WO2009125784A1 - Copolymère de β-pinène et son procédé de fabrication - Google Patents

Copolymère de β-pinène et son procédé de fabrication Download PDF

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WO2009125784A1
WO2009125784A1 PCT/JP2009/057174 JP2009057174W WO2009125784A1 WO 2009125784 A1 WO2009125784 A1 WO 2009125784A1 JP 2009057174 W JP2009057174 W JP 2009057174W WO 2009125784 A1 WO2009125784 A1 WO 2009125784A1
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pinene
copolymer
mass
parts
reaction
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PCT/JP2009/057174
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English (en)
Japanese (ja)
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淳裕 中原
仁 徳安
堀　啓志
大木　弘之
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株式会社クラレ
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Priority to JP2009519071A priority Critical patent/JP5461180B2/ja
Publication of WO2009125784A1 publication Critical patent/WO2009125784A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the present invention relates to a novel ⁇ -pinene copolymer having higher heat resistance and higher light resistance than before, a molded article comprising the same, and a method for producing the same.
  • 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.
  • 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 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.
  • ⁇ -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 ⁇ -pinene polymer is a material having high heat resistance and low water absorption. It has also attracted attention as a carbon neutral material that suppresses the emission of carbon dioxide, which has become a problem in recent years.
  • Non-Patent Document 1 since it is easily oxidized and deteriorated, it has a problem that it is easily colored by light or heat. Further, the ⁇ -pinene polymer described in Non-Patent Document 1 has an example of high light resistance, but in that case, the heat resistance is insufficient.
  • an object of the present invention is to provide a ⁇ -pinene copolymer having excellent heat resistance and light resistance, low water absorption and high transparency, and a molded product thereof.
  • the present invention a ⁇ -pinene copolymer comprising 30 to 80% by mass of ⁇ -pinene units and 70 to 20% by mass of aromatic monomer units, wherein 80 mol% or more of olefinic double bonds are hydrogenated, and This is a molded article made of the ⁇ -pinene copolymer.
  • the present invention also provides It is characterized in that an olefinic double bond and an aromatic ring are hydrogenated in the presence of a palladium catalyst in which a copolymer obtained by copolymerizing ⁇ -pinene and an aromatic monomer is fixed to carbon. This is a method for producing the ⁇ -pinene copolymer.
  • the ⁇ -pinene copolymer of the present invention is particularly suitable for optical applications because it has excellent heat resistance and light resistance, low water absorption, and high transparency.
  • the ⁇ -pinene copolymer of the present invention is a copolymer containing ⁇ -pinene units and aromatic monomer units as structural units. This is a polymer obtained by hydrogenating the coalescence.
  • the copolymer used for hydrogenation is obtained by copolymerizing monomers including ⁇ -pinene and an aromatic monomer.
  • ⁇ -pinene for use in the present invention can be used. That is, those collected from plants such as pine, ⁇ -pinene synthesized from other raw materials such as ⁇ -pinene, and the like can also be used.
  • Aromatic monomer The aromatic monomer used in the present invention is not particularly limited as long as it is a polymerizable monomer having an aromatic group, and examples thereof include styrene, ⁇ -methylstyrene, 3 -Methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene, indene and the like can be mentioned. From the viewpoint of availability and easy copolymerization with ⁇ -pinene, styrene, ⁇ -methylstyrene, and indene are preferable. These aromatic monomers may be used alone or in combination of two or more.
  • the copolymer used in the present invention is a copolymer obtained by polymerizing the above ⁇ -pinene and an aromatic monomer in combination at a predetermined copolymerization ratio.
  • Specific examples of the copolymer include ⁇ -pinene / styrene copolymer, ⁇ -pinene / ⁇ -methylstyrene copolymer, ⁇ -pinene / 3-methylstyrene copolymer, ⁇ -pinene / 4-methylstyrene copolymer.
  • the structure of the copolymer is not particularly limited, and any of random, block and tapered copolymers may be used.
  • the copolymer is particularly preferably a random copolymer from the viewpoint of heat resistance.
  • the mass ratio of ⁇ -pinene units to aromatic monomer units ( ⁇ -pinene / aromatic monomer) in the copolymer used in the present invention is the heat resistance of the copolymer obtained after the hydrogenation reaction. From the viewpoint of property and mechanical strength, the range of 30/70 to 80/20 is preferable, and the range of 40/60 to 80/20 is more preferable. If the amount of ⁇ -pinene is too small, the heat resistance of the copolymer obtained after hydrogenation becomes low, and if the amount of ⁇ -pinene is too large, the copolymer obtained after hydrogenation becomes brittle.
  • the copolymer of the present invention may contain other monomer units copolymerizable with ⁇ -pinene and aromatic monomers as constituent units.
  • the copolymerizable monomer is not particularly limited as long as it is a vinyl monomer. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid.
  • (Meth) acrylic monomers such as butyl, 2-hydroxyethyl (meth) acrylate and glycidyl (meth) acrylate; maleic anhydride, maleic acid, fumaric acid, maleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, and norbornene; Oil-derived double bond-containing compounds; vinyl acetate, piva Examples thereof include vinyl phosphate, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.
  • 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 amount of copolymerization is preferably 0.001 to 20 mol% per total monomer unit in the polymer, More preferred is ⁇ 10 mol%. If the amount of copolymerization is too large, polymerization may become difficult, and heat resistance often decreases.
  • the number average molecular weight of the copolymer containing ⁇ -pinene and aromatic monomer used in the present invention is not particularly limited, but the mechanical properties and processability of the copolymer obtained after hydrogenation In view of the above, about 10,000 to 1,000,000 g / mol is preferable. If the number average molecular weight is too small, the mechanical strength is insufficient, and if it is too large, molding becomes difficult.
  • the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.
  • the copolymer used for hydrogenation has an olefinic double bond of a cyclohexene ring derived from a ⁇ -pinene unit and an aromatic ring derived from an aromatic monomer.
  • the hydrogenated copolymer of the present invention preferably has an olefinic double bond derived from ⁇ -pinene at 20 mol% based on ⁇ -pinene units in the copolymer in order to prevent deterioration due to oxygen in the air. Below, more preferably 10 mol% or less, still more preferably 1 mol% or less, and most preferably 0.5 mol% or less.
  • the ⁇ -pinene copolymer of the present invention is not generally determined by the copolymerization ratio, but it is 4.5 to 6 ppm in its 1 H-NMR spectrum [the proton of tetramethylsilane (TMS) is 0 ppm].
  • the ratio of the integral value of protons to the integral value of all protons is preferably 1.1 ⁇ 10 ⁇ 2 or less, more preferably 5 .6 ⁇ 10 ⁇ 3 or less.
  • the quantity of an olefinic double bond may increase and may deteriorate easily.
  • the hydrogenated copolymer of the present invention preferably has an aromatic ring derived from an aromatic monomer in the aromatic monomer unit in the copolymer in order to improve heat resistance and transmittance. It is 50 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and most preferably 1 mol% or less.
  • the ⁇ -pinene-based copolymer of the present invention is not generally defined by the copolymerization ratio, but it is 6-8 ppm proton in its 1 H-NMR spectrum [tetramethylsilane (TMS) proton is 0 ppm].
  • TMS tetramethylsilane
  • the ratio of the integral value of 1 to the integral value of all protons (6-8 ppm proton integral value / total proton integral value) is preferably 4.3 ⁇ 10 ⁇ 2 or less, more preferably 2.2 ⁇ 10 -2 or less.
  • Tg Glass transition temperature
  • DSC differential scanning calorimetry
  • Tg cannot be generally defined by the type and content of the aromatic monomer used, the hydrogenation rate of the olefinic double bond, and the hydrogenation rate of the aromatic ring, but is preferably 135 ° C to 250 ° C, more preferably 140 ° C More preferred is ⁇ 240 ° C. If Tg is low, the heat resistance is insufficient, and if it is too high, the ⁇ -pinene copolymer becomes brittle.
  • the ⁇ -pinene copolymer of the present invention preferably has a high total light transmittance particularly when used in an optical material.
  • the total light transmittance of the ⁇ -pinene copolymer 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 of total light transmittance of transparent materials—Part 1: Jingle beam method”.
  • the ⁇ -pinene copolymer of the present invention preferably has higher light resistance and weather resistance.
  • an accelerated exposure test for 100 hours with UVB light is performed according to ASTM-G53, and the yellowing degree ( ⁇ YI) 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.
  • a copolymer having a high 5% mass reduction temperature can be obtained.
  • the 5% mass reduction temperature of the ⁇ -pinene copolymer 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) in accordance with JIS-K-7120-1987 “Thermo mass measurement method for plastics”.
  • a copolymer containing ⁇ -pinene and an aromatic monomer as a structural unit is a cationic polymerization, radical polymerization method, coordination polymerization method, etc. It can be obtained by a known method. From the viewpoint that it can be easily carried out industrially and a high molecular weight product can be obtained, a cationic polymerization method is particularly preferred.
  • Cationic polymerization 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 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 ⁇ -pinene and aromatic monomers are dissolved and is inert to the polymerization catalyst.
  • 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.
  • 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.
  • the amount of the inert organic solvent is not particularly limited, but is usually 100 to 10,000 parts by weight, preferably 100 to 10,000 parts by weight, preferably 100 parts by weight of ⁇ -pinene and aromatic monomers. 150-5000 parts by mass, more preferably 200-3000 parts by mass. 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.
  • 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
  • oxo acid Contact Beauty polymer compounds such as ion-exchange resins having these groups; phosphomolybdic acid, heteropoly acids such as phosphotungstic acid; SiO 2, Al 2 O 3 , SiO 2 -Al 2 O 3, MgO-SiO 2, B 2 O 3 -Al 2 O 3 , WO 3 -Al 2 O 3 , Zr 2 O 3 -SiO 2 , sulfated zirconia, tungstate zirconia, zeolite exchanged with H + or rare earth elements, activated clay, acidic clay, ⁇ -Al 2 Examples thereof include solid acids such as solid phosphoric acid in which O 3 and P 2 O 5 are supported on diatomaceous earth.
  • 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.
  • 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.
  • the amount used is ⁇ -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.
  • the amount used is preferably 0.1 to 10,000 parts by mass with respect to 100 parts by mass of ⁇ -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 for performing cationic polymerization is not particularly limited as long as it is a compound that generates more cations as a polymerization catalyst, but an organic compound having at least one functional group represented by the following formula is preferably used. .
  • R 1 represents hydrogen, an alkyl group, or an aryl group
  • R 2 represents hydrogen, an alkyl group, or an aryl group
  • X represents a halogen, an alkoxy group, an acyloxy group, or a hydroxyl group.
  • the amount of the polymerization initiator used in the cationic polymerization varies depending on the molecular weight of the target copolymer, it is difficult to generally define the amount used, but the amount of ⁇ -pinene and aromatic monomer is 100 parts by mass. On the other hand, it is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and most preferably 0.01 to 1 part by mass.
  • 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.
  • the molecular weight of the copolymer obtained will become small and a copolymer will become weak.
  • the polymerization reaction when cationic polymerization is performed, the polymerization reaction can be further controlled by adding an electron-donating compound.
  • 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 copolymer that can produce a large amount of low molecular weight compounds is lowered. Conversely, when there are too many electron donors, the polymerization reaction rate is remarkably suppressed, and the cationic polymerization reaction takes a long time, and the productivity is lowered. Therefore, 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 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.
  • copolymer after the cationic polymerization is isolated from the solution by, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. It can be separated and obtained from the reaction mixture by ordinary operations.
  • the hydrogenated ⁇ -pinene copolymer according to the present invention can be obtained by a hydrogenation reaction, but the hydrogenation method is not particularly limited, and any known method can be used. Can be taken.
  • -Hydrogenation catalyst In this invention, what can hydrogenate an olefin compound and an aromatic compound can be used for the catalyst in the case of performing hydrogenation reaction. Usually, a heterogeneous catalyst or a homogeneous catalyst is used.
  • the catalyst when the hydrogenation reaction is performed using a heterogeneous catalyst is not particularly limited, but specific examples include sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper.
  • sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper.
  • the catalyst when the hydrogenation reaction is carried out using a homogeneous catalyst is not particularly limited, but specific examples include a catalyst comprising a transition metal compound and alkylaluminum or alkyllithium. It is done.
  • the transition metal compound include nickel salts such as nickel acetate, nickel octylate and nickel acetylacetonate, cobalt salts such as cobalt acetate, cobalt octylate and cobalt acetylacetonate, titanocene dichloride, zirconocene dichloride and the like. It is done.
  • alkylaluminum examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum and the like.
  • alkyl lithium examples include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium and the like.
  • the homogeneous catalyst may be used alone or in combination. Moreover, you may mix and use a heterogeneous catalyst.
  • the copolymer is hydrogenated, so that the reaction activity is generally low for low molecular weight compounds.
  • reaction conditions relatively high temperature and high pressure conditions are often preferred as reaction conditions, and it is preferable to carry out with a heterogeneous catalyst having high thermal stability.
  • nickel or palladium is preferably used as the metal having hydrogenation activity, and a palladium compound is more preferably used.
  • calcium carbonate or a carbon support in order to suppress an undesirable side reaction that proceeds during hydrogenation, it is preferable to use calcium carbonate or a carbon support, and it is more preferable to use a carbon support.
  • the solvent which can be used for this invention is not specifically limited, What dissolves a copolymer easily is preferable. Since the solvent differs depending on the comonomer, it is difficult to limit, but specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene; pentane, hexane, heptane, octane, Aliphatic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, tricyclodecane; halogens such as methyl chloride, methylene chloride, propane chloride, butane chloride, 1,2-dichloroethane, 1,1,2-trichloroethylene Hydrocarbon solvents; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane, tetra
  • the solvent used in the polymerization step when the hydrogenation reaction is performed, 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.
  • 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 is such that the concentration of the copolymer is from 1% by mass to 30% by mass.
  • the productivity is remarkably reduced, and when it is 30% by mass or more, the solution viscosity is remarkably increased and the mixing efficiency is lowered.
  • the pressure of the hydrogenation reaction may vary depending on the catalyst used and cannot necessarily be specified, but usually the total pressure of the hydrogenation reaction is 0.1 MPa. -30 MPa, preferably 0.5 MPa to 20 MPa, more preferably 1 MPa to 15 MPa. In general, the higher the hydrogen gas partial pressure is, the more advantageous it is for hydrogenation. However, when the pressure is 30 MPa or more, the cost for the equipment for boosting pressure and the equipment having a pressure-resistant structure increases, which is not desirable.
  • the hydrogenation reaction is carried out under the condition where hydrogen gas is present. However, in addition to hydrogen gas, the hydrogenation reaction may be carried out by mixing with any gas as long as it is inert to the hydrogenation reaction. Specific examples of the inert gas include nitrogen, helium, argon, carbon dioxide and the like.
  • the solvent used for the reaction may have a partial pressure at a significant ratio as a gas component, but there is no problem.
  • the temperature of the hydrogenation reaction may vary depending on the catalyst used and cannot always be specified, but is usually 10 ° C to 300 ° C, preferably Is from 60 ° C to 250 ° C, more preferably from 70 ° C to 220 ° C. In general, a heterogeneous catalyst may be used at a higher temperature than a homogeneous system.
  • the hydrogenation reaction time varies depending on the type of catalyst used, the amount of catalyst, and the reaction temperature, and thus is not necessarily limited, but is usually 5 minutes to 20 hours, preferably 10 minutes to 15 hours. If the reaction time is too short, the desired hydrogenation rate cannot be obtained. Moreover, when reaction time is too long, the progress of the undesired side reaction will become remarkable and the hydrogenated polymer of the desired physical property may not be obtained.
  • embodiment of hydrogenation reaction can take arbitrary well-known methods.
  • a batch reaction a semi-continuous reaction, or a continuous reaction system can be adopted.
  • a plug flow format PFR
  • CSTR continuous flow stirring format
  • a fixed bed reaction tank can be used.
  • two or more reaction forms which are the same or different can be connected to carry out the hydrogenation reaction.
  • the amount of catalyst used is difficult to limit because it varies, but generally when using a heterogeneous catalyst in a suspended bed,
  • the amount of catalyst used per 100 parts by mass of the hydrogenation reaction liquid is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass.
  • the amount used is small, the hydrogenation reaction requires a long time.
  • the amount used is large, a large amount of power for mixing the heterogeneous catalyst is required.
  • the concentration of the transition metal compound in the hydrogenation reaction solution is 0.001 mmol / liter to 100 mmol / liter, more preferably 0.01 mmol / liter to 10 mmol / liter. is there.
  • the used hydrogenation catalyst can be separated from the copolymer as necessary after completion of the hydrogenation reaction.
  • the separation can be carried out by any known method, but when a heterogeneous catalyst is used, the separation can be carried out by continuous or batch filtration, centrifugal separation, or settling / decantation by standing.
  • a homogeneous catalyst it can be separated from the catalyst by using, for example, an aggregation precipitation method, an adsorption method, a washing method, an aqueous phase extraction method, or the like.
  • the catalyst is separated using these separation methods, a trace amount of metal components may remain in the copolymer. Also in this case, since the metal component is dissolved, as described above, the remaining metal can be separated by using the coagulation precipitation method, the adsorption method, the washing method, the aqueous phase extraction method, and the like.
  • the catalyst recovered by the separation can be used again in the hydrogenation reaction after removing a part of the catalyst or adding a new catalyst as necessary.
  • the ⁇ -pinene copolymer after hydrogenation is prepared by, for example, re-precipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc.
  • the product can be separated and obtained from the reaction mixture by a normal operation for isolation from the reaction mixture.
  • the ⁇ -pinene copolymer of the present invention may be used alone, or may be polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, It can also be used as a composition blended with other polymers such as polystyrene and styrenic block copolymers.
  • stabilizers 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.
  • a molded product of the ⁇ -pinene copolymer of the present invention can be obtained according to a conventional 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.
  • an injection molding method, a hot press molding method, and an extrusion molding method are preferably used.
  • the ⁇ -pinene-based copolymer of the present invention can be used for various optical materials, and the range thereof is not particularly limited, but is excellent in heat resistance, and is required to have low water absorption and high transparency. Suitable for material.
  • 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.
  • 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.
  • 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.
  • 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.
  • the light diffusible molded body is a mixture of the above-mentioned ⁇ -pinene copolymer and further containing a conventional light diffusing agent, and the obtained light diffusibility.
  • a molded body having a predetermined shape such as a plate shape or a block shape is formed using the composition.
  • Functional thin film A functional thin film formed by coating on at least one surface of a substrate using a ⁇ -pinene copolymer is not particularly limited, but preferably an antistatic layer, an antireflection layer, a hard It is a thin film having functionality such as a coat layer, a transparent conductive layer, and an antiglare layer.
  • Optical film An optical film using a ⁇ -pinene copolymer is particularly suitable for a polarizing plate protective film.
  • the method for forming such an optical film is not particularly limited, and various conventionally known methods such as a solution casting method and a melt extrusion method can be employed.
  • 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.
  • 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.
  • 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 f ⁇ lens, a pickup lens, and the like. Various lenses are applicable.
  • Vehicle 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.
  • 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.
  • Reference example 1 The well-dried glass flask with a cock was sufficiently purged with nitrogen, and then, 1100 parts by mass of dehydrated N-hexane, 1100 parts by mass of dehydrated methylene chloride, and 23 parts by mass of distilled purified ⁇ -pinene. Part, 20 parts by mass of ⁇ -methylstyrene, 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.
  • the obtained ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) has a weight average molecular weight of 33,000, a number average molecular weight of 20,000, and ⁇ -pinene / ⁇ -methylstyrene determined from 1 H-NMR. The mass ratio of the units was 51/49.
  • the obtained ⁇ -pinene / ⁇ -methylstyrene copolymer (A2) has a weight average molecular weight of 38,000, a number average molecular weight of 22,000, and ⁇ -pinene / ⁇ -methylstyrene determined from 1 H-NMR. The mass ratio of the units was 81/19.
  • Reference example 3 The well-dried glass flask with a cock was sufficiently purged with nitrogen, and then added 208 parts by mass of dehydrated N-hexane, 240 parts by mass of dehydrated methylene chloride, and 0.58 parts by mass of dehydrated diethyl ether. Cooled down. Further, 8.2 parts by mass of a 1.0 mol / L hexane solution of ethylaluminum dichloride was added with stirring at ⁇ 78 ° C. Furthermore, when 4.4 parts by mass of a 0.1 mol / L hexane solution of p-dicumulyl chloride was added while maintaining at -78 ° C., the color changed to red.
  • the obtained organic layer was reprecipitated in 5000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%) and sufficiently dried to obtain 45 parts by mass of ⁇ -pinene / ⁇ -methylstyrene copolymer (A3). It was.
  • the obtained ⁇ -pinene / ⁇ -methylstyrene copolymer (A3) has a weight average molecular weight of 150,000, a number average molecular weight of 39,000, and a ⁇ -pinene / ⁇ -methylstyrene unit determined from 1 H-NMR.
  • the mass ratio was 78/22, and the glass transition temperature was 103 ° C.
  • the mixed monomer solution was changed to a mixed monomer solution of 23 parts by mass of purified ⁇ -pinene, 20 parts by mass of ⁇ -methylstyrene and 1.6 parts by mass of p-diisopropenylbenzene. 44 parts by mass of ⁇ -pinene / ⁇ -methylstyrene copolymer (A4) was obtained.
  • the obtained ⁇ -pinene / ⁇ -methylstyrene copolymer (A4) has a weight average molecular weight of 199,000, a number average molecular weight of 41,000, and a ⁇ -pinene / ⁇ -methylstyrene unit determined from 1 H-NMR.
  • the mass ratio was 48/52, and the glass transition temperature was 133 ° C.
  • Reference Example 5 44 parts by mass of the ⁇ -pinene / indene copolymer (A5) was obtained in the same manner as in Reference Example 3 except that the mixed monomer solution was changed to a mixed monomer solution having 23 parts by mass of purified ⁇ -pinene and 20 parts by mass of indene. Obtained.
  • the resulting ⁇ -pinene / indene copolymer (A5) has a weight average molecular weight of 59,400, a number average molecular weight of 25,900, and a mass ratio of ⁇ -pinene / indene units determined from 1 H-NMR of 52/400. 48.
  • the glass transition temperature was 140 ° C.
  • Example 1 Next, 123 parts by mass of cyclohexane and 30 parts by mass of the ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) obtained above are accommodated and stirred in a pressure vessel equipped with a stirrer purged with nitrogen. Thus, the ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) was completely dissolved. Thereafter, 15 parts by mass of 5% palladium-supported carbon (product number: E1002NN / W manufactured by Evonik Degussa Japan Co., Ltd.) was added as a hydrogenation catalyst, stirred, and sufficiently dispersed. After replacing with hydrogen and stirring, reaction was performed at 130 ° C.
  • palladium-supported carbon product number: E1002NN / W manufactured by Evonik Degussa Japan Co., Ltd.
  • Example 2 Next, in the same manner as in Example 1, except that ⁇ -pinene / ⁇ -methylstyrene copolymer (A2) was used instead of ⁇ -pinene / ⁇ -methylstyrene copolymer (A1), ⁇ -pinene was used. A system copolymer (H2) was obtained. The ⁇ -pinene copolymer (H2) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 1.6 mol%, and the remaining aromatic ring was 2.5 mol%. there were. The glass transition temperature was 142 ° C.
  • Example 3 A ⁇ -pinene copolymer was used in the same manner as in Example 1 except that ⁇ -pinene / ⁇ -methylstyrene copolymer (A3) was used instead of ⁇ -pinene / ⁇ -methylstyrene copolymer (A1). A polymer (H3) was obtained. The ⁇ -pinene copolymer (H3) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 1.9 mol%, and the remaining aromatic ring was 8.1 mol%. there were. The glass transition temperature was 144 ° C.
  • Example 4 A ⁇ -pinene copolymer was used in the same manner as in Example 1 except that a ⁇ -pinene / ⁇ -methylstyrene copolymer (A4) was used instead of the ⁇ -pinene / ⁇ -methylstyrene copolymer (A1). A polymer (H4) was obtained. The ⁇ -pinene copolymer (H4) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 0.6 mol% and the remaining aromatic ring was 2.8 mol%. there were. The glass transition temperature was 160 ° C.
  • Example 5 A ⁇ -pinene copolymer (A5) was used in the same manner as in Example 1 except that a ⁇ -pinene / indene copolymer (A5) was used instead of the ⁇ -pinene / ⁇ -methylstyrene copolymer (A1). H5) was obtained. The ⁇ -pinene copolymer (H5) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 2.9 mol%, and the remaining aromatic ring was 9.8 mol%. there were. The glass transition temperature was 188 ° C.
  • the physical-property measurement was performed as follows.
  • ⁇ Molding The obtained ⁇ -pinene copolymer was prepared as a test piece by press molding or injection molding. In press molding, a molded body of 50 mm ⁇ 50 mm ⁇ 3 mmt size was obtained at 180 ° C. Injection molding was performed using a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and a mold of 50 mm ⁇ 50 mm ⁇ 3 mmt.
  • the residual double bond ratio was calculated by setting the integrated value of 4.5 to 6 ppm as the olefinic double bond derived from ⁇ -pinene and the integrated value of 6 to 8 ppm as the aromatic ring.
  • Tg Glass transition temperature
  • DSC30 product number manufactured by METTLER TOLEDO Co., Ltd. was used as the measuring device.
  • HR-100 product number manufactured by Murakami Color Research Co., Ltd.
  • ⁇ Light Resistance Test According to ASTM-G53, an accelerated exposure test for 100 hours was performed, and the yellowing degree ( ⁇ YI) before and after the test of YI (yellow index) was measured.
  • ⁇ YI yellowing degree
  • an ultraviolet exposure tester ATLAS-UVCON manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • YI was measured according to JIS-K-7373. And it evaluated according to the following criteria.
  • ⁇ YI (YI after 100 hours of UV exposure) ⁇ (YI before UV exposure) ⁇ : ⁇ YI ⁇ 10 Good long-term light resistance ⁇ : 10 ⁇ YI Long-term light resistance is poor
  • Comparative 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 ⁇ -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.
  • ⁇ -pinene polymer (B1) had a weight average molecular weight of 53,000 and a number average molecular weight of 32,000.
  • Comparative Example 2 The ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) obtained in Reference Example 1 was used as this comparative example.
  • Comparative Example 3 The ⁇ -pinene / ⁇ -methylstyrene copolymer (A2) obtained in Reference Example 2 was used as this comparative example. The evaluation results are shown in Table 2.
  • Comparative Example 4 Indene / ⁇ -pinene copolymer (B3) was obtained in the same manner as in Example 12 of JP-A No. 2002-121231.
  • the resulting indene / ⁇ -pinene copolymer (B3) had a weight average molecular weight of 64,000 and a number average molecular weight of 24,300.
  • Table 2 shows the evaluation results of the indene / ⁇ -pinene copolymer (B3).
  • Comparative Example 5 A ⁇ -pinene / ⁇ -methylstyrene copolymer (in the same manner as in Reference Example 3, except that the mixed monomer solution was changed to a distilled monomer-purified mixed monomer solution of 42 parts by weight of ⁇ -pinene and 4 parts by weight of ⁇ -methylstyrene. A6) 45 parts by mass were obtained.
  • the obtained ⁇ -pinene / ⁇ -methylstyrene copolymer (A6) has a weight average molecular weight of 43,000, a number average molecular weight of 23,700, and a ⁇ -pinene / ⁇ -methylstyrene unit determined from 1 H-NMR. The mass ratio was 90/10, and the glass transition temperature was 97 ° C.
  • Example 6 A ⁇ -pinene copolymer was used in the same manner as in Example 1 except that ⁇ -pinene / ⁇ -methylstyrene copolymer (A6) was used instead of ⁇ -pinene / ⁇ -methylstyrene copolymer (A1). A polymer (H6) was obtained. The ⁇ -pinene copolymer (H6) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 0.5 mol%, and the remaining aromatic ring was 3.7 mol%. there were. The glass transition temperature was 134 ° C.
  • Comparative Example 7 In a pressure vessel equipped with a stirring apparatus purged with nitrogen, 123 parts by mass of cyclohexane and 30 parts by mass of the ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) obtained above were accommodated and stirred. The ⁇ -pinene / ⁇ -methylstyrene copolymer (A1) was completely dissolved. The inside of the pressure vessel was sufficiently replaced with hydrogen, and 7 parts by mass of the hydrogenation catalyst prepared in Reference Example 6 was added while stirring at 1000 rpm at room temperature. Immediately, the pressure was increased to 1 MPa with hydrogen and the temperature was raised to 50 ° C.
  • the obtained cyclohexane layer was re-precipitated in 3000 parts by mass of a mixed solvent of methanol / acetone (60/40 vol%), and then sufficiently dried to obtain 29 parts by mass of ⁇ -pinene copolymer (H7). Obtained.
  • the ⁇ -pinene copolymer (H7) thus obtained was measured for 1 H-NMR. As a result, the remaining olefinic double bond was 50 mol% and the remaining aromatic ring was 94 mol%.
  • the glass transition temperature was 139 ° C.
  • ⁇ -pinene units comprising 30 to 80% by mass of ⁇ -pinene units and 70 to 20% by mass of aromatic monomer units, and hydrogenated and added with an olefinic double bond of 80 mol% or more. It can be seen that the coalescence has high heat resistance and is excellent in total light transmittance and light resistance. From Examples and Comparative Examples 1, 5 and 6, it can be seen that heat resistance is low when the aromatic monomer is not included or is less than 20% by mass. From Examples and Comparative Examples 2, Comparative Example 3, Comparative Example 4, and Comparative Example 7, it can be seen that light resistance and heat resistance are improved by hydrogenating 80 mol% or more of olefinic double bonds.

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Abstract

Cette invention concerne un copolymère de β-pinène très transparent ayant une excellente résistance à la chaleur et tenue à la lumière et manifestant une basse absorption d'eau; et un article moulé le contenant. Le copolymère de β-pinène selon l'invention comprend de 30 à 80 % en poids de motifs β-pinène et de 70 à 20 % en poids de motifs monomères aromatiques du type α-méthylstyrène, et est obtenu par hydrogénation et ajout d'au moins 80 % en mole de doubles liaisons oléfiniques et, de préférence, d'au moins 50 % en mole de cycles aromatiques dérivés de monomères aromatiques.
PCT/JP2009/057174 2008-04-10 2009-04-08 Copolymère de β-pinène et son procédé de fabrication WO2009125784A1 (fr)

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JPWO2009125828A1 (ja) * 2008-04-10 2011-08-04 株式会社クラレ β−ピネン系重合体及びそれからなる成形体
JP5478249B2 (ja) * 2008-04-10 2014-04-23 株式会社クラレ 水素化β−ピネン系重合体及びそれからなる成形体
CN112646099A (zh) * 2020-12-03 2021-04-13 宁波职业技术学院 一种β-蒎烯-异丁烯-茚共聚树脂的制备方法及其在聚丙烯增韧改性中的应用
CN116162196A (zh) * 2022-12-26 2023-05-26 广西民族大学 浅色高稳定性氢化萜烯酚苯乙烯树脂及其制备方法和应用

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WO2008044640A1 (fr) * 2006-10-11 2008-04-17 Yasuhara Chemical Co., Ltd. POLYMÈRE DE β-PINÈNE ET SON PROCÉDÉ DE PRODUCTION
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Publication number Priority date Publication date Assignee Title
JPWO2009125828A1 (ja) * 2008-04-10 2011-08-04 株式会社クラレ β−ピネン系重合体及びそれからなる成形体
JP5478249B2 (ja) * 2008-04-10 2014-04-23 株式会社クラレ 水素化β−ピネン系重合体及びそれからなる成形体
CN112646099A (zh) * 2020-12-03 2021-04-13 宁波职业技术学院 一种β-蒎烯-异丁烯-茚共聚树脂的制备方法及其在聚丙烯增韧改性中的应用
CN112646099B (zh) * 2020-12-03 2022-08-19 宁波职业技术学院 一种β-蒎烯-异丁烯-茚共聚树脂的制备方法及其在聚丙烯增韧改性中的应用
CN116162196A (zh) * 2022-12-26 2023-05-26 广西民族大学 浅色高稳定性氢化萜烯酚苯乙烯树脂及其制备方法和应用

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