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WO2024209710A1 - Procédé de production d'une résine époxyde, procédé de production d'une composition de résine époxyde, procédé de production d'un produit durci, procédé de production d'une composition de résine époxyde contenant des fibres, procédé de production de carbonate de diphényle et procédé de production de résine de polycarbonate - Google Patents

Procédé de production d'une résine époxyde, procédé de production d'une composition de résine époxyde, procédé de production d'un produit durci, procédé de production d'une composition de résine époxyde contenant des fibres, procédé de production de carbonate de diphényle et procédé de production de résine de polycarbonate Download PDF

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Publication number
WO2024209710A1
WO2024209710A1 PCT/JP2023/024898 JP2023024898W WO2024209710A1 WO 2024209710 A1 WO2024209710 A1 WO 2024209710A1 JP 2023024898 W JP2023024898 W JP 2023024898W WO 2024209710 A1 WO2024209710 A1 WO 2024209710A1
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Prior art keywords
epoxy resin
producing
mass
reaction
polycarbonate
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PCT/JP2023/024898
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English (en)
Japanese (ja)
Inventor
航 深山
馨 内山
正人 安藤
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority claimed from JP2023062925A external-priority patent/JP2024149194A/ja
Priority claimed from JP2023062948A external-priority patent/JP2024149214A/ja
Priority claimed from JP2023098025A external-priority patent/JP2024179291A/ja
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of WO2024209710A1 publication Critical patent/WO2024209710A1/fr
Anticipated expiration legal-status Critical
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for producing an epoxy resin, a method for producing an epoxy resin composition containing the obtained epoxy resin, a method for producing a fiber-containing epoxy resin composition containing recycled fibers obtained together with an epoxy resin, a method for producing diphenyl carbonate from a dialkyl carbonate obtained together with an epoxy resin, and a method for producing a polycarbonate resin from the obtained diphenyl carbonate.
  • Polycarbonate resin has excellent mechanical properties, electrical properties, heat resistance, cold resistance, transparency, etc., and is a material used for a variety of applications. Demand for it is increasing, and the amount of discarded polycarbonate resin is also increasing accordingly. Therefore, it is becoming important to reuse discarded polycarbonate resin.
  • the present inventors have found that epoxy resins can be obtained by subjecting polycarbonate resins to a decomposition reaction in epihalohydrin, and have completed a new chemical recycling technology for polycarbonate resins. That is, the present invention includes the following inventions.
  • a method for producing an epoxy resin comprising a reaction step of obtaining an epoxy resin, the reaction step including a decomposition reaction of decomposing a polycarbonate resin in epihalohydrin.
  • a method for producing a fiber-containing epoxy resin composition comprising a step of mixing the epoxy resin obtained by the method according to [6] or [7] with recycled fibers.
  • a method for producing a fiber-containing epoxy resin cured product comprising a step of curing the fiber-containing epoxy resin composition obtained by the method according to [12].
  • a method for producing diphenyl carbonate comprising a step of reacting the dialkyl carbonate obtained by the method according to any one of [3] to [5] with phenol.
  • a method for producing a polycarbonate resin comprising: a step of polymerizing the diphenyl carbonate obtained by the production method according to [14] through an ester exchange reaction.
  • the present invention provides a new chemical recycling technology for polycarbonate resin. Specifically, it provides a new production method that can provide industrially useful epoxy resins and dialkyl carbonates, and a new production method that can provide epoxy resins and recycled fibers. It also provides a method for producing an epoxy resin composition containing the obtained epoxy resin, a method for producing a fiber-containing epoxy resin composition from the obtained epoxy resin and recycled fibers, a method for producing diphenyl carbonate from the obtained dialkyl carbonate, and a method for producing polycarbonate resin from the obtained diphenyl carbonate.
  • a first embodiment of the present invention is a method for producing an epoxy resin, which includes a reaction step of obtaining an epoxy resin, which includes a decomposition reaction of decomposing a polycarbonate resin in epihalohydrin, and the decomposition reaction is preferably carried out in the presence of a metal hydroxide.
  • the process includes a decomposition reaction of decomposing a polycarbonate resin in epihalohydrin, the decomposition reaction being carried out in the presence of a metal hydroxide and an alcohol-based compound, and co-producing a dialkyl carbonate together with an epoxy resin.
  • the third embodiment is a production method which includes a decomposition reaction of decomposing a polycarbonate resin in epihalohydrin, the decomposition reaction being carried out in the presence of a metal alkoxide, and which co-produces a dialkyl carbonate together with an epoxy resin.
  • the fourth embodiment is a production method that includes a decomposition reaction in which a polycarbonate resin is decomposed in epihalohydrin, the polycarbonate resin being a fiber-containing polycarbonate resin, and producing regenerated fibers together with an epoxy resin.
  • the "method of co-producing dialkyl carbonate together with epoxy resin” means recovering industrially useful epoxy resin and dialkyl carbonate together by chemically recycling polycarbonate resin. This method has a different objective from the method of obtaining dihydroxy compounds such as bisphenol A and dialkyl carbonate recovered in the conventional chemical recycling of polycarbonate resin.
  • the term "recycled fiber” refers to a fiber that was once contained in a resin, extracted from the resin, and recycled so that it can be reused. For example, it is a fiber extracted from a composite material of polycarbonate resin and fiber, such as fiber-reinforced plastic (FRP).
  • the reaction process includes a decomposition reaction in which polycarbonate resin is decomposed in epihalohydrin to obtain epoxy resin.
  • This process relates to a new chemical recycling technology for polycarbonate resin, in which polycarbonate resin is decomposed in epihalohydrin to obtain epoxy resin.
  • the aromatic polycarbonate resin may be a polycarbonate resin containing a structural unit derived from an aromatic dihydroxy compound.
  • the aromatic dihydroxy compound include bisphenols such as bisphenol A, bisphenol C, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetramethyl bisphenol F, tetra-t-butyl bisphenol A, and tetramethyl bisphenol S; biphenol, tetramethyl biphenol, dimethyl biphenol, and tetra-t-butyl bisphenol;
  • the phenol-based compounds include biphenols such as tylbiphenol; benzenediols such as hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, and methylresorcin (here, "benzenediols" are compounds having one
  • aromatic dihydroxy compounds those having bisphenol A or bisphenol C as a main structural unit are particularly preferred from the viewpoints of reactivity, ease of availability of raw materials, and versatility of the resulting epoxy resin.
  • aromatic polycarbonates may be used alone or in combination of two or more.
  • the polycarbonate resin is not limited to polycarbonate resin alone, but may be a composition containing one or more resins other than polycarbonate, such as polyester resins, polyarylate resins, etc.
  • a composition containing a resin other than polycarbonate resin it is preferable that the polycarbonate resin composition contains 50% by mass or more of polycarbonate resin, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
  • the raw polycarbonate resin preferably contains used polycarbonate resin (hereinafter, sometimes abbreviated as "waste polycarbonate”) that is treated as waste plastic.
  • waste polycarbonate used polycarbonate resin
  • waste plastics containing polycarbonate resin it is preferable to remove substances other than polycarbonate resin contained in the waste plastics as necessary.
  • a method for removing substances other than polycarbonate resin include a method of dissolving waste plastics in epihalohydrin and, if necessary, an organic solvent, and filtering the solution to remove substances other than polycarbonate resin.
  • the fiber contained in the fiber-containing polycarbonate resin is not particularly limited as long as it is a fiber that can be contained in the polycarbonate resin, and examples thereof include glass fiber and carbon fiber.
  • the shape, fiber diameter, aspect ratio, etc. of the fiber are not particularly limited, and it is sufficient that it can be contained in the polycarbonate. It is preferable that the fiber is capable of improving the mechanical strength of the cured product of the epoxy resin obtained from the decomposition reaction of polycarbonate and the recycled fiber, and is preferably carbon fiber.
  • epihalohydrin examples include epichlorohydrin, ⁇ -methylepichlorohydrin, epibromohydrin, etc.
  • epichlorohydrin is particularly preferred from the viewpoints of reactivity, ease of availability of raw materials, and versatility of the resulting epoxy resin.
  • epihalohydrins may be used alone or in combination of two or more.
  • the amount of epihalohydrin used in the reaction step is not particularly limited, but is preferably 1 to 20 moles, more preferably 3 to 16 moles, and particularly preferably 6 to 14 moles per mole of carbonate bond in the raw polycarbonate resin. If the amount of epihalohydrin used is equal to or greater than the above lower limit, it is preferable in that undesirable side reactions such as crosslinking reactions can be suppressed. Also, if the amount of epihalohydrin used is equal to or less than the above upper limit, it is preferable in that industrial production efficiency is improved.
  • the metal hydroxide may be subjected to the reaction together with an alcohol-based compound as an alcohol solution of the metal hydroxide.
  • the alcohol-based compound is not particularly limited as long as it is used as a solvent or dispersant for the metal hydroxide, and may be a monoalcohol or a polyol such as a diol-based compound or a glycol-based compound, but is preferably a monoalcohol, and more preferably a lower alcohol.
  • the metal hydroxide concentration in the alcohol solution of the metal hydroxide used in the reaction step is not particularly limited, but is usually 5% by mass or more and 50% by mass or less.
  • the metal hydroxide is continuously supplied within the reaction time, preferably 1 to 10 moles, more preferably 2.4 to 8 moles, and particularly preferably 3 to 6 moles per mole of carbonate groups contained in the polycarbonate resin.
  • the amount of metal hydroxide used is equal to or greater than the above lower limit, the reaction rates of the decomposition reaction and the epoxy group formation reaction can be sufficiently ensured, which is preferable from the standpoint of the quality and production efficiency of the obtained epoxy resin.
  • the amount is equal to or less than the above upper limit, it is preferable from the standpoint of suppressing over-reaction and side reactions such as crosslinking reactions.
  • the reaction step is preferably carried out in the presence of a metal alkoxide.
  • the metal in the metal alkoxide include alkali metals such as lithium, sodium, potassium, rubidium, and cesium; and alkaline earth metals such as magnesium, calcium, strontium, and barium.
  • the alkoxide include methoxide, ethoxide, and propoxide.
  • the alkoxide include methoxide, ethoxide, propoxide, and glycoxide.
  • the alcohol of the metal alkoxide is not particularly limited, and may be a monoalcohol or a polyol such as a glycol-based compound, but is preferably a monoalcohol.
  • Examples of the monoalcohol include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, and t-butanol.
  • Examples of the polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, and glycerin.
  • the glycol compound is a compound in which one hydroxyl group is bonded to each of two carbon atoms of an alkyl group having two or more carbon atoms, and examples of the glycol compound include ethylene glycol and propylene glycol.
  • the metal alkoxide may be used alone or in combination of two or more kinds. Among them, sodium methoxide is preferred from the viewpoint of industrial availability.
  • the metal alkoxide is continuously supplied within the reaction time, preferably 1 to 10 moles, more preferably 2.4 to 8 moles, and particularly preferably 3 to 6 moles per mole of carbonate groups contained in the polycarbonate resin.
  • the amount of metal alkoxide used is equal to or greater than the above lower limit, the reaction rates of the decomposition reaction and the epoxy group formation reaction can be sufficiently ensured, which is preferable from the standpoint of the quality and production efficiency of the obtained epoxy resin.
  • the amount is equal to or less than the above upper limit, it is preferable from the standpoint of suppressing over-reaction and side reactions such as crosslinking reactions.
  • the reaction temperature in the reaction process is preferably 30 to 100°C, in order to ensure a sufficient reaction rate.
  • the reaction time is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes, in order to allow the reaction to proceed sufficiently.
  • a post-treatment step can be carried out if necessary.
  • insoluble by-product salts are removed by filtration or washing with water, and unreacted epihalohydrin is then removed by distillation under reduced pressure to obtain the desired epoxy resin and dialkyl carbonate.
  • catalysts such as quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; and phosphines such as triphenylphosphine may be used.
  • quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide
  • tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol
  • imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimid
  • inert organic solvents such as alcohols such as ethanol and isopropanol; glycols such as ethylene glycol, diethylene glycol, propylene glycol and polyethylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as propylene glycol monomethyl ether; aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide; and aromatic hydrocarbon solvents such as toluene and xylene may be used.
  • alcohols such as ethanol and isopropanol
  • glycols such as ethylene glycol, diethylene glycol, propylene glycol and polyethylene glycol
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as dioxane and ethylene glycol dimethyl ether
  • glycol ethers such as propylene glycol monomethyl ether
  • the epoxy resin obtained as described above has too much saponifiable halogen, it is possible to obtain a purified epoxy resin with a sufficiently reduced amount of saponifiable halogen by reprocessing. That is, the crude epoxy resin obtained by the reaction is redissolved in an inert organic solvent such as isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, or dimethyl sulfoxide, and an alkali metal hydroxide or metal alkoxide is added as a solid or aqueous solution to carry out a ring-closing reaction at a temperature of about 30 to 120°C, more preferably 40 to 110°C, and even more preferably 50 to 100°C for 0.1 to 8 hours, more preferably 0.3 to 7 hours, and even more preferably 0.5 to 6 hours, and then the excess metal hydroxide or secondary salt is removed by a method
  • reaction temperature is too low or the reaction time is too short, the ring-closing reaction may not proceed, whereas if the reaction temperature is too high or the reaction time is too long, the reaction may proceed, but may result in problems such as high molecular weight, high epoxy equivalent, and high viscosity.
  • the decomposition reaction of polycarbonate in the reaction step is carried out by azeotroping the reaction liquid while maintaining a predetermined temperature as necessary, to obtain volatile vapor.
  • the resulting vapor is then cooled to obtain a condensate, which is then subjected to oil/water separation, and the dehydrated oil is returned to the reaction system, whereby the water produced by glycidylation and the water derived from the aqueous metal hydroxide solution are dehydrated. This can reduce the amount of water in the system, and promote the formation of epoxy groups by the metal hydroxide.
  • the method for separating epihalohydrin from the azeotropic condensate is not particularly limited, but for example, the azeotropic condensate can be separated by settling in a settling separator and only the epihalohydrin in the lower layer is continuously returned to the system, thereby circulating the epihalohydrin.
  • the amount of epihalohydrin remaining in the settling separator is preferably 5 mass% or less relative to the total amount of charged epihalohydrin.
  • the content of water relative to the total amount of the raw materials is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, and it is particularly preferable that no water is present in the reaction system.
  • the content of water relative to the total amount of raw materials indicates the mass ratio of water contained in all raw materials used relative to the total amount of all raw materials used in the reaction, and does not include water produced by the reaction.
  • the reaction step of the fourth embodiment preferably includes a separation step of performing solid-liquid separation of the fiber and the solution.
  • the separation step separates the epoxy resin solution and the regenerated fiber, and each can be obtained.
  • an organic solvent such as toluene and water are added to the reaction solution, and the regenerated fiber can be separated by filtering.
  • the epoxy equivalent of the epoxy resin obtained through the reaction step is preferably 50 to 10,000 g/eq, more preferably 100 to 5,000 g/eq, and particularly preferably 150 to 3,000 g/eq, as measured according to JIS K 7236.
  • the epoxy equivalent of the obtained epoxy resin is within the above range, the crosslink density increases when cured with various curing agents, and a cured product having excellent chemical resistance and the like can be obtained.
  • the dialkyl carbonate obtained through the reaction process can be used as a raw material for producing polycarbonate by the melting method. It is preferable that the dialkyl carbonate is recovered by distillation. Therefore, the alkyl of the dialkyl carbonate is preferably an alkyl having 10 or less carbon atoms, more preferably an alkyl having 6 or less carbon atoms, and particularly preferably an alkyl having 4 or less carbon atoms. Specifically, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate are particularly preferable.
  • the dialkyl carbonate thus obtained is preferably converted to diphenyl carbonate by transesterification with phenol and used as a raw material for the production of polycarbonate by a melt process.
  • the diphenyl carbonate can be produced by a known method for producing diphenyl carbonate from dialkyl carbonate (for example, JP-A-3-291257).
  • diphenyl carbonate can be produced by a method in which dialkyl carbonate and phenol are used as raw materials, an ester exchange reaction is carried out to obtain an alkylphenyl carbonate, and the alkylphenyl carbonate is then subjected to a disproportionation reaction to obtain diphenyl carbonate.
  • a catalyst for this ester exchange reaction a known catalyst used for producing diphenyl carbonate can be used.
  • an organic titanium catalyst such as tetraphenoxytitanium can be used.
  • Epoxy resin composition The epoxy resin obtained above can be mixed with a curing agent to produce an epoxy resin composition.
  • other epoxy compounds, curing accelerators, other components, etc. can be appropriately mixed into the epoxy resin composition as necessary.
  • a fiber-containing epoxy resin composition can be produced by mixing the obtained epoxy resin with recycled fibers. Also, a fiber-containing epoxy resin composition can be produced by mixing the obtained epoxy resin with recycled fibers and a curing agent. If necessary, other epoxy compounds, curing accelerators, other components, etc. may be appropriately blended into the fiber-containing epoxy resin composition.
  • a curing agent is a substance that contributes to the crosslinking reaction and/or chain extension reaction between epoxy groups of an epoxy compound.
  • curing accelerators even substances that are usually called “curing accelerators” are considered to be curing agents as long as they contribute to the crosslinking reaction and/or chain extension reaction between epoxy groups of an epoxy compound.
  • the amount of hardener to be added is preferably 0.1 to 1000 parts by mass, more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less, per 100 parts by mass of epoxy resin.
  • the amount of the curing agent is preferably 0.1 to 1000 parts by mass, more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less, per 100 parts by mass of the total epoxy resin components as solids.
  • the more preferred amounts of the curing agent are as follows, depending on the type of curing agent:
  • solids refers to the components excluding the solvent, and includes not only solid epoxy compounds, but also semi-solid and viscous liquid substances. Also, “total epoxy resin components” refers to the sum of the above epoxy resins and other epoxy resins described below.
  • the curing agent at least one selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines.
  • polyfunctional phenols examples include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, and tetrabromobisphenol A; biphenols such as 4,4'-biphenol and 3,3',5,5'-tetramethyl-4,4'-biphenol; catechol, resorcin, hydroquinone, and dihydroxynaphthalenes; and compounds in which the hydrogen atoms bonded to the aromatic rings of these compounds are substituted with non-interfering substituents such as halogen groups, alkyl groups, aryl groups, ether groups, ester groups, and organic substituents containing hetero elements such as sulfur, phosphorus, and silicon.
  • Further examples include novolaks and resols which are polycondensates of these phenols, or monofunctional phenols such as phenol, cresol, and alkylphenol with aldehydes.
  • polyisocyanate compounds include polyisocyanate compounds such as tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, and lysine triisocyanate.
  • polyisocyanate compounds such as tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid
  • polyisocyanate compounds obtained by reacting these polyisocyanate compounds with compounds having at least two active hydrogen atoms such as amino groups, hydroxyl groups, carboxyl groups, and water, or trimers to pentamers of the above polyisocyanate compounds.
  • amine compounds include aliphatic primary, secondary, and tertiary amines, aromatic primary, secondary, and tertiary amines, cyclic amines, guanidines, and urea derivatives, and specific examples include triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)-5-nonene, dimethylurea, and guanylurea.
  • acid anhydride compounds include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and condensates of maleic anhydride and unsaturated compounds.
  • imidazole compounds examples include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and benzimidazole. Note that imidazole compounds also function as curing accelerators, which will be described later, but in the present invention they are classified as curing agents.
  • amide compounds include dicyandiamide and its derivatives, polyamide resins, etc.
  • the cationic polymerization initiator generates cations by heat or irradiation with active energy rays
  • examples of the cationic polymerization initiator include aromatic onium salts. Specific examples include compounds consisting of an anion component such as SbF 6 - , BF 4 - , AsF 6 - , PF 6 - , CF 3 SO 3 2- , or B(C 6 F 5 ) 4 - and an aromatic cation component containing an atom such as iodine, sulfur, nitrogen, or phosphorus. Diaryliodonium salts and triarylsulfonium salts are particularly preferred.
  • organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.
  • phosphonium salts include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate.
  • tetraphenylboron salts include 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate.
  • the above curing agents may be used alone or in combination of two or more of the same or different types.
  • the equivalent ratio of the functional groups in the curing agent hydroxyl groups of polyfunctional phenols, amino groups of amine compounds, or acid anhydride groups of acid anhydride compounds
  • the equivalent ratio of the functional groups in the curing agent hydroxyl groups of polyfunctional phenols, amino groups of amine compounds, or acid anhydride groups of acid anhydride compounds
  • polyisocyanate compounds it is preferable to use them in an equivalent ratio of 1:0.01 to 1:1.5, in terms of the number of isocyanate groups in the polyisocyanate compound to the number of hydroxyl groups in the epoxy resin composition.
  • imidazole compounds When using imidazole compounds, it is preferable to use them in a range of 0.5 to 10 parts by mass per 100 parts by mass of all epoxy resin components as solids in the epoxy resin composition.
  • amide compounds When using amide compounds, it is preferable to use them in a range of 0.1 to 20% by mass with respect to the total amount of all epoxy resin components and amide compounds as solids in the epoxy resin composition.
  • a cationic polymerization initiator it is preferably used in the range of 0.01 to 15 parts by mass relative to 100 parts by mass of all epoxy resin components as solid contents in the epoxy resin composition.
  • organic phosphines When organic phosphines are used, it is preferably used in the range of 0.1 to 20% by mass relative to the total amount of all epoxy resin components as solid contents in the epoxy resin composition and organic phosphines.
  • mercaptan compounds for example, mercaptan compounds, organic acid dihydrazides, boron halide amine complexes, etc. can also be used as curing agents in the epoxy resin composition. These curing agents may be used alone or in combination of two or more.
  • epoxy resins In the method for producing an epoxy resin composition and the method for producing a fiber-containing epoxy resin composition, epoxy resins other than the above-mentioned epoxy resins (sometimes referred to as "other epoxy resins" in this specification) can be used.
  • Examples of the other epoxy resins include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, tetrabromobisphenol A type epoxy resins, and other polyfunctional phenol type epoxy resins, epoxy resins obtained by hydrogenating the aromatic rings of the above-mentioned aromatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
  • the above-mentioned other epoxy resins may be used alone or in combination of two or more.
  • the proportion of the other epoxy resin in the total epoxy resin components as solids in the epoxy resin composition and the fiber-containing epoxy resin composition is preferably 1 mass% or more, more preferably 5 mass% or more, and on the other hand, is preferably 99 mass% or less, more preferably 95 mass% or less.
  • the proportion of the other epoxy resin be equal to or more than the above lower limit the physical property improvement effect by blending the other epoxy resin can be sufficiently obtained.
  • the proportion of the other epoxy resin be equal to or less than the above upper limit the effect of chemical recyclability by the above-mentioned epoxy resin can be sufficiently obtained.
  • the epoxy resin composition may be diluted by blending a solvent in order to adjust the viscosity of the epoxy resin composition appropriately when handling it, such as when forming a coating film.
  • the solvent is used to ensure ease of handling and workability when molding the epoxy resin composition, and there is no particular limit to the amount used.
  • solvent and “solvent” are used to distinguish between the forms of use, but the same or different substances may be used independently.
  • the solvent one or more of the organic solvents exemplified as reaction solvents used in the production of epoxy resins can be used.
  • the epoxy resin composition and fiber-containing epoxy resin composition may contain other components in addition to the components listed above.
  • other components include curing accelerators (excluding those that fall under the category of curing agents), coupling agents, flame retardants, antioxidants, light stabilizers, plasticizers, reactive diluents, pigments, inorganic fillers, organic fillers, etc.
  • curing accelerators excluding those that fall under the category of curing agents
  • coupling agents include flame retardants, antioxidants, light stabilizers, plasticizers, reactive diluents, pigments, inorganic fillers, organic fillers, etc.
  • reactive diluents pigments
  • inorganic fillers organic fillers, etc.
  • the epoxy resin composition and the fiber-containing epoxy resin composition can be cured to obtain a cured product.
  • the term "curing” used here means intentionally curing an epoxy compound by heat and/or light, and the degree of curing can be controlled depending on the desired physical properties and applications.
  • the method of curing the epoxy resin composition and fiber-containing epoxy resin composition to produce a cured product varies depending on the ingredients and amounts of the epoxy resin composition and fiber-containing epoxy resin composition, and the shape of the compound, but typically involves heating at 50-200°C for 5 seconds to 180 minutes. This heating is preferably performed in two stages, with a primary heating at 50-160°C for 5 seconds to 30 minutes, and a secondary heating at 90-200°C, which is 40-120°C higher than the primary heating temperature, for 1 minute to 150 minutes, in order to reduce poor curing.
  • the curing reaction of the epoxy resin composition and the fiber-containing epoxy resin composition may be allowed to proceed to an extent that the shape can be maintained by heating or the like. If the epoxy resin composition and the fiber-containing epoxy resin composition contain a solvent, most of the solvent is removed by heating, reducing pressure, air drying, or other methods, but up to 5% by mass of the solvent may remain in the semi-cured product.
  • the dialkyl carbonate obtained together with the epoxy resin by the above method can be reacted with phenol to give diphenyl carbonate, which can be polymerized by transesterification to give polycarbonate resin.
  • the production of the above diphenyl carbonate and the production of the polycarbonate resin can be carried out according to a conventional method.
  • Example A First Form (Example A1) A separable flask reactor having a thermometer, a dropping funnel, a stirrer, a nitrogen inlet tube, and a cooling tube was charged with 150 parts by mass of Iupilon S-3000R (Mitsubishi Engineering Plastics bisphenol A type polycarbonate resin), 653 parts by mass of epichlorohydrin (12.0 moles per mole of carbonate bonds in polycarbonate), and heated to 100 ° C. to dissolve the polycarbonate. After cooling, 255 parts by mass of isopropanol and 90 parts by mass of water were added, and the temperature was raised to about 40 ° C. under a nitrogen gas atmosphere.
  • Iupilon S-3000R Mitsubishi Engineering Plastics bisphenol A type polycarbonate resin
  • epichlorohydrin 12.0 moles per mole of carbonate bonds in polycarbonate
  • the reaction solution obtained was gradually heated and the pressure in the system was reduced, and the system was held at 150°C and 5 mmHg for 30 minutes, after which isopropanol and excess epichlorohydrin were completely removed from the system. After that, the system was returned to normal pressure while nitrogen was sealed in, and 300 parts by mass of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution of crude resin. 100 parts by mass of water was added to this solution to separate the water layer, and then the water layer removed with 100 parts by mass of water was repeatedly washed with water several times until it became neutral, obtaining a methyl isobutyl ketone solution of epoxy resin.
  • the solution was heated and reduced pressure to distill off methyl isobutyl ketone, and the system was held at 150°C and 5 mmHg for 30 minutes to completely remove methyl isobutyl ketone, obtaining a liquid epoxy resin.
  • the obtained epoxy resin had an epoxy equivalent of 222 g/eq.
  • Example A2 In the same apparatus as in Example A1, 75 parts by mass of Iupilon S-3000R (Mitsubishi Engineering Plastics bisphenol A type polycarbonate resin), 327 parts by mass of epichlorohydrin (12.0 moles per mole of carbonate bonds in polycarbonate) were charged, and the polycarbonate resin was dissolved by heating to 100 ° C. After cooling, 191 parts by mass of propylene glycol monomethyl ether and 52 parts by mass of water were added, and the temperature was raised to about 65 ° C. under a nitrogen gas atmosphere.
  • Iupilon S-3000R Mitsubishi Engineering Plastics bisphenol A type polycarbonate resin
  • epichlorohydrin 12.0 moles per mole of carbonate bonds in polycarbonate
  • aqueous sodium hydroxide solution sodium hydroxide was supplied so that the amount was 5.0 moles per mole of carbonate bonds in polycarbonate
  • the reaction was carried out for 120 minutes.
  • 214 parts by mass of water was added, and the oil-water separated water layer was separated to remove salts generated by the reaction from the resin solution, residual sodium hydroxide, etc., and the reaction was stopped.
  • the reaction solution obtained was gradually heated and the pressure in the system was reduced, and the system was held at 150°C and 5 mmHg for 30 minutes, after which propylene glycol monomethyl ether and excess epichlorohydrin were completely removed from the system. After that, the system was returned to normal pressure while nitrogen was sealed in the system, and 150 parts by mass of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution of crude resin.
  • Example A3 A separable flask reactor equipped with a thermometer, a dropping funnel, a stirrer, a nitrogen inlet tube, and an oil-water separator having a cooling tube was charged with 300 parts by mass of Iupilon S-3000R (bisphenol A type polycarbonate resin manufactured by Mitsubishi Engineering Plastics Corporation) and 833 parts by mass of epichlorohydrin (7.6 mol per mol of carbonate bonds in polycarbonate), and the mixture was heated to 100° C. to dissolve the polycarbonate resin.
  • Iupilon S-3000R bisphenol A type polycarbonate resin manufactured by Mitsubishi Engineering Plastics Corporation
  • the toluene was distilled off from this solution under heating and reduced pressure, and the toluene was completely removed by holding it at 150°C and 5 mmHg for 30 minutes, and a liquid epoxy resin was obtained.
  • the obtained epoxy resin had an epoxy equivalent of 189 g/eq.
  • Example B Second Form> [Method of producing tetraphenoxytitanium] (Reference Example B1) A 500 mL three-neck flask equipped with a receiver and a distillation tube was charged with 200 parts by mass of phenol and 100 parts by mass of toluene, and the flask was circulated and replaced with nitrogen. The flask was immersed in a 100 ° C. oil bath to obtain a uniform solution. 57 parts by mass of tetraisopropoxytitanium was added thereto. When the internal temperature of the bottom of the flask was maintained at 100 ° C., distillation of the generated isopropyl alcohol began.
  • the internal temperature was gradually raised to 116 ° C., and 80 parts by mass of a distillate, which is a mixture of isopropyl alcohol and toluene, was distilled. 50 parts by mass of hexane was added to the obtained residue, and the mixture was cooled to room temperature and crystallized.
  • the precipitated red crystals were obtained by filtration, and dried in a rotary evaporator equipped with an oil bath at an oil bath temperature of 140 ° C. and a pressure of 50 Torr to obtain 60 parts by mass of tetraphenoxytitanium.
  • Example B1 A separable flask reactor having a thermometer, a dropping funnel, a stirrer, a nitrogen inlet tube, and a cooling tube was charged with 75 parts by mass of 7027J (Mitsubishi Chemical's bisphenol A type polycarbonate resin), 327 parts by mass of epichlorohydrin (12 moles per mole of carbonate bonds in polycarbonate), and heated to 100 ° C. to dissolve the polycarbonate resin, and then cooled to about 40 ° C. under a nitrogen gas atmosphere.
  • 7027J Mitsubishi Chemical's bisphenol A type polycarbonate resin
  • epichlorohydrin (12 moles per mole of carbonate bonds in polycarbonate
  • a 10% by mass ethanolic potassium hydroxide solution was continuously added dropwise to 65 ° C., which was prepared by dissolving 47 parts by mass of potassium hydroxide (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade, purity 85.0 +%, water content 14%) in 349 parts by mass of ethanol (Nacalai Tesque, special grade, purity 85.0 +%, water content 14%) (2.4 moles per mole of carbonate bonds in polycarbonate), and the reaction was carried out for 120 minutes. The content of water relative to the total amount of the raw materials used was 0.8%. Then, 230 parts by mass of water was added, and the insoluble matter was removed by filtering with filter paper. The water layer obtained by the oil-water separation was separated to remove salts generated by the reaction, residual potassium hydroxide, etc. from the resin solution, and the reaction was terminated.
  • the reaction liquid obtained was gradually heated and the pressure in the system was reduced, and the temperature was kept at 150°C and 5 mmHg for 30 minutes, and ethanol, excess epichlorohydrin, and diethyl carbonate were completely distilled out of the system.
  • the distillate was 757 parts by mass.
  • a part of the distillate obtained was extracted and analyzed by gas chromatography, which showed that diethyl carbonate was 3% by mass and the recovery rate was 65%.
  • the system was returned to normal pressure while nitrogen was sealed in the system, and 150 parts by mass of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution of crude resin.
  • Example B2 A portion of the distillate obtained in Example B1 was extracted and analyzed by gas chromatography. It was found to consist of 44% by mass of ethanol, 3% by mass of diethyl carbonate, and 35% by mass of epichlorohydrin (the remaining component was presumed to be water). The obtained fraction (750 parts by mass) was placed in a distillation column equipped with a Sulzer Lab Packing (structured packing) rectification column, a distillation tube, a reflux timer, a pressure regulator, a thermometer, a stirrer and an oil bath. First, the internal temperature was raised to 110°C under normal pressure, and ethanol and water were distilled off under total distillation conditions.
  • Sulzer Lab Packing structured packing
  • Example B3 In a 45 mL glass reaction vessel equipped with a stirrer and a distillation tube, 10 parts by mass of bisphenol A (manufactured by Mitsubishi Chemical Group), 10 parts by mass of the diphenyl carbonate obtained in Example B2, and 18 ⁇ 10 ⁇ 6 parts by mass of a 400 ppm by mass aqueous cesium carbonate solution were placed.
  • the glass reaction vessel was depressurized to about 100 Pa, and then the operation of returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Thereafter, the reaction vessel was immersed in an oil bath at 220° C. to dissolve the contents.
  • the stirrer was rotated at 100 revolutions per minute, and the pressure in the reaction vessel was reduced from 101.3 kPa to 13.3 kPa absolute pressure over a period of 40 minutes while distilling off phenol produced as a by-product in the oligomerization reaction of bisphenol A and diphenyl carbonate in the reaction vessel.
  • the pressure inside the reaction vessel was then maintained at 13.3 kPa, and the ester exchange reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reaction vessel was raised to 290° C., and the pressure inside the reaction vessel was reduced from 13.3 kPa to 399 Pa absolute over a period of 40 minutes, and the distilled phenol was removed outside the system. Thereafter, the absolute pressure of the reaction vessel was reduced to 30 Pa, and the polycondensation reaction was carried out. When the agitator of the reaction vessel reached a predetermined stirring power, the polycondensation reaction was terminated. The time from raising the temperature to 290° C. to completing the polymerization was 120 minutes. Next, the reaction vessel was restored to an absolute pressure of 101.3 kPa with nitrogen, and then the pressure was increased to a gauge pressure of 0.2 MPa, and the polycarbonate resin was extracted from the reaction vessel to obtain a polycarbonate resin.
  • Example B1 The raw materials used in Example B1, the epoxy equivalent of the resulting epoxy resin, and the dialkyl carbonate recovery rate are summarized in Table 2.
  • Example C Third Form> In the same manner as in Reference Example B1 of Example B, 60 parts by mass of tetraphenoxytitanium was obtained.
  • Example C1 A separable flask reactor having a thermometer, a dropping funnel, a stirrer, a nitrogen inlet tube, and a cooling tube was charged with 75 parts by mass of 7027J (Mitsubishi Chemical's bisphenol A type polycarbonate resin), 327 parts by mass of epichlorohydrin (12 moles per mole of carbonate bonds in polycarbonate), and heated to 100 ° C. to dissolve the polycarbonate resin, and then cooled to about 40 ° C. under a nitrogen gas atmosphere.
  • 7027J Mitsubishi Chemical's bisphenol A type polycarbonate resin
  • epichlorohydrin (12 moles per mole of carbonate bonds in polycarbonate
  • the reaction liquid obtained was gradually heated and the pressure in the system was reduced, and the system was held at 150°C and 5 mmHg for 30 minutes, and methanol, excess epichlorohydrin, and dimethyl carbonate were completely distilled out of the system.
  • the distillate was 287 parts by mass.
  • a part of the distillate obtained was extracted and measured by gas chromatography, and the dimethyl carbonate was 5% by mass and the recovery rate was 54%.
  • the system was returned to normal pressure while nitrogen was sealed in the system, and 150 parts by mass of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution of crude resin.
  • Example C2 A part of the distillate obtained in Example C1 was extracted and analyzed by gas chromatography, which revealed that it was 10% by mass of methanol, 5% by mass of dimethyl carbonate, and 69% by mass of epichlorohydrin (the remaining components were estimated to be water).
  • 287 parts by mass of the distillate and 100 parts by mass of molecular sieves 3A were fed into an eggplant-shaped flask and allowed to stand overnight.
  • the internal temperature was increased to 100° C., and methanol was distilled off.
  • the internal temperature was increased from 100° C. to 200° C., and the pressure was gradually decreased from normal pressure to 10 kPa, whereby phenol and dimethyl carbonate were distilled off, and then 0.5 parts by mass of diphenyl carbonate was distilled off.
  • Example C3 In a 45 mL glass reaction vessel equipped with a stirrer and a distillation tube, 10 parts by mass of bisphenol A (manufactured by Mitsubishi Chemical Group), 10 parts by mass of the diphenyl carbonate obtained in Example C2, and 18 ⁇ 10 ⁇ 6 parts by mass of a 400 ppm by mass aqueous cesium carbonate solution were placed.
  • the glass reaction vessel was depressurized to about 100 Pa, and then the operation of returning the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reaction vessel with nitrogen. Thereafter, the reaction vessel was immersed in an oil bath at 220° C. to dissolve the contents.
  • the stirrer was rotated at 100 revolutions per minute, and the pressure in the reaction vessel was reduced from 101.3 kPa to 13.3 kPa absolute pressure over a period of 40 minutes while distilling off phenol produced as a by-product in the oligomerization reaction of bisphenol A and diphenyl carbonate in the reaction vessel.
  • the pressure inside the reaction vessel was then maintained at 13.3 kPa, and the ester exchange reaction was carried out for 80 minutes while further distilling off phenol. Thereafter, the temperature outside the reaction vessel was raised to 290° C., and the pressure inside the reaction vessel was reduced from 13.3 kPa to 399 Pa in absolute pressure over 40 minutes, and the distilled phenol was removed from the system. Thereafter, the absolute pressure inside the reaction vessel was reduced to 30 Pa, and the polycondensation reaction was carried out. When the agitator in the reaction vessel reached a predetermined stirring power, the polycondensation reaction was terminated. The time from raising the temperature to 290° C. to completing the polymerization was 120 minutes. Next, the reaction vessel was restored to an absolute pressure of 101.3 kPa with nitrogen, and then the pressure was increased to a gauge pressure of 0.2 MPa, and the polycarbonate resin was extracted from the reaction vessel to obtain a polycarbonate resin.
  • Example C1 The raw materials used in Example C1, the epoxy equivalent of the resulting epoxy resin, and the dialkyl carbonate recovery rate are summarized in Table 3.
  • Example D Fourth Form> (Example D1) A thermometer, a dropping funnel, a stirrer, a nitrogen inlet tube, and a separable flask reactor having a cooling tube were charged with 93 parts by mass of Pyrofil pellets PC-C-20 (Mitsubishi Chemical carbon fiber-containing BPA type polycarbonate fiber content 20 wt%) and 327 parts by mass of epichlorohydrin (epichlorohydrin was supplied so that the amount of epichlorohydrin was 12 moles per mole of carbonate bonds in the polycarbonate), and the mixture was heated to 100 ° C. to dissolve the polycarbonate resin, and then cooled to about 40 ° C. under a nitrogen gas atmosphere.
  • PC-C-20 Mitsubishi Chemical carbon fiber-containing BPA type polycarbonate fiber content 20 wt
  • epichlorohydrin epichlorohydrin was supplied so that the amount of epichlorohydrin was 12 moles per mole of carbonate bonds in the polycarbonate
  • the reaction solution obtained was gradually heated and the pressure in the system was reduced, and the system was held at 150°C and 5 mmHg for 30 minutes, during which methanol, excess epichlorohydrin, and dimethyl carbonate were completely removed from the system. After that, nitrogen was sealed in the system and the system was returned to normal pressure, and 233 parts by mass of toluene and 500 parts by mass of water were added, and the carbon fiber was separated by filtration.
  • the oil layer obtained by separating and removing the aqueous layer of the filtrate was then added with 100 parts by mass of water, and the separated and removed aqueous layer was repeatedly washed with water several times until it became neutral, to obtain a toluene solution of epoxy resin.
  • the toluene was removed from this solution by heating and reducing the pressure, and the system was held at 150°C and 5 mmHg for 30 minutes to completely remove the toluene, to obtain a liquid epoxy resin.
  • the epoxy resin obtained had an epoxy equivalent of 261 g/eq.
  • the carbon fiber separated by filtration was washed with water and acetone to remove any attached resin or inorganic salts, and then dried at 120°C for 2 hours to obtain 17.5 parts by mass of recycled carbon fiber.
  • the recycled fiber recovery rate was 94%.
  • Example D2 8 parts by mass of the epoxy resin produced in Example D1, 2 parts by mass of the recycled carbon fiber produced in Example D1, and 3 parts by mass of jER Cure ST14 (amine curing agent manufactured by Mitsubishi Chemical) were mixed to obtain a resin composition.
  • the obtained composition was poured into a mold and heated at 100°C for 2 hours and then at 170°C for 1 hour to obtain a recycled carbon fiber reinforced plastic.

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  • Epoxy Resins (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un nouveau recyclage chimique par lequel une résine époxyde industriellement utile peut être fournie. Le problème est résolu par un procédé de production d'une résine époxyde, le procédé comprenant une réaction de décomposition pour décomposer une résine de polycarbonate dans de l'épihalohydrine, et une étape de réaction pour obtenir une résine époxyde.
PCT/JP2023/024898 2023-04-07 2023-07-05 Procédé de production d'une résine époxyde, procédé de production d'une composition de résine époxyde, procédé de production d'un produit durci, procédé de production d'une composition de résine époxyde contenant des fibres, procédé de production de carbonate de diphényle et procédé de production de résine de polycarbonate Pending WO2024209710A1 (fr)

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JP2023062925A JP2024149194A (ja) 2023-04-07 2023-04-07 エポキシ樹脂及び炭酸ジアルキルの併産方法、エポキシ樹脂組成物の製造方法、炭酸ジフェニルの製造方法、及びポリカーボネート樹脂の製造方法
JP2023062948A JP2024149214A (ja) 2023-04-07 2023-04-07 エポキシ樹脂及び再生繊維の製造方法、繊維含有エポキシ樹脂組成物の製造方法、並びに繊維含有エポキシ樹脂硬化物の製造方法
JP2023-062925 2023-04-07
JP2023-062948 2023-04-07
JP2023098025A JP2024179291A (ja) 2023-06-14 2023-06-14 エポキシ樹脂及び炭酸ジアルキルの併産方法、エポキシ樹脂組成物の製造方法、炭酸ジフェニルの製造方法、及びポリカーボネート樹脂の製造方法
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CN120005164A (zh) * 2025-04-21 2025-05-16 浙江大学 一种利用聚碳酸酯制备环氧树脂前驱体的方法及其应用

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JPH06287295A (ja) * 1993-04-05 1994-10-11 Teijin Chem Ltd 芳香族ポリカーボネート樹脂のリサイクル方法
WO2022092176A1 (fr) * 2020-10-30 2022-05-05 三菱ケミカル株式会社 Procédé de production de bisphénol, procédé de production de résine de polycarbonate recyclée, procédé de production de dioxyde de carbone, procédé de production de diester carbonique, procédé de production de résine époxy et procédé de production de produit durci de résine époxy
WO2022113847A1 (fr) * 2020-11-27 2022-06-02 三菱ケミカル株式会社 Procédé de décomposition de résine de polycarbonate, procédé de production de bisphénol, procédé de production de carbonate de dialkyle, procédé de production de carbonate d'arylalkyle, procédé de production de carbonate de diaryle, procédé de production de résine de polycarbonate recyclée, procédé de production de résine époxy et procédé de production de produit durci de résine époxy
WO2022145366A1 (fr) * 2020-12-28 2022-07-07 三菱ケミカル株式会社 Procédé de production de bisphénol a et procédé de production de résine de polycarbonate
JP2023101259A (ja) * 2022-01-07 2023-07-20 三菱ケミカル株式会社 エポキシ樹脂の製造方法、エポキシ樹脂組成物の製造方法、及び硬化物の製造方法

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Publication number Priority date Publication date Assignee Title
JPH06287295A (ja) * 1993-04-05 1994-10-11 Teijin Chem Ltd 芳香族ポリカーボネート樹脂のリサイクル方法
WO2022092176A1 (fr) * 2020-10-30 2022-05-05 三菱ケミカル株式会社 Procédé de production de bisphénol, procédé de production de résine de polycarbonate recyclée, procédé de production de dioxyde de carbone, procédé de production de diester carbonique, procédé de production de résine époxy et procédé de production de produit durci de résine époxy
WO2022113847A1 (fr) * 2020-11-27 2022-06-02 三菱ケミカル株式会社 Procédé de décomposition de résine de polycarbonate, procédé de production de bisphénol, procédé de production de carbonate de dialkyle, procédé de production de carbonate d'arylalkyle, procédé de production de carbonate de diaryle, procédé de production de résine de polycarbonate recyclée, procédé de production de résine époxy et procédé de production de produit durci de résine époxy
WO2022145366A1 (fr) * 2020-12-28 2022-07-07 三菱ケミカル株式会社 Procédé de production de bisphénol a et procédé de production de résine de polycarbonate
JP2023101259A (ja) * 2022-01-07 2023-07-20 三菱ケミカル株式会社 エポキシ樹脂の製造方法、エポキシ樹脂組成物の製造方法、及び硬化物の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120005164A (zh) * 2025-04-21 2025-05-16 浙江大学 一种利用聚碳酸酯制备环氧树脂前驱体的方法及其应用

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