WO2009125828A1 - Β-pinene-based polymer and molded article comprising the same - Google Patents

Abstract

Provided are a β-pinene-based polymer, which has an excellent heat resistance, an excellent light resistance, a low water absorptivity and a high transparency; and a molded article thereof. A β-pinene-based polymer which is a polymer containing 60% by mass or more of a β-pinene unit, wherein 1% by mol or more but not more than 10% by mol of 6-membered rings derived from β-pinene are aromatic 6-membered rings or the p-phenylene group content is 0.55% by mass or more but not more than 5.5% by mass, and preferably 90% by mol or more of olefinic double bonds have been hydrogenated or the cyclohexene-1,4-diyl group content is 5.6% by mass or less; and a molded article which comprises this β-pinene-based polymer.

Description

β-pinene polymer and molded article comprising the same

The present invention relates to a β-pinene polymer having both a high refractive index and a low birefringence, a molded product comprising the same, and a method for producing the same.

In recent years, the demand for optical resins has become higher, and there is 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 highly transparent optical resins. 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.

Β-pinene-based polymers have been proposed as optical resins that have 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. Moreover, it attracts attention also as a carbon neutral material which suppresses the discharge | emission of the carbon dioxide which has become a problem in recent years (nonpatent literature 1). However, since the specific gravity is small, the refractive index is small. In order to improve the refractive index, a method of copolymerizing with an aromatic vinyl monomer has been studied (Patent Document 5). The copolymer of β-pinene and indene described in Patent Document 5 (Examples 7 to 12) has high heat resistance, but has an olefinic double bond derived from β-pinene and an aromatic double bond derived from indene. Since it remains and is easily oxidized and deteriorated, it has a problem of being easily colored by light or heat. Further, when a monomer having an aromatic ring in the side chain such as indene is copolymerized, there is a problem that birefringence increases.

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

Accordingly, an object of the present invention is to provide a β-pinene-based polymer having a high refractive index while maintaining the inherent high heat resistance and light resistance, low water absorption, and high transparency, and a molded product thereof.

That is, the present invention
A polymer containing 60% by mass or more of β-pinene units, wherein a β-pinene-based polymer in which 1 mol% or more and 10 mol% or less of the 6-membered ring derived from β-pinene is an aromatic 6-membered ring And a molded body comprising the β-pinene-based polymer.

The present invention also provides
A polymer containing 60% by mass or more of β-pinene units, wherein the p-phenylene group is 0.55% by mass or more and 5.5% by mass or less, and the β-pinene polymer It is a molded body made of coalescence.

Furthermore, the present invention provides
Production of the above-mentioned β-pinene polymer wherein a polymer containing 60% by mass or more of β-pinene units is hydrogenated in the presence of a heterogeneous catalyst at a hydrogen pressure of 0.1 MPa to 25 MPa. Is the method.

The β-pinene polymer of the present invention is particularly suitable for optical applications because it has excellent heat resistance and light resistance, low water absorption, high refractive index, low birefringence and high transparency.

FIG. 3 is a diagram showing a ¹ H-NMR spectrum of a β-pinene polymer (H3) obtained in Example 3. Deuterated tetrahydrofuran was used as deuterated solvent. FIG. 3 is a diagram showing a ¹ H-NMR spectrum of a β-pinene polymer (B3) obtained in Comparative Example 3. Deuterated tetrahydrofuran was used as deuterated solvent.

[I] β-Pinene Polymer The β-pinene polymer of the present invention is a polymer obtained by hydrogenating a polymer containing β-pinene units.

Β-Pinene As the β-pinene monomer used in the present invention, known ones can be used. That is, 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 Copolymeric Monomer The polymer of the present invention may contain another monomer unit copolymerizable with β-pinene as a structural unit. 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 vinyl 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 carene; 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 0.001 to 50 mol%, and 0.01 to 20 mol% per total monomer unit of the polymer. More preferred is 0.01 to 10 mol%. If the amount of copolymerization is too large, polymerization may become difficult, and heat resistance often decreases. The monomer having an aromatic side chain is preferably less because the birefringence increases, and the amount of copolymerization is preferably 0.001 to 10 mol% per total monomer unit of the polymer, ˜5 mol% is most preferred.

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.

Number average molecular weight The number average molecular weight of the β-pinene polymer is not particularly limited, but is preferably from 600 to 1,000,000 g / mol from the viewpoint of mechanical properties and processability, more preferably from 10,000 to 500,000 g / mol. It is preferably 30,000 to 200,000, more 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.

-Hydride The polymer of the present invention can be obtained by hydrogenating (hydrogenating (hydrogenating)) an olefinic double bond of a cyclohexene ring, which is a 6-membered ring derived from a β-pinene unit. In the hydrogenation reaction, the dehydrogenation reaction of the cyclohexene ring proceeds at the same time as the hydrogenation reaction, although the amount is very small. The β-pinene-based polymer of the present invention is a polymer having a high content of an aromatic 6-membered ring derived from a cyclohexene ring while hydrogenating an olefinic double bond. Since the aromatic ring produced here is a 6-membered ring (p-phenylene group) derived from β-pinene, it is symmetric with respect to the main chain, and birefringence can be reduced.

In the β-pinene-based polymer of the present invention, in order to prevent deterioration due to oxygen in the air and to suppress coloring of the molded product, the olefinic double bond derived from β-pinene has an aromatic ring-forming unit in the polymer. It is preferably hydrogenated to 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less with respect to the removed β-pinene unit. The β-pinene-based polymer of the present invention has a ratio of the integral value of 4.5 to 6 ppm proton to the integral value of all protons in its ¹ H-NMR spectrum [the proton of tetramethylsilane (TMS) is 0 ppm]. (Integral value of proton of 4.5 to 6 ppm / Integral value of all protons) is preferably 1.1 × 10 ⁻² or less (in the case of β-pinene homopolymer, the hydrogenation rate is 80 mol% or more) More preferably, 8.5 × 10 ⁻³ or less (corresponding to a hydrogenation rate of 85 mol% or more), and even more preferably 5.6 × 10 ⁻³ or less (same as 90% by hydrogenation rate). Equivalent to the above). The cyclohexene-1,4-diyl group (—C ₆ H ₈ —) is preferably 10.7% by mass or less (corresponding to a hydrogenation rate of 80% by mol or more), more preferably 8.4% by mass or less. (Corresponding to a hydrogenation rate of 85 mol% or more), more preferably 5.6% by mass or less (corresponding to a hydrogenation rate of 90 mol% or more). When the said ratio is large, the quantity of an olefinic double bond may increase and may deteriorate easily.

In the β-pinene-based polymer of the present invention, the aromatic 6-membered ring formed from the cyclohexene ring derived from β-pinene during hydrogenation is 1 mol% or more and 10 mol% or less with respect to the β-pinene unit in the polymer. More preferably, it is 5 mol% or more and 10 mol% or less. The β-pinene-based polymer of the present invention has a ratio of the integral value of 6 to 8 ppm proton to the integral value of all protons in its ¹ H-NMR spectrum (the proton of tetramethylsilane (TMS) is 0 ppm) (6 (Integral value of protons of ˜8 ppm / integral value of all protons) is preferably 2.2 × 10 ⁻³ or more (corresponding to 1 mol% or more of aromatic ring in the case of β-pinene homopolymer) 2.3 × 10 ⁻² or less (corresponding to 10 mol% or less of the aromatic ring), preferably 1.1 × 10 ⁻² or more (corresponding to 5 mol% or more of the aromatic ring) 2.3 × 10 ⁻² The following (corresponding to 10 mol% or less of the aromatic ring). Further, the p-phenylene group (—C ₆ H ₄ —) is 0.55% by mass or more and 5.5% by mass or less, preferably 2.7% by mass or more and 5.5% by mass or less. When the ratio is small, the amount of aromatic rings is small and the refractive index is small. On the other hand, when the ratio is large, the glass transition temperature is small and the light resistance is also lowered.

Incidentally, since the ¹ H-NMR spectrum of a polymer having a high hydrogenation rate integrates a very small spectrum, a high SN ratio and resolution are required. Usually, it is preferable to use a nuclear magnetic resonance apparatus having a magnet of 270 MHz or higher and to increase the number of integrations to 8000 times or more. If the S / N ratio is bad or the resolution is low, the integral value is estimated to be small, and a correct value cannot be obtained.
The heavy solvent for dissolving the β-pinene polymer is not particularly limited as long as it is a heavy solvent in which the β-pinene polymer is dissolved, but the spectrum of the non-deuterated solvent in the heavy solvent is β- It is preferable to select a heavy solvent having a spectrum of 0 to 4 ppm which does not overlap with the spectrum of the pinene polymer or has little influence even if it overlaps. Examples of such heavy solvents include heavy tetrahydrofuran and heavy hexane.

・ Glass transition temperature (Tg)
The Tg of the β-pinene-based polymer of the present invention cannot be generally defined by the type and ratio of monomers to be copolymerized and the amount of aromatic ring, but is preferably 70 ° C to 250 ° C, more preferably 100 ° C to 230 ° C. Further preferred. If Tg is low, the heat resistance is insufficient, and if it is too high, the β-pinene polymer becomes brittle. It can be measured by differential scanning calorimetry (DSC).

-Total light transmittance The β-pinene polymer 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 polymer is preferably 80% or more, and more preferably 85% or more. The total light transmittance is measured according to JIS-K-7361-1-1997 “Plastics—Testing method for total light transmittance of transparent materials—Part 1: Jingle beam method”.

-Refractive index The β-pinene polymer of the present invention preferably has a high refractive index, particularly when used in an optical material. The refractive index of the β-pinene polymer is preferably 1.505 or more, and more preferably 1.507 or more. The refractive index is measured by D-line according to JIS K7142 (Method A) “Method for measuring refractive index of plastic”.

-Light resistance The β-pinene-based polymer of the present invention preferably has high 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-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, it is possible to obtain a polymer having a high 5% mass reduction temperature. The 5% mass reduction temperature of the β-pinene polymer of the present invention is preferably 300 ° C. or higher, 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 “Thermogravimetry of plastics”.

[II] Production Method / Polymerization Reaction of β-Pinene Polymer The β-pinene polymer of the present invention can be obtained by a known method such as cationic polymerization, radical polymerization method or coordination polymerization 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 the cationic polymerization, the amount of the inert organic solvent is not particularly limited, but is usually 100 to 10,000 parts by mass, preferably 150 to 10,000 parts per 100 parts by mass of the monomer containing β-pinene. 5000 parts by mass, more preferably 200 to 3000 parts by mass. If the amount of the inert solvent is small, the viscosity when the polymer is formed becomes high and stirring becomes difficult, so that the reaction becomes non-uniform and a uniform polymer 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 halide compounds 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 Oxo acids such as ₃ SO ₃ H, H ₃ PO ₄ , P ₂ O ₅ , And polymer compounds such as ion exchange resins having these groups; heteropolyacids such as phosphomolybdic acid and 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- Examples thereof include solid acids such as solid phosphoric acid in which Al ₂ 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 metal halide compounds as acidic compounds 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 define the amount to be used. However, in the case of a homogeneous catalyst, the amount used is β-pinene and The amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and most preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the aromatic monomer. When a heterogeneous catalyst such as a solid acid or an 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 aromatic monomers. More preferred is ~ 1000 parts by mass. 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 in the case of performing cationic polymerization is not particularly limited as long as it is a compound that generates a cation by 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, and an aryl group, R ² represents hydrogen, an alkyl group, and an aryl group, and X represents a halogen, an alkoxy group, an acyloxy group, and a hydroxyl group.)

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 to be used, but with respect to 100 parts by mass of β-pinene and aromatic monomers. 0.001 to 10 parts by mass is preferable, 0.001 to 5 parts by mass is more preferable, and 0.01 to 1 part by mass is 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 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.

The electron donating compound is preferably 0.01 to 500 parts by weight, more preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the polymerization catalyst in the reaction system. 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, a more preferable amount of the electron donating compound is 0.1 to 100 parts by mass with respect to the polymerization catalyst.

The reaction temperature in the cationic polymerization 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 carrying out the cationic polymerization is not particularly limited, but is preferably 0.5 to 50 atm, 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.

[III] Hydrogenation The hydrogenation reaction can take any known method. In the present invention, an aromatic ring is formed on a β-pinene polymer by dehydrogenating a part of the cyclohexene ring of the β-pinene unit. In this case, a high temperature may be advantageous as the reaction temperature, and a heterogeneous catalyst having high thermal stability is often used. Therefore, the case where a heterogeneous catalyst (solid catalyst) is used will be described.

-Hydrogenation catalyst Although the heterogeneous catalyst used in the present invention is not particularly limited, specific examples include sponge metal catalysts such as sponge nickel, sponge cobalt, sponge copper; nickel silica, nickel alumina, nickel zeolite, nickel diatomaceous earth, Palladium silica, palladium alumina, palladium zeolite, palladium diatomaceous earth, palladium carbon, palladium graphite, palladium calcium carbonate, platinum silica, platinum alumina, platinum zeolite, platinum diatomaceous earth, platinum carbon, platinum graphite, platinum calcium carbonate, ruthenium silica, ruthenium alumina, Ruthenium zeolite, ruthenium diatomaceous earth, ruthenium carbon, ruthenium graphite, ruthenium calcium carbonate, iridium silica, iridium alumina, Examples include supported metal catalysts such as iridium zeolite, iridium diatomaceous earth, iridium carbon, iridium graphite, iridium calcium carbonate, cobalt silica, cobalt alumina, cobalt zeolite, cobalt diatomaceous earth, cobalt carbon, cobalt graphite, 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.
In the hydrogenation reaction, nickel or palladium is preferably used as the metal having hydrogenation activity from the viewpoint of hydrogenation activity, availability, and ease of handling. In order to further suppress undesirable side reactions that proceed during hydrogenation, it is preferable to use calcium carbonate or a carbon support.

-Solvent The hydrogenation reaction is usually performed in an organic solvent. The solvent that can be used is not particularly limited, but a solvent that can easily dissolve the β-pinene polymer is preferable. Since the solvent differs depending on the type of copolymerization, it is difficult to limit, but specific examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene; pentane, hexane, heptane, octane, cyclohexane Aliphatic hydrocarbon solvents such as pentane, cyclohexane, methylcyclohexane, decalin, tricyclodecane; halogenated methyl chloride, methylene chloride, propane chloride, butane chloride, 1,2-dichloroethane, 1,1,2-trichloroethylene, etc. 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, 1-butanol and the like Alcohol The solvent or the like can be used.
In the hydrogenation reaction, 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.
The amount of the organic solvent used in the hydrogenation reaction is 50 parts by mass or more and 10,000 parts by mass or less, preferably 100 parts by mass or more and 3000 parts by mass or less, more preferably 150 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the polymer. is there. When it is carried out at 10000 parts by mass or more, the productivity is remarkably lowered, and when it is less than 100 parts by mass, the solution viscosity is remarkably increased and the hydrogenation reaction efficiency is lowered.

When a polymer containing β-pinene units is hydrogenated at a high temperature, the main chain may break, and a hydrogenated product having a desired degree of polymerization may not be obtained. In that case, hydrogenation may be carried out in the presence of substances corresponding to I to IV below. By carrying out hydrogenation in the presence of these substances, it becomes possible to greatly suppress the main chain cleavage during the high-temperature reaction caused by the support.
I. M (OR) _n
II. M (OC (= O) R ') _n
III. (R ") ₃ N
IV. Pyridines

I. M represents an alkali metal or an alkaline earth metal, and is not particularly limited, but specific examples include lithium, sodium, potassium, calcium, and magnesium. n represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal. R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group; an aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group A 2-methylphenyl group and an aralkyl group having 7 to 11 carbon atoms.
II. M and n shown in FIG. Is equivalent to R ′ represents a C 1-8 alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, or an octyl group.
III. R ″ shown in the above may be the same or different from each other, and may have a ring structure formed by bonding any two or more of them. An alkyl group having 8 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, an alkylene group having 2 to 10 carbon atoms, and an alkylene substitution having 6 to 12 carbon atoms When an alkylene group is represented and R ″ is other than a hydrogen atom, it may be substituted with another substituent, and a part of the substituent may be replaced with an oxygen atom, a nitrogen atom or the like.
IV. Any compound having a pyridine skeleton in the molecule can be used as the pyridines shown in FIG.

These I. To IV. Only one type of the compounds listed above may be used alone, or a plurality of types may be used simultaneously. These compounds are used in a total amount of 0.005 to 10 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of the hydrogenation reaction solution. If the amount used is small, the effect of suppressing undesirable reactions cannot be obtained, and if too much, the ability to suppress undesirable reactions does not improve.

-Reaction temperature of hydrogenation reaction The temperature of the hydrogenation reaction in the present invention may vary depending on the catalyst used and cannot be specified, but is usually 60 ° C to 300 ° C, preferably 120 ° C to 250 ° C. More preferably, the temperature is 150 ° C to 220 ° C. For example, the dehydrogenation reaction proceeds significantly under a high temperature condition of 150 ° C. or higher, and a desired hydrogenated polymer is easily obtained. In the present invention, the hydrogenation reaction temperature of 160 ° C. or higher, and in some cases 180 ° C. or higher can be set.

Reaction time The hydrogenation reaction time varies depending on the type of catalyst used, the amount of catalyst, and the reaction temperature, and 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.

-Hydrogen pressure The hydrogenation reaction in the present invention is aimed at hydrogenating the carbon-carbon unsaturated bond of the cyclohexene ring contained in the β-pinene polymer. On the other hand, a part of the cyclohexene ring is dehydrated. An aromatic ring is formed by rubbing. For this reason, the hydrogen pressure in the hydrogenation reaction is limited. The pressure of the hydrogenation reaction may vary depending on the catalyst used, but the hydrogen pressure is 0.1 MPa to 5 MPa. In general, the higher the hydrogen gas partial pressure is, the more advantageous it is for hydrogenation. Above this range, aromatization by dehydrogenation proceeds only slightly.
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 in the reaction may have a significant amount of partial pressure as a gas component. When an inert gas exists in these hydrogenation reactions, the partial pressure is preferably 0.01 MPa or more and less than 5 MPa. In the case of 5 MPa or more, the reaction apparatus becomes large and requires a lot of equipment costs.

-Embodiment of hydrogenation reaction Embodiment of the hydrogenation reaction in this invention can take arbitrary well-known methods. There may be an appropriate reaction form depending on the shape of the catalyst used. 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, 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.
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.

The amount of hydrogenation catalyst used is difficult to limit because the amount of catalyst used varies depending on the type of hydrogenation catalyst used, polymer concentration, reaction mode, etc. The amount of the catalyst used per 100 parts by mass of the chemical reaction solution 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 the hydrogenation reaction is performed in a fixed bed, a known method can be used. A vertical column reactor such as a multi-tubular type is charged with a catalyst, and a β-pinene polymer solution and hydrogen are supplied thereto for hydrogenation. At this time, both the polymer solution and hydrogen are used. Examples thereof include a method of supplying from the upper part, a method of supplying both from the lower part, and a method of supplying the polymerization solution from the upper part and hydrogen from the lower part.
The used hydrogenation catalyst can be separated from the polymer if 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. Even when the catalyst is separated using these separation methods, a trace amount of metal components may remain in the polymer. In this case, the performance (such as weather resistance) of the obtained hydride of β-pinene polymer may be lowered. In order to remove the dissolved metal component, the remaining metal can be separated by using an aggregation precipitation method, an adsorption method, a washing method, an aqueous phase extraction method, or the like. The catalyst recovered by the separation can be used again for the hydrogenation reaction after taking necessary means such as partly removing or partly adding new catalyst.

The β-pinene-based polymer after hydrogenation is obtained by removing the polymer from the solution by, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, or solvent removal with steam (steam stripping). It can be separated and obtained from the reaction mixture by a normal operation during separation.

The β-pinene polymer of the present invention can be used alone, or can be used alone, polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene. It can also be used as a composition blended with other polymers such as styrene 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 polymer 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 polymer of the present invention has a high symmetry and a large amount of aromatics in the main chain, so it can be used for various optical materials because it can achieve both high refractive index and low birefringence. Although the range is not particularly limited, it is excellent in heat resistance and suitable for optical materials that require low water absorption and high transparency. 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 polymer and further containing a conventional light diffusing agent, and the obtained light diffusible composition. A molded body having a predetermined shape such as a plate shape or a block shape is formed using the object.
Functional thin film The functional thin film formed by coating on at least one surface of a substrate using a β-pinene polymer is not particularly limited, but is preferably an antistatic layer, an antireflection layer, or a hard coat. It is a thin film having functionality such as a layer, a transparent conductive layer, and an antiglare layer.

Optical film An optical film using a β-pinene polymer 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 substances and the like 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 thoroughly substituting a 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 40 parts by mass of distilled and purified β-pinene. And 4.5 parts by mass of dehydrated triethylamine were added and cooled to a temperature of -78 ° C. Further, while stirring at −78 ° C., 70 parts by mass of 1.0 mol / L hexane solution of ethylaluminum dichloride was added 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 (A1). . The obtained β-pinene polymer (A1) had a weight average molecular weight of 53,000 and a number average molecular weight of 32,000.

Reference example 2
After thoroughly substituting the well-dried glass flask with a cock, 184 parts by mass of dehydrated N-hexane, 210 parts by mass of dehydrated methylene chloride, and 0.5 parts by mass of dehydrated diethyl ether were added to -78 ° C. Cooled down. Further, 7.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at −78 ° C. Furthermore, when 3.0 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 the addition of 60 parts by weight of distilled and purified β-pinene over 1 hour, it gradually became dark blue and the viscosity of the solution increased. After the addition of β-pinene, 30 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 60 parts by mass of β-pinene polymer (A2). The obtained β-pinene polymer (A2) had a weight average molecular weight of 116,000, a number average molecular weight of 51,000, and a glass transition temperature of 95 ° C.

Example 1
In a pressure vessel equipped with a stirrer substituted with nitrogen, 27 parts by mass of cyclohexane and 1 part by mass of isopropanol and 12 parts by mass of the β-pinene polymer (A1) obtained above were accommodated and stirred. -The pinene polymer (A1) was completely dissolved. Thereafter, 7 parts by mass of 36.6% nickel-supported alumina (product number: N163A, manufactured by JGC Chemical Co., Ltd.) was added as a hydrogenation catalyst, and the mixture was stirred and sufficiently dispersed. The reaction was continued for 30 minutes at 150 ° C. and a hydrogen pressure of 3 MPa 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%). By sufficiently drying, 11 parts by mass of β-pinene polymer (H1) was obtained. The β-pinene polymer (H1) thus obtained was measured by ¹ H-NMR. As a result, the remaining olefinic double bond was 6.5 mol% and the remaining aromatic ring was 6.3 mol%. It was. The glass transition temperature was 124 ° 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 1.4 × 10 ⁻² , and the integral value of 4.5 to 6 ppm proton to the integral value of all protons Was 3.7 × 10 ⁻³ . The obtained β-pinene polymer (H1) had a weight average molecular weight of 52,000 and a number average molecular weight of 31,200. The evaluation results of β-pinene polymer (H1) are shown in Table 1.

Example 2
In the hydrogenation reaction of Example 1, a β-pinene polymer (H2) was obtained in the same manner as in Example 1 except that the reaction time was changed from 30 minutes to 3 hours and 30 minutes. The evaluation results of β-pinene polymer (H2) are shown in Table 1.

Example 3
A β-pinene polymer (H3) is obtained in the same manner as in Example 1 except that the β-pinene polymer (A2) obtained in Reference Example 3 is used in place of the β-pinene polymer (A1). It was. When ¹ H-NMR of the β-pinene polymer (H3) was measured, the remaining olefinic double bond was 6.5 mol% and the remaining aromatic ring was 6.3 mol%. The glass transition temperature was 125 ° 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 1.4 × 10 ⁻² , and the integral value of 4.5 to 6 ppm proton to the integral value of all protons Was 3.7 × 10 ⁻³ . The obtained β-pinene polymer (H3) had a weight average molecular weight of 114,000 and a number average molecular weight of 49,300. The evaluation results of β-pinene polymer (H3) are shown in Table 1.

Example 4
In a pressure vessel equipped with a stirrer purged with nitrogen, 103 parts by mass of cyclohexane and 45 parts by mass of the β-pinene polymer (A2) obtained in Reference Example 3 were placed, and stirred, The union (A2) was completely dissolved. Thereafter, 0.5 parts by mass of 5% by mass palladium-supported carbon (product number: E106O / W made by Evonik Degussa Japan Co., Ltd.) was added as a hydrogenation catalyst, and the mixture was stirred and sufficiently dispersed. Was sufficiently replaced with hydrogen, and the mixture was reacted at 200 ° C. and hydrogen pressure: 3 MPa for 9 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, 42 parts by mass of β-pinene polymer (A3) was obtained.
In a pressure vessel equipped with a stirrer purged with nitrogen, 27 parts by mass of cyclohexane and 1 part by mass of isopropanol and 3.0 parts by mass of the obtained β-pinene polymer (A3) were accommodated and stirred. -The pinene polymer (A3) was completely dissolved. Thereafter, 1.8 parts by mass of 36.6% by mass nickel-supported alumina (product number: N163A, manufactured by JGC Chemical Co., Ltd.) was added as a hydrogenation catalyst, stirred, and sufficiently dispersed. After sufficiently substituting with hydrogen and stirring, it was reacted at 200 ° C. and hydrogen pressure: 3 MPa for 6 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 300 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%). It was sufficiently dried to obtain 2.7 parts by mass of β-pinene polymer (H4). The β-pinene polymer (H4) thus obtained was measured by ¹ H-NMR. As a result, the remaining olefinic double bond was 0.5 mol% and the remaining aromatic ring was 3.4 mol%. It was. The glass transition temperature was 129 ° C. In ¹ H-NMR, the ratio of the integral value of 6-8 ppm proton to the integral value of all protons is 7.7 × 10 ⁻³ , and the integral value of 4.5-6 ppm proton to the integral value of all protons Was 2.7 × 10 ⁻⁴ . The obtained β-pinene polymer (H4) had a weight average molecular weight of 100,000 and a number average molecular weight of 43,700. The evaluation results of β-pinene polymer (H4) are shown in Table 1.

Comparative Example 1
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 (A1) 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 continued at 160 ° C. and hydrogen pressure: 6 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%). By sufficiently drying, 24 parts by mass of β-pinene polymer (B1) was obtained. The β-pinene polymer (B1) thus obtained was measured for ¹ H-NMR. As a result, the remaining olefinic double bond was 1.7 mol% and the remaining aromatic ring was 0.4 mol%. It was. 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 (B1) had a weight average molecular weight of 51,900 and a number average molecular weight of 31,600. Table 1 shows the evaluation results of the β-pinene polymer (B1).

Comparative Example 2
Indene / β-pinene (mass ratio 60/40) copolymer (B2) was obtained in the same manner as in Example 12 of JP-A No. 2002-121231. The resulting indene / β-pinene copolymer (B2) had a weight average molecular weight of 64,000 and a number average molecular weight of 24,300. Table 1 shows the evaluation results of the indene / β-pinene copolymer (B2).

Comparative Example 3
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 (A2) obtained in Reference Example 3 were placed, and stirred, The union (A2) was completely dissolved. Thereafter, 7.5 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, and the mixture was stirred and sufficiently dispersed. After sufficiently substituting with hydrogen and stirring, the mixture was reacted at 130 ° C. and hydrogen pressure: 15 MPa for 25 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, 24 parts by mass of β-pinene polymer (B3) was obtained. The β-pinene polymer (B3) thus obtained was measured for ¹ H-NMR. As a result, the remaining olefinic double bond was 0.023 mol%, and the remaining aromatic ring was 0.0027 mol%. It was. The glass transition temperature was 132 ° 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 5.9 × 10 ⁻⁶ , and the ratio of the integral value of 4.5 to 6 ppm proton to the integral value of all protons Was 1.3 × 10 ⁻⁵ . The obtained β-pinene polymer (B3) had a weight average molecular weight of 103,400 and a number average molecular weight of 45,400. Table 1 shows the evaluation results of the β-pinene polymer (B3). Table 1 shows the evaluation results of the β-pinene polymer (B3).

Reference Example 3 [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. A toluene solution (nickel 6%) of nickel 2-ethylhexanoate (manufactured by Kishida Chemical Co., Ltd.) was placed in a nitrogen stream at 7.4 m.
1 was added to prepare a homogeneous hydrogenation catalyst.

Comparative Example 4
In a pressure vessel equipped with a stirrer purged with nitrogen, 470 parts by mass of cyclohexane and 30 parts by mass of the β-pinene polymer (A2) obtained in Reference Example 3 were accommodated and stirred, The union (A2) 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 4 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 6000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and then sufficiently dried to obtain 29 parts by mass of β-pinene polymer (B4). It was. The β-pinene polymer (B4) thus obtained was measured by ¹ H-NMR. As a result, the remaining olefinic double bond was 50.0 mol% and the remaining aromatic ring was 0.4 mol%. It was. The glass transition temperature was 115 ° 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 9.4 × 10 ⁻⁴ , and the integral value of 4.5 to 6 ppm proton to the integral value of all protons Was 2.9 × 10 ⁻² . The obtained β-pinene polymer (B4) had a weight average molecular weight of 113,000 and a number average molecular weight of 50,800. Table 1 shows the evaluation results of the β-pinene polymer (B4).

In addition, about the material obtained at each process mentioned above and the material manufactured at the following process, the physical-property measurement was performed as follows.

○ Molding The obtained β-pinene polymer 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 two 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 is β-pinene-derived olefinic double bond (1H), the integral value of 6-8 ppm is aromatic ring (4H), the residual double bond rate and the aromatic ring formation rate Was calculated. The aromatic ring production rate was calculated as mol% based on the total number of monomer units. The double bond hydrogenation rate was calculated as mol% based on the total number of monomer units excluding the aromatic ring-forming units.
○ 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 Measured according to JIS-K-7361-1 using HR-100 (product number) manufactured by Murakami Color Research Co., Ltd.
○ Refractive index (n _D )
Measurement was performed at 25 ° C. in accordance with JIS-K-7142 using DR-M2 (product number) manufactured by Atago Co., Ltd.

○ Photoelastic coefficient After annealing a 200 μm film prepared by press molding overnight at a temperature 20 ° C. lower than Tg, a tensile stress was applied in the major axis direction at a temperature 20 ° C. higher than Tg. Retardation was measured with an ellipsometer M220 (manufactured by JASCO Corporation), and the photoelastic coefficient K was calculated from the amount of change in retardation with respect to stress.
○: K ≦ 2.0 × 10 ⁻¹⁰ cm ² / dyn Good ×: 2.0 × 10 ⁻¹⁰ cm ² / dyn <K Poor

○ 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

From the results of the examples, all are polymers containing 60% by mass or more of β-pinene units, and 1-mol% of the 6-membered ring derived from β-pinene is an aromatic 6-membered ring. Since it is a polymer, it can be seen that the refractive index is high and the total light transmittance, photoelastic coefficient, and light resistance are well balanced.
From Examples and Comparative Examples 1 and 3, it can be seen that the refractive index decreases when the aromatic ring is small. If the refractive index is low, the lens becomes thick when used in a lens, and not only the amount of β-pinene polymer used is increased, but also the product incorporating the lens itself becomes large.
From Comparative Example 2, when there are many aromatic rings other than those derived from β-pinene due to copolymerization with a copolymerizable monomer, the heat resistance and refractive index are good, but the total light transmittance and photoelastic coefficient are poor. It turns out that performance is inferior. Moreover, it turns out that light resistance is low when the hydrogenation rate of an olefinic double bond is low.
Hydrogenation catalyst for hydrogenating 90 mol% or more of olefinic double bonds from Examples and Comparative Example 5 and converting 1 mol% or more of β-pinene-derived 6-membered rings to aromatic 6-membered rings It is understood that a supported metal catalyst (heterogeneous catalyst) is preferable.

Claims (7)

1. A polymer containing 60% by mass or more of β-pinene units, wherein a β-pinene-based polymer in which 1 mol% or more and 10 mol% or less of the 6-membered ring derived from β-pinene is an aromatic 6-membered ring .
2. The β-pinene polymer according to claim 1, wherein the olefinic double bond is hydrogenated in an amount of 90 mol% or more.
3. A β-pinene-based polymer containing 60% by mass or more of β-pinene units and having a p-phenylene group of 0.55% by mass or more and 5.5% by mass or less.
4. The β-pinene polymer according to claim 3, wherein the cyclohexene-1,4-diyl group is 5.6% by mass or less.
5. The β-pinene polymer according to claim 1 or 3, wherein the content of β-pinene units is 90% by mass or more.
6. A molded body comprising the β-pinene polymer according to claim 1 or 3.
7. The β-pinene unit according to claim 1 or 3, wherein a polymer containing 60 mass% or more of β-pinene units is hydrogenated at a hydrogen pressure of 0.1 MPa to 5 MPa in the presence of a heterogeneous catalyst. A method for producing a pinene polymer.

Images