Polycarbonate and resin moldings

Abstract

To provide polycarbonate which is excellent in heat resistance.SOLUTION: Polycarbonate has a constitutional unit represented by formula (1). In the formula, R1 to R13 each independently represent a substituent selected from the group consisting of hydrogen, an alkyl group and an alkoxy group; a is an integer of 0 to 10; b is an integer of 0 to 10.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polycarbonate. The present invention also relates to a resin molded article containing the polycarbonate. [Background technology]

[0002] 2. Description of the Related Art Plastic materials such as polyesters and polycarbonates have traditionally been used for molded articles in a variety of fields, including automobile parts, electronic parts, optical parts, and daily necessities, because of their excellent properties such as heat resistance, transparency, and moldability.

[0003] For example, Patent Document 1 proposes an aromatic-aliphatic polycarbonate copolymer of tricyclodecane dimethanol and bisphenol A as an optical material having transparency, low water absorption, low photoelastic constant, and a well-balanced refractive index and dispersion value. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 64-66234 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there is room for improvement in the heat resistance of the polycarbonate proposed in Patent Document 1.

[0006] Therefore, an object of the present invention is to provide a polycarbonate having excellent heat resistance. It is also an object of the present invention to provide a resin molded article containing such a polycarbonate. [Means for solving the problem]

[0007] As a result of intensive investigations, the present inventors have found that a polycarbonate having excellent heat resistance can be obtained by using a polycarbonate having a structural unit derived from a specific alicyclic olefin. The present invention is based on this finding.

[0008] The present invention includes the following inventions. [1] The following formula (1): [ka] [In the formula, R 1 ~R 13 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. Polycarbonate having a structural unit represented by the formula: [2] In the above formula (1), R 1 ~R 13 The polycarbonate according to [1], wherein all of the R 1 and R 2 are hydrogen. [3] The polycarbonate according to [1] or [2], wherein in the above formula (1), a is an integer of 0 to 3, and b is an integer of 0 to 3. [4] Formula (2): [ka] [In the formula, R 21 ~R 28 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is one of the following formulae: [ka] R 29 and R 30 are each independently a hydrogen atom, an alkyl group, or an aryl group; R 29 and R 30 and may be bonded to form a ring. The polycarbonate according to any one of [1] to [3], further comprising a structural unit represented by the following formula: [5] The polycarbonate according to any one of [1] to [4], which is a reaction product of a diol and a carbonyl compound. [6] The diol is represented by the following formula (3): [ka] [In the formula, R 1 ~R 13 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. The polycarbonate according to [5], comprising a compound represented by the following formula: [7] The polycarbonate according to [5] or [6], wherein the diol contains a diol other than that represented by the above formula (3). [8] The other diol is represented by the following formula (4): [ka] [In the formula, R 21 ~R 28 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is one of the following formulae: [ka] R 29 and R 30 are each independently a hydrogen atom, an alkyl group, or an aryl group; R 29 and R 30 and may be bonded to form a ring. The polycarbonate according to [7], comprising a compound represented by the following formula: [9] The carbonyl compound is represented by the following formula (5): [ka] [In the formula, R 31 and R 32 each independently represents chlorine, an alkyloxy group which may have a substituent, or an aryloxy group which may have a substituent. The polycarbonate according to any one of [5] to [8], represented by the formula:

[10] A resin molded product comprising the polycarbonate according to any one of [1] to [9]. Effect of the Invention

[0009] According to the present invention, a polycarbonate having excellent heat resistance can be provided. Furthermore, the polycarbonate according to the present invention has excellent mechanical properties such as toughness, bending strength, and bending modulus. In particular, according to the present invention, a polycarbonate having an excellent balance between heat resistance and mechanical properties can be provided. Furthermore, according to the present invention, a resin molded product containing such a polycarbonate can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Polycarbonate] The polycarbonate of the present invention has the following formula (1): [ka] [In the formula, R 1 ~R 13 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. It has a structural unit represented by the following formula:

[0011] In the above formula (1), R 1 ~R 13are each independently selected from the group consisting of hydrogen, an alkyl group, and an alkoxy group. Among these, hydrogen is particularly preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. The alkyl group may be linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 5. Particularly preferred is R 1 ~R 13 are all hydrogen.

[0012] In the above formula (1), a is an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, even more preferably 1 or 2, and even more preferably 1. Furthermore, b is an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, even more preferably 1 or 2, and even more preferably 1.

[0013] The polycarbonate of the present invention contains, in addition to the structural unit represented by formula (1) above, a structural unit represented by the following formula (2): [ka] [In the formula, R 21 ~R 28 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is one of the following formulae: [ka] R 29 and R 30 are each independently a hydrogen atom, an alkyl group, or an aryl group; R 29 and R 30 and may be bonded to form a ring. The compound may have a constitutional unit represented by the following formula:

[0014] In the above formula (2), R 21 ~R28 are each independently selected from the group consisting of hydrogen, halogen, an alkyl group, an alkoxyl group, a cycloalkyl group, an aryl group, a cycloalkoxyl group, and an aryloxy group. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. The alkyl group may be linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 5. The number of carbon atoms in the cycloalkyl group is preferably 6 to 20, and more preferably 6 to 12. The number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 12. The number of carbon atoms in the cycloalkoxyl group is preferably 6 to 20, and more preferably 6 to 12. The number of carbon atoms in the aryloxy group is preferably 6 to 20, and more preferably 6 to 12.

[0015] Also, R 29 and R 30 are each independently a hydrogen atom, an alkyl group, or an aryl group; R 29 and R 30 may be bonded to form a ring. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. The alkyl group may be linear or branched. The number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 12.

[0016] The content of the structural unit represented by the above formula (1) in the polycarbonate of the present invention is preferably 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more, relative to all structural units, and is preferably 100 mol% or less, and may be less than 100 mol% or may be 100 mol%. The content of the structural unit represented by the above formula (2) in the polycarbonate of the present invention is preferably 50 mol % or less, preferably 30 mol % or less, and more preferably 10 mol % or less, relative to all structural units, and is preferably 0 mol % or more, and may be more than 0 mol %, or may be 0 mol %.

[0017] [Manufacturing method of polycarbonate] The polycarbonate of the present invention can be obtained by a polymerization reaction between a diol and a carbonyl compound. Preferred embodiments of the raw materials for the polycarbonate and the polymerization reaction will be described in detail below.

[0018] [Diol] The diol that is the raw material of the polycarbonate of the present invention is represented by the following formula (3): [ka] The compound includes a compound represented by the formula:

[0019] R in the above formula (3) 1 ~R 13 , a, and b are as defined in the above formula (1). 1 ~R 13 The preferred embodiments of a, b are also as explained in relation to formula (1) above. In a particularly preferred embodiment, R 1 ~R 13 are both hydrogen, a is 1, and b is 1.

[0020] The polycarbonate using the diol represented by the above formula (3) as a raw material can improve heat resistance compared to the polycarbonate using the conventionally known tricyclodecane dimethanol as a raw material. Furthermore, the polycarbonate using the diol represented by the above formula (3) as a raw material has excellent mechanical properties such as toughness, bending strength, and bending modulus compared to the polycarbonate using the conventionally known dicyclopentadiene as a raw material. This is because the polycarbonate contains more structural units having a cyclic skeleton structure derived from the diol represented by the above formula (3) compared to dicyclopentadiene.

[0021] In addition, polycarbonates using the diol represented by the above formula (3) as a raw material are superior in mechanical properties such as toughness, flexural strength, and flexural modulus, and have a good balance between heat resistance and mechanical properties, compared to polycarbonates using the diol represented by the following formula (6) as a raw material. [ka] [In the formula, R 2 ~R 4 and R 6 ~R 13 , a, and b are as defined in formula (3) above.]

[0022] The method for producing the diol represented by the above formula (3) is not particularly limited, but includes, for example, a step of obtaining an aldehyde by a hydroformylation reaction of an alicyclic olefin represented by the following formula (7), and a step of obtaining a diol by a reduction reaction of the aldehyde. 1 ~R 13 are all as defined in the above formula (1). Similarly, R 1 ~R 13 The preferred embodiment of is also as explained in the above formula (1). [ka]

[0023] (Hydroformylation reaction) An aldehyde can be obtained by introducing a formyl group (-CH=O) into each of two carbon double bonds by the hydroformylation reaction of the alicyclic olefin represented by the above formula (7). The hydroformylation reaction is not particularly limited, and an example thereof includes a method in which an internal olefin is reacted with hydrogen and carbon monoxide in the presence of a catalyst consisting of a Group 8, 9, or 10 metal complex obtained by modifying a Group 8, 9, or 10 metal compound with a ligand such as an organic phosphorus compound to convert it into an aldehyde.

[0024] The Group 8, 9 and 10 metal compounds used in the hydroformylation reaction are compounds that originally have catalytic ability to promote the hydroformylation reaction of internal olefins or that acquire such catalytic ability under hydroformylation reaction conditions, and examples of such compounds include rhodium compounds, cobalt compounds, ruthenium compounds and iron compounds that have been used as catalysts in hydroformylation reactions in the past. Among these compounds, it is preferable to use cobalt compounds and rhodium compounds, from the viewpoint that the reaction conditions for the hydroformylation reaction are mild.

[0025] Examples of cobalt compounds include Co2(CO)8, and examples of rhodium compounds include rhodium oxides such as RhO, Rh2O, Rh2O3, and RhO2; rhodium salts such as rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium iodide, and rhodium acetate; and Rh4(CO). 12 , Rh6(CO) 16 Examples of rhodium complex compounds include RhH(CO)(PPh3)3, RhCl(CO)(PPh3)2, RhCl(PPh3)3, RhBr(CO)(PPh3)2, RhCl(CO)(AsPPh3)2, and Rh(acac)(CO)2 (where acac represents an acetylacetonato ligand; the same applies below).

[0026] The organic phosphorus compound used in the hydroformylation reaction is not particularly limited, and examples thereof include tricyclohexylphosphine, triisopropylphosphine, tributylphosphine, tri-t-butylphosphine, tribenzylphosphine, triphenylphosphine, tris(para-methoxyphenyl)phosphine, tris(para-N,N-dimethylaminophenyl)phosphine, tris(para-fluorophenyl)phosphine, tris(para-chlorophenyl)phosphine, tri-o-tolylphosphine, tri-meta-tolylphosphine, tri-para-tolylphosphine, tris(pentafluorophenyl)phosphine, bis(pentafluorophenyl) Examples of the organic phosphorus compounds include phenylphosphine, diphenyl(pentafluorophenyl)phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, cyclohexyldiphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine, meta-diphenylphosphinobenzenesulfonic acid or a metal salt thereof, para-diphenylphosphinobenzoic acid or a metal salt thereof, para-diphenylphosphinophenylphosphonic acid or a metal salt thereof, and the like. Triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, etc. are preferred. These organic phosphorus compounds may be used alone or in combination of two or more.

[0027] From the viewpoint of obtaining good catalyst stability and reaction rate, the amount of the organic phosphorus compound used is preferably in the range of 1 to 10,000 mol, more preferably in the range of 1 to 1,000 mol, and even more preferably in the range of 1.5 to 100 mol, calculated as phosphorus atoms, per 1 mol of the Group 8, 9 or 10 metal compound calculated as Group 8, 9 or 10 metal atom.

[0028] The method for preparing the Group 8, 9, and 10 metal complexes is not particularly limited, but for example, the complexes can be prepared by separately introducing a Group 8, 9, and 10 metal compound solution and an organophosphorus compound solution, which have been separately prepared using a solvent that does not affect the hydroformylation reaction, into a hydroformylation reaction system, and reacting the two in the system to form a complex. Alternatively, the complexes can be prepared by adding an organophosphorus compound to the Group 8, 9, and 10 metal compound solution, and then adding a solvent that does not affect the hydroformylation reaction to prepare a homogeneous solution.

[0029] The H2 / CO molar ratio of the mixed gas of hydrogen and carbon monoxide used in the hydroformylation reaction is preferably in the range of 0.1 to 10, more preferably in the range of 0.5 to 2, from the viewpoint of easy maintenance of the mixed gas composition at the time of feeding. The reaction pressure is preferably in the range of 0.1 to 10 MPa, more preferably in the range of 0.5 to 8 MPa from the viewpoint of the reaction rate. The reaction temperature is preferably in the range of 40 to 150°C, more preferably in the range of 60 to 140°C from the viewpoint of suppressing the deactivation of the catalyst.

[0030] The hydroformylation reaction can be carried out using a stirred reactor, a liquid circulation reactor, a gas circulation reactor, a bubble column reactor, etc. The reaction can be carried out in a continuous or batch manner.

[0031] From the viewpoints of reaction rate and catalyst cost, the amount of the Group 8, 9, or 10 metal complex used is preferably selected so as to be in the range of 0.1 to 1000 mmol, and more preferably in the range of 0.5 to 100 mmol, calculated as Group 8, 9, or 10 metal atom per 1000 g of raw material.

[0032] When the internal olefin is hydroformylated using a metal complex of Group 8, Group 9, or Group 10, a solvent may be present in the reaction system. Examples of the solvent include aprotic polar solvents such as toluene, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone, sulfolane, dimethylformamide, acetonitrile, acetone, 1,4-dioxane, and tetrahydrofuran; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, s-butyl alcohol, and t-butyl alcohol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol, triethylene glycol dimethyl ether, tetraethylene glycol, and tetraethylene glycol dimethyl ether; and polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more. Among these, it is preferable to use aprotic polar solvents such as toluene, dimethyl sulfoxide, acetone, and tetrahydrofuran. The amount of these solvents used is preferably selected so that it accounts for 50% by volume or less of the hydroformylation reaction mixture, and more preferably 20% by volume or less.

[0033] There is no particular limitation on the method of charging the raw materials in the hydroformylation reaction, but it is preferable to charge an internal olefin, a separately prepared solution of a metal complex of Groups 8, 9, and 10, and a solvent as necessary, and then introduce a mixed gas of hydrogen and carbon monoxide at a predetermined pressure and stir the mixture at a predetermined temperature to carry out the reaction in a homogeneous system.

[0034] (Reduction reaction) A diol can be obtained by converting the two formyl groups (-CH=O) of the aldehyde obtained by the above hydroformylation reaction into alkoxy groups by a reduction reaction.

[0035] The reduction reaction is not particularly limited, but it is preferable to carry out a hydrogen reduction reaction. The hydrogen reduction reaction is not particularly limited, and hydrogen reduction may be carried out by a known method, for example, a method of adding NaBH4 (sodium borohydride) to reduce, a method of reducing with hydrogen gas in the presence of a metal catalyst, etc.

[0036] In the method of hydrogen reduction by adding NaBH4, the amount of NaBH4 added is preferably equimolar or more relative to the aldehyde, more preferably 1 to 3 times the molar amount, and even more preferably 1.2 to 1.5 times the molar amount. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 50°C, and even more preferably 10 to 30°C.

[0037] In the method of reducing with hydrogen gas using a metal catalyst, the metal catalyst used for hydrogen reduction is not particularly limited, but is preferably a catalyst in which Ru, Pd, Rh, or Pt is supported on alumina, activated carbon, silica, zirconia, or silica alumina, or a Cu-based catalyst such as Cu-Cr, Cu-Fe, or Cu-Zn, or a Ni-based catalyst such as Raney Ni, nickel / diatomaceous earth, or nickel / silica alumina. The amount of metal catalyst added is preferably 20% by weight or less, more preferably 0.1 to 5% by weight, based on the aldehyde. The reaction temperature varies depending on the catalyst used, but is preferably 300° C. or less, more preferably 20 to 250° C., and even more preferably 20 to 150° C. The pressure of hydrogen gas is preferably normal pressure to 30 MPa, more preferably normal pressure to 25 MPa.

[0038] [Other diols] The raw material of the polycarbonate of the present invention may contain other diols in addition to the compound represented by the above formula (3). The other diols are not particularly limited, but for example, the following formula (4): [ka] [In the formula, R 21 ~R 28 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is one of the following formulae: [ka] R 29 and R 30 are each independently a hydrogen atom, an alkyl group, or an aryl group; R 29 and R 30 and may be bonded to form a ring. A compound represented by the following formula can be used.

[0039] R in the above formula (4) 21 ~R 28 , X are as defined in the above formula (2). 21 ~R 28 The preferred embodiments of X are also as explained in the above formula (2).

[0040] Specific examples of other diols include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxy-3-bromophenyl)propane. propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methoxyphenyl)propane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and the like. These diols may be used alone or in combination of two or more.

[0041] [Carbonyl compounds] The carbonyl compound which is the raw material of the polycarbonate of the present invention is represented by the following formula (5): [ka] The compound includes a compound represented by the formula:

[0042] In the above formula (5), R 31 and R 32 each independently represents chlorine, an alkyloxy group which may have a substituent, or an aryloxy group which may have a substituent. The number of carbon atoms in the alkyloxy group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. The alkyloxy group may be linear or branched. The number of carbon atoms in the aryloxy group is preferably 6 to 32, more preferably 6 to 24, and even more preferably 6 to 12. Substituents for the alkyloxy group and the aryloxy group include halogens such as chlorine and bromine.

[0043] In the above formula (5), R 31 and R 32 An example of the carbonyl compound in which represents chlorine is phosgene.

[0044] In the above formula (5), R 31 and R 32 Examples of the carbonyl compound in which R represents an alkyloxy group include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, diisopropyl carbonate, methyl isopropyl carbonate, ethyl isopropyl carbonate, propyl isopropyl carbonate, methyl isobutyl carbonate, ethyl isobutyl carbonate, propyl isobutyl carbonate, and diisobutyl carbonate. 31 and R 32 Examples of the carbonyl compound in which the alkyloxy group has a halogen as a substituent include triphosgene and bromophosgene.

[0045] In the above formula (5), R 31 and R 32Examples of the carbonyl compound in which at least one of the groups represents an aryloxy group include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, phenyl propyl carbonate, phenyl isopropyl carbonate, butyl phenyl carbonate, and isobutyl phenyl carbonate.

[0046] The carbonyl compound represented by the formula (5) may be used alone or in combination of two or more. From the viewpoint of reactivity, the amount of the carbonyl compound used is preferably 1 to 5 moles, more preferably 1 to 2.5 moles, and more preferably 1 to 1.2 moles, per mole of the total amount of the diol represented by the formula (2) and the other diol used.

[0047] (Polymerization reaction) In the production of the polycarbonate of the present invention, the polymerization reaction between the diol and the carbonyl compound is not particularly limited and can be carried out by a conventionally known method. For example, when phosgene or the like is used as the carbonyl compound, the polycarbonate can be synthesized by interfacial polycondensation. In addition, when diphenyl carbonate or the like is used, the polycarbonate can be synthesized by transesterification.

[0048] A catalyst may or may not be used in the polymerization reaction. The catalyst used may be a catalyst that is conventionally known as a catalyst for polymerization of polycarbonate. A basic compound is used as the catalyst. Such basic compounds include, in particular, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing and phosphorus-containing compounds, etc.

[0049] Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, sodium tetraphenylborate, disodium salt, dipotassium salt, dicesium salt, and dilithium salt of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol.

[0050] Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, strontium stearate, barium stearate, calcium benzoate, magnesium phenylphosphate, magnesium salts, calcium salts, strontium salts and barium salts of phenol.

[0051] Specific examples of the nitrogen-containing compound and phosphorus-containing compound include quaternary ammonium hydroxides having an alkyl, aryl or aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole and 2-phenylimidazole; and basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate.

[0052] The amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 part by weight per 100 parts by weight of the total amount of the raw material monomers.

[0053] The polymerization reactor is not particularly limited, but a reactor generally used for reactions of high-viscosity fluids is preferably used. Examples of such reactors include stirring tank-type polymerization reactors having stirring devices with stirring blades of various shapes, such as anchor type, multi-stage type, spiral belt type, spiral shaft type, etc., or modified versions of these, and mixing devices generally used for kneading resins, such as kneaders, roll mills, and Banbury mixers.

[0054] [Resin molding] The resin molded article of the present invention contains the above-mentioned polycarbonate. The resin molded article of the present invention may further contain various additives within a range that does not impair its properties. Examples of additives include fillers, silane coupling agents, antifoaming agents, antioxidants, light stabilizers, colorants such as pigments and dyes, plasticizers, pH adjusters, UV stabilizers, coloring inhibitors, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, thread friction reducers, slip agents, mold release agents, antioxidants, ion exchange agents, etc. The resin molded article of the present invention may contain one or more of the above-mentioned additives.

[0055] The use of the resin molded article of the present invention is not particularly limited, and it can be used for various things such as automobile parts, electronic parts, optical parts, and daily necessities.Specific examples include paints applied to substrates such as metals, resin films, glass, paper, and wood, surface protective films for semiconductor elements and organic thin-film elements (for example, organic electroluminescence elements and organic thin-film solar cell elements), coating agents such as hard coat agents, antifouling films and antireflection films, adhesives, pressure-sensitive adhesives, lenses, prisms, filters, image display materials, lens arrays, sealing materials and reflector materials for optical semiconductor elements, sealing materials for semiconductor elements, various optical members such as optical waveguides, light guide plates, light diffusion plates, diffraction elements, and optical adhesives, casting materials, interlayer insulators, protective insulating films for printed alignment substrates, and materials such as fiber-reinforced composite materials. EXAMPLES

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0057] [Synthesis example of aldehyde (A1)] Under argon flow, 1997g (10.72mol) of 3a,4,4a,5,8,8a,9,9a-octahydro-4,9-methanocyclopenta[b]naphthalene (hereinafter also referred to as DCPB), 1.48g (1.608mmol) of RhH(CO)(PPh3)3, and 28.12g (0.1072mol) of PPh3 were charged into a 3L autoclave. H2 / CO gas (3.5MPa) was introduced into the vessel, the internal temperature was raised to 120℃, and after 30 minutes of reaction, the internal temperature was raised to 130℃ and the reaction of the following formula was carried out for 9 hours. H2 / CO gas was further introduced until the pressure reached 4.5MPa, and the reaction was continued for 2 days. The reaction solution was then diluted with 48 L of tetrahydrofuran (THF), and 7.44 kg of saturated aqueous NaHCO3 was added, followed by overnight reaction at 50°C under an argon atmosphere. After cooling to room temperature, the THF layer was removed by liquid separation, and the resulting aqueous layer was washed twice with 8 L of chloroform. The resulting aqueous layer was adjusted to pH 12 by adding 15 wt% aqueous NaOH solution (13.34 kg), and the resulting suspension was extracted three times with 4 L of chloroform. The organic layers were combined, dried over MgSO4, filtered, and concentrated to obtain 2536 g of aldehyde (A1) with a purity of 98%. [ka]

[0058] [Synthesis example of diol (B1)] Under an argon stream, 634 g (2.57 mol) of the aldehyde (A1) obtained above and 5 L of MeOH were charged into a 10 L flask, and NaBH4 was added little by little so that the temperature did not exceed 20 ° C. Finally, 71.1 g (1.879 mol) was added, and the reaction of the following formula was carried out. After the addition was completed, the temperature was raised to room temperature. 0.5 L of water was added to the reaction liquid to terminate the reaction, and MeOH was distilled off. 5 L of AcOEt and 5 L of water were added to the obtained crude product, and the organic layer was separated. Furthermore, the aqueous layer was extracted twice with 5 L of AcOEt, mixed with the previous organic layer, washed with 2 L of saturated saline, dried with Na2SO4, filtered, and concentrated to obtain 647 g of a crude product. The obtained crude product was purified by distillation at 0.05 mmHg, and 480 g of diol (B1) with a purity of 99.9% was obtained at a column top temperature of 185 to 193 ° C. [ka]

[0059] [Synthesis example of diol (B2)] Aldehyde (A2) was obtained in the same manner as in the synthesis example of aldehyde (A1), except that dicyclopentadiene (DCPD) was used instead of DCPB. Next, diol (B2) was obtained in the same manner as in the synthesis example of diol (B1), except that aldehyde (A2) was used instead of aldehyde (A1).

[0060] (Polycarbonate synthesis example 1) [Example 1] 100.2g (0.40mol) of the diol (B1) derived from DCPB obtained above, 86.5g (0.404mol) of diphenyl carbonate, and 1.0mg (0.012mmol) of sodium carbonate were charged in a 500ml flask equipped with a stirring blade and a distillation device, heated to 180°C under a nitrogen atmosphere, and stirred for 30 minutes. After that, the degree of vacuum was adjusted to 150mmHg, the temperature was raised to 200°C at a rate of 60°C / hr, and the reaction was carried out while maintaining that temperature for 40 minutes. Furthermore, the temperature was raised to 225°C at a rate of 75°C / hr, and 40 minutes after the end of the temperature rise, the pressure was reduced to 1mmHg over 1 hour while maintaining 225°C. After reaching 1mmHg, the temperature was raised to 235°C at a rate of 105°C / hr, and the reaction was carried out for 150 minutes. After the reaction was completed, nitrogen was blown into the reactor to return to normal pressure, and the contents were taken out. The mixture was then cooled to room temperature and pulverized in a coarse pulverizer to obtain 86.1 g of polycarbonate (D1).

[0061] [Example 2] Polycarbonate (D2) was obtained in the same manner as in Example 1, except that 88.3 g (0.412 mol) of diphenyl carbonate was added.

[0062] [Comparative Example 1] Polycarbonate (D3) was obtained in the same manner as in Example 1, except that 39.3 g (0.20 mol) of the diol (B2) derived from DCPD obtained above and 44.1 g (0.21 mol) of diphenyl carbonate were added instead of diol (B1).

[0063] (Evaluation of the thermal properties of polycarbonate 1) The glass transition temperature (Tg) and thermal decomposition temperature (Td) of the polycarbonates (D1) to (D3) obtained above were measured by the following method. The measurement results are shown in Table 1.

[0064] (Glass transition temperature (Tg)) The glass transition temperature (Tg) was measured using differential scanning calorimetry (DSC, Hitachi High-Tech Science Corporation, model number: X-DSC-7000). First, the temperature was raised from room temperature to 280°C at a rate of 10°C / min, then lowered to 30°C at a rate of 10°C / min, and then further raised to 280°C at a rate of 10°C / min. The inflection point obtained when the temperature was raised to 280°C at a rate of 10°C / min was taken as the glass transition temperature (Tg).

[0065] (Thermal decomposition temperature (Td)) Using a simultaneous differential thermal calorimeter (manufactured by SII Nanotechnology, model number: TG / DTA7200), the temperature was raised from room temperature to 500°C at a constant rate of 10°C / min in dry air, and the temperature at which the weight of the polycarbonate had decreased by 1% compared to the start of the measurement (1% Td) was measured.

[0066] [Table 1]

[0067] From the results of Examples 1 and 2 and Comparative Example 1, it was found that the polycarbonate obtained using the diol derived from DCPB as the raw material had superior heat resistance compared to the polycarbonate obtained from the diol derived from DCPD.

Claims

1. The following formula (1): 【Chemistry 1】 [In the formula, R １ ~R １３ each independently represents a hydrogen atom, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. Polycarbonate having a structural unit represented by the formula:

2. In the above formula (1), R １ ~R １３ The polycarbonate of claim 1 , wherein all of are hydrogen.

3. The polycarbonate according to claim 1 or 2, wherein in the above formula (1), a is an integer of 0 to 3, and b is an integer of 0 to 3.

4. The following formula (2): 【Chemistry 2】 [In the formula, R ２１ ~R ２８ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is any one of the following formulae: 【Chemistry 3】 R ２９ and R ３０ are each independently a hydrogen atom, an alkyl group, or an aryl group; R ２９ and R ３０ and may be bonded to form a ring. The polycarbonate according to any one of claims 1 to 3, further comprising a structural unit represented by:

5. The polycarbonate according to any one of claims 1 to 4, which is a reaction product of a diol and a carbonyl compound.

6. The diol is represented by the following formula (3): 【Chemistry 4】 [In the formula, R １ ~R １３ each independently represents a hydrogen atom, an alkyl group, or an alkoxy group; a is an integer from 0 to 10, b is an integer from 0 to 10. The polycarbonate according to claim 5 , comprising a compound represented by the formula:

7. The polycarbonate according to claim 5 or 6, wherein the diol comprises a diol other than that represented by the above formula (3).

8. The other diol is represented by the following formula (4): 【Chemistry 5】 [In the formula, R ２１ ~R ２８ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, a cycloalkoxy group, or an aryloxy group; X is any one of the following formulae: 【Chemistry 6】 R ２９ and R ３０ are each independently a hydrogen atom, an alkyl group, or an aryl group; R ２９ and R ３０ and may be bonded to form a ring. The polycarbonate according to claim 7, comprising a compound represented by the formula:

9. The carbonyl compound is represented by the following formula (5): 【Chemistry 7】 [In the formula, R ３１ and R ３２ each independently represents chlorine, an alkyloxy group which may have a substituent, or an aryloxy group which may have a substituent. The polycarbonate according to any one of claims 5 to 8, comprising a compound represented by the formula:

10. A resin molded article comprising the polycarbonate according to any one of claims 1 to 9.

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