstyrene determined from ¹ H-NMR. The mass ratio of the units was 81/19.

Reference example 3
After thoroughly substituting the well-dried flask with a glass cock with nitrogen, 208 parts by mass of dehydrated N-hexane, 240 parts by mass of dehydrated methylene chloride and 0.58 parts by mass of dehydrated diethyl ether were added, Cooled down. Furthermore, 8.2 mass parts of 1.0 mol / L hexane solutions of ethylaluminum dichloride were added, stirring at -78 degreeC. Further, when 4.4 parts by mass of a 0.1 mol / L hexane solution of p-dicumulyl chloride was added while maintaining at -78 ° C, the color changed to red. Immediately after addition of a mixed monomer solution of 38 parts by mass of β-pinene, 8 parts by mass of α-methylstyrene, and 1.6 parts by mass of p-diisopropenylbenzene, which were purified by distillation, the solution gradually became dark blue. The viscosity increased. After completion of the addition of the mixed monomer solution, 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 45 parts by mass of β-pinene / α-methylstyrene copolymer (A3). It was. The obtained β-pinene / α-methylstyrene copolymer (A3) has a weight average molecular weight of 150,000, a number average molecular weight of 39,000, and a β-pinene / α-methylstyrene unit determined from ¹ H-NMR. The mass ratio was 78/22, and the glass transition temperature was 103 ° C.

Reference example 4
The same procedure as in Reference Example 3 was conducted except that the mixed monomer solution was changed to a mixed monomer solution comprising 23 parts by mass of purified β-pinene, 20 parts by mass of α-methylstyrene, and 1.6 parts by mass of p-diisopropenylbenzene. 44 parts by mass of β-pinene / α-methylstyrene copolymer (A4) was obtained. The obtained β-pinene / α-methylstyrene copolymer (A4) has a weight average molecular weight of 199,000, a number average molecular weight of 41,000, and a β-pinene / α-methylstyrene unit determined from ¹ H-NMR. The mass ratio was 48/52, and the glass transition temperature was 133 ° C.

Reference Example 5
44 parts by mass of β-pinene / indene copolymer (A5) was obtained in the same manner as in Reference Example 3 except that the mixed monomer solution was changed to a mixed monomer solution having 23 parts by mass of purified β-pinene and 20 parts by mass of indene. Obtained. The obtained β-pinene / indene copolymer (A5) had a weight average molecular weight of 59,400, a number average molecular weight of 25,900, and a mass ratio of β-pinene / indene unit determined from ¹ H-NMR of 52 / 48. The glass transition temperature was 140 ° C.

Example 1
Next, 123 parts by mass of cyclohexane and 30 parts by mass of the β-pinene / α-methylstyrene copolymer (A1) obtained above are accommodated and stirred in a pressure vessel equipped with a stirrer purged with nitrogen. Thus, the β-pinene / α-methylstyrene copolymer (A1) was completely dissolved. Thereafter, 15 parts by mass of 5% palladium-supported carbon (product number: E1002NN / W manufactured by Evonik Degussa Japan Co., Ltd.) was added as a hydrogenation catalyst, stirred and sufficiently dispersed. After replacing with hydrogen and stirring, reaction was performed at 130 ° C. and hydrogen pressure: 20 MPa for 15 hours, and then returned to normal pressure. The solution after the reaction was filtered through a 0.5 μm Teflon (registered trademark) 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%). After sufficiently drying, 29 parts by mass of a β-pinene copolymer (H1) was obtained. When the ¹ H-NMR of the β-pinene copolymer (H1) thus obtained was measured, the remaining olefinic double bond was 0.4 mol%, and the remaining aromatic ring was 2.3 mol%. there were. The glass transition temperature was 156 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm protons to the integral value of all protons is 5.2 × 10 ⁻³ , and the integral value of 4.5-6 ppm protons to the integral value of all protons Was 2.1 × 10 ⁻⁴ . The obtained β-pinene copolymer (H1) had a weight average molecular weight of 31,000 and a number average molecular weight of 18,400. The evaluation results are shown in Table 1.

Example 2
Subsequently, β-pinene was changed in the same manner as in Example 1 except that β-pinene / α-methylstyrene copolymer (A2) was used instead of β-pinene / α-methylstyrene copolymer (A1). A system copolymer (H2) was obtained. When ¹ H-NMR of the β-pinene copolymer (H2) thus obtained was measured, the remaining olefinic double bond was 1.6 mol%, and the remaining aromatic ring was 2.5 mol%. there were. The glass transition temperature was 142 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm protons to the integral value of all protons is 5.5 × 10 ⁻³ , and the ratio of 4.5-6 ppm protons to the integral value of all protons Was 9.0 × 10 ⁻⁴ . The obtained β-pinene copolymer (H2) had a weight average molecular weight of 36,000 and a number average molecular weight of 20,100. The evaluation results are shown in Table 1.

Example 3
A β-pinene copolymer was used in the same manner as in Example 1 except that the β-pinene / α-methylstyrene copolymer (A3) was used instead of the β-pinene / α-methylstyrene copolymer (A1). A polymer (H3) was obtained. When the ¹ H-NMR of the β-pinene copolymer (H3) thus obtained was measured, the remaining olefinic double bond was 1.9 mol%, and the remaining aromatic ring was 8.1 mol%. there were. The glass transition temperature was 144 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm proton to the integral value of all protons is 5.6 × 10 ⁻³ , and the ratio of 4.5-6 ppm proton to the integral value of all protons Was 9.1 × 10 ⁻⁴ . The obtained β-pinene copolymer (H3) had a weight average molecular weight of 98,000 and a number average molecular weight of 29,300. The evaluation results are shown in Table 1.

Example 4
The β-pinene copolymer was used in the same manner as in Example 1 except that the β-pinene / α-methylstyrene copolymer (A4) was used instead of the β-pinene / α-methylstyrene copolymer (A1). A polymer (H4) was obtained. When the ¹ H-NMR of the β-pinene copolymer (H4) thus obtained was measured, the remaining olefinic double bond was 0.6 mol%, and the remaining aromatic ring was 2.8 mol%. there were. The glass transition temperature was 160 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm protons to the integral value of all protons is 5.2 × 10 ⁻³ , and the integral value of 4.5-6 ppm protons to the integral value of all protons Was 2.1 × 10 ⁻⁴ . The obtained β-pinene copolymer (H4) had a weight average molecular weight of 79,200 and a number average molecular weight of 24,300. The evaluation results are shown in Table 1.

Example 5
A β-pinene copolymer (A) was used in the same manner as in Example 1 except that a β-pinene / indene copolymer (A5) was used instead of the β-pinene / α-methylstyrene copolymer (A1). H5) was obtained. When ¹ H-NMR of the β-pinene copolymer (H5) thus obtained was measured, the remaining olefinic double bond was 2.9 mol%, and the remaining aromatic ring was 9.8 mol%. there were. The glass transition temperature was 188 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm protons to the integral value of all protons is 1.3 × 10 ⁻² , and the ratio of 4.5-6 ppm protons to the integral value of all protons Was 9.2 × 10 ⁻⁴ . The obtained β-pinene copolymer (H5) had a weight average molecular weight of 41,000 and a number average molecular weight of 23,800. The evaluation results are shown in Table 1.

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, HLC-8020 (product number) manufactured by Tosoh Co., Ltd. is used as the GPC device, and TSKgel / GMH-M manufactured by Tosoh Co., Ltd. and one G2000H are connected in series as the column. Using.
○ Residual double bond rate: Measured 1000 times at room temperature using a 400 MHz magnet nuclear magnetic resonance apparatus manufactured by JEOL. ¹ H-NMR spectrum obtained (the proton of tetramethylsilane (TMS) is 0 ppm). The integral value of 4.5-6 ppm was defined as β-pinene-derived olefinic double bond, the integral value of 6-8 ppm was defined as an aromatic ring, and the residual 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 Co., Ltd. was used as the measuring device.
-Total light transmittance It measured based on JIS-K-7361-1 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 Co., Ltd.) was used. YI was measured according to JIS-K-7373. And it evaluated according to the following criteria.
ΔYI = (YI after 100 hours of UV exposure) − (YI before UV exposure)
○: ΔYI ≦ 10 Good long-term light resistance ×: 10 <ΔYI Long-term light resistance is poor

Comparative Example 1
After thoroughly substituting the well-dried flask with a glass cock with nitrogen, 1100 parts by mass of dehydrated N-hexane, 1100 parts by mass of dehydrated methylene chloride, and 40 parts by mass of distilled purified β-pinene. And 4.5 parts by weight of dehydrated triethylamine were added and cooled to a temperature of -78 ° C. Furthermore, 70 mass parts of 1.0 mol / L hexane solution of ethylaluminum dichloride was added while stirring at −78 ° C. to initiate polymerization. After polymerization for 10 minutes, 10 parts by mass of methanol was added to terminate the polymerization. Then, after reducing the pressure at room temperature to remove methylene chloride, an aqueous solution obtained by adding 20 parts by mass of citric acid to 800 parts by mass of distilled water was added and stirred for 30 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the catalyst was removed. The methylcyclohexane layer thus obtained was reprecipitated in 10000 parts by mass of a mixed solvent of methanol / acetone (60/30 vol%) and then sufficiently dried to obtain 39 parts by mass of β-pinene polymer (B1). . The obtained β-pinene polymer (B1) had a weight average molecular weight of 53,000 and a number average molecular weight of 32,000.

In a pressure vessel equipped with a stirrer purged with nitrogen, 127 parts by mass of cyclohexane and 25 parts by mass of the β-pinene polymer (B1) obtained above were accommodated and stirred to obtain a β-pinene polymer ( A1) was completely dissolved. Thereafter, 7.5 parts by mass of 5% palladium-supported alumina powder (manufactured by N.E. Chemcat Co., Ltd.) was added as a hydrogenation catalyst, and the mixture was stirred and sufficiently dispersed. The reaction was carried out at 160 ° C. and hydrogen pressure: 5 MPa for 25 hours with stirring, and then returned to normal pressure. The solution after the reaction was filtered through a 0.5 μm Teflon (registered trademark) 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%). After sufficiently drying, 24 parts by mass of the β-pinene polymer (B2) was obtained. When ¹ H-NMR of the β-pinene polymer (B2) thus obtained was measured, the remaining olefinic double bond was 1.7 mol%. The glass transition temperature was 129 ° C. In ¹ H-NMR, the ratio of the integral value of 6 to 8 ppm proton to the integral value of all protons is 9.1 × 10 ⁻⁴ , and the ratio of the integral value of 4.5 to 6 ppm proton to the integral value of all protons Was 9.7 × 10 ⁻⁴ . The obtained β-pinene polymer (B2) had a weight average molecular weight of 51,900 and a number average molecular weight of 31,600. The evaluation results are shown in Table 2.

Comparative Example 2
The β-pinene / α-methylstyrene copolymer (A1) obtained in Reference Example 1 was used as this comparative example.

Comparative Example 3
The β-pinene / α-methylstyrene copolymer (A2) obtained in Reference Example 2 was used as this comparative example. The evaluation results are shown in Table 2.

Comparative Example 4
An indene / β-pinene copolymer (B3) was obtained in the same manner as in Example 12 of JP-A No. 2002-121231. The resulting indene / β-pinene copolymer (B3) had a weight average molecular weight of 64,000 and a number average molecular weight of 24,300. Table 2 shows the evaluation results of the indene / β-pinene copolymer (B3).

Comparative Example 5
A β-pinene / α-methylstyrene copolymer (in the same manner as in Reference Example 3 except that the mixed monomer solution was changed to a mixed monomer solution consisting of 42 parts by mass of purified β-pinene and 4 parts by mass of α-methylstyrene. A6) 45 parts by mass were obtained. The obtained β-pinene / α-methylstyrene copolymer (A6) has a weight average molecular weight of 43,000, a number average molecular weight of 23,700, and a β-pinene / α-methylstyrene unit determined from ¹ H-NMR. The mass ratio was 90/10, and the glass transition temperature was 97 ° C.

Comparative Example 6
In the same manner as in Example 1, except that β-pinene / α-methylstyrene copolymer (A6) was used instead of β-pinene / α-methylstyrene copolymer (A1), a β-pinene copolymer was used. A polymer (H6) was obtained. When the ¹ H-NMR of the β-pinene copolymer (H6) thus obtained was measured, the remaining olefinic double bond was 0.5 mol%, and the remaining aromatic ring was 3.7 mol%. there were. The glass transition temperature was 134 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm protons to the integral value of all protons is 5.2 × 10 ⁻³ , and the integral value of 4.5-6 ppm protons to the integral value of all protons Was 2.5 × 10 ⁻⁴ . The obtained β-pinene copolymer (H6) had a weight average molecular weight of 39,000 and a number average molecular weight of 23,500. The evaluation results are shown in Table 2.

Reference Example 6 [Preparation of hydrogenation catalyst]
Add 29.2 ml of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.), dissolved beforehand in cyclohexane at a concentration of 20%, to a nitrogen-substituted glass eggplant flask under a nitrogen stream and cool to 0 ° C. did. 7.4 ml of a toluene solution (nickel 6%) of nickel 2-ethylhexanoate (manufactured by Kishida Chemical Co., Ltd.) was added thereto under a nitrogen stream to prepare a homogeneous hydrogenation catalyst.

Comparative Example 7
In a pressure vessel equipped with a stirring device purged with nitrogen, 123 parts by mass of cyclohexane and 30 parts by mass of the β-pinene / α-methylstyrene copolymer (A1) obtained above were accommodated and stirred. The β-pinene / α-methylstyrene copolymer (A1) was completely dissolved. The inside of the pressure vessel was sufficiently replaced with hydrogen, and 7 parts by mass of the hydrogenation catalyst prepared in Reference Example 6 was added while stirring at 1000 rpm at room temperature. Immediately, the pressure was increased to 1 MPa with hydrogen and the temperature was raised to 50 ° C. After raising the temperature to 50 ° C., 7 parts by mass of a hydrogenation catalyst was further added, and the temperature was raised to 120 ° C. After reacting at 120 ° C. for 9 hours, the pressure was returned to normal pressure and room temperature. An aqueous solution obtained by adding 8.1 parts by mass of citric acid and 4.8 parts by mass of a 30% aqueous hydrogen peroxide solution to 100 parts by mass of distilled water was added to a pressure vessel and stirred for 30 minutes. The aqueous layer was extracted, washed with distilled water until the aqueous layer became neutral, and the catalyst was removed. The obtained cyclohexane layer was reprecipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%), and then sufficiently dried, and 29 parts by mass of the β-pinene copolymer (H7) was added. Obtained. When the ¹ H-NMR of the β-pinene copolymer (H7) thus obtained was measured, the remaining olefinic double bond was 50 mol% and the remaining aromatic ring was 94 mol%. The glass transition temperature was 139 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm proton to the integral value of all protons is 0.17, and the ratio of the integral value of 4.5-6 ppm protons to the integral value of all protons is 0.019. Met. The obtained β-pinene copolymer (H7) had a weight average molecular weight of 29,600 and a number average molecular weight of 17,100. The evaluation results are shown in Table 2.

From the examples, β-pinene units consisting of 30 to 80% by mass of β-pinene units and 70 to 20% by mass of aromatic monomer units, hydrogenated and added with 80 mol% or more of olefinic double bonds It can be seen that the coalescence has high heat resistance and is excellent in total light transmittance and light resistance.
From Examples and Comparative Examples 1, 5 and 6, it can be seen that heat resistance is low when the aromatic monomer is not included or is less than 20% by mass.
From Examples and Comparative Examples 2, Comparative Example 3, Comparative Example 4, and Comparative Example 7, it can be seen that light resistance and heat resistance are improved by hydrogenating 80 mol% or more of olefinic double bonds.
From Example 1 and Comparative Example 7, hydrogenation of the olefinic double bond and aromatic ring in the presence of a palladium catalyst fixed on carbon resulted in an olefinic double bond of 90 mol% or more and aromaticity. It can be seen that aromatics derived from monomers are hydrogenated by 80% or more.

Claims (6)

  A β-pinene copolymer comprising 30 to 80% by mass of β-pinene units and 70 to 20% by mass of aromatic monomer units, and hydrogenated and added with 80 mol% or more of olefinic double bonds.   The β-pinene copolymer according to claim 1, wherein an aromatic ring derived from an aromatic monomer is hydrogenated by 50 mol% or more.   The β-pinene copolymer according to claim 1, wherein the aromatic monomer is at least one selected from styrene, α-methylstyrene, and indene.   2. The β-pinene copolymer according to claim 1, wherein the olefinic double bond is 90 mol% or more and the aromatic derived from the aromatic monomer is hydrogenated 80% or more.   A molded body comprising the β-pinene copolymer according to claim 1.   It is characterized in that an olefinic double bond and an aromatic ring are hydrogenated in the presence of a palladium catalyst in which a copolymer obtained by copolymerizing β-pinene and an aromatic monomer is fixed to carbon. The manufacturing method of the beta-pinene-type copolymer of Claim 1.