Aromatic polyester and method for producing the same

Abstract

To provide a method for producing an aromatic polyester with an alkenyl group at one end, the aromatic polyester being suitably applicable as a synthesis material for polyesters or block copolymers selectively modified at both ends and being soluble in common organic solvents.SOLUTION: A method for producing an aromatic polyester represented by formula (3), the method comprising polymerizing a halocarboxylic acid metal salt compound using a compound represented by formula (1) as an initiator in the presence of a phase transfer catalyst, wherein X is a halogen group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aromatic polyester and a method for producing the same. [Background technology]

[0002] To improve the heat resistance, mechanical properties, and electrical properties of organic materials, hybrid materials (nanocomposites) that mix inorganic particles such as silica gel and titanium oxide with organic polymers have been widely studied. However, because the properties of organic and inorganic materials are fundamentally very different, problems with the above hybrid materials include the inability to incorporate so many inorganic particles into the organic material, the difficulty of dispersing the inorganic particles neatly within the organic material, and the aggregation of the inorganic particles within the organic material over time.

[0003] To solve these problems, the surfaces of inorganic particles have been modified with organic low-molecular-weight compounds or organic polymers. The two main methods used for modifying with organic polymers are: (1) introducing an initiation site onto the inorganic surface and then carrying out living polymerization from there; and (2) introducing functional groups (e.g., -Si(OR)3, -PO3H, -COOH, -SH, etc.) capable of bonding with inorganic substances into the terminals of the living polymers and then reacting them with the surface of the inorganic particles. For example, the latter method has been shown to improve heat resistance and transparency when silica particles surface-modified by introducing -Si(OR)3 groups into the terminals of linear and hyperbranched aromatic polyamides are added to aromatic polyimides, compared to when conventional unmodified silica is added (Patent Documents 1 to 3).

[0004] Thus, modifying silica particles with organic polymers is important for developing hybrid materials. For example, Patent Document 4 discloses a magnet wire insulation system in which a hybrid coating layer in which silica particles are introduced into polyimide and a polyester coating layer are produced to ensure insulation. However, in terms of the production process, multi-layer coating as in Patent Document 4 leads to reduced productivity. On the other hand, Patent Document 5 discloses a polyesterimide into which an ester structure, which generally has a low dielectric constant and low water absorption, has been introduced. However, the polyesterimide disclosed in Patent Document 5 has a limited structure and is therefore not very versatile.

[0005] Hybrid materials made from polyester-incorporated silica particles and high-performance plastics such as polyimide are expected to be useful in the development of new high-performance films, so it is important to develop a simple method for easily introducing ester structures into polyimide. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2017 / 130905 [Patent Document 2] Japanese Patent Application Publication No. 2018-123295 [Patent Document 3] Japanese Patent Application Laid-Open No. 2018-127599 [Patent Document 4] Japanese Patent Application Publication No. 2023-165640 [Patent Document 5] Japanese Patent Application Laid-Open No. 2006-013149 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and aims to provide a method for producing an aromatic polyester having an alkenyl group at one end, which can be suitably used as a raw material for synthesizing polyesters or block copolymers selectively modified at both ends and which is soluble in general-purpose organic solvents; a method for producing an aromatic polyester derived therefrom and having an alkoxysilyl group at the end; and metal oxide particles modified with a polyester having an alkoxysilyl group at the end, which can be stably stored even after purification. [Means for solving the problem]

[0008] The present inventors have found that aromatic polyesters having an alkenyl group at one end (hereinafter also referred to as "single-end alkenyl-substituted polyesters") can be efficiently obtained by polymerizing a benzoate having an alkoxy group at the 2-position and a haloalkyl group at the 4-position using a haloalkylbenzene having an alkenyl group as an initiator, and have also found that terminally modified polyesters and block copolymers can be efficiently synthesized by using this aromatic polyester having an alkenyl group substituted at one end, thereby completing the present invention.

[0009] That is, the present invention provides: 1. In the presence of a phase transfer catalyst, [ka] (In the formula, R 1 ~R 5 any one of represents an alkenyl group having 2 to 6 carbon atoms, and R 1 ~R 5 The other four of each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms, and X represents a halogen group. The compound represented by the following formula (2) is used as an initiator. [ka] (In the formula, R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, M represents a monovalent metal, and X represents a halogen group. A halocarboxylic acid metal salt compound represented by the following formula (3) is polymerized: [ka] (wherein n represents a natural number, R 1 ~R 10 and X have the same meaning as above. A method for producing an aromatic polyester represented by the formula: 2. The above R 5 is a vinyl group, and the R 1 ~R 4 wherein R is a hydrogen atom; 3. The aromatic polyester obtained by the production method 2 is reacted with trialkoxysilane in the presence of a platinum catalyst, to form a compound represented by the following formula (4): [ka] (In the formula, R 7 ~R 10 , X and n have the same meanings as above, R 16 represents an alkyl group having 1 to 6 carbon atoms. A method for producing an aromatic polyester represented by the formula: 4. An aromatic polyester represented by the following formula (3), having a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less: [ka] (In the formula, R 1 ~R 5 any one of represents an alkenyl group having 2 to 6 carbon atoms, and R 1 ~R 5 the other four of each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, X represents a halogen group, and n represents a natural number. 5. An aromatic polyester represented by the following formula (4), having a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less: [ka] (In the formula, R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, and R 16 represents an alkyl group having 1 to 6 carbon atoms, X represents a halogen group, and n represents a natural number. 6. Surface-modified metal oxide particles in which the aromatic polyester of 5 is attached to the surface of metal oxide particles to provide. [Effects of the Invention]

[0010] According to the present invention, aromatic polyesters substituted with an alkenyl group at one end can be efficiently obtained. By using such aromatic polyesters substituted with an alkenyl group at one end, polyesters and block copolymers further modified with an alkenyl group or a halogen atom at the end can be efficiently produced, and polyesters having silyl groups at the end can also be derived, which are useful as surface modification materials for inorganic fine particles. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in more detail below. [1] Method for producing aromatic polyester substituted with an alkenyl group at one end The method of the present invention for producing an aromatic polyester represented by the following formula (3) (hereinafter referred to as "polyester (3)") is characterized by polymerizing a halocarboxylic acid metal salt compound represented by the following formula (2) (hereinafter referred to as "compound (2)") using a benzene compound represented by the following formula (1) (hereinafter referred to as "compound (1)") as an initiator in the presence of a phase transfer catalyst.

[0012] [ka]

[0013] In each of the above formulas, R 1 ~R 5 any one of represents an alkenyl group having 2 to 6 carbon atoms, and R 1 ~R 5 the other four of which are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; X represents a halogen group; R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, M represents a monovalent metal, and n represents a natural number, preferably an integer of 2 or more.

[0014] The alkyl group having 1 to 5 carbon atoms may be either linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, tert-butyl, and n-pentyl. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group and an allyl group.

[0015] Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl and propargyl groups. Examples of aromatic groups having 1 to 12 carbon atoms include phenyl, naphthyl, furyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, and tetrazolyl groups, and those having 5 or more atoms constituting the aromatic ring are preferred. R 10The alkyl group having 3 to 20 carbon atoms may be either linear or branched, and specific examples thereof include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, and 1-methyl-n-pentyl. , 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl , 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1- Ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,Examples include 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosyl.

[0016] Examples of the halogen atom for X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In consideration of reactivity, a chlorine atom, a bromine atom, and an iodine atom are preferred, and a bromine atom is more preferred. M is a monovalent metal, and specific examples thereof include lithium, sodium, and potassium, with sodium and potassium being preferred, and potassium being more preferred.

[0017] In formula (1), R 1 ~R 5 One of them is alkenyl having 2 to 6 carbon atoms, and R 5 is preferably an alkenyl group, more preferably a vinyl group. 1 ~R 5 The remaining four are preferably hydrogen atoms. Specific examples of the compound (1) include p-vinyl-α-bromotoluene.

[0018] In equation (2), R 7 ~R 9 is preferably a hydrogen atom, and R 10 is preferably an alkyl group having 5 to 20 carbon atoms. In addition, in formula (2), a halomethyl group and R 7 ~R 9 The substitution position on the benzene ring is optional, but the substitution position shown in (2') below is preferred.

[0019] [ka] (In the formula, R 7 ~R 10 , X and M have the same meanings as above.)

[0020] In the production method of the present invention, the amount of compound (1) used is not particularly limited, but is preferably in the range of 0.002 to 0.2 moles per mole of compound (2) as a substrate. In consideration of the selectivity and reaction efficiency of the subsequent polymerization reaction, the amount is more preferably in the range of 0.001 to 0.3 moles, and even more preferably in the range of 0.05 to 0.2 moles.

[0021] Examples of the phase transfer catalyst used in the polymerization reaction include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium chloride, tetraethylammonium iodide, tetrabutylammonium iodide, and tributylammonium hydrogen sulfate; crown ethers such as 15-crown-5 and 18-crown-6; and quaternary phosphonium salts such as tributyloctylphosphonium bromide and tributyldodecylphosphonium bromide. The phase transfer catalyst is usually used in an amount of 0.1 to 5 times by mole, preferably 0.5 to 1.5 times by mole, per mole of compound (2).

[0022] The temperature of the polymerization reaction is not particularly limited, but is preferably about -20 to 80°C, more preferably about -10 to 70°C, and even more preferably about -5 to 60°C. The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.

[0023] The solvent used in the polymerization reaction is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, 1,2-dichloroethane, and chlorobenzene; ethers such as diethyl ether, diisopropyl ether, diglyme, dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ureas such as N,N'-dimethylimidazolinone; water; and mixed solvents thereof.

[0024] After the polymerization reaction, the reaction is quenched with an acid such as hydrochloric acid to obtain polyester (3). In this case, the concentration of the acid is not particularly limited, but is usually about 1 to 12M, preferably about 3 to 10M, and more preferably about 4 to 7M. After quenching with acid, the pure polyester (3) can be obtained by post-treatment and purification according to conventional methods. The polyester (3) has a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less. The number average molecular weight is a value calculated as polystyrene by GPC (the same applies hereinafter).

[0025] In the production method of the present invention, the initiator compound (1), the substrate compound (2), the phase transfer catalyst, the solvent, etc. may be added in any order, but it is preferable to use the following method. That is, in this method, compound (1) is mixed with a solvent to prepare mixture A, the obtained mixture A is mixed with compound (2) to prepare mixture B, and a solution of a phase transfer catalyst mixed with a solvent is further mixed into mixture B to polymerize compound (1) to compound (2). In this case, the methods for preparing mixtures A and B and the method for mixing mixture B with a solution of a phase-transfer catalyst are also arbitrary. However, a preferred method is one in which compound (2) does not dissolve in a solvent until the phase-transfer catalyst is mixed therein, and compound (2) is polymerized after the phase-transfer catalyst is added.

[0026] The initiator compound (1) may be a commercially available product or may be produced by a conventional method. Furthermore, as will be described in detail in the Examples, compound (2) can be obtained, for example, by reacting a 4-methylsalicylic acid derivative represented by the following formula (2-1) with an alkyl halide, hydrolyzing the resulting compound (2-2), and protecting the carboxylic acid to give compound (2-4), which is then reacted with a halogenating agent to halogenate the methyl group, and then hydrolyzing the carboxylic acid moiety to give a metal salt.

[0027] [ka] (In the formula, R 7 ~R 10 and X have the same meaning as above, J represents a chlorine atom, a bromine atom, or an iodine atom, and R represents an alkyl group or the like.

[0028] [2] Synthesis of polyesters with terminal silyl groups The polyester (3) obtained by the above production method can be derived into a polythiophene compound having a terminal silyl group such as a trialkoxysilyl group, using the terminal alkenyl group as a foothold. For example, R 5 is a vinyl group, and R 1 ~R 4 Polyester (3) in which is a hydrogen atom is reacted with HSi(OR 16 )3(wherein, R 16represents an alkyl group having 1 to 6 carbon atoms.) to obtain a polyester having a trialkoxysilyl group at one end represented by the following formula (4) (hereinafter referred to as "polyester (4)"). In this case, polyester (4) also has the characteristics of a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less.

[0029] [ka] (In the formula, R 7 ~R 10 , R 16 , X and n have the same meanings as above.)

[0030] Above R 16 Specific examples of the alkyl group having 1 to 6 carbon atoms may be either linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, tert-butyl, n-pentyl, and n-hexyl groups. Specific examples of trialkoxysilanes include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, and tri-i-propoxysilane.

[0031] Specific examples of platinum catalysts include chloroplatinic acid, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, hexachloroplatinum hexahydrate, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and platinum-activated carbon.

[0032] The amount of the platinum catalyst used is, for example, preferably 0.0001 to 2 mol, more preferably 0.01 to 1 mol, per 1 mol of the polyester (3).

[0033] The reaction temperature is not particularly limited, but is preferably 0 to 100° C., more preferably 10 to 50° C. The reaction time is also not particularly limited, but is preferably 0.1 to 10 hours, more preferably 0.2 to 5 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon. After the reaction, the target product can be recovered by distillation, reprecipitation purification, or the like.

[0034] A solvent can also be used in the reaction. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; and aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The water content is not particularly limited, but a dehydrated solvent is preferred to prevent side reactions.

[0035] [3] Surface-modified metal oxide fine particles The polyester (4) obtained by the above production method can be used as a surface treatment agent for metal oxides by utilizing its terminal trialkoxysilyl group, and as a result, metal oxide microparticles whose surfaces are modified with the polyester can be obtained. The metal oxide particles are not particularly limited, and may be appropriately selected from various conventionally known metal oxides such as SiO2, SnO2, TiO2, WO3, ZnO, ZrO2, In2O3, Sb2O5, etc., depending on the intended use, etc. From the viewpoints of versatility and transparency, SiO2 is preferred. The size of the metal oxide particles is not particularly limited, but from the viewpoint of versatility, it is preferably 5 nm to 10 μm, from the viewpoint of elastic modulus, it is more preferably 10 nm to 10 μm, and from the viewpoint of transparency, it is even more preferably 10 to 100 nm, and even more preferably 10 to 50 nm.

[0036] The surface of the metal oxide particles can be modified with polyester (4) by a known method, for example, by adding polyester (4) to a dispersion of metal oxide particles, heating the mixture to 50 to 80°C, and treating for 1 to 10 hours. [Example]

[0037] The present invention will be described in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples. The measuring devices used in the examples are as follows. [GPC] Apparatus: Shodex GPC-101 (Showa Denko K.K.) Column: Shodex KF-804L (Showa Denko K.K.) x 2 Column temperature: 40℃ Solvent: Chloroform 1 mL / min Detector: UV (254 nm), RI Calibration curve: Standard polystyrene [ 1 H-NMR] Equipment: JEOL ECA-500 and ECA-600 [ 13 C-NMR] Equipment: JEOL ECA-500 and ECA-600 [IR] Equipment: JASCO FT / IR-410 [TG-DTA] Equipment: Seiko Instruments Inc. TG / DTA 6200 [MALDI-TOFF] Equipment: AXIMA-CFR plus Shimadzu / Kratos Reflection mode: Laser (λ=337nm) Matrix:1,8-dihydroxy-9[10H]-anthracenone

[0038] [1] Monomer synthesis for phase transfer polymerization [Synthesis Example 1] Synthesis of intermediate compound (A) [ka]

[0039] The reaction was carried out in a 200 mL recovery flask equipped with a fin condenser. 10.12 g (66.5 mmol) of 4-methylsalicylic acid and 150 mL of dry acetone were added to the flask and stirred. 29 mL (166.7 mmol) of 1-bromooctane, 27.25 g (197 mmol) of potassium carbonate, and 1.75 g (6.62 mmol) of 18-crown-6 were added and refluxed for 60 hours, followed by filtration. The solvent was removed under reduced pressure, followed by extraction with ether, washing with water, and drying over anhydrous magnesium sulfate. After filtration and distillation of the solvent under reduced pressure, 28.9 g (117% yield) of crude intermediate compound (A) was obtained as a cloudy white liquid.

[0040] 1 H-NMR(400MHz, CDCl3) δ7.75(d,J=7.2Hz,1H),6.75(d,J=8.4Hz,1H),6.74(s,1H),4.00(t,J=6.6Hz,2H),2.36(s,3H),1.83(q uint,J=7.2Hz,2H),1.47(quint,J=7.4Hz,2H),1.37-1.27(m,8H),0.88(t,J=6.8Hz,3H),0.37(s,3H).

[0041] [Synthesis Example 2] Synthesis of intermediate compound (B) [ka]

[0042] The reaction was carried out in a 200 mL recovery flask equipped with a finder. 10.03 g (26.6 mmol) of intermediate compound (A), 7.84 g (140 mmol) of potassium hydroxide, and 90 mL of ethanol were added to the flask and refluxed for 14.5 hours. After this, the solvent was removed under reduced pressure, 1 M hydrochloric acid was added, and the mixture was extracted with ether, washed with water, and dried over anhydrous magnesium sulfate. The crude product obtained by filtration and distillation of the solvent under reduced pressure was distilled at 60 °C / 0.4 mmHg to remove the octanol. The residue was recovered, yielding 4.35 g (62% yield) of intermediate compound (B) as a brown viscous liquid.

[0043] 1 H NMR(400MHz, CDCl3) δ11.0(s,1H),8.06(d,J=8.4Hz,1H),6.93(d,J=8.4Hz,1H),6.84(s,1H),4.23(t,J=6.4Hz,2H),2.41(s ,3H),1.91(quint,J=7.1Hz,2H),1.49(quint,J=7.3Hz,2H),1.39-1.26(m,8H),0.89(t,J=6.8Hz,3H). 13 C NMR(150MHz,CDCl3) δ165.5,157.5,146.3,133.6,123.0,114.9,113.1,70.1,31.7,29.1,29.1,28.9,25.8,22.6,22.0,14.0. IR (neat)3282,2927,2856,1738,1612,1574,1501,1405,1252,1173,1134,1088,1020,829,775,736,684cm -1 .

[0044] [Synthesis Example 3] Synthesis of intermediate compound (C) [ka]

[0045] The reaction was carried out in a 20 mL recovery flask equipped with a Vigreux tube. 2.05 g (7.75 mmol) of intermediate compound (B), 71.2 mg (0.39 mmol) of o-sulfobenzimide, and 7.5 mL of chloroform were added to the flask and stirred. 2 mL (9.54 mmol) of 1,1,1,3,3,3-hexamethyldisilazane was added, and the mixture was purged with argon and refluxed for 2.5 hours. The solvent was then removed under reduced pressure, and the resulting crude product was distilled at 150 °C / 0.4 mmHg to obtain 2.03 g (80% yield) of intermediate compound (C) as a colorless, transparent liquid.

[0046] 1 H NMR(400MHz,CDCl-3) δ7.75(d,J=7.2Hz,1H),6.75(d,J=8.4Hz,1H),6.74(s,1H),4.00(t,J=6.6Hz,2H),2.36(s,3H),1.83(q uint,J=7.2Hz,2H),1.47(quint,J=7.4Hz,2H),1.37-1.27(m,8H),0.88(t,J=6.8Hz,3H),0.37(s,9H). 13 C NMR(150MHz,CDCl3) δ166.4,159.4,144.5,132.7,120.7,118.3,113.9,68.8,31.9,29.4,29.3,29.3,26.1,22.7,21.9,14.1. IR (neat)2955,2927,2857,1709,1611,1502,1417,1307,1253,1180,1140,1079,851,782cm -1 .

[0047] [Synthesis Example 4] Synthesis of intermediate compound (D) [ka]

[0048] The reaction was carried out in a 200 mL recovery flask equipped with a Vigreux tube. To the flask were added 26.8 g (79.7 mmol) of intermediate compound (C), 110 mL of carbon tetrachloride, 3.62 g (20.3 mmol) of N-bromosuccinimide, and 0.17 g (1.04 mmol) of 2,2'-azobis(isobutyronitrile). After refluxing for 45 minutes, 3.67 g (20.6 mmol) of N-bromosuccinimide and 0.16 g (0.99 mmol) of 2,2'-azobis(isobutyronitrile) were added again. This procedure was repeated five times, and finally 14.2 g (80 mmol) of N-bromosuccinimide and 0.64 g (3.97 mmol) of 2,2'-azobis(isobutyronitrile) were added. After refluxing for 8 hours, the mixture was filtered, water was added, extracted with ether, and dried over anhydrous magnesium sulfate. The solvent was removed by filtration under reduced pressure to obtain a crude product as a pale yellow solid. This was further recrystallized five times from carbon tetrachloride and methylene chloride / hexane to obtain 5.9 g (21% yield) of intermediate compound (D) as a white solid (mp 79-80°C).

[0049] 1 H NMR(400MHz, CDCl3) δ10.9(s,1H),8.16(d,J=8.4Hz,1H),7.14(d,J=7.6Hz,1),7.07(s,1H),4.47(s,2H),4.28(t,J=6.8Hz ,2H),1.93(quint,J=7.6Hz,2H),1.50(quint,J=7.6Hz,2H),1.42-1.25(m,8H),0.89(t,J=6.8Hz,3H). 13 C NMR(100MHz,CDCl3) δ164.7,157.6,145.0,134.3,122.5,117.5,113.1,70.5,31.8,31.7,29.1,29.0.28.8,25.8,22.6,14.1. IR (KBr)3074,2953,2913,2871,2853,2637,2560,2362,1710,1678,1609,1572,1503,1471,1450,1425,1409 ,1309,1260,1210,1184,1144,1090,1055,1014,951,863,794,780,769,743,727,702,662,599,542,430cm -1 .

[0050] [Synthesis Example 5] Synthesis of Monomer (E) [ka]

[0051] The reaction was carried out in a 50 mL recovery flask. 1.61 g (4.7 mmol) of intermediate compound (D), 30 mL of dry methanol, and several drops of phenolphthalein solution were added to the flask and stirred. 0.42 g (7.5 mmol) of potassium hydroxide and 60 mL of dry methanol were added to a 30 mL recovery flask and stirred. The latter solution was added in small portions to the former solution until the pH reached 7. The solvent was removed by distillation under reduced pressure, and the solid was washed with ether and filtered. The resulting solid was dried under reduced pressure overnight in a desiccator containing diphosphorus pentoxide, yielding 1.09 g (60% yield) of monomer (E) as a white solid.

[0052] IR (KBr)3423,2956,2924,2854,2361,1584,1421,1389,1252,1212,1177,1103,1020,829cm -1 .

[0053] [2] Synthesis of aromatic polyester [Example 1] Synthesis of Polyester (g) Substituted with a Vinyl Group at One End [ka]

[0054] The reaction was carried out in a 10 mL recovery flask equipped with a three-way stopcock. 374.47 mg (0.982 mmol) of monomer (E) was added to the flask and the atmosphere was purged with argon. 19.28 mg (0.0978 mmol) of p-vinyl-α-bromotoluene was added to a separate 5 mL pear-bottomed flask and the atmosphere was purged with argon. 1.5 mL of dry acetone was added under a nitrogen stream and stirred. The latter solution was added to the former solution using a syringe under a nitrogen stream. 18.54 mg (0.05 mmol) of tetrabutylammonium iodide was added to a separate 5 mL pear-bottomed flask and the atmosphere was purged with argon. 1.5 mL of dry acetone was added under a nitrogen stream and stirred. The latter solution was added to the former solution using a syringe under a nitrogen stream and stirred at room temperature for 24 hours. 6 M hydrochloric acid was added, extracted with methylene chloride, washed with water, and dried over anhydrous magnesium sulfate. The mixture was filtered and the solvent was distilled off under reduced pressure to obtain 260.6 mg (yield 94%) of a pale yellow viscous liquid single-terminated vinyl polyester. GPC and MALDI-TOF MS of the obtained product were measured (M n =3980,M w / M n =1.17).

[0055] 1 H NMR(400MHz,CDCl3) δ7.86-7.78(m,1nH),7.40(s,4H),7.07-6.96(m,1nH),7.07-6.96(m,1nH),6.74-6.67(dd,J=10.8 and 18Hz,1H),5.75(d,J=17.6Hz,1H),5.39-5.32(m,2nH),5.39-5.32(m,2H),4.43-4.39(s,2H),5.27(d,J=10.4Hz,1H) ,4.43(s,2H),4.04(t,J=6.4Hz,2nH),1.79(t,J=8.0Hz,2nH),1.42(m,2nH),1.26-1.18(m,8nH),(t,J=6.8Hz,3nH).

[0056] [Example 2] Synthesis of polyester (h) substituted with triethylsilyl group at one end [ka]

[0057] The reaction was carried out in a glovebox using a 100 mL recovery flask equipped with a three-way stopcock heated with a heat gun under reduced pressure. 24.7 mg (0.047 mmol) of hexachloroplatinic acid hexahydrate was added to the flask. 1.24 g (0.283 mmol) of the vinyl-terminated polyester (g) and 47 mL of dry THF were added to a separate vial. The latter solution and 2.9 mL (14.1 mmol) of triethoxysilane were added to the former flask and stirred at room temperature for 30 minutes. The flask was removed from the glovebox and stirred at 55 °C for 6 days. The solvent was removed under reduced pressure, followed by precipitation purification (good solvent / poor solvent = THF / hexane), extraction with methylene chloride, washing with water, and drying over anhydrous sodium sulfate. After filtration and evaporation of the solvent under reduced pressure, 1.10 g (86% yield) of the mono-terminally triethylsilyl-substituted polyester (h) was obtained.

[0058] 1 H NMR(400MHz, CDCl3) δ8.05-7.73(m,nH),7.41-7.20(m,4H),7.14-7.00(m,2nH),5.38-5.30(m,2nH),4.05-3.97(m,2nH),3.86-3.75(m,6H ),1.94-1.90(m,2H),1.81-1.74(m,2nH),1.40(m,2nH),1.26-1.16(m,8n+9H),1.04-0.98(m,2H),0.86-0.83(m,3nH). 13 C NMR(100MHz,CDCl3) δ165.8,165.4,164.4,159.2,159.1,158.3,142.7,142.5,1355.5,132.2,132.1,132.0,119.5,119.3,119. 2,112.5,112.4,112.3,77.2,69.4,69.1,69.0,68.9,65.8,65.7,31.8,29.3,29.2,29.0,25.9,22.6,14.1. IR (neat)953,2926,2871,2855,2355,2348,1732,1708,1613,1577,1428,1372,1295,1234,1179,1138,1083,778cm -1 .

[0059] [3] Synthesis of surface-modified metal oxides [Example 3] Synthesis of polyester-modified silica sol (i) 21 g of 1,3-dimethylimidazolidinone (hereinafter referred to as DMI) was added to 30 g of MT-ST (methanol silica sol manufactured by Nissan Chemical Industries, Ltd.), and the methanol was removed using an evaporator to obtain a 30 wt % DMI sol (i). Next, 3 mL of a THF solution containing 300 mg of the one-terminal triethylsilyl-substituted polyester (h) obtained in Example 2 was added, and the THF was removed using an evaporator. Then, 10 mL of methyl ethyl ketone was added, and the mixture was heated at 80°C for 6 hours. The methyl ethyl ketone was then removed using an evaporator, yielding the desired polyester-modified silica sol (i).

[0060] [4] Preparation of hybrid film of polyamic acid and polyester-modified silica sol (i) [Synthesis Example 6] Synthesis of polyamic acid (P1) The polymerization solvent was a mixture of 320 g of N-methylpyrrolidone and 80 g of N,N-dimethylacetamide in a mass ratio of 8:2. Then, 249 g of this mixed solvent was added to a recovery flask, and 24.6 g of 4,4'-diaminodiphenyl ether (DDE) was added, followed by 26.3 g of pyromellitic dianhydride (PMDA). Polymerization was carried out at 50°C to obtain polyamic acid (P1). The physical properties of P1 were a solids content of 17% by mass, a viscosity of 13,640 mPa·s at 25°C measured using an E-type viscometer, and a weight-average molecular weight of 63,000.

[0061] [Reference Example 1] Hybrid film production A 20 mL sample bottle containing 3.0 g of polyamic acid (P1) and 1.7 g of polyester-modified silica sol (i) was stirred at 1500 rpm for 10 minutes using a vacuum stirring and degassing mixer (V-mini300, manufactured by EME Co., Ltd.) to obtain a transparent yellow varnish with a component ratio of polyamic acid (P1):polyester-modified silica sol (i) = 1:1. The resulting varnish was bar-coated onto a 10 x 10 cm alkali-free glass substrate (Corning, product name: Eagle XG) with a gap of 250 μm. The substrate was then baked in nitrogen on a hot plate at 100°C for 30 minutes, then baked at 230°C for another 30 minutes, and immersed in pure water to obtain the desired coating film. The resulting coating film exhibited no haze and was self-supporting.

Claims

1. In the presence of a phase transfer catalyst, 【Chemical 1】 (In the formula, R 1 ~R 5 any one of R represents an alkenyl group having 2 to 6 carbon atoms; 1 ~R 5 The other four of each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms, and X represents a halogen group. The compound represented by the following formula (2) is used as an initiator. 【Chemistry 2】 (In the formula, R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, M represents a monovalent metal, and X represents a halogen group. A halocarboxylic acid metal salt compound represented by the following formula (3) is polymerized: 【Chemistry 3】 (wherein n represents a natural number, R 1 ~R 10 and X have the same meaning as above. A method for producing an aromatic polyester represented by the formula:

2. The R 5 is a vinyl group, and the R 1 ~R 4 The method for producing an aromatic polyester according to claim 1, wherein is a hydrogen atom.

3. The aromatic polyester obtained by the method of claim 2 is reacted with trialkoxysilane in the presence of a platinum catalyst to form a compound represented by the following formula (4): 【Chemistry 4】 (In the formula, R 7 ~R 10 , X and n have the same meanings as above, R 16 represents an alkyl group having 1 to 6 carbon atoms. A method for producing an aromatic polyester represented by the formula:

4. An aromatic polyester represented by the following formula (3), having a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less: 【Chemistry 5】 (In the formula, R 1 ~R 5 any one of represents an alkenyl group having 2 to 6 carbon atoms, and R 1 ~R 5 the other four of R each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, X represents a halogen group, and n represents a natural number.

5. An aromatic polyester represented by the following formula (4), having a number average molecular weight of 1,000 to 100,000 and a molecular weight distribution of 1.3 or less: 【Chemistry 6】 (In the formula, R 7 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cyano group, a hydroxyl group, a hydroxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aromatic group having 1 to 12 carbon atoms; R 10 represents an alkyl group having 3 to 20 carbon atoms, and R 16 represents an alkyl group having 1 to 6 carbon atoms, X represents a halogen group, and n represents a natural number.

6. 6. Surface-modified metal oxide fine particles, comprising metal oxide particles having the aromatic polyester of claim 5 attached to the surface thereof.

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