TW201231493A - Alicyclic polyester and production method therefor - Google Patents

Abstract

Provided is an alicyclic polyester with high temperature resistance excellent in heat-resisting property and transparency. The alicyclic polyester has a structural unit represented by general formula (I).

Description

201231493 6. EMBODIMENT OF THE INVENTION The present invention relates to an optical material typified by electronic components for semiconductors, liquid crystals, optical fibers, optical lenses, and the like, and alicyclic polymerizations for display-related materials and medical materials. Ester and its method of manufacture. [Prior Art] Various polyester resins have been used in a wide range of fields because they can be formed into a film, a sheet, a profiled material, a fiber, a tube, a container, or the like by various molding methods and the like. The polyester which is most frequently used is an aromatic polyester which is an aromatic carboxylic acid such as terephthalic acid or isophthalic acid, and is excellent in heat resistance, toughness, and the like because it contains an aromatic group. However, in recent years, semiconductor laser light sources have progressed toward low-wavelength regions, and in order to use blue lasers, ultraviolet lasers, and the like as light sources of light signals, transparency of polymer materials used for optical materials or electronic components is required. 'But the aromatic polyester is difficult to use in these fields because of poor UV resistance, light transmittance, and the like. The polyester having an alicyclic structure is excellent in heat resistance, transparency, and water resistance, and has been used in the field of the above-mentioned required transparency. A method for producing an alicyclic polyester has been proposed in various ways using a saturated cyclic aliphatic primary diol such as 1,4-cyclohexanedimethanol (refer to Patent Document 1) 'but a saturated cyclic aliphatic primary diol Since the alkyl group is inserted between the hydroxyl group and the saturated cyclic aliphatic group, the resulting alicyclic polyester resin has an aliphaticity. The heat resistance of the cyclohexane ring structure is low, and it cannot be obtained as the former-5- 201231493 The full characteristics of the use. Further, in order to improve the heat resistance of the alicyclic polyester, an alicyclic polymer formed from a dicarboxylic acid component having 4,4'-dicyclohexyldicarboxylic acid as a main component and an alicyclic diol has been proposed. Ester (see Patent Document 2), a polyester having a norbornane structure (see Patent Documents 3 to 5), and a polyester having a tricyclodecane structure (see Patent Documents 6 to 8), but heat resistance is still not known. full. [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2007-517926 Patent Document 2: JP-A-2006-1 1 794 Patent Document 3: JP-A-200-643 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention has been made in view of the above problems, and a problem is to provide a high heat-resistant grease excellent in both heat resistance and transparency. Ring polyester and its method of manufacture. [Means for Solving the Problem] -6 - 201231493 The means to solve the above problems are as follows. (o) an alicyclic polyester having a structural unit represented by the following formula (°, [Chem. 1]

(2) The method for producing an alicyclic polyester according to the above (1), which is obtained by polymerizing a tricyclodecane monomethanol monodecanoic acid derivative represented by the following formula (II). [Chemical 2]

(However, in the formula (II), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group, or a benzyl group). [Effect of the Invention] According to the present invention, an alicyclic polyester excellent in both heat resistance and transparency and a method for producing the same can be provided. Since the alicyclic polyester of the present invention is excellent in heat resistance and transparency, it can be used as an optical material represented by an electronic component, an optical fiber, or an optical transmissive material, such as a mirror, etc., for semiconductors and liquid crystals. Can be used for display, medical materials. [Embodiment] Hereinafter, the present invention will be described in detail. <Cycloaliphatic polyester> The following formula (the alicyclic polyester of the present invention is characterized by having a structural unit represented by I), [Chemical 3]

The alicyclic polyester of the present invention is excellent in a full-alicyclic structure, has a tricyclodecane structure, and can be used as a semiconductor, liquid electronic component, an optical fiber, or an optical lens because of its heat resistance. The optical material represented by the like can be used as a display related material or a medical material. The number average molecular weight of the alicyclic polyester of the present invention (calculated using a calibration line made of standard polystyrene) is more preferably 3,000 to 220,000 as compared with 250,000 ». The number average molecular j has a tendency to lower in heat resistance and the like, and the tendency to decrease when it exceeds 250,000. The material used for the transparency and the aromatic phase crystal is formed, and the GPC method is preferably 2,000 Å to 2,000 Å, and there is a molding -8 - 201231493 <Method for producing alicyclic polyester> The alicyclic ring of the present invention A method for producing a polyester, that is, a method for producing an alicyclic polyester represented by the above formula (I), characterized by a tricyclodecane monomethanol monocarboxylic acid derivative represented by the following formula (II) All are aggregated.

(However, in the formula (II), 'R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group, or a benzyl group). The alkyl group represented by 'R in the formula (II) is not particularly limited as long as it is an alkyl group having a carbon number id, a vinyl group, or a benzyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or the like. Isobutyl, pentyl and isopentyl are preferred. Specific examples of the tricyclodecane monomethanol monocarboxylic acid derivative represented by the formula (II) are 4-hydroxymethyl-8-carboxy-tricyclo[5·5.2·υ2,6]decane, 3- Hydroxymethyl-8-carboxy-tricyclo[]decane, 3-hydroxymethyl-9-carboxy-tricyclo[5.2.1, 〇2,6]nonane, 4·hydroxymethyl-8-methoxy Carbonyl-tricyclo[5.2.1.0''6]nonane, 3-hydroxymethyl-8-methoxycarbonyl-tricyclo[5.2.1.0''6]nonane' 3-hydroxymethyl-9-methoxy Carbonyl-tricyclo[5.2.1.0''6]nonane, 4-hydroxymethyl-8-butoxycarbonyl-tricyclo[5.2.1.02'6]nonane, 3-hydroxymethyl-8-butoxy Carbonyl-tricyclo[5.2.1.02'6]decane, 3-hydroxymethyl-9-butoxycarbonyl-tricyclo[-9- 201231493 5.2.1.0,]decane, 4-hydroxymethyl·8_ Pentyloxycarbonyl-tricyclo[5.2.1.02'6]decane, 3-hydroxymethylpentyloxycarbonyltricyclo[5.2.1_02'6]nonane, 3-hydroxymethyl-9-pentyloxy Carbonyl-tricyclo[5.2.1.02'6]decane, 4-hydroxymethyl-8-vinyloxycarbonyl-tricyclo[5.2.1.02'6]nonane, 3-hydroxymethyl-8-vinyloxy Carbonyl-tricyclic [5.2.1.02'6 Decane, 3-hydroxymethyl_9-vinyloxycarbonyltricyclo[5·2.1·02'6]decane, 4-hydroxymethyl·8-benzyloxycarbonyl-tricyclo[5.2.1.02'6 ] decane, 3-hydroxymethyl-8-benzyloxycarbonyl-tricyclo[5.2.1·02'6]nonane, 3-hydroxymethyl-9-benzyloxycarbonyl-tricyclo[5.2.1.02 '6] 癸 等 etc. 'In terms of cost and reactivity in the production of a tricyclic terpene monocarboxylic acid derivative, it is preferably 4-hydroxymethyl-8-methoxycarbonyl-tricyclo[ 5.2_1_〇2'6]decane, 3-hydroxymethyl-8-methoxycarbonyl-tricyclo[5.2.1. 02,6]decane, 3-hydroxymethyl-9-methoxycarbonyl - Tricyclo [5.2.1.0''6] decane. The tricyclodecane monomethanol monocarboxylic acid derivative (hereinafter sometimes abbreviated as "tricyclodecane monomethanol monocarboxylic acid derivative") represented by the formula (II) used in the present invention can be used as follows The compound represented by the following formula (IV) obtained by hydroformylation of the six-membered ring side of dicyclopentadiene represented by the formula (III) is obtained by hydroformylation. [Chemical 5]

-10- 201231493 [Chem. 6]

(IV) (However, in the formula (IV), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group, or a benzyl group). When the tricyclodecane monomethanol monocarboxylic acid derivative used in the present invention is produced, first, in the presence of a catalyst system containing a ruthenium compound, a cobalt compound, and a halogen compound salt, the following formula (III) is used. The cyclopentadiene is reacted with a formic acid compound (HCOOR) to produce a tricyclodecene monocarboxylic acid derivative represented by the following formula (IV) of addition-C(0)R. Here, R in the above formic acid compound (HCOOR) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a vinyl group or a benzyl group. [Chemistry 7]

As for the formic acid compound (HCOOR), when a formic acid having R is a hydrogen atom, a carboxyl group may be added to the dicyclopentadiene which causes the hydrocarboxylation reaction, and an alkyl group having a carbon number of 1 to 5, a vinyl group or a benzyl group may be used. In the case of the formate, the ester group can be added to the dicyclopentadiene which causes the hydrogen esterification reaction. The formic acid compound is a formic acid compound (HCOOR) corresponding to the target tricyclodecane monomethanol monocarboxyl-11 - 201231493 acid derivative -C(0)0R, and is exemplified by for example, formic acid, methyl formate, ethyl formate, Propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, vinyl formate, benzyl formate, and the like. Among these, methyl formate is preferred from the viewpoint of cost and reactivity. The reaction of the dicyclopentadiene and the formic acid compound represented by the above formula (III) is carried out in the presence of a catalyst system containing a ruthenium compound, a cobalt compound, and a halide salt as described above. The hydrazine compound which can be used in the present invention is not particularly limited. Specific examples of the preferred compound are exemplified by [Ru(CO)3C12]2, [RuC12(CO)2]n (η is an unspecified natural number), [Ru (CO)3C13], [Ru3(CO)hC1]-, [Ru4(CO)13C1]·, etc., together with a ruthenium compound having a carbonyl ligand and a halogen ligand, etc., wherein the reaction rate is improved From the viewpoint, it is more preferably [Ru(CO)3C12]2, [RuC12(CO)2]n. - RuC13, Ru3(CO)2, RuC12(C8H12), Ru(CO)3(C8H8), Ru(CO)3(C8H12) and Ru(C8H1() can also be used as the ruthenium compound having the above ligand. 1) (C8H12) or the like as a precursor compound, the ruthenium compound may be formed before or during the reaction of hydrocarboxylation or hydroesterification, and then introduced into a reaction system. The amount of the ruthenium compound used is relative to the raw material. The divalent pentadiene 1 equivalent ' is preferably 1/10000 to 1 equivalent, more preferably 1/1000 to 1/5 equivalent. When the manufacturing cost is considered, the smaller the amount of the ruthenium compound is used, but it is less than 1 When the ratio is /1 0 0 0 0, the reaction tends to be extremely slow. Moreover, when the amount exceeds 1 equivalent, the reaction rate is not accelerated, and the manufacturing cost is increased. -12- 201231493 The cobalt compound which can be used in the present invention There is no particular limitation. Specific examples of preferred compounds are cobalt compounds with a carbonyl ligand such as Co2(CO)8, c〇(CO)4, Co4(CO)12, cobalt acetate, cobalt propionate, and benzene. A cobalt compound such as cobalt formate or cobalt citrate, which has a carboxylic acid compound, cobalt phosphate, etc., among them, from the viewpoint of improving the reaction rate More preferably, Co2(CO)8, cobalt acetate, and cobalt citrate. The amount of the cobalt compound used is 1/100 to 10 equivalents per 1 equivalent of the hydrazine compound, preferably 1/10 to 5 equivalents. When the ratio of the above ruthenium compound is less than 1/100 or higher than 10, the amount of the tricyclic terpene monocarboxylic acid derivative represented by the above formula (IV) tends to be remarkably lowered. The halide salt to be used is not particularly limited as long as it is a compound composed of a halide ion such as a chloride ion, a bromide ion or an iodide ion, and a cation. The cation may be either an inorganic ion or an organic ion. The halide salt may also contain more than one halogen ion in the molecule. The inorganic ion constituting the halide salt may be a metal ion selected from an alkali metal or an alkaline earth metal. Specifically, it is exemplified as lithium, sodium, potassium, and cesium. Further, the organic ion may be an organic group derived from an organic compound or more, and an example thereof is ammonium, squama, pyrrolidine, pyridinium, imidazole, And an imine bond, etc. The hydrogen atom of the plasma may be substituted with a hydrocarbon group such as an alkyl group or an aryl group. Although not particularly limited, specific examples of preferred organic ion are tetramethylammonium, tetraethylammonium, and tetrapropylamine. Ammonium, tetrabutylammonium, tetra-13- 201231493 amyl ammonium, tetrahexylammonium, tetraheptyl ammonium, tetraoctyl ammonium, trioctylmethyl ammonium 'benzyl trimethyl ammonium, benzyl triethyl Ammonium, benzyltributylammonium, tetramethylscale, tetraethylscale, tetraphenyliron, benzyltriphenyl scale, butylmethylpyrrolidine, octylmethylpyrrolidine, bis(triphenyl) The phosphine) imide key is more preferably a butylmethylpyrrolidine key, a bis(triphenylphosphine) imide key, a trioctylmethylammonium or the like in terms of improving the reaction rate. The halide salt used in the present invention is not necessarily a solid salt, and may be a liquid halide ion-containing ionic liquid in a temperature range near room temperature or below 100 °C. Specific examples of the cation used in the plasma liquid are exemplified by 1-ethyl-3-methylimidazole key, 1-propyl-3-mercaptoimidazole key '1-butyl-3-methylimidazole key, 1 -pentyl-3-methylimidazole gun, 1-hexyl-3-methylimidazole key, 1 ·heptyl-3-methylimidazole key, 1-octyl-3-methylimidazole key, 1-mercapto -3-methylimidazolium, 1-dodecyl-3-methylimidazole, 1-tetradecyl-3-methylimidazole, 1-hexadecyl-3-methylimidazolium, 1-octadecyl-3-methylimidazole gun, 1-ethyl-2,3-dimethylimidazole gun, 1-butyl-2,3-dimethylimidazole, 1-hexyl-2, 3-dimethylimidazole, 1-ethylpyridine, 1-butylpyridine, 1-hexylpyridine, 8-methyl-1,8-azabicyclo[5.4_0]-7--] --carbon, 8-ethyl-1,8-diazabicyclo[5.4.0]-7-undecene, 8·propyl·indole, 8-diazabicyclo[5.4.0]- 7-undecene, 8_butyl-hydrazine, 8•diazabicyclo[5.4〇]-7_ carbon,8·pentyl-indole, 8-diazabicyclo[5_4.〇]-7-~ 1 - Carbene 8-hexyl-1,8-azabicyclo[5.4.0]-7-undecene, 8-heptyl_ 1,8- —Azabicyclo[5·4.〇]--organic ion of carbene, 8-octyl-1,8-diazabicyclo[5.4.0]undecene. In the present invention, -14-201231493 may be used alone or in combination of plural kinds. Among the above halide salts, preferred halide salts are chloride salts, bromine salts, and iodide salts, and the cation is an organic ion. Although not particularly limited, specific examples of the preferred halide salt in the present invention include chloromethylpyrrolidium chloride, bis(triphenylphosphine)imide, and trioctylmethylammonium chloride. The amount of the halide salt to be added is, for example, 1 to 100 equivalents, preferably 2 to 50 equivalents per equivalent of the hydrazine compound. By increasing the amount of one equivalent or more, the reaction rate can be effectively increased. On the other hand, when the amount is more than 100 eq, the effect of further improving the reaction cannot be obtained even if the amount of addition is further increased. The reaction of dicyclopentadiene with a formic acid compound for obtaining a tricyclodecane monomethanol monocarboxylic acid derivative used in the present invention is carried out in a specific catalyst system containing a ruthenium compound, a cobalt compound, and a halide salt. The effect of promoting the reaction by the aforementioned catalyst system can be further enhanced by adding at least one selected from the basic compound, the phenol compound and the organic halogen compound as needed. The basic compound used in the present invention may be an inorganic compound or an organic compound. Specific examples of the basic inorganic compound are carbonates, hydrogencarbonates, hydroxide salts, alkoxides, and the like of alkali metals and alkaline earth metals. Specific examples of the basic organic compound are a primary amine compound, a secondary amine compound, a tertiary amine compound, a pyridine compound, an imidazole compound, and a quinoline compound. Among the above basic compounds, a tertiary amine compound is preferred from the viewpoint of promoting the reaction effect. Specific examples of preferred tertiary amine compounds which can be used in the present invention are exemplified by trialkylamine, N-alkylpyrrolidine, quinuclidine ring, -15-201231493 and triethylenediamine. The amount of the basic compound to be added is not particularly limited, but is, for example, 1 to 1,000 equivalents, more preferably 2 to 200 equivalents, per equivalent of the hydrazine compound. By setting the addition amount to 1 equivalent or more, the tendency to promote the effect is more prominently exhibited. Further, when the amount is more than 1,000 equivalents, the reaction-promoting effect is not obtained even if the amount of addition is further increased. The phenol compound used in the present invention is not particularly limited. Specific examples of the phenol compound which can be used are phenol, cresol, alkylphenol, methoxyphenol, phenoxyphenol, chlorophenol, trifluoromethylphenol, hydroquinone, catechol, etc. The amount is not particularly limited, but is, for example, 1 to 1000 equivalents, preferably 2 to 200 equivalents per equivalent of the hydrazine compound. When the amount of addition is 1 equivalent or more, the reaction promoting effect is more prominently exhibited. In addition, when the amount of addition exceeds 1,000 equivalents, there is a tendency that the effect of further improving the reaction cannot be obtained even if the amount of addition is further increased. The organohalogen compound used in the present invention is not particularly limited. Specific examples of the organohalogen compound which can be used are, for example, monohalogenated methane, dihalogenated methane, dihalogenated ethane, trihalogenated methane, tetrahalomated methane, halogenated benzene, etc., and the amount of the organohalogen compound added is not particularly limited, but The nail compound 1 equivalent is, for example, 1 to 1 equivalent, preferably 2 to 200 equivalents. By adding the amount of addition to 1 equivalent or more, there is a tendency to exhibit a reaction promoting effect more remarkably. In addition, when the amount added exceeds 1 〇〇〇 equivalent, there is a tendency that the effect of further improving the reaction cannot be obtained even if the amount of addition is further increased. The reaction of dicyclopentadiene with a formic acid compound which is obtained by using tricyclodecane monomethanol monoacid derivative -16-201231493 used in the present invention can be carried out especially without using a solvent. However, a solvent can also be used as needed. The solvent which can be used is not particularly limited as long as it can dissolve the compound used as a raw material. Specific examples of suitable solvents are n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, p-xylene, m-xylene, ethylbenzene, isopropyl. Benzene, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethyl Glycol dimethyl ether and the like. The reaction of dicyclopentadiene with a formic acid compound for obtaining a tricyclodecane monomethanol monocarboxylic acid derivative used in the present invention is preferably carried out at a temperature ranging from 80 °C to 200 °C. The above reaction is more preferably carried out in a temperature range of 10 (TC to 160 ° C. By carrying out the reaction at a temperature of 8 ° C or higher, the reaction rate is easily accelerated ' and the reaction proceeds efficiently. On the other hand, When the reaction temperature is controlled to 200 ° C or lower, decomposition of the formic acid compound used as a raw material can be suppressed. When the formic acid compound is decomposed, since the addition of a carboxyl group or an ester group to dicyclopentadiene cannot be achieved, it is not desirable to be too high. Reaction temperature. When the reaction temperature exceeds the boiling point of either __cyclopentane or formic acid compound used as a raw material, it is necessary to carry out the reaction in a pressure-resistant container. The end of the reaction can be analyzed by gas chromatography, NMR, or the like. Further, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The above formula (IV) is obtained by reacting a dicyclopentadiene which is represented by the formula (III) with a formic acid compound. The tricyclic terpene monocarboxylic acid derivative represented by the addition of -C(0)0R to the dicyclopentadiene represented by the above formula (111) is formed in the tricyclic ring [5.2.1_〇 2'6]癸-3-嫌Architecture 8 or -17- 201231493 Structure in which the addition-C(0)0R is added at the 9-position. In order to obtain the tricyclodecane monomethanol monocarboxylic acid derivative used in the present invention, the following formula is obtained by the above method. The trimethyl decene monocarboxylic acid derivative represented by the above (IV) is hydroformylated, and a tricyclodecane monomethanol monocarboxylic acid derivative represented by the following formula (11) can be obtained.

(IV) (II)

〇 II

R-0-C The hydroformylation reaction of the tricyclic terpene monocarboxylic acid derivative represented by the above formula (IV) is carried out by a conventional hydroformylation method, for example, in the catalyst lecture volume 7 According to the editor of the Catalyst Association, as described in the lecturer (1985), a transition metal complex catalyst such as cobalt, ruthenium or osmium may be used to react carbon monoxide with hydrogen to form an aldehyde, then hydrogenation or use. A method in which carbon monoxide is reacted with hydrogen and directly added to an alcohol. On the other hand, in the conventional hydroformylation method, since carbon monoxide is used with high toxicity, it is less preferable from the viewpoints of workability, safety, reactivity, etc., and therefore it is more preferable to use carbon dioxide and hydrogen as described below. Hydroformylation. At this time, carbon dioxide and hydrogen may be supplied as a mixed gas, or may be supplied separately. The mixed gas system is a mixed gas (raw material gas) containing carbon dioxide and hydrogen as main components, and the content of carbon dioxide is preferably 10 to 95 vol%, more preferably 50 to 80 vol%, and the hydrogen content is preferably 5 to 90 vol%, more preferably It is 20~50vol%. When the hydrogen content exceeds 90 vol%, the raw material tends to be hydrogenated. When the amount is less than 5%, the reaction rate tends to decrease. In -18- 201231493, it is not necessary to mix carbon monoxide gas into the raw material gas, but it is not necessary to mix it. The catalyst system of the hydroformylation reaction preferably contains a ruthenium compound, and the ruthenium compound to be used is not particularly limited as long as it contains ruthenium. Specific examples of preferred compounds are [Ru(CO)3C12]2, [RuC12(CO)2]η (η is an unspecified natural number), [1111((:0)3(:13]-, [ 11113 ((:0)11(::1]·, [Ru4(CO)13C1]-), etc., together with a ruthenium compound having a carbonyl ligand and a halogen ligand, among them, the viewpoint of improving the reaction rate More preferably, it is [Ru(CO)3C12]2, [RuC12(CO)2]η. For the ruthenium compound having the above ligand, RuC13, Ru3(CO)12, RuC12(C8H12) can also be used. Ru(CO)3(C8H8), Ru(CO)3(C8H12), and Ru(C8H1q)(C8H12) are used as precursor compounds, and the ruthenium compound is prepared before or during the reaction of hydroformylation. Further, it is introduced into the reaction system. The amount of the ruthenium compound used is 1 equivalent of the tricyclodecene monocarboxylic acid derivative represented by the formula (IV) of the starting material, preferably 1/100 〇〇 to 1 equivalent, more It is preferably 1 / 1 000 - 1 / 50 equivalent. When the manufacturing cost is considered, the use of the ruthenium compound is as small as possible, but when it is less than 1 / 1 0000 equivalent, the reaction tends to be extremely slow, and when it exceeds 1 equivalent There will be no reaction speed It is only a tendency to increase the manufacturing cost. The hydroformylation of the tricyclic terpene monocarboxylic acid derivative represented by the formula (IV) of the present invention may be required to additionally add a cobalt compound to the catalyst system containing the ruthenium compound. At least one of a halide salt, a phenol compound and an acid is selected to further enhance the effect of promoting the reaction by the aforementioned catalyst system. -19- 201231493 A cobalt compound which can be used as a catalyst for hydroformylation reaction is not particularly Specific examples of preferred compounds are c〇2(co)8, hc〇(co)4, &lt;:〇4((:0)12, etc. cobalt compound with carbonyl ligand, cobalt acetate' a cobalt compound such as cobalt propionate, cobalt benzoate or cobalt citrate having a carboxylic acid compound, cobalt phosphate, etc. Among them, C〇2(CO)8 is preferable from the viewpoint of improving the reaction rate. Cobalt acetate and cobalt citrate. The amount of the cobalt compound used is 1/100 to 10 equivalents, preferably 1/10 to 5 equivalents per equivalent of the hydrazine compound. The ratio of the above cobalt compound to the above hydrazine compound is less than 1 /100, or higher than 10, tricyclodecane monomethanol monocarboxylic acid derivative The amount of the halide salt to be used in the present invention is not particularly limited as long as it is a compound composed of a halide ion such as a chloride ion, a bromide ion or an iodide ion, and a cation. The cation may be an inorganic substance. Any one of an ion and an organic ion. The halide salt may further contain one or more halogen ions in the molecule. The inorganic ion constituting the halide salt may be a metal ion selected from an alkali metal or an alkaline earth metal. Specifically, it is exemplified by lithium, sodium, potassium, rubidium, planer, calcium, and barium. Further, the organic ion may be an organic group derived from an organic compound or more. An example of this is ammonium, squama, pyrrolidinium, pyridyl, imi- and imine. The hydrogen atom of the plasma may also be substituted with a hydrocarbon group such as an alkyl group or an aryl group. Although not particularly limited, specific examples of preferred organic ions are tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraamylammonium, tetrahexylammonium, tetraheptylammonium, and tetra. Octyl ammonium, trioctylmethyl ammonium, -20- 201231493 benzyl trimethyl ammonium, benzyl triethyl ammonium, benzyl tributyl ammonium, cetyl trimethyl ammonium, tetramethyl scale, Tetraethyl scale, tetraphenylphosphonium, benzyltriphenylphosphonium, butylmethylpyrrolidine, octylmethylpyrrolidine, bis(triphenylphosphine)imide. Among them, in view of improving the reaction rate, a quaternary ammonium salt such as cetyltrimethylammonium chloride or cetyltrimethylammonium bromide is preferred. The halide salt which can be used in the present invention is not necessarily a solid salt, and may be an ionic liquid containing a halide ion which is liquid in a temperature range near room temperature or below 100 °C. Specific examples of the cation used in the plasma liquid are 1-ethyl-3-methylimidazole, 1-propyl-3-methylimidazole gun, 1-butyl-3-methylimidazole, 1 -pentyl-3-methylimidazole gun, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-decyl -3-methylimidazole key, 1 · dodecyl-3-methylimidazole key, 1-tetradecyl-3-methylimidazole key, 1-hexadecyl-3-methylimidazole key, 1-octadecyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-2, 3-dimethylimidazole, 1-ethylpyridine, 1-butylpyridine, 1-hexylpyridine, 8-methyl-1,8-diazabicyclo[5.4.0]-7- Monocarbene, 8-ethyl-1,8-diazabicyclo[5.4.0]-7-undecene, 8-propyl-1,8-diazabicyclo[5·4·0] -7-undecene, 8-butyl-1,8-diazabicyclo[5.4.0]-7-undecene, 8-pentyl-1,8-diazabicyclo[5.4. 0]-7-undecene, 8-hexyl-1,8-diazabicyclo[5.4.0]-7-undecene, 8-heptyl-1,8-diazabicyclo[ 5.4.0] Organic ions of 7-undecene, 8-octyl-1,8-diazabicyclo[5.4.0]-7-undecene. In the present invention, the above-mentioned halide salts may be used singly or in combination of plural kinds. In the above halide salt, a preferred halide salt is a chloride salt, a bromine salt, or an iodide salt, and the cation is an organic ion. Although not particularly limited, specific examples of the preferred halide salt in the present invention are cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and the like. The amount of the halide salt to be added is, for example, 1 to 1000 equivalents, preferably 2 to 50 equivalents per equivalent of the hydrazine compound. By increasing the amount of one equivalent or more, the reaction rate can be effectively increased. On the other hand, when the amount added exceeds 1 当量, the effect of further improving the reaction cannot be obtained even if the amount of addition is further increased. The phenol compound used in the present invention is not particularly limited. Specific examples of the phenol compound which can be used are phenol, cresol, alkylphenol, methoxyphenol, phenoxyphenol, chlorophenol, trifluoromethylphenol, hydroquinone, and catechol. The amount of the phenol compound to be added is not particularly limited, but is, for example, 1 to 1,000 equivalents, preferably 2 to 200 equivalents per equivalent of the hydrazine compound. When the amount of addition is 1 equivalent or more, the reaction promoting effect is more remarkably exhibited. In addition, when the amount added exceeds 1,000 equivalents, there is a tendency that the effect of further improving the reaction cannot be obtained even if the amount of addition is further increased. As the acid which can be used in the present invention, all of the acids corresponding to the definition of Lewis can be used. According to this definition, when a substance A is supplied with an electron pair by another substance B, then A is defined as an acid, B is defined as a base, and the owner corresponding to the A of the receiving electron pair can be used. As the above acid, A is preferably an acid which is a proton donor, that is, a Brandy acid. As for the Brilliant acid system, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methylphosphoric acid, alkylphosphonic acid, phenylphosphoric acid, diphenyl phosphite, benzene-22-201231493-based phosphonic acid, 4-methoxyphenylphosphine Acid, diethyl 4-methoxyphenylphosphonate, phenylphosphite, boric acid, phenylboronic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, phenol, tungstic acid, phosphotungstic acid, and formic acid An alkyl carboxylic acid represented by acetic acid, trifluoroacetic acid, propionic acid or butyric acid, an aromatic carboxylic acid represented by benzoic acid, phthalic acid or naphthoic acid, preferably phosphoric acid, alkylphosphoric acid or phenyl Phosphorous acid such as phosphoric acid, diphenyl phosphite, or phosphonic acid derivative. The amount of the acid to be added is, for example, 0.1 to 100 equivalents, preferably 1 to 10 equivalents per equivalent of the hydrazine compound. By setting the amount to be added in an amount of 1 equivalent or more, the reaction rate can be effectively increased. On the other hand, when the amount added exceeds 100 equivalents, the effect of further promoting the reaction cannot be obtained even if the amount of addition is further increased. Hydroformylation is preferably carried out in a temperature range of from 100 ° C to 200 ° C, more preferably in a temperature range of from ll ° ° C to 180 ° C, preferably at a temperature of from 120 ° C to 160 ° C. Implemented within the scope. By carrying out the reaction at a temperature of 10 ° C or higher, the reaction is accelerated, and the reaction is easily carried out efficiently. On the other hand, by controlling the reaction temperature to 200 ° C or lower, hydrogenation of the unsaturated bond of the tricyclic terpene monocarboxylic acid derivative represented by the general formula (IV) can be suppressed. When hydrogenation of the unsaturated bond of the tricyclic terpene monocarboxylic acid derivative represented by the general formula (IV) is caused, hydroformylation cannot be achieved, so that a reaction temperature which is too high is not desired. Hydroformylation is necessary in a pressure vessel. The pressure of the reaction is preferably in the range of 1 MPa to 20 MPa, more preferably in the range of 2 MPa to 15 MPa. When the pressure is less than IMP a, the reaction tends to be slow. When the pressure exceeds 20 MPa, there is a tendency that the reaction is promoted to further improve the effect even if the pressure is further increased. -23- 201231493 The hydroformylation reaction for obtaining the tricyclodecane monomethanol monocarboxylic acid derivative used in the present invention may optionally be present in a solvent. The solvent to be used is not particularly limited as long as it can dissolve the tricyclodecene monocarboxylic acid derivative represented by the above formula (IV). Specific examples of suitable solvents are n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, p-xylene, m-xylene, ethylbenzene, isopropyl. Benzene, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylimidazolidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, -B - alcohol monomethyl ether, γ - butane vinegar, and the like. When a solvent is used, it is preferably used in such a range that the concentration of the tricyclic terpene monocarboxylic acid derivative represented by the above formula (IV) is in the range of 10 to 1000% by mass. The method of uniformly polymerizing a tricyclodecane monomethanol monocarboxylic acid derivative represented by the formula (II) of the present invention to form an alicyclic polyester represented by the general formula (I) is not particularly limited, and for example, Obtained by excluding the alcohol produced by heating out of the system in the presence or absence of a solvent. The polymerization temperature is preferably from 4 to 22 ° C, more preferably from 60 to 2 Torr (TC, preferably from 80 to 180 ° C. When the polymerization temperature is less than 80 ° C, the polymerization rate tends to be extremely slow, exceeding At 220 ° C, the polymerization reaction may cause decomposition of the tricyclodecane monomethanol monocarboxylic acid derivative represented by the general formula (π). The reaction time may be appropriately selected depending on the batch size and the reaction conditions employed. A catalyst may also be used. The catalyst to be used is not particularly limited, and for example, a basic substance such as a metal alkoxide or an alkali metal salt may be used. Among them, an alkali alkoxide of an alkali (earth) metal is preferably used. It is easy to use lithium, sodium, potassium methoxide, ethoxylate, propoxide. The amount of the above catalyst is -24-201231493. It is preferably the raw material tricyclodecane monomethanol monocarboxylic acid derivative 〇〇 1~ 1〇〇% by mole, more preferably 0.03~7.0% by mole, preferably 〇〇5~5 〇mol%. When the amount of catalyst used is less than 0.01 mil%, there is a tendency for the polymerization rate to be extremely slow. When it exceeds 10.0 mol%, the polymerization proceeds rapidly, or there is a possibility of causing excessive heat generation. The solvent can be used in the absence of a solvent. The solvent to be used is not particularly limited as long as it can dissolve the tricyclodecane monomethanol monocarboxylic acid derivative of the starting material. Specific examples of the solvent which can be suitably used Examples thereof include a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, an ester solvent such as ethyl acetate, butyl acetate or γ-butyrolactone, and diethylene glycol dimethyl ether. , an ether solvent such as triethylene glycol dimethyl ether, diethylene glycol diethyl ether or triethylene glycol diethyl ether, butyl cellosolve acetate, ethyl cellosolve acetate, methyl a cellosolve such as cellosolve acetate, a solvent such as toluene, xylene, p-isopropylbenzene or 1,2,3,4-tetrahydroxynaphthalene, tetrahydrofuran, dioxins, hydrazine - Methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl hydrazine, cyclobutyl, etc., but if the cost is 'workability, etc., then More preferably, it is carried out without a solvent. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited by the following examples. (Synthesis Example 1) [Synthesis of Tricyclic Terpene Monocarboxylic Acid Methyl Ester] At room temperature, in a 50 ml internal pressure stainless steel pressure reactor, -25-201231493, mixed with 0.025 «1111〇1 [1^((:〇)3(:12]2, 0.025 mmol of Co2(CO)8 as a cobalt compound, 0.5 mmol of trioctylmethylammonium chloride as a halide salt, 2.0 mmol The catalyst system obtained as a basic compound of triethylamine was added with 1 〇 mmol of dicyclopentadiene and 5.0 mL of methyl formate. Then, the inside of the reaction apparatus was blown with nitrogen 〇 5 MPa, at 12 (TC was maintained for 8 hours. The reaction apparatus was then cooled to room temperature.) The pressure was released and a portion of the residual organic phase was taken and analyzed using a gas chromatograph. According to the analysis results, the tricyclodecene monocarboxylic acid methyl ester represented by the above formula (IV) was 9.23 mmol (yield based on dicyclopentadiene was 92.3%). As a result of gas chromatography-mass spectrometry (GC-MS) analysis, the obtained tricyclodecene monocarboxylic acid methyl ester was identified as 8-methoxycarbonyl-tricyclo[5.2.1.02'6]non-3-ene and A mixture of 9-methoxycarbonyl-tricyclo[5.2.1.0''6]non-3-ene. The obtained tricyclodecene monocarboxylic acid methyl ester was isolated by distillation under reduced pressure. The chemical reaction formula of this synthesis example is shown below. [Chemistry 9]

(Synthesis Example 2) [Synthesis of tricyclodecane monomethanol monocarboxylic acid methyl ester] In a stainless steel pressure reaction apparatus having an internal volume of 50 ml at room temperature, 0.05 mmol of Ru2 (CO) as a ruthenium compound was mixed. 6C14, 0.05mmol of Co2(CO)8 as a cobalt compound, 2.5mmol of cetyltrimethylammonium chloride as a halide salt, and 0.25mmol of diphenyl phosphite as an acid 10. Ommol of the additionally synthesized tricyclic terpene monocarboxylic acid methyl ester, 10. Oml of toluene as a solvent, dissolved by stirring -26-201231493, and then pressed into 4 MPa of carbon dioxide, 4 MPa of hydrogen' Maintain at 140 ° C for 15 hours. Subsequently, the reaction apparatus was cooled to room temperature to release the pressure and extract a portion of the residual organic phase, which was analyzed by a gas chromatograph. Based on the analysis results, 7.45 mmol (yield 74.5% based on tricyclodecene monocarboxylic acid methyl ester) was produced as the tricyclodecane monomethanol monocarboxylic acid methyl ester represented by the above formula (II). Using a gas chromatography-mass spectrometer (GC_MS) analysis, the obtained tricyclodecane monomethanol monocarboxylic acid methyl ester was identified as 4-hydroxymethyl-8-methoxycarbonyl-tricyclo[5.2.1.02'6 ] decane, 3-hydroxymethyl-8-methoxycarbonyl-tricyclo[5.2.1 ·02'6]nonane and 3-hydroxymethyl-9-methoxycarbonyl-tricyclo[5.2.1.02 '6] a mixture of decane. The chemical reaction formula of this synthesis example is shown below. [化10]

The obtained tricyclodecane monomethanol monocarboxylic acid methyl ester was isolated by distillation under reduced pressure, and W-NMR spectrum and IR spectrum were measured. Further, in the W-NMR spectrum, a solution obtained by dissolving a sample in dimethyl sulfoxide (DMS0-d6) was poured into a sample tube of Φ 5 mm, and measured by a 400 MHz nuclear magnetic resonance device "AV400M" manufactured by BRUKER. Further, the IR spectrum was measured using a Fourier transform infrared spectrophotometer (JIR-6 5 00, manufactured by JEOL Ltd.). The iH-NMR spectrum is shown in Fig. 1. Each proton is classified as follows. For the purpose of analysis, 4-hydroxymethyl-8-methoxycarbonyl-tricyclo[5·2.1.02'6]nonane represented by the following formula is exemplified. The results of 1H-NMR analysis (Fig. 1), each proton is classified as follows -27- 201231493 [Chem. 11]

Ch2oh (11) (12) Proton (1): peak proton near 2.1ppm (2): peak proton near 2.4ppm (3): peak proton near 1. 2ppm and around 1.7ppm (4) : 2.3ppm Nearby peak protons (5): peak protons around 1.2ppm and around 1 _8ppm (6): peak protons around 2.6ppm (7): 2. Peak protons around Ippm (8): peak protons around 1.9ppm ( 9) : Peak proton near 0.9ppm and around 1.7ppm (10): Peak proton near 1.4~1.5ppm (1 1 ): Peak proton near 3.2ppm (12): Peak proton near 4.4ppm (1 3 ) : The peak near 3.6ppm and the proton of the tricyclic decane moiety (1) ~ (1〇) / proton of hydroxymethyl group and proton of (11) / hydroxymethyl group (12) / methoxycarbonyl group The integrated intensity ratio of proton (13) is 13.93/2.00/1.04/3.08 (theoretical 値: 14/2/1/3) 'It can be confirmed that the obtained tricyclodecane monomethanol monocarboxylic acid methyl ester has the above formula (V) Indicates the construction. Further, the IR spectrum is shown in Fig. 2. It can be confirmed that the methyl -28-201231493 and the methine peak of the tricyclodecane moiety are in the vicinity of 8 00 to 1 450 CXTT1, and the methyl group peak due to the hydroxymethyl group is in the vicinity of 1465 0111^, resulting from the hydroxyl group. The peak of the hydroxyl group of the methyl group is in the vicinity of 3400 CHT1, and the peak of the carbonyl group due to the methoxycarbonyl group is around 1 760 011 ^1, and the peak of the methyl group resulting from the methoxycarbonyl group is near 2870 CHT1 and 2960 CHT1. Synthesis Example 3 [Tricyclic Synthesis of decane dimethanol] In a stainless steel pressure reactor equipped with an internal volume of 50 ml at room temperature, 0.13 mmol of Ru3(CO)12 and 0.5 mmol as a ruthenium compound were poured as a halide salt. Bis(triphenylphosphine)imide pin, 0.5 mmol of phenylphosphoric acid as acid, 5.0 mmol of dicyclopentadiene as a raw material organic compound, 10. OmL of toluene as an organic solvent, dissolved by stirring Thereafter, 4 MPa of carbon dioxide and 4 MPa of hydrogen were injected while stirring, and maintained at 140 ° C for 10 hours. Subsequently, the reaction apparatus was cooled to room temperature, the pressure was released, and the residual organic phase was taken and analyzed by a gas chromatograph. Based on the analysis results, 3.73 mmol (yield 74.6% based on cyclopentadiene) of tricyclodecane dimethanol was produced. The chemical reaction formula of this synthesis example is shown below. [化 12]

(Example 1) [Production of alicyclic polyester] In a 10 ml flask equipped with a stirrer, a nitrogen gas introduction tube, and a cooling tube, a tricyclodecane monomethanol monocarboxylic acid methyl ester 5 g obtained in Synthesis Example 2 was fed. And 4-29-201231493 iodine iodine bismuth. 5 g, stirred in an oil bath at 130 ° C for 6 hours to obtain a polyester having a tricyclodecane structure having a number average molecular weight of 30,00. The glass transition temperature (Tg) and the thermal decomposition onset temperature (5% mass reduction temperature, Td5) of the obtained polyester having a tricyclodecane structure were measured under the following conditions. The results are shown in Table 1. (1) Glass transition temperature (Tg)

It was measured by a differential scanning calorimeter (Rigaku Co., Ltd. Model 8230 DSC). Heating rate: 5 ° C / min Atmosphere: Air (2) Thermal decomposition starting temperature (5% mass reduction temperature, Td5) Measured with a differential thermal balance (Seiko Electronics Co., Ltd. Model 5200 TG-DTA). Heating rate: 5 ° C / min. Atmosphere: air, and the light transmittance of the polyester having a tricyclodecane structure at each wavelength was measured by a V-570 type UV/VIS spectrometer manufactured by JASCO Corporation. The evaluation results are summarized in Table 1. (Comparative Example 1) [Production of Polyester] In a 10 ml flask equipped with a stirrer, a nitrogen gas introduction tube and a cooling tube, 2.94 g (0.015 mol) of tricyclodecane dimethanol obtained in Synthesis Example 3 was fed. Dimethyl isophthalate 2.91 g (0.015 mol) and titanium tetraisopropoxide-30-201231493 〇.5g, stirred in an oil bath at 130 ° C for 6 hours to obtain a tricyclic fluorene having a number average molecular weight of 28,000 Alkane-structured polyester. The properties of the obtained polyester having a tricyclodecane structure were measured in the same manner as in Example 1. The results are shown in Table 1. [Table 1] Item Example 1 Comparative Example 1 Polymer property Glass transition temperature (. 〇 160 112 Thermal decomposition onset temperature rc) 417 390 Light transmittance (%) 400 nm 100 22 500 nm 100 45 600 nm 100 70 As shown in Table 1 The glass transition temperature and the thermal decomposition temperature of Example 1 were both higher than that of Comparative Example 1, and the alicyclic polyester of the present invention has high heat resistance. Further, the light transmittance of Example 1 was 100% at any wavelength, showing excellent transparency. That is, it was confirmed that the alicyclic polyester of the present invention is excellent in both heat resistance and transparency. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a W-NMR spectrum of a tricyclodecane monomethanol monocarboxylic acid methyl ester obtained in Synthesis Example 2. Fig. 2 is a FT-IR spectrum of tricyclodecane monomethanol monocarboxylic acid methyl ester obtained in Synthesis Example 2. -31 -

Claims (1)

201231493 VII. Patent application scope: Formula (I) 1. An alicyclic polyester having the following structural unit, [Chem. 1] 2. An alicyclic method according to the first aspect of the patent application, which comprises polymerizing a tricyclic acid derivative represented by the following formula (II), and producing a decane monomethanol of the polyester. Carboxylate An alkyl group of 5 or ethylene (however, in the formula (II), R represents a hydrogen atom, a carbon number of 1 to a group, or a benzyl group). -32-