Polythioester compounds and polythioester-containing compositions

Abstract

To provide a novel polymer prepared by Michael addition reaction.SOLUTION: A polythioester compound according to one embodiment of the present invention comprises a repeating structure represented by the formula (1). In the formula (1), Y represents a divalent organic group with an aromatic ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to polythioester compounds and polythioester-containing compositions. [Background technology]

[0002] Michael addition reactions proceed at room temperature and are widely used in organic synthesis. For example, polymer synthesis via Michael addition of polyfunctional acrylates and polyfunctional amines has advantages such as yielding polymers under relatively mild conditions and producing no byproducts. Such polymer synthesis methods are rare, and due to the diversity of monomer species, research and development are actively being conducted. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Brian D.Mathera, Kalpana Viswanathana, Kevin M.Miller, Timothy E.Longa,Michael addition reactions in macromolecular design for technologies emerging, Progress in Polymer Science, Volume 31, Issue 5, May 2006, Pages 487-531 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Polymers obtained from polyfunctional acrylates and polyfunctional amines have the drawback of low heat resistance. While the use of polyfunctional methacrylates can be expected to improve heat resistance, the Michael addition reaction does not proceed with methacrylates under mild conditions. This invention addresses the above-mentioned problems and aims to provide a novel polymer obtained by a Michael addition reaction.

Means for Solving the Problem

[0005] The inventors of the present invention have found that thiomethacrylate having a thioester group functions as a Michael acceptor due to the electron delocalization peculiar to thioesters, and that a polymer is formed by the reaction of dithiomethacrylate and an aromatic diamine proceeding at room temperature under a base catalyst, and thus have completed the present invention.

[0006] One aspect of the present invention is a polythioester compound. The polythioester compound includes a repeating structure represented by the following formula (1).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0007] According to the present invention, it is possible to provide technology relating to novel polymers obtained by Michael addition reactions. [Modes for carrying out the invention]

[0008] Embodiments of the present invention will be described in detail below. In this specification, unless otherwise specified, the notation "a~b" in the description of numerical ranges means a or greater and b or less.

[0009] (Polythioester compounds) The polythioester compound according to the embodiment has a repeating structure represented by the following formula (1). [ka] In formula (1), Y is a divalent organic group having an aromatic ring. The number of carbon atoms in the organic group is preferably 4 to 40, and more preferably 6 to 34. The organic group in question is a group containing a benzene ring, such as a benzene skeleton, a biphenyl skeleton, or a bisphenol skeleton, and examples include the following: [ka] (Here, A is a single bond, -CH2-, -O-, -CO-, -S-, -SO2-, -NHCO-, -C(CF3)2-, or -C(CH3)2-.)

[0010] More specifically, the polythioester compound according to the embodiment has a repeating structure represented by the following formula (2). [ka] In formula (2), R1 is selected from a single bond, an oxygen atom, or any of the structural sites represented by formula (3) below. Also, in formula (2), R2 and R3 are independently a hydrogen atom, a hydroxyl group, or a trifluoromethyl group. [ka] In the above formula, "*" indicates the joining position.

[0011] More specifically, the polythioester compound according to the embodiment includes a repeating structure represented by the following formula (4). [ka]

[0012] The polythioester compound according to the embodiment more specifically includes any of the repeating structures represented by the following formulas (5) to (9). [ka] [ka] [ka] [ka] [ka]

[0013] The mass-average molecular weight (Mw) of the polythioester compound according to the embodiment is not particularly limited, but is typically between 10,000 and 400,000. "Mass-average molecular weight" refers to the mass-average molecular weight on a polystyrene standard basis, calculated by gel permeation chromatography (GPC). Furthermore, the degree of dispersion (Mw / Mn) of the polythioester compound according to the embodiment is typically 2 to 8.

[0014] The glass transition temperature (Tg) of the polythioester compound according to the embodiment is 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher, and exhibits excellent heat resistance.

[0015] (Method for synthesizing polythioester compounds) The polythioester compound according to this embodiment is produced from bis(4-methacryloylthiophenyl) sulfide and an aromatic diamine by the Michael addition reaction shown below (an example of a case having a repeating structure represented by formula (2) above). [ka] Specifically, the polythioester compound according to the embodiment is synthesized by dissolving an appropriate amount of bis(4-methacryloylthiophenyl) sulfide, an aromatic diamine, and a basic catalyst in a solvent, and then heating the mixture under air at 20-30°C for 60 minutes or more to allow a Michael addition reaction as shown in the above formula to proceed.

[0016] The aromatic diamines used as raw materials include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, and other aromatic diamines having one aromatic ring; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether. Minodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis Aromatic diamines having two or more aromatic rings, such as (trifluoromethyl)benzidine (TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, and 9,9-bis(4-amino-3-fluorophenyl)fluorene; 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Examples of dihydroxydiamines in which a hydroxyl group is bonded to an aromatic ring include bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. These can be used individually or in combination of two or more.

[0017] Examples of basic catalysts include diazabicycloundecene (DBU), diazabicyclononene (DBN), phosphazene bases, and various tertiary amines. These basic catalysts may be used individually or in combination of two or more types.

[0018] In this embodiment, the polythioester compound may have its methacrylic or amino groups remaining at the ends of the molecular structure encapsulated, from the viewpoint of molecular weight control, solubility in solvents, and compatibility with other components in the composition. When encapsulating the ends, monomers are used that have one amino group that can react with a methacrylic group, or one functional group such as a methacrylic group or acid anhydride group that can react with an amino group. Specifically, examples include 3-aminophenol, 2-isocyanatoethyl methacrylate, and maleic anhydride.

[0019] Examples of solvents include N-methylpyrrolidone and propylene glycol methyl ether acetate.

[0020] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted.

[0021] <Composition> The polythioester compounds of this embodiment can be combined with other components to form compositions. In particular, the polythioester compounds represented by formula (4), specifically formulas (5) to (7), have phenolic hydroxyl groups, and can therefore be combined with epoxy compounds to form thermosetting compositions, or with naphthoquinone diazide compounds to form photosensitive compositions that can be patterned by photolithography. [Examples]

[0022] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0023] (Example 1) <Synthesis> 1.94 parts by mass of bis(4-methacryloylthiophenyl) sulfide (monomer 1) and 1.82 parts by mass of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (monomer 2) were dissolved by stirring in 13 parts by mass of N-methylpyrrolidone (solvent 1). 0.04 parts by mass of diazabicycloundecene (catalyst) was added dropwise, and the Michael addition reaction was carried out under atmospheric conditions at 25°C for 8 hours to obtain the reaction product. The obtained reaction product was slowly added dropwise to a water / methanol (1:1) solution to precipitate the polymer. The polymer was separated by filtration and dried at 100°C for 10 hours to obtain a pale yellow solid compound in 90% yield.

[0024] Regarding the obtained compound, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by the following formula (10). 1 The assignment of the H-NMR spectrum is shown below. [ka]

[0025] 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0026] (Example 2) <Synthesis> Using the components and formulation of Example 2 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a pale yellow solid compound was obtained in a yield of 90%. Regarding the obtained product, 1H-NMR measurement was carried out, and it was confirmed that it is a polythioester compound represented by the above formula (10). The 1 attribution of H-NMR of the polythioester compound represented by the above formula (10) is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3)-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0027] (Example 3) <Synthesis> With the components and formulations of Example 3 shown in Table 1, under the same conditions as in Example 1, the Michael addition reaction was allowed to proceed. After obtaining the reaction product, purification was carried out in the same manner as in Example 1, and a transparent compound was obtained with a yield of 90%. Regarding the obtained product, 1 H-NMR measurement was carried out, and it was confirmed that it is a polythioester compound represented by the above formula (10). The 1 attribution of H-NMR of the polythioester compound represented by the above formula (10) is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3)-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0028] (Example 4) <Synthesis> With the components and formulations of Example 4 shown in Table 1, under the same conditions as in Example 1, the Michael addition reaction was allowed to proceed. After obtaining the reaction product, purification was carried out in the same manner as in Example 1, and a transparent compound was obtained with a yield of 90%. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0029] (Example 5) <Synthesis> Using the components and formulation of Example 5 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0030] (Example 6) <Synthesis> Using the components and formulation of Example 6 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a clear compound was obtained in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0031] (Example 7) <Synthesis> Using the components and formulation of Example 7 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0032] (Example 8) <Synthesis> Using the components and formulation of Example 8 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0033] (Example 9) <Synthesis> Using the components and formulation of Example 9 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0034] (Example 10) <Synthesis> Using the components and formulation of Example 10 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0035] (Example 11) <Synthesis> Using the components and formulation of Example 11 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a clear compound was obtained in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0036] (Example 12) <Synthesis> Using the components and formulation of Example 12 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a clear compound was obtained in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by formula (10) above. 1 The assignment of the H-NMR spectrum is shown below. 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.87(m,4H,Ar-H),7.23-7.31(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.35(br,2H,Ar-OH)

[0037] (Example 13) <Synthesis> Using the components and formulation of Example 13 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a clear compound was obtained in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by the following formula. 1The assignment of the H-NMR spectrum is shown below. [ka] 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(C H3)-CH2-NH-),7.18(m,4H,Ar-H),7.32(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.33(br,2H,Ar-OH)

[0038] (Example 14) <Synthesis> Using the components and formulation of Example 14 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After purification in the same manner as in Example 1, a clear compound was obtained in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by the following formula. 1 The assignment of the H-NMR spectrum is shown below. [ka] 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,-CO-CH(CH3 )-CH2-NH-),6.79(m,4H,Ar-H),7.20-7.35(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-),9.30(br,2H,Ar-OH)

[0039] (Example 15) <Synthesis> Using the components and formulation of Example 15 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by the following formula. 1 The assignment of the H-NMR spectrum is shown below. [ka] 1 H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,- CO-CH(CH3)-CH2-NH-),6.87(m,4H,Ar-H),7.18-7.32(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-)

[0040] (Example 16) <Synthesis> Using the components and formulation of Example 16 shown in Table 1, the Michael addition reaction was carried out under the same conditions as in Example 1 to obtain the reaction product. After that, the product was purified in the same manner as in Example 1 to obtain a clear compound in 90% yield. Regarding the obtained product, 1 ¹H-NMR measurements were performed to confirm that it is a polythioester compound represented by the following formula. 1 The assignment of the H-NMR spectrum is shown below. [ka] 1H NMR(300MHz,DMSO-d6):δ(ppm)=1.18(br,6H,-CH3),2.97(br,4H,-CO-CH(CH3)-CH2-NH-),3.20(br,2H,- CO-CH(CH3)-CH2-NH-),6.90(m,4H,Ar-H),7.25-7.38(m,10H,Ar-H),8.10(br,2H,-CO-CH(CH3)-CH2-NH-)

[0041] <Mass spectrometry> The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the polythioester compounds in each example were determined by gel permeation chromatography (GPC). In GPC, a Shodex K-805L column was used, with a column temperature of 40°C, a flow rate of 1 mL / min, chloroform as the eluent, and polystyrene as the standard substance. Table 1 shows the mass-average molecular weight (Mw) and dispersion (Mw / Mn) of the polythioester compounds in each example.

[0042] <Glass transition temperature> The glass transition temperature of the polythioester compound in each example was measured using the following procedure. For the polymer powders of the polythioester compounds obtained in each example, differential scanning calorimetry (DSC) was performed using a Q-100 TAInstruments instrument and analysis software (Universal analysis, TAInstruments). The temperature was increased and decreased at a rate of 10°C / min, the measurement range was a 20°C to 200°C cycle, under a nitrogen atmosphere, and the extrapolation start temperature of the baseline shift was defined as the glass transition temperature (Tg). The measurement results are shown in Table 1.

[0043] [Table 1]

[0044] In Table 1, monomers 1-9, catalysts, and solvents 1 and 2 are as follows: Monomer 1: Bis(4-methacryloylthiophenyl) sulfide Monomer 2: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane Monomer 3: Bis(3-amino-4-hydroxyphenyl)sulfone Monomer 4: 2,2-bis(3-amino-4-hydroxyphenyl)propane Monomer 5: 2,2'-Bis(trifluoromethyl)-4,4'-diaminodiphenyl ether Monomer 6: 2,2'-Bis(trifluoromethyl)benzidine Monomer 7: Maleic anhydride Monomer 8: 2-isocyanatoethyl methacrylate Monomer 9:3-aminophenol Catalyst: diazabicycloundecene Solvent 1: N-methylpyrrolidone Solvent 2: Propylene glycol methyl ether acetate

Claims

1. A polythioester compound comprising at least one of the repeating structures represented by the following formulas (2), (8), and (9). 【Chemistry 1】 In formula (2) above, R1 is selected from a single bond, an oxygen atom, or any of the structural sites represented by formula (3) below. Also, in the above formula, R2 and R3 are independently a hydrogen atom or a hydroxyl group. 【Chemistry 2】 In the above formula (3), "*" indicates the bonding position. 【Transformation 3】 【Chemistry 4】

2. The polythioester compound according to claim 1, comprising a repeating structure represented by the following formula (4). 【Transformation 5】

3. A polythioester-containing composition comprising the polythioester compound described in claim 1 or 2.

4. The process comprises a step of carrying out a Michael addition reaction using bis(4-methacryloylthiophenyl) sulfide and an aromatic diamine as raw materials, The aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4 A method for producing a polythioester compound, wherein the compound is one or more selected from -(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, and 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

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