JP2012036280A - METHOD FOR PRODUCING β-PINENE-BASED POLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for advantageously producing a β-pinene-based polymer with a high molecular weight, especially a high number-average molecular weight, through regulating the cationic (co)polymerization of cationically polymerizable monomer(s) including at least β-pinene.SOLUTION: The method for producing the β-pinene-based polymer by cationic polymerization or cationic copolymerization of cationically polymerizable monomer(s) including at least β-pinene is provided. In this method, a Lewis acid is used as a polymerization catalyst, and an isocyanide compound is used as an electron donor.

Description

  The present invention relates to a method for producing a β-pinene polymer, and more particularly to a method for industrially advantageously producing a β-pinene polymer having a large number average molecular weight (hereinafter also simply referred to as molecular weight). It is.

  In recent years, the demand for optical resins has been increasing, and there is a demand for resins having low water absorption and high transparency as well as excellent heat resistance and light resistance. However, it is difficult to say that conventional optical resins are provided with these required performances in a well-balanced manner with high dimensions, and have various drawbacks.

  For example, polymethyl methacrylate, polycarbonate, and the like have been conventionally used as highly transparent optical resins. Polymethyl methacrylate is excellent in optical properties such as high transparency and low birefringence, but has the disadvantages that its dimensions are easily changed and its heat resistance is low due to its large water absorption. On the other hand, polycarbonate 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 optical resins with high heat resistance, low water absorption, and excellent transparency, ring-opening polymer hydrogenated products of norbornene monomers and addition copolymers of norbornene monomers and ethylene are known. ing. However, tetracyclododecene polycyclic monomers used as norbornene monomers are not always easy to produce, and molybdenum and tungsten chlorides are used as catalysts when polymerizing such monomers. It is necessary to use rare metals such as.

  As optical resins that have improved the above problems, β-pinene polymers and indene polymers have been proposed (see Patent Document 1, Non-Patent Documents 1 and 2). In particular, the β-pinene-based polymer is a material having high heat resistance and low water absorption, and is also attracting attention as a so-called carbon neutral material that suppresses the emission of carbon dioxide, which has been a problem in recent years. In the present specification and claims, the β-pinene polymer is not only a β-pinene homopolymer obtained by using only β-pinene as a monomer, but also β-pinene and one or more other types. And a copolymer obtained by copolymerizing the above monomer.

  However, there are a number of problems in the industrial production of β-pinene polymers, and at present, they have not been put into practical use. For example, according to the production method shown in Patent Document 2, β- having a molecular weight (number average molecular weight: 45000 or more) necessary to produce a molded product having the same strength as other commercially available plastics. A pinene polymer has been obtained. However, the β-pinene polymer described in Patent Document 2 is produced under limited conditions at an extremely low temperature of −78 ° C., has a large environmental load, and is a major obstacle to industrial production. It becomes. Further, at a high temperature (−10 ° C.), the molecular weight of the polymer decreases, and a molded product having sufficient strength cannot be produced. The reason is considered that β-pinene undergoes polymerization while isomerizing, so that the degree of polymerization does not increase so much. In fact, there is a description that it is preferable to introduce a crosslinking agent in order to obtain a β-pinene polymer having a target molecular weight (see Patent Document 2).

  About the manufacturing method of (beta) -pinene-type polymer, various things other than patent document 2 are reported (refer patent documents 3-5). For example, a method using pyridines, dimethyl sulfoxide, dimethylacetamide or the like that has an effect of stabilizing the polymerization has been reported as a method for producing a β-pinene polymer (see Patent Document 3). However, electron donors such as pyridine are generally high in basicity and are known to form insoluble complexes with the polymerization catalyst. As a result, the polymer solution may be suspended or in some cases Large amounts of deposits can form on the walls. For this reason, the polymer obtained from such a solution is often accompanied by white turbidity and has a problem of reducing the quality of the product (see Patent Document 3).

  Further, from the viewpoint of controlling the molecular weight of the polymer, several examples of polymerization aimed at increasing the molecular weight have been reported. For example, when isobutylene is cationically polymerized using a proton-donating compound such as alcohol and a Lewis acid, amines (including pyridines), amides, and esters are used as an electron donor to increase the molecular weight. It has been reported that a polymer of (1) can be obtained.

  However, in the production method shown in Patent Document 4, it is difficult to obtain a polymer having a narrow molecular weight distribution by controlling the molecular weight (see Patent Document 5).

  On the other hand, by using phosphines and phosphites, it has been reported that the polymerization control becomes easy, a high molecular weight polymer having a narrow molecular weight distribution can be synthesized, and the functionalization of the terminal can be easily performed. (See Patent Document 5).

  However, phosphorus compounds such as phosphines and phosphites have an emulsifying action, and in the steps of quenching the catalyst after the polymerization, washing the polymer solution, and taking out the polymer, a quench solution or washing solution (mainly water) Or weakly acidic water) and the polymerization solution are remarkably reduced, which is a major obstacle to industrial production.

  In addition, a production method using a metal alkoxide as an electron donor has been reported (see Patent Document 7). However, it is difficult to control the molecular weight, and no polymer having the desired molecular weight has been obtained.

JP 2002-121231 A WO2008 / 044640 JP 9-291115 A JP 47-11139 A Japanese Examined Patent Publication No. 7-59602

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

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is cation (co) polymerization of a cationic polymerizable monomer containing at least β-pinene. An object of the present invention is to provide a method capable of controlling and advantageously producing a β-pinene polymer having a large molecular weight, particularly a number average molecular weight.

  And when the present inventors diligently studied to solve the above-mentioned problems, the above-mentioned problems can be solved by using isocyanides as electron donors in the cationic (co) polymerization. As a result, the present invention has been completed.

  That is, the present invention uses a Lewis acid as a polymerization catalyst in a method for producing a β-pinene polymer by cationic polymerization or cationic copolymerization of a cationic polymerizable monomer containing at least β-pinene, and The gist of the method for producing a β-pinene polymer, characterized in that isocyanides are used as an electron donor.

〔式中、Ｒ¹ はアルキル基又は置換基を有してもよいアリール基であり、Ｘ¹ はハロ ゲン原子である。α及びβは０〜３であり、α＋β＝３を満たす。〕 In the first preferred embodiment of the method for producing a β-pinene polymer according to the present invention, the Lewis acid is a compound represented by the following chemical formula (1).

[Wherein, R ¹ represents an alkyl group or an aryl group which may have a substituent, and X ¹ represents a halogen atom. α and β are 0 to 3 and satisfy α + β = 3. ]

  In a second preferred embodiment of the method for producing a β-pinene polymer according to the present invention, the isocyanide is t-butyl isocyanide or 2,6-dimethylphenyl isocyanide.

  Furthermore, a preferred third embodiment in the method for producing a β-pinene polymer of the present invention further uses a polymerization initiator.

〔式中、Ｒ² 〜Ｒ⁵ はそれぞれ独立して、水素原子、アルキル基又はアリール基であ り、Ｘ² 及びＸ³ はそれぞれ独立して、アルコキシ基、アシロキシ基、水酸基又は ハロゲン原子であり。Ｒ⁶ は、置換基を有していてもよいアルキレン基、シクロア ルキレン基又はアリーレン基である。〕 In addition, in a fourth preferred embodiment of the present invention, the polymerization initiator is a compound represented by the following chemical formula (2).

[Wherein, R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group or an aryl group, and X ² and X ³ are each independently an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. . R ⁶ is an alkylene group, a cycloalkylene group or an arylene group which may have a substituent. ]

  In a fifth preferred embodiment of the method for producing a β-pinene polymer of the present invention, the isocyanides are used in a proportion of 0.01 to 10 molar equivalents based on the amount of the Lewis acid used.

  Furthermore, in a sixth preferred embodiment of the production method of the present invention, the Lewis acid is used in a proportion of 0.001 to 1 molar equivalent based on the amount of the cationic polymerizable monomer used.

  In addition, in a seventh preferred embodiment of the production method of the present invention, the cationic polymerization initiator is used in a proportion of 0.00001 to 0.1 molar equivalent based on the amount of the cationic polymerizable monomer used. To do.

  In a preferred eighth aspect of the production method of the present invention, the cationic polymerization or cationic copolymerization is carried out according to a solution polymerization method.

  Thus, in the method for producing a β-pinene-based polymer according to the present invention, a cation (co) polymerization of a cationically polymerizable monomer containing at least β-pinene is used, and a Lewis acid is used as a polymerization catalyst. Since an isocyanide is used as an electron donor, a method for producing a β-pinene polymer having a large molecular weight, particularly a number average molecular weight, can be advantageously produced.

  Specifically, in the production method according to the present invention, when the cation (co) polymerization of the cationic polymerizable monomer proceeds, the isocyanides act on the Lewis acid or the active carbocation, and the polymerization is effectively controlled. Thus, a β-pinene polymer having a narrow molecular weight distribution and a large number average molecular weight can be obtained. In addition, since isocyanides easily react with acids and alkalis and are hydrolyzed, they can be easily removed by washing the reaction solution after completion of polymerization with, for example, citric acid water.

  As described above, the method for producing a β-pinene polymer according to the present invention provides a β-pinene polymer having a narrow molecular weight distribution and a large number average molecular weight, as well as the isocyanides used as an electron donor. Since removal is relatively easy, it can also be advantageously carried out on an industrial scale.

  In producing a β-pinene polymer according to the production method of the present invention, first, β-pinene is prepared. In the present invention, β-pinene may be a conventionally known one. Any of them can be used. That is, β-pinene collected from plants such as pine, β-pinene synthesized from α-pinene, and the like can be used.

  In general, cationic (co) polymerization may be affected by electron donating compounds present in the polymerization system. For this reason, in the present invention, a monomer (cationic polymerizable monomer containing β-pinene) or a solvent used in the polymerization is preferably used with a low content of an electron-donating compound as an impurity. Specific examples of impurities include water, methanol, protic compounds such as ethanol and hydrochloric acid, oxides and peroxides of olefinic compounds, and antioxidants such as ascorbic acid and tocopherol.

  In producing the β-pinene polymer according to the present invention, the amount of the protic compound present as an impurity in the polymerization system is in the range of 0.0001 to 0.1 molar equivalents relative to the amount of Lewis acid used later. It is preferable to be within. Further, the amount of oxide or peroxide present as an impurity in the polymerization system is preferably 0.01 molar equivalent or less, and preferably 0.001 molar equivalent or less with respect to the amount of Lewis acid used. More preferred. Furthermore, it is preferable that the content of the antioxidant in the monomer (cation polymerizable monomer containing β-pinene) is 10 ppm or more and 2000 ppm or less. In addition, when there is too little content of antioxidant, oxidation of a monomer is accelerated | stimulated and there exists a possibility that an oxide and a peroxide may become easy to refine | purify.

  For example, generally commercially available β-pinene contains more impurities such as the above-mentioned protic compound than the above range, and thus it is often necessary to purify β-pinene. As a method for purification, distillation or a method using an adsorbent is preferable, but in the case of distillation, the antioxidant is also completely removed, and therefore a method using an adsorbent is more preferable. In addition, as an adsorbent, if it is a common thing marketed, it can be used without a problem in particular. Specifically, alumina type such as activated alumina, silica type such as silica gel, aerogel, colloidal gel, zeolite type such as aluminosilicate zeolite, metallosilicate zeolite, aluminophosphate zeolite, clay such as activated clay, montmorillonite, smectite, etc. , Mesoporous systems such as mesoporous silica, activated carbon, carbon fiber, carbon-based adsorbents such as charcoal, synthetic adsorbents such as ion-exchange resin, chelate resin, biomass adsorbent, hydroxyapatite, heteropolyacid salt, porous manganese oxide Etc. can be illustrated. Among them, activated alumina and silica gel are preferable for purification of β-pinene, and activated alumina (trade name: MA4B) manufactured by Sumitomo Chemical Co., Ltd. is particularly preferable. For purification of the solvent, synthetic zeolite (trade name: Zeolum A-4) manufactured by Tosoh Corporation is particularly preferable.

  In the method for producing a β-pinene polymer according to the present invention, a cationic polymerizable monomer can be used as a monomer together with β-pinene. The cationically polymerizable monomer that can be used in the present invention is not particularly limited as long as it is a monomer having cationic polymerizability, and specifically, styrene, α-methylstyrene, 3-methylstyrene. Aromatic vinyl such as 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 1-vinylnaphthalene and indene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic monomers such as butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate; maleic anhydride, maleic acid, fumaric acid, maleimide; acrylonitrile, methacrylonitrile Nitrile group-containing vinyl monomers such as acrylamide, amide group-containing vinyls such as acrylamide and methacrylamide Monomers: Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, norbornene; compounds containing double bonds derived from terpine oil other than β-pinene, such as limonene, α-pinene, myrcene, camphene, and carene; vinyl acetate, pivalin Examples thereof include vinyl esters such as vinyl acid vinyl and vinyl benzoate; styrene derivatives having a polar group, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. In addition, bifunctional monomers such as p-divinylbenzene, p-diisopropenylbenzene, ethylene glycol divinyl ether, and the like can be used. One or more of these are used as the cationic polymerizable monomer together with β-pinene.

  When β-pinene and other cationic polymerizable monomers are copolymerized according to the production method of the present invention, the copolymerization amount of monomers other than β-pinene is 0 per total monomer unit of the polymer. 0.001 to 50 mass% is preferable, 0.01 to 20 mass% is more preferable, and 0.01 to 10 mass% is most preferable. This is because if the copolymerization amount of monomers other than β-pinene is too large, polymerization may become difficult, and the heat resistance of the resulting polymer often decreases. When β-pinene and other cationic polymerizable monomers are copolymerized, the structure of the obtained copolymer is not particularly limited. For example, a random copolymer, a block copolymer, or a tapered copolymer is used. Any of copolymers may be used. Among these, a random copolymer is particularly preferable.

  In the method for producing a β-pinene polymer of the present invention, a Lewis acid is used as a polymerization catalyst when the cationic polymerization (or cationic copolymerization) of a cationic polymerizable monomer containing at least β-pinene is allowed to proceed. At the same time, there is a great feature in using isocyanides as electron donors. That is, in particular, by using isocyanides as electron donors, cationically polymerizable monomers are cationically (co) polymerized in the presence of these specific compounds, resulting in a narrow molecular weight distribution and a number average molecular weight. A large β-pinene-based polymer can be advantageously produced.

〔式中、Ｒ¹ はアルキル基又は置換基を有してもよいアリール基であり、Ｘ¹ はハロ ゲン原子である。α及びβは０〜３であり、α＋β＝３を満たす。〕 Here, as the Lewis acid used in the method for producing a β-pinene polymer according to the present invention, any Lewis acid can be used as long as it is conventionally used for cationically (co) polymerizing a cationic polymerizable monomer. Even if it exists, it can be used. Among these conventionally known Lewis acids, an aluminum-based Lewis acid represented by the following chemical formula (1) is particularly preferably used in the present invention.

[Wherein, R ¹ represents an alkyl group or an aryl group which may have a substituent, and X ¹ represents a halogen atom. α and β are 0 to 3 and satisfy α + β = 3. ]

Among the Lewis acids represented by the above chemical formula (1) (hereinafter also referred to as aluminum-based Lewis acid catalyst), AlCl ₃ , EtAlCl ₂ , Et _1.5 AlCl _1.5 , Et ₂ AlCl, i-BuAlCl, n-HexAlCl _{2 and the} like are particularly preferred. Are advantageously used.

  In the present invention, the amount of Lewis acid used is difficult to define unconditionally because the catalytic ability differs depending on the type of Lewis acid used. However, in the case of a homogeneous catalyst, the amount used is β-pinene and, if desired, Based on the amount of monomers used in combination, 0.001 to 1 molar equivalent is preferable, and 0.01 to 0.1 molar equivalent is more preferable. When a heterogeneous catalyst such as a solid acid or an ion exchange resin is used in combination as a polymerization catalyst, 0.001 to 100 molar equivalents are preferable based on the amount of a cationic polymerizable monomer containing β-pinene, and 0.01 to 10 molar equivalents are more preferred. If the amount of Lewis acid used is too small, the progress of cationic polymerization may be slow, and the productivity may be reduced. On the other hand, if the amount used is too large, the molecular weight will be reduced, which is also disadvantageous economically.

  Further, in the method for producing a β-pinene polymer according to the present invention, by using isocyanides as an electron donor, the cation (co) polymerization reaction is controlled, the molecular weight distribution is narrow, and the number average molecular weight It is now possible to advantageously produce a β-pinene-based polymer having a large size. As isocyanides that can be used in the present invention, conventionally known isocyanides can be widely used. Specifically, t-butyl isocyanide, t-octyl isocyanide, trityl isocyanide, 1-methylcyclohexyl isocyanide, tris (methoxymethyl) methyl isocyanide, tris (ethoxymethyl) methyl isocyanide, tris (n-propoxymethyl) methyl isocyanide, Tris (isopropoxymethyl) methyl isocyanide, tris (n-butoxymethyl) methyl isocyanide, tris (s-butoxymethyl) methyl isocyanide, tris (t-butoxymethyl) methyl isocyanide, phenyl isocyanide, 4-methylphenyl isocyanide, 2- Methylphenyl isocyanide, 2,6-dimethylphenyl isocyanide, 4-nitrophenyl isocyanide, 4-methoxyphenyl isocyanide, 4-chlorophenyl isocyanide Enid, 2,3,4,5,6 pentafluorophenyl isocyanide etc., can be exemplified. Among these, t-butyl isocyanide and 2,6-dimethylphenyl isocyanide are particularly advantageously used.

  In the present invention, the isocyanides are preferably used in a proportion of 0.01 to 10 molar equivalents, more preferably 0.1 to 1 molar equivalents based on the Lewis acid amount used for the polymerization, and 0.1 to 0.1 molar equivalents. Most preferred is 5 molar equivalents. If the amount of isocyanides used is too small, side reactions tend to increase, and a large amount of low molecular weight products are formed, which may reduce the strength of the resulting polymer. On the other hand, when the amount of isocyanides used is too large, the polymerization reaction rate is remarkably suppressed, and a long time is required for the cation (co) polymerization reaction, which may reduce productivity.

  While using the aforementioned Lewis acid as a polymerization catalyst and using an isocyanide as an electron donor, a polymerization initiator is preferably further used in the present invention.

〔式中、Ｒ² 〜Ｒ⁵ はそれぞれ独立して、水素原子、アルキル基又はアリール基であ り、Ｘ² 及びＸ³ はそれぞれ独立して、アルコキシ基、アシロキシ基、水酸基又は ハロゲン原子であり。Ｒ⁶ は、置換基を有していてもよいアルキレン基、シクロア ルキレン基又はアリーレン基である。〕 As the polymerization initiator that can be used in the present invention, any polymerization initiator that can generate a tertiary cation can be used. The compounds represented are advantageously used.

[Wherein, R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group or an aryl group, and X ² and X ³ are each independently an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. . R ⁶ is an alkylene group, a cycloalkylene group or an arylene group which may have a substituent. ]

  Examples of the compound represented by the chemical formula (2) include t-butyl methyl ether, t-butyl acetate, t-butanol, 2,5-dimethoxy-2,5-dimethylhexane, 2,5-dimethyl-2, 5-hexanediol, 2,5-dimethyl-2,5-hexanediol diacetate, cumyl methoxide, cumyl alcohol acetate, cumyl alcohol, p-dicumyl methoxide, p-dicumyl alcohol diacetate, p-dicumyl Alcohol, 1,3,5-tricumyl methoxide, cumyl laroid, dicumyl chloride, cumyl bromide, dicumyl bromide, cumyl iodide, dicumyl iodide, etc. can be mentioned.

  Since the amount of the polymerization initiator used in the present invention varies depending on the molecular weight of the target polymer, it is difficult to define it generally, but it is 0.00001 based on the amount of the cationic polymerizable monomer containing β-pinene. It is preferably used at a ratio of ˜0.1 molar equivalent, more preferably 0.0001 to 0.05 molar equivalent, and most preferably 0.0001 to 0.01 equivalent. If the amount of the polymerization initiator used is small, the polymerization reaction rate may be slow, or polymerization may start from impurities, which may make it difficult to produce a stable β-pinene polymer. On the other hand, if the amount of the polymerization initiator used is too large, the molecular weight of the resulting β-pinene polymer may be small, and the polymer may become brittle.

  In the method for producing a β-pinene polymer of the present invention, cationic (co) polymerization of a cationic polymerizable monomer containing at least β-pinene can be carried out according to various conventionally known methods. Advantageously, a solution polymerization method is used in which cationic (co) polymerization proceeds in a solvent. As the solvent used in the solution polymerization method, β-pinene and other cationic polymerizable monomers used as needed are dissolved, and an organic solvent inert to the Lewis acid as a polymerization catalyst (hereinafter, referred to as “polymerization catalyst”). If it is also called an inert organic solvent, it can be used without particular limitation. 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 advantageously used. These organic solvents can be used alone or in combination of two or more.

  In addition, when using such an inert organic solvent, the usage-amount is although it does not specifically limit, It is with respect to 100 mass parts of (beta) -pinene (and the cationically polymerizable monomer used together depending on necessity). Usually, it is used at a ratio of 100 to 10000 parts by mass, preferably 150 to 5000 parts by mass, more preferably 200 to 3000 parts by mass. If the amount of the inert organic solvent used is too small, the viscosity of the reaction solution after the polymer is formed becomes high, which may make stirring difficult and the reaction non-uniform, making it difficult to control the reaction. On the other hand, if the amount of the inert organic solvent used is too large, the productivity may decrease.

  In the method for producing a β-pinene polymer according to the present invention, the polymerization or copolymerization of a cationic polymerizable monomer containing at least β-pinene proceeds by cation (co) polymerization. In the polymerization, the Lewis acid as a polymerization catalyst, the type and amount of isocyanide as an electron donor, the type and amount of solvent used in the above solution polymerization method, the reaction temperature, the reaction pressure, It can be controlled by adjusting the reaction time and the like.

  In the method for producing a β-pinene polymer of the present invention, the reaction temperature at the time of polymerization or copolymerization of a cationic polymerizable monomer containing at least β-pinene is preferably −120 ° C. to 60 ° C., − 80 to 0 degreeC is more preferable, and -40 to 0 degreeC is still more preferable. This is because if the reaction temperature is too low, it is uneconomical, and if it is too high, it becomes difficult to control the reaction. Considering economical reasons, it is most preferable to set the temperature around −10 ° C.

  In the present invention, the reaction pressure at the time of performing cationic (co) polymerization is not particularly limited, but is preferably 0.5 to 50 atm, and more preferably 0.7 to 10 atm. Usually, cationic (co) polymerization is carried out at around 1 atm.

  Furthermore, the reaction time for carrying out the cationic (co) polymerization is not particularly limited, and is appropriately determined according to the conditions such as the type and amount of the polymerization catalyst, the reaction temperature, the reaction pressure and the like. Usually, it is 0.01 hours to 72 hours, preferably 0.1 hours to 24 hours.

  The β-pinene polymer produced by cationic (co) polymerization is, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal with steam (steam stripping), etc. The polymer can be separated and obtained from the reaction mixture by the usual procedure in isolating the polymer from the solution.

  As described above, the method for producing the β-pinene polymer according to the production method of the present invention has been described in detail, but the number average molecular weight of the target β-pinene polymer in the production method of the present invention is particularly limited. Is not to be done. In general, from the viewpoint of mechanical properties and processability of the obtained polymer, the number average molecular weight is preferably 10,000 to 500,000, more preferably 30,000 to 200,000, and most preferably 40,000 to 200,000. When the number average molecular weight is too small, the strength of the molded product is remarkably lowered or molding becomes difficult. On the other hand, if it is too large, melt molding becomes difficult. Here, the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.

  In addition, the glass transition temperature (Tg) of the β-pinene polymer obtained according to the production method of the present invention cannot be specified unconditionally depending on the type and ratio of the cationic polymerizable monomer in the case of copolymerization. 250 degreeC is preferable and 100 to 230 degreeC is more preferable. Tg can be increased by hydrogenating the double bond of the β-pinene polymer obtained by the present invention by a known method. If Tg is low, the heat resistance is insufficient, while if it is too high, the β-pinene polymer may become brittle. The glass transition temperature can be measured by differential scanning calorimetry (DSC) or the like.

  Furthermore, when the β-pinene-based polymer obtained according to the production method of the present invention is used for, for example, an optical material, it is preferable that the total light transmittance is high. In the β-pinene polymer used as the optical material, the total light transmittance is preferably 80% or more, and more preferably 85% or more. The total light transmittance is measured according to JIS-K 7361-1-1997 “Plastic—Testing method for total light transmittance of transparent material—Part 1: Jingle beam method”.

  In addition, the β-pinene polymer obtained according to the production method of the present invention can be used alone, as well as polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, It can also be used as a composition blended with other polymers such as ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, styrene block copolymer and the like. 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 polymer obtained according to the production method of the present invention can be used as various optical materials. The range of use as an optical material is not particularly limited, but is advantageously used for optical materials that require excellent heat resistance, low water absorption and high transparency. Specifically, lenses, aspheric lenses, Fresnel lenses, silver salt camera lenses, digital electronic camera lenses, video camera lenses, projector lenses, copier lenses, mobile phone camera lenses, glasses lenses, Aspheric pickup lens for digital optical disc device using blue light emitting diode, rod lens, rod lens array, micro lens, micro lens array, various lens arrays, step index type, gradient index type, single mode type, multi-core type, polarization plane Storage type, side emission type optical fiber, optical fiber connector, optical fiber adhesive, digital optical disc (compact disc, magneto-optical disc, digital disc, video disc, computer disc, light guide, light diffusivity Form, functional glass thin film substitute film, retardation film, antistatic layer, antireflection layer, hard coat layer, transparent conductive layer, antiglare layer and other functional thin films, antireflection film for flat panel displays, touch panel Substrate, transparent conductive film, anti-reflection film, anti-glare 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, piezoelectric element For light guide plate that diffuses the light of a specific part in front, prism that constitutes polarizer, analyzer, etc., diffraction grating, endoscope, endoscope that guides high energy laser, and Dach mirror Mirror or half mirror, Transparent materials used in vehicular lamps (lenses, reflectors for headlights for automobiles, etc.), front protective plates for solar cells, window glass for houses, moving objects (automobiles, trains, ships, aircraft, spacecraft, space bases, Window glass for artificial satellites, anti-reflection film for window glass, dust-proof film at the time of semiconductor exposure, protective film for electrophotographic photosensitive material, semiconductor (EPROM etc.) sealing material that can be written or rewritten by ultraviolet light, light-emitting diode sealing Stop material, ultraviolet light emitting diode encapsulating material, white light emitting diode encapsulating material, SAW filter, optical bandpass filter, second harmonic generator, Kerr effect generator, optical switch, optical interconnection, optical isolator, Optical waveguide, surface light emitting member using organic electroluminescence, surface light emitting member dispersed with semiconductor fine particles, fluorescent light In applications such as phosphors in which a light substance is dissolved or dispersed, the β-pinene polymer obtained according to the present invention is advantageously used.

  The representative embodiment of the present invention has been described above, but the present invention is not limited to the above specific example. Needless to say, the exemplified materials can be used alone or in combination of two or more unless otherwise specified.

  Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the above-described specific description. It should be understood that modifications, improvements, etc. can be made.

  In addition, the dicumulyl chloride in the following examples and comparative examples was synthesized according to the method described in Japanese Patent No. 3810846.

  In addition, the β-pinene polymers obtained in the following Examples and Comparative Examples are each converted to polystyrene based on measurement by gel permeation chromatography (GPC), thereby obtaining a weight average molecular weight (Mw). And the number average molecular weight (Mn) was calculated. Here, HLC-8020 (product number) manufactured by Tosoh Co., Ltd. was used as the GPC device, and TSKgel / Multipore HZ manufactured by Tosoh Corporation was connected in series as the column.

Example 1
After sufficiently substituting the inside of the glass-made three-necked flask thoroughly dried with argon, dehydrated n-heptane: 135 parts by mass, dehydrated methylene chloride: 260 parts by mass, and Lewis acid (polymerization catalyst). A 1.0 mol / L hexane solution of ethylaluminum chloride: 9 parts by mass and t-butylisocyanide as an electron donor: 0.2 parts by mass were added and stirred at room temperature for 1 hour. Next, this solution was cooled to −10 ° C., while stirring, 0.1 mol / L hexane solution of dicumyl chloride as a polymerization initiator: 3 parts by mass was added, and β-pinene: 30 parts by mass over 5 hours. After dropwise addition and cationic polymerization, methanol: 5 parts by mass was added to complete the polymerization. Thereafter, 300 mass of distilled water was added and stirred for 10 minutes. A part of the obtained n-hexane layer was reprecipitated in a mixed solvent of methanol / acetone (2/1 vol%): 60 parts by mass, and then sufficiently dried to obtain a β-pinene polymer (A1). The obtained β-pinene polymer (A1) had a weight average molecular weight (Mw) of 118600 and a number average molecular weight (Mn) of 36700.

-Example 2-
In accordance with the same procedure as in Example 1, except that t-butylisocyanide: 0.2 part by mass was used instead of t-butylisocyanide: 0.2 part by mass as an electron donor, β-pinene heavy Combined (A2) was obtained. Table 1 shows the weight average molecular weight (Mw) and number average molecular weight (Mn) of the β-pinene polymer (A2).

-Comparative Example 1-
In accordance with the same procedure as in Example 1 except that the operation of “t-butylisocyanide as an electron donor: 0.2 part by mass and stirring at room temperature for 1 hour” in Example 1 was omitted. A polymer (B1) was obtained. Table 1 shows the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the β-pinene polymer (B1).

-Comparative Example 2-
A β-pinene polymer (B2) was prepared in the same manner as in Example 1 except that diethyl ether: 0.5 part by mass was used instead of t-butyl isocyanide: 0.2 part by mass as an electron donor. Obtained. Table 1 shows the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the β-pinene polymer (B2).

-Comparative Example 3-
The β-pinene polymer (B3) was prepared in the same manner as in Example 1 except that t-butyl isocyanide: 0.6 parts by mass was used instead of 0.2 parts by mass as the electron donor. Got. Table 1 shows the weight average molecular weight (Mw) and number average molecular weight (Mn) of the β-pinene polymer (B3).

-Comparative Example 4-
Cationic polymerization proceeds at −78 ° C. using 1.8 parts by mass of titanium tetrachloride as a Lewis acid (polymerization catalyst) and 0.1 parts by mass of titanium tetraisopropoxide as an electron donor. A β-pinene polymer (B4) was obtained according to the same procedure as in Example 1 except that. Table 1 shows the weight average molecular weight (Mw) and number average molecular weight (Mn) of the β-pinene polymer (B4).

As is apparent from the results in Table 1, in the method for producing a β-pinene polymer according to the present invention, a β-pinene polymer having a large molecular weight, particularly a number average molecular weight, can be advantageously produced. It was recognized.

Claims (9)

In a method for producing a β-pinene polymer by cationic polymerization or cationic copolymerization of a cationic polymerizable monomer containing at least β-pinene,
A process for producing a β-pinene polymer, characterized in that a Lewis acid is used as a polymerization catalyst and an isocyanide is used as an electron donor. The method for producing a β-pinene polymer according to claim 1, wherein the Lewis acid is a compound represented by the following chemical formula (1).

[Wherein, R ¹ represents an alkyl group or an aryl group which may have a substituent, and X ¹ represents a halogen atom. α and β are 0 to 3 and satisfy α + β = 3. ]   The method for producing a β-pinene polymer according to claim 1 or 2, wherein the isocyanides are t-butyl isocyanide or 2,6-dimethylphenyl isocyanide.   The method for producing a β-pinene polymer according to any one of claims 1 to 3, further comprising using a polymerization initiator. The method for producing a β-pinene polymer according to any one of claims 1 to 4, wherein the polymerization initiator is a compound represented by the following chemical formula (2).

[Wherein, R ^{2 to} R ⁵ are each independently a hydrogen atom, an alkyl group or an aryl group, and X ² and X ³ are each independently an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. . R ⁶ is an alkylene group, a cycloalkylene group or an arylene group which may have a substituent. ]   The method for producing a β-pinene polymer according to any one of claims 1 to 5, wherein the isocyanides are used in a proportion of 0.01 to 10 molar equivalents based on the amount of the Lewis acid used. .   The β-pinene-based weight according to any one of claims 1 to 6, wherein the Lewis acid is used in a proportion of 0.001 to 1 molar equivalent based on the amount of the cationic polymerizable monomer used. Manufacturing method of coalescence.   The β according to any one of claims 4 to 7, wherein the cationic polymerization initiator is used in a proportion of 0.00001 to 0.1 molar equivalent based on the amount of the cationic polymerizable monomer used. -Method for producing pinene polymer. The method for producing a β-pinene polymer according to any one of claims 1 to 8, wherein the cationic polymerization or cationic copolymerization is performed according to a solution polymerization method.