Alicyclic structure-containing polymer, molded body, method for producing alicyclic structure-containing polymer, and method for producing molded body

Abstract

The purpose of the present invention is to provide an alicyclic structure-containing polymer having excellent optical characteristics and moldability. The present invention is an alicyclic structure-containing polymer containing a prescribed structural unit (I) and having a glass transition temperature of more than 100°C and 200°C or less.

Description

A polymer containing an alicyclic structure and a molded article, as well as a method for producing a polymer containing an alicyclic structure and a method for producing a molded article.

[0001] The present invention relates to alicyclic structure-containing polymers and molded articles, as well as to methods for producing alicyclic structure-containing polymers and molded articles.

[0002] Polymers containing alicyclic structures are used in the manufacture of optical components such as optical recording media, optical lenses, prisms, and light guide plates. For example, norbornene-based polymers, which are one type of polymer containing alicyclic structures, are used as suitable materials for optical components due to their excellent optical properties and moldability (see, for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2007-238899

[0004] In recent years, in addition to norbornene-based polymers, there has been a demand for the development of alicyclic structure-containing polymers that exhibit excellent optical properties and moldability.

[0005] Therefore, the present invention aims to provide an alicyclic structure-containing polymer with excellent optical properties and moldability. The present invention also aims to provide a molded article containing the above-mentioned alicyclic structure-containing polymer. Furthermore, the present invention aims to provide a method for producing an alicyclic structure-containing polymer with excellent optical properties and moldability. Furthermore, the present invention aims to provide a method for producing a molded article using an alicyclic structure-containing polymer obtained by the above-mentioned method for producing an alicyclic structure-containing polymer.

[0006] The inventors diligently conducted research to achieve the above objectives. They then discovered that the above problems can be solved if the polymer contains a predetermined structural unit and has a glass transition temperature within a predetermined temperature range, and thus completed the present invention.

[0007] In other words, the purpose of this invention is to advantageously solve the above problems, and [1] the present invention is based on the following formula (I): [In formula (I), R １ ~R １４Each of these is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The polymer contains a structural unit (I) represented by [ ] and has a glass transition temperature greater than 100°C and less than or equal to 200°C. The above-described alicyclic structure-containing polymer has excellent optical properties and moldability. In this specification, the glass transition temperature of the alicyclic structure-containing polymer can be measured according to the method described in the examples.

[0008] [2] In the alicyclic structure-containing polymer described in [1] above, the weight-average molecular weight is preferably greater than 10,000 and less than or equal to 4,000,000. If the weight-average molecular weight is within the above range, the moldability of the alicyclic structure-containing polymer can be effectively improved. In this specification, the weight-average molecular weight (Mw) of the alicyclic structure-containing polymer is a value measured by gel permeation chromatography (GPC), and specifically can be measured using the method described in the examples of this specification.

[0009] [3] The alicyclic structure-containing polymer described in [1] or [2] above is preferably used in the manufacture of optical components. Using an alicyclic structure-containing polymer in the manufacture of optical components can improve the optical properties of the optical components.

[0010] Furthermore, this invention aims to advantageously solve the above problems, and [4] the present invention is a molded article containing any of the alicyclic structure-containing polymers described in [1] to [3] above. The above-described molded article has excellent performance.

[0011] Furthermore, this invention aims to advantageously solve the above problems, and [5] the present invention is a method for producing an alicyclic structure-containing polymer, wherein the following formula (i): [In formula (i), R １ ~R １４ Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A mixture containing compound (i) represented by ] and an anionic polymerization initiator is polymerized to obtain the following formula (ii): [In formula (ii), R １ ~R １４ R in equation (i) １ ~R １４To obtain a first polymer containing a structural unit (ii) represented by [which is the same as].], a polymerization step, reacting the first polymer with a cyclization catalyst, and the following formula (iii): [In formula (iii), R １ ~R １４ are the same as R １ ~R １４ in formula (i).].], a cyclization step of obtaining a second polymer containing a structural unit (iii) represented by, and a hydrogenation step of hydrogenating the second polymer to obtain a polymer containing an alicyclic structure. A method for producing a polymer containing an alicyclic structure. The polymer containing an alicyclic structure obtained by the production method as described above is excellent in optical properties and moldability.

[0012] [6] In the method for producing a polymer containing an alicyclic structure according to [5] above, the cyclization catalyst is preferably an acid catalyst. If the cyclization catalyst is an acid catalyst, the cyclization rate and moldability of the polymer containing an alicyclic structure can be improved.

[0013] [7] In the method for producing a polymer containing an alicyclic structure according to [5] or [6] above, the anionic polymerization initiator is preferably an organic alkali metal compound. If the anionic polymerization initiator is an organic alkali metal compound, the moldability of the polymer containing an alicyclic structure can be improved.

[0014] Further, the present invention aims to advantageously solve the above problems. [8] The present invention is a method for producing a molded body by molding using a polymer containing an alicyclic structure obtained by the method for producing a polymer containing an alicyclic structure according to any one of [5] to [7] above. The molded body obtained by the method for producing a molded body as described above is excellent in performance.

[0015] According to the present invention, a polymer containing an alicyclic structure excellent in optical properties and moldability can be provided. Further, according to the present invention, a molded body containing the polymer containing an alicyclic structure can be provided. Further, according to the present invention, a method for producing a polymer containing an alicyclic structure excellent in optical properties and moldability can be provided. Further, according to the present invention, a method for producing a molded body by molding using the polymer containing an alicyclic structure obtained by the method for producing a polymer containing an alicyclic structure can be provided.

[0016] Each component disclosed herein, as well as preferred embodiments, numerical ranges, and thresholds defining such numerical ranges, can be independently combined with each other in any manner.

[0017] The embodiments of the present invention will be described in detail below.

[0018] (Alicyclic structure-containing polymer) The alicyclic structure-containing polymer of the present invention is of the following formula (I): [In formula (I), R １ ~R １４ Each of these is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The polymer contains structural unit (I) represented by [ ]. Furthermore, the alicyclic structure-containing polymer of the present invention has a glass transition temperature greater than 100°C and 200°C or less. The alicyclic structure-containing polymer as described above has excellent optical properties and moldability. It is presumed that the reason for this is that the crystallinity of the polymer decreases when it contains a predetermined alicyclic structure, and as a result the transparency, refractive index, birefringence, etc. of the polymer reach a desired state, improving the optical properties. In addition, the glass transition temperature of a polymer may have a certain correlation with the molecular weight of the polymer and the amount of structural unit (I) present in the alicyclic structure-containing polymer. If the glass transition temperature of the polymer is within a predetermined range, the amount of structural unit (I) in the alicyclic structure-containing polymer can reach a desired level, and as a result, the moldability of the polymer is improved. The alicyclic structure-containing polymer of the present invention may optionally contain structural units other than the above structural unit (I).

[0019] <Structural Unit (I)> In structural unit (I), R in formula (I) １ ~R １４ Examples of alkyl groups having 1 to 4 carbon atoms that can constitute the formula include methyl groups; ethyl groups; propyl groups such as n-propyl groups and iso-propyl groups; butyl groups such as n-butyl groups, sec-butyl groups, iso-butyl groups, and tert-butyl groups; and so on. Among these, R in formula (I) １ ~R １４ The alkyl group having 1 to 4 carbon atoms that can constitute the molecule is preferably a methyl group or an ethyl group, with a methyl group being more preferred.

[0020] Here, the structural unit (I) is R in equation (I). １ ~R １４ However, each is preferably a hydrogen atom or a methyl group independently. And the structural unit (I) is R in formula (I). １ , R ８ and R ９ is a methyl group, and R in formula (I) ２ ~R ７ and R １０ ~R １４ It is particularly preferable that the atom is a hydrogen atom. That is, the structural unit (I) is given by the following formula (Ia): It is particularly preferable that the structural unit (Ia) is represented by the above. The above-described structural unit (Ia) can be formed by β-farnesene, which will be described later. Here, since β-farnesene is usually derived from biomass, if structural unit (I) is structural unit (Ia), the fossil fuel-derived components in the alicyclic structure-containing polymer can be effectively reduced, and as a result, carbon offsetting can be achieved. In this specification, "biomass" means all renewable natural raw materials and their residues, including fungi, yeasts, algae and bacteria, of plant or animal origin, etc., and "fossil fuel" means petroleum, coal, natural gas, shale gas, etc., which are fossilized remains of plants and animals that have been accumulated and pressurized over hundreds of millions of years.

[0021] The proportion of structural units (I) in an alicyclic structure-containing polymer is preferably 5% by mass or more, and more preferably 10% by mass or more, when the total structural units (repeating units) in the alicyclic structure-containing polymer are taken as 100% by mass. If the proportion of structural units (I) in the alicyclic structure-containing polymer is above the above lower limit, the optical properties and moldability of the alicyclic structure-containing polymer can be effectively improved. On the other hand, the proportion of structural units (I) in an alicyclic structure-containing polymer is, for example, 95% by mass or less, and may also be 80% by mass or less, when the total structural units (repeating units) in the alicyclic structure-containing polymer are taken as 100% by mass. In this specification, the proportion of structural units in a polymer is １ It can be measured using nuclear magnetic resonance (NMR) methods such as 1H-NMR.

[0022] <Properties of Alicyclic Structure-Containing Polymers> The glass transition temperature of alicyclic structure-containing polymers is not particularly limited as long as it is between 100°C and 200°C, but is preferably 110°C or higher, more preferably 120°C or higher, preferably 150°C or lower, and more preferably 135°C or lower. The glass transition temperature of alicyclic structure-containing polymers can be adjusted by the type and amount of anionic polymerization initiator used in the production of the alicyclic structure-containing polymer, the production conditions, etc.

[0023] The weight-average molecular weight of the alicyclic structure-containing polymer is preferably greater than 10,000, more preferably 40,000 or more, even more preferably 60,000 or more, preferably 4,000,000 or less, more preferably 2,000,000 or less, and even more preferably 500,000 or less. If the weight-average molecular weight is within the above range, the moldability of the alicyclic structure-containing polymer can be effectively improved. The weight-average molecular weight of the alicyclic structure-containing polymer can be adjusted by the type and amount of anionic polymerization initiator used in the production of the alicyclic structure-containing polymer, the production conditions, etc.

[0024] The cyclization rate of the alicyclic structure-containing polymer is preferably 70% or higher, more preferably 85% or higher, and even more preferably 88% or higher. If the cyclization rate of the alicyclic structure-containing polymer is above the lower limit mentioned above, the optical properties of the alicyclic structure-containing polymer can be effectively improved. In addition, the glass transition temperature (Tg) of the alicyclic structure-containing polymer will be increased, and as a result, the heat resistance can be improved. On the other hand, the cyclization rate of the alicyclic structure-containing polymer may be, for example, 99% or less, or 95% or less. In this specification, the cyclization rate of the polymer can be measured according to the method described in the examples. The cyclization rate of the alicyclic structure-containing polymer can be adjusted by the type and amount of cyclization catalyst used in the production of the alicyclic structure-containing polymer, the production conditions, etc.

[0025] The birefringence of the alicyclic structure-containing polymer is, for example, 1.0 or higher, may be 3.0 or higher, may be 7.0 or higher, and may be, for example, 50.0 or lower, may be 30.0 or lower, may be 20.0 or lower, or may be 10.0 or lower. In this specification, the birefringence of the alicyclic structure-containing polymer can be measured according to the method described in the examples. The birefringence of the alicyclic structure-containing polymer can be adjusted by the type and amount of anionic polymerization initiator used in the production of the alicyclic structure-containing polymer, the type and amount of cyclization catalyst used, the production conditions, etc.

[0026] The refractive index of the alicyclic structure-containing polymer is, for example, 1.000 or higher, preferably 1.300 or higher, more preferably 1.400 or higher, and even more preferably 1.500 or higher. On the other hand, the refractive index of the alicyclic structure-containing polymer is, for example, 3.000 or lower, may be 2.000 or lower, 1.700 or lower, or 1.600 or lower. In this specification, the refractive index of the alicyclic structure-containing polymer can be measured according to the method described in the examples. The refractive index of the alicyclic structure-containing polymer can be adjusted by the type and amount of anionic polymerization initiator used in the production of the alicyclic structure-containing polymer, the type and amount of cyclization catalyst used, the production conditions, etc.

[0027] <Applications of Alicyclic Structure-Containing Polymers> The alicyclic structure-containing polymer of the present invention is a polymer that can be used in various fields as a resin material for various molded articles. However, because it has excellent optical properties and can improve the optical properties of optical components, it is preferably used in the manufacture of optical components such as optical recording media, optical lenses, prisms, and light guide plates.

[0028] (Molded Article) The molded article of the present invention contains the alicyclic structure-containing polymer of the present invention described above. Because the molded article of the present invention contains an alicyclic structure-containing polymer that has excellent optical properties and moldability, it has excellent performance such as optical properties. The molded article of the present invention may also contain components other than the above-mentioned alicyclic structure-containing polymer (hereinafter sometimes referred to as "other components").

[0029] The shape of the molded body is not particularly limited and can be selected as appropriate depending on its application, but examples include prism shape, lens shape, film shape, plate shape, syringe shape, bag shape, cup shape, bottle shape, tube shape, etc.

[0030] (Method for Producing Alicyclic Structure-Containing Polymers) The method for producing alicyclic structure-containing polymers of the present invention (hereinafter sometimes simply referred to as the "production method") includes a polymerization step, a cyclization step, and a hydrogenation step, as described below, and may optionally include steps other than the polymerization step, the cyclization step, and the hydrogenation step (hereinafter sometimes referred to as "other steps"). Examples of other steps include a purification step for purifying the crude products obtained in each step, and a solvent removal step for removing the solvent used. Alicyclic structure-containing polymers obtained by the above-described production method have excellent optical properties and moldability. The alicyclic structure-containing polymers of the present invention described above can be obtained by the production method of the present invention.

[0031] <Polymerization Process> In the polymerization process, the following formula (i): [In formula (i), R １ ~R １４ Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A mixture comprising compound (i) represented by [ ] and an anionic polymerization initiator, and optionally further comprising a randomizer and a solvent, is polymerized to obtain the following formula (ii): [In formula (ii), R １ ~R １４ R in equation (i) １ ~R １４ This is the same as [ ]. A first polymer containing the structural unit (ii) represented by [ ] is obtained.

[0032] <<Compound (i)>> In compound (i) contained in the mixture, R in formula (i) １ ~R １４ The alkyl group having 1 to 4 carbon atoms that can constitute it is R in formula (I). １ ~R １４ Examples include alkyl groups having 1 to 4 carbon atoms that can constitute the formula. Among these, R in formula (i) １ ~R １４The alkyl group having 1 to 4 carbon atoms that can constitute the molecule is preferably a methyl group or an ethyl group, with a methyl group being more preferred.

[0033] Here, compound (i) is R in formula (i). １ ~R １４ However, each is preferably independently a hydrogen atom or a methyl group. And compound (i) is R in formula (i). １ , R ８ and R ９ is a methyl group, and R in formula (i) ２ ~R ７ and R １０ ~R １４ It is particularly preferable that the atom is a hydrogen atom. That is, compound (i) is given by the following formula (ia): The compound represented by (ia), so-called β-farnesene, is particularly preferred. Since β-farnesene is usually derived from biomass, using it in the production method of the present invention can effectively reduce the fossil fuel-derived components in the alicyclic structure-containing polymer, thereby achieving carbon offsetting.

[0034] <<Anionic polymerization initiators>> Examples of anionic polymerization initiators included in the mixture include organic alkali metal compounds; organic alkaline earth metal compounds; polymerization initiators that use lanthanum series metal compounds as the main catalyst; and so on. Examples of organic alkali metal compounds include organic lithium compounds, organic sodium compounds, and organic potassium compounds. Specifically, examples of organic lithium compounds include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenithium; and organic polyvalent lithium compounds such as dilithinomyethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and 1,3,5-tris(lithiomethyl)benzene. Examples of organic sodium compounds include sodium naphthalene, and examples of organic potassium compounds include potassium naphthalene. Examples of organic alkaline earth metal compounds include diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium, diisopropoxybarium, diethylmercaptobarium, di-t-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, and diketilbarium. Examples of polymerization initiators using lanthanum series metal compounds as the main catalyst include polymerization initiators that use a salt of a lanthanum series metal, consisting of a lanthanum series metal such as lanthanum, cerium, praseodymium, neodymium, samarium, or gadolinium, and an acid such as a carboxylic acid or phosphorus-containing organic acid, as the main catalyst, and use alkylaluminum compounds, organoaluminum hydride compounds, organoaluminum halide compounds, etc. as co-catalysts. Among the above-mentioned anionic polymerization initiators, organic alkali metal compounds are preferred, organolithium compounds are more preferred, organomonolithium compounds are even more preferred, and n-butyllithium is even more preferred, as they can improve the moldability of polymers containing alicyclic structures. Furthermore, the anionic polymerization initiators described above may be used individually or in combination of two or more.

[0035] The content of the anionic polymerization initiator in the mixture is not particularly limited as long as a first polymer is obtained, but is preferably 0.0005 mmol or more, more preferably 0.0010 mmol or more, even more preferably 0.0030 mmol or more, preferably 5000 mmol or less, more preferably 500 mmol or less, and even more preferably 50 mmol or less, when compound (i) is 1 mol. If the content of the anionic polymerization initiator in the mixture is within the above range, the moldability and optical properties of the obtained alicyclic structure-containing polymer can be effectively improved.

[0036] <<Randomizer>> A randomizer that may be optionally included in the mixture is a compound that adjusts the ratio of 1,2 or 3,4-vinyl bonds to 1,4-vinyl bonds in the resulting polymer (i.e., the first polymer) when polymerizing a compound having a conjugated diene such as compound (i). For example, a polar compound can be used. Note that structural unit (ii) in the first polymer corresponds to a 1,4-vinyl bond.

[0037] Examples of polar compounds used as randomizers include ether compounds such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, dibutyl ether, and tetrahydrofuran; tertiary amines such as N,N,N',N'-tetramethylethylenediamine (TMEDA); alkali metal alkoxides; phosphine compounds; and the like. Among these, ether compounds and tertiary amines are preferred, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and tertiary amines are more preferred, tertiary amines are even more preferred, and N,N,N',N'-tetramethylethylenediamine is even more preferred. The above polar compounds may be used individually or in combination of two or more.

[0038] The amount of randomizer that may be included in the mixture can be appropriately changed depending on the proportion of structural unit (ii) in the first polymer, but when the anionic polymerization initiator is 1 mmol, it is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, preferably 100 mmol or less, and more preferably 10 mmol or less. If the amount of randomizer is within the above range, it is easy to adjust the proportion of structural unit (ii) in the first polymer and the deactivation of the anionic polymerization initiator can be effectively suppressed.

[0039] <<Solvent>> The solvent that may be optionally included in the mixture is not particularly limited as long as the first polymer can be obtained, and examples include chain-like aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane; and so on. These solvents may be used individually or in combination of two or more in any ratio.

[0040] <<First Polymer>> The first polymer obtained in the polymerization process is given by the following formula (ii): [In formula (ii), R １ ~R １４ R in equation (i) １ ~R １４ It is the same as . It contains structural unit (ii) represented by ]. The first polymer may optionally contain structural units other than the above structural unit (ii). The first polymer obtained in the polymerization step is usually obtained in the form of a crude product containing the first polymer, but the obtained crude product may optionally be subjected to further purification steps and solvent removal steps.

[0041] Here, if compound (i) is β-farnesene, in the polymerization step, the first polymer is given by the following formula (iia): A polymer (so-called polyfarnesene) containing the structural unit (iiia) represented by can be obtained.

[0042] <<Polymerization Conditions>> The polymerization temperature in the polymerization process is not particularly limited as long as a first polymer is obtained, but for example it may be 30°C or higher, 40°C or higher, 70°C or lower, or 60°C or lower.

[0043] The polymerization time in the polymerization process is not particularly limited as long as a first polymer is obtained, but may be, for example, 5 minutes or more, 20 minutes or more, or, for example, 2 hours or less, or 1 hour or less.

[0044] <Cyclization Process> In the cyclization process, the first polymer obtained in the polymerization process above is reacted with a cyclization catalyst to produce the following formula (iii): [In formula (iii), R １ ~R １４ R in equation (i) １ ~R １４ This is the same as [ ]. A second polymer containing the structural unit (iii) represented by [ ] is obtained.

[0045] <<Cyclization Catalyst>> The cyclocatalyst is not particularly limited as long as a second polymer can be obtained, but it is preferable to use an acid catalyst because it can improve the cycloification rate of the alicyclic structure-containing polymer, thereby reducing the crystallinity of the alicyclic structure-containing polymer and improving its optical properties, and also function as a polymerization initiator, improving the moldability of the alicyclic structure-containing polymer. Examples of acid catalysts include Lewis acids and Brønsted acids. Specifically, BF ３ BF ３ OET ２ ("Et" means ethyl group.), 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 WCl ６ MoCl ５ SbCl ５ TeCl ２Metal halide compounds from Group IIIA to Group VIII of the periodic table such as; hydrofluoric acids such as HF, HCl, HBr; H ２ SO ４ 、H ３ BO ３ 、HClO ４ 、CH ３ COOH、CH ２ ClCOOH、CHCl ２ COOH、CCl ３ COOH、CF ３ COOH、p-toluenesulfonic acid monohydrate, CF ３ SO ３ H、H ３ PO ４ 、P ２ O ５ and other oxoacids such as these, and polymer compounds such as ion exchange resins having these groups; heteropolyacids such as phosphomolybdic acid and phosphotungstic acid; SiO ２ 、Al ２ O ３ 、SiO ２ -Al ２ O ３ 、MgO-SiO ２ 、B ２ O ３ -Al ２ O ３ 、WO ３ -Al ２ O ３ 、Zr ２ O ３ -SiO ２ 、sulfated zirconia, zirconia tungstate, H ＋ or zeolite exchanged with rare earth elements, activated clay, acid clay, γ-Al ２ O ３ 、P ２ O ５ supported on diatomaceous earth such as solid acids such as solid phosphoric acid. These acid catalysts may be used alone or in combination, and other compounds etc. which can improve the activity of the acid catalyst may also be added. Here, examples of the compound which improves the activity of the acid catalyst include MeLi, EtLi, BuLi (「Bu」 means a butyl group.), Et ２ Mg, EtMgBr, Et ３ Al, Et ２AlCl, EtAlCl ２ , Et ３ Al ２ Cl ３ (i-Bu) ３ Al, Et ２ Al(OEt), Me ４ Sn, Et ４ Sn, Bu ４ Sn, Bu ３ Examples include metal alkyl compounds such as SnCl; 2-methoxy-2-phenylpropane, t-butanol, 1,4-bis(2-methoxy-2-propyl)benzene, 2-phenyl-2-propanol, etc.

[0046] The amount of cyclization catalyst used is not particularly limited as long as a second polymer is obtained, but is, for example, 1 g to 20 g when the amount of the first polymer compound (i) is 100 g.

[0047] <<Solvent>> In the cyclization step, a solvent may be added as desired, without any particular limitations. The solvent that can be used in the cyclization step is the same as the solvent that can be included in the mixture of the polymerization step described above.

[0048] <<Second Polymer>> The second polymer obtained in the polymerization process is given by the following formula (iii): [In formula (iii), R １ ~R １４ R in equation (i) １ ~R １４ It is the same as . It contains structural unit (iii) represented by ]. The second polymer may optionally contain structural units other than the above structural unit (iii). The second polymer obtained in the cyclization step is usually obtained in the form of a crude product containing the second polymer, but the obtained crude product may optionally be subjected to further purification steps and solvent removal steps.

[0049] Here, if the first polymer obtained in the polymerization step is a polymer containing structural unit (iiia), then in the cyclization step, the second polymer is given by the following formula (iiia): A polymer containing the structural unit (iiia) represented by can be obtained.

[0050] The cyclization rate of the second polymer is preferably 70% or higher, more preferably 85% or higher, and even more preferably 88% or higher. If the cyclization rate of the second polymer is above the lower limit mentioned above, the optical properties of the resulting alicyclic structure-containing polymer can be effectively improved. In addition, the glass transition temperature of the resulting alicyclic structure-containing polymer will be higher, and as a result, the heat resistance can be improved. On the other hand, the cyclization rate of the second polymer may be, for example, 99% or less, or 95% or less. The cyclization rate of the second polymer can be adjusted by the type and amount of cyclization catalyst used, the cyclization conditions described later, etc.

[0051] <<Cyclization Conditions>> The reaction temperature in the cyclonization step is, for example, 50°C or higher, may be 70°C or higher, and may be, for example, 100°C or lower, or 85°C or lower.

[0052] The reaction time in the cyclization step is preferably 3 hours or more, more preferably 6 hours or more, even more preferably 9 hours or more, even more preferably 12 hours or more, preferably 30 hours or less, more preferably 24 hours or less, and even more preferably 18 hours or less. If the reaction time in the cyclization step is above the lower limit, the cyclization rate of the alicyclic structure-containing polymer can be effectively improved. On the other hand, if the reaction time in the cyclization step is below the upper limit, the productivity of the alicyclic structure-containing polymer can be effectively improved.

[0053] <Hydrogenation Step> In the hydrogenation step, the second polymer obtained in the cyclization step is hydrogenated to obtain an alicyclic structure-containing polymer. Here, the hydrogenation step can usually be carried out by supplying hydrogen gas to a polymer solution (or polymer dispersion) containing the second polymer and a solvent in the presence of a hydrogenation catalyst. The solvent used in hydrogenation is not particularly limited and can be the same as the solvent that can be contained in the mixture in the polymerization step.

[0054] <<Hydrogenation Catalyst>> The hydrogenation catalyst is not particularly limited, and those commonly used in the hydrogenation reaction of olefin compounds can be used. For example, Ziegler catalysts consisting of combinations of transition metal compounds and alkali metal compounds such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium; dichlorotris(triphenylphosphine)rhodium, Japanese Patent Publication No. 7-2929. Examples include homogeneous catalysts such as noble metal complex catalysts consisting of ruthenium compounds described in Japanese Patent Publication No. 7-149823, Japanese Patent Publication No. 11-209460, Japanese Patent Publication No. 11-158256, Japanese Patent Publication No. 11-193323, Japanese Patent Publication No. 11-209460, etc.; supported heterogeneous catalysts in which metals such as nickel, palladium, platinum, rhodium, and ruthenium are supported on carriers such as carbon, silica, diatomaceous earth, alumina, and titanium oxide.

[0055] The hydrogenation catalyst may be used alone or in combination of two or more types. A supported heterogeneous catalyst is preferred as the hydrogenation catalyst because it can be easily removed by filtering the reaction solution after the hydrogenation reaction. Specific examples of preferred supported heterogeneous catalysts include combinations of nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

[0056] <<Conditions for Hydrogenation Reaction>> The conditions for the hydrogenation reaction (amount of hydrogenation catalyst used, reaction time, reaction temperature, hydrogen pressure, etc.) are not particularly limited and can be set as appropriate according to the desired physical properties of the alicyclic structure-containing polymer (e.g., hydrogenation rate, etc.).

[0057] <<Obtained Alicyclic Structure-Containing Polymer>> In one embodiment of the present invention, the alicyclic structure-containing polymer obtained in the hydrogenation step is given by the following formula (I): [In formula (I), R １ ~R １４Each of these is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The polymer may also contain an alicyclic structure containing a structural unit (I) represented by ].

[0058] Here, if the second polymer obtained in the cyclization step is a polymer containing structural unit (iiia), then in the hydrogenation step, as an alicyclic structure-containing polymer, the following formula (Ia): A polymer containing the structural unit (Ia) represented by can be obtained.

[0059] (Method for Manufacturing Molded Articles) The method for manufacturing molded articles of the present invention involves molding using an alicyclic structure-containing polymer obtained by the method for manufacturing alicyclic structure-containing polymers of the present invention described above. Since the method for manufacturing molded articles of the present invention uses an alicyclic structure-containing polymer that has excellent optical properties and moldability, the resulting molded articles have excellent performance such as optical properties. The alicyclic structure-containing polymer may also be used in the form of a polymer composition containing the alicyclic structure-containing polymer and other components, for example. That is, in the method for manufacturing molded articles of the present invention, a molded article may be obtained by molding a polymer composition containing the alicyclic structure-containing polymer and other components.

[0060] The molding method in the present invention for manufacturing a molded article is not particularly limited and can be appropriately selected from known molding methods depending on the desired shape of the molded article. Examples of such known molding methods include extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, foam molding, and thermoforming.

[0061] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing quantities refer to mass unless otherwise specified. In addition, in the examples and comparative examples, the cyclization rate, glass transition temperature, weight-average molecular weight, birefringence, refractive index, and moldability were measured or evaluated using the following methods, respectively.

[0062] <Cyclization Rate> The cyclization rate of polymers containing alicyclic structures is: １３The cyclization rate was determined by 13C-NMR spectral analysis. Specifically, the cyclization rate was calculated by dividing the peak area value of saturated carbon in the alicyclic structure-containing polymer by the peak area value of the unsaturated and saturated carbon combined.

[0063] <Glass Transition Temperature> The glass transition temperature (Tg) was measured using a differential scanning calorimetry analyzer (Nanotechnology Inc., product name: DSC6220S II) with a heating rate of 10°C / min, in accordance with JIS K 6911, after pelletizing the alicyclic structure-containing polymers obtained in the examples and comparative examples.

[0064] <Weight-Average Molecular Weight> The weight-average molecular weight (Mw) of the alicyclic structure-containing polymers obtained in the examples and comparative examples was measured by gel permeation chromatography (GPC) using cyclohexane as the eluent, and determined as a value equivalent to standard polyisoprene. Standard polyisoprene (manufactured by Tosoh Corporation, Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) was used as the standard polyisoprene. The measurement was performed using three columns (manufactured by Tosoh Corporation, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL) connected in series, under conditions of a flow rate of 1.0 mL / min, a sample injection volume of 100 μL, and a column temperature of 40°C.

[0065] <Birefringence> In measuring the birefringence (δn) per unit thickness, first, the alicyclic structure-containing polymer obtained in the example was pelletized and formed into a sheet of 35 mm × 10 mm × 1 mm. After fixing both ends of this sheet with clips, a 160 g weight was attached to one of the clips. Next, the sheet was suspended in an oven at [glass transition temperature (Tg) of the alicyclic structure-containing polymer (-15)] °C for 10 minutes, starting from the clip without the weight, and stretched to obtain the measurement sample. For the obtained measurement sample, the retardation value at the center of the measurement sample with light at a wavelength of 650 nm was measured using a birefringent (Oji Keisokuki Co., Ltd., product name: KOBRA-CCD / X) (this measured value is denoted as a (nm)). In addition, the thickness at the center of the measurement sample was measured (this measured value is denoted as b (mm)), and the δn value was obtained using the formula: δn = a × (1 / b). A δn value closer to 0 indicates lower birefringence. Furthermore, a lower birefringence value (for example, approximately 50.0 or less) indicates superior optical properties of the alicyclic structure-containing polymer. Note that the alicyclic structure-containing polymer obtained in the comparative example could not be molded into a sheet, so its birefringence was not measured.

[0066] <Refractive Index> For the refractive index measurement, the alicyclic structure-containing polymer obtained in the example was first pelletized, formed into a 5 mm thick sheet, and left for 20 hours in an atmosphere at [glass transition temperature (Tg) of the alicyclic structure-containing polymer - 15]°C to be used as the measurement sample. The refractive index (n) at 25°C was measured for the obtained measurement sample using a precision refractometer (Shimadzu Corporation, product name: KPR-200, light source = He lamp (587.6 nm)). A higher refractive index value (for example, approximately 1.300 or higher) indicates that the alicyclic structure-containing polymer has superior optical properties. Note that the alicyclic structure-containing polymer obtained in the comparative example could not be formed into a sheet, so the refractive index was not measured.

[0067] <Moldability> The moldability of the alicyclic structure-containing polymer was evaluated according to the following criteria. A: The alicyclic structure-containing polymer could be molded into a sheet. B: The alicyclic structure-containing polymer could not be molded into a sheet.

[0068] (Example 1) <Polymerization Process> 55 g (269 mmol) of β-farnesene, 220 g of cyclohexane, 0.0017 g (0.0142 mmol) of N,N,N',N'-tetramethylethylenediamine (TMEDA), and 0.0607 g (0.948 mmol) of n-butyllithium (n-BuLi) as an anionic polymerization initiator were placed in an autoclave containing 1 L of ampoule, and polymerized at 50°C for 0.5 hours to obtain crude product A. Next, 0.5 ml of ethanol was added to the ampoule and mixed for 0.5 hours to deactivate the anionic polymerization initiator. Then, crude product A was extracted with cyclohexane, and the solvent (cyclohexane, etc.) was removed using an evaporator to obtain the following formula (iiia): A polyfarnesene was obtained as a first polymer containing the structural unit (iia) represented by .

[0069] <Cyclization Step> In a 1 L four-necked round-bottom flask, 55 g of the polyfarnesene obtained above, 495 g of cyclohexane, and 2.75 g (14.46 mmol) of p-toluenesulfonic acid monohydrate (p-TsOH) as a cyclization catalyst were added and reacted at 82°C for 15 hours to obtain crude product B. Next, at room temperature, Na was added to the crude product B obtained above. ２ CO ３ The aqueous solution was added and stirred with a stirrer for 30 minutes. Cyclohexane was then added, and impurities such as salts were extracted three times with water. The solvent (cyclohexane, etc.) was removed using an evaporator, and the following formula (iiia) was obtained: A second polymer containing the structural unit (iiia) represented by was obtained.

[0070] <Hydrogenation Process> 50 g of the second polymer obtained above, 200 g of cyclohexane, and 5.0 g of diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Co., Ltd., product name "T8400RL", nickel support rate 58%) were transferred to an autoclave with a stirrer, and after replacing the inside of the autoclave with hydrogen, the hydrogenation reaction was carried out at 200°C and under a hydrogen pressure of 4.5 MPa for 6 hours. After the hydrogenation reaction was completed, diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., product name "Radiolite® #500") was used as a filter bed and the following formula (Ia): A colorless, transparent solution containing an alicyclic structure-containing polymer with structural unit (Ia) represented by was obtained. The cyclization rate, glass transition temperature, weight-average molecular weight, birefringence, refractive index, and moldability of the obtained alicyclic structure-containing polymer were measured or evaluated. The results are shown in Table 1.

[0071] (Example 2) In the polymerization process, the amount of n-butyllithium (n-BuLi) used as an anionic polymerization initiator was changed from 0.0607 g (0.948 mmol) to 0.1068 g (1.667 mmol). Except for this change, various operations, measurements, and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

[0072] (Comparative Example 1) <Polymerization Process and Cyclization Process> In a 1 L four-necked round-bottom flask, 20 g of cyclohexane and anhydrous aluminum chloride (AlCl) as a cationic polymerization initiator were added. ３ 2 g of β-farnesene was added and mixed at room temperature. Next, 100 g of β-farnesene diluted with 100 g of cyclohexane was continuously added to the flask at a rate of 2 ml / min. After the addition of β-farnesene, the mixture was reacted at 40°C for 1 hour to obtain the crude product. The reaction was then completely terminated by adding 10 g of 25% aqueous sodium hydroxide solution and 10 g of ethanol. Next, cyclohexane was added to the obtained crude compound, and then impurities such as salts were extracted three times with water. The solvent (cyclohexane, etc.) was removed using an evaporator to obtain a liquid containing the second polymer containing structural unit (iiia). Then, ethanol was added to the obtained liquid to precipitate the second polymer and obtain the solid second polymer.

[0073] <Hydrogenation Process> The hydrogenation process was carried out in the same manner as in Example 1, except that the second polymer solid obtained above was used, to obtain an alicyclic structure-containing polymer. Various measurements and evaluations were then performed in the same manner as in Example 1, except that the birefringence and refractive index were not measured. The results are shown in Table 1.

[0074] (Comparative Example 2) Except for changing the amount of anhydrous aluminum chloride used as a cationic polymerization initiator from 2 g to 1 g, various operations, measurements, and evaluations were performed in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0075]

[0076] As is clear from Table 1, the alicyclic structure-containing polymers obtained in Examples 1 and 2 exhibit excellent optical properties and moldability.

[0077] According to the present invention, it is possible to provide an alicyclic structure-containing polymer with excellent optical properties and moldability. Furthermore, according to the present invention, it is possible to provide a molded article containing the above alicyclic structure-containing polymer. Furthermore, according to the present invention, it is possible to provide a method for producing an alicyclic structure-containing polymer with excellent optical properties and moldability. Furthermore, according to the present invention, it is possible to provide a method for producing a molded article using an alicyclic structure-containing polymer obtained by the above method for producing an alicyclic structure-containing polymer.

Claims

1. The following formula (I): [In formula (I), R １ ~R １４ Each of these is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The polymer contains a structural unit (I) represented by ] and has a glass transition temperature greater than 100°C and less than or equal to 200°C, and is an alicyclic structure-containing polymer.

2. The alicyclic structure-containing polymer according to claim 1, wherein the weight-average molecular weight is greater than 10,000 and less than or equal to 4,000,000.

3. The alicyclic structure-containing polymer according to claim 1, used in the manufacture of optical components.

4. A molded article comprising an alicyclic structure-containing polymer according to any one of claims 1 to 3.

5. A method for producing a polymer containing an alicyclic structure, comprising polymerizing a mixture containing a compound (i) represented by the following formula (i): [In formula (i), R １ ~R １４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.] to obtain a first polymer containing a structural unit (ii) represented by the following formula (ii): [In formula (ii), R １ ~R １４ are the same as R １ ~R １４ in formula (i).], a polymerization step; reacting the first polymer with a cyclization catalyst to obtain a second polymer containing a structural unit (iii) represented by the following formula (iii): [In formula (iii), R １ ~R １４ are the same as R １ ~R １４ in formula (i).], a cyclization step; and hydrogenating the second polymer to obtain a polymer containing an alicyclic structure, a hydrogenation step. A method for producing a polymer containing an alicyclic structure, comprising the above steps.

6. The method for producing an alicyclic structure-containing polymer according to claim 5, wherein the cyclization catalyst is an acid catalyst.

7. The method for producing an alicyclic structure-containing polymer according to claim 5, wherein the anionic polymerization initiator is an organoalkali metal compound.

8. A method for producing a molded article, comprising molding using an alicyclic structure-containing polymer obtained by the method for producing an alicyclic structure-containing polymer according to any one of claims 5 to 7.

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