WO2023228613A1 - ポリイミド、イミド化合物の製造方法、及び再生ポリイミドの製造方法 - Google Patents

ポリイミド、イミド化合物の製造方法、及び再生ポリイミドの製造方法 Download PDF

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WO2023228613A1
WO2023228613A1 PCT/JP2023/014789 JP2023014789W WO2023228613A1 WO 2023228613 A1 WO2023228613 A1 WO 2023228613A1 JP 2023014789 W JP2023014789 W JP 2023014789W WO 2023228613 A1 WO2023228613 A1 WO 2023228613A1
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polyimide
group
main chain
compound
independently
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French (fr)
Japanese (ja)
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康太 安藤
輝彦 齊藤
穂波 伊延
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202380038546.3A priority Critical patent/CN119137188A/zh
Priority to JP2024522965A priority patent/JPWO2023228613A1/ja
Publication of WO2023228613A1 publication Critical patent/WO2023228613A1/ja
Priority to US18/935,673 priority patent/US20250059327A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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 disclosure relates to polyimide, a method for producing an imide compound, and a method for producing recycled polyimide.
  • thermosetting resins such as polyimide have excellent chemical resistance, so they tend to be difficult to dissolve in all kinds of solvents. Because this molded product has excellent heat resistance, it also tends to be difficult to melt and reuse, unlike thermoplastics such as polystyrene. Therefore, this molded article is difficult and inappropriate to be recycled or recycled, and is disposed of by landfilling or incineration.
  • the molded article includes a film.
  • thermosetting resins especially polyimide
  • the present disclosure aims to provide a new polyimide suitable for reuse.
  • the polyimide in one aspect of the present disclosure is Consists of a non-crosslinked structure including a main chain,
  • the main chain includes Si--O--C bonds.
  • the present disclosure provides a new polyimide suitable for reuse.
  • FIG. 1 is a flowchart regarding a method for producing an imide compound according to an embodiment of the present disclosure.
  • FIG. 2 is a flowchart regarding a method for manufacturing recycled polyimide according to an embodiment of the present disclosure.
  • FIG. 3 is a graph showing the 1 H-NMR spectrum of polyamic acid in Measurement Example 1.
  • FIG. 4 is a graph showing the infrared absorption spectrum of polyimide in Measurement Example 1.
  • FIG. 5 is a graph showing the 1 H-NMR spectrum of the polyimide decomposition product in Measurement Example 1.
  • Polyimide as an engineering plastic, has excellent heat resistance, mechanical properties, sliding properties, etc. Therefore, in recent years, demand for polyimide has increased rapidly in electrical and electronic equipment applications, automotive parts applications, aerospace industry applications, office equipment applications, and the like.
  • a polyimide film is produced by applying a coating solution containing polyamic acid, which is a precursor of polyimide, drying the resulting coating film, and then imidizing the polyamic acid through a dehydration cyclization reaction by heating etc. can.
  • Resin molded products such as polyimide films are extremely rigid and have good electrical properties, abrasion resistance, etc., as well as excellent chemical resistance and heat resistance.
  • polyimide is insoluble in chemicals such as organic solvents and does not melt even at high temperatures.
  • resin molded products such as polyimide films do not have sufficient bonding at the resin interface in the molded product, even if the molded product is re-produced after being crushed. Unable to obtain satisfactory characteristics.
  • Composite materials of polyimide and fiber materials such as glass fibers and carbon fibers are also known from the viewpoint of improving mechanical properties, insulation properties, etc.
  • polyimide has high heat resistance and solvent resistance, fiber materials are also crushed and disposed of by landfilling.
  • silicon-oxygen bonds can be used as bonds that can be formed and broken.
  • a silyl protecting group known as an alcohol protecting group the silicon-oxygen bond is cleaved by reaction with a fluorine anion, thereby allowing deprotection.
  • Patent Document 1 discloses alkaline hydrolysis of polyimide using a basic aqueous solution. According to this method, polyimide can be decomposed into low molecular weight substances. By decomposition, the polyimide film can be uniformly dissolved in the solvent. However, according to this method, it is difficult to reuse the decomposed products because the decomposed products have a complicated composition.
  • Patent Document 2 and 3 each disclose a polyimide containing a silicon atom.
  • the polyimides disclosed in these documents were not prepared with the assumption that they would be decomposed and reused.
  • the polyimide of Non-Patent Document 1 has a complicated crosslinked structure.
  • the polyimide of Non-Patent Document 1 has a crosslinked structure derived from a carbon-carbon triple bond and a crosslinked structure containing a silicon atom. This results in low degradability.
  • the polyimide of Non-Patent Document 1 is decomposed, the resulting decomposed product has a complicated crosslinked structure, making it difficult to reuse.
  • the polyimides of Patent Documents 2 and 3 tend to have low solvent resistance and high thermal expansion coefficients.
  • Polyimides tend to have high heat resistance, flame retardancy, and mechanical properties. Furthermore, since polyimide has high electrical insulation properties, it can be used as an insulating material or a substrate material for electronic circuits. The coefficient of linear thermal expansion of polyimide is extremely low for an organic material, and is close to that of metals. Therefore, when polyimide is used as an insulating material for electronic circuits, distortion due to thermal expansion with metal wiring is less likely to occur, and wiring can be processed with high precision.
  • Polyimide can usually be synthesized by condensing diamine and acid anhydride in equimolar amounts. For example, it can be synthesized by reacting a diamine and an acid anhydride in a highly polar organic solvent and heating the resulting polyamic acid at a high temperature.
  • the process of synthesizing polyimide by subjecting polyamic acid to heat treatment or the like may be referred to as imidization.
  • Polyimide molding method Polyimide usually does not have thermoplasticity and is insoluble in various organic solvents. Therefore, molding is performed by applying a solution containing a high concentration of polyamic acid as a precursor and imidizing it.
  • Polyimide decomposition method Molded polyimide products usually do not have thermoplasticity and are often insoluble in various solvents. Therefore, unlike thermoplastic resins, this molded product is difficult to melt and reuse. Regarding molded products, methods such as hydrolysis reaction under high temperature and high pressure conditions, decomposition and recovery methods using aqueous alkaline solutions, etc. have been proposed. However, decomposition under high temperature and high pressure conditions requires a large amount of energy input. When using a strong base for decomposition, a neutralization step is required after treatment.
  • polyimide properties such as thermal properties, mechanical properties, electrical insulation properties, optical properties, etc. can be appropriately designed according to the intended use by adjusting the types of diamines and acid anhydrides used as raw materials as necessary. be able to. Therefore, two or more types of diamines may be used in combination. For example, rigid and highly linear diamines and acid anhydrides may be selected to achieve low thermal expansion. However, polyimides composed only of rigid monomers tend to have poor entanglement between main chains. Therefore, if necessary, a method may be used in which polyimide is synthesized by partially mixing a diamine that can impart flexibility.
  • a diamine or acid anhydride having a fluorine-containing group such as a trifluoromethyl group may be selected.
  • a polyimide with a low dielectric constant and high transparency can be obtained.
  • diamines having a polysiloxane structure may be selected. In this case, the longer the polysiloxane structure in the diamine, the more clearly the polyimide has a phase-separated structure.
  • the properties of polyimide including the surface state, change significantly. Large changes in properties can result in polyimides that are soluble in organic solvents. This polyimide can be used for applications such as adhesives.
  • the polyimide according to the first aspect of the present disclosure is Consists of a non-crosslinked structure including a main chain,
  • the main chain includes Si--O--C bonds.
  • the polyimide according to the first aspect can be easily decomposed, for example, by reaction with a fluorine-containing compound. This polyimide is suitable for reuse.
  • the main chain may include a C—O—Si—OC bond.
  • the imide compound that is the decomposed product has, for example, two hydroxyl groups. This imide compound can be easily reused.
  • the main chain may include a group represented by -OSi(R 1 )(R 2 )O-, At least one oxygen atom contained in the group may bond to a carbon atom adjacent to the group to form the Si--O--C bond.
  • R 1 and R 2 may each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • the non-crosslinked structure includes a first structural unit represented by the following formula (A1).
  • R 1 and R 2 independently of each other contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I
  • X and Y are each independently a divalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I
  • Z is a tetravalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I
  • At least one selected from the group consisting of X and Y may contain a carbon atom that combines with an adjacent oxygen atom to form the Si--O--C bond.
  • the non-crosslinked structure includes a second structural unit represented by the following formula (A2). Good too.
  • R 1 to R 10 independently of each other contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I
  • Z may be a tetravalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • the imide compound that is the decomposed product has an alcohol structure such as a phenol structure at its terminal. This imide compound can be reused more easily.
  • the non-crosslinked structure includes a third structural unit represented by the following formula (A3).
  • A3 a third structural unit represented by the following formula (A3).
  • R 1 to R 12 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I; Good too.
  • the non-crosslinked structure includes a fourth structural unit represented by the following formula (A4).
  • R 1 to R 10 and R 13 to R 18 are each independently at least one selected from the group consisting of H, C, N, O, S, F, Cl, Br, and I. May contain two atoms.
  • the polyimides according to the sixth and seventh aspects tend to have excellent solvent resistance and thermal properties. Coating liquids containing polyamic acid, which is a precursor of polyimide, also tend to have excellent coating properties and film-forming properties.
  • the polyimide according to the sixth aspect and the seventh aspect can be easily decomposed by, for example, reaction with a fluorine-containing compound when unnecessary. When this polyimide is decomposed, an imide compound having a phenol structure at the end and suitable for reuse can be obtained.
  • R 1 and R 2 are each independently a hydrogen atom, or a carbonized carbon having 1 or more and 6 or less carbon atoms. It may be a hydrogen group.
  • the polyimide according to the eighth aspect can be easily synthesized. Furthermore, this polyimide can be easily decomposed, for example, by reaction with a fluorine-containing compound.
  • the polyimide according to the ninth aspect of the present disclosure has a main chain containing a Si-O-C bond, and the ratio of the number of silicon atoms contained in the main chain to the number of imide groups contained in the main chain is 2. % or more and 50% or less.
  • the polyimide according to the first or ninth aspect may have a weight average molecular weight of 1000 or more.
  • the polyimides according to the ninth and tenth aspects tend to have good solvent resistance and thermal properties.
  • the non-crosslinked structure may include a plurality of structural units.
  • the non-crosslinked structure may include the third structural unit represented by the formula (A3) and the fourth structural unit represented by the formula (A4).
  • the method for producing an imide compound according to the eleventh aspect of the present disclosure includes: Contacting the polyimide according to any one of the first to tenth aspects with a fluorine-containing compound; Reacting the polyimide and the fluorine-containing compound to obtain an imide compound that is a decomposition product of the polyimide; including.
  • an imide compound can be easily produced by decomposing polyimide.
  • the fluorine-containing compound may include a fluoride salt.
  • an imide compound can be produced using a relatively easily available and inexpensive fluoride salt.
  • the fluoride salt may include tetrabutylammonium fluoride.
  • an imide compound can be produced by decomposing polyimide at room temperature.
  • the method for producing recycled polyimide according to the fourteenth aspect of the present disclosure includes: Decomposing the polyimide according to any one of the first to tenth aspects to obtain a decomposed product of the polyimide; Synthesizing recycled polyimide using the decomposition product; including.
  • polyimide can be reused.
  • Polyimide P according to this embodiment has a Si--O--C bond in its main chain.
  • polyimide P includes a structural unit A having a Si--O--C bond in its main chain.
  • polyimide P may have a C—O—Si—O—C bond in its main chain.
  • an imide compound having two hydroxyl groups is obtained. This imide compound can be easily reused.
  • Polyimide P consists of a non-crosslinked structure. That is, polyimide P does not have a crosslinked structure, excluding those having a crosslinked structure. Specifically, polyimide P has a plurality of main chains, excluding those in which the plurality of main chains are crosslinked with each other. In other words, the polyimide P according to this embodiment has one main chain. In polyimide P, the main chain extends linearly, for example. Note that the polyimide P according to this embodiment has one main chain containing a Si--O--C bond and does not have multiple main chains. Such polyimide P may include a structural unit having a crosslinkable structure.
  • Polyimide P may have a group g represented by -OSi(R 1 )(R 2 )O-.
  • the above structural unit A may have the group g.
  • At least one oxygen atom contained in the group g is bonded to a carbon atom adjacent to the group g to form a Si--O--C bond, for example.
  • R 1 and R 2 may be the same or different.
  • R 1 and R 2 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 1 and R 2 may each independently contain at least one atom selected from the group consisting of H, C, O, F, Cl, Br and I.
  • R 1 and R 2 may independently be a hydrogen atom, a halogen atom, or a hydrocarbon group.
  • halogen atom examples include F, Cl, Br, I, and the like.
  • a halogen atom may be referred to as a halogen group.
  • the number of carbon atoms in the hydrocarbon group is not particularly limited, and is, for example, 1 or more and 20 or less, may be 1 or more and 10 or less, or may be 1 or more and 6 or less.
  • the hydrocarbon group may be linear, branched, or cyclic.
  • hydrocarbon group examples include an aliphatic saturated hydrocarbon group, an alicyclic hydrocarbon group, an aliphatic unsaturated hydrocarbon group, and an aromatic hydrocarbon group.
  • the aliphatic saturated hydrocarbon group may be an alkyl group.
  • Examples of aliphatic saturated hydrocarbon groups include -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 , -C(CH 3 ) 3 , -CH2CH ( CH3 ) 2 , -( CH2 ) 3CH3 , -( CH2 ) 4CH3 , -C( CH2CH3 ) ( CH3 ) 2 , -CH2C (CH 3 ) 3 , -(CH 2 ) 5 CH 3 , -(CH 2 ) 6 CH 3 , -(CH 2 ) 7 CH 3 , -(CH 2 ) 8 CH 3 , -(
  • Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
  • Examples of aromatic hydrocarbon groups include phenyl groups.
  • R 1 and R 2 may independently be a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, a methyl group or a phenyl group, or a methyl group. .
  • R 1 and R 2 are hydrogen atoms or hydrocarbon groups having 1 or more and 6 or less carbon atoms, the steric hindrance of R 1 and R 2 is small, so that, for example, the reaction between polyimide P and a fluorine-containing compound is inhibited. Hateful. In other words, the reaction with the fluorine-containing compound can easily break the Si--O bonds in polyimide P, so polyimide P can be easily decomposed.
  • R 1 and R 2 are hydrogen atoms or hydrocarbon groups having 1 or more and 6 or less carbon atoms, the polyimide P tends to be easily synthesized because raw materials can be obtained relatively easily.
  • polyimide P the above structural unit A may be represented by the following formula (A1).
  • polyimide P may include a structural unit A1 represented by the following formula (A1).
  • R 1 and R 2 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 1 and R 2 include those mentioned above for group g.
  • X and Y are divalent groups containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I, independently of each other. At least one selected from the group consisting of X and Y includes, for example, a carbon atom that combines with an adjacent oxygen atom to form a Si--O--C bond.
  • X and Y may independently be a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include an arylene group and an alkylene group.
  • Each of X and Y may be a phenylene group which may have a substituent.
  • substituents for the divalent hydrocarbon group include those mentioned above for R 1 and R 2 of group g.
  • Z is a tetravalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • Examples of Z include a group represented by the following formula (i), a group represented by the following formula (ii), and the like.
  • R 11 and R 12 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 11 and R 12 include those mentioned above for R 1 and R 2 in group g.
  • Each of R 11 and R 12 may be a hydrogen atom.
  • R 13 to R 18 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 13 to R 18 include those mentioned above for R 1 and R 2 in group g.
  • Each of R 13 to R 18 may be a hydrogen atom.
  • Q is a single bond or a divalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • the divalent group includes, for example, at least one functional group selected from the group consisting of an ether group, an acyl group, an ester group, and a sulfonyl group.
  • the divalent group may include an acyl group.
  • the divalent group may include a divalent hydrocarbon group instead of or in addition to the above functional group.
  • the divalent hydrocarbon group may further have a substituent other than the above-mentioned functional groups. Examples of the divalent hydrocarbon group include those mentioned above for X and Y.
  • polyimide P tends to have flexibility.
  • Z may be a group other than the group represented by formula (i) and the group represented by formula (ii).
  • Z may be a group containing an alicyclic hydrocarbon group.
  • polyimide P tends to have high transparency.
  • polyimide P may include a structural unit A2 represented by the following formula (A2).
  • R 1 to R 10 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 1 to R 10 include those mentioned above for R 1 and R 2 in group g.
  • Each of R 3 to R 10 may be a hydrogen atom.
  • Z is a tetravalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I. Examples of Z include those described above for formula (A1).
  • the above structural unit A may be represented by the following formula (A3) or the following formula (A4).
  • the polyimide P may include at least one selected from the group consisting of the structural unit A3 represented by the following formula (A3) and the structural unit A4 represented by the following formula (A4).
  • R 1 to R 12 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 1 to R 12 include those mentioned above for R 1 and R 2 in group g.
  • R 1 to R 10 and R 13 to R 18 are each independently at least one selected from the group consisting of H, C, N, O, S, F, Cl, Br, and I. Contains atoms. Examples of R 1 to R 10 and R 13 to R 18 include those mentioned above for R 1 and R 2 in group g.
  • the content of the structural unit A in polyimide P is, for example, 2 mol% or more, may be 5 mol% or more, may be 10 mol% or more, may be 30 mol% or more, and may be 50 mol% or more. It may be mol% or more, 80 mol% or more, or 90 mol% or more.
  • the polyimide P may be substantially composed only of the structural unit A. However, depending on the case, the content of the structural unit A in the polyimide P may be 80 mol% or less.
  • Polyimide P may further contain other structural units B other than the above-mentioned structural unit A.
  • Constituent unit B typically does not contain Si--O--C bonds.
  • the structural unit B is represented by the following formula (B1), for example.
  • G is a divalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • the divalent group includes, for example, at least one functional group selected from the group consisting of an ether group, an acyl group, an ester group, an amide group, a sulfide group, a disulfide group, and a sulfonyl group.
  • the divalent group may include an ether group.
  • the divalent group includes, for example, a divalent hydrocarbon group in addition to the above functional group.
  • the divalent hydrocarbon group may further have a substituent other than the above-mentioned functional groups. Examples of the divalent hydrocarbon group include those mentioned above for X and Y.
  • the divalent group may include a phenylene group as well as an ether group.
  • L is a tetravalent group containing at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I. Examples of L include those mentioned above for Z.
  • the structural unit B may be represented by the following formula (B2) or the following formula (B3).
  • the polyimide P may include at least one selected from the group consisting of the structural unit B2 represented by the following formula (B2) and the structural unit B3 represented by the following formula (B3).
  • R 19 to R 28 each independently contain at least one atom selected from the group consisting of H, C, N, O, S, F, Cl, Br and I.
  • R 19 to R 28 include those mentioned above for R 1 and R 2 in group g.
  • Each of R 19 to R 28 may be a hydrogen atom.
  • R 19 to R 26 and R 29 to R 34 are each independently at least one selected from the group consisting of H, C, N, O, S, F, Cl, Br, and I. Contains atoms. Examples of R 19 to R 26 and R 29 to R 34 include those mentioned above for R 1 and R 2 in group g. Each of R 19 to R 26 and R 29 to R 34 may be a hydrogen atom.
  • the content of structural unit B in polyimide P is not particularly limited, and is, for example, 98 mol% or less, may be 95 mol% or less, may be 90 mol% or less, or may be 70 mol% or less. It may be 50 mol% or less, 20 mol% or less, or 10 mol% or less.
  • Polyimide P does not need to contain structural unit B. However, depending on the case, the content of the structural unit B in the polyimide P may be 20 mol% or more.
  • Polyimide P may be represented by the following formula (1).
  • A means structural unit A
  • B means structural unit B
  • n, m and l are each independently arbitrary integers.
  • the physical properties of polyimide P represented by formula (1) can be easily adjusted based on the same molecular design as conventional polyimides.
  • the ratio p of the number of silicon atoms to the number of imide groups is, for example, 2% or more. More specifically, in polyimide P having a main chain containing a Si-O-C bond, the ratio p of the number of silicon atoms contained in the main chain to the number of imide groups contained in the main chain is 2%. 50% or less.
  • the ratio p may be 2% or more and 40% or less, 2% or more and 30% or less, or 2% or more and 10% or less. In other words, the ratio p may satisfy 2% ⁇ p ⁇ 50%, 2% ⁇ p ⁇ 40%, 2% ⁇ p ⁇ 30%, or 2% ⁇ p ⁇ 10%.
  • polyimide P the main chain containing Si--O--C bonds is easily decomposed. Thereby, an imide compound which is a decomposition product of polyimide P can be easily obtained. Furthermore, the obtained imide compound exhibits good solubility in organic solvents and can be used for producing recycled polyimide.
  • the weight average molecular weight of polyimide P is, for example, 1000 or more, may be 2500 or more, may be 5000 or more, or may be 10000 or more.
  • the upper limit of the weight average molecular weight of polyimide P is not particularly limited, and is, for example, 1,000,000.
  • Polyimide P can be synthesized by a reaction between a diamine and a tetracarboxylic dianhydride.
  • tetracarboxylic dianhydride may be simply referred to as acid anhydride.
  • diamines for forming structural unit A include the following.
  • diamines for forming polyimide P include the following.
  • acid anhydrides for forming polyimide P include the following.
  • the physical properties of polyimide P can be appropriately adjusted by the combination of diamine and acid anhydride used in the synthesis.
  • Physical properties of polyimide P include heat resistance, solvent resistance, transparency, dielectric constant, coefficient of thermal expansion, and the like.
  • the diamine or acid anhydride contains an aromatic ring in its main chain and has a rigid structure, it is possible to improve the heat resistance and solvent resistance of polyimide P and adjust the coefficient of thermal expansion to a low value. can.
  • the diamine or acid anhydride contains an alicyclic hydrocarbon group, the transparency of polyimide P can be improved and the dielectric constant can be adjusted to a low value.
  • two or more diamines and acid anhydrides may be used in combination.
  • Polyimide P can achieve heat resistance and solvent resistance comparable to conventional polyimides. Therefore, polyimide P can be used for the same purposes as before.
  • polyimide P can be used as a substrate material or a resin included in a composite material such as fiber-reinforced plastic.
  • polyimide P has a Si--O--C bond in its main chain and has a non-crosslinked structure. Polyimide P having such a structure can be easily decomposed, and thereby an imide compound which is a decomposition product of polyimide P can be obtained.
  • the imide compound can be produced, for example, by the following method.
  • FIG. 1 is a flowchart regarding a method for producing an imide compound.
  • polyimide P is brought into contact with a fluorine-containing compound.
  • the fluorine-containing compound may include a fluoride salt. Fluoride salts are soluble in water, organic solvents, and the like.
  • the fluoride salt may be an inexpensive ammonium-based fluoride salt that is relatively easily available. Ammonium-based fluoride salts tend to have adequate solubility in solvents.
  • the fluoride salt may include tetrabutylammonium fluoride, which is an ammonium-based fluoride salt.
  • the polyimide P and the fluorine-containing compound may be contacted in a solvent.
  • a solvent for example, polar solvents such as water and tetrahydrofuran (THF) can be used.
  • step S12 polyimide P is reacted with a fluorine-containing compound.
  • the reaction between the polyimide P and the fluorine-containing compound can be carried out, for example, by leaving the polyimide P in contact with the fluorine-containing compound.
  • the reaction can be promoted by adjusting the amount of the fluorine-containing compound used, the reaction temperature, the presence or absence of stirring, and the like.
  • the recycled polyimide P1 can be produced, for example, by the following method.
  • FIG. 2 is a flowchart regarding the method for manufacturing recycled polyimide P1.
  • polyimide P is decomposed.
  • the polyimide P can be decomposed by, for example, steps S11 and S12 described above.
  • a decomposed product of polyimide P can be obtained.
  • the decomposition product of polyimide P is, for example, an imide compound having an alcohol structure at the end.
  • recycled polyimide P1 is synthesized using the decomposed product of polyimide P.
  • the conditions for synthesizing the recycled polyimide P1 can be appropriately set depending on the composition of the above decomposed product, the composition of the intended recycled polyimide P1, and the like. In this way, according to the manufacturing method of this embodiment, recycled polyimide P1 can be manufactured from polyimide P, and polyimide P can be reused.
  • an acid anhydride and a diamine were prepared as raw materials for polyimide synthesis.
  • the following Compound A manufactured by Tokyo Chemical Industry Co., Ltd.
  • Compound B manufactured by Sigma-Aldrich Co., Ltd.
  • the following Compound C and Compound D were prepared as diamines.
  • dimethylacetamide manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., super dehydration grade
  • a dimethylacetamide solution of polyamic acid was applied to the glass plate.
  • the dimensions of the glass plate were 5 cm square and 1 cm thick.
  • a film made of polyamic acid was obtained by heating and drying on a hot plate at 50° C. for 16 hours.
  • Example 1 By heating a film composed of polyamic acid on a hot plate at 80°C for 1 hour, at 100°C for 1 hour, and at 130°C for 1 hour, the results of Example 1 were obtained. Polyimide was obtained. Polyimide was identified by infrared absorption spectrum. When compared with the infrared absorption spectrum of polyamic acid, it was confirmed that in the infrared absorption spectrum of polyimide, absorption derived from imide groups increased at 1715 cm -1 .
  • Example 2 Polyimide of Example 2 was synthesized by the same method as Example 1, except that 0.682 g (2.5 mmol) of Compound C was used and 0.500 g (2.5 mmol) of Compound D. . Furthermore, when the synthesized polyimide was evaluated for degradability using the same method as in Example 1, the same results as in Example 1 were obtained.
  • Example 3 Polyimide of Example 3 was synthesized by the same method as Example 1, except that 0.137 g (0.5 mmol) of Compound C was used and 0.900 g (4.5 mmol) of Compound D. . Furthermore, when the synthesized polyimide was evaluated for degradability using the same method as in Example 1, the same results as in Example 1 were obtained.
  • Example 4 Polyimide of Example 4 was synthesized by the same method as Example 1, except that 0.068 g (0.25 mmol) of Compound C was used and 0.950 g (4.75 mmol) of Compound D. . Furthermore, when the synthesized polyimide was evaluated for degradability using the same method as in Example 1, the same results as in Example 1 were obtained.
  • Example 5 Polyimide of Example 5 was synthesized by the same method as Example 3 except that 1.610 g (5 mmol) of Compound B was used instead of Compound A. Furthermore, when the synthesized polyimide was evaluated for degradability using the same method as in Example 1, the same results as in Example 1 were obtained.
  • Example 6 Polyimide of Example 6 was synthesized in the same manner as in Example 1, except that 1.365 g (5 mmol) of Compound C was used and Compound D was not used. However, in Example 6, the viscosity of the dimethylacetamide solution of polyamic acid was low, and it was not possible to produce a film made of polyamic acid. Therefore, in Example 6, a powder made of polyamic acid was produced and the powder was heat-treated to obtain a powder made of polyimide. Furthermore, when the synthesized polyimide was evaluated for degradability using the same method as in Example 1, the same results as in Example 1 were obtained.
  • the degradability of the synthesized polyimide was evaluated using the same method as in Example 1. As a result, even when a THF solution containing tetrabutylammonium fluoride at a concentration of 1 mol/L was used and left at room temperature for 48 hours, the polyimide did not dissolve in the solution and no change was observed in appearance. . Similarly, no change in appearance was observed even after the product was allowed to stand at room temperature for 120 hours. In a comparative experiment, no change was observed in appearance when compared to when only THF was added to polyimide.
  • Comparative example 2 A polyimide of Comparative Example 2 was synthesized by the same method as Comparative Example 1, except that 1.610 g (5 mmol) of Compound B was used instead of Compound A.
  • the degradability of the synthesized polyimide was evaluated using the same method as in Example 1. As a result, even when a THF solution containing tetrabutylammonium fluoride at a concentration of 1 mol/L was used and left at room temperature for 48 hours, the polyimide did not dissolve in the solution and no change was observed in appearance. . Similarly, no change in appearance was observed even after the product was allowed to stand at room temperature for 120 hours. In a comparative experiment, no change was observed in appearance when compared to when only THF was added to polyimide.
  • ⁇ Measurement of weight average molecular weight> The molecular weight distribution of the polyamic acids synthesized in Examples and Comparative Examples was measured under the following conditions, and the weight average molecular weight was determined. The results are shown in Table 1.
  • ⁇ Measurement conditions device Liquid chromatograph device (Shimadzu Corporation, LC-Vp) Column: TSKgel SuperAWM-HLSuperAW2500 (manufactured by Tosoh Corporation) Eluent: N,N-dimethylformamide + 30 mmol/L lithium bromide + 10 mmol/L phosphoric acid Flow rate: 0.5 mL/min Injection volume: 40 ⁇ L Column temperature: 40°C Standard sample: Monodisperse polyethylene oxide, polyethylene glycol Detector: Differential refractometer (RI)
  • the degradability of polyimide dissolved in a THF solution containing TBAF is described as "good", and the degradability of polyimide that is not dissolved in a THF solution containing TBAF is described as “poor”.
  • the polyimide of the example having a Si--O--C bond in its main chain had better degradability than the comparative example and was suitable for reuse.
  • the polyimide of the example could be easily decomposed at room temperature by using a fluorine-containing compound.
  • Example 6 since the weight average molecular weight of the polyamic acid was relatively small at 1200, the viscosity of the polyamic acid solution in dimethylacetamide was low, resulting in poor coating and film forming properties.
  • the polyamic acid had a weight average molecular weight suitable for coating and film formation.
  • FIG. 3 is a graph showing the 1 H-NMR spectrum of polyamic acid in Measurement Example 1.
  • the 1 H-NMR spectrum of polyamic acid was as follows.
  • FIG. 4 is a graph showing the infrared absorption spectrum of polyimide in Measurement Example 1. As can be seen from FIG. 4, the infrared absorption spectrum of polyimide confirmed absorption derived from imide groups.
  • FIG. 5 is a graph showing the 1 H-NMR spectrum of the polyimide decomposition product in Measurement Example 1.
  • the decomposition product was identified as a compound represented by the following formula (3). This compound is obtained by cleaving the Si--O bonds of polyimide. The terminal O - of this compound formed a salt with + NBu 4 .
  • Polyimide P of the present disclosure tends to have excellent solvent resistance and thermal properties. Furthermore, polyimide P can be easily decomposed and removed when unnecessary. Therefore, polyimide P can be used as a substrate material or a resin included in a composite material such as fiber-reinforced plastic.

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