Compound decomposition method

Abstract

The invention provides a novel depolymerization method for super engineering plastics such as polysulfone. A compound depolymerization method including a decomposition step in which a first compound represented by general formula (1) is decomposed by reacting the first compound with a second compound represented by general formula (8) or a hydroxide in the presence of a base (in the formula, n1 is an integer of 2 or more; z11 and Z12 are each independently a non-hydrogen atom group; each of m11 and m12 independently represents an integer of 0 to 4; ar1 represents a group represented by general formula (91), (92) or (93); r8 is alkyl, aryl or aralkyl; x < 11 >, X < 12 >, X < 21 >, X < 31 > and X < 32 > are each independently a non-hydrogen atom group; and each of l11, l12, l21, l31 and l32 independently represents an integer of 0-4).

Description

Technical Field

[0001] The present invention relates to a method for depolymerizing a compound (decomposition method). Background Art

[0002] As a super-engineering plastic, polysulfone not only possesses excellent heat resistance, a wide operating temperature range, hydrolysis resistance, chemical resistance, and electrical properties, but also combines mechanical strength, transparency, moldability, and weather resistance, making it a thermoplastic resin with ideal properties as a processable material. Due to these properties, polysulfone is widely used in medical and food applications such as biofilm replacements, artificial kidneys, medical devices, food containers, and cooking utensil components, as well as in electronic equipment components such as connectors and printed circuit boards. Other high-stability thermoplastic resins with similar properties to polysulfone include polyetherethersulfone and polyphenylsulfone, all of which share the same excellent material properties as polysulfone. Furthermore, these resins have a characteristic: a portion of their backbone is composed of bisphenols or hydroquinones, which are also widely used in other organic materials, thus offering significant value advantages as molecular materials. As of 2019, the combined production of polysulfone and polyphenylsulfone reached 26,600 tons, and polyethersulfone reached 16,870 tons. While these figures may seem low, considering these are high-priced resins, they are actually quite high. These superior properties have made these super engineering plastics indispensable materials in the industry today and into the future.

[0003] However, precisely because these super-engineering plastics are highly stable, their waste disposal and recycling are extremely difficult. For example, because their molecular structures contain a large number of benzene ring skeletons, these materials are difficult to decompose via microorganisms. Consequently, these materials impose a significant environmental burden, potentially posing significant challenges in the future. In fact, regarding chemical recycling technologies for super-engineering plastics, only a few examples have been disclosed to date, including the reduction of the molecular weight of polysulfone materials (see Patent Document 1) and the decomposition of monomeric or oligomeric units of polyphenylene sulfide and polyethersulfone (see Patent Document 2 and Non-Patent Documents 1-6). Among these, chemical recycling technologies for polyethersulfone utilize subcritical water, making them unsuitable for large-scale implementation. On the other hand, a related reaction is known in which the methoxy group of benzophenone, a constituent unit of polyetheretherketone, is replaced by an amino group in the presence of an organic superbase catalyst and an aromatic amine (see Non-Patent Document 7). However, this method has not yet been applied to the depolymerization of polymers such as polysulfone, polyphenylsulfone, and polyethersulfone.

[0004] Maintaining the current status quo will not only continue to place a heavy burden on the environment, but will also make it impossible to cope with potential future bans on the use of non-recyclable plastics. Furthermore, since these super-engineering plastics are high-value products, their direct disposal would result in significant economic losses. Therefore, the development of new depolymerization methods for super-engineering plastics is urgently needed.

[0005] [Patent Document 1] International Publication No. 2008 / 004642

[0006] [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-249324

[0007] [Non-patent document 1] Yu, ZL; Miao, GX; Chen, YR. Macromol Chem Phys 1996, 197, 4061.

[0008] [Non-patent document 2] Wang, S.J.; Bian, S.G.; Yan, H.; Xiao, M.; Meng, Y.Z.J. Appl. Poly. Sci. 2008, 110, 4049.

[0009] [Non-patent document 3] Lian, Z.; Bhawal, B. N.; Morandi, B. Science 2017, 356, 1059.

[0010] [Non-patent document 4] Minami, Y.; Matsuyama, N.; Matsuo, Y.; Tamura, M.; Sato, K.; Nakajima, Y. Synthesis 2021, 53, 3351.

[0011] [Non-Patent Document 5] Delcaillau, T.; Woenckhaus-Alvarez, A.; Morandi, B. Org. Lett. 2021, 23, 7018.

[0012] [Non-Patent Document 6] Minami, Y.; Matsuyama, N.; Takeichi, Y.; Watanabe, R.; Mathew, S.; Nakajima, Y. Communications Chemistry, 2023, 6, 14. DOI: 10.1038 / s42004-023-00814-8.

[0013] [Non-patent document 7] Shigeno, M.; Hayashi, K.; Nozawa-Kumada, K.; Kondo, Y. Org. Lett. 2019, 21, 5505. Summary of the Invention

[0014] The object of the present invention is to provide a novel depolymerization method (decomposition method) of super engineering plastics such as polysulfone.

[0015] In order to solve the above problems, the present invention adopts the following technical solutions:

[0016] [1] A method for decomposing a compound, characterized by comprising a decomposition step:

[0017] The following general formula (1)

[0018]

Chemical Formula 1

[0019]

[0020] (wherein n1 is an integer greater than 2 (preferably 10 to 200); Z 11 and Z 12 Each independently is a non-hydrogen atom group; m 11 and m 12 Each independently represents an integer from 0 to 4. 11 When n1×m is an integer greater than 1, 11 Z 11 Can be the same or different, when m 12 When n1×m is an integer greater than 1, 12 Z 12 Can be the same or different; Ar 1 The following general formula (91), (92) or (93)

[0021]

Chemical Formula 2

[0022]

[0023] (Where, X 11 、X 12 、X 21 、X 31 and X 32 Each independently is a non-hydrogen atom group; 11 、l 12 、l 21 、l 31 and l 32 Each independently represents an integer from 0 to 4. 11 When n1×l is an integer greater than 1, 11 X 11 Can be the same or different, when l 12 When n1×l is an integer greater than 1, 12 X 12 Can be the same or different, when l 21 When n1×l is an integer greater than 1,21 X 21 Can be the same or different, when l 31 When n1×l is an integer greater than 1, 31 X 31 Can be the same or different, when l 32 When n1×l is an integer greater than 1, 32 X 32 (which may be the same or different), and the bonds marked with the symbol * and the bonds marked with the symbol ** in the general formulae (91), (92) and (93) respectively form covalent bonds with the oxygen atom in the general formula (1), and

[0024] In the presence of a base, by reacting with the following general formula (8)

[0025] R 8 -SH(8)

[0026] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the first compound.

[0027] [2] A method for decomposing a compound, characterized by comprising a decomposition step:

[0028] The following general formula (2)

[0029]

Chemical Formula 3

[0030]

[0031] (wherein n2 is an integer greater than 2 (preferably 10 to 200); Z 21 、Z 22 and Z 23 Each independently is a non-hydrogen atom group; m 21 、m 22 and m 23 Each independently represents an integer from 0 to 4. 21 When n2×m is an integer greater than 1, 21 Z 21 Can be the same or different, when m 22 When n2×m is an integer greater than 1, 22 Z 22 Can be the same or different, when m 23When n2×m is an integer greater than 1, 23 Z 23 Can be the same or different)

[0032] A third compound represented by

[0033] In the presence of a base, by reacting with the following general formula (8)

[0034] R 8 -SH(8)

[0035] (Where R 8 wherein the alkyl, aryl or aralkyl group is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl, aryl or aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl, aryl or aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the third compound.

[0036] [3] A method for decomposing a compound, characterized by comprising a decomposition step:

[0037] The following general formula (4)

[0038]

Chemical Formula 4

[0039]

[0040] (wherein n4 is an integer greater than 2 (preferably 10 to 200); Z 41 and Z 42 Each independently is a non-hydrogen atom group; m 41 and m 42 Each independently represents an integer from 0 to 4. 41 When n4×m is an integer greater than 1, 41 Z 41 Can be the same or different, when m 42 When n4×m is an integer greater than 1, 42 Z 42 Can be the same or different)

[0041] The fourth compound represented by

[0042] In the presence of a base, by reacting with the following general formula (8)

[0043] R 8 -SH(8)

[0044] (Where R 8is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the fourth compound.

[0045] [4] The compound decomposition method according to any one of [1] to [3], wherein the base is at least a phosphazene base or sodium tert-butoxide.

[0046] [5] The compound decomposition method as described in any one of [1] to [3], wherein the compound represented by the general formula (8) is one or more selected from the group consisting of alkyl mercaptans having 1 to 15 carbon atoms, aryl mercaptans having 6 to 12 carbon atoms, arylalkyl mercaptans having 7 to 14 carbon atoms, halogenated alkyl mercaptans having 1 to 15 carbon atoms, halogenated aryl mercaptans having 6 to 12 carbon atoms, hydroxyalkyl mercaptans having 1 to 15 carbon atoms, polymercaptoalkanes having 1 to 15 carbon atoms, (mercaptoalkyl)trialkoxysilanes having 4 to 15 carbon atoms, and alkoxycarbonylalkyl mercaptans having 3 to 15 carbon atoms.

[0047] [6] The compound decomposition method according to any one of [1] to [3], wherein a dehydrating agent is further used in the decomposition step.

[0048] [7] The compound decomposition method according to any one of [1] to [3], wherein the hydroxide is an alkali metal hydroxide.

[0049] [8] The compound decomposition method as described in [6], wherein the dehydrating agent is one or more selected from the group consisting of sodium hydride, potassium hydride, calcium hydride, calcium oxide, cesium chloride, calcium chloride, magnesium sulfate and zeolite.

[0050] [9] A method for preparing an ether compound, comprising the following steps:

[0051] In the compound decomposition method according to any one of [1] to [3], the compound represented by the following general formula (11)

[0052]

Chemical Formula 5

[0053]

[0054] (Where Z 11 、Z 12 、m 11 and m 12 Same as above) or a salt thereof,

[0055] The following general formula (121)

[0056]

Chemical Formula 6

[0057]

[0058] (Where, X 11 、X 12 、l 11 and l 12 Same as above) and its salt,

[0059] The following general formula (122)

[0060]

Chemical Formula 7

[0061]

[0062] (Where, X 21 and l 21 Same as above) and its salt, and

[0063] The following general formula (123)

[0064]

Chemical Formula 8

[0065]

[0066] (Where, X 31 、X 32 、l 31 and l 32 Same as above) and one or more selected from the group consisting of compounds and salts thereof,

[0067] The following general formula (21)

[0068]

Chemical Formula 9

[0069]

[0070] (Where Z 21 、Z 22 、m 21 and m 22 Same as above) and its salt, and

[0071] The following general formula (22)

[0072]

Chemical Formula 10

[0073]

[0074] (Where Z 23 and m 23Same as above) and one or more selected from the group consisting of compounds and salts thereof,

[0075] Or the following general formula (41)

[0076]

Chemical Formula 11

[0077]

[0078] (Where Z 41 、Z 42 、m 41 and m 42 The ether compound is obtained by etherifying one or more phenolic hydroxyl groups or salt groups formed by the phenolic hydroxyl groups in one or more selected from the group consisting of the compounds represented by (same as above) and salts thereof.

[0079]

[12] A method for decomposing a compound, characterized by comprising a decomposition step:

[0080] The following general formula (3)

[0081]

Chemical Formula 12

[0082]

[0083] (wherein n3 is an integer greater than 2 (preferably 10 to 200); Z 31 、Z 32 、Z 33 、Z 34 and Z 35 Each independently is a non-hydrogen atom group; m 31 and m 32 are each independently an integer of 0 to 3, m 33 、m 34 and m 35 Each independently represents an integer from 0 to 4. 31 When n3×m is an integer greater than 1, 31 Z 31 Can be the same or different, when m 32 When n3×m is an integer greater than 1, 32 Z 32 Can be the same or different, when m 33 When n3×m is an integer greater than 1, 33 Z 33 Can be the same or different, when m 34 When n3×m is an integer greater than 1, 34 Z 34 Can be the same or different, when m 35 When n3×m is an integer greater than 1, 35Z 35 Can be the same or different)

[0084] The fifth compound represented by

[0085] In the presence of a base, by reacting with the following general formula (8)

[0086] R 8 -SH(8)

[0087] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), thereby reacting with a second compound represented by the present invention to decompose the fifth compound.

[0088] According to the present invention, a novel depolymerization method (decomposition method) applicable to super engineering plastics such as polysulfone is provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1 For the reaction mixture in Example 1 of embodiment 2 1 H NMR analysis results.

[0090] Figure 2 For the reaction mixture in Example 2 of embodiment 2 1 H NMR analysis results.

[0091] Figure 3 For the reaction mixture in Example 3 of embodiment 2 1 H NMR analysis results.

[0092] Figure 4 For the reaction mixture in Example 4 of embodiment 2 1 H NMR analysis results.

[0093] Figure 5 For the reaction mixture in Example 5 of embodiment 2 1 H NMR analysis results.

[0094] Figure 6 For the reaction mixture in Example 6 of embodiment 2 1 H NMR analysis results.

[0095] Figure 7 For the reaction mixture in Example 7 of embodiment 2 1 H NMR analysis results.

[0096] Figure 8 For the reaction mixture in Example 8 of embodiment 2 1 H NMR analysis results.

[0097] Figure 9 For the reaction mixture in Example 9 of embodiment 2 1 H NMR analysis results.

[0098] Figure 10 The reaction mixture of Example 10 of embodiment 2 1 H NMR analysis results.

[0099] Figure 11 The reaction mixture of Example 11 of embodiment 2 1 H NMR analysis results.

[0100] Figure 12 The reaction mixture in Example 12 of embodiment 2 1 H NMR analysis results.

[0101] Figure 13 For bisphenol S in Example 13 of embodiment 2 1 H NMR analysis results.

[0102] Figure 14 For the bisphenol A in Example 13 of embodiment 2 1 H NMR analysis results.

[0103] Figure 15 For the target product in Example 14 of embodiment 2 1 H NMR analysis results.

[0104] Figure 16 For the target product in Example 15 of embodiment 2 1 H NMR analysis results.

[0105] Figure 17 For the target product in Example 16 of embodiment 2 1 H NMR analysis results.

[0106] Figure 18 For bisphenol S in Example 17 of embodiment 2 1 H NMR analysis results.

[0107] Figure 19 For the target product in Example 18 of embodiment 2 1 H NMR analysis results.

[0108] Figure 20 For bisphenol S in Example 19 of embodiment 2 1H NMR analysis results.

[0109] Figure 21 4,4'-dihydroxybiphenyl in Example 19 of Embodiment 2 1 H NMR analysis results.

[0110] Figure 22 For bisphenol S in Example 20 of embodiment 2 1 H NMR analysis results.

[0111] Figure 23 For the target product in Example 21 of embodiment 2 1 H NMR analysis results.

[0112] Figure 24 4-((4-(4-hydroxyphenoxy)phenyl)sulfonyl)phenol in Example 22 of Embodiment 2 1 HNMR analysis results.

[0113] Figure 25 4,4'-dihydroxybenzophenone in Example 23 of Embodiment 2 1 H NMR analysis results.

[0114] Figure 26 4-((4-(4-hydroxyphenoxy)phenyl)sulfonyl)phenol in Example 23 of Embodiment 2 1 HNMR analysis results. DETAILED DESCRIPTION

[0115] The following describes an embodiment of the compound decomposition method according to the present invention. It should be noted that the present invention is not limited to the following embodiment. In addition, the contents of Japanese patent application (Special Application No. 2023-016683) and Japanese patent application (Special Application No. 2023-016684), which constitute a part of this specification, are hereby cited herein.

[0116] In this specification, the concentration unit "M" means "mol / L".

[0117] In this specification, when a compound is represented by a general formula or a non-general formula (a non-general formula may be referred to as a "formula" in this specification), a symbol may be attached to the general formula or non-general formula. In this case, the compound may be given a name with the symbol. For example, the compound represented by the general formula (1) described below may be referred to as "Compound (1)" in this specification.

[0118] (Implementation 1)

[0119] ◎Compound depolymerization method

[0120] <<Depolymerization method (i)>>

[0121] A compound depolymerization method (decomposition method) according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[0122] The following general formula (1)

[0123]

Chemical Formula 13

[0124]

[0125] (wherein n1 is an integer greater than 2 (preferably 10 to 200); Z 11 and Z 12 Each independently is a non-hydrogen atom group; m 11 and m 12 Each independently represents an integer from 0 to 4. 11 When n1×m is an integer greater than 1, 11 Z 11 Can be the same or different, when m 12 When n1×m is an integer greater than 1, 12 Z 12 Can be the same or different; Ar 1 The following general formula (91), (92) or (93)

[0126]

Chemical Formula 14

[0127]

[0128] (Where, X 11 、X 12 、X 21 、X 31 and X 32 Each independently is a non-hydrogen atom group; 11 、l 12 、l 21 、l 31 and l 32 Each independently represents an integer from 0 to 4. 11 When n1×l is an integer greater than 1, 11 X 11 Can be the same or different, when l 12 When n1×l is an integer greater than 1, 12 X 12 Can be the same or different, when l 21 When n1×l is an integer greater than 1, 21 X 21 Can be the same or different, when l 31 When n1×l is an integer greater than 1, 31 X 31Can be the same or different, when l 32 When n1×l is an integer greater than 1, 32 X 32 (may be the same or different), and the bonds marked with the symbol * and the bonds marked with the symbol ** in the general formula (91), (92) and (93) respectively form covalent bonds with the oxygen atom in the general formula (1)

[0129] The compound represented by (compound (1)), and in the presence of a base, by reacting with the following general formula (8)

[0130] R 8 -SH(8)

[0131] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted with a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted with an oxycarbonyl group or a carbonyloxy group) (sometimes referred to as "compound (8)" in this specification) to obtain the following general formula (18) [Chemical Formula 15]

[0132]

[0133] (Where Z 11 、Z 12 、m 11 、m 12 and R 8 The compound represented by the formula (same as above) (sometimes referred to as "compound (18)" in this specification), and the following general formula (121), (122) or (123)

[0134]

Chemical Formula 16

[0135]

[0136] (Where, X 11 、X 12 、X 21 、X 31 、X 32 、l 11 、l 12 、l 21 、l 31 and l 32The compound represented by (same as above) (in this specification, it may be referred to as "Compound (121)", "Compound (122)", "Compound (123)"). In this specification, the compound depolymerization method (decomposition method) of this embodiment may be referred to as "depolymerization method (i)".

[0137] The depolymerization method (depolymerization method (i)) of this embodiment is a novel depolymerization method for compound (1) containing super engineering plastics.

[0138] Compound (1) has a benzene ring skeleton bonded to an electron-withdrawing sulfonyl group (-SO2-) in its structure, and contains an electron-deficient aromatic ring group. In depolymerization method (i), compound (1) can be depolymerized (decomposed) by compound (8) in the presence of a base due to its aforementioned characteristics. Furthermore, as the depolymerization product (product), not only compound (121), compound (122), or compound (123) can be obtained, but also compound (18), a thioether compound depending on the structure of compound (8), can be obtained.

[0139] When the Ar 1 When the group is represented by the general formula (91), the compound (1) includes polysulfone (sometimes referred to as "PSU" in this specification) and its derivatives.

[0140] When the Ar 1 When the group is represented by the general formula (92), the compound (1) includes polyetherethersulfone (sometimes referred to as "PEES" in this specification) and its derivatives.

[0141] When the Ar 1 When the group is represented by the general formula (93), the compound (1) includes polyphenylsulfone (sometimes referred to as "PPSU" in this specification) and its derivatives.

[0142] In this specification, when a specific compound has a structure in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom, the compound having such a substituted structure is referred to as a "derivative" of the specific compound.

[0143] In this specification, unless otherwise specified, a "group" refers not only to an atomic group composed of a plurality of atoms bonded together but also includes a single atom.

[0144] When Ar 1 When the group is represented by the general formula (91), the depolymerization method (i) includes a depolymerization step (decomposition step):

[0145] The following general formula (1-1)

[0146]

Chemical Formula 17

[0147]

[0148] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 11 、X 12 、l 11 and l 12 Same as above)

[0149] The compound represented by, and in the presence of a base, by reacting with the following general formula (8)

[0150] R 8 -SH(8)

[0151] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) (compound (8)) is reacted to obtain the following general formula (18):

[0152]

Chemical Formula 18

[0153]

[0154] (Where Z 11 、Z 12 、m 11 、m 12 and R 8 Same as above)

[0155] The compound represented by (compound (18)), and the following general formula (121)

[0156]

Chemical Formula 19

[0157]

[0158] (Where, X 11 、X 12 、l 11 and l 12 Same as above)

[0159] The compound represented by (Compound (121)).

[0160] When Ar 1 When the group is represented by the general formula (92), the depolymerization method (i) includes a depolymerization step (decomposition step):

[0161] The following general formula (1-2)

[0162]

Chemical Formula 20

[0163]

[0164] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 21 and l 21 Same as above)

[0165] The compound represented by, and in the presence of a base, by reacting with the following general formula (8)

[0166] R 8 -SH(8)

[0167] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) (compound (8)) is reacted to obtain the following general formula (18):

[0168]

Chemical Formula 21

[0169]

[0170] (Where Z 11 、Z 12 、m 11 、m 12 and R 8 Same as above)

[0171] The compound represented by (compound (18)), and the following general formula (122)

[0172]

Chemical Formula 22

[0173]

[0174] (Where, X 21 and l 21 Same as above)

[0175] The compound represented by (Compound (122)).

[0176] When Ar 1When the group is represented by the general formula (93), the depolymerization method (i) includes a depolymerization step (decomposition step):

[0177] The following general formula (1-3)

[0178]

Chemical Formula 23

[0179]

[0180] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 31 、X 32 、l 31 and l 32 Same as above)

[0181] The compound represented by, and in the presence of a base, by reacting with the following general formula (8)

[0182] R 8 -SH(8)

[0183] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) (compound (8)) is reacted to obtain the following general formula (18):

[0184]

Chemical Formula 24

[0185]

[0186] (Where Z 11 、Z 12 、m 11 、m 12 and R 8 Same as above)

[0187] The compound represented by (compound (18)), and the following general formula (123)

[0188]

Chemical Formula 25

[0189]

[0190] (Where, X 31 、X 32 、l 31 and l 32 Same as above)

[0191] The compound represented by (Compound (123)).

[0192] <Compound (1)>

[0193] Compound (1) is the target of depolymerization in the depolymerization method (i).

[0194] In the general formula (1), n1 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (1), and is an integer of 2 or greater.

[0195] For example, compound (1) with n1 of 10 to 200 is suitable for high molecular weight super engineering plastics polysulfone (PSU), polyetherethersulfone (PEES) or polyphenylsulfone (PPSU), which are difficult to depolymerize using traditional methods and are particularly suitable as the application objects of depolymerization method (i).

[0196] In the general formula (1), Z 11 and Z 12 Each is independently a non-hydrogen atom group (sometimes referred to as a "substituent" in this specification). 11 and Z 12 It can be the same or different.

[0197] As Z 11 and Z 12 (Substituent) includes, for example, an alkyl group, an alkylcarbonylamino group, a fluoroalkyl group, a fluorine atom, and the like.

[0198] Z 11 and Z 12 The alkyl group in the formula (I) may be linear, branched, or cyclic, and may also have both a linear structure (linear or branched) and a cyclic structure. In this specification, an alkyl group having a cyclic structure is referred to as a cyclic alkyl group regardless of whether it contains other linear structures. The cyclic structure in a cyclic alkyl group (an alkyl group having a cyclic structure but no linear structure, and an alkyl group having both a cyclic structure and a linear structure) may be monocyclic or polycyclic.

[0199] Z 11 and Z 12 The alkyl group in the group preferably has 1 to 15 carbon atoms.

[0200] In Z 11 and Z 12Examples of the chain (straight or branched) alkyl group include chain alkyl groups having 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.

[0201] In Z 11 and Z 12 Among the alkyl groups in, examples of cyclic alkyl groups (alkyl groups having a monocyclic or polycyclic structure) include cyclic alkyl groups having 3 to 15 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, and cyclopropylmethyl.

[0202] Z 11 and Z 12 The alkyl group in the formula (I) may be, for example, an alkyl group having 1 to 10 carbon atoms (a chain alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), an alkyl group having 1 to 8 carbon atoms (a chain alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a chain alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), or any one of an alkyl group having 1 to 3 carbon atoms.

[0203] As Z 11 and Z 12 The alkylcarbonylamino group (formula "-NH-C(=O)-R 01 (Where R 01 is an alkyl group), for example, a monovalent group having the following structure can be mentioned: 11 and Z 12 The carbon atom having a free valence bond of the alkyl group is bonded to the carbon atom in the carbonylamino group (-NH-C(=O)-).

[0204] Examples of the alkylcarbonylamino group include methylcarbonylamino (—NH—C(═O)—CH 3 ) and the like, but are not limited thereto.

[0205] Z 11 and Z 12The alkylcarbonylamino group preferably has 2 to 16 carbon atoms.

[0206] As Z 11 and Z 12 The fluorinated alkyl group in the embodiment may be, for example, a monovalent group having the following structure: 11 and Z 12 wherein one or more hydrogen atoms (—H) of the alkyl group are replaced by fluorine atoms (—F).

[0207] The number of fluorine atoms in the fluorinated alkyl group depends on the number of carbon atoms in the fluorinated alkyl group and is not particularly limited, and can be, for example, 1 to 3. The fluorinated alkyl group can be, for example, a perfluoroalkyl group (a monovalent group having a structure in which all hydrogen atoms in the alkyl group are replaced by fluorine atoms) such as a trifluoromethyl group.

[0208] Z 11 and Z 12 The fluorinated alkyl group preferably has 1 to 15 carbon atoms.

[0209] In the general formula (1), m 11 Represents Z bonded to a benzene ring skeleton 11 The number of m 12 Indicates that Z 11 Z bonded to another benzene ring skeleton with a different bond 12 The number of m 11 and m 12 are each independently an integer from 0 to 4. 11 and m 12 It can be the same or different.

[0210] Compound (1) contains n1×m 11 Z 11 , when m 11 When n1×m is an integer greater than 1 (ie, an integer from 1 to 4), 11 Z 11 can be the same or different. That is, m 11 When n1×m is an integer greater than 1, 11 Z 11 They may be all the same, all different, or partially the same.

[0211] Z 12 Likewise, compound (1) contains n1×m 12 Z 12 , m 12 When n1×m is an integer greater than 1 (ie, an integer from 1 to 4), 12 Z 12can be the same or different. That is, m 12 When n1×m is an integer greater than 1, 12 Z 12 They may be all the same, all different, or partially the same.

[0212] In the general formula (1), Ar 1 It is a group represented by the general formula (91), a group represented by the general formula (92), or a group represented by the general formula (93).

[0213] In these groups, the bond marked with the symbol * forms a covalent bond with an oxygen atom not bonded to the sulfur atom (S) in the general formula (1), and the bond marked with the symbol ** forms a covalent bond with another oxygen atom not bonded to the sulfur atom in the general formula (1).

[0214] In the general formula (91), X 11 and X 12 Each independently is a non-hydrogen atom group (substituent). 11 and X 12 It can be the same or different.

[0215] As X 11 and X 12 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0216] In the general formula (91), 11 represents X bonded to a benzene ring skeleton 11 The number of. 12 Indicates that X 11 X bonded to another benzene ring skeleton with a different bond 12 The number of. 11 and l 12 are each independently an integer from 0 to 4. 11 and l 12 It can be the same or different.

[0217] Compound (1) contains n1×l in one molecule 11 X 11 , when l 11 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 11 X 11 Can be the same or different. That is, when l 11 When n1×l is an integer greater than 1, 11 X 11They may be all the same, all different, or partially the same.

[0218] X 12 Likewise, compound (1) contains n1×l in one molecule. 12 X 12 , when l 12 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 12 X 12 Can be the same or different. That is, when l 12 When n1×l is an integer greater than 1, 12 X 12 They may be all the same, all different, or partially the same.

[0219] In the general formula (91), 11 and l 12 For example, each independently may be 0 to 3, 0 to 2, 0 to 1 or 0.

[0220] Preferred examples of the group represented by the general formula (91) include: 11 and l 12 All are 0 (that is, without X 11 and X 12 ) group.

[0221] In the general formula (92), X 21 A non-hydrogen atom group (substituent).

[0222] As X 21 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0223] In the general formula (92), 21 represents X bonded to a benzene ring skeleton 21 The number is an integer from 0 to 4.

[0224] Compound (1) contains n1×l in one molecule 21 X 21 , when l 21 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 21 X 21 Can be the same or different. That is, when l 21 When n1×l is an integer greater than 1, 21 X 21 They may be all the same, all different, or partially the same.

[0225] In the general formula (92), 21 For example, it may be 0-3, 0-2, 0-1 or 0.

[0226] Preferred examples of the group represented by the general formula (92) include: 21 is 0 (i.e., does not contain X 21 ) group.

[0227] In the general formula (93), X 31 and X 32 Each independently is a non-hydrogen atom group (substituent). 31 and X 32 It can be the same or different.

[0228] As X 31 and X 32 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0229] In the general formula (93), 31 represents X bonded to a benzene ring skeleton 31 The number of. 32 Indicates that X 31 X bonded to another benzene ring skeleton with a different bond 32 The number of. 31 and l 32 are each independently an integer from 0 to 4. 31 and l 32 It can be the same or different.

[0230] Compound (1) contains n1×l in one molecule 31 X 31 , when l 31 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 31 X 31 Can be the same or different. That is, when l 31 When n1×l is an integer greater than 1, 31 X 31 They may be all the same, all different, or partially the same.

[0231] X 32 Likewise, compound (1) contains n1×l in one molecule. 32 X 32 , when l 32 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4),32 X 32 Can be the same or different. That is, when l 32 When n1×l is an integer greater than 1, 32 X 32 They may be all the same, all different, or partially the same.

[0232] In the general formula (93), 31 and l 32 For example, each independently may be 0 to 3, 0 to 2, 0 to 1 or 0.

[0233] Preferred examples of the group represented by the general formula (93) include: 31 and l 32 All are 0 (that is, without X 31 and X 32 ) group.

[0234] As an example of a preferred compound (1), there can be mentioned any of Ar 1 is a group represented by the general formula (91), a group represented by the general formula (92), or a group represented by the general formula (93), m 11 and m 12 All are 0 (that is, without Z 11 and Z 12 ) of compound (1).

[0235] As an example of a more preferred compound (1), Ar 1 is a group represented by the general formula (91), and 11 and l 12 is 0, m 11 and m 12 The compound (1) is 0.

[0236] As another example of a more preferred compound (1), Ar 1 is a group represented by the general formula (92), and 21 is 0, m 11 and m 12 The compound (1) is 0.

[0237] As another example of a more preferred compound (1), Ar 1 is a group represented by the general formula (93), and 31 and l 32 is 0, m 11 and m 12 The compound (1) is 0.

[0238] However, the compound (1) is not limited to these examples.

[0239] The compound (1) for depolymerization may be a fiber-reinforced material. That is, in the depolymerization method (i), depolymerization of the fiber-reinforced compound (1) may be achieved.

[0240] Examples of the fiber-reinforced compound (1) include a carbon fiber-reinforced compound (1) and a glass fiber-reinforced compound (1).

[0241] In the fiber-reinforced compound (1) (referred to as "fiber-reinforced resin" in this paragraph), the content of compound (1) relative to the total mass of the fiber-reinforced compound (1) (mass of compound (1) contained in the fiber-reinforced resin / total mass of the fiber-reinforced resin) × 100) is preferably 10 to 90 mass%, for example, it may be in the range of 10 to 70 mass%, 10 to 50 mass%, or 10 to 30 mass%, or in the range of 30 to 90 mass%, 50 to 90 mass%, or 70 to 90 mass%, or in the range of 30 to 70 mass%. By controlling the ratio to be above the lower limit, the yield of compound (18), compound (121), compound (122), or compound (123) is significantly improved. By controlling the ratio to be below the upper limit, the versatility of the fiber-reinforced compound (1) is enhanced.

[0242] The hydrogen atoms of one (1) or two (2) hydroxyl groups (-OH, hydroxyl groups at one or both ends of the general formula (1)) in the compound (1) may be substituted by non-hydrogen atom groups (hereinafter represented by the symbol "M") to form a group represented by the formula "-OM". That is, the compound (1) may be a salt. The formula "-OM" may also be represented by the formula "-O - M + ”.

[0243] When the hydrogen atoms of two hydroxyl groups in compound (1) are both substituted by M, the two M's may be the same or different.

[0244] As the M, for example, a substance that serves as a counter cation may be mentioned, which may be a metal atom (in this case, the salt of compound (1) may be in the form of an alkoxide). + , the counter cation may be, for example, a phosphazenium cation.

[0245] <Alkali>

[0246] The base is used to promote the depolymerization of compound (1).

[0247] The base may be an inorganic base (basic inorganic compound) or an organic base (basic organic compound).

[0248] Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates (alkali metal carbonates) such as potassium carbonate and cesium carbonate; and phosphates (alkali metal triphosphates) such as tripotassium phosphate.

[0249] The organic base may be, for example, an alkali metal tert-butoxide such as lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide;

[0250] Alkali metal bis(trimethylsilyl)amide compounds such as lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide;

[0251] Diazabicyclo (DBU);

[0252] Phosphazene base P4-t-Bu (alias: 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphazenylamino]-2λ 5 , 4λ 5 -diphosphazene), phosphazene base P2-t-Bu (alias: 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2λ 5 , 4λ 5 -diphosphazene), phosphazene base P1-t-Bu (also known as tert-butylimidazole-tris(dimethylamino)phosphacyclopentane), phosphazene base P4-t-Oct (also known as 1-tert-octyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphazeneamino]-2λ 5 , 4λ 5 -diphosphazene), phosphazene base P2-Et (also known as: 1-ethyl-2,2,4,4,4-penta(dimethylamino)-2λ 5 , 4λ 5 -diphosphazene), phosphazene base P1-t-Bu-tris(tetramethylene) (also known as tert-butylimino-tris(pyrrolidinyl)phosphane) and the like.

[0253] The structural formula of a typical phosphazene base is shown below.

[0254]

Chemical Formula 26

[0255]

[0256] The base used in the depolymerization step may be only one kind or two or more kinds. When two or more kinds of bases are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0257] For example, when two or more bases are used, two or more inorganic bases may be used instead of an organic base, two or more organic bases may be used instead of an inorganic base, or one or more inorganic bases and one or more organic bases may be used.

[0258] The base used in the depolymerization step is preferably one or more selected from the group consisting of phosphazene bases, carbonates, and alkali metal tert-butoxides, and more preferably one or more selected from the group consisting of phosphazene bases, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide. By using such a base, the depolymerization of compound (1) is facilitated.

[0259] It is particularly noteworthy that the depolymerization of compound (1) is easier to proceed. Therefore, in the depolymerization step, it is preferred to use at least a phosphazene base or sodium tert-butoxide as the base, more preferably a phosphazene base in combination with an inorganic base or sodium tert-butoxide, further preferably a phosphazene base in combination with a phosphate or sodium tert-butoxide, and particularly preferably a phosphazene base in combination with tripotassium phosphate or sodium tert-butoxide. When sodium tert-butoxide is used, the base may be used alone or in combination with other inorganic bases.

[0260] In the depolymerization step, the amount (in moles) of the base used is preferably 4 to 23 mol% relative to the amount (in moles) of the repeating units in the compound (1) (the structural unit designated by the symbol n1 in the general formula (1)). For example, it can be in any range of 4 to 13 mol%, 13 to 23 mol%, or 8 to 18 mol%. By controlling the amount of the base used to be above the lower limit, the depolymerization of the compound (1) proceeds more easily. By controlling the amount of the base used to be below the upper limit, the excessive use of the base can be suppressed.

[0261] <Compound (8)>

[0262] Compound (8) is a reaction partner of compound (1).

[0263] In the general formula (8), R 8 It is an alkyl group, an aryl group or an aralkyl group, and one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group (-OH), a mercapto group (-SH) or a trialkoxysilyl group (these groups are sometimes collectively referred to as "monovalent substituents" in this specification); when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups (-CH2CH2CH2-), the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group (-OC(=O)-) or a carbonyloxy group (-C(=O)-O-) (these groups are sometimes collectively referred to as "divalent substituents" in this specification).

[0264] As R 8 The alkyl group in Z can be exemplified by 11 and Z 12 The same group as the alkyl group in Z 8The alkyl group in the formula (I) may be linear, branched, or cyclic, or may have both a linear structure (linear or branched) and a cyclic structure. The cyclic structure in a cyclic alkyl group (an alkyl group having a cyclic structure but no chain structure, or an alkyl group having both a cyclic structure and a chain structure) may be monocyclic or polycyclic.

[0265] R 8 The number of carbon atoms of the alkyl group in is preferably 1 to 15. 8 When the compound (8) is an alkyl group, it is preferably an alkylthiol (alkanethiol) having 1 to 15 carbon atoms.

[0266] When R 8 When the alkyl group is a chain (straight or branched), examples of compound (8) include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, neopentyl mercaptan, tert-pentyl mercaptan, 1-methylbutyl mercaptan, n-hexyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 2,2-dimethylbutyl mercaptan, 2,3-dimethylbutyl mercaptan, n-heptyl mercaptan, 2-methylhexyl mercaptan, 3-methyl ... 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1-methylbutyl mercaptan, 2-methylpentyl mercaptan, 3-methylpentyl mercaptan, 1 -Chained alkyl mercaptans (alkanethiols) having 1 to 15 carbon atoms, such as methylhexyl mercaptan, 2,2-dimethylpentyl mercaptan, 2,3-dimethylpentyl mercaptan, 2,4-dimethylpentyl mercaptan, 3,3-dimethylpentyl mercaptan, 3-ethylpentyl mercaptan, 2,2,3-trimethylbutyl mercaptan, n-octyl mercaptan, isooctyl mercaptan, 2-ethylhexyl mercaptan, nonyl mercaptan, decyl mercaptan, 3,7-dimethyloctyl mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, and pentadecyl mercaptan.

[0267] When R 8 When the alkyl group is cyclic (monocyclic or polycyclic), examples of compound (8) include cyclic alkyl mercaptans (alkanethiols) having 3 to 15 carbon atoms, such as cyclopropyl mercaptan, cyclobutyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, cycloheptyl mercaptan, cyclooctyl mercaptan, cyclononyl mercaptan, cyclodecyl mercaptan, norbornyl mercaptan, isobornyl mercaptan, 1-adamantyl mercaptan, 2-adamantyl mercaptan, tricyclodecyl mercaptan, and cyclopropylmethyl mercaptan.

[0268] R 8The alkyl group in the alkyl group may be, for example, an alkyl group having 1 to 15 carbon atoms (a chain alkyl group having 1 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms), an alkyl group having 1 to 10 carbon atoms (a chain alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), an alkyl group having 1 to 8 carbon atoms (a chain alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a chain alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), or an alkyl group having 1 to 3 carbon atoms.

[0269] R 8 The aryl group in may be monocyclic or polycyclic.

[0270] R 8 The number of carbon atoms of the aryl group in the aryl group is preferably 6 to 15. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, 4-tert-butylphenyl, and xylyl (dimethylphenyl). In addition, groups having the following structure can be listed: the group is formed by replacing one or more hydrogen atoms in these aryl groups with the aryl group, or Z 11 and Z 12 The aryl group having these substituents preferably has 6 to 15 carbon atoms.

[0271] R 8 The aryl group in the aryl group preferably has 6 to 12 carbon atoms.

[0272] When R 8 When it is the aryl group, more specific examples of compound (8) include thiophenol, 1-naphthol, 2-naphthol, o-toluenethiol (also known as o-toluenethiol), m-toluenethiol (also known as m-toluenethiol), p-toluenethiol (also known as p-toluenethiol), 4-tert-butylthiophenol (also known as 4-tert-butylbenzenethiol), xylenethiophenol (dimethylthiophenol), and the like. Examples of compound (8) include thiophenols in which one or more hydrogen atoms are replaced by the aryl group, or Z 11 and Z 12 The structural thiol is formed by substitution of the alkyl group in the thiol.

[0273] When R 8 When it is the above-mentioned aryl group, compound (8) is preferably an arylthiol having 6 to 12 carbon atoms.

[0274] As R 8 The aralkyl group in the above mentioned structure may be, for example, a monovalent group having the following structure: 11 and Z 12 One hydrogen atom bonded to the carbon atom without free valence bond of the alkyl group is replaced by the above R 8The aryl group in is substituted to form.

[0275] R 8 The number of carbon atoms of the aralkyl group in the aralkyl group is preferably 7 to 17, and examples of the aralkyl group include benzyl (phenylmethyl), 4-tert-butylbenzyl ((4-tert-butylphenyl)methyl), phenethyl (phenylethyl), 4-tert-butylphenethyl (2-(4-tert-butylphenyl)ethyl), 1-naphthylmethyl, 2-naphthylmethyl, o-tolylmethyl, m-tolylmethyl, p-tolylmethyl, and xylylmethyl.

[0276] R 8 The aralkyl group in the group more preferably has 7 to 14 carbon atoms.

[0277] When R 8 The compound (8) includes phenylethyl mercaptan, and more specifically, benzyl mercaptan (also known as benzyl mercaptan), 4-tert-butylbenzyl mercaptan (also known as (4-tert-butylphenyl)methanethiol, or (4-tert-butylphenyl)methanethiol), phenylethyl mercaptan (also known as 2-phenylethyl mercaptan), 4-tert-butylphenylethyl mercaptan (also known as 2-(4-tert-butylphenyl))ethanethiol, or 2-(4-tert-butylphenyl)ethanethiol), 1-naphthylmethyl mercaptan, 2-naphthylmethyl mercaptan, o-tolumethyl mercaptan, m-tolumethyl mercaptan, p-tolumethyl mercaptan, xylmethyl mercaptan, and the like.

[0278] When R 8 When it is the above-mentioned aralkyl group, the compound (8) is more preferably an aralkylthiol having 7 to 14 carbon atoms.

[0279] R 8 In the monovalent substituent in , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0280] In R 8 In the trialkoxysilyl group as the monovalent substituent, the alkoxy group constituting the group may be, for example, a monovalent group having the following structure: 11 and Z 12 The carbon atom having a free valence bond of the alkyl group is bonded to an oxygen atom.

[0281] The alkoxy group may be linear, branched, or cyclic, or may have both a linear structure (linear or branched) and a cyclic structure. The cyclic structure in a cyclic alkoxy group (an alkoxy group having a cyclic structure but no chain structure, or an alkoxy group having both a cyclic structure and a chain structure) may be monocyclic or polycyclic.

[0282] The alkoxy group preferably has 1 to 15 carbon atoms.

[0283] Examples of the chain (straight or branched) alkoxy group include chain alkoxy groups having 1 to 15 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a neopentoxy group, a tert-pentoxy group, a 1-methylbutoxy group, an n-hexyloxy group, a 2-methylpentoxy group, a 3-methylpentoxy group, a 2,2-dimethylbutoxy group, a 2,3-dimethylbutoxy group, an n-heptyloxy group, a 2-methylhexyloxy group, a 3-methylhexyloxy group, a 2,2-dimethylpentoxy group, a 2,3-dimethylpentoxy group, a 2,4-dimethylpentoxy group, a 3,3-dimethylpentoxy group, a 3-ethylpentoxy group, a 2,2,3-trimethylbutoxy group, an n-octyloxy group, an isooctyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, and a pentadecyloxy group.

[0284] Among the alkoxy groups, examples of cyclic (monocyclic or polycyclic) alkoxy groups include cyclic alkoxy groups having 3 to 15 carbon atoms, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, norbornyloxy, isobornyloxy, 1-adamantyloxy, 2-adamantyloxy, tricyclodecyloxy, and cyclopropylmethoxy.

[0285] The alkoxy group may be, for example, an alkoxy group having 1 to 15 carbon atoms (a chain alkoxy group having 1 to 15 carbon atoms, or a cyclic alkoxy group having 3 to 15 carbon atoms), an alkoxy group having 1 to 10 carbon atoms (a chain alkoxy group having 1 to 10 carbon atoms, or a cyclic alkoxy group having 3 to 10 carbon atoms), an alkoxy group having 1 to 8 carbon atoms (a chain alkoxy group having 1 to 8 carbon atoms, or a cyclic alkoxy group having 3 to 8 carbon atoms), an alkoxy group having 1 to 6 carbon atoms (a chain alkoxy group having 1 to 6 carbon atoms, or a cyclic alkoxy group having 3 to 6 carbon atoms), or an alkoxy group having 1 to 3 carbon atoms.

[0286] In R 8 In the trialkoxysilyl group as the monovalent substituent, the three alkoxy groups may be the same or different. That is, the three alkoxy groups may all be the same, all different, or some (two) of them may be the same. When two or three of the alkoxy groups are different, the combination of these alkoxy groups is not particularly limited.

[0287] Particularly from the viewpoint of easier acquisition or preparation of compound (8), it is preferred that all three alkoxy groups are the same.

[0288] R 8Among the trialkoxysilyl groups as the monovalent substituents, preferred examples include trimethoxysilyl and triethoxysilyl.

[0289] When R 8 When one or two or more hydrogen atoms in the alkyl group, aryl group or aralkyl group are substituted by the monovalent substituent, the substitution position is not particularly limited.

[0290] The number of the hydrogen atoms substituted with the monovalent substituent is not particularly limited as long as it is equal to or less than the number of carbon atoms in the alkyl group, aryl group, or aralkyl group.

[0291] When the monovalent substituent is a hydroxyl group, a mercapto group, or a trialkoxysilyl group, the number of hydrogen atoms substituted by these substituents is preferably 1 to 2, more preferably 1.

[0292] When the monovalent substituent is a halogen atom, the number of hydrogen atoms substituted by the substituent may be 1 to 2, or 3 or more, or all hydrogen atoms in the alkyl, aryl, or aralkyl group may be substituted by halogen atoms. In other words, the alkyl, aryl, or aralkyl group in which one or more hydrogen atoms are substituted by halogen atoms may be a perhaloalkyl, perhaloaryl, or perhaloaralkyl group.

[0293] When R 8 When it is an alkyl group and one or more hydrogen atoms thereof are substituted by halogen atoms, examples of compound (8) include 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanethiol, and preferably a halogenated alkylthiol having 1 to 15 carbon atoms (halogenated alkylthiol).

[0294] When R 8 When it is an aryl group and one or more hydrogen atoms thereof are substituted with halogen atoms, examples of compound (8) include 4-chlorothiophenol (also known as 4-chlorobenzenethiol), and halogenated arylthiols having 6 to 12 carbon atoms are preferred.

[0295] When R 8 When it is an alkyl group and one or more hydrogen atoms thereof are substituted with hydroxyl groups, examples of compound (8) include 2-hydroxyethanethiol (also known as 2-hydroxyethanethiol), and hydroxyalkylthiols having 1 to 15 carbon atoms (hydroxyalkanethiols) are preferred.

[0296] When R 8 When it is an alkyl group and one or more hydrogen atoms thereof are substituted by a mercapto group, examples of the compound (8) include 1,2-dimercaptoethane (also known as 1,2-ethanedithiol), and polythioalkanes (alkane polythiols, alkanes having two or three or more mercapto groups) having 1 to 15 carbon atoms are preferred.

[0297] When R 8 When it is an alkyl group and one or more hydrogen atoms thereof are substituted by a trialkoxysilyl group, examples of compound (8) include (3-mercaptopropyl)triethoxysilane (also known as 3-(triethoxysilyl)-1-propanethiol), and preferably a (mercaptoalkyl)trialkoxysilane having 4 to 15 carbon atoms.

[0298] R 8 The case where the aryl group contains one or two or more trimethylene groups refers to, for example, a case where an alkyl group having 3 or more carbon atoms is bonded to the aromatic hydrocarbon ring skeleton in the aryl group, and the alkyl group contains a trimethylene group.

[0299] R 8 The case where the aralkyl group contains one or more trimethylene groups, for example, refers to any one or both of the following situations: the number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring skeleton in the aralkyl group is 3 or more, and the aralkyl group contains a trimethylene group, and / or the aromatic hydrocarbon ring skeleton in the aralkyl group is bonded to an alkyl group with 3 or more carbon atoms, and the aralkyl group contains a trimethylene group.

[0300] When R 8 When the alkyl, aryl or aralkyl group contains one or more trimethylene groups (-CH2CH2CH2-), the central methylene group in the trimethylene group refers to a methylene group bonded to two methylene groups (-CH2-)(-CH2-).

[0301] The central methylene group in the trimethylene group may be substituted by an oxycarbonyl group (-OC(=O)-) or a carbonyloxy group (-C(=O)-O-) divalent substituent), which means that in the trimethylene group after substitution, the bonding direction of the group represented by the asymmetric formula "-C(=O)-O-" may be either of the two directions.

[0302] In the present specification, the carbon atom at one end of the trimethylene group may be bonded to a hydrogen atom, that is, when the alkyl group, aryl group or aralkyl group is regarded as a group represented by the formula "CH3CH2CH2-", the group may be converted into a group represented by the formula "CH3-OC(=O)-CH2-" or a group represented by the formula "CH3-C(=O)-O-CH2-" through the divalent substituent.

[0303] When R 8 When the central methylene group in one or more trimethylene groups in the alkyl group, aryl group or aralkyl group is substituted with the divalent substituent, the substitution position is not particularly limited.

[0304] The number of the methylene groups substituted with the divalent substituent is not particularly limited as long as it is less than the number of trimethylene groups in the alkyl, aryl, or aralkyl group. In particular, the number of the methylene groups substituted with the divalent substituent is preferably 1 to 2, and more preferably 1.

[0305] When R 8 When the alkyl group is one or more trimethylene groups in which the central methylene group is substituted with the divalent substituent, examples of the compound (8) include 1-mercapto-2-methoxycarbonylethane (also known as 2-methoxycarbonylethanethiol, CH3OC(=O)CH2CH2SH), 1-mercapto-2-methylcarbonyloxyethane (also known as 2-(2-methylcarbonyloxyethanethiol, CH3C(=O)OCH2CH2SH), and the like.

[0306] When R 8 When it is an alkyl group containing the above-mentioned divalent substituent, the compound (8) is more preferably an alkoxycarbonylalkanethiol group having 3 to 15 carbon atoms.

[0307] The compound (8) used in the depolymerization step may be one or more than one compound. When two or more compounds are used, their combination and ratio may be arbitrarily selected according to the purpose. When two or more compounds (8) are used, two or more compounds (18) may be generated.

[0308] From the viewpoint of making the depolymerization of compound (1) easier to proceed, compound (8) is preferably one or more selected from the group consisting of alkylthiols having 1 to 15 carbon atoms, arylthiols having 6 to 12 carbon atoms, arylalkylthiols having 7 to 14 carbon atoms, halogenated alkylthiols having 1 to 15 carbon atoms, halogenated arylthiols having 6 to 12 carbon atoms, hydroxyalkylthiols having 1 to 15 carbon atoms, polythioalkanes having 1 to 15 carbon atoms, (mercaptoalkyl)trialkoxysilanes having 4 to 15 carbon atoms, and alkoxycarbonylalkylthiols having 3 to 15 carbon atoms.

[0309] In the depolymerization step, the amount (molar number) of compound (8) used relative to the amount (molar number) of the repeating unit in compound (1) (the structural unit marked with the symbol n1 in general formula (1)) can be 1.5 to 6 times the molar amount, preferably 2 to 6 times the molar amount, more preferably 2 to 4 times the molar amount, and even more preferably 2 to 3 times the molar amount. By controlling the amount of compound (8) used to be above the lower limit, the depolymerization of compound (1) proceeds more easily. By controlling the amount of compound (8) used to be below the upper limit, excessive use of compound (8) can be suppressed.

[0310] <Compound (18)>

[0311] Compound (18) is a product obtained by the depolymerization method (i).

[0312] Compound (18) is a derivative of bisphenol S (sometimes referred to as "BPS" in this specification).

[0313] Z in the general formula (18) 11 、Z 12 、m 11 and m 12 Respectively with Z in the general formula (1) 11 、Z 12 、m 11 and m 12 same.

[0314] R in the general formula (18) 8 and R in general formula (8) 8 same.

[0315] When two or more compounds (8) are used, the two R 8 It may be the same or different.

[0316] <Compound (121)>

[0317] Compound (121) is when Ar 1 When it is a group represented by the general formula (91), another product obtained by the depolymerization method (i).

[0318] Compound (121) is bisphenol A (sometimes referred to as "BPA" in this specification) and its derivatives.

[0319] X in the general formula (121) 11 、X 12 、l 11 and l 12 Respectively with X in general formula (91) 11 、X 12 、l 11 and l 12 same.

[0320] <Compound (122)>

[0321] Compound (122) is when Ar 1 When it is a group represented by the general formula (92), another product obtained by the depolymerization method (i).

[0322] Compound (122) is hydroquinone (sometimes referred to as "HQ" in this specification) and its derivatives.

[0323] X in the general formula (122) 21 and l 21 Respectively with X in general formula (92)21 and l 21 same.

[0324] <Compound (123)>

[0325] Compound (123) is when Ar 1 When it is a group represented by the general formula (93), another product obtained by the depolymerization method (i).

[0326] Compound (123) is 4,4'-dihydroxybiphenyl (also known as 4,4'-biphenol) (sometimes referred to as "4,4'-DHBP" in this specification) and its derivatives.

[0327] X in the general formula (123) 31 、X 32 、l 31 and l 32 Respectively with X in general formula (93) 31 、X 32 、l 31 and l 32 same.

[0328] Solvents

[0329] In the depolymerization step, it is further preferred to use a solvent. By using a solvent, particularly by dissolving compound (1) in a solvent and then performing the depolymerization step, depolymerization of compound (1) proceeds more easily.

[0330] In this specification, unless otherwise specified, the term "solvent" encompasses both components that are liquid at room temperature and dissolve a solute, and components that are liquid at room temperature and function as a dispersion medium for dispersing a dispersoid. Furthermore, "room temperature" refers to a temperature that is not specifically cooled or heated, i.e., a normal temperature, such as 15 to 25°C.

[0331] The solvent is preferably an organic solvent.

[0332] Examples of the organic solvent include amides such as 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP); nitriles such as benzonitrile; and ethers (cyclic ethers) such as 1,4-dioxane.

[0333] The solvent used in the depolymerization step may be only one kind or two or more kinds. When two or more kinds of solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0334] When a solvent is used in the depolymerization step, the amount of the solvent used is preferably 0.2 to 1.5 L relative to 100 g of the compound (1). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.4 to 1.5 L or 0.6 to 1.5 L, or 0.4 to 1 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (1) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, the excessive use of the solvent can be suppressed.

[0335] <Other ingredients>

[0336] In the depolymerization step, other components other than compound (1), base, compound (8) and the solvent added as needed may be used to depolymerize compound (1), unless the effects of the present invention are impaired. Alternatively, compound (1) may be depolymerized without using the other components.

[0337] The other components can be arbitrarily selected according to the purpose and are not particularly limited.

[0338] The other components used in the depolymerization step may be one or more than one. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0339] When depolymerization of compound (1) is performed in the depolymerization step, the ratio of the total amount (parts by mass) of the base, compound (8) and solvent to the total amount (parts by mass) of the base, compound (8), solvent and other components (([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent]) / ([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent] + [amount (parts by mass) of other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (1) can be more easily performed.

[0340] On the other hand, the ratio is 100% by mass or less.

[0341] When no optional components (ie, solvent or other components) are used in the depolymerization of compound (1), the amount of the optional components used in calculating the above ratio is 0 parts by mass.

[0342] <Other conditions>

[0343] In the depolymerization step, the compound (1) can be depolymerized by mixing the compound (1), a base, the compound (8), a solvent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[0344] In the depolymerization step, the temperature (reaction temperature) at which the mixture is heated and stirred may be room temperature or higher, preferably 90° C. or higher, for example, 110° C. or higher or 140° C. or higher. The higher the reaction temperature, the easier it is for compound (1) to depolymerize.

[0345] On the other hand, from the perspective of suppressing the formation of by-products, the reaction temperature is preferably 200° C. or lower, more preferably 160° C. or lower, for example, 120° C. or lower.

[0346] In the depolymerization step, the time for heating and stirring the mixture (reaction time) is preferably 1 hour or longer, more preferably 8 hours or longer, and even more preferably 15 hours or longer. By controlling the reaction time to be greater than the lower limit, the yield of compound (18), compound (121), compound (122), or compound (123) is significantly improved.

[0347] On the other hand, from the perspective of avoiding an excessively long reaction time, the reaction time is preferably 70 hours or less, more preferably 40 hours or less, and even more preferably 20 hours or less.

[0348] The above reaction time is particularly suitable when the reaction temperature is within the above numerical range.

[0349] In the depolymerization step, the depolymerization of compound (1) may be carried out in an atmosphere of an inert gas such as argon, helium, or nitrogen, or in an air atmosphere.

[0350] In depolymerization method (i), after the depolymerization step is completed, the resulting reaction mixture can be post-treated as needed using known methods to isolate the target product (product). Specifically, one or a combination of two or more post-treatment operations, such as filtration, washing, extraction, pH adjustment, dehydration, and concentration, can be appropriately performed as needed, and the target product can be isolated by methods such as concentration, crystallization, reprecipitation, and column chromatography. Furthermore, the isolated target product can be purified one or more times as needed by one or a combination of two or more operations, such as crystallization, reprecipitation, column chromatography, extraction, and solvent-stirred washing and crystallization. Alternatively, after the depolymerization step is completed, the resulting reaction mixture can be post-treated as needed and used directly for the next intended purpose without isolating the target product. For example, the target product can be used directly in the next target reaction without isolating it.

[0351] The structure of the product obtained by the depolymerization method (i) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[0352] <<Depolymerization method (ii)>>

[0353] A compound depolymerization method according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[0354] The following general formula (2)

[0355]

Chemical Formula 27

[0356]

[0357] (wherein n2 is an integer greater than 2 (preferably 10 to 200); Z 21 、Z 22 and Z 23 Each independently is a non-hydrogen atom group; m 21 、m 22 and m 23 Each independently represents an integer from 0 to 4. 21 When n2×m is an integer greater than 1, 21 Z 21 Can be the same or different, when m 22 When n2×m is an integer greater than 1, 22 Z 22 Can be the same or different, when m 23 When n2×m is an integer greater than 1, 23 Z 23 Can be the same or different)

[0358] The compound represented by (sometimes referred to as "compound (2)" in this specification) and in the presence of a base, by reacting with the following general formula (8)

[0359] R 8 -SH(8)

[0360] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) (compound (8)) is reacted to obtain the following general formula (28)

[0361]

Chemical Formula 28

[0362]

[0363] (Where Z 21 、Z 22 、m 21 、m 22 and R 8 Same as above)

[0364] The compound represented by (sometimes referred to as "compound (28)" in this specification) and the following general formula (22)

[0365]

Chemical Formula 29

[0366]

[0367] (Where Z 23 and m 23 Same as above)

[0368] The compound represented by (may be referred to as "compound (22)" in this specification). In this specification, the depolymerization method of the compound of this embodiment may be referred to as "depolymerization method (ii)".

[0369] The depolymerization method (depolymerization method (ii)) of this embodiment is a novel depolymerization method for compound (2) containing super engineering plastics.

[0370] Compound (2) has a benzene ring skeleton bonded to an electron-withdrawing carbonyl group (-CO-) in its structure, and contains an electron-deficient aromatic ring group. In depolymerization method (ii), compound (2) can be depolymerized by compound (8) in the presence of a base due to its aforementioned characteristics. Furthermore, as the depolymerization product (product), not only compound (22) but also compound (28), a thioether compound dependent on the structure of compound (8), can be obtained.

[0371] Depolymerization method (ii) uses compound (2) instead of compound (1) as the depolymerization target, that is, except for the difference in the depolymerization target, the rest is the same as depolymerization method (i).

[0372] The compound (2) includes polyetheretherketone (sometimes referred to as "PEEK" in this specification) and its derivatives.

[0373] <Compound (2)>

[0374] Compound (2) is the target of depolymerization in the depolymerization method (ii).

[0375] In the general formula (2), n2 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (2), and is an integer greater than or equal to 2.

[0376] For example, compound (2) with n2 of 20 to 200 is suitable for high molecular weight super engineering plastic polyetheretherketone (PEEK), which is difficult to depolymerize using traditional methods and is particularly suitable for application in depolymerization method (ii).

[0377] In the general formula (2), Z 21 、Z 22 and Z 23 Each is independently a non-hydrogen atom group (substituent). 21 、Z 22 and Z 23 They may be all the same, all different, or partially (any two) the same.

[0378] As Z 21 、Z 22 and Z 23 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0379] In the general formula (2), m 21 Represents Z bonded to a benzene ring skeleton 21 The number of m 22 Indicates that Z 21 Z bonded to another benzene ring skeleton with a different bond 22 The number of m 23 Indicates that Z 21 The bonded benzene ring skeleton and Z 22 The Z bonded to another benzene ring skeleton is different from the bonded benzene ring skeleton 23 The number of

[0380] m 21 、m 22 and m 23 are each independently an integer from 0 to 4. 21 、m 22 and m 23 They may be all the same, all different, or partially (any two) the same.

[0381] Compound (2) contains n2×m 21 Z 21 , when m 21 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 21 Z 21 can be the same or different. That is, m 21 When n2×m is an integer greater than 1, 21 Z21 They may be all the same, all different, or partially the same.

[0382] Z 22 Likewise, compound (2) contains n2×m 22 Z 22 , m 22 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 22 Z 22 can be the same or different. That is, m 22 When n2×m is an integer greater than 1, 22 Z 22 They may be all the same, all different, or partially the same.

[0383] Z 23 Likewise, compound (2) contains n2×m 23 Z 23 , m 23 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 23 Z 23 can be the same or different. That is, m 23 When n2×m is an integer greater than 1, 23 Z 23 They may be all the same, all different, or partially the same.

[0384] As examples of preferred compounds (2), m 21 、m 22 and m 23 All are 0 (that is, without Z 21 、Z 22 and Z 23 ) of compound (2).

[0385] However, compound (2) is not limited to these examples.

[0386] The compound (2) for depolymerization may be a fiber-reinforced material. That is, in the depolymerization method (ii), depolymerization of the fiber-reinforced compound (2) may be achieved.

[0387] Examples of the fiber-reinforced compound (2) include a carbon fiber-reinforced compound (2) and a glass fiber-reinforced compound (2).

[0388] In the fiber-reinforced compound (2), the ratio of the content of compound (2) to the total mass of the fiber-reinforced compound (2) ([content of compound (2) in the fiber-reinforced compound (2) (mass parts)] / [total mass of the fiber-reinforced compound (2) (mass parts)]×100) is preferably 10 to 90 mass%, for example, it may be any range of 10 to 70 mass%, 10 to 50 mass%, or 10 to 30 mass%, or any range of 30 to 90 mass%, 50 to 90 mass%, or 70 to 90 mass%, or 30 to 70 mass%. By controlling the ratio to be above the lower limit, the yield of compound (28) and compound (22) is significantly improved. By controlling the ratio to be below the upper limit, the versatility of the fiber-reinforced compound (2) is enhanced.

[0389] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a single-terminal or double-terminal hydroxyl group in the general formula (2)) in the compound (2) may be substituted with a group (M) other than a hydrogen atom, as in the case of the above-mentioned compound (1), to form a group represented by the formula "-OM", or to form a group represented by the formula "-O - M + ". That is, compound (2) may be a salt.

[0390] The manner in which compound (2) forms a salt is the same as the manner in which compound (1) forms a salt. That is, the salt of compound (2) is formed in the same manner as the salt of compound (1), and is identical to the salt of compound (1) except for the difference in the group to which the group represented by the formula "-OM" is bonded.

[0391] <Alkali>

[0392] The base in the depolymerization method (ii) is the same as the base in the depolymerization method (i).

[0393] The base used in the depolymerization step of the depolymerization method (ii) may be only one kind or two or more kinds. When two or more kinds of bases are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0394] For example, when two or more bases are used, two or more inorganic bases may be used instead of an organic base, two or more organic bases may be used instead of an inorganic base, or one or more inorganic bases and one or more organic bases may be used.

[0395] The base used in the depolymerization step of depolymerization method (ii) is preferably one or more selected from the group consisting of phosphazene bases, carbonates, and alkali metal tert-butoxides, and more preferably one or more selected from the group consisting of phosphazene bases, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide. By using such a base, depolymerization of compound (2) is facilitated.

[0396] It is particularly noteworthy that the depolymerization of compound (2) is easier to proceed. Therefore, in the depolymerization step, it is preferred to use at least a phosphazene base or sodium tert-butoxide as the base, more preferably a phosphazene base in combination with an inorganic base or sodium tert-butoxide, further preferably a phosphazene base in combination with a phosphate or sodium tert-butoxide, and particularly preferably a phosphazene base in combination with tripotassium phosphate or sodium tert-butoxide. When sodium tert-butoxide is used, the base may be used alone or in combination with other inorganic bases.

[0397] In the depolymerization step of depolymerization method (ii), the amount (in moles) of the base used is preferably 4 to 23 mol% relative to the amount (in moles) of the repeating units in compound (2) (the structural unit designated by the symbol n2 in general formula (2)). For example, it can be any range of 4 to 13 mol%, 13 to 23 mol%, or 8 to 18 mol%. By controlling the amount of the base used to be above the lower limit, depolymerization of compound (2) proceeds more easily. By controlling the amount of the base used to be below the upper limit, excessive use of the base can be suppressed.

[0398] <Compound (8)>

[0399] The compound (8) in the depolymerization method (ii) is the same as the compound (8) in the depolymerization method (i).

[0400] The compound (8) used in the depolymerization step of the depolymerization method (ii) may be one or more compounds. When two or more compounds are used, their combination and ratio may be arbitrarily selected according to the purpose. When two or more compounds (8) are used, two or more compounds (28) may be generated.

[0401] Preferred compounds (8) in the depolymerization method (ii) include the same compounds as the preferred compounds (8) in the depolymerization method (i).

[0402] In the depolymerization step of the depolymerization method (ii), the amount (molar amount) of compound (8) used relative to the amount (molar amount) of the repeating unit in compound (2) (the structural unit marked with the symbol n2 in the general formula (2)) can be, for example, 1.5 to 6 times the molar amount, preferably 2 to 6 times the molar amount, more preferably 2 to 4 times the molar amount, and even more preferably 2 to 3 times the molar amount. By controlling the amount of compound (8) used to be above the lower limit, the depolymerization of compound (2) proceeds more easily. By controlling the amount of compound (8) used to be below the upper limit, excessive use of compound (8) can be suppressed.

[0403] <Compound (28)>

[0404] Compound (28) is a product obtained by the depolymerization method (ii).

[0405] Compound (28) is a derivative of 4,4'-dihydroxybenzophenone.

[0406] Z in the general formula (28) 21 、Z 22 、m 21 and m 22 Respectively with Z in general formula (2) 21 、Z 22 、m 21 and m 22 same.

[0407] R in the general formula (28) 8 and R in general formula (8) 8 same.

[0408] When two or more compounds (8) are used, the two R 8 It may be the same or different.

[0409] <Compound (22)>

[0410] Compound (22) is another product obtained by the depolymerization method (ii).

[0411] Compound (22) is 1,4-dihydroxybenzene (also known as hydroquinone) and its derivatives.

[0412] Z in the general formula (22) 23 and m 23 Respectively with Z in general formula (2) 23 and m 23 same.

[0413] Solvents

[0414] In the depolymerization step of the depolymerization method (ii), it is further preferred to use a solvent. By using a solvent, particularly by dissolving the compound (2) in a solvent and then performing the depolymerization step, the depolymerization of the compound (2) proceeds more easily.

[0415] The solvent in the depolymerization method (ii) is the same as the solvent in the depolymerization method (i).

[0416] The solvent used in the depolymerization step of depolymerization method (ii) may be one or more than one solvent. When two or more solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0417] When a solvent is used in the depolymerization step of the depolymerization method (ii), the amount of the solvent used is preferably 0.2 to 1.5 L per 100 g of the compound (2). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.4 to 1.5 L or 0.6 to 1.5 L, or 0.4 to 1 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (2) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, the excessive use of the solvent can be suppressed.

[0418] <Other ingredients>

[0419] In the depolymerization step of the depolymerization method (ii), other components other than the compound (2), the base, the compound (8) and the solvent added as needed may be used to depolymerize the compound (2), or the compound (2) may be depolymerized without using the other components, as long as the effects of the present invention are not impaired.

[0420] The other components in the depolymerization method (ii) are the same as the other components in the depolymerization method (i).

[0421] The other components used in the depolymerization step of depolymerization method (ii) may be one or more. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0422] When depolymerizing compound (2) in the depolymerization step of depolymerization method (ii), the ratio of the total amount (parts by mass) of the base, compound (8) and solvent to the total amount (parts by mass) of the base, compound (8), solvent and other components (([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent]) / ([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent] + [amount (parts by mass) of other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (2) proceeds more easily.

[0423] On the other hand, the ratio is 100% by mass or less.

[0424] When no optional components (ie, solvent or other components) are used in the depolymerization of compound (2), the amount of the optional components used in calculating the above ratio is 0 parts by mass.

[0425] <Other conditions>

[0426] In the depolymerization step of the depolymerization method (ii), the compound (2) can be depolymerized by mixing the compound (2), a base, the compound (8), a solvent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[0427] In the depolymerization step of the depolymerization method (ii), the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (2) are respectively the same as the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (1) in the depolymerization step of the depolymerization method (i).

[0428] In the depolymerization method (ii), after the depolymerization step is completed, the resulting reaction mixture may be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) to isolate the target product (products), and the isolated target product may be further purified as needed. Alternatively, after the depolymerization step is completed, the resulting reaction mixture may be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) and used directly for the next intended purpose without isolating the target product.

[0429] The structure of the product obtained by the depolymerization method (ii) can be confirmed by a known method such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), etc.

[0430] <<Depolymerization method (iii)>>

[0431] A compound depolymerization method according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[0432] The following general formula (3)

[0433]

Chemical Formula 30

[0434]

[0435] (wherein n3 is an integer greater than 2 (preferably 10 to 200); Z 31 、Z 32 、Z 33 、Z 34 and Z 35 Each independently is a non-hydrogen atom group; m 31 and m 32 are each independently an integer of 0 to 3, m 33 、m 34 and m 35Each independently represents an integer from 0 to 4. 31 When n3×m is an integer greater than 1, 31 Z 31 Can be the same or different, when m 32 When n3×m is an integer greater than 1, 32 Z 32 Can be the same or different, when m 33 When n3×m is an integer greater than 1, 33 Z 33 Can be the same or different, when m 34 When n3×m is an integer greater than 1, 34 Z 34 Can be the same or different, when m 35 When n3×m is an integer greater than 1, 35 Z 35 Can be the same or different)

[0436] The compound represented by (sometimes referred to as "compound (3)" in this specification) and in the presence of a base, by reacting with the following general formula (8)

[0437] R 8 -SH(8)

[0438] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) (compound (8)) is reacted to obtain the following general formula (38)

[0439]

Chemical Formula 31

[0440]

[0441] (Where Z 31 、Z 32 、Z 33 、m 31 、m 32 、m 33 and R 8 Same as above)

[0442] The compound represented by (sometimes referred to as "compound (38)" in this specification) and the following general formula (32)

[0443]

Chemical Formula 32

[0444]

[0445] (Where Z 34 、Z 35 、m 34 and m 35 Same as above)

[0446] The compound represented by (in this specification, sometimes referred to as "compound (32)"). In this specification, the depolymerization method of the compound of this embodiment may be referred to as "depolymerization method (iii)".

[0447] The depolymerization method (depolymerization method (iii)) of this embodiment is a novel depolymerization method for compound (3) containing super engineering plastics.

[0448] Compound (3) has a benzene ring skeleton bonded to an electron-withdrawing carbonyl group (-CO-) in its structure, and contains an electron-deficient aromatic ring group. In depolymerization method (iii), compound (3) can be depolymerized by compound (8) in the presence of a base due to its aforementioned characteristics. Furthermore, as the depolymerization product (product), not only compound (32) but also compound (38), a thioether compound dependent on the structure of compound (8), can be obtained.

[0449] Depolymerization method (iii) uses compound (3) instead of compound (1) as the depolymerization target, that is, except for the difference in the depolymerization target, the rest is the same as depolymerization method (i).

[0450] The compound (3) includes polyetherimide (sometimes referred to as "PEI" in this specification) and its derivatives.

[0451] <Compound (3)>

[0452] Compound (3) is the target of depolymerization in the depolymerization method (iii).

[0453] In the general formula (3), n3 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (3), and is an integer greater than or equal to 2.

[0454] For example, when n3 is 10 to 100, compound (3) is suitable for high molecular weight super engineering plastic polyetherimide (PEI), which is difficult to depolymerize using traditional methods and is particularly suitable as an application object of depolymerization method (iii).

[0455] In the general formula (3), Z 31 、Z 32 、Z 33 、Z 34 and Z 35 Each is independently a non-hydrogen atom group (substituent). 31 、Z 32、Z 33 、Z 34 and Z 35 They may all be the same, all different, or some (any two, three, or four) may be the same.

[0456] As Z 31 、Z 32 、Z 33 、Z 34 and Z 35 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0457] In the general formula (3), m 31 Represents Z bonded to a benzene ring skeleton 31 The number of m 32 Indicates that Z 31 Z bonded to another benzene ring skeleton with a different bond 32 The number of m 33 Indicates that Z 31 The bonded benzene ring skeleton and Z 32 The Z bonded to another benzene ring skeleton is different from the bonded benzene ring skeleton 33 The number of m 34 Indicates that Z 31 Bonded benzene ring skeleton, and Z 32 The bonded benzene ring skeleton and Z 33 The Z bonded to another benzene ring skeleton is different from the bonded benzene ring skeleton 34 The number of m 35 Indicates that Z 31 Bonded benzene ring skeleton, and Z 32 Bonded benzene ring skeleton, and Z 33 The bonded benzene ring skeleton and Z 34 The Z bonded to another benzene ring skeleton is different from the bonded benzene ring skeleton 35 The number of

[0458] m 31 and m 32 are each independently an integer from 0 to 3. 31 and m 32 It can be the same or different.

[0459] m 33 、m 34 and m 35 are each independently an integer from 0 to 4. 33 、m 34 and m 35They may be all the same, all different, or partially (any two) the same.

[0460] Compound (3) contains n3×m 31 Z 31 , when m 31 When n3×m is an integer greater than 1 (i.e., an integer from 1 to 3), 31 Z 31 can be the same or different. That is, m 31 When n3×m is an integer greater than 1, 31 Z 31 They may be all the same, all different, or partially the same.

[0461] Z 32 Likewise, compound (3) contains n3×m 32 Z 32 , m 32 When n3×m is an integer greater than 1 (i.e., an integer from 1 to 3), 32 Z 32 can be the same or different. That is, m 32 When n3×m is an integer greater than 1, 32 Z 32 They may be all the same, all different, or partially the same.

[0462] Z 33 Likewise, compound (3) contains n3×m 33 Z 33 , m 33 When n3×m is an integer greater than 1 (ie, an integer from 1 to 4), 33 Z 33 can be the same or different. That is, m 33 When n3×m is an integer greater than 1, 33 Z 33 They may be all the same, all different, or partially the same.

[0463] Z 34 Likewise, compound (3) contains n3×m 34 Z 34 , m 34 When n3×m is an integer greater than 1 (ie, an integer from 1 to 4), 34 Z 34 can be the same or different. That is, m 34 When n3×m is an integer greater than 1, 34 Z 34They may be all the same, all different, or partially the same.

[0464] Z 35 Likewise, compound (3) contains n3×m 35 Z 35 , m 35 When n3×m is an integer greater than 1 (ie, an integer from 1 to 4), 35 Z 35 can be the same or different. That is, m 35 When n3×m is an integer greater than 1, 35 Z 35 They may be all the same, all different, or partially the same.

[0465] As examples of preferred compounds (3), m 31 、m 32 、m 33 、m 34 and m 35 All are 0 (that is, without Z 31 、Z 32 、Z 33 、Z 34 and Z 35 ) of compound (3).

[0466] However, compound (3) is not limited to these examples.

[0467] The compound (3) for depolymerization may be a fiber-reinforced material. That is, in the depolymerization method (iii), depolymerization of the fiber-reinforced compound (3) may be achieved.

[0468] Examples of the fiber-reinforced compound (3) include a carbon fiber-reinforced compound (3) and a glass fiber-reinforced compound (3).

[0469] In the fiber-reinforced compound (3), the ratio of the content of compound (3) to the total mass of the fiber-reinforced compound (3) ([content of compound (3) in the fiber-reinforced compound (3) (mass parts)] / [total mass of the fiber-reinforced compound (3) (mass parts)]×100) is preferably 10 to 90 mass%, for example, it may be any range of 10 to 70 mass%, 10 to 50 mass%, or 10 to 30 mass%, or any range of 30 to 90 mass%, 50 to 90 mass%, or 70 to 90 mass%, or 30 to 70 mass%. By controlling the ratio to be above the lower limit, the yield of compound (38) and compound (32) is significantly improved. By controlling the ratio to be below the upper limit, the versatility of the fiber-reinforced compound (3) is enhanced.

[0470] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a single-terminal or double-terminal hydroxyl group in the general formula (3)) in the compound (3) may be substituted with a group (M) other than a hydrogen atom, as in the case of the above-mentioned compound (1), to form a group represented by the formula "-OM", or to form a group represented by the formula "-O - M + ". That is, compound (3) may be a salt.

[0471] The manner in which compound (3) forms a salt is the same as the manner in which compound (1) forms a salt. That is, the salt of compound (3) is formed in the same manner as the salt of compound (1), and is identical to the salt of compound (1) except for the difference in the group to which the group represented by the formula "-OM" is bonded.

[0472] <Alkali>

[0473] The base in the depolymerization method (iii) is the same as the base in the depolymerization method (i).

[0474] The base used in the depolymerization step of depolymerization method (iii) may be only one kind or two or more kinds. When two or more kinds of bases are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0475] For example, when two or more bases are used, two or more inorganic bases may be used instead of an organic base, two or more organic bases may be used instead of an inorganic base, or one or more inorganic bases and one or more organic bases may be used.

[0476] The base used in the depolymerization step of depolymerization method (iii) is preferably one or more selected from the group consisting of phosphazene bases, carbonates, and alkali metal tert-butoxides, and more preferably one or more selected from the group consisting of phosphazene bases, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide. By using such a base, depolymerization of compound (3) is facilitated.

[0477] It is particularly noteworthy that the depolymerization of compound (3) is easier to proceed. Therefore, in the depolymerization step, it is preferred to use at least a phosphazene base or sodium tert-butoxide as the base, more preferably a phosphazene base in combination with an inorganic base or sodium tert-butoxide, further preferably a phosphazene base in combination with a phosphate or sodium tert-butoxide, and particularly preferably a phosphazene base in combination with tripotassium phosphate or sodium tert-butoxide. When sodium tert-butoxide is used, the base may be used alone or in combination with other inorganic bases.

[0478] In the depolymerization step of depolymerization method (iii), the amount (molar number) of the base used is preferably 4 to 23 mol% relative to the amount (molar number) of the repeating units in compound (3) (structural units marked with the symbol n2 in general formula (3)). For example, it can be any range of 4 to 13 mol%, 13 to 23 mol%, or 8 to 18 mol%. By controlling the amount of the base used to be above the lower limit, depolymerization of compound (3) proceeds more easily. By controlling the amount of the base used to be below the upper limit, excessive use of the base can be suppressed.

[0479] <Compound (8)>

[0480] The compound (8) in the depolymerization method (iii) is the same as the compound (8) in the depolymerization method (i).

[0481] The compound (8) used in the depolymerization step of the depolymerization method (iii) may be one or more compounds. When two or more compounds are used, their combination and ratio may be arbitrarily selected according to the purpose. When two or more compounds (8) are used, two or more compounds (38) may be generated.

[0482] Preferred compounds (8) in the depolymerization method (iii) include the same compounds as the preferred compounds (8) in the depolymerization method (i).

[0483] In the depolymerization step of the depolymerization method (iii), the amount (molar amount) of compound (8) used relative to the amount (molar amount) of the repeating unit in compound (3) (the structural unit marked with the symbol n3 in the general formula (3)) can be, for example, 1.5 to 6 times the molar amount, preferably 2 to 6 times the molar amount, more preferably 2 to 4 times the molar amount, and even more preferably 2 to 3 times the molar amount. By controlling the amount of compound (8) used to be above the lower limit, the depolymerization of compound (3) proceeds more easily. By controlling the amount of compound (8) used to be below the upper limit, excessive use of compound (8) can be suppressed.

[0484] <Compound (38)>

[0485] Compound (38) is a product obtained by the depolymerization method (iii).

[0486] Compound (38) is a derivative of N,N'-(1,3-phenylene)bis(5-hydroxyphthalimide).

[0487] Z in the general formula (38) 31 、Z 32 、Z 33 、m 31 、m 32 and m 33Respectively with Z in general formula (3) 31 、Z 32 、Z 33 、m 31 、m 32 and m 33 same.

[0488] R in the general formula (38) 8 and R in general formula (8) 8 same.

[0489] When two or more compounds (8) are used, the two R 8 It may be the same or different.

[0490] <Compound (32)>

[0491] Compound (32) is another product obtained by the depolymerization method (iii).

[0492] Compound (32) is bisphenol A (BPA) and its derivatives.

[0493] Z in the general formula (32) 34 、Z 35 、m 34 and m 35 Respectively with Z in general formula (3) 34 、Z 35 、m 34 and m 35 same.

[0494] Solvents

[0495] In the depolymerization step of depolymerization method (iii), it is further preferred to use a solvent. By using a solvent, particularly by dissolving compound (3) in a solvent and then performing the depolymerization step, depolymerization of compound (3) proceeds more easily.

[0496] The solvent in the depolymerization method (iii) is the same as the solvent in the depolymerization method (i).

[0497] The solvent used in the depolymerization step of depolymerization method (iii) may be only one type or two or more types. When two or more types of solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0498] When a solvent is used in the depolymerization step of the depolymerization method (ii), the amount of the solvent used is preferably 0.2 to 1.5 L per 100 g of the compound (3). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.4 to 1.5 L or 0.6 to 1.5 L, or 0.4 to 1 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (3) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, the excessive use of the solvent can be suppressed.

[0499] <Other ingredients>

[0500] In the depolymerization step of the depolymerization method (iii), other components other than the compound (3), the base, the compound (8) and the solvent added as needed may be used to depolymerize the compound (3), or the compound (3) may be depolymerized without using the other components, as long as the effects of the present invention are not impaired.

[0501] The other components in the depolymerization method (iii) are the same as the other components in the depolymerization method (i).

[0502] The other components used in the depolymerization step of depolymerization method (iii) may be one or more. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0503] When depolymerizing compound (3) in the depolymerization step of depolymerization method (iii), the ratio of the total amount (parts by mass) of the base, compound (8) and solvent to the total amount (parts by mass) of the base, compound (8), solvent and other components (([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent]) / ([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent] + [amount (parts by mass) of other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (3) proceeds more easily.

[0504] On the other hand, the ratio is 100% by mass or less.

[0505] When no optional components (ie, solvent or other components) are used in the depolymerization of compound (3), the amount of the optional components used in calculating the above ratio is 0 parts by mass.

[0506] <Other conditions>

[0507] In the depolymerization step of the depolymerization method (iii), the compound (3) can be depolymerized by mixing the compound (3), a base, the compound (8), a solvent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[0508] In the depolymerization step of the depolymerization method (iii), the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (3) are respectively the same as the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (1) in the depolymerization step of the depolymerization method (i).

[0509] In the depolymerization method (iii), after the depolymerization step is completed, the resulting reaction mixture may be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) to isolate the target product (product), and the isolated target product may be further purified as needed. Alternatively, after the depolymerization step is completed, the resulting reaction mixture may be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) and then used directly for the next intended purpose without isolating the target product.

[0510] The structure of the product obtained by the depolymerization method (iii) can be confirmed by a known method such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), etc.

[0511] <<Depolymerization method (iv)>>

[0512] A compound depolymerization method (decomposition method) according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[0513] The following general formula (4)

[0514]

Chemical Formula 33

[0515]

[0516] (wherein n4 is an integer greater than 2 (preferably 10 to 200); Z 41 and Z 42 Each independently is a non-hydrogen atom group; m 41 and m 42 Each independently represents an integer from 0 to 4. 41 When n4×m is an integer greater than 1, 41 Z 41 Can be the same or different, when m 42When n4×m is an integer greater than 1, 42 Z 42 Can be the same or different)

[0517] The compound represented by (sometimes referred to as "compound (4)" in this specification) and in the presence of a base, by reacting with the following general formula (8)

[0518] R 8 -SH(8)

[0519] (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms of the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group) to obtain the following general formula (48):

[0520]

Chemical Formula 34

[0521]

[0522] (Where Z 41 、Z 42 、m 41 、m 42 and R 8 Same as above)

[0523] The compound represented by (in this specification, sometimes referred to as "Compound (48)"). In this specification, the depolymerization method of the compound of this embodiment may be referred to as "depolymerization method (iv)".

[0524] The depolymerization method (depolymerization method (iv)) of this embodiment is a novel depolymerization method for compound (4) containing super engineering plastics.

[0525] Compound (4) has a benzene ring skeleton bonded to an electron-withdrawing sulfonyl group (-SO2-) in its structure, and contains an electron-deficient aromatic ring group. In depolymerization method (iv), compound (4) can be depolymerized by compound (8) in the presence of a base due to its aforementioned characteristics. Compound (48), a thioether compound depending on the structure of compound (8), can be obtained as the depolymerization product (product).

[0526] Depolymerization method (iv) uses compound (4) instead of compound (1) as the depolymerization target, that is, except for the difference in the depolymerization target, the rest is the same as depolymerization method (i).

[0527] The compound (4) includes polyethersulfone (sometimes referred to as "PESU" in this specification) and its derivatives.

[0528] <Compound (4)>

[0529] Compound (4) is the target of depolymerization in the depolymerization method (iv).

[0530] In the general formula (4), n4 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (4), and is an integer greater than or equal to 2.

[0531] For example, when n4 is 30 to 350, compound (4) is suitable for high molecular weight super engineering plastic polyethersulfone (PESU), which is difficult to depolymerize using traditional methods and is particularly suitable as an application object of depolymerization method (iv).

[0532] In the general formula (4), Z 41 and Z 42 Each is independently a non-hydrogen atom group (substituent). 41 and Z 42 It can be the same or different.

[0533] As Z 41 and Z 42 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0534] In general formula (4), m 41 Represents Z bonded to a benzene ring skeleton 41 The number of m 42 Indicates that Z 41 Z bonded to another benzene ring skeleton with a different bond 42 The number of

[0535] m 41 and m 42 are each independently an integer from 0 to 4. 41 and m 42 It can be the same or different.

[0536] Compound (4) contains n4×m 41 Z 41 , when m 41 When n4×m is an integer greater than 1 (ie, an integer from 1 to 4), 41 Z 41 can be the same or different. That is, m 41 When n4×m is an integer greater than 1, 41Z 41 They may be all the same, all different, or partially the same.

[0537] Z 42 Likewise, compound (4) contains n4×m 42 Z 42 , m 42 When n4×m is an integer greater than 1 (ie, an integer from 1 to 4), 42 Z 42 can be the same or different. That is, m 42 When n4×m is an integer greater than 1, 42 Z 42 They may be all the same, all different, or partially the same.

[0538] As examples of preferred compounds (4), m 41 and m 42 All are 0 (that is, without Z 41 and Z 42 ) of compound (4).

[0539] However, compound (4) is not limited to these examples.

[0540] The compound (4) for depolymerization may be a fiber-reinforced material. That is, in the depolymerization method (iv), depolymerization of the fiber-reinforced compound (4) may be achieved.

[0541] Examples of the fiber-reinforced compound (4) include a carbon fiber-reinforced compound (4) and a glass fiber-reinforced compound (4).

[0542] In the fiber-reinforced compound (4), the ratio of the content of compound (4) to the total mass of the fiber-reinforced compound (4) ([content of compound (4) in the fiber-reinforced compound (4) (parts by mass)] / [total mass of the fiber-reinforced compound (4) (parts by mass)]×100) is preferably 10 to 90 mass%, for example, it may be any range of 10 to 70 mass%, 10 to 50 mass%, or 10 to 30 mass%, or any range of 30 to 90 mass%, 50 to 90 mass%, or 70 to 90 mass%, or 30 to 70 mass%. By controlling the ratio to be above the lower limit, the yield of compound (48) is significantly improved. By controlling the ratio to be below the upper limit, the versatility of the fiber-reinforced compound (4) is enhanced.

[0543] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a single-terminal or double-terminal hydroxyl group in the general formula (4)) in the compound (4) may be substituted with a group (M) other than a hydrogen atom, as in the case of the above-mentioned compound (1), to form a group represented by the formula "-OM", or to form a group represented by the formula "-O - M + ". That is, compound (4) may be a salt.

[0544] The manner in which compound (4) forms a salt is the same as the manner in which compound (1) forms a salt. That is, the salt of compound (4) is formed in the same manner as the salt of compound (1), and is identical to the salt of compound (1) except for the difference in the group to which the group represented by the formula "-OM" is bonded.

[0545] <Alkali>

[0546] The base in the depolymerization method (iv) is the same as the base in the depolymerization method (i).

[0547] The base used in the depolymerization step of depolymerization method (iv) may be one or more bases. When two or more bases are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0548] For example, when two or more bases are used, two or more inorganic bases may be used instead of an organic base, two or more organic bases may be used instead of an inorganic base, or one or more inorganic bases and one or more organic bases may be used.

[0549] The base used in the depolymerization step of depolymerization method (iv) is preferably one or more selected from the group consisting of phosphazene bases, carbonates, and alkali metal tert-butoxides, and more preferably one or more selected from the group consisting of phosphazene bases, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide. By using such a base, depolymerization of compound (4) is facilitated.

[0550] It is particularly noteworthy that the depolymerization of compound (4) is easier to proceed. Therefore, in the depolymerization step, it is preferred to use at least a phosphazene base or sodium tert-butoxide as the base, more preferably a phosphazene base in combination with an inorganic base or sodium tert-butoxide, further preferably a phosphazene base in combination with a phosphate or sodium tert-butoxide, and particularly preferably a phosphazene base in combination with tripotassium phosphate or sodium tert-butoxide. When sodium tert-butoxide is used, the base may be used alone or in combination with other inorganic bases.

[0551] In the depolymerization step of depolymerization method (iv), the amount (in moles) of the base used is preferably 4 to 23 mol% relative to the amount (in moles) of the repeating units in compound (4) (the structural unit designated by the symbol n4 in general formula (4)). For example, it can be in any range of 4 to 13 mol%, 13 to 23 mol%, or 8 to 18 mol%. By controlling the amount of the base used to be above the lower limit, depolymerization of compound (4) proceeds more easily. By controlling the amount of the base used to be below the upper limit, excessive use of the base can be suppressed.

[0552] <Compound (8)>

[0553] The compound (8) in the depolymerization method (iv) is the same as the compound (8) in the depolymerization method (i).

[0554] The compound (8) used in the depolymerization step of depolymerization method (iv) may be one or more compounds. When two or more compounds are used, their combination and ratio may be arbitrarily selected according to the purpose. When two or more compounds (8) are used, two or more compounds (38) may be generated.

[0555] Preferred compounds (8) in the depolymerization method (iv) include the same compounds as the preferred compounds (8) in the depolymerization method (i).

[0556] In the depolymerization step of depolymerization method (iv), the amount (molar amount) of compound (8) used relative to the amount (molar amount) of the repeating unit in compound (4) (the structural unit marked with the symbol n4 in general formula (4)) can be, for example, 1.5 to 6 times the molar amount, preferably 2 to 6 times the molar amount, more preferably 2 to 4 times the molar amount, and even more preferably 2 to 3 times the molar amount. By controlling the amount of compound (8) used to be above the lower limit, depolymerization of compound (4) proceeds more easily. By controlling the amount of compound (8) used to be below the upper limit, excessive use of compound (8) can be suppressed.

[0557] <Compound (48)>

[0558] Compound (48) is a product obtained by the depolymerization method (iv).

[0559] Compound (48) is a derivative of bisphenol S (BPS).

[0560] Z in the general formula (48) 41 、Z 42 、m 41 and m 42 Respectively with Z in general formula (4) 41 、Z 42 、m 41 and m42 same.

[0561] R in the general formula (48) 8 and R in general formula (8) 8 same.

[0562] When two or more compounds (8) are used, the two R 8 It may be the same or different.

[0563] Solvents

[0564] In the depolymerization step of depolymerization method (iv), it is further preferred to use a solvent. By using a solvent, particularly by dissolving compound (4) in a solvent and then performing the depolymerization step, depolymerization of compound (4) can be facilitated.

[0565] The solvent in the depolymerization method (iv) is the same as the solvent in the depolymerization method (i).

[0566] The solvent used in the depolymerization step of depolymerization method (iv) may be only one type or two or more types. When two or more types of solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0567] When a solvent is used in the depolymerization step of depolymerization method (iv), the amount of the solvent used is preferably 0.2 to 1.5 L per 100 g of compound (4), and can be, for example, any range of 0.2 to 1 L or 0.2 to 0.6 L, or any range of 0.4 to 1.5 L or 0.6 to 1.5 L, or 0.4 to 1 L. By controlling the amount of the solvent used to be above the lower limit, depolymerization of compound (4) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, excessive use of the solvent can be suppressed.

[0568] <Other ingredients>

[0569] In the depolymerization step of the depolymerization method (iv), other components other than the compound (4), the base, the compound (8) and the solvent added as needed may be used to depolymerize the compound (4), or the compound (4) may be depolymerized without using the other components, as long as the effects of the present invention are not impaired.

[0570] The other components in the depolymerization method (iv) are the same as the other components in the depolymerization method (i).

[0571] The other components used in the depolymerization step of depolymerization method (iv) may be one or more. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0572] When depolymerizing compound (4) in the depolymerization step of depolymerization method (iv), the ratio of the total amount (parts by mass) of the base, compound (8) and solvent to the total amount (parts by mass) of the base, compound (8), solvent and other components (parts by mass) (([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent]) / ([amount (parts by mass) of base] + [amount (parts by mass) of compound (8)] + [amount (parts by mass) of solvent] + [amount (parts by mass) of other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (4) proceeds more easily.

[0573] On the other hand, the ratio is 100% by mass or less.

[0574] When no optional components (ie, solvent or other components) are used in the depolymerization of compound (4), the amount of the optional components used in calculating the above ratio is 0 parts by mass.

[0575] <Other conditions>

[0576] In the depolymerization step of depolymerization method (iv), compound (4) can be depolymerized by mixing compound (4), a base, compound (8), a solvent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[0577] In the depolymerization step of the depolymerization method (iv), the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (4) are respectively the same as the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (1) in the depolymerization step of the depolymerization method (i).

[0578] In the depolymerization method (iv), after the depolymerization step is completed, the reaction mixture obtained can be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) to isolate the target product (product), and the isolated target product can be further purified as needed. Alternatively, after the depolymerization step is completed, the reaction mixture can be subjected to post-treatment as needed in the same manner as in the depolymerization method (i) and used directly for the next intended purpose without isolating the target product.

[0579] The structure of the product obtained by the depolymerization method (iv) can be confirmed by a known method such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), etc.

[0580] <Example>

[0581] The present invention will be described in more detail below by way of specific examples. However, the present invention is not limited to the following examples.

[0582] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0583] [Example 1]

[0584] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (12.5 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu relative to the amount in the general formula (1)) was added to a colorless, transparent granular polysulfone (44.7 mg; the amount of the repeating unit in the general formula (1) is 0.101 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302) in 1% ethanol was added. The repeating unit is 10 mol%), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (alias: 2-ethylhexanethiol, equivalent to compound (8)) (36.5 mg, 0.250 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)), after the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0585] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the mixture was taken as a sample and dissolved in deuterated chloroform (CDCl 3 ). 1 H NMR analysis confirmed that the target products (depolymerization products): bis[4-(2-ethylhexylthio)phenyl]sulfone (BEHTPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained quantitatively (yields exceeded 95%).

[0586] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0587] The target products: bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 45.3 mg, yield 89%) and bisphenol A (BPA) (yield 21.3 mg, yield 94%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0588] The results of NMR analysis of the obtained bis(4-(2-ethylhexylthio)phenyl)sulfone and bisphenol A are shown below.

[0589] Bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS):

[0590] 1 H NMR(600MHz, CDCl3)δ0.87-0.90(m,12H,methyl),1.24-1.31(m,8H,methylene),1.36-1.49(m,8H,methylene),1.61( sept,J=6.3Hz,2H,methyne),2.92(d,J=6.4Hz,4H,SCH2),7.30(AA'BB',4H,aromatic),7.77(AA'BB',4H,aromatic).

[0591] 13 C NMR (151MHz, CDCl3) δ10.7,14.1,22.9,25.7,28.7,32.4,36.3,38.6,126.7,127.7,137.6,146.2.

[0592] Bisphenol A (BPA):

[0593] 1 H NMR(600MHz,acetone-d6)δ1.58(s,6H,methyl),6.72(AA'BB',4H,aromatic),7.05(AA'BB',4H,aromatic),8.07(s,2H,OH).

[0594]

Chemical Formula 35

[0595]

[0596] (where n 101 is an integer (preferably 10 to 200).

[0597] [Example 2]

[0598] Under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 mM of the phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421)) of phosphazene base P4-t-Bu was added to a colorless, transparent granular polysulfone (45.3 mg; the repeating unit in the general formula (1) is 0.102 mmol; the weight-average molecular weight is 60,000; manufactured by Nacalai Tesque, Cat. No. 178910050) in the presence of argon. ol, 10 mol% relative to the repeating unit in the general formula (1), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (36.5 mg, 0.250 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1), after the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0599] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): bis[4-(2-ethylhexylthio)phenyl]sulfone (BEHTPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained quantitatively (yields exceeded 95%).

[0600] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0601] The target products: bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 51 mg, yield 99%) and bisphenol A (BPA) (yield 25.3 mg, yield over 99%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30). 1 H NMR and 13 C NMR analysis also obtained the same results as in Example 1.

[0602]

Chemical Formula 36

[0603]

[0604] (where n 102is an integer (preferably 10 to 200).

[0605] The results of Examples 1 and 2 show that even when polysulfones with different degrees of polymerization are used, the depolymerization can proceed smoothly and the target products bis(4-(2-ethylhexylthio)phenyl)sulfone and bisphenol A can be obtained in high yields.

[0606] During the depolymerization process, the carbon-sulfur bonds of the diphenyl sulfone structural units in polysulfone were basically not broken, indicating that the carbon-oxygen bonds with higher bond energy than conventional carbon-sulfur bonds were selectively cut.

[0607] Depolymerization of polysulfone (conventional method)

[0608] [Comparative Example 1]

[0609] According to the method described in Non-Patent Document 6, depolymerization of polysulfone was carried out by a conventional method.

[0610] That is, under an argon atmosphere, sodium tert-butoxide (28.8 mg, 0.3 mmol, 3 times the molar amount (3 equivalents) of the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), and phenylethanethiol (C6H5CH2CH2SH) (equivalent to compound (8)) (55.6 mg, 0.4 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)) were added in sequence to colorless, transparent granular polysulfone (43.8 mg; the amount of the repeating unit in the general formula (1) is 0.099 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). After the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0611] The reaction mixture was then cooled to room temperature, 41.4 mg (0.3 mmol) of iodomethane was added, and the mixture was stirred at 100°C for 1 hour. Ethyl acetate (1.5 mL) was added to the reaction mixture, and the organic phase was washed with water and a saturated aqueous sodium chloride solution in that order. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[0612] Subsequently, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added to the crude product as an internal standard, and a small amount of the resultant was taken as a sample and dissolved in deuterated acetone (CD3)2CO). 1 H NMR and 13C NMR analysis confirmed that the target products (depolymerization products): bis(4-methylthiophenyl)sulfone (BMTPS, equivalent to compound (18)) (yield 84%) and bisphenol A (yield 80%) were obtained. The yields of these target products were lower than those in Examples 1 and 2.

[0613] The analysis results at this time are shown below.

[0614] Bis(4-methylthiophenyl)sulfone (BMTPS):

[0615] 1 H NMR(600MHz,acetone-d6)δ2.48(s,6H,SCH3),7.27(AA'BB',4H,aromatic),7.79(AA'BB',4H,aromatic).

[0616] 13 C NMR (151MHz, acetone-d6) δ14.8,125.5,127.8,137.5,146.5.

[0617]

Chemical Formula 37

[0618]

[0619] (where n 101 is an integer (preferably 10 to 200).

[0620] <<Depolymerization of polyetherethersulfone (depolymerization method (i))>>

[0621] [Example 3]

[0622] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (13.2 μL, containing 0.0105 mmol of the phosphazene base P4-t-Bu relative to the repeating unit in the general formula (1)) was added to brown granular polysulfone (34.1 mg; the repeating unit in the general formula (1) is 0.105 mmol; manufactured by Sigma-Aldrich, Cat. No. 440965) in the form of 1% phosphazene. The mixture was prepared by mixing the following ingredients: polyether ether sulfone (PES) (10 mol%), potassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (equivalent to compound (8)) (38.7 mg, 0.263 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)). After the polyether ether sulfone was dissolved, the resulting mixture was stirred at 150°C for 16 hours.

[0623] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): bis[4-(2-ethylhexylthio)phenyl]sulfone (BEHTPS, equivalent to compound (18)) and hydroquinone (HQ, equivalent to compound (122)) were obtained quantitatively (yields exceeded 95%).

[0624] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0625] The target products: bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 57.6 mg, yield over 99%) and hydroquinone (HQ) (yield 9.3 mg, yield 80%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0626] The obtained bis(4-(2-ethylhexylthio)phenyl)sulfone 1 H NMR and 13 The results of C NMR analysis were consistent with those in Example 1.

[0627] The obtained hydroquinone 1 The results of H NMR analysis are shown below.

[0628] Hydroquinone (HQ):

[0629] 1 H NMR(600MHz,acetone-d6)δ6.66(s,4H).

[0630]

Chemical Formula 38

[0631]

[0632] (where n 103 is an integer (preferably 10 to 200).

[0633] <<Depolymerization of polyphenylene sulfone (depolymerization method (i))>>

[0634] [Example 4]

[0635] Sheet-like polyphenylsulfone (manufactured by Standard-Testpiece Co., Ltd., Cat. No. RMOLDED0050) was processed into a powder.

[0636] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (12.5 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu, which is 10 mol% relative to the repeating unit in the general formula (1)), phosphoric acid, and the like were added to the colorless powdered polyphenylsulfone (40.1 mg; the amount of the repeating unit in the general formula (1) is 0.1 mmol) obtained above. Tripotassium (K3PO4) (1.3 mg, 0.006 mmol, 6 mol% relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (equivalent to compound (8)) (36.7 mg, 0.251 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)). After the polyphenylsulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0637] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis showed that the target products (depolymerization products): bis[4-(2-ethylhexylthio)phenyl]sulfone (BEHTPS, equivalent to compound (18)) and 4,4'-dihydroxybiphenyl (4,4'-DHBP, equivalent to compound (123)) were obtained quantitatively (yields exceeded 95%).

[0638] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0639] The target products: bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 49 mg, yield 95%) and 4,4'-dihydroxybiphenyl (4,4'-DHBP) (yield 19 mg, yield over 99%) were separated from the obtained crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0640] The obtained bis(4-(2-ethylhexylthio)phenyl)sulfone 1 H NMR and 13 The results of C NMR analysis were consistent with those in Example 1.

[0641] The obtained 4,4'-dihydroxybiphenyl 1 The results of H NMR analysis are shown below.

[0642] 4,4'-Dihydroxybiphenyl (4,4'-DHBP):

[0643] 1 H NMR(600MHz,acetone-d6)δ6.87(AA'BB',4H,aromatic),7.40(AA'BB',4H,aromatic),8.32(s,2H,OH).

[0644]

Chemical Formula 39

[0645]

[0646] (where n 104 is an integer (preferably 10 to 200).

[0647] <<Depolymerization of polyethersulfone (depolymerization method (iv))>>

[0648] [Example 5]

[0649] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (12.5 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu relative to the repeating unit in the general formula (4)) was added to yellow transparent granular polyethersulfone (23.2 mg; the amount of the repeating unit in the general formula (4) is 0.1 mmol; manufactured by Sigma-Aldrich, Cat. No. 191094) in 1% ethanol was added. Unit is 10 mol%), potassium phosphate (K3PO4) (1.2 mg, 0.0057 mmol, 6 mol% relative to the repeating unit in the general formula (4)), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (equivalent to compound (8)) (22.1 mg, 0.151 mmol, 1.5 times the molar amount (1.5 equivalents) relative to the repeating unit in the general formula (4)), after the polyethersulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0650] The resulting yellow reaction mixture was then cooled to at least room temperature and distilled under reduced pressure to obtain a crude product.

[0651] The target products bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 10.9 mg, yield 22%), 4-(2-ethylhexylthio)-4'-hydroxydiphenylsulfone (compound (a)) (yield 7.8 mg, yield 21%), bisphenol S (BPS) (yield 3.3 mg, yield 13%), and 4-((4-(4-((2-ethylhexyl)thio)phenyl)-sulfonyl)phenoxy)phenyl)sulfonyl)phenol (compound (b)) (yield 4.7 mg, yield 15%) were separated from the obtained crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0652] The obtained bis(4-(2-ethylhexylthio)phenyl)sulfone 1 H NMR and 13 The results of C NMR analysis were consistent with those in Example 1.

[0653] The NMR analysis results of other compounds obtained above are shown below.

[0654] Compound (a):

[0655] 1 H NMR(600MHz, CDCl3)δ0.88(t,J=7.0Hz,3H,methyl),0.89(t,J=7.5Hz,3H,methyl),1.25-1.29(m,4H,methylene),1.37-1.48(m,4H,methylene),1.61(sept,J=6.3H z,1H,methyne),2.92(d,J=6.2Hz,4H,SCH2),6.89(AA'BB',2H,aromatic),7.30(AA'BB',2H,aromatic),7.76(AA'BB',2H,aromatic),7.80(AA'BB',2H,aromatic).

[0656] 13 C NMR (151MHz, CDCl3) δ10.7,14.1,22.9,25.7,28.7,32.4,36.3,38.6,116.0,126.7,127.6,130.0,133.6,137.9,146.0,159.8.

[0657] Bisphenol S (BPS):

[0658] 1H NMR(600MHz,acetone-d6)δ6.97(AA'BB',4H,aromatic),7.77(AA'BB',4H,aromatic),9.44(br,2H,OH).

[0659] Compound (b):

[0660] 1 H NMR(600MHz,acetone-d6)δ0.87(t,J=7.1Hz,3H,methyl),0.91(t,J=7.5Hz,3H,methyl),1.27-1.33(m,4H,methylene ),1.40-1.51(m,4H,methylene),1.65(sept,J=6.2Hz,1H,methyne),3.07(d,J=6.3Hz,4H,SCH2),7.01(AA'BB',2H,aro matic),7.238(AA'BB',2H,aromatic),7.242(AA'BB',2H,aromatic),7.49(AA'BB',2H,aromatic),7.83(AA'BB',2H, aromatic),7.86(AA'BB',2H,aromatic),7.98(AA'BB',2H,aromatic),8.00(AA'BB',2H,aromatic),9.59(br,1H,OH).

[0661] 13 C NMR (151MHz, acetone-d6) δ11.0,14.3,23.6,26.3,29.4,33.1,36.5,39.4,117.0,120.5,120. 6,127.7,128.8,130.7,130.9,131.0,133.4,138.6,138.9,139.7,147.1,160.3,160.9,162.8.

[0662]

Chemical Formula 40

[0663]

[0664] (where n 401 is an integer (preferably 10 to 200).

[0665] <<Depolymerization of polyetherimide (depolymerization method (iii))>>

[0666] [Example 6]

[0667] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (Sigma-Aldrich, Cat. No. 79421) (13.2 μL, containing 0.0105 mmol of the phosphazene base P4-t-Bu, equivalent to 0.1 mmol of the general formula (3)) was added to yellow transparent granular polyetherimide (59.2 mg; the repeating unit in the general formula (3) is 0.1 mmol; manufactured by Sigma-Aldrich, Cat. No. 700193) in the form of 59.2 mg of ...) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 59.2 mg of yellow transparent granular polyetherimide) in the form of 11 mol% of the repeating unit in formula (3)), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in formula (3)), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (38.7 mg, 0.263 mmol, 2.6 times the molar amount (2.6 equivalents) relative to the repeating unit in formula (3), after the polyetherimide is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0668] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): compound (c) (equivalent to compound (38)) and bisphenol A (BPA, equivalent to compound (31)) were obtained quantitatively (yields exceeded 95%).

[0669] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0670] The target products: compound (c) (yield 49.2 mg, yield 75%) and bisphenol A (BPA) (yield 24.9 mg, yield over 99%) were separated from the obtained crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0671] The obtained bisphenol A 1 The analysis results of H NMR were consistent with those in Example 1.

[0672] Compound (c) 1 H NMR and 13 The results of C NMR analysis are shown below.

[0673] Compound (c):

[0674] 1H NMR(600MHz, CDCl3)δ0.90-0.95(m,12H,methyl),1.30-1.34(m,8H,methylene),1.43-1.53(m,8H ,methylene),1.68(sept,J=6.4Hz,2H,methyne),3.04(d,J=6.4Hz,4H,SCH2),7.52(dd,J=2.0,8. 0Hz,2H,aromatic),7.59(dd,J=1.7,7.9Hz,2H,aromatic),7.62-7.63(m,1H,aromatic),7.67(t, J=2.0Hz,1H,aromatic),7.76(d,J=1.3Hz,2H,aromatic),7.79(dd,J=0.26,7.9Hz,2H,aromatic).

[0675] 13 C NMR (151MHz, CDCl3) δ10.8,14.1,22.9,25.7,28.8,32.5,36.7,38.6,120.7,123.78,123.85,125.4,127.2,129.4,131.8,132.4(two signals),148.7,166.6,166.7.

[0676]

Chemical Formula 41

[0677]

[0678] (where n 301 is an integer (preferably 10 to 200).

[0679] <<Depolymerization of polyetheretherketone (depolymerization method (ii))>>

[0680] [Example 7]

[0681] Under an argon atmosphere, potassium tert-butoxide (KOt-Bu) (1.1 mg, 0.01 mmol; manufactured by Sigma-Aldrich, Cat. No. 156671-25G, 10 mol% relative to the repeating unit in the general formula (2)), 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL), and 2-ethylhexyl mercaptan (31 mg, 0.2 mmol, 2 times the molar amount (2 equivalents) relative to the repeating unit in the general formula (2)) were added in sequence to powdered polyetheretherketone (28.8 mg; the amount of the repeating unit in the general formula (2) is 0.1 mmol; weight average molecular weight 20800; number average molecular weight 10300; manufactured by Sigma-Aldrich, Cat. No. 456640). After the polyetheretherketone was dissolved, the resulting mixture was stirred at 150°C for 16 hours.

[0682] The reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 H NMR analysis was performed. Furthermore, the yields of the target product, bis(4-(2-ethylhexylthio)phenyl)methanone (BEHTPM, equivalent to compound (28)), hydroquinone (HQ, equivalent to compound (22)), and the intermediate compound (d) were calculated. The results are shown in Table 1.

[0683] The obtained hydroquinone 1 The results of H NMR analysis were consistent with those in Example 3.

[0684] The NMR analysis results of BEHTPM and compound (d) are shown below.

[0685] BEHTPM:

[0686] 1 H NMR(600MHz,CDCl3)δ0.89-0.93(m,12H,methyl),1.29-1.31(m,8H,methylene),1.39-1.53(m,8H,methylene),1.64(se pt,J=6.2Hz,2H,methyne),2.98(d,J=6.4Hz,4H,SCH2),7.30(d,8.4Hz,4H,aromatic),7.69(d,J=8.4Hz,4H,aromatic).

[0687] 13C NMR (151MHz, CDCl3) δ10.8,14.1,23.0,25.7,28.8,32.5,36.5,38.7,126.3,130.4,134.1,144.6,195.0.

[0688] Compound (d):

[0689] 1 H NMR(600MHz, CDCl3)δ0.89(t,J=7.0Hz,3H,methyl),0.91(t,J=7.5Hz,3H,methyl),1.30-1. 51(m,8H,methyl),1.64(sept,J=6.2Hz,1H,methyne),2.97(d,J=6.4Hz,2H,SCH2),4.80(s,1 H,OH),6.87(AA'BB',2H,aromatic),6.97(AA'BB',2H,aromatic),6.99(AA'BB',2H,aromatic),7.32(AA'BB',2H,aromatic),7.69(AA'BB',2H,aromatic),7.76(AA'BB',2H,aromatic).

[0690] In Table 1, "base (amount (mol%))" means, as described above, the percentage of the amount (molar number) of the base relative to the amount (molar number) of the repeating units in the general formula (2).

[0691] [Examples 8 to 13]

[0692] Depolymerization of polyetheretherketone was carried out according to the method of Example 7, except that the bases shown in Table 1 (0.01 mmol, 10 mol% relative to the repeating units in general formula (2)) were used instead of potassium tert-butoxide (0.01 mmol). Specifically, the bases used were potassium hydroxide (KOH) in Example 8, tripotassium phosphate (K3PO4) in Example 9, cesium carbonate (Cs2CO3) in Example 10, phosphazene base P4-t-Bu in Example 11, phosphazene base P2-t-Bu in Example 12, and phosphazene base P2-Et in Example 13. The results are shown in Table 1.

[0693] In Table 1, “phosphazene base P4-t-Bu” (Example 11), “phosphazene base P2-t-Bu” (Example 12), and “phosphazene base P2-Et” (Example 13) are abbreviated as “P4-t-Bu”, “P2-t-Bu”, and “P2-Et”, respectively.

[0694] [Example 14]

[0695] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that the amount of phosphazene base P4-t-Bu was adjusted from 0.01 mmol (10 mol % relative to the repeating unit in general formula (2)) to 0.005 mmol (5 mol % relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0696] [Example 15]

[0697] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that the amount of 2-ethylhexylmercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating unit in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0698] [Example 16]

[0699] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that not only the phosphazene base P4-t-Bu (0.01 mmol, 10 mol% relative to the repeating units in general formula (2)) but also tripotassium phosphate (K3PO4) (0.005 mmol, 5 mol% relative to the repeating units in general formula (2)) was used as the base; 1,3-dimethyl-2-imidazolidinone (0.2 mL) was replaced with N,N-dimethylacetamide (DMAc) (0.2 mL); and the amount of 2-ethylhexyl mercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating units in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating units in general formula (2)). The results are shown in Table 1.

[0700] [Example 17]

[0701] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that the reaction temperature during depolymerization was adjusted from 150°C to 120°C and the amount of 2-ethylhexylmercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating unit in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0702] [Example 18]

[0703] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that the reaction temperature during depolymerization was adjusted from 150°C to 100°C and the amount of 2-ethylhexylmercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating unit in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0704] [Example 19]

[0705] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that 1,3-dimethyl-2-imidazolidinone (0.2 mL) was replaced with pyrrolidone (C6H5CN) (0.2 mL) and the amount of 2-ethylhexylmercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating unit in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0706] [Example 20]

[0707] Depolymerization of polyetheretherketone was carried out according to the method of Example 11, except that 1,3-dimethyl-2-imidazolidinone (0.2 mL) was replaced with xylene (C6H4(CH3)2) (0.2 mL); and the amount of 2-ethylhexylmercaptan was adjusted from 0.2 mmol (2 times the molar amount (2 equivalents) relative to the repeating unit in general formula (2)) to 0.25 mmol (2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in general formula (2)). The results are shown in Table 1.

[0708] In addition, the NMR analysis results of the obtained BEHTPM, hydroquinone, and compound (d) in Examples 8 to 20 were consistent with those in Example 7.

[0709]

Chemical Formula 42

[0710]

[0711] (where n 201 is an integer (preferably 10 to 200).

[0712]

Table 1

[0713]

[0714] The above results indicate that BEHTPM and hydroquinone can be obtained in good yields even when the type of base is changed, for example, whether it is an organic base or an inorganic base.

[0715] Among them, when the phosphazene base P4-t-Bu (Examples 11, 14 to 16), the phosphazene base P2-t-Bu (Example 12), cesium carbonate (Example 10) or potassium tert-butoxide (Example 7) was used as the base, the yields of BEHTPM and hydroquinone were higher; and when the phosphazene base P4-t-Bu and tripotassium phosphate were used simultaneously as the base (Example 16), the yields of BEHTPM and hydroquinone were particularly significantly improved.

[0716] Comparison of Examples 15, 17, and 18 demonstrates that the higher the reaction temperature during depolymerization (e.g., 140-180° C.), the higher the yields of BEHTPM and hydroquinone.

[0717] Comparison of Examples 11 and 14 demonstrates that the greater the amount of base used (eg, 0.1 to 0.3 equivalents), the higher the yields of BEHTPM and hydroquinone.

[0718] Comparison of Examples 11 and 15 confirmed that the greater the amount of compound (8) used (eg, 2.2 to 4 equivalents, preferably 2.2 to 4 equivalents), the higher the yield of BEHTPM and hydroquinone.

[0719] Comparison of Examples 17, 19, and 20 demonstrates that the yields of BEHTPM and hydroquinone are improved by using 1,3-dimethyl-2-imidazolidinone as the solvent.

[0720] <<Depolymerization of polyetheretherketone (depolymerization method (ii))>>

[0721] [Example 21]

[0722] In the same manner as in Example 16, depolymerization of polyetheretherketone was carried out.

[0723] That is, under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 M of the phosphazene base P4-t-Bu) was added to a powdered polyetheretherketone (28.8 mg; the amount of the repeating unit in the general formula (2) is 0.1 mmol; the weight average molecular weight is 20800; the number average molecular weight is 10300; manufactured by Sigma-Aldrich, Cat. No. 456640) in the form of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421). mol, 10 mol% relative to the repeating unit in the general formula (2), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (2), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-ethylhexyl mercaptan (equivalent to compound (8)) (31 mg, 0.2 mmol, 2 times the molar amount (2 equivalents) relative to the repeating unit in the general formula (2)), after the polyetheretherketone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0724] The resulting yellow reaction mixture was then cooled to at least room temperature and distilled under reduced pressure to obtain a crude product.

[0725] The target products: bis(4-(2-ethylhexylthio)phenyl)methanone (BEHTPM) (yield 39.9 mg, yield 85%) and hydroquinone (HQ) (yield 6.6 mg, yield 61%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0726] The NMR analysis results of the obtained BEHTPM and hydroquinone were consistent with those in Example 7.

[0727]

Chemical Formula 43

[0728]

[0729] (where n 201 is an integer (preferably 10 to 200).

[0730] <<Depolymerization of Carbon Fiber Reinforced Polyetheretherketone (Depolymerization Method (ii))>>

[0731] [Example 22]

[0732] Carbon fiber reinforced polyetheretherketone (TECAPEEK CF30, Cat. No. 3-3094-02 manufactured by Ensinger) was prepared. The content of polyetheretherketone in the carbon fiber reinforced polyetheretherketone accounted for 70% by mass of the total mass of the carbon fiber reinforced polyetheretherketone.

[0733] The carbon fiber reinforced polyetheretherketone is processed into a powder.

[0734] Except for replacing the powdered polyetheretherketone (the repeating unit in the general formula (2) was 0.1 mmol) with the powdered carbon fiber-reinforced polyetheretherketone (the repeating unit in the general formula (2) was 0.1 mmol), the remaining operations were carried out according to the method of Example 21 to depolymerize the polyetheretherketone and isolate the target product. As a result, the target products: bis(4-(2-ethylhexylthio)phenyl)methanone (BEHTPM) (yield 86%) and hydroquinone (HQ) (yield 70%) were obtained.

[0735] The NMR analysis results of the obtained BEHTPM and hydroquinone were consistent with those in Example 7.

[0736] <<Depolymerization of glass fiber reinforced polyetheretherketone (depolymerization method (ii))>>

[0737] [Example 23]

[0738] Glass fiber reinforced polyetheretherketone (TECAPEEK GF30, Cat. No. 3-3095-01 manufactured by Ensinger) was prepared. The content of polyetheretherketone in the glass fiber reinforced polyetheretherketone was 30% by mass of the total mass of the glass fiber reinforced polyetheretherketone.

[0739] The glass fiber reinforced polyetheretherketone is processed into powder.

[0740] Depolymerization of polyetheretherketone and isolation of the target product were carried out according to the method of Example 21, except that the powdered polyetheretherketone (the repeating unit in the general formula (2) was 0.1 mmol) was replaced with the powdered glass fiber-reinforced polyetheretherketone (the repeating unit in the general formula (2) was 0.1 mmol). The target products, bis(4-(2-ethylhexylthio)phenyl)methanone (BEHTPM) (yield 76%) and hydroquinone (HQ) (yield 33%), were obtained.

[0741] The NMR analysis results of the obtained BEHTPM and hydroquinone were consistent with those in Example 7.

[0742] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0743] [Example 24]

[0744] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (12.6 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu relative to the phosphazene base) was added sequentially to colorless, transparent granular polysulfone (44.6 mg; the amount of the repeating unit in the general formula (1) is 0.100 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). The following were prepared: polysulfone (10 mol %), potassium phosphate (K 3 PO 4 ) (1.1 mg, 0.005 mmol, 5 mol % relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), and 2-phenylethanethiol (also known as 2-ethanethiol, equivalent to compound (8)) (35.0 mg, 0.253 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)). After the polysulfone was dissolved, the resulting mixture was stirred at 100° C. for 64 hours.

[0745] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform.1 HNMR analysis confirmed that the target products (depolymerization products): bis[4-(2-phenylethylthio)phenyl]sulfone (BPETPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained.

[0746] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0747] The target products bis(4-(2-phenylethylthio)phenyl)sulfone (BPETPS) (yield 46.9 mg, yield 95%) and bisphenol A (BPA) (yield 24.7 mg, yield 95%) were separated from the obtained crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0748] The resulting BPETPS 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis showed the same results as in Example 1.

[0749] BPETPS:

[0750] 1 H NMR(600MHz, CDCl3) δ2.96(t,J=7.9Hz,4H,methyne),3.22(d,J=7.9Hz,4H,SCH2),7.20(d,J=7.0Hz,4H ,aromatic),7.22-7.24(m,2H,aromatic),7.30-7.33(m,8H,aromatic),7.79(AA'BB',4H,aromatic).

[0751] 13 C NMR (151MHz, CDCl3) δ33.5,35.0,1268,126.9,127.9,128.5,128.7,138.0,139.4,145.0.

[0752]

Chemical Formula 44

[0753]

[0754] (where n 101 is an integer (preferably 10 to 200).

[0755] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0756] [Example 25]

[0757] Under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 mM of the phosphazene base P4-t-Bu) was added to a colorless, transparent granular polysulfone (44.3 mg; the amount of the repeating unit in the general formula (1) is 0.10 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). ol, 10 mol% relative to the repeating unit in the general formula (1), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1), N,N-dimethylacetamide (DMAc) (0.2 mL), 2-mercaptoethanol (equivalent to compound (8)) (19.6 mg, 0.25 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)), after the polysulfone is dissolved, the resulting mixture is stirred at 100°C for 64 hours.

[0758] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): bis[4-(2-hydroxyethylthio)phenyl]sulfone (BHETPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained.

[0759] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0760] The target products: bis(4-(2-hydroxyethylthio)phenyl)sulfone (BHETPS) (yield 29.1 mg, yield 79%) and bisphenol A (BPA) (yield 17.0 mg, yield 71%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0761] The resulting BPETPS 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis showed the same results as in Example 1.

[0762] BHETPS:

[0763] 1 H NMR (600MHz, CDCl3) δ3.21 (t, J = 6.6Hz, 4H, SCH2), 3.76-3.78 (m, 4H, HOCH2), 4.12 (br, 2H, OH), 7.50 (AA'BB', 4H, aromatic), 7.84 (AA'BB', 4H, aromatic). 13 C NMR (151MHz, CDCl3) δ35.0, 61.1, 127.7, 128.7, 139.2, 146.3.

[0764]

Chemical Formula 45

[0765]

[0766] (where n 101 is an integer (preferably 10 to 200).

[0767] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0768] [Example 26]

[0769] Under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu, relative to the phosphazene base P4-t-Bu) was added to a colorless, transparent granular polysulfone (44.5 mg; the amount of the repeating unit in the general formula (1) is 0.101 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). For the repeating unit in the general formula (1), 10 mol%), tripotassium phosphate (K3PO4) (1.3 mg, 0.006 mmol, 5 mol%) relative to the repeating unit in the general formula (1), N,N-dimethylacetamide (DMAc) (0.2 mL), 3-(triethoxysilyl)propanethiol (equivalent to compound (8)) (59.4 mg, 0.25 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1), after the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0770] The resulting orange reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1HNMR analysis confirmed that the target products (depolymerization products): bis[4-(3-(triethoxysilyl)propylthio)phenyl]sulfone (BTEOSPTPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained.

[0771] Use the above for 1 The sample for H NMR analysis was returned to the orange reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0772] The target products: bis(4-(3-(triethoxysilyl)propylthio)phenyl)sulfone (BTEOSPTPS) (yield 18.5 mg, yield 26%) and bisphenol A (BPA) (yield 24.9 mg, yield 99%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0773] The obtained BTEOSPTPS 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis showed the same results as in Example 1.

[0774] BPETPS:

[0775] 1 H NMR(600MHz, CDCl3)δ0.75-80(m,4H,methylene),1.19(t,J=7.0Hz,18H,methyl),1.79(tt,J=7.7Hz,4H,methylene) ,2.99(t,J=7.5Hz,4H,SCH2),3.79(q,J=7.0Hz,4H,OCH2),7.30(AA'BB',4H,aromatic),7.76(AA'BB',4H,aromatic). 13 C NMR (151MHz, CDCl3) δ9.93,18.3,22.4,34.6,58.5,126.7,127.8,137.7,145.5.

[0776]

Chemical Formula 46

[0777]

[0778] (where n 101 is an integer (preferably 10 to 200).

[0779] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0780] [Example 27]

[0781] Under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 M of the phosphazene base P4-t-Bu) was added to a colorless, transparent granular polysulfone (44.1 mg; the amount of the repeating unit in the general formula (1) is 0.100 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). mol, 10 mol% relative to the repeating unit in the general formula (1), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1), N,N-dimethylacetamide (DMAc) (0.2 mL), cyclopentanethiol (equivalent to compound (8)) (25.4 mg, 0.25 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)), after the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 16 hours.

[0782] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): bis(4-(cyclopentylthio)phenyl)sulfone (BcyPenTPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained.

[0783] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0784] The target products: bis(4-(cyclopentylthio)phenyl)sulfone (BcyPenTPS) (yield 39.3 mg, yield 94%) and bisphenol A (BPA) (yield 26.3 mg, yield 99%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0785] The income of BcyPenTPS 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis showed the same results as in Example 1.

[0786] BPETPS:

[0787] 1 H NMR(600MHz,CDCl3)δ1.59-1.67(m,8H,methylene),1.75-1.81(m,4H,methylene),2.09-2.16(m,4 H,methylene),3.65-3.70(m,2H,SCH),7.32(AA'BB',4H,aromatic),7.77(AA'BB',4H,aromatic). 13 C NMR (151MHz, CDCl3) δ24.9,33.4,44.1,127.2,127.7,137.6,146.2.

Chemical Formula 47

[0788]

[0789] (where n 101 is an integer (preferably 10 to 200).

[0790] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0791] [Example 28]

[0792] Under an argon atmosphere, a 0.8 M n-hexane solution (12.5 μL, containing 0.01 mM of the phosphazene base P4-t-Bu) was added to a colorless, transparent granular polysulfone (44.1 mg; the amount of the repeating unit in the general formula (1) is 0.100 mmol; the weight average molecular weight is 35,000; the number average molecular weight is 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). ol, 10 mol% relative to the repeating unit in the general formula (1), tripotassium phosphate (K3PO4) (1.1 mg, 0.005 mmol, 5 mol% relative to the repeating unit in the general formula (1), N,N-dimethylacetamide (DMAc) (0.2 mL), trimethylsilyl mercaptan (equivalent to compound (8)) (30.2 mg, 0.25 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)), after the polysulfone is dissolved, the resulting mixture is stirred at 150°C for 64 hours.

[0793] The brown reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the obtained product was taken as a sample and dissolved in deuterated chloroform.1 HNMR analysis confirmed that depolymerization products, bis(4-methylthiophenyl)sulfone (BMTPS, corresponding to compound (18)) and bisphenol A (BPA, corresponding to compound (121)), were obtained.

[0794] Use the above for 1 The sample for H NMR analysis was returned to the brown reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0795] Bis(4-methylthiophenyl)sulfone (BMTPS) (yield 23.0 mg, yield 74%) and bisphenol A (BPA) (yield 23.3 mg, yield over 99%) were separated from the obtained crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0796] The resulting BMTPS 1 H NMR and bisphenol A were performed 1 H NMR analysis showed the same results as in Comparative Example 1.

[0797]

Chemical Formula 48

[0798]

[0799] (where n 101 is an integer (preferably 10 to 200).

[0800] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0801] [Example 29]

[0802] Under an argon atmosphere, sodium tert-butoxide (2.0 mg, 0.02 mmol, 20 mol% relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.2 mL), and 4-tert-butylthiophenol (also known as 4-tert-butylbenzenethiol) (41.4 mg, 0.25 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)) were added in sequence to colorless, transparent granular polysulfone (44.3 mg; 0.100 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). After the polysulfone was dissolved, the resulting mixture was stirred at 150°C for 16 hours.

[0803] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the target products (depolymerization products): bis(4-(4-tert-butylphenylthio)phenyl)sulfone (BBPTPS, equivalent to compound (18)) and bisphenol A (BPA, equivalent to compound (121)) were obtained.

[0804] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0805] The target products: bis(4-(4-tert-butylphenylthio)phenyl)sulfone (BBPTPS) (yield 53.8 mg, yield 98%) and bisphenol A (BPA) (yield 23.2 mg, yield over 99%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0806] The resulting BBPTPS 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis obtained the same results as in Example 1.

[0807] BBPTPS:

[0808] 1 H NMR (600MHz, CDCl3) δ1.34(s,18H,tBu),7.19(AA'BB',4H,aromatic),7.42-7.46(m,8H,aromatic),7.64(AA'BB',4H,aromatic). 13 C NMR (151MHz, CDCl3) δ31.3,34.8,126.7,126.8,128.1,130.6,134.0,134.5,144.9,152.4,194.9.

[0809]

Chemical Formula 49

[0810]

[0811] (where n 101 is an integer (preferably 10 to 200).

[0812] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0813] [Example 30]

[0814] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (12.5 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu relative to the general formula (1)) was added to a powdered polyetheretherketone (29.0 mg; the amount of the repeating unit in the general formula (2) is 0.1 mmol; the weight average molecular weight is 20800; the number average molecular weight is 10300; manufactured by Sigma-Aldrich, Cat. No. 456640) in argon atmosphere. The polysulfone was dissolved in 150 ° C. and the resulting mixture was stirred for 109 hours.

[0815] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1 HNMR analysis confirmed that the depolymerization products, bis(4-(4-tert-butylphenylthio)phenyl)ketone (BBPTPK, equivalent to compound (18)) and hydroquinone (HQ, equivalent to compound (121), yield 75%), were obtained.

[0816] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0817] The target product, bis(4-(4-tert-butylphenylthio)phenyl)ketone (BBPTPK) (yield 44.1 mg, 86%), was separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0818] The resulting BBPTPK 1 H NMR and 13 The results of C NMR analysis are shown below. 1 H NMR analysis showed the same results as those in Comparative Example 7.

[0819] BMTPK:

[0820] 1 H NMR (600MHz, CDCl3) δ1.34(s,18H,tBu),7.19(AA'BB',4H,aromatic),7.42-7.46(m,8H,aromatic),7.64(AA'BB',4H,aromatic). 13 C NMR (151MHz, CDCl3) δ31.3,34.8,126.7,126.8,128.1,130.6,134.0,134.5,144.9,152.4,194.9.

Chemical Formula 50

[0821]

[0822] (where n 201 is an integer (preferably 10 to 200).

[0823] <<Depolymerization of polysulfone (depolymerization method (i))>>

[0824] [Example 31]

[0825] A polyphenylsulfone (PPSU) baby bottle (manufactured by ChuChu Co., Ltd.) was cut into 5 mm square pieces.

[0826] Under an argon atmosphere, a 0.8 M n-hexane solution of a phosphazene base P4-t-Bu (manufactured by Sigma-Aldrich, Cat. No. 79421) (25.0 μL, containing 0.01 mmol of the phosphazene base P4-t-Bu, representing 10 mol% relative to the repeating unit in the general formula (1)), triphosphate, and the like were added to the pale yellow polyphenylsulfone (81.4 mg; the amount of the repeating unit in the general formula (1) was 0.2 mmol) obtained above. Potassium (K3PO4) (2.1 mg, 0.001 mmol, 5 mol% relative to the repeating unit in the general formula (1)), N,N-dimethylacetamide (DMAc) (0.4 mL), 2-ethylhexyl mercaptan (equivalent to compound (8)) (72.5 mg, 0.50 mmol, 2.5 times the molar amount (2.5 equivalents) relative to the repeating unit in the general formula (1)), after the polyphenylsulfone is dissolved, the resulting mixture is stirred at 150°C for 20 hours.

[0827] The yellow reaction mixture was cooled to room temperature, 1,4-dioxane (5.2 mg, 5.0 μL, 0.059 mmol) was added as an internal standard, and a small amount of the resulting mixture was taken as a sample and dissolved in deuterated chloroform. 1HNMR analysis confirmed the formation of the target products (depolymerization products): bis[4-(2-ethylhexylthio)phenyl]sulfone (BEHTPS, equivalent to compound (18)) and 4,4'-dihydroxybiphenyl (4,4'-DHBP, equivalent to compound (123)).

[0828] Use the above for 1 The sample for H NMR analysis was returned to the yellow reaction mixture and the crude product was obtained by distillation under reduced pressure.

[0829] The target products: bis(4-(2-ethylhexylthio)phenyl)sulfone (BEHTPS) (yield 87 mg, yield 84%) and 4,4'-dihydroxybiphenyl (4,4'-DHBP) (yield 34 mg, yield 91%) were separated from the crude product by silica gel column chromatography (eluent: n-hexane / ethyl acetate 96 / 4→70 / 30).

[0830] The obtained bis(4-(2-ethylhexylthio)phenyl)sulfone 1 H NMR and 13 The results of C NMR analysis were consistent with those in Example 1.

[0831] The obtained 4,4'-dihydroxybiphenyl 1 The results of H NMR analysis were consistent with those of Example 4.

[0832]

Chemical Formula 51

[0833]

[0834] (where n 104 is an integer (preferably 10 to 200).

[0835] (Implementation Method 2)

[0836] The following describes the second embodiment of the present invention. However, even if the same terms as those in the above embodiment are used, they may have different meanings. In addition, Examples 1 to 23 described below are different from those in the above embodiment 1.

[0837] ◎Compound depolymerization method

[0838] <<Depolymerization method (1)>>

[0839] A compound depolymerization method (decomposition method) according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[0840] The following general formula (1)

[0841]

Chemical Formula 52

[0842]

[0843] (wherein n1 is an integer greater than 2 (preferably 10 to 200); Z 11 and Z 12 Each independently is a non-hydrogen atom group; m 11 and m 12 Each independently represents an integer from 0 to 4. 11 When n1×m is an integer greater than 1, 11 Z 11 Can be the same or different, when m 12 When n1×m is an integer greater than 1, 12 Z 12 Can be the same or different; Ar 1 The following general formula (91), (92) or (93)

[0844]

Chemical Formula 53

[0845]

[0846] (Where, X 11 、X 12 、X 21 、X 31 and X 32 Each independently is a non-hydrogen atom group; 11 、l 12 、l 21 、l 31 and l 32 Each independently represents an integer from 0 to 4. 11 When n1×l is an integer greater than 1, 11 X 11 Can be the same or different, when l 12 When n1×l is an integer greater than 1, 12 X 12 Can be the same or different, when l 21 When n1×l is an integer greater than 1, 21 X 21 Can be the same or different, when l 31 When n1×l is an integer greater than 1, 31 X 31 Can be the same or different, when l 32 When n1×l is an integer greater than 1, 32 X 32The compound (compound (1)) represented by the general formula (91), (92) and (93) is depolymerized in the presence of a hydroxide to obtain the following general formula (11):

[0847]

Chemical Formula 54

[0848]

[0849] (Where Z 11 、Z 12 、m 11 and m 12 Same as above)

[0850] The compound represented by (sometimes referred to as "compound (11)" in this specification) or a salt thereof, and the following general formula (121), (122) or (123)

[0851]

Chemical Formula 55

[0852]

[0853] (Where, X 11 、X 12 、X 21 、X 31 、X 32 、l 11 、l 12 、l 21 、l 31 and l 32 Same as above)

[0854] The compound represented by (in this specification, it may be referred to as "Compound (121)", "Compound (122)", "Compound (123)" respectively) or a salt thereof. In this specification, the compound depolymerization method of this embodiment may be referred to as "depolymerization method (1)".

[0855] The depolymerization method (depolymerization method (1)) of the present embodiment is a novel depolymerization method (decomposition method) for the compound (1) containing super engineering plastics.

[0856] When the Ar 1 When the group is represented by the general formula (91), the compound (1) includes polysulfone (sometimes referred to as "PSU" in this specification) and its derivatives.

[0857] When the Ar 1When the group is represented by the general formula (92), the compound (1) includes polyetherethersulfone (sometimes referred to as "PEES" in this specification) and its derivatives.

[0858] When the Ar 1 When the group is represented by the general formula (93), the compound (1) includes polyphenylsulfone (sometimes referred to as "PPSU" in this specification) and its derivatives.

[0859] In this specification, when a specific compound has a structure in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom, the compound having such a substituted structure is referred to as a "derivative" of the specific compound.

[0860] In this specification, unless otherwise specified, a "group" refers not only to an atomic group composed of a plurality of atoms bonded together but also includes a single atom.

[0861] When Ar 1 When the group is represented by the general formula (91), the depolymerization method (1) includes a depolymerization step (decomposition step):

[0862] The following general formula (1-1)

[0863]

Chemical Formula 56

[0864]

[0865] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 11 、X 12 、l 11 and l 12 Same as above)

[0866] The compound represented by is depolymerized in the presence of a hydroxide to obtain the following general formula (11):

[0867]

Chemical Formula 57

[0868]

[0869] (Where Z 11 、Z 12 、m 11 and m 12 Same as above)

[0870] The compound represented by (compound (11)) or a salt thereof, and the following general formula (121)

[0871]

Chemical Formula 58

[0872]

[0873] (Where, X 11 、X 12 、l 11 and l 12 Same as above)

[0874] The compound represented by (compound (121)) or a salt thereof.

[0875] When Ar 1 When the group is represented by the general formula (92), the depolymerization method (1) includes a depolymerization step (decomposition step):

[0876] The following general formula (1-2)

[0877]

Chemical Formula 59

[0878]

[0879] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 21 and l 21 Same as above)

[0880] The compound represented by is depolymerized in the presence of a hydroxide to obtain the following general formula (11):

[0881]

Chemical Formula 60

[0882]

[0883] (Where Z 11 、Z 12 、m 11 and m 12 Same as above)

[0884] The compound represented by (compound (11)) or a salt thereof, and the following general formula (122)

[0885]

Chemical Formula 61

[0886]

[0887] (Where, X 21 and l 21 Same as above)

[0888] The compound represented by (compound (122)) or a salt thereof.

[0889] When Ar 1When the group is represented by the general formula (93), the depolymerization method (1) includes a depolymerization step (decomposition step):

[0890] The following general formula (1-3)

[0891]

Chemical Formula 62

[0892]

[0893] (where n1, Z 11 、Z 12 、m 11 、m 12 、X 31 、X 32 、l 31 and l 32 Same as above)

[0894] The compound represented by is depolymerized in the presence of a hydroxide to obtain the following general formula (11):

[0895]

Chemical Formula 63

[0896]

[0897] (Where Z 11 、Z 12 、m 11 and m 12 Same as above)

[0898] The compound represented by (compound (11)) or a salt thereof, and the following general formula (123)

[0899]

Chemical Formula 64

[0900]

[0901] (Where, X 31 、X 32 、l 31 and l 32 Same as above)

[0902] The compound represented by (compound (123)) or a salt thereof.

[0903] <Compound (1)>

[0904] Compound (1) is the target of depolymerization in the depolymerization method (1).

[0905] In the general formula (1), n1 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (1), and is an integer of 2 or greater.

[0906] For example, compound (1) with n1 of 35 to 150 is suitable for high molecular weight super engineering plastics polysulfone (PSU), polyetherethersulfone (PEES) or polyphenylsulfone (PPSU), which are difficult to depolymerize using traditional methods and are particularly suitable as application objects of depolymerization method (1).

[0907] In the general formula (1), Z 11 and Z 12 Each is independently a non-hydrogen atom group (sometimes referred to as a "substituent" in this specification). 11 and Z 12 It can be the same or different.

[0908] As Z 11 and Z 12 (Substituent) includes, for example, an alkyl group, an alkylcarbonylamino group, a fluoroalkyl group, a fluorine atom, and the like.

[0909] Z 11 and Z 12 The alkyl group in the formula (I) may be linear, branched, or cyclic, and may also have both a linear structure (linear or branched) and a cyclic structure. In this specification, an alkyl group having a cyclic structure is referred to as a cyclic alkyl group regardless of whether it contains other linear structures. The cyclic structure in a cyclic alkyl group (an alkyl group having a cyclic structure but no linear structure, and an alkyl group having both a cyclic structure and a linear structure) may be monocyclic or polycyclic.

[0910] Z 11 and Z 12 The alkyl group in the group preferably has 1 to 15 carbon atoms.

[0911] In Z 11 and Z 12 Examples of the chain (straight or branched) alkyl group include chain alkyl groups having 1 to 15 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.

[0912] In Z 11 and Z 12Among the alkyl groups in, examples of cyclic alkyl groups (alkyl groups having a monocyclic or polycyclic structure) include cyclic alkyl groups having 3 to 15 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, and cyclopropylmethyl.

[0913] Z 11 and Z 12 The alkyl group in the formula (I) may be, for example, an alkyl group having 1 to 10 carbon atoms (a chain alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), an alkyl group having 1 to 8 carbon atoms (a chain alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a chain alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), or any one of an alkyl group having 1 to 3 carbon atoms.

[0914] As Z 11 and Z 12 The alkylcarbonylamino group (formula "-NH-C(=O)-R 01 (Where R 01 is an alkyl group), for example, a monovalent group having the following structure can be mentioned: 11 and Z 12 The carbon atom having a free valence bond of the alkyl group is bonded to the carbon atom in the carbonylamino group (-NH-C(=O)-).

[0915] Examples of the alkylcarbonylamino group include methylcarbonylamino (—NH—C(═O)—CH 3 ) and the like, but are not limited thereto.

[0916] Z 11 and Z 12 The alkylcarbonylamino group preferably has 2 to 16 carbon atoms.

[0917] As Z 11 and Z 12 The fluorinated alkyl group in the embodiment may be, for example, a monovalent group having the following structure: 11 and Z 12 wherein one or more hydrogen atoms (—H) of the alkyl group are replaced by fluorine atoms (—F).

[0918] The number of fluorine atoms in the fluorinated alkyl group depends on the number of carbon atoms in the fluorinated alkyl group and is not particularly limited, and can be, for example, 1 to 3. The fluorinated alkyl group can be, for example, a perfluoroalkyl group (a monovalent group having a structure in which all hydrogen atoms in the alkyl group are replaced by fluorine atoms) such as a trifluoromethyl group.

[0919] Z 11and Z 12 The fluorinated alkyl group preferably has 1 to 15 carbon atoms.

[0920] In the general formula (1), m 11 Represents Z bonded to a benzene ring skeleton 11 The number of m 12 Indicates that Z 11 Z bonded to another benzene ring skeleton with a different bond 12 The number of m 11 and m 12 are each independently an integer from 0 to 4. 11 and m 12 It can be the same or different.

[0921] Compound (1) contains n1×m 11 Z 11 , when m 11 When n1×m is an integer greater than 1 (ie, an integer from 1 to 4), 11 Z 11 can be the same or different. That is, m 11 When n1×m is an integer greater than 1, 11 Z 11 They may be all the same, all different, or partially the same.

[0922] Z 12 Likewise, compound (1) contains n1×m 12 Z 12 , m 12 When n1×m is an integer greater than 1 (ie, an integer from 1 to 4), 12 Z 12 can be the same or different. That is, m 12 When n1×m is an integer greater than 1, 12 Z 12 They may be all the same, all different, or partially the same.

[0923] In the general formula (1), Ar 1 It is a group represented by the general formula (91), a group represented by the general formula (92), or a group represented by the general formula (93).

[0924] In these groups, the bond marked with the symbol * forms a covalent bond with an oxygen atom not bonded to the sulfur atom (S) in the general formula (1), and the bond marked with the symbol ** forms a covalent bond with another oxygen atom not bonded to the sulfur atom in the general formula (1).

[0925] In the general formula (91), X 11 and X12 Each independently is a non-hydrogen atom group (substituent). 11 and X 12 It can be the same or different.

[0926] As X 11 and X 12 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0927] In the general formula (91), 11 represents X bonded to a benzene ring skeleton 11 The number of. 12 Indicates that X 11 X bonded to another benzene ring skeleton with a different bond 12 The number of. 11 and l 12 are each independently an integer from 0 to 4. 11 and l 12 It can be the same or different.

[0928] Compound (1) contains n1×l in one molecule 11 X 11 , when l 11 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 11 X 11 Can be the same or different. That is, when l 11 When n1×l is an integer greater than 1, 11 X 11 They may be all the same, all different, or partially the same.

[0929] X 12 Likewise, compound (1) contains n1×l in one molecule. 12 X 12 , when l 12 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 12 X 12 Can be the same or different. That is, when l 12 When n1×l is an integer greater than 1, 12 X 12 They may be all the same, all different, or partially the same.

[0930] In the general formula (91), 11 and l 12For example, each independently may be 0 to 3, 0 to 2, 0 to 1 or 0.

[0931] Preferred examples of the group represented by the general formula (91) include: 11 and l 12 All are 0 (that is, without X 11 and X 12 ) group.

[0932] In the general formula (92), X 21 A non-hydrogen atom group (substituent).

[0933] As X 21 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0934] In the general formula (92), 21 represents X bonded to a benzene ring skeleton 21 The number is an integer from 0 to 4.

[0935] Compound (1) contains n1×l in one molecule 21 X 21 , when l 21 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 21 X 21 Can be the same or different. That is, when l 21 When n1×l is an integer greater than 1, 21 X 21 They may be all the same, all different, or partially the same.

[0936] In the general formula (92), 21 For example, it may be 0-3, 0-2, 0-1 or 0.

[0937] Preferred examples of the group represented by the general formula (92) include: 21 is 0 (i.e., does not contain X 21 ) group.

[0938] In the general formula (93), X 31 and X 32 Each independently is a non-hydrogen atom group (substituent). 31 and X 32 It can be the same or different.

[0939] As X 31 and X 32 (Substituent), for example, the same as the above Z11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[0940] In the general formula (93), 31 represents X bonded to a benzene ring skeleton 31 The number of. 32 Indicates that X 31 X bonded to another benzene ring skeleton with a different bond 32 The number of. 31 and l 32 are each independently an integer from 0 to 4. 31 and l 32 It can be the same or different.

[0941] Compound (1) contains n1×l in one molecule 31 X 31 , when l 31 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 31 X 31 Can be the same or different. That is, when l 31 When n1×l is an integer greater than 1, 31 X 31 They may be all the same, all different, or partially the same.

[0942] X 32 Likewise, compound (1) contains n1×l in one molecule. 32 X 32 , when l 32 When n1×l is an integer greater than 1 (i.e., an integer from 1 to 4), 32 X 32 Can be the same or different. That is, when l 32 When n1×l is an integer greater than 1, 32 X 32 They may be all the same, all different, or partially the same.

[0943] In the general formula (93), 31 and l 32 For example, each independently may be 0 to 3, 0 to 2, 0 to 1 or 0.

[0944] Preferred examples of the group represented by the general formula (93) include: 31 and l 32 All are 0 (that is, without X 31 and X 32 ) group.

[0945] As an example of a preferred compound (1), there can be mentioned any of Ar 1 is a group represented by the general formula (91), a group represented by the general formula (92), or a group represented by the general formula (93), m 11 and m 12 All are 0 (that is, without Z 11 and Z 12 ) of compound (1).

[0946] As an example of a more preferred compound (1), Ar 1 is a group represented by the general formula (91), and 11 and l 12 is 0, m 11 and m 12 The compound (1) is 0.

[0947] As another example of a more preferred compound (1), Ar 1 is a group represented by the general formula (92), and 21 is 0, m 11 and m 12 The compound (1) is 0.

[0948] As another example of a more preferred compound (1), Ar 1 is a group represented by the general formula (93), and 31 and l 32 is 0, m 11 and m 12 The compound (1) is 0.

[0949] However, the compound (1) is not limited to these examples.

[0950] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a terminal or dual terminal hydroxyl group in the general formula (1)) in compound (1) may be substituted with a non-hydrogen group (M) to form a group represented by the formula "-OM", as in the case of compound (11) described later. That is, compound (1) may be a salt.

[0951] <Compound (11)>

[0952] Compound (11) is a product obtained by the depolymerization method (1).

[0953] Compound (11) is bisphenol S (sometimes referred to as "BPS" in this specification) and its derivatives.

[0954] Z in the general formula (11) 11 、Z 12 、m 11and m 12 Respectively with Z in the general formula (1) 11 、Z 12 、m 11 and m 12 same.

[0955] <Compound (121)>

[0956] Compound (121) is when Ar 1 When it is a group represented by the general formula (91), it is another product obtained by the depolymerization method (1).

[0957] Compound (121) is bisphenol A (sometimes referred to as "BPA" in this specification) and its derivatives.

[0958] X in the general formula (121) 11 、X 12 、l 11 and l 12 Respectively with X in general formula (91) 11 、X 12 、l 11 and l 12 same.

[0959] <Compound (122)>

[0960] Compound (122) is when Ar 1 When it is a group represented by the general formula (92), it is another product obtained by the depolymerization method (1).

[0961] Compound (122) is hydroquinone and its derivatives.

[0962] X in the general formula (122) 21 and l 21 Respectively with X in general formula (92) 21 and l 21 same.

[0963] <Compound (123)>

[0964] Compound (123) is when Ar 1 When it is a group represented by the general formula (93), it is another product obtained by the depolymerization method (1).

[0965] Compound (123) is 4,4'-biphenol (also known as 4,4'-dihydroxybiphenyl) and its derivatives.

[0966] X in the general formula (123) 31 、X 32 、l 31 and l 32 Respectively with X in general formula (93)31 、X 32 、l 31 and l 32 same.

[0967] <Salt of Compound (11), Salt of Compound (121), Salt of Compound (122), Salt of Compound (123)>

[0968] The salt of compound (11) refers to a compound in which the hydrogen atoms on one (1) or two (2) hydroxyl groups (-OH) in compound (11) are replaced by non-hydrogen groups (hereinafter represented by the symbol "M") to form a group represented by the formula "-OM". The formula "-OM" can also be represented by the formula "- - M + ”.

[0969] When the hydrogen atoms of the two hydroxyl groups in compound (11) are both substituted by M, the two M's may be the same or different.

[0970] Whether or not the hydrogen atom is substituted by M, and if substitution occurs, the type of M, can be determined, for example, by the post-treatment conditions of the reaction solution obtained after depolymerization of compound (1). For example, if the reaction solution is treated with an acid after depolymerization of compound (1), compound (11) may be obtained as the main component, rather than a salt of compound (11).

[0971] Examples of M include substances derived from hydroxides (substances serving as counter cations) described later, and are preferably metal atoms (the salt of compound (11) is an alkoxide).

[0972] The manner in which compound (121), compound (122), and compound (123) form salts is the same as the manner in which compound (11) forms salts. That is, the salts of compound (121), compound (122), and compound (123) are formed in the same manner as the salt of compound (11), and are identical to the salt of compound (11) except for the difference in the group to which the group represented by the formula "-OM" is bonded.

[0973] Hydroxide

[0974] The hydroxide refers to a compound containing hydroxide ions (OH - ) compound (a compound that can generate hydroxide ions when dissolved in water), the specific type of which is not particularly limited, and can be either an organic hydroxide or an inorganic hydroxide.

[0975] Examples of the organic hydroxide include compounds such as ammonium hydroxide salts and phosphonium hydroxide salts.

[0976] Examples of the ammonium hydroxide salt include tetraalkylammonium hydroxide compounds such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide.

[0977] Examples of the phosphonium hydroxide salt include tetraalkylphosphonium hydroxide compounds such as tetrabutylphosphonium hydroxide.

[0978] Examples of the inorganic hydroxide include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide monohydrate, hydrates of cesium hydroxide other than monohydrate, and anhydrous cesium hydroxide.

[0979] The aforementioned cesium hydroxide hydrates other than monohydrate refer to cesium hydroxide hydrates containing two or more water molecules in one molecule (eg, cesium hydroxide dihydrate).

[0980] The hydroxide used in the depolymerization step is preferably an alkali metal hydroxide.

[0981] In the depolymerization step, it is preferred to use a hydroxide that has been subjected to a reduced pressure heating and drying treatment. In this manner, the effect obtained by using the hydroxide is significantly enhanced, and the depolymerization of compound (1) is facilitated. This is presumably because the presence of water hinders the depolymerization of compound (1), and the reduced pressure heating and drying treatment can reduce the water content.

[0982] The hydroxide is preferably heated and dried under a pressure of 1333.22 Pa (10 mmHg) or less, more preferably under a pressure of 666.61 Pa (5 mmHg) or less, and even more preferably under a pressure of 399.966 Pa (3 mmHg) or less. By controlling the pressure during decompression to be below the upper limit, the degree of drying of the hydroxide can be further improved.

[0983] On the other hand, the hydroxide is preferably dried by heating under a pressure condition of 133.322 Pa (1 mmHg) or higher, as the reduced pressure is easier to achieve.

[0984] The drying temperature (heating temperature) when drying the hydroxide under reduced pressure and heating is preferably 100° C. or higher, more preferably 120° C. or higher, and even more preferably 140° C. or higher. By controlling the drying temperature to be above the lower limit, the degree of drying of the hydroxide can be further improved.

[0985] On the other hand, the drying temperature is preferably not higher than 180° C. By controlling the drying temperature in this manner, excessive heating can be suppressed.

[0986] The drying time (heating time) when the hydroxide is subjected to reduced pressure heating and drying can be appropriately adjusted according to the pressure and drying temperature during the reduced pressure. For example, when the pressure and drying temperature during the reduced pressure are both within the above numerical ranges, the drying time is preferably 2 to 8 hours. By controlling the drying time to be above the lower limit, the degree of drying of the hydroxide can be further improved. By controlling the drying time to be below the upper limit, excessive heating can be suppressed.

[0987] When a hydrate such as cesium hydroxide monohydrate is used as the hydroxide, the hydrate can be converted to an anhydrate (e.g., anhydrous cesium hydroxide) by drying under reduced pressure and heating, and the anhydrate can be used in the depolymerization step. Furthermore, a hydrate that has not been completely converted to an anhydrate (still in a hydrated state) can be used directly in the depolymerization step. For example, hydrates other than the monohydrate of the cesium hydroxide can be partially or completely converted to cesium hydroxide monohydrate by drying under reduced pressure and heating, and the cesium hydroxide monohydrate can be used in the depolymerization step.

[0988] The hydroxide used in the depolymerization step may be one type or two or more types. When two or more types of hydroxide are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0989] For example, when a hydrate such as cesium hydroxide monohydrate is dried under reduced pressure and heat, a mixture of a hydroxide hydrate and an anhydrate of hydroxide may be obtained. This mixture of a hydroxide hydrate and an anhydrate can be used as the hydroxide in the depolymerization step. When a hydrate of cesium hydroxide other than monohydrate is dried under reduced pressure and heat, a mixture of a cesium hydroxide monohydrate and an anhydrate of cesium hydroxide may be obtained. This mixture can be used as the hydroxide in the depolymerization step.

[0990] In the depolymerization step, the amount of the hydroxide used is preferably 2 to 8 times the molar amount of the repeating unit in the compound (1) (the structural unit marked with the symbol n1 in the general formula (1)), and can be, for example, 3 to 6 times or 3.5 to 4.5 times the molar amount. By controlling the amount of the hydroxide used to be above the lower limit, the depolymerization of the compound (1) proceeds more easily. By controlling the amount of the hydroxide used to be below the upper limit, the excessive use of the hydroxide can be suppressed.

[0991] Solvents

[0992] In the depolymerization step, it is further preferred to use a solvent. By using a solvent, particularly by dissolving compound (1) in a solvent and then performing the depolymerization step, depolymerization of compound (1) proceeds more easily.

[0993] In this specification, unless otherwise specified, the term "solvent" encompasses both components that are liquid at room temperature and dissolve a solute, and components that are liquid at room temperature and function as a dispersion medium for dispersing a dispersoid. Furthermore, "room temperature" refers to a temperature that is not specifically cooled or heated, i.e., a normal temperature, such as 15 to 25°C.

[0994] The solvent is preferably an organic solvent.

[0995] Examples of the organic solvent include amides such as 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP); nitriles such as benzonitrile; and ethers (cyclic ethers) such as 1,4-dioxane.

[0996] The solvent used in the depolymerization step may be only one kind or two or more kinds. When two or more kinds of solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[0997] When a solvent is used in the depolymerization step, the amount of the solvent used is preferably 0.2 to 1.5 L relative to 100 g of the compound (1). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.5 to 1.5 L or 0.7 to 1.5 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (1) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, the excessive use of the solvent can be suppressed.

[0998] Dehydrating agent

[0999] In the depolymerization step, it is further preferred to use a dehydrating agent. In the depolymerization step, if water is present, depolymerization of compound (1) will be difficult to proceed. That is, in the depolymerization step, by using a dehydrating agent, depolymerization of compound (1) is facilitated, and the yield of compound (11) or its salt, and the yield of compound (121), (122) or (123) or its salt are significantly improved.

[1000] Examples of the dehydrating agent include water-reactive components that react with water to form other components and hygroscopic components that do not react with water but adsorb (in other words, absorb) moisture.

[1001] Examples of the water-reactive component include sodium hydride (NaH), potassium hydride (KH), calcium hydride (CaH 2 ), calcium oxide (CaO), cesium chloride (CsCl 2 ), calcium chloride (CaCl 2 ), and magnesium sulfate (MgSO 4 ).

[1002] Examples of the hygroscopic component include zeolite, etc. As zeolite, a commercially available product with the trade name Molecular Sieve can be used.

[1003] The dehydrating agent used in the depolymerization step may be only one kind or two or more kinds. When two or more dehydrating agents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1004] The dehydrating agent used in the depolymerization step is preferably one or more selected from the group consisting of sodium hydride, potassium hydride, calcium hydride, calcium oxide, cesium chloride, calcium chloride, magnesium sulfate and zeolite.

[1005] When a dehydrating agent is used in the depolymerization step, the amount of the dehydrating agent used is preferably 2 to 8 times the molar amount of the repeating unit in compound (1) (the structural unit marked with the symbol n1 in general formula (1)), and can be, for example, 4 to 6 times or 3.5 to 4.5 times the molar amount. By controlling the amount of the dehydrating agent to be above the lower limit, the depolymerization of compound (1) proceeds more easily. By controlling the amount of the dehydrating agent to be below the upper limit, excessive use of the dehydrating agent can be suppressed.

[1006] <Other ingredients>

[1007] In the depolymerization step, other components other than compound (1), the hydroxide, the solvent added as needed, and the dehydrating agent added as needed may be used to depolymerize compound (1), or compound (1) may be depolymerized without using the other components, as long as the effects of the present invention are not impaired.

[1008] The other components can be arbitrarily selected according to the purpose and are not particularly limited.

[1009] The other components used in the depolymerization step may be one or more than one. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1010] When depolymerizing compound (1) in the depolymerization step, the ratio of the total amount (mass parts) of the hydroxide, the solvent, and the dehydrating agent to the total amount (mass parts) of the hydroxide, the solvent, the dehydrating agent, and the other components (([amount (mass parts) of the hydroxide] + [amount (mass parts) of the solvent] + [amount (mass parts) of the dehydrating agent]) / ([amount (mass parts) of the hydroxide] + [amount (mass parts) of the solvent] + [amount (mass parts) of the dehydrating agent] + [amount (mass parts) of the other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (1) proceeds more easily.

[1011] On the other hand, the ratio is 100% by mass or less.

[1012] When no optional components (ie, solvent, dehydrating agent or other components) are used in the depolymerization of compound (1), the amount of the optional components used in calculating the above ratio is 0 parts by mass.

[1013] <Other conditions>

[1014] In the depolymerization step, the compound (1) can be depolymerized by mixing the compound (1), the hydroxide, a solvent added as needed, a dehydrating agent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[1015] In the depolymerization step, the temperature (reaction temperature) at which the mixture is heated and stirred is preferably 100° C. or higher, more preferably 115° C. or higher, and may be, for example, 130° C. or higher or 145° C. or higher. By controlling the reaction temperature to be above the lower limit, depolymerization of compound (1) proceeds more easily.

[1016] On the other hand, from the viewpoint of suppressing the generation of by-products, the reaction temperature is preferably 170° C. or lower.

[1017] In the depolymerization step, the temperature (reaction temperature) at which the mixture is heated and stirred is preferably 10 to 40 hours, for example, 10 to 24 hours or 24 to 40 hours.

[1018] The above reaction time is particularly suitable when the reaction temperature is within the above numerical range.

[1019] In the depolymerization step, the depolymerization of compound (1) is preferably carried out under an inert gas atmosphere such as argon, helium, or nitrogen. In this way, the water content in the mixture can be effectively reduced, achieving the same effect as when a dehydrating agent is used. In other words, the depolymerization of compound (1) is more easily carried out, and the yield of compound (11) or its salt, as well as the yield of compound (121), compound (122), or compound (123) or its salt are significantly improved.

[1020] In the depolymerization step, it is more preferable to depolymerize compound (1) using a dehydrating agent under the inert gas atmosphere, or more preferably to depolymerize compound (1) using a hydroxide that has been subjected to a reduced pressure heating and drying process under the inert gas atmosphere. It is further preferable to depolymerize compound (1) using both a dehydrating agent and a hydroxide that has been subjected to a reduced pressure heating and drying process under the inert gas atmosphere. In this manner, the yield of the target product (compound (11) or a salt thereof, and compound (121), compound (122), or compound (123) or a salt thereof) can be further improved.

[1021] In the depolymerization method (1), after the depolymerization step is completed, the reaction mixture obtained can be post-treated by a known method as needed to isolate the target product (product). That is, one or a combination of two or more post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration can be appropriately performed as needed, and the target product can be isolated by methods such as concentration, crystallization, reprecipitation, column chromatography, etc. In addition, the separated target product can be purified one or more times as needed by one or a combination of two or more operations such as crystallization, reprecipitation, column chromatography, extraction, solvent stirring, washing, and crystallization. Alternatively, after the depolymerization step is completed, the reaction mixture can be post-treated as needed and used directly for the next intended purpose without isolating the target product. For example, the target product can be used directly for the next target reaction without isolating it.

[1022] The structure of the product obtained by the depolymerization method (1) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[1023] <<Depolymerization method (2)>>

[1024] A compound depolymerization method according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[1025] The following general formula (2)

[1026]

Chemical Formula 65

[1027]

[1028] (wherein n2 is an integer greater than 2 (preferably 10 to 200); Z 21 、Z 22 and Z 23 Each independently is a non-hydrogen atom group; m 21 、m 22 and m 23 Each independently represents an integer from 0 to 4. 21 When n2×m is an integer greater than 1, 21 Z 21 Can be the same or different, when m 22 When n2×m is an integer greater than 1, 22 Z 22 Can be the same or different, when m 23 When n2×m is an integer greater than 1, 23 Z 23 Can be the same or different)

[1029] The compound represented by (sometimes referred to as "compound (2)" in this specification) is depolymerized in the presence of a hydroxide to obtain the following general formula (21):

[1030]

Chemical Formula 66

[1031]

[1032] (Where Z 21 、Z 22 、m 21 and m 22 Same as above)

[1033] The compound represented by (sometimes referred to as "compound (21)" in this specification) or a salt thereof, and the following general formula (22)

[1034]

Chemical Formula 67

[1035]

[1036] (Where Z 23 and m 23 Same as above)

[1037] The compound represented by (sometimes referred to as "compound (22)" in this specification) or a salt thereof. In this specification, the compound depolymerization method of this embodiment may be referred to as "depolymerization method (2)".

[1038] The depolymerization method (depolymerization method (2)) of this embodiment is a novel depolymerization method for compound (2) containing super engineering plastics.

[1039] Depolymerization method (2) uses compound (2) instead of compound (1) as the depolymerization target, that is, except for the difference in the depolymerization target, the rest is the same as depolymerization method (1).

[1040] The compound (2) includes polyetheretherketone (sometimes referred to as "PEEK" in this specification) and its derivatives.

[1041] <Compound (2)>

[1042] Compound (2) is the target of depolymerization in the depolymerization method (2).

[1043] In the general formula (2), n2 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (2), and is an integer greater than or equal to 2.

[1044] For example, compound (2) with n2 of 20 to 100 is suitable for high molecular weight super engineering plastic polyetheretherketone (PEEK), which is difficult to depolymerize using traditional methods and is particularly suitable as an application object of depolymerization method (2).

[1045] In the general formula (2), Z 21 、Z 22 and Z 23 Each is independently a non-hydrogen atom group (substituent). 21 、Z 22 and Z 23 They may be all the same, all different, or partially (any two) the same.

[1046] As Z 21 、Z 22 and Z 23 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[1047] In the general formula (2), m 21 Represents Z bonded to a benzene ring skeleton 21 The number of m 22 Indicates that Z 21 Z bonded to another benzene ring skeleton with a different bond 22 The number of m 23 Indicates that Z 21 The bonded benzene ring skeleton and Z 22 The Z bonded to another benzene ring skeleton is different from the bonded benzene ring skeleton 23 The number of

[1048] m 21 、m 22 and m23 are each independently an integer from 0 to 4. 21 、m 22 and m 23 They may be all the same, all different, or partially (any two) the same.

[1049] Compound (2) contains n2×m 21 Z 21 , when m 21 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 21 Z 21 can be the same or different. That is, m 21 When n2×m is an integer greater than 1, 21 Z 21 They may be all the same, all different, or partially the same.

[1050] Z 22 Likewise, compound (2) contains n2×m 22 Z 22 , m 22 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 22 Z 22 can be the same or different. That is, m 22 When n2×m is an integer greater than 1, 22 Z 22 They may be all the same, all different, or partially the same.

[1051] Z 23 Likewise, compound (2) contains n2×m 23 Z 23 , m 23 When n2×m is an integer greater than 1 (i.e., an integer from 1 to 4), 23 Z 23 can be the same or different. That is, m 23 When n2×m is an integer greater than 1, 23 Z 23 They may be all the same, all different, or partially the same.

[1052] As examples of preferred compounds (2), m 21 、m 22 and m 23 All are 0 (that is, without Z 21 、Z 22 and Z 23 ) of compound (2).

[1053] However, compound (2) is not limited to these examples.

[1054] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a terminal or dual terminal hydroxyl group in the general formula (2)) in compound (2) may be substituted with a non-hydrogen group (M) to form a group represented by the formula "-OM", as in the case of compound (21) described later. In other words, compound (2) may be a salt.

[1055] <Compound (21)>

[1056] Compound (21) is a product obtained by the depolymerization method (2).

[1057] Compound (21) is 4,4'-dihydroxybenzophenone and its derivatives.

[1058] Z in the general formula (21) 21 、Z 22 、m 21 and m 22 Respectively with Z in general formula (2) 21 、Z 22 、m 21 and m 22 same.

[1059] <Compound (22)>

[1060] Compound (22) is another product obtained by the depolymerization method (2).

[1061] Compound (22) is 1,3-dihydroxybenzene (also known as resorcinol) and its derivatives.

[1062] Z in the general formula (22) 23 and m 23 Respectively with Z in general formula (2) 23 and m 23 same.

[1063] <Salts of Compound (21), Salts of Compound (22)>

[1064] The salt of compound (21), like the above-mentioned compound (11), refers to a compound (21) in which one (1) or two (2) hydrogen atoms on the hydroxyl (-OH) group are replaced by a non-hydrogen atom group (M) to form a salt of the formula "-OM" (formula "-O - M + ”) represented by a group.

[1065] When the hydrogen atoms of the two hydroxyl groups in compound (21) are both substituted by M, the two M's may be the same or different.

[1066] Whether or not the hydrogen atom is substituted by M, and if substitution occurs, the type of M, can be determined, for example, by the post-treatment conditions of the reaction solution obtained after depolymerization of compound (2). For example, if the reaction solution is treated with an acid after depolymerization of compound (2), compound (21) rather than a salt of compound (21) may be obtained as the main component.

[1067] The M is the same as that defined in the salt of the above-mentioned compound (11).

[1068] The manner in which compound (22) forms a salt is the same as the manner in which compound (21) forms a salt. That is, the salt of compound (22) is formed in the same manner as the salt of compound (21), and is identical to the salt of compound (21) except for the difference in the group to which the group represented by the formula "-OM" is bonded.

[1069] Hydroxide

[1070] The hydroxide in the depolymerization method (2) is the same as the hydroxide in the depolymerization method (1).

[1071] The hydroxide used in the depolymerization step of the depolymerization method (2) may be only one type or two or more types. When two or more types of hydroxides are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1072] The hydroxide used in the depolymerization step of the depolymerization method (2) is preferably an alkali metal hydroxide.

[1073] In the depolymerization step of the depolymerization method (2), it is preferred to use a hydroxide that has been subjected to a reduced pressure heating and drying treatment. In this manner, the effect obtained by using the hydroxide is significantly enhanced, and the depolymerization of the compound (2) is facilitated.

[1074] The hydroxide dried by heating under reduced pressure used in the depolymerization method (2) is the same as the hydroxide dried by heating under reduced pressure used in the depolymerization method (1) and can be obtained by the same method as in the depolymerization method (1).

[1075] In the depolymerization step of the depolymerization method (2), the amount of the hydroxide used is preferably 2 to 8 times the molar amount of the repeating unit in the compound (2) (the structural unit marked with the symbol n2 in the general formula (2)), and can be, for example, 3 to 6 times or 3.5 to 4.5 times the molar amount. By controlling the amount of the hydroxide used to be above the lower limit, the depolymerization of the compound (2) proceeds more easily. By controlling the amount of the hydroxide used to be below the upper limit, the excessive use of the hydroxide can be suppressed.

[1076] Solvents

[1077] In the depolymerization step of the depolymerization method (2), it is further preferred to use a solvent. By using a solvent, particularly by dissolving the compound (2) in a solvent and then performing the depolymerization step, the depolymerization of the compound (2) proceeds more easily.

[1078] The hydroxide in the depolymerization method (2) is the same as the hydroxide in the depolymerization method (1).

[1079] The solvent used in the depolymerization step of the depolymerization method (2) may be only one type or two or more types. When two or more types of solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1080] When a solvent is used in the depolymerization step of the depolymerization method (2), the amount of the solvent used is preferably 0.2 to 1.5 L per 100 g of the compound (2). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.5 to 1.5 L or 0.7 to 1.5 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (2) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, the excessive use of the solvent can be suppressed.

[1081] Dehydrating agent

[1082] In the depolymerization step of the depolymerization method (2), it is further preferred to use a dehydrating agent. In the depolymerization step, if water is present, depolymerization of compound (2) will be difficult to proceed. That is, in the depolymerization step, by using a dehydrating agent, depolymerization of compound (2) is facilitated, and the yield of compound (21) or its salt, and the yield of compound (22) or its salt are significantly improved.

[1083] The dehydrating agent in the depolymerization method (2) is the same as the dehydrating agent in the depolymerization method (1).

[1084] The dehydrating agent used in the depolymerization step of the depolymerization method (2) may be only one kind or two or more kinds. When two or more kinds of dehydrating agents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1085] The dehydrating agent used in the depolymerization step of the depolymerization method (2) is preferably one or more selected from the group consisting of sodium hydride, potassium hydride, calcium hydride, calcium oxide, cesium chloride, calcium chloride, magnesium sulfate and zeolite.

[1086] When a dehydrating agent is used in the depolymerization step of the depolymerization method (2), the amount of the dehydrating agent used is preferably 2 to 8 times the molar amount of the repeating unit in the compound (2) (the structural unit marked with the symbol n2 in the general formula (2)), and can be, for example, 4 to 6 times the molar amount or 3.5 to 4.5 times the molar amount. By controlling the amount of the dehydrating agent to be above the lower limit, the depolymerization of the compound (2) proceeds more easily. By controlling the amount of the dehydrating agent to be below the upper limit, excessive use of the dehydrating agent can be suppressed.

[1087] <Other ingredients>

[1088] In the depolymerization step of the depolymerization method (2), other components other than the compound (2), the hydroxide, the solvent added as needed, and the dehydrating agent added as needed may be used to carry out the depolymerization of the compound (2), or the depolymerization of the compound (2) may be carried out without using the other components, as long as the effects of the present invention are not impaired.

[1089] The other components in the depolymerization method (2) are the same as those in the depolymerization method (1).

[1090] The other components used in the depolymerization step of the depolymerization method (2) may be only one or two or more. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1091] When depolymerizing compound (2) in the depolymerization step of depolymerization method (2), the ratio of the total amount (parts by mass) of the hydroxide, the solvent, and the dehydrating agent to the total amount (parts by mass) of the hydroxide, the solvent, the dehydrating agent, and the other components (([amount (parts by mass) of the hydroxide] + [amount (parts by mass) of the solvent] + [amount (parts by mass) of the dehydrating agent]) / ([amount (parts by mass) of the hydroxide] + [amount (parts by mass) of the solvent] + [amount (parts by mass) of the dehydrating agent] + [amount (parts by mass) of the other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (2) proceeds more easily.

[1092] On the other hand, the ratio is 100% by mass or less.

[1093] When no arbitrary component (ie, solvent, dehydrating agent or other components) is used in the depolymerization of compound (2), the amount of the arbitrary component used in calculating the above ratio is 0 parts by mass.

[1094] <Other conditions>

[1095] In the depolymerization step of the depolymerization method (2), the compound (2) can be depolymerized by mixing the compound (2), a hydroxide, a solvent added as needed, a dehydrating agent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[1096] In the depolymerization step of the depolymerization method (2), the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (2) are respectively the same as the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (1) in the depolymerization step of the depolymerization method (1).

[1097] In the depolymerization step of the depolymerization method (2), it is more preferred to depolymerize compound (2) using a dehydrating agent under the inert gas atmosphere, or more preferably to depolymerize compound (2) using a hydroxide that has been subjected to a reduced pressure heating and drying treatment under the inert gas atmosphere. It is further preferred to depolymerize compound (2) using both a dehydrating agent and a hydroxide that has been subjected to a reduced pressure heating and drying treatment under the inert gas atmosphere. In this manner, the yield of the target product (compound (21) or a salt thereof, and compound (22) or a salt thereof) can be further improved.

[1098] In the depolymerization method (2), after the depolymerization step is completed, the reaction mixture obtained can be subjected to post-treatment as needed in the same manner as in the depolymerization method (1) to isolate the target product (product), and the separated target product can be further purified as needed. Alternatively, after the depolymerization step is completed, the reaction mixture can be subjected to post-treatment as needed in the same manner as in the depolymerization method (1) and directly used for the next intended purpose without isolating the target product.

[1099] The structure of the product obtained by the depolymerization method (2) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[1100] <<Depolymerization method (4)>>

[1101] A compound depolymerization method according to one embodiment of the present invention includes a depolymerization step (decomposition step):

[1102] The following general formula (4)

[1103]

Chemical Formula 68

[1104]

[1105] (wherein n4 is an integer greater than 2 (preferably 10 to 200); Z 41 and Z 42 Each independently is a non-hydrogen atom group; m 41 and m 42 Each independently represents an integer from 0 to 4. 41 When n4×m is an integer greater than 1, 41 Z 41 Can be the same or different, when m 42 When n4×m is an integer greater than 1, 42 Z 42 Can be the same or different)

[1106] The compound represented by (sometimes referred to as "compound (4)" in this specification) is depolymerized in the presence of a hydroxide to obtain the following general formula (41):

[1107]

Chemical Formula 69

[1108]

[1109] (Where Z 41 、Z 42 、m 41 and m 42 Same as above)

[1110] The compound represented by (sometimes referred to as "compound (41)" in this specification) or a salt thereof. In this specification, the compound depolymerization method of this embodiment may be referred to as "depolymerization method (4)".

[1111] The depolymerization method (depolymerization method (4)) of this embodiment is a novel depolymerization method for compound (4) containing super engineering plastics.

[1112] Depolymerization method (4) uses compound (4) instead of compound (1) as the depolymerization target, that is, except for the difference in the depolymerization target, the rest is the same as depolymerization method (1).

[1113] The compound (4) includes polyethersulfone (sometimes referred to as "PESU" in this specification) and its derivatives.

[1114] <Compound (4)>

[1115] Compound (4) is the target of depolymerization in the depolymerization method (4).

[1116] In the general formula (4), n4 represents the number of repetitions of the repeating unit, is used to define the molecular size of the compound (4), and is an integer greater than or equal to 2.

[1117] For example, when n4 is 30 to 350, compound (4) is suitable for high molecular weight super engineering plastic polyethersulfone (PESU), which is difficult to depolymerize using traditional methods and is particularly suitable as an application object of depolymerization method (4).

[1118] In the general formula (4), Z 41 and Z 42 Each is independently a non-hydrogen atom group (substituent). 41 and Z 42 It can be the same or different.

[1119] As Z 41 and Z 42 (Substituent), for example, the same as the above Z 11 and Z 12 The same groups (such as alkyl, alkylcarbonylamino, fluoroalkyl, fluorine atom, etc.).

[1120] In general formula (4), m 41 Represents Z bonded to a benzene ring skeleton 41 The number of m 42 Indicates that Z 41 Z bonded to another benzene ring skeleton with a different bond 42 The number of

[1121] m 41 and m 42 are each independently an integer from 0 to 4. 41 and m 42 It can be the same or different.

[1122] Compound (4) contains n4×m 41 Z 41 , when m 41 When n4×m is an integer greater than 1 (ie, an integer from 1 to 4), 41 Z 41 can be the same or different. That is, m 41 When n4×m is an integer greater than 1, 41 Z 41 They may be all the same, all different, or partially the same.

[1123] Z 42 Likewise, compound (4) contains n4×m 42 Z 42 , m 42 When n4×m is an integer greater than 1 (ie, an integer from 1 to 4), 42 Z 42 can be the same or different. That is, m42 When n4×m is an integer greater than 1, 42 Z 42 They may be all the same, all different, or partially the same.

[1124] As examples of preferred compounds (4), m 41 and m 42 All are 0 (that is, without Z 41 and Z 42 ) of compound (4).

[1125] However, compound (4) is not limited to these examples.

[1126] The hydrogen atoms in one (1) or two (2) hydroxyl groups (-OH, a terminal or dual terminal hydroxyl group in the general formula (4)) in compound (4) may be substituted with a non-hydrogen group (M) to form a group represented by the formula "-OM", as in the case of compound (41) described later. In other words, compound (4) may be a salt.

[1127] <Compound (41)>

[1128] Compound (41) is a product obtained by the depolymerization method (4).

[1129] Compound (41) is bisphenol S (BPS) and its derivatives.

[1130] Z in the general formula (41) 41 、Z 42 、m 41 and m 42 Respectively with Z in general formula (4) 41 、Z 42 、m 41 and m 42 same.

[1131] <Salt of Compound (41)>

[1132] The salt of compound (41), like the above-mentioned compound (11), refers to a compound (41) in which one (1) or two (2) hydrogen atoms on the hydroxyl (-OH) groups are replaced by non-hydrogen atom groups (M) to form a salt of the formula "-OM" (formula "-O - M + ”) represented by a group.

[1133] When the hydrogen atoms of the two hydroxyl groups in compound (41) are both substituted by M, the two M's may be the same or different.

[1134] Whether or not the hydrogen atom is substituted by M, and if substitution occurs, the type of M, can be determined, for example, by the post-treatment conditions of the reaction solution obtained after depolymerization of compound (4). For example, if the reaction solution is treated with an acid after depolymerization of compound (4), compound (41) rather than a salt of compound (41) may be obtained as the main component.

[1135] The M is the same as that defined in the salt of the above-mentioned compound (41).

[1136] Hydroxide

[1137] The hydroxide in the depolymerization method (4) is the same as the hydroxide in the depolymerization method (1).

[1138] The hydroxide used in the depolymerization step of the depolymerization method (4) may be only one type or two or more types. When two or more types of hydroxides are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1139] The hydroxide used in the depolymerization step of the depolymerization method (4) is preferably an alkali metal hydroxide.

[1140] In the depolymerization step of the depolymerization method (4), it is preferred to use a hydroxide that has been subjected to a reduced pressure heating and drying treatment. In this manner, the effect obtained by using the hydroxide is significantly enhanced, and the depolymerization of the compound (4) is facilitated.

[1141] The hydroxide dried by heating under reduced pressure used in the depolymerization method (4) is the same as the hydroxide dried by heating under reduced pressure used in the depolymerization method (1) and can be obtained by the same method as in the depolymerization method (1).

[1142] In the depolymerization step of the depolymerization method (4), the amount of the hydroxide used is preferably 2 to 8 times the molar amount of the repeating unit in the compound (4) (the structural unit marked with the symbol n4 in the general formula (4)), for example, it can be any range of 2 to 6 times the molar amount or 2 to 4.5 times the molar amount.

[1143] By controlling the amount of the hydroxide to be above the lower limit, depolymerization of compound (4) can be facilitated. By controlling the amount of the hydroxide to be below the upper limit, excessive use of the hydroxide can be suppressed.

[1144] Solvents

[1145] In the depolymerization step of the depolymerization method (4), it is further preferred to use a solvent. By using a solvent, particularly by dissolving the compound (4) in a solvent and then performing the depolymerization step, the depolymerization of the compound (4) proceeds more easily.

[1146] The hydroxide in the depolymerization method (4) is the same as the hydroxide in the depolymerization method (1).

[1147] The solvent used in the depolymerization step of the depolymerization method (4) may be only one or two or more solvents. When two or more solvents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1148] When a solvent is used in the depolymerization step of the depolymerization method (4), the amount of the solvent used is preferably 0.2 to 1.5 L relative to 100 g of the compound (4). For example, it can be in the range of 0.2 to 1 L or 0.2 to 0.6 L, or in the range of 0.5 to 1.5 L or 0.7 to 1.5 L. By controlling the amount of the solvent used to be above the lower limit, the depolymerization of the compound (4) proceeds more easily. By controlling the amount of the solvent used to be below the upper limit, excessive use of the solvent can be suppressed.

[1149] Dehydrating agent

[1150] In the depolymerization step of the depolymerization method (4), it is further preferred to use a dehydrating agent. In the depolymerization step, if water is present, depolymerization of compound (4) will be difficult to proceed. That is, in the depolymerization step, by using a dehydrating agent, depolymerization of compound (4) is facilitated, and the yield of compound (41) is significantly improved.

[1151] The dehydrating agent in the depolymerization method (4) is the same as the dehydrating agent in the depolymerization method (1).

[1152] The dehydrating agent used in the depolymerization step of the depolymerization method (4) may be only one kind or two or more kinds. When two or more kinds of dehydrating agents are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1153] The dehydrating agent used in the depolymerization step of the depolymerization method (4) is preferably one or more selected from the group consisting of sodium hydride, potassium hydride, calcium hydride, calcium oxide, cesium chloride, calcium chloride, magnesium sulfate and zeolite.

[1154] When a dehydrating agent is used in the depolymerization step of the depolymerization method (4), the amount of the dehydrating agent used is preferably 2 to 8 times the molar amount of the repeating unit in the compound (4) (the structural unit marked with the symbol n4 in the general formula (4)), and can be, for example, 2 to 6 times or 2 to 4.5 times the molar amount. By controlling the amount of the dehydrating agent to be above the lower limit, the depolymerization of the compound (4) proceeds more easily. By controlling the amount of the dehydrating agent to be below the upper limit, excessive use of the dehydrating agent can be suppressed.

[1155] <Other ingredients>

[1156] In the depolymerization step of the depolymerization method (4), other components other than the compound (4), the hydroxide, the solvent added as needed, and the dehydrating agent added as needed may be used to carry out the depolymerization of the compound (4), or the depolymerization of the compound (4) may be carried out without using the other components, as long as the effects of the present invention are not impaired.

[1157] The other components in the depolymerization method (4) are the same as the other components in the depolymerization method (1).

[1158] The other components used in the depolymerization step of the depolymerization method (4) may be only one or two or more. When two or more other components are used, their combination and ratio may be arbitrarily selected according to the purpose.

[1159] When depolymerizing compound (4) in the depolymerization step of depolymerization method (4), the ratio of the total amount (mass parts) of the hydroxide, the solvent, and the dehydrating agent to the total amount (mass parts) of the hydroxide, the solvent, the dehydrating agent, and the other components (([amount (mass parts) of the hydroxide] + [amount (mass parts) of the solvent] + [amount (mass parts) of the dehydrating agent]) / ([amount (mass parts) of the hydroxide] + [amount (mass parts) of the solvent] + [amount (mass parts) of the dehydrating agent] + [amount (mass parts) of the other components]) × 100) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. For example, it can be any ratio of 97% by mass or more or 99% by mass or more. By controlling the ratio to be above the lower limit, depolymerization of compound (4) proceeds more easily.

[1160] On the other hand, the ratio is 100% by mass or less.

[1161] When no arbitrary component (ie, solvent, dehydrating agent or other components) is used in the depolymerization of compound (4), the amount of the arbitrary component used in calculating the above ratio is 0 parts by mass.

[1162] <Other conditions>

[1163] In the depolymerization step of the depolymerization method (4), the compound (4) can be depolymerized by mixing the compound (4), a hydroxide, a solvent added as needed, a dehydrating agent added as needed, and the other components added as needed, and heating and stirring the resulting mixture.

[1164] In the depolymerization step of the depolymerization method (4), the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (4) are respectively the same as the temperature (reaction temperature) when the mixture is heated and stirred, the time (reaction time) when the mixture is heated and stirred, and the atmosphere during the depolymerization of the compound (1) in the depolymerization step of the depolymerization method (1).

[1165] In the depolymerization step of the depolymerization method (4), it is more preferred to depolymerize compound (4) using a dehydrating agent under the inert gas atmosphere, or more preferably to depolymerize compound (4) using a hydroxide that has been subjected to a reduced pressure heating and drying treatment under the inert gas atmosphere. It is further preferred to depolymerize compound (4) using both a dehydrating agent and a hydroxide that has been subjected to a reduced pressure heating and drying treatment under the inert gas atmosphere. In this manner, the yield of the target product (compound (41)) can be further increased.

[1166] In the depolymerization method (4), after the depolymerization step is completed, the reaction mixture obtained can be subjected to post-treatment as needed in the same manner as in the depolymerization method (1) to isolate the target product (product), and the separated target product can be further purified as needed. Alternatively, after the depolymerization step is completed, the reaction mixture can be subjected to post-treatment as needed in the same manner as in the depolymerization method (1) and directly used for the next intended purpose without isolating the target product.

[1167] The structure of the product obtained by the depolymerization method (4) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and infrared spectroscopy (IR).

[1168] ◎ Preparation method of ether compound

[1169] The method for preparing an ether compound according to one embodiment of the present invention comprises the following steps (sometimes referred to as "etherification step" in this specification):

[1170] One or more selected from the group consisting of the compound represented by the general formula (11) (compound (11)) and its salt, the compound represented by the general formula (121) (compound (121)) and its salt, the compound represented by the general formula (122) (compound (122)) and its salt, and the compound represented by the general formula (123) (compound (123)) and its salt, obtained by the compound depolymerization method according to one embodiment of the present invention;

[1171] One or more selected from the group consisting of the compound represented by the general formula (21) (compound (21)) and a salt thereof, and the compound represented by the general formula (22) (compound (22)) and a salt thereof;

[1172] or one or more selected from the group consisting of compounds represented by the general formula (41) (compound (41)) and salts thereof

[1173] In the method, one or more phenolic hydroxyl groups or salt groups formed by the phenolic hydroxyl groups are etherified to obtain an ether compound.

[1174] In this specification, the compound (11) and the like obtained by the above-mentioned depolymerization method may be collectively referred to as a "monomer".

[1175] According to the preparation method of this embodiment, the monomer product obtained by the depolymerization method (depolymerization method (1), depolymerization method (2), or depolymerization method (4)) can be easily etherified at its hydroxyl group or salt group formed by the hydroxyl group. In particular, the monomer can be directly etherified without isolation. This is because when the depolymerization of compound (1), compound (2), or compound (4) is carried out by the depolymerization method, side reactions are effectively suppressed, and the reaction proceeds cleanly and efficiently.

[1176] Among the monomers, the salt of compound (11), the salt of compound (121), the salt of compound (122), the salt of compound (123), the salt of compound (21), the salt of compound (22), and the salt of compound (41) are all target products of the depolymerization methods (1), (2) or (4) described above.

[1177] The ether compound has the following structural characteristics: the hydrogen atom (H) in one or two phenolic hydroxyl groups (-OH) of the monomer, or the M in the group represented by the formula "-OM" is substituted by a monovalent hydrocarbon group. The group represented by the formula "-OM" is a salt group formed by the phenolic hydroxyl group.

[1178] Examples of the ether compound obtained from compound (11) or a salt thereof include compounds represented by the following general formula (110).

[1179] Examples of the ether compound obtained from compound (121) or a salt thereof include compounds represented by the following general formula (1210).

[1180] Examples of the ether compound obtained from compound (122) or a salt thereof include compounds represented by the following general formula (1220).

[1181] Examples of the ether compound obtained from compound (123) or a salt thereof include compounds represented by the following general formula (1230).

[1182]

Chemical Formula 70

[1183]

[1184] (Where Z 11 、Z 12 、X 11 、X 12 、X 21 、X 31 、X 32 、m 11 、m 12 、l 11 、l 12 、l 21 、l 31 and l 32 Same meaning as above; R 111 and R 112 are each independently a hydrogen atom or a hydrocarbon group, but R 111 and R 112 When R 111 or R 112 When it is a hydrogen atom, the formula "-OR 111 "The group or formula "-OR 112 " can form a group represented by the formula "-OM"; R 121 and R 122 are each independently a hydrogen atom or a hydrocarbon group, but R 121 and R 122 When R 121 or R 122 When it is a hydrogen atom, the formula "-OR 121 "The group or formula "-OR 122 " can form a group represented by the formula "-OM"; R 131 and R 132 are each independently a hydrogen atom or a hydrocarbon group, but R 131 and R 132 When R 131 or R 132 When it is a hydrogen atom, the formula "-OR 131 "The group or formula "-OR 132 " can form a group represented by the formula "-OM"; R 141 and R 142 Each independently represents a hydrogen atom or a hydrocarbon group, but 141 and R 142 When R 141 or R 142 When it is a hydrogen atom, the formula "-OR 141 "The group or formula "-OR142 " can form a group represented by the formula "-OM".)

[1185] In the compound represented by the general formula (110), when R 111 or R 112 When it is a hydrogen atom, the formula "-OR 111 "The group or formula "-OR 112 " forms a group represented by the formula "-OM", which means that when the compound represented by the general formula (110) contains a hydroxyl group (-OH), the compound has formed a salt at the hydroxyl group.

[1186] This explanation also applies to the compound represented by the general formula (110), the compound represented by the general formula (1210), the compound represented by the general formula (1220), and the compound represented by the general formula (1230).

[1187] Examples of the ether compound obtained from compound (21) or a salt thereof include compounds represented by the following general formula (210).

[1188] Examples of the ether compound obtained from compound (22) or a salt thereof include compounds represented by the following general formula (220).

[1189]

Chemical Formula 71

[1190]

[1191] (Where Z 21 、Z 22 、Z 23 、m 21 、m 22 and m 23 Same meaning as above; R 21 and R 22 are each independently a hydrogen atom or a hydrocarbon group, but R 21 and R 22 When R 21 or R 22 When there is a hydrogen atom, the formula is "-OR 21 "The group or formula "-OR 22 " can form a group represented by the formula "-OM"; R 231 and R 232 are each independently a hydrogen atom or a hydrocarbon group, but R 231 and R 232 When R 231 or R 232 When hydrogen atom, the formula is "-OR 231"The group or formula "-OR 232 " can form a group represented by the formula "-OM".)

[1192] In the compound represented by the general formula (210), when R 21 or R 22 When it is a hydrogen atom, the formula "-OR 21 "The group or formula "-OR 22 " forms a group represented by the formula "-OM", which means that when the compound represented by the general formula (210) contains a hydroxyl group (-OH), the compound has formed a salt at the hydroxyl group.

[1193] This explanation also applies to the compound represented by the general formula (220).

[1194] Examples of the ether compound obtained from compound (41) or a salt thereof include compounds represented by the following general formula (410).

[1195]

Chemical Formula 72

[1196]

[1197] (Where Z 41 、Z 42 、m 41 and m 42 Same meaning as above; R 41 and R 42 are each independently a hydrogen atom or a hydrocarbon group, but R 41 and R 42 When R 41 or R 42 When there is a hydrogen atom, the formula is "-OR 41 "The group or formula "-OR 42 " can form a group represented by the formula "-OM".)

[1198] In the compound represented by the general formula (410), when R 41 or R 42 When it is a hydrogen atom, the formula "-OR 41 "The group or formula "-OR 42 " forms a group represented by the formula "-OM", which means that when the compound represented by the general formula (410) contains a hydroxyl group (-OH), the compound has formed a salt at the hydroxyl group.

[1199] As the hydrocarbon group (R 111 、R 112 、R 121 、R122 、R 131 、R 132 、R 141 、R 142 、R 21 、R 22 、R 231 、R 232 、R 41 and R 42 alkyl group, aralkyl group (also known as arylalkyl group), etc.

[1200] Examples of the alkyl group in which the hydrogen atom is substituted include 11 and Z 12 The alkyl group substituted with a hydrogen atom may be linear, branched, or cyclic, or may have both a linear structure (linear or branched) and a cyclic structure. The cyclic structure in a cyclic alkyl group (an alkyl group having a cyclic structure but no chain structure, or an alkyl group having both a cyclic structure and a chain structure) may be monocyclic or polycyclic.

[1201] The alkyl group substituted by a hydrogen atom is preferably an alkyl group having 1 to 15 carbon atoms (a chain alkyl group having 1 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms), for example, it may be any one of an alkyl group having 1 to 10 carbon atoms (a chain alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), an alkyl group having 1 to 8 carbon atoms (a chain alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms), an alkyl group having 1 to 6 carbon atoms (a chain alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), or an alkyl group having 1 to 3 carbon atoms.

[1202] Examples of the aralkyl group substituted with a hydrogen atom include a monovalent group having the following structure: 11 and Z 12 The alkyl group is formed by replacing one hydrogen atom bonded to a carbon atom without a free valence bond of the alkyl group with an aryl group.

[1203] The aryl group may be monocyclic or polycyclic.

[1204] The number of carbon atoms of the aryl group is preferably 6 to 15. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, xylyl (dimethylphenyl), and the like. In addition, groups having the following structure can be listed: the group is formed by replacing one or more hydrogen atoms in these aryl groups with the aryl group, or Z 11 and Z 12 The aryl group having these substituents preferably has 6 to 15 carbon atoms.

[1205] The aryl group more preferably has 6 to 12 carbon atoms.

[1206] The number of carbon atoms of the aralkyl group in which hydrogen atoms are substituted is preferably 7 to 17. Examples of the aralkyl group include benzyl (benzyl), phenethyl (phenylethyl), 1-naphthylmethyl, 2-naphthylmethyl, o-tolylmethyl, m-tolylmethyl, p-tolylmethyl, and xylylmethyl.

[1207] The aralkyl group preferably has 7 to 14 carbon atoms.

[1208] In the etherification step, one or more (more specifically one or two) phenolic hydroxyl groups or salified phenolic hydroxyl groups in the monomer can be etherified by reacting the hydrogen atom in the hydroxyl group or the M in the group represented by the formula "-OM" with the etherifying agent that can be substituted by the hydrocarbon group and the monomer.

[1209] The etherifying agent may be a known etherifying agent.

[1210] When the etherification is alkyl etherification, examples of the etherifying agent include halogenated alkanes and alkyl ester acids.

[1211] Examples of the halogenated alkanes include iodoalkanes such as methyl iodide (CH3I); brominated alkanes such as (bromomethyl)cyclopropane (c-(C3H5)CH2Br) and 1-bromo-3,7-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH2Br); and the like.

[1212] Examples of the alkyl ester acid include methyl trifluoromethanesulfonate (CF3SO3CH3) and dimethyl sulfate ((CH3)2SO4).

[1213] When the etherification is aralkyl etherification, examples of the etherifying agent include halogenated aralkyl (eg, brominated aralkyl) such as benzyl bromide (C6H5CH2Br).

[1214] When the ether compound is a compound formed by etherifying two phenolic hydroxyl groups or salified phenolic hydroxyl groups in the monomer, in the etherification step, regardless of the type of monomer, the amount of the etherifying agent used is preferably 2 to 5 times the molar amount of the monomer, and can be, for example, 2 to 4 times or 2 to 3 times the molar amount. By controlling the amount of the etherifying agent to be above the lower limit, the yield of the target ether compound is significantly improved. By controlling the amount of the etherifying agent to be below the upper limit, excessive use of the etherifying agent can be suppressed.

[1215] When the ether compound is a compound in which one phenolic hydroxyl group or a salified phenolic hydroxyl group in the monomer is etherified, in the etherification step, regardless of the type of monomer, the amount of the etherifying agent used is preferably 1 to 2.5 times the molar amount of the monomer, for example, 1 to 2 times or 1 to 1.5 times the molar amount. By controlling the amount of the etherifying agent to be above the lower limit, the yield of the target ether compound is significantly improved. By controlling the amount of the etherifying agent to be below the upper limit, excessive use of the etherifying agent can be suppressed.

[1216] When the monomer obtained by the depolymerization method (1) is directly subjected to the etherification step without isolating the monomer, and the monomer is one or more selected from the group consisting of compound (11) and its salt, compound (121) and its salt, compound (122) and its salt, and compound (123) and its salt, and the ether compound is a compound in which two phenolic hydroxyl groups or phenolic hydroxyl groups in a salt are etherified in the monomer, the amount of the etherifying agent used in the etherification step can be, for example, 4 to 10 times the molar amount, 4 to 8 times the molar amount, or 4 to 6 times the molar amount relative to the number of moles of the repeating unit in compound (1) (the structural unit marked with the symbol n1 in the general formula (1)). By controlling the amount of the etherifying agent to be above the lower limit, the yield of the target ether compound is significantly improved. By controlling the amount of the etherifying agent to be below the upper limit, excessive use of the etherifying agent can be suppressed.

[1217] When the ether compound is a compound in which one phenolic hydroxyl group or a phenolic hydroxyl group that has formed a salt in the monomer is etherified, based on the same reasons as above, the amount of the etherifying agent used can be, for example, 2 to 5 times the molar amount, 2 to 4 times the molar amount, or 2 to 3 times the molar amount relative to the molar number of the repeating units in compound (1).

[1218] The same applies when using the depolymerization method (2).

[1219] That is, when the monomer obtained by the depolymerization method (2) is directly subjected to the etherification step without separation, and the monomer is one or more selected from the group consisting of compound (21) and its salt, and compound (22) and its salt, and the ether compound is a compound in which two phenolic hydroxyl groups or phenolic hydroxyl groups in the monomer are etherified, the amount of the etherifying agent used in the etherification step can be, for example, 4 to 10 times the molar amount, 4 to 8 times the molar amount, or 4 to 6 times the molar amount relative to the number of moles of the repeating unit in compound (2) (the structural unit marked with the symbol n2 in the general formula (2)). By controlling the amount of the etherifying agent to be above the lower limit, the yield of the target ether compound is significantly improved. By controlling the amount of the etherifying agent to be below the upper limit, excessive use of the etherifying agent can be suppressed.

[1220] When the ether compound is a compound in which one phenolic hydroxyl group or a phenolic hydroxyl group that has formed a salt in the monomer is etherified, based on the same reasons as above, the amount of the etherifying agent used relative to the molar number of the repeating units in compound (2) can be, for example, any range of 2 to 5 times the molar amount, 2 to 4 times the molar amount, or 2 to 3 times the molar amount.

[1221] As described below, when the monomer obtained by the depolymerization method (4) is directly subjected to the etherification step without isolating the monomer, and the monomer is one or more selected from the group consisting of compound (41) and its salts, and the ether compound is a compound in which two phenolic hydroxyl groups or phenolic hydroxyl groups that have formed a salt in the monomer are etherified, the amount of the etherifying agent used in the etherification step can be, for example, 2 to 5 times the molar amount, 2 to 4 times the molar amount, or 2 to 3 times the molar amount relative to the number of moles of the repeating unit in compound (4) (the structural unit marked with the symbol n4 in the general formula (4)). By controlling the amount of the etherifying agent to be above the lower limit, the yield of the target ether compound is significantly improved. By controlling the amount of the etherifying agent to be below the upper limit, excessive use of the etherifying agent can be suppressed.

[1222] When the ether compound is a compound in which one phenolic hydroxyl group or a phenolic hydroxyl group that has formed a salt in the monomer is etherified, based on the same reasons as above, the amount of the etherifying agent used relative to the molar number of the repeating units in compound (4) can be, for example, any range of 1 to 2.5 times the molar amount, 1 to 2 times the molar amount, or 1 to 1.5 times the molar amount.

[1223] The etherification reaction in the etherification step is preferably carried out using a solvent.

[1224] Examples of the solvent include the same solvents as those used in the depolymerization step of the depolymerization method (1), (2) or (4).

[1225] When the monomers obtained by the depolymerization method (1), (2) or (4) are directly subjected to the etherification step without isolating them, the reaction mixture obtained can be subjected to post-treatment as described above as needed after the depolymerization step in the depolymerization method (1), (2) or (4), and the etherification of the monomers can then be directly performed using the obtained solution.

[1226] In the preparation method, after the etherification step is completed, the resulting reaction mixture can be post-treated by known methods as needed to isolate the target product (ether compound). That is, as needed, one or a combination of two or more post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration can be appropriately performed, and the target product can be isolated by methods such as concentration, crystallization, reprecipitation, column chromatography, etc. In addition, as needed, the isolated target product can be purified one or more times by one or a combination of two or more operations such as crystallization, reprecipitation, column chromatography, extraction, solvent stirring, washing, and crystallization. Alternatively, after the etherification step is completed, the resulting reaction mixture can be post-treated as needed and used directly for the next intended purpose without isolating the target product. For example, the target product can be used directly in the next target reaction without isolating it.

[1227] The structure of the product obtained by the above-mentioned preparation method can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), etc.

[1228] <Example>

[1229] The present invention will be described in more detail below by way of specific examples. However, the present invention is not limited to the following examples.

[1230] <<Depolymerization of polysulfone (Depolymerization method (1))>>

[1231] [Example 1]

[1232] Under an argon atmosphere, sodium hydroxide (NaOH) (0.8 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in formula (1)) and 1,3-dimethyl-2-imidazolidinone (DMI) (0.4 mL) were added sequentially to granular polysulfone (89.2 mg; 0.20 mmol of the repeating unit in general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). The mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 18 hours. The sodium hydroxide used had been previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1233] Subsequently, the temperature of the reaction mixture was cooled to room temperature, 1 M hydrochloric acid (1.0 mL) was added and stirred uniformly. Then, mesitylene (5.0 μL, 0.036 mmol) and deuterated chloroform (CDCl3) (0.5 mL) were added to extract the organic phase. 1H NMR confirmed that the target products (depolymerization products): bisphenol S (BPS, equivalent to compound (11)) and bisphenol A (BPA, equivalent to compound (121)) were obtained, and the yields of these products and intermediate products (such as compound (A) represented by the following formula (A) and compound (B) represented by the following formula (B)) were calculated. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 1 shown.

[1234] [Example 2]

[1235] Under an argon atmosphere, potassium hydroxide (KOH) (2.0 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in formula (1)) and 1,3-dimethyl-2-imidazolidinone (DMI) (1.0 mL) were added sequentially to granular polysulfone (222 mg; 0.50 mmol of the repeating unit in general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). The mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 20 hours. The potassium hydroxide used had been previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1236] The reaction mixture was then cooled to room temperature and 2M hydrochloric acid (1.0 mL) and N,N-dimethylformamide (10 μL, 0.13 mmol) were added. A small amount of the solution was dissolved in deuterated acetone ((CD3)2CO) (0.50 mL) and the mixture was stirred for 2 h. 1 H NMR analysis. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 2 shown.

[1237] [Example 3]

[1238] Depolymerization of polysulfone was carried out according to the method of Example 2, except that potassium hydroxide (2.0 mmol) was replaced with cesium hydroxide monohydrate (CsOH·H2O) (2.0 mmol, representing 4 times the molar amount (4 equivalents) relative to the repeating unit in general formula (1)). The cesium hydroxide monohydrate used was previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours. The depolymerization was performed so that the polysulfone dissolved.

[1239] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 2 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 3 shown.

[1240] [Example 4]

[1241] Except for adjusting the reaction temperature from 150°C to 120°C and the reaction time from 20 hours to 18 hours, the depolymerization of polysulfone was carried out according to the method of Example 3. During depolymerization, the polysulfone was dissolved.

[1242] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 2 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 4 shown.

[1243] [Example 5]

[1244] The depolymerization of polysulfone was carried out according to the method of Example 1, except that the amount of sodium hydroxide was adjusted from 0.8 mmol to 1.2 mmol (6 times the molar amount (6 equivalents) relative to the repeating unit in general formula (1)). During depolymerization, the polysulfone was dissolved.

[1245] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 5 shown.

[1246] [Example 6]

[1247] The depolymerization of polysulfone was carried out according to the method of Example 5, except that sodium hydroxide (1.2 mmol) was replaced by potassium hydroxide (1.2 mmol) and the reaction time was adjusted from 18 hours to 19 hours. During the depolymerization, the polysulfone was dissolved.

[1248] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 1. In addition, 1The results of H NMR analysis are as follows Figure 6 shown.

[1249] [Example 7]

[1250] The depolymerization of polysulfone was carried out according to the method of Example 3, except that the amount of cesium hydroxide monohydrate was adjusted from 2.0 mmol to 3.0 mmol (6 times the molar amount (6 equivalents) relative to the repeating unit in general formula (1)). During depolymerization, the polysulfone was dissolved.

[1251] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 1. In addition, 1 The results of H NMR analysis are as follows Figure 7 shown.

[1252]

Chemical Formula 73

[1253]

[1254] (where n 101 is an integer (preferably 10 to 200).

[1255]

Table 2

[1256]

[1257] The above results show that even when the type of hydroxide is changed, bisphenol S and bisphenol A can be obtained in good yields. In particular, when cesium hydroxide monohydrate is used as the hydroxide, the yields of bisphenol S and bisphenol A are significantly improved.

[1258] By comparing Examples 1 to 3 with Examples 5 to 7, it is confirmed that increasing the amount of hydroxide can increase the yield of bisphenol S and bisphenol A.

[1259] Comparison of Example 3 and Example 4 demonstrates that increasing the reaction temperature helps to increase the yields of bisphenol S and bisphenol A.

[1260] Separately, depolymerization of polysulfone was carried out according to the method of Example 3, except that cesium hydroxide monohydrate that had been subjected to a heat drying treatment at 150°C under reduced pressure for 5 hours was replaced with cesium hydroxide monohydrate that had not been subjected to such a heat drying treatment. The results showed that the yields of bisphenol S (BPS) and bisphenol A (BPA) were lower than those in Example 3. These results specifically confirmed that the depolymerization of compound (1) is preferably carried out under dehydration conditions.

[1261] <<Depolymerization of polysulfone (Depolymerization method (1))>>

[1262] [Example 8]

[1263] Under an argon atmosphere, calcium hydride (CaH2, dehydrating agent) (0.4 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), cesium hydroxide monohydrate (CsOH·H2O) (0.4 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added to granular polysulfone (44.3 mg; 0.10 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302) in this order. The resulting mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 18 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150° C. under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1264] Subsequently, the reaction mixture was cooled to room temperature, 1 M hydrochloric acid (1.0 mL) and ethyl acetate were added, and the organic phase was washed with water and a saturated sodium chloride aqueous solution in sequence. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1265] The crude product was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 2. 1 The results of H NMR analysis are as follows Figure 8 shown.

[1266] [Example 9]

[1267] The depolymerization of polysulfone was carried out according to the method of Example 8, except that the amount of sodium hydroxide was adjusted from 0.4 mmol to 0.2 mmol (twice the molar amount (2 equivalents) relative to the repeating unit in general formula (1)). During depolymerization, the polysulfone was dissolved.

[1268] Furthermore, the crude product was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 2. 1 The results of H NMR analysis are as follows Figure 9 shown.

[1269] [Example 10]

[1270] Depolymerization of polysulfone was carried out according to the method of Example 8, except that calcium hydride (0.4 mmol) was replaced with calcium oxide (CaO) (0.4 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in general formula (1)). During depolymerization, the polysulfone was dissolved.

[1271] Furthermore, the crude product was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 2. 1 The results of H NMR analysis are as follows Figure 10 shown.

[1272] [Example 11]

[1273] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (0.4 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), cesium chloride (CsCl2O) (0.3 mmol, 3 times the molar amount (3 equivalents) relative to the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added to granular polysulfone (45.6 mg; 0.10 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302) in this order. The mixture was heated at 150°C to dissolve the polysulfone. The resulting mixture was then stirred at 150°C for 20 hours. The cesium hydroxide monohydrate and cesium chloride used were previously dried by heating at 150° C. under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1274] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 2. In addition, 1 The results of H NMR analysis are as follows Figure 11 shown.

[1275] [Example 12]

[1276] Depolymerization of polysulfone was carried out according to the method of Example 11, except that cesium chloride (0.3 mmol) was replaced with zeolite (molecular sieve 4A, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (3 pellets) and the reaction time was changed from 20 hours to 18 hours. During depolymerization, the polysulfone was dissolved.

[1277] Subsequently, the obtained reaction mixture was analyzed in the same manner as in Example 1 to confirm that bisphenol S (BPS) and bisphenol A (BPA) had been obtained, and the yields of these target products, compound (A), and compound (B) were further calculated. The results are shown in Table 2. In addition, 1 The results of H NMR analysis are as follows Figure 12 shown.

[1278]

Chemical Formula 74

[1279]

[1280] (where n 101 is an integer (preferably 10 to 200).

[1281]

Table 3

[1282]

[1283] Comparison of Example 3 with Examples 8 and 9 demonstrates that the use of calcium hydride as a dehydrating agent allows for more efficient depolymerization. In Examples 8 and 9, no compound (B) was detected.

[1284] In Examples 10 to 12, the use of a dehydrating agent resulted in a decrease in the yield of bisphenol S and bisphenol A. This is presumably due to the reaction or interaction between the dehydrating agent and some hydroxides.

[1285] By comparing Example 8 and Example 9, it is confirmed that increasing the amount of dehydrating agent can increase the yield of bisphenol S and bisphenol A.

[1286] <<Gram-scale depolymerization of polysulfone (depolymerization method for scale-up (1))>>

[1287] [Example 13]

[1288] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (20 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), calcium hydride (CaH2) (20 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (10 mL) were added sequentially to granular polysulfone (2.21 g; 5.0 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). The resulting mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 18 hours. The cesium hydroxide monohydrate used had been previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1289] The resulting reaction mixture was then cooled to room temperature, and 0.5M hydrochloric acid (20 mL) and ethyl acetate (30 mL) were added and stirred. The mixture was then filtered through diatomaceous earth (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and ethyl acetate (30 mL) and water (30 mL) were added and stirred. The organic phase was then separated from the aqueous phase. The organic phase was washed with water (50 mL × 3), dried over anhydrous magnesium sulfate, and distilled under reduced pressure to obtain a crude product (C1).

[1290] To the aqueous phase obtained by separation was added 2M hydrochloric acid (10 mL), and the organic phase was extracted with ethyl acetate (50 mL). After washing with water (50 mL × 3), the organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product (C2).

[1291] Subsequently, the crude product (C1) was recrystallized using acetone to separate bisphenol A (BPA) (yield 532 mg, yield 47%). On the other hand, the crude product (C2) was purified by silica gel column chromatography to separate not only bisphenol S (BPS) (yield 897 mg, yield 72%) but also bisphenol A (BPA) (yield 127 mg, yield 11%). 1 The results of H NMR analysis are as follows Figure 13 As shown, bisphenol A 1 The results of H NMR analysis are as follows Figure 14 .

[1292] <<Depolymerization of polysulfone (depolymerization method (1)), preparation of ether compound>>

[1293] [Example 14]

[1294] <Depolymerization of polysulfone>

[1295] Under an argon atmosphere, calcium hydride (CaH2, dehydrating agent) (50.5 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), cesium hydroxide monohydrate (CsOH·H2O) (201 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added to granular polysulfone (131.2 mg; 0.296 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302) in this order. The resulting mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150° C. under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1296] <Preparation of ether compounds>

[1297] The reaction mixture was then cooled to room temperature, and benzyl bromide (C6H5CH2Br) (1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in general formula (1)) was added, followed by stirring at 100°C for 3 hours. The reaction mixture was cooled to room temperature, and 1M hydrochloric acid (1.0 mL) and ethyl acetate (2.0 mL) were added. The organic phase was washed sequentially with water and a saturated sodium chloride aqueous solution. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1298] Mesitylene (5.0 μL, 0.036 mmol) was added to the obtained crude product and the mixture was stirred for 2 h. 1 H NMR analysis confirmed the acquisition of the target products (ether compounds): bisphenol S dibenzyl ether (equivalent to compound (110)) and bisphenol A dibenzyl ether (equivalent to compound (1210)). Calculation of the yields of these target products revealed a 92% yield of bisphenol S dibenzyl ether and an 89% yield of bisphenol A dibenzyl ether. 1 The results of H NMR analysis are as follows Figure 15 shown.

[1299]

Chemical Formula 75

[1300]

[1301] (where n 101 is an integer (preferably 10 to 200).

[1302] <<Depolymerization of polysulfone (depolymerization method (1)), preparation of ether compound>>

[1303] [Example 15]

[1304] <Depolymerization of polysulfone>

[1305] Under an argon atmosphere, calcium hydride (CaH2, dehydrating agent) (50.5 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), cesium hydroxide monohydrate (CsOH·H2O) (201 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added to granular polysulfone (132.1 mg; 0.3 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302) in this order. The resulting mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150° C. under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1306] <Preparation of ether compounds>

[1307] Subsequently, the temperature of the reaction mixture obtained above was cooled to room temperature, and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) and (bromomethyl)cyclopropane (c-(C3H5)CH2Br) (1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)) were stirred at 100°C for 3 hours.

[1308] After the reaction mixture was cooled to room temperature, mesitylene (5.0 μL, 0.036 mmol) and deuterated chloroform (CDCl 3 ) (0.5 mL) were added to extract the organic phase. 1 H NMR analysis confirmed the acquisition of the target products (ether compounds): bisphenol S di(cyclopropyl methyl) ether (equivalent to compound (110)) and bisphenol A di(cyclopropyl methyl) ether (equivalent to compound (1210)). Further yield calculations of these target products revealed a 71% yield of bisphenol S di(cyclopropyl methyl) ether and a 56% yield of bisphenol A di(cyclopropyl methyl) ether. 1 The results of H NMR analysis are as follows Figure 16 shown.

[1309]

Chemical Formula 76

[1310]

[1311] (where n 101is an integer (preferably 10 to 200).

[1312] <<Depolymerization of polysulfone (depolymerization method (1)), preparation of ether compound>>

[1313] [Example 16]

[1314] <Depolymerization of polysulfone>

[1315] Under an argon atmosphere, calcium hydride (CaH2, dehydrating agent) (50.7 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), cesium hydroxide monohydrate (CsOH·H2O) (201 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added sequentially to granular polysulfone (133.6 mg; 0.3 mmol of the repeating unit in the general formula (1); weight average molecular weight 35,000; number average molecular weight 16,000; manufactured by Sigma-Aldrich, Cat. No. 428302). The resulting mixture was heated at 150°C to dissolve the polysulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150° C. under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1316] <Preparation of ether compounds>

[1317] Subsequently, the temperature of the reaction mixture obtained above was cooled to room temperature, and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) and 1-bromo-3,7-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH2Br) (1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in the general formula (1)) were added, and the mixture was stirred at 100°C for 3 hours.

[1318] After the reaction mixture was cooled to room temperature, mesitylene (5.0 μL, 0.036 mmol) and deuterated chloroform (CDCl 3 ) (0.5 mL) were added to extract the organic phase. 1 H NMR analysis confirmed the acquisition of the target products (ether compounds): bisphenol S di(3,7-dimethyloctyl) ether (equivalent to compound (110)) and bisphenol A di(3,7-dimethyloctyl) ether (equivalent to compound (1210)). Further yield calculations for these target products revealed a 92% yield for bisphenol S di(3,7-dimethyloctyl) ether and an 89% yield for bisphenol A di(3,7-dimethyloctyl) ether. 1 The results of H NMR analysis are as follows Figure 17 shown.

[1319]

Chemical Formula 77

[1320]

[1321] (where n 101 is an integer (preferably 10 to 200).

[1322] The results of Examples 14 to 16 demonstrate that the target ether compound can be readily obtained by subjecting the depolymerization product (monomer) of polysulfone to an etherifying agent (here, a halogenated alkane or halogenated aralkane). Furthermore, even when the type of etherifying agent is changed, the ether compound can be obtained in good yield.

[1323] <<Depolymerization of polyethersulfone (Depolymerization method (4))>>

[1324] [Example 17]

[1325] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (51.2 mg, 0.3 mmol, 3 times the molar amount (3 equivalents) relative to the repeating unit in general formula (1)) and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added to granular polyethersulfone (23.2 mg; the amount of the repeating unit in general formula (4) is 0.100 mmol; manufactured by Sigma-Aldrich, Cat. No. 191094). The resulting mixture was heated at 150°C to dissolve the polyethersulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used had been previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1326] Subsequently, the temperature of the obtained reaction mixture was cooled to room temperature, 1M hydrochloric acid (2.0 mL) was added, and dichloromethane (3 mL) was added to extract the organic phase. Then, the organic layer was washed with water and a saturated sodium chloride aqueous solution in sequence. The obtained organic phase was dried over anhydrous magnesium sulfate, and the precipitated solid was washed with n-hexane. After vacuum distillation, the target product bisphenol S (BPS) (equivalent to compound (41)) was finally obtained (yield 20.7 mg, yield 83%). The obtained bisphenol S 1 The results of H NMR analysis are as follows Figure 18 shown.

[1327]

Chemical Formula 78

[1328]

[1329] (where n 401 is an integer (preferably 10 to 200).

[1330] <<Depolymerization of polyethersulfone (depolymerization method (4)), preparation of ether compound>>

[1331] [Example 18]

[1332] Depolymerization of polyethersulfone

[1333] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (50.4 mg, 0.3 mmol, equivalent to 3 times the molar amount (3 equivalents) of the repeating unit in general formula (4)) and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added to granular polyethersulfone (23.8 mg; the amount of the repeating unit in general formula (4) is 0.103 mmol; manufactured by Sigma-Aldrich, Cat. No. 191094). The resulting mixture was heated at 150°C to dissolve the polyethersulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1334] <Preparation of ether compounds>

[1335] Subsequently, the temperature of the resulting reaction mixture was cooled to room temperature, and benzyl bromide (C6H5CH2Br) (0.3 mmol, 3 times the molar amount (3 equivalents) relative to the repeating unit in the general formula (4)) and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added, and the mixture was stirred at 100°C for 2 hours.

[1336] The reaction mixture was cooled to room temperature, and water (1.0 mL) and dichloromethane (2.0 mL) were added in sequence, followed by washing the organic phase with water and a saturated sodium chloride aqueous solution. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1337] The crude product was purified by silica gel column chromatography to separate bisphenol S dibenzyl ether (equivalent to compound (410)) (yield 38.4 mg, yield 87%). 1 The results of H NMR analysis are as follows Figure 19 shown.

[1338]

Chemical Formula 79

[1339]

[1340] (where n 401 is an integer (preferably 10 to 200).

[1341] <<Depolymerization of polyphenylene sulfone (Depolymerization method (1))>>

[1342] [Example 19]

[1343] Under an argon atmosphere, powdered polyphenylsulfone (120 mg; 0.3 mmol of the repeating unit in general formula (1); manufactured by Standard-Testpiece, Cat. No. RMOLDED0050), cesium hydroxide monohydrate (CsOH·H2O) (202 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in general formula (1)), calcium hydride (CaH2, dehydrating agent) (50.7 mg, 1.2 mmol, 4 times the molar amount (4 equivalents) relative to the repeating unit in general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added in this order. The resulting mixture was heated at 150°C to dissolve the polyphenylsulfone. The mixture was then stirred at 150°C for 19 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1344] Subsequently, the temperature of the resulting reaction mixture was cooled to room temperature, 1M hydrochloric acid (3.6 mL) was added, and water (10 mL) and ethyl acetate (20 mL) were added in sequence to extract the organic phase. The organic layer was then washed with water and a saturated sodium chloride aqueous solution in sequence. The resulting organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1345] The crude product was purified by silica gel column chromatography to obtain not only bisphenol S (equivalent to compound (110)) (yield 65.2 mg, yield 87%) but also 4,4'-dihydroxybiphenyl (equivalent to compound (123)) (yield 44.7 mg, yield 80%). 1 The results of H NMR analysis are as follows Figure 20 As shown, 4,4'-dihydroxybiphenyl 1 The results of HNMR analysis are as follows Figure 21 shown.

[1346]

Chemical Formula 80

[1347]

[1348] (where n 102 is an integer (preferably 10 to 200).

[1349] <<Depolymerization of polyetherethersulfone (Depolymerization method (1))>>

[1350] [Example 20]

[1351] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (1.2 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), calcium hydride (CaH2) (1.2 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added sequentially to granular polyetherethersulfone (95.4 mg; the amount of the repeating unit in the general formula (1) is 0.30 mmol; manufactured by Sigma-Aldrich, Cat. No. 79421). The resulting mixture was heated at 150°C for 18 hours to dissolve the polyetherethersulfone. The mixture was then stirred at 150°C for 22 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1352] Subsequently, the reaction mixture was cooled to room temperature, and 2M hydrochloric acid (1 mL) was added. N,N-dimethylformamide (DMF) (5.0 μL, 0.065 mmol) was then added. 1 H NMR analysis confirmed the acquisition of the target products, bisphenol S (equivalent to compound (11)) and hydroquinone (equivalent to compound (122)). Further yield calculations of these target products revealed a 75% yield of bisphenol S and a 68% yield of hydroquinone.

[1353] Subsequently, ethyl acetate (5 mL) and water (5 mL) were added to the reaction mixture obtained above, stirred uniformly, and the organic phase was extracted. The obtained organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1354] The crude product was purified by silica gel column chromatography to separate bisphenol S (BPS) (yield 40.6 mg, yield 55%). 1 The results of H NMR analysis are as follows Figure 22 shown.

[1355]

Chemical Formula 81

[1356]

[1357] (where n 103 is an integer (preferably 10 to 200).

[1358] <<Depolymerization of polyetheretherketone (Depolymerization method (2))>>

[1359] [Example 21]

[1360] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (1.2 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in general formula (2)), calcium hydride (CaH2) (1.2 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in general formula (2)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.6 mL) were added sequentially to granular polyetheretherketone (86.6 mg; the amount of the repeating unit in general formula (2) is 0.30 mmol; manufactured by Sigma-Aldrich, Cat. No. 79421). The resulting mixture was heated at 150°C for 18 hours to dissolve the polyetheretherketone. The mixture was then stirred at 150°C for 22 hours. The cesium hydroxide monohydrate used was previously dried by heating at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1361] Subsequently, the temperature of the resulting reaction mixture was cooled to room temperature, and 2M hydrochloric acid (1 mL) was added. Ethyl acetate (5 mL) and water (5 mL) were added, stirred evenly, and the organic phase was extracted. The resulting organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1362] The crude product was subjected to 1 H NMR analysis confirmed that the target product 4,4'-dihydroxybenzophenone (equivalent to compound (21)) was obtained (yield 53%). The crude product also contained another target product hydroquinone (equivalent to compound (22)) (yield about 5%). 1 The results of H NMR analysis are as follows Figure 23 shown.

[1363]

Chemical Formula 82

[1364]

[1365] (where n 201 is an integer (preferably 10 to 200).

[1366] <<Depolymerization of polyphenylene sulfone (Depolymerization method (1))>>

[1367] [Example 22]

[1368] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (68 mg, 0.4 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), calcium hydride (CaH2, dehydrating agent) (18 mg, 0.4 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (0.2 mL) were added sequentially to a sheet of polyphenylsulfone (45 mg; the amount of the repeating unit in the general formula (1) is 0.1 mmol; PPSU bottles manufactured by ChuChu Co.) cut from a PPSU bottle. The resulting mixture was heated at 150°C to dissolve the polyphenylsulfone. The mixture was then stirred at 150°C for 24 hours. The cesium hydroxide monohydrate used was previously dried at 150°C under reduced pressure (266.644 Pa (2 mmHg)) for 5 hours.

[1369] Subsequently, the temperature of the resulting reaction mixture was cooled to room temperature, 1M hydrochloric acid (3.6 mL) was added, and water (2 mL) and ethyl acetate (5 mL) were added in sequence to extract the organic phase. The organic layer was then washed with water and a saturated sodium chloride aqueous solution in sequence. The resulting organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain a crude product.

[1370] The crude product was purified by thin layer chromatography to obtain not only bisphenol S (equivalent to compound (110)) (yield 15.9 mg, yield 64%) but also 4,4'-dihydroxybiphenyl (equivalent to compound (123)) (yield 14.3 mg, yield 77%). 1 The results of H NMR analysis were consistent with those of Example 19.

[1371]

Chemical Formula 83

[1372]

[1373] (where n 102 is an integer (preferably 10 to 200).

[1374] <<Depolymerization of polyetherethersulfone (Depolymerization method (5))>>

[1375] [Example 22]

[1376] Under an argon atmosphere, cesium hydroxide monohydrate (CsOH·H2O) (704 mg; 12.6 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), calcium hydride (CaH2) (513 mg; 12 mmol, 4 times the molar amount (4 equivalents) of the repeating unit in the general formula (1)), and 1,3-dimethyl-2-imidazolidinone (DMI) (6.0 mL) were added sequentially to granular polyetherethersulfone (982 mg; 3.0 mmol of the repeating unit in the general formula (1); manufactured by Sigma-Aldrich, Cat. No. 79421). The res...

Claims

1. A compound decomposition method, characterized in that: Including decomposition process: The following general formula (1) (where n1 is an integer greater than 2; Z 11 and Z 12 Each independently is a non-hydrogen atom group; m 11 and m 12 Each independently represents an integer from 0 to 4. 11 When n1×m is an integer greater than 1, 11 Z 11 Can be the same or different, when m 12 When n1×m is an integer greater than 1, 12 Z 12 Can be the same or different; Ar 1 The following general formula (91), (92) or (93) (Where, X 11 、X 12 、X 21 、X 31 and X 32 Each independently is a non-hydrogen atom group; 11 、l 12 、l 21 、l 31 and l 32 Each independently represents an integer from 0 to 4. 11 When n1×l is an integer greater than 1, 11 X 11 Can be the same or different, when l 12 When n1×l is an integer greater than 1, 12 X 12 Can be the same or different, when l 21 When n1×l is an integer greater than 1, 21 X 21 Can be the same or different, when l 31 When n1×l is an integer greater than 1, 31 X 31 Can be the same or different, when l 32 When n1×l is an integer greater than 1, 32 X 32 (may be the same or different), and the bonds marked with the symbol * and the bonds marked with the symbol ** in the general formula (91), (92) and (93) respectively form covalent bonds with the oxygen atom in the general formula (1) The first compound represented by In the presence of a base, by reacting with the following general formula (8) R 8 -SH(8) (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the first compound.

2. A compound decomposition method, characterized in that: Including decomposition process: The following general formula (2) (where n2 is an integer greater than 2; Z 21 、Z 22 and Z 23 Each independently is a non-hydrogen atom group; m 21 、m 22 and m 23 Each independently represents an integer from 0 to 4. 21 When n2×m is an integer greater than 1, 21 Z 21 Can be the same or different, when m 22 When n2×m is an integer greater than 1, 22 Z 22 Can be the same or different, when m 23 When n2×m is an integer greater than 1, 23 Z 23 Can be the same or different) A third compound represented by In the presence of a base, by reacting with the following general formula (8) R 8 -SH(8) (Where R 8 wherein the alkyl, aryl or aralkyl group is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl, aryl or aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl, aryl or aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the third compound.

3. A compound decomposition method, characterized in that: Including decomposition process: The following general formula (4) (where n4 is an integer greater than 2; Z 41 and Z 42 Each independently is a non-hydrogen atom group; m 41 and m 42 Each independently represents an integer from 0 to 4. 41 When n4×m is an integer greater than 1, 41 Z 41 Can be the same or different, when m 42 When n4×m is an integer greater than 1, 42 Z 42 Can be the same or different) The fourth compound represented by In the presence of a base, by reacting with the following general formula (8) R 8 -SH(8) (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), or reacts with a hydroxide to decompose the fourth compound.

4. The compound decomposition method according to any one of claims 1 to 3, wherein The base is at least phosphazene base or sodium tert-butoxide.

5. The compound decomposition method according to any one of claims 1 to 3, wherein The second compound represented by the general formula (8) is one or more selected from the group consisting of alkyl mercaptans having 1 to 15 carbon atoms, aryl mercaptans having 6 to 12 carbon atoms, arylalkyl mercaptans having 7 to 14 carbon atoms, halogenated alkyl mercaptans having 1 to 15 carbon atoms, halogenated aryl mercaptans having 6 to 12 carbon atoms, hydroxyalkyl mercaptans having 1 to 15 carbon atoms, polythioalkanes having 1 to 15 carbon atoms, (mercaptoalkyl)trialkoxysilanes having 4 to 15 carbon atoms, and alkoxycarbonylalkyl mercaptans having 3 to 15 carbon atoms.

6. The compound decomposition method according to any one of claims 1 to 3, wherein A dehydrating agent is also used in the decomposition process.

7. The compound decomposition method according to any one of claims 1 to 3, wherein The hydroxide is an alkali metal hydroxide.

8. The compound decomposition method according to claim 6, wherein: The dehydrating agent is one or more selected from the group consisting of sodium hydride, potassium hydride, calcium hydride, calcium oxide, cesium chloride, calcium chloride, magnesium sulfate and zeolite.

9. A method for preparing an ether compound, comprising the following steps: In the compound obtained by the decomposition method of any one of claims 1 to 3, (Where Z 11 、Z 12 、m 11 and m 12 Same as above) or a salt thereof, The following general formula (121) (Where, X 11 、X 12 、l 11 and l 12 Same as above) and its salt, The following general formula (122) (Where, X 21 and l 21 Same as above) and its salt, and The following general formula (123) (Where, X 31 、X 32 、l 31 and l 32 Same as above) and one or more selected from the group consisting of compounds and salts thereof, The following general formula (21) (Where Z 21 、Z 22 、m 21 and m 22 Same as above) or a salt thereof, and the following general formula (22) (Where Z 23 and m 23 Same as above) and one or more selected from the group consisting of compounds and salts thereof, Or the following general formula (41) (Where Z 41 、Z 42 、m 41 and m 42 The ether compound is obtained by etherifying one or more phenolic hydroxyl groups or salt groups formed by the phenolic hydroxyl groups in one or more selected from the group consisting of the compounds represented by (same as above) and salts thereof.

10. A method for decomposing a compound, characterized in that: Including decomposition process: The following general formula (3) (where n3 is an integer greater than 2; Z 31 、Z 32 、Z 33 、Z 34 and Z 35 Each independently is a non-hydrogen atom group; m 31 and m 32 are each independently an integer of 0 to 3, m 33 、m 34 and m 35 Each independently represents an integer from 0 to 4. 31 When n3×m is an integer greater than 1, 31 Z 31 Can be the same or different, when m 32 When n3×m is an integer greater than 1, 32 Z 32 Can be the same or different, when m 33 When n3×m is an integer greater than 1, 33 Z 33 Can be the same or different, when m 34 When n3×m is an integer greater than 1, 34 Z 34 Can be the same or different, when m 35 When n3×m is an integer greater than 1, 35 Z 35 Can be the same or different) The fifth compound represented by In the presence of a base, by reacting with the following general formula (8) R 8 -SH(8) (Where R 8 is an alkyl group, an aryl group or an aralkyl group, one or two or more hydrogen atoms in the alkyl group, the aryl group or the aralkyl group may be substituted by a halogen atom, a hydroxyl group, a mercapto group or a trialkoxysilyl group, and when the alkyl group, the aryl group or the aralkyl group contains one or two or more trimethylene groups, the central methylene group in the trimethylene group may be substituted by an oxycarbonyl group or a carbonyloxy group), thereby reacting with a second compound represented by the present invention to decompose the fifth compound.

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