JP5307597B2 - Hydrogenation method of polymer and hydrogenated polymer obtained by hydrogenation reaction - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reaction method which allows elevated hydrogenation reaction temperature resulting in substantially shortened reaction time and which allows setting a low used amount of a catalyst, in obtaining a &beta;-pinene-based polymer by converting unsaturated bonds contained in a polymer containing &beta;-pinene as its constitutional unit into saturated bonds by a hydrogenation reaction. <P>SOLUTION: A method of hydrogenating a &beta;-pinene-based polymer is provided, which in a hydrogenation reaction obtaining the &beta;-pinene-based polymer by converting unsaturated bonds present in main chains and/or side chains of a polymer containing 30 mass% or more of a &beta;-pinene unit into saturated bonds, comprises using a metal-supported hydrogenating catalyst and making it coexistent with at least one basic compound selected from, specified, organic alkali metals, organic alkaline earth metals, amines, and pyridines. A &beta;-pinene-based polymer obtained by the hydrogenation method is also provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a reaction method for obtaining a β-pinene polymer by converting an unsaturated bond contained in a polymer containing β-pinene units into a saturated bond by a hydrogenation reaction, and a β-pinene heavy polymer obtained by a hydrogenation reaction. It is about coalescence.

  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 polymer containing β-pinene as a constituent component has been proposed as an optical resin that has improved the above problems (Patent Document 5, Non-Patent Document 2). A polymer containing β-pinene as a constituent component 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, these β-pinene-based polymers have a problem that they are easily colored by light or heat because they have olefinic double bonds derived from β-pinene and are easily oxidized and deteriorated.

  In order to solve these problems, a technique for improving weather resistance and heat resistance by hydrogenating a polymer containing β-pinene as a constituent component has been reported (Non-patent Documents 1 and 3). According to Non-Patent Document 1, a hydrogenation reaction is carried out with a reagent using a large excess of a hydrazide compound of 5 mole times the unsaturated bond in the β-pinene-based polymer, and the reaction rate is 91%. I am getting a monster. However, this method requires the use of a large amount of reagent for the polymer to be hydrogenated, and the production efficiency is low.

  Further, according to Non-Patent Document 3, for a polymer containing β-pinene as a constituent component, an approximately equal mass of 5% palladium alumina compound is used with respect to the polymer over a period of 7 hours at 160 ° C. and 5 MPa. A hydrogenation reaction is performed, and a hydrogenated product having a reaction rate of 99.9% is obtained. However, even with this method, it is necessary to use a very large amount of catalyst. Unless many catalysts are used repeatedly, the production cost is high and the reaction time is long, so it is necessary to develop a more efficient production method. It becomes.

  A polymer containing β-pinene as a constituent component has a characteristic trisubstituted olefin inside the ring structure in the main chain from its structure, and the hydrogenation rate itself is extremely low. As an example of a polymer having a trisubstituted olefin, a polymer having a polyisoprene skeleton or a block copolymer including an isoprene skeleton is known, and one of the substituents of the trisubstituted olefin is most sterically. In many cases, it was a small methyl group, and a decrease in the hydrogenation rate was not a substantial problem. The β-pinene polymer has a quaternary carbon in the vicinity of the olefin as well as the number of substitutions of the olefin, and the hydrogenation rate is reduced due to the steric bulk due to this adjacent substituent. Conceivable.

  As described above, when β-pinene-based polymers are hydrogenated, they have problems that are very different from hydrogenation of polymers such as polyisoprene. It was necessary to develop a high activation method.

  As a method for improving the hydrogenation reaction rate, there is a means for increasing the reaction temperature. However, when the reaction temperature is increased, the molecular weight of the polymer is decreased during the hydrogenation reaction, and an undesirable reaction tends to proceed. According to the evaluation by the present inventors, it was found that the phenomenon was observed even when the method of Non-Patent Document 3 was used.

  Therefore, until now, when a β-pinene polymer is subjected to a hydrogenation reaction, no method has been found so far in which a side reaction causing a decrease in molecular weight does not proceed and a reaction is carried out promptly.

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 Proceedings of the 56th Polymer Symposium 2Z10

  The present invention makes it possible to increase the hydrogenation reaction temperature in obtaining a β-pinene polymer by converting an unsaturated bond contained in a polymer containing β-pinene as a structural unit into a saturated bond by a hydrogenation reaction. As a result, an object of the present invention is to provide a reaction method capable of substantially reducing the reaction time and setting a small amount of catalyst to be used.

  As a result of intensive studies by the present inventors, it has been found that an undesirable reaction that causes a decrease in molecular weight or the like seen during hydrogenation of a β-pinene-based polymer may be caused by a hydrogenation catalyst support. Although not necessarily clear, when the hydrogenation reaction is carried out at a relatively high temperature, it is considered that the acid sites on the surface of the support cause a main chain breaking reaction.

  And as a result of intensive studies, the present inventors have solved the above problem by taking the following method.

That is, one of the solving means of the present invention is the following method.
In the hydrogenation reaction in which an unsaturated bond in the main chain and / or side chain of a polymer containing 30% by mass or more of β-pinene units is converted to a saturated bond to obtain a β-pinene polymer, a metal is included. A method for hydrogenating a β-pinene polymer, characterized by using a heterogeneous hydrogenation catalyst and coexisting at least one of compounds selected from I to IV below.
I. M (OR) _n
II. M (OC (= O) R ') _n
III. R ¹ R ² R ³ N
IV. Pyridines (wherein M is selected from lithium, sodium, potassium, magnesium and calcium;
R represents an alkyl group having a carbon number of 1-4, an aryl group or an aralkyl group having a carbon number of 7-11 having 6 to 10 carbon atoms,
n represents 1 or 2,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ^{1 to} R ³ may be different from each other, and may have a ring structure by bonding any two or more, each of which is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. Represents a cycloalkyl group having 12 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 or an alkylene-substituted alkylene group having 6 to 12 carbon atoms, and R ^{1 to} R ³ other than a hydrogen atom 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)

As another solution to the problem,
A β-pinene polymer obtained by the above method and having a ratio (A / B) of the integral value A of protons of 4 to 6 ppm and the integral value B of all protons in the ¹ H-NMR spectrum of 0.002 or less. It is.

  According to the method of the present invention, the hydrogenation reaction temperature can be increased. As a result, the reaction time can be substantially shortened and a small amount of catalyst used can be set, which is industrially advantageous. It becomes possible to obtain the desired hydrogenated polymer.

[I] Polymer to be used in hydrogenation method / β-pinene The polymer to be used in the hydrogenation method of the present invention is a polymer or copolymer containing β-pinene as a structural unit in an amount of 30% by mass or more. The copolymer is obtained by copolymerizing β-pinene and other polymerizable monomers.
Known β-pinene used as the monomer can be used. In other words, those collected from plants such as pine, β-pinene synthesized from other raw materials such as α-pinene, and the like can also be used.

-Other polymerizable monomer When using a copolymer in this invention, you may contain the other monomer copolymerizable with (beta) -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 compounds such as naphthalene and indene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) (Meth) acrylic acid monomers such as glycidyl acrylate; maleic anhydride, maleic acid, fumaric acid, maleimide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; ethylene , Propylene, isobutylene, butadiene, isoprene, norbornene, etc. Olefins; 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, vinyl benzoate; methyl vinyl ether, Vinyl ethers such as ethyl vinyl ether, t-butyl vinyl ether, and trimethylsilyl vinyl ether; styrene derivatives having polar groups, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like; conjugated diolefin compounds such as butadiene, isoprene, and limonene; α-pinene And compounds having a distorted ring structure such as methylenecyclopropane. 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.

  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.

  When a copolymer is used in the present invention, the mass ratio of β-pinene to other monomers in the copolymer (β-pinene / other monomers) is the same as that of the polymer obtained after the hydrogenation reaction. From the viewpoint of heat resistance and mechanical strength, it is in the range of 30/70 to 100/0, preferably in the range of 30/70 to 99/1, and more preferably in the range of 40/60 to 99/1. When there is too little beta-pinene, the heat resistance of the polymer obtained after hydrogenation will become low.

  The copolymer used in the present invention may be a copolymer obtained by polymerizing any combination of the above-mentioned β-pinene and other monomers. 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, β-pinene- (meth) acrylic acid copolymer, β-pinene- (meth) methyl acrylate copolymer, β-pinene- (meth) ethyl acrylate copolymer, β-pinene- (meth) acrylic acid Butyl copolymer, β-pinene- (meth) acrylic acid 2-hydroxyethyl copolymer, β-pinene- (meth) acrylic acid glycidyl copolymer, β-pinene-maleic anhydride copolymer, β-pinene -Maleic acid co Polymer, β-pinene-fumaric acid copolymer, β-pinene-maleimide copolymer, β-pinene-acrylonitrile copolymer, β-pinene-methacrylonitrile copolymer, β-pinene- (meth) acrylamide Copolymer, β-pinene-ethylene copolymer, β-pinene-propylene copolymer, β-pinene-isobutylene copolymer, β-pinene-butadiene copolymer, β-pinene-isoprene copolymer, β -Pinene-norbornene copolymer, β-pinene-limonene copolymer, β-pinene-α-pinene copolymer, β-pinene-myrcene copolymer, β-pinene-camphene copolymer, β-pinene- Karen copolymer, β-pinene-vinyl acetate copolymer, β-pinene-vinyl pivalate copolymer, β-pinene-vinyl benzoate copolymer, β-pinene-methyl vinyl ether copolymer , Β-pinene-ethyl vinyl ether copolymer, β-pinene-t-butyl vinyl ether copolymer, β-pinene-trimethylsilyl vinyl ether copolymer, β-pinene-vinyl chloride copolymer, β-pinene-vinylidene chloride Examples include copolymers, β-pinene-allyl chloride copolymers, β-pinene-allyl alcohol copolymers, and the like.

-Number average molecular weight The number average molecular weight of the β-pinene polymer used in the present invention is not particularly limited, but from the viewpoint of mechanical properties and processability of the polymer obtained after hydrogenation, about 10,000 to 1,000,000 g. / Mol is preferred. 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.

[II] Production method and polymerization reaction of β-pinene polymer A polymer of β-pinene alone or a copolymer containing β-pinene and another monomer as a structural unit is cationic polymerization, radical polymerization method, It can be obtained by a known method such as coordination polymerization. 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 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.
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.

Initiator In the present invention, 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 with a polymerization catalyst, but an organic compound having at least one functional group represented by the following formula is preferable. Used for. 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 _") 2 X
(In the formula, R ″ represents a hydrogen atom, an alkyl group or an aryl group which may be different from each other, 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 polymer, it is difficult to generally define the amount used, but it is based on 100 parts by mass of β-pinene and other monomers used. 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.

-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, zirconia tungstate, 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 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 other monomers to be used, 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.

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

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

-Cationic polymerization solvent Cationic polymerization can be performed 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 other monomers to be used 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 used is not particularly limited, but is usually 100 to 10,000 parts by weight, preferably 100 parts by weight of β-pinene and other monomers to be used, 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.

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

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

  The reaction time for carrying out the cationic polymerization is not particularly limited, and if the reaction time is appropriately determined according to conditions such as the type of other monomers used, the amount thereof, the type and amount of the polymerization catalyst, the reaction temperature, the reaction pressure, etc. Good. Usually, it is 0.01 hours to 24 hours, preferably 0.1 hours to 10 hours.

  The copolymer after cationic polymerization is used for isolating the polymer from the solution, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. These can be separated and obtained from the reaction mixture by the usual operation.

[III] Hydrogenation The hydrogenation [hydrogenation (hydrogenation)] reaction in the present invention uses a heterogeneous hydrogenation catalyst containing a metal and causes a specific coexisting compound to coexist.

-Hydrogenation catalyst The heterogeneous hydrogenation catalyst used in the present invention is not particularly limited. Examples of the metal contained in the hydrogenation catalyst include nickel, cobalt, copper, palladium, iridium, platinum and the like. Among these, nickel and palladium are preferably used from the viewpoint of hydrogenation activity. In addition, as the heterogeneous hydrogenation catalyst, metal catalysts such as fine particles and porous bodies, and hydrogenation catalysts in which a metal is supported on a carrier are used. From the viewpoint of operability, a supported metal in which a metal is supported on a carrier. A catalyst is preferred. Examples of the carrier for supporting the metal include carbon such as activated carbon, graphite, silica, alumina, zeolite, diatomaceous earth, calcium carbonate and the like. Among these, silica, alumina, zeolite, and diatomaceous earth are particularly effective. Can be mentioned. Specific examples of such heterogeneous hydrogenation catalysts containing metals include sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper; nickel silica, nickel alumina, nickel zeolite, nickel diatomaceous earth, palladium silica, and 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, iridium zeolite, iri Um diatomaceous earth, iridium carbon, iridium graphite, iridium calcium carbonate, cobalt silica, cobalt alumina, cobalt zeolite, cobalt diatomaceous earth, cobalt carbon, cobalt graphite, and a supported metal catalyst such as cobalt calcium carbonate.
These catalysts may be modified with iron, molybdenum, magnesium or the like for the purpose of improving activity, improving selectivity and stability. Moreover, these catalysts may be used alone or in combination.

  In the hydrogenation reaction in the present invention, nickel or palladium is preferably used as the metal having hydrogenation activity, and a palladium compound is more preferably used from the viewpoint of hydrogenation activity, availability, and ease of handling. Also, it is preferable to use a carbon support in order to further suppress undesirable side reactions that proceed during the hydrogenation.

-Solvent The hydrogenation reaction in this invention is normally 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-based 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, and 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 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.

  The amount of the organic solvent used in the hydrogenation reaction in the present invention 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 with respect to 100 parts by mass of the copolymer. There are 1000 parts by mass or less. 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.

Hereinafter, the hydrogenation reaction in the present invention is carried out in the presence of compounds corresponding to I to IV. 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 ¹ R ² R ³ N
IV. Pyridines

I. M represented by represents an alkali metal or an alkaline earth metal, and is not particularly limited, but is specifically selected from lithium, sodium, potassium, magnesium and calcium. n represents 1 when M is an alkali metal, and 2 when M is an alkaline earth metal. R is ethyl group, a propyl group, an isopropyl group, a butyl group, an alkyl group having 1 to 4 carbon atoms, such as t- butyl group; a phenyl group, an aryl group having 6 to 10 carbon atoms such as naphthyl group; carbon The aralkyl group of several 7-11 is mentioned. I. The compounds represented by, but not limited, specifically, Li Chiumumetokishido, sodium methoxide, potassium methoxide, magnesium methoxide, calcium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, magnesium ethoxy Calcium ethoxide, lithium propoxide, sodium propoxide, potassium propoxide, magnesium propoxide, calcium propoxide, lithium butoxide, sodium butoxide, potassium butoxide, magnesium butoxide, calcium butoxide, lithium phenoxide, sodium phenoxide, potassium phenoxide, Magnesium phenoxide, calcium phenoxide, lithium naphthoxide, sodium naphthoxide, potassium naphth Kishido, magnesium naphthoquinone butoxide, calcium naphthenate butoxide, lithium 2-methyl phenoxide, sodium 2-methyl phenoxide, potassium 2-methyl phenoxide, magnesium 2-methyl phenoxide, calcium 2-methyl phenoxide.

  II. M and n shown in FIG. Is equivalent to R 'represents a C1-C8 alkyl group such as a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group or the like. II. The compound represented by is not particularly limited, specifically, lithium formate, sodium formate, potassium formate, magnesium formate, calcium formate, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, Lithium propionate, sodium propionate, potassium propionate, magnesium propionate, calcium propionate, lithium butanoate, sodium butanoate, potassium butanoate, magnesium butanoate, calcium butanoate, Lithium hexanoate, sodium hexanoate, potassium hexanoate, magnesium hexanoate, calcium hexanoate, lithium octanoe DOO, sodium octanoate, potassium octanoate, magnesium octanoate, calcium octanoate.

III. R ^{1 to} R ^{3, which} may be the same as or different from each other, may have a ring structure formed by bonding any two or three of them, and each represents a hydrogen atom, a carbon number An alkyl group having 1 to 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; a carbon number 2 to which any two of R ^{1 to} R ³ are bonded Represents an alkylene group having 6 to 12 carbon atoms to which ^three of R ^{1 to} R ³ are bonded [example: —R ¹ —CH (—R ² —) — R ³ —], and When R ^{1 to} R ³ are other than a hydrogen atom, they may be substituted with other substituents, and a part of the substituents may be replaced with oxygen atoms, nitrogen atoms, or the like. R ^{1 to} R ³ are not particularly limited, and specifically include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, benzyl Group, 1-phenylethyl group, 2-phenylethyl group, methylene-α-naphthyl group, methylene-β-naphthyl group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene Group, decylene group, dodecylene group, 3-oxapentylene group, 3-aza-3-methylpe Nthylene group, 3-methylenepentylene group, 3-ethylenepentylene group, 3-aza-3-ethylenepentylene group and the like can be mentioned.

When R ^{1 to} R ³ are other than a hydrogen atom, they may be substituted with other substituents, but are not particularly limited, but specifically include alkyl groups having 1 to 6 carbon atoms, hydroxyl groups, methoxy groups, and ethoxy groups. , Propyloxy group, butyloxy group, 2-methoxyethyleneoxy group, 2-ethoxyethyleneoxy group, amino group, (mono, di) methylamino group, (mono, di) ethylamino group, (mono, di) propylamino Group, 2-dimethylamino (methyl) amino group, chlorine atom, bromine atom, iodine atom and the like.

  III. The compound represented by is not particularly limited, and specifically, ammonia, (mono, di, tri) methylamine, (mono, di, tri) ethylamine, (mono, di, tri) propylamine, (mono, di) , Tri) isopropylamine, (mono, di, tri) butylamine, (mono, di, tri) sec-butylamine, (mono, di, tri) t-butylamine, (mono, di, tri) pentylamine, (mono, Di, tri) hexylamine, (mono, di, tri) octylamine, (mono, di, tri) dodecylamine, (mono, di, tri) cyclopentylamine, (mono, di, tri) cyclohexylamine, (mono, Di, tri) cyclooctylamine, (mono, di, tri) cyclododecylamine, (mono, di, tri) phenylamine, (mono, di, tri) α-naphthyla , (Mono, di, tri) β-naphthylamine, (mono, di, tri) benzylamine, pyrrolidine, (saturated 5-membered ring with 2 N), piperidine, (saturated 6-membered with 2 N) Ring), morpholine, 1,3-diazabicyclo [2.2.2] octane, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, nonanediamine, dimethylaminoethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylbutylenediamine , Tetramethylhexylenediamine, tetramethylnonanediamine, bis (dimethylaminoethyl) methylamine, (mono, di, tri) ethanolamine, (mono, di, tri) propanolamine and the like.

  IV. Any compound having a pyridine skeleton in the molecule can be used as the pyridines shown in FIG. Although not particularly limited, specifically, pyridine, α-picoline, β-picoline, γ-picoline, 3,5-lutidine, 2,6-lutidine, 2,4-lutidine, 2,5-lutidine, 3, 4-lutidine, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2,2′-bipyridine, 4,4′-bipyridine, quinoline, 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, o-Phenanthroline, 4-dimethylaminopyridine and the like can be mentioned.

  These I.D. ~ IV. Only one type of compound 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 pressure Although the pressure of the hydrogenation reaction in this invention may differ from a suitable value by the catalyst to be used, and it cannot necessarily prescribe | regulate, it is 0.1MPa-30MPa as a total pressure of hydrogenation reaction normally, Preferably it is 0.8. 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 performed under the condition where hydrogen gas is present. However, in addition to the hydrogen gas, the hydrogenation reaction may be performed 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.

-Reaction temperature and reaction time The temperature of the hydrogenation reaction in the present invention may vary depending on the catalyst used and cannot always be specified, but is usually 60 ° C to 300 ° C, preferably 100 ° C to 250 ° C, More preferably, it is 120 to 220 ° C. The higher the temperature, the higher the reaction rate and the shorter the reaction time required for hydrogenation. In the present invention, the hydrogenation reaction temperature of 160 ° C. or higher, and in some cases 180 ° C. or higher can be set.
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 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, copolymer concentration, reaction mode, etc. The amount of catalyst used per 100 parts by mass of the hydrogenation reaction liquid is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass. 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 to hydrogenate. At this time, both the polymer solution and hydrogen are Examples thereof include a method of supplying from the upper part, a method of supplying both from the lower part, 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 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.

  Even when the catalyst is separated using these separation methods, a trace amount of metal components may remain in the copolymer. In this case, the performance (such as weather resistance) of the hydride of the obtained β-pinene polymer may be deteriorated. 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.

[IV] Hydride The hydrogenation method of the present invention hydrogenates an olefinic double bond of a cyclohexene ring derived from a β-pinene unit, but uses a monomer having an aromatic ring for copolymerization. If present, hydrogenation of the aromatic ring may also be included.

-Hydrogenation of Olefinic Double Bond The hydride of the present invention preferably has an olefinic double bond derived from β-pinene having a olefinic double bond of 20 relative to β-pinene units in the polymer in order to prevent deterioration due to oxygen in the air. It is at most 10 mol%, more preferably at most 1 mol%, most preferably at most 0.5 mol%. The β-pinene polymer of the present invention has an integral value A of 4 to 6 ppm protons and an integral value B of all protons in its ¹ H-NMR spectrum (tetramethylsilane (TMS) proton is 0 ppm). The ratio (A / B) is 1.1 × 10 ⁻² or less (corresponding to a hydrogenation rate of 80% or more in the case of β-pinene homopolymer), more preferably 5.6 × 10 ⁻³ or less (same as above). , Equivalent to a hydrogenation rate of 90% or more). When the said ratio is large, the quantity of an olefinic double bond may increase and may deteriorate easily.

-Hydrogenation of aromatic ring In the present invention, when a copolymer with an aromatic monomer is used, the hydride is derived from an aromatic monomer to improve heat resistance and transmittance. It is desirable to subject the aromatic ring to hydrogenation. The aromatic ring derived from the aromatic monomer is 50 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, most preferably relative to the aromatic monomer unit in the copolymer. 1 mol% or less.

・ Glass transition temperature (Tg)
Tg of a β-pinene polymer can be measured by a 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 90 ° C to 250 ° C, preferably 120 ° C to 250 ° C. is more preferable. When Tg is low, heat resistance is insufficient, and when it is too high, the β-pinene polymer becomes brittle.

-Total light transmittance The β-pinene-based polymer preferably has a high total light transmittance particularly when used for an optical material. The total light transmittance of the β-pinene polymer 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-based polymer 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, 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 mass is reduced by 5%, as measured by a thermobalance (TGA) according to JIS-K-7120-1987 “Thermogravimetry of plastics”.

・ Usage The β-pinene polymer obtained by the present invention can be used alone, or polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer. It can also be used as a composition blended with other polymers such as polyolefin, polystyrene and 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.

  The β-pinene-based polymer can be used for various optical materials, and the range thereof is not particularly limited. However, the β-pinene polymer is suitable for optical materials that are excellent in heat resistance and 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. , Aspherical pickup lens for digital optical disc device using blue light emitting diode, rod lens, rod lens array, microlens, microlens array, the above various lenses used in a relatively high temperature thermal environment, various lens arrays, steps Index type, gradient index type, single mode type, multi-core type, polarization plane preserving type, side emission type optical fiber, optical fiber connector, optical fiber adhesive, digital optical disc (compact disc, magneto-optical disc, digital disc) Video disk, computer disk, light guide, light diffusion plate, glass substrate substitute film for liquid crystal, retardation film, antireflection film for flat panel display, touch panel substrate, transparent conductive film, antireflection film, anti-skin film , Substrate for electronic paper, substrate for organic electroluminescence, front protective plate for plasma display, anti-electromagnetic wave plate for plasma display, front protective plate for field emission display, light guide plate that uses piezoelectric elements to diffuse the light of a specific part to the front, Prisms, diffraction gratings, endoscopes, endoscopes guiding high energy lasers, camera mirrors or half mirrors represented by Dach mirrors, automotive headlight lenses, automotive heads Light reflector Front protective plate for solar cells, window glass for housing, window glass for moving objects (automobile, train, ship, aircraft, spacecraft, space base, artificial satellite, etc.), antireflection film for window glass, dustproof film for semiconductor exposure , Protective film for electrophotographic photosensitive material, semiconductor (EPROM etc.) sealing material writable or rewritable by ultraviolet light, light emitting diode sealing material, ultraviolet light emitting diode sealing material, white light emitting diode sealing material, SAW filter, Optical band-pass filter, second harmonic generator, Kerr effect generator, optical switch, optical interconnection, optical isolator, optical waveguide, surface light emitting member using organic electroluminescence, surface on which semiconductor fine particles are dispersed Examples thereof include a phosphor member and a phosphor in which a phosphor substance is dissolved or dispersed.

  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.

The evaluation in the polymerization or hydrogenation reaction was carried out by the following method. Both the number average molecular weight and the weight average molecular weight were 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.
○ Monomer conversion rate This was determined by gas chromatography analysis of the solution when the polymerization was stopped. Here, GC14-B (Shimadzu Corporation) was used as the gas chromatograph body, and DB-1MS was used as the column.
○ Hydrogenation rate Measured 10 to 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 integrated value of 4.5 to 6.0 ppm was defined as β-pinene-derived olefinic double bond, and the residual double bond rate was calculated.

Reference 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 (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
The fully dried pressure vessel equipped with a stirrer was sufficiently purged with nitrogen, and then, 1100 parts by mass of dehydrated N-hexane, 1100 parts by mass of dehydrated methylene chloride, and 32 parts by mass of distilled purified β-pinene. And 8 parts by mass of isobutylene 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 39 parts by mass of β-pinene / isobutylene copolymer (A2). Got. When ¹ H-NMR of the β-pinene / isobutylene copolymer (A2) was measured, the content of β-pinene was 81% by mass and isobutylene was 19% by mass. The obtained β-pinene / isobutylene copolymer (A2) had a weight average molecular weight of 45,000 and a number average molecular weight of 28,100.

Reference example 3
After thoroughly substituting the well-dried glass flask with a cock with nitrogen, 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 while stirring at -78 ° C. Further, 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 addition of 60 parts by mass 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 (A3). Monomer conversion was 100%. The obtained β-pinene polymer (A3) 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 an autoclave made of SUS316 equipped with an electromagnetic stirrer, pressure gauge, and gas introduction tube, 0.3 part by mass of 5% palladium / carbon catalyst (Evonik Degussa Japan, E1002NN / W) and 24 parts by mass of cyclohexane, Reference Example 1 6 parts by mass of the obtained β-pinene polymer (A1) and 0.1 parts by mass of triethylamine were added, and the inside was substituted three times with 1 MPa of hydrogen. Next, after pressurizing with 5 MPa of hydrogen and raising the temperature of the autoclave to 220 ° C., the pressure was adjusted with hydrogen so that the total pressure in the autoclave was 8 MPa. The reaction was carried out while maintaining the total pressure of the autoclave at 8 MPa by constantly supplying the hydrogen consumed in the reaction. The reaction was allowed to proceed for 5 hours from the time when the temperature reached 220 ° C., followed by cooling and depressurization to obtain a crude reaction solution, and the catalyst was removed by filtration by pressure filtration using a 0.5 μm mesh Teflon (registered trademark) filter cloth. 5 parts by mass of the filtrate was reprecipitated using 50 parts by mass of methanol / acetone (60/30 vol%) and then sufficiently dried to obtain a β-pinene-based polymer. Table 1 shows the results of analysis of the obtained polymer.

Example 2
Example 1 except that 0.3 parts by mass of a nickel / silica catalyst (manufactured by JGC Chemical Co., Ltd., N102F) was used as the hydrogenation catalyst, and the reaction temperature was changed to 0.1 parts by mass of pyridine instead of triethylamine. The same operation was performed to obtain a β-pinene-based polymer. Table 1 shows the results of analysis of the obtained polymer.

Example 3
Except that 6.0 parts by mass of 5% palladium / alumina catalyst (manufactured by NE Chemcat) as the hydrogenation catalyst, the reaction temperature was changed to 160 parts by mass, and 0.1 parts by mass of t-butoxy potassium instead of triethylamine. The same operation as in Example 1 was performed to obtain a β-pinene polymer. Table 1 shows the results of analysis of the obtained polymer.

Comparative Example 1
A β-pinene polymer was obtained in the same manner as in Example 3 except that t-butoxypotassium was not used and the reaction temperature was 100 ° C. Table 1 shows the results of analysis of the obtained polymer.

Comparative Example 2
Except that pyridine was not used, the same operation as in Example 2 was performed to obtain a β-pinene polymer. Table 1 shows the results of analysis of the obtained polymer.

Comparative Example 3
Except that t-butoxypotassium was not used, the same operation as in Example 3 was performed to obtain a β-pinene polymer. Table 1 shows the results of analysis of the obtained polymer.

Example 4
Β-pinene polymer (A2) obtained in Reference Example 2 as a hydrogenation raw material, nickel / diatomite catalyst (manufactured by JGC Chemical Co., Ltd., N103L) as a hydrogenation catalyst, 6.0 parts by mass, reaction temperature of 180 ° C., triethylamine The β-pinene polymer was obtained in the same manner as in Example 1 except that the content was changed to 0.1 parts by mass of sodium octanoate. Table 1 shows the results of analysis of the obtained polymer.

Comparative Example 4
Except that sodium octoate was not used, the same operation as in Example 4 was performed to obtain a β-pinene polymer. Table 1 shows the results of analysis of the obtained polymer.

Example 5
Using a SUS316 autoclave equipped with a magnetic stirrer, a pressure gauge, and a gas introduction tube, 5% / alumina catalyst (manufactured by NE Chemcat) 1.5 parts by mass, cyclohexane 10 parts by mass, triethylamine 0.02 parts by mass, The interior was replaced three times with 1 MPa of hydrogen. Next, after pressurizing with 5 MPa of hydrogen and raising the temperature of the autoclave to 200 ° C., 3 parts by mass of the β-pinene polymer (A3) obtained in Reference Example 3 and 14 parts by mass of cyclohexane were added, and hydrogen was added to the inside of the autoclave. The pressure was adjusted so that the total pressure was 8 MPa. The reaction was carried out while maintaining the total pressure of the autoclave at 8 MPa by constantly supplying the hydrogen consumed in the reaction. The reaction was allowed to proceed for 5 hours from the time when the temperature reached 200 ° C., followed by cooling and depressurization to obtain a crude reaction solution, and the catalyst was removed by filtration by pressure filtration using a 0.5 μm mesh Teflon (registered trademark) filter cloth. 5 parts by mass of the filtrate was reprecipitated using 500 parts by mass of methanol / acetone (60/30 vol%) and then sufficiently dried to obtain a β-pinene-based polymer. The resulting polymer had a glass transition temperature of 131 ° C. Table 1 shows the results of analysis of the obtained polymer.

Example 6
Using a SUS316 autoclave equipped with a magnetic stirrer, pressure gauge, and gas introduction tube, nickel / silica alumina catalyst (manufactured by JGC Chemical Co., Ltd., E22) 1.5 parts by mass and cyclohexane 24 parts by mass, obtained in Reference Example 3 The β-pinene polymer (A3) (3 parts by mass) and triethylamine (0.02 parts by mass) were added, and the interior was replaced with 1 MPa of hydrogen three times. Next, after pressurizing with 5 MPa of hydrogen and raising the temperature of the autoclave to 200 ° C., the pressure was adjusted with hydrogen so that the total pressure in the autoclave was 8 MPa. The reaction was carried out while maintaining the total pressure of the autoclave at 8 MPa by constantly supplying the hydrogen consumed in the reaction. The reaction was allowed to proceed for 5 hours from the time when the temperature reached 200 ° C., followed by cooling and depressurization to obtain a crude reaction solution, and the catalyst was removed by filtration by pressure filtration using a 0.5 μm mesh Teflon (registered trademark) filter cloth. 5 parts by mass of the filtrate was reprecipitated using 500 parts by mass of methanol / acetone (60/30 vol%) and then sufficiently dried to obtain a β-pinene-based polymer. The resulting polymer had a glass transition temperature of 131 ° C. Table 1 shows the results of analysis of the obtained polymer.

  The examples show that the reaction time is short and the hydrogenation addition rate is as high as 99% or more. From a comparison between Example 3 and Comparative Example 1, it can be seen that when the reaction temperature is lowered, the rate of the hydrogenation reaction is slow. On the other hand, as shown in Comparative Examples 2 to 4, the compound selected from I to IV is not added, and the hydrogenation reaction rate for raising the reaction temperature is increased, but the molecular weight is decreased.

Claims (3)

In a hydrogenation reaction in which an unsaturated bond in the main chain and / or side chain of a polymer containing 30% by mass or more of β-pinene units is converted to a saturated bond to obtain a β-pinene polymer, a metal-containing component is not included. A method for hydrogenating a β-pinene polymer, characterized by using a homogeneous hydrogenation catalyst and coexisting at least one of compounds selected from I to IV below.
I. M (OR) _n
II. M (OC (= O) R ') _n
III. R ¹ R ² R ³ N
IV. Pyridines (wherein M is selected from lithium, sodium, potassium, magnesium and calcium;
R represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms,
n represents 1 or 2,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ^{1 to} R ³ may be different from each other, and may have a ring structure by bonding any two or more, each of which is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. Represents a cycloalkyl group having 12 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 or an alkylene-substituted alkylene group having 6 to 12 carbon atoms, and R ^{1 to} R ³ other than a hydrogen atom 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)   The method according to claim 1, wherein M is any one selected from lithium, sodium, and potassium. The method according to claim 1 or 2, wherein the hydrogenation reaction is carried out at 160 ° C or higher .