Polyester imide, epoxy-polyester imide matrix resins, and methods of making and using the same

Abstract

The application discloses a polyester imide with the following structure: wherein n is 1-100; R1 is an alkylene group with 2-20 carbon atoms or =(C2H4) x O, x is 1-10; R2 is an alkylene group with 2-20 carbon atoms or an arylene group with 6-18 carbon atoms. The application further provides a polyester imide preparation method, an epoxy-polyester imide matrix resin and a preparation method and application thereof.

Description

Technical Field

[0001] This application relates to the field of polymer materials, and in particular to a polyesterimide and its epoxy-polyesterimide matrix resin, as well as its preparation method and uses. Background Technology

[0002] Polyesterimide is a polyimide containing ester groups. Because its molecular structure contains both ester bonds and imide structures, polyimide resins possess the properties of both polyester and polyimide resins. For example, its processability and flowability are superior to polyimide, while its heat resistance, radiation resistance, and various mechanical properties are superior to polyester. Currently, methods for preparing high-temperature resistant epoxy resins have been reported. Chinese invention patent application CN115678287A discloses a method for preparing and applying a high-temperature resistant epoxy resin. Its main feature is the use of 2-ethyl-4-methylimidazolium as an epoxy resin curing agent, and the modification of the epoxy resin by adding a toughening agent, end-carboxyl-terminated nitrile rubber, and a coupling agent to prepare a high-temperature resistant epoxy resin adhesive. However, its heat resistance still has significant limitations and cannot meet the requirements of high-temperature operating environments.

[0003] Chinese invention patent application CN115785398A discloses a silicone-modified epoxy resin and its preparation method. Its main feature is the application of silicone intermediates to graft epoxy resin to obtain a side-chain modified epoxy resin. Further, diallyl bisphenol A and phenyl hydrogen-containing silicone oil are used to extend the epoxy backbone and construct a silicone crosslinking network. The resulting silicone-modified epoxy resin exhibits good thermal stability. While opening some epoxy groups to generate more reactive sites facilitates the introduction of silicone, it also consumes some epoxy groups, thus reducing the crosslinking density of the resin and leading to a decrease in mechanical properties.

[0004] Imides possess excellent heat resistance, with thermal decomposition temperatures generally above 400℃, and also exhibit toughening properties. Therefore, polyimide resins are commonly used as modifiers to enhance the heat resistance and toughness of epoxy resins. However, polyimide resins have relatively poor compatibility with epoxy resins and are difficult to process. Summary of the Invention

[0005] To address the aforementioned issues, this application provides a long-chain macromolecular polyester imide that exhibits good high-temperature resistance and excellent flexibility. Furthermore, the polyester imide of this application can effectively improve the heat resistance and toughness of epoxy resins.

[0006] This application provides the following technical solution.

[0007] This application provides a polyesterimide having the following structure:

[0008]

[0009] Where n is 1-100;

[0010] R1 is an alkylene group with 2-20 carbon atoms or = (C2H4). x O, x is 1-10;

[0011] R2 is an alkylene group having 2-20 carbon atoms or an aryl group having 6-18 carbon atoms.

[0012] 2. The polyester imide according to claim 1, wherein R1 is an alkylene group having 2-6 carbon atoms or -(C2H4O). x - and x is 1-5;

[0013] Preferably, R1 is ethylene or (C2H4)2O.

[0014] 3. The polyester imide according to item 1, wherein R2 is an alkylene group having 5-15 carbon atoms or an arylene group having 8-18 carbon atoms;

[0015] Preferably, R2 is a straight-chain alkylene group having 5-12 carbon atoms or Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0016] 4. The polyester imide according to item 1, wherein the weight-average molecular weight to number-average molecular weight ratio Mw / Mn of the polyester imide is 1.01-1.3.

[0017] 5. The polyester imide according to item 1, wherein the weight-average molecular weight of the polyester imide is 20000 g / mol to 49000 g / mol.

[0018] 6. A method for preparing a polyesterimide, comprising the following steps:

[0019] The diamine and trimellitic anhydride were added to an organic solvent and stirred to react.

[0020] An azeotropic dehydrating agent and a cyclization catalyst were added to the above reaction. After removing the azeotropic dehydrating agent, a precipitating agent was added dropwise while stirring to obtain an imide dicarboxylic acid.

[0021] The imide dicarboxylic acid and diol are added to a catalyst and an organic solvent, and then the organic solvent is removed to obtain polyester imide.

[0022] 7. The preparation method according to item 6, wherein the molar ratio of the diamine to trimellitic anhydride is 1:(2-2.5).

[0023] 8. The preparation method according to item 6, wherein the primary diamine is selected from aliphatic or aromatic diamines, preferably ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, heptaethylenediamine, octanediamine, nonanediamine, decanediamine, undecyldiamine, tridecyldiamine, tetradecyldiamine, pentadecyldiamine, hexadecyldiamine, heptadecanyldiamine, octadecyldiamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, methyl-m-phenylenediamine, methyl-p-phenylenediamine, methyl-o-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5 5'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 3,3',5,5'-Tetraethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dichloro-4,4'-Diaminodiphenylmethane, 4,4'-Diaminobiphenyl, 2,2'-Di(trifluoromethyl)-4,4'-Diaminobiphenyl, 3,3',5,5'-Tetramethyl-4,4'-Diaminobiphenyl, 4,4'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl ether, 4,4'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfone, 3,3'- Diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 2,6-bis(4-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)benzonitrile, 3,5-bis(4-aminophenoxy)benzoic acid, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,6-bis(4-aminophenoxy)toluene, 2,5-bis(4-aminophenoxy)toluene, 3,5-bis(2-trifluoromethyl-4-aminophenoxy)benzoic acid, 2 6-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,5-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)diphenylmethane, 4,4'-bis(3-aminophenoxy)diphenylmethane, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfone, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 4,4'-bis(3-aminophenoxy)diphenyl sulfide, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfide, 4,4'-bis(4-aminophenoxy)diphenyl ether, 4,4'-bis(3-aminophenoxy)diphenyl sulfide The mixture comprises one or more of the following: diphenyl ether, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, and 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, preferably m-phenylenediamine or 1,10-decanediamine.

[0024] 9. The preparation method according to item 6, wherein the azeotropic dehydrating agent is selected from one or more of o-xylene, m-xylene, p-xylene, benzene, monochlorobenzene, and dichlorobenzene, preferably toluene; and / or

[0025] The cyclization catalyst is selected from one or more of sulfuric acid, phosphoric acid, methanesulfonic acid, and methylbenzenesulfonic acid, with methylbenzenesulfonic acid being preferred.

[0026] 10. The preparation method according to item 6, wherein after adding the azeotropic dehydrating agent and the cyclization catalyst, heating is started until the temperature reaches T1, preferably 80°C-150°C, and the reaction system is maintained at the T1 temperature for 1 hour-12 hours, after which the azeotropic dehydrating agent is removed.

[0027] 11. According to the preparation method described in item 6, after removing the azeotropic dehydrating agent, the temperature of the reaction system is lowered to T2, preferably 60℃-80℃, and then room temperature water with a mass twice that of the material is prepared. The material is slowly poured into the water while stirring, thereby obtaining the imide dicarboxylic acid.

[0028] 12. The preparation method according to item 6, wherein the molar ratio of the imide dicarboxylic acid to the diol is 1:(0.6-1.5).

[0029] 13. The preparation method according to item 6, wherein the diol is selected from one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecyladiol, dodecadiol, tridecadiol, tetradecadiol, pentadecyldiol, hexadecyldiol, heptadecadiol, octadecyldiol, ethylene glycol monohydrate, diethylene glycol, triethylene glycol, tetraethylene glycol, and benzyldimethylethanol, preferably diethylene glycol or ethylene glycol.

[0030] 14. The preparation method according to item 6, wherein the catalyst is selected from one or more of sulfuric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid, strongly acidic H-type cation exchange resin, and TP-284; and / or

[0031] The precipitant is methanol, ethanol, or deionized water.

[0032] 15. According to the preparation method described in item 6, after the imide dicarboxylic acid and diol are added to the system consisting of a catalyst and an organic solvent, heating is started until the temperature reaches T3, preferably 80°C-130°C. After the reaction system is maintained at the T3 temperature for 1 hour to 5 hours, the organic solvent is removed.

[0033] 16. The preparation method according to item 6, wherein the organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,4-dioxane.

[0034] 17. The preparation method according to item 6, wherein the organic solvent is removed by gradually increasing the temperature, and the temperature shall not exceed 260°C.

[0035] 18. The preparation method according to any one of items 6-17, wherein the polyesterimide obtained is the polyesterimide according to any one of items 1-5.

[0036] 19. An epoxy-polyesterimide matrix resin, comprising the polyesterimide, epoxy resin, and curing agent described in any one of claims 1-5.

[0037] 20. The epoxy-polyesterimide matrix resin according to item 19, wherein the mass ratio of the epoxy resin, the polyesterimide and the curing agent is 100:(5-30):(30-90).

[0038] 21. A method for preparing an epoxy-polyester imide matrix resin, comprising the following steps:

[0039] Take any one of the polyesterimide described in items 1-5, and mix it with epoxy resin and curing agent to obtain the epoxy-polyesterimide matrix resin.

[0040] 22. The application of the epoxy-polyesterimide matrix resin of item 19 or 20 or the epoxy-polyesterimide matrix resin prepared according to item 21 in aerospace, electronics, and shipbuilding.

[0041] The polyester imide provided in this application exhibits relatively good toughness due to the relatively long molecular chain of R1. Simultaneously, the imide structure formed by R2 and its two attached nitrogen atoms contributes to its good heat resistance. Therefore, the polyester imide of this application possesses excellent high-temperature resistance and superior flexibility. Furthermore, the preparation process of the polyester imide provided in this application is simple, the reaction conditions are mild, and the yield is high. Additionally, the solvent can be recycled and reused, meeting economic and environmental requirements. Attached Figure Description

[0042] Figure 1 Fourier transform infrared spectrum of the imide dicarboxylic acid prepared in Example 1-1 provided in this application.

[0043] Figure 2 The DSC spectrum of the imide dicarboxylic acid prepared in Example 1-1 provided in this application.

[0044] Figure 3 Fourier transform infrared spectrum of the polyesterimide prepared in Example 1-1 provided in this application. Detailed Implementation

[0045] The following description provides exemplary embodiments of this application, including various details to aid understanding, and should be considered merely exemplary. Therefore, those skilled in the art will recognize that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of this application. Similarly, for clarity and brevity, descriptions of well-known functions and structures are omitted in the following description.

[0046] This application provides a polyesterimide having the following structure:

[0047]

[0048] Where n is 1-100; n can be any positive integer from 1 to 100. When n is greater than 1, multiple R1s can be the same group or different groups, and multiple R2s can be the same group or different groups.

[0049] R1 is an alkylene group with 2-20 carbon atoms or = (C2H4). x O, x is 1-10, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.;

[0050] R2 is an alkylene group having 2-20 carbon atoms or an aryl group having 6-18 carbon atoms.

[0051] In R1, "alkylene" is branched or unbranched, and preferably has 2 to about 20 carbon atoms. More preferably, a class of alkylenes has 2 to about 6 carbon atoms. Even more preferably, alkylenes have 1, 2, 3, or 4 carbon atoms. Alkylenes include, but are not limited to, methylene, ethylene, n-propyl, isopropylene, butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, and octylene. Alkylenes can be substituted or unsubstituted.

[0052] In this application, R1 is an alkylene group having 2-6 carbon atoms or =(C2H4). x O, and x is 1-5.

[0053] Preferably, R1 is ethylene or (C2H4)2O.

[0054] In this application, R2 is an alkylene group having 5-15 carbon atoms or an arylene group having 8-18 carbon atoms;

[0055] Preferably, R2 is a straight-chain alkylene group having 5-12 carbon atoms or Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0056] In R2, the "alkylene" is branched or unbranched, and preferably has 5 to about 12 carbon atoms. Even more preferably, it is an alkylene having 5, 6, 7, 8, or 9 carbon atoms. Alkylenes include, but are not limited to, methylene, ethylene, n-propyl, isopropylene, butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, etc. The alkylene can be substituted or unsubstituted.

[0057] When R1 is an alkylene group having 2-20 carbon atoms, and R2 is an alkylene group having 2-20 carbon atoms.

[0058] When R1 is an alkylene group with 2-20 carbon atoms, and R2 is an aryl group with 6-18 carbon atoms.

[0059] When R1 is an alkylene group with 2-20 carbon atoms, and R2 is an alkylene group with 5-15 carbon atoms.

[0060] When R1 is an alkylene group with 2-20 carbon atoms, and R2 is an aryl group with 8-18 carbon atoms.

[0061] When R1 is an alkylene group with 2-20 carbon atoms, and R2 is a straight-chain alkylene group with 5-12 carbon atoms.

[0062] When R1 is an alkylene group with 2-20 carbon atoms, R2 is... Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0063] When R1 is = (C2H4) x O, x is 1-10, and R2 is an alkylene group having 2-20 carbon atoms.

[0064] When R1 is = (C2H4) x O, x is 1-10, and R2 is an arylene group with 6-18 carbon atoms.

[0065] When R1 is = (C2H4) x O, x is 1-10, and R2 is an alkylene group with 5-15 carbon atoms.

[0066] When R1 is = (C2H4) x O, x is 1-10, and R2 is an arylene group with 8-18 carbon atoms.

[0067] When R1 is = (C2H4) x O, x is 1-10, and R2 is a straight-chain alkylene group with 5-12 carbon atoms.

[0068] When R1 is = (C2H4) x O, x is 1-10, R2 is Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0069] When R1 is an alkylene group with 2-6 carbon atoms, and R2 is an alkylene group with 2-20 carbon atoms.

[0070] When R1 is an alkylene group with 2-6 carbon atoms, and R2 is an aryl group with 6-18 carbon atoms.

[0071] When R1 is an alkylene group with 2-6 carbon atoms, and R2 is an alkylene group with 5-15 carbon atoms.

[0072] When R1 is an alkylene group with 2-6 carbon atoms and R2 is an aryl group with 8-18 carbon atoms.

[0073] When R1 is an alkylene group with 2-6 carbon atoms, and R2 is a straight-chain alkylene group with 5-12 carbon atoms.

[0074] When R1 is an alkylene group with 2-6 carbon atoms, and R2 is... Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0075] When R1 is -(C2H4O) x- and x is 1-5, R2 is an alkylene group having 2-20 carbon atoms.

[0076] When R1 is -(C2H4O) x - and x is 1-5, R2 is an arylene group with 6-18 carbon atoms.

[0077] When R1 is -(C2H4O) x - and x is 1-5, R2 is an alkylene group having 5-15 carbon atoms.

[0078] When R1 is -(C2H4O) x - and x is 1-5, R2 is an arylene group with 8-18 carbon atoms.

[0079] When R1 is -(C2H4O) x - and x is 1-5, R2 is a straight-chain alkylene group with 5-12 carbon atoms.

[0080] When R1 is -(C2H4O) x - and x is 1-5, R2 is Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0081] When R1 is ethylene and R2 is alkylene with 2-20 carbon atoms.

[0082] When R1 is ethylene and R2 is arylene with 6-18 carbon atoms.

[0083] When R1 is ethylene and R2 is alkylene with 5-15 carbon atoms.

[0084] When R1 is ethylene and R2 is arylene with 8-18 carbon atoms.

[0085] When R1 is ethylene and R2 is a straight-chain alkylene with 5-12 carbon atoms.

[0086] When R1 is ethylene and R2 is Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0087] When R1 is (C2H4)2O, R2 is an alkylene group having 2-20 carbon atoms.

[0088] When R1 is (C2H4)2O, R2 is an arylene group with 6-18 carbon atoms.

[0089] When R1 is (C2H4)2O, R2 is an alkylene group with 5-15 carbon atoms.

[0090] When R1 is (C2H4)2O, R2 is an arylene group with 8-18 carbon atoms.

[0091] When R1 is (C2H4)2O, R2 is a straight-chain alkylene group with 5-12 carbon atoms.

[0092] When R1 is = (C2H4)2O, R2 is Among them, R3 and R4 are alkylene groups with 1-6 carbon atoms, respectively.

[0093] When R1 is = (C2H4)2O, R2 is R3 and R4 are methylene groups with a carbon atom number of 1.

[0094] When R1 is (C2H4)2O, R2 is a straight-chain alkylene group with 10 carbon atoms.

[0095] In this application, the weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) of the polyesterimide is 1.01-1.3, for example, it can be 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.2 or 1.3.

[0096] In this paper, gel permeation chromatography was used to determine the weight-average molecular weight and Mw / Mn value of polyimide resin.

[0097] The detection method is as follows:

[0098] 1. Use a graduated cylinder to take 500 ml of DMF mobile phase and pour it into a brown vial, and add 100 μL of toluene as a solvent for later use.

[0099] 2. Accurately weigh 0.0060–0.0120 g (accurate to 0.0001 g) of sample into a dissolution bottle. Use a 5 ml glass syringe to draw the corresponding volume of solution from the brown vial to dissolve the sample, preparing a 0.3% (m / v) sample solution. The concentration can be adjusted according to the absorption of special samples.

[0100] 3. Shake the sample to ensure it is completely dissolved.

[0101] 4. Filter the sample into a new 2ml sample vial, and place the filtered sample into the sample tray of the autosampler in sequence; the detection wavelength is 270nm and the detection temperature is 40℃.

[0102] In this application, the weight-average molecular weight of the polyesterimide is 20,000 g / mol to 49,000 g / mol, for example, it can be 20,000 g / mol, 21,000 g / mol, 22,000 g / mol, 23,000 g / mol, 24,000 g / mol, 25,000 g / mol, 26,000 g / mol, 27,000 g / mol, 28,000 g / mol, 29,000 g / mol, 30,000 g / mol, 31,000 g / mol, or 32,000 g / mol. , 33000g / mol, 34000g / mol, 35000g / mol, 36000g / mol, 37000g / mol, 38000g / mol, 39000g / mol, 40000g / mol, 41000g / mol, 42000g / mol, 43000g / mol, 44000g / mol, 45000g / mol, 46000g / mol, 47000g / mol, 48000g / mol, or 49000g / mol, etc.

[0103] This application provides a method for preparing polyesterimide, comprising the following steps:

[0104] Step 1: Add the diamine and trimellitic anhydride to an organic solvent and stir to react;

[0105] Step 2: Add an azeotropic dehydrating agent and a cyclization catalyst to the above reaction, then remove the azeotropic dehydrating agent, and then add a precipitating agent dropwise while stirring to obtain an imide dicarboxylic acid;

[0106] Step 3: Add the imide dicarboxylic acid and diol to the catalyst and organic solvent, then remove the organic solvent to obtain polyester imide.

[0107] In step one, the molar ratio of the diamine to trimellitic anhydride is 1:(2-2.5), for example, it can be 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, etc.

[0108] In some embodiments, the molar ratio of the diamine to trimellitic anhydride is 1:2-2.2.

[0109] In some embodiments, the molar ratio of the diamine to trimellitic anhydride is 1:2-2.4.

[0110] The primary diamine is selected from aliphatic or aromatic diamines, preferably ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, heptaethylenediamine, octanediamine, nonanediamine, decanediamine, undecyldiamine, tridecyldiamine, tetradecyldiamine, pentadecyldiamine, hexadecyldiamine, heptadecanyldiamine, octadecyldiamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, methyl-m-phenylenediamine, methyl-p-phenylenediamine, methyl-o-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane. Alkane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 2 6-bis(4-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)benzonitrile, 3,5-bis(4-aminophenoxy)benzoic acid, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,6-bis(4-aminophenoxy)toluene, 2,5-bis(4-aminophenoxy)toluene, 3,5-bis(2-trifluoromethyl-4-aminophenoxy)benzoic acid, 2,6-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,5-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)diphenylmethane, 4,4'-bis(3-aminophenoxy)diphenylmethane, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfone, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 4,4'-bis(3-aminophenoxy)diphenyl sulfide, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfide, 4,4'-bis(4-aminophenoxy)diphenyl ether, 4,4'-bis(3-aminophenoxy)diphenyl ether, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy)diphenyl sulfide The methyl ethyl ketone, 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl, preferably one or more of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-phenylenediamine, and 1,10-decanediamine, more preferably m-phenylenediamine or 1,10-decanediamine.

[0111] In some embodiments, the diamine is 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0112] In some embodiments, the diamine is 4,4'-diaminodiphenylmethane.

[0113] In some embodiments, the primary diamine is 1,10-decanediamine.

[0114] In some embodiments, the primary diamine is m-phenylenediamine.

[0115] The organic solvent is selected from one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone, and 1,4-dioxane.

[0116] In step two, the azeotropic dehydrating agent is selected from one or more of o-xylene, m-xylene, p-xylene, toluene, benzene, monochlorobenzene, and dichlorobenzene.

[0117] In some embodiments, the azeotropic dehydrating agent is toluene.

[0118] The cyclization catalyst is selected from one or more of sulfuric acid, phosphoric acid, methanesulfonic acid, and methylbenzenesulfonic acid.

[0119] In some embodiments, the cyclization catalyst is methylbenzenesulfonic acid.

[0120] In some embodiments, the azeotropic dehydrating agent is toluene, the cyclization catalyst is methylbenzenesulfonic acid, and the organic solvent is DMF.

[0121] The roles of azeotropic dehydrating agents and cyclization catalysts are: cyclization catalysts lower the activation energy of the ring-closing reaction, making the cyclization reaction easier to carry out; and azeotropic dehydrating agents remove the water generated by the cyclization reaction from the reaction system, which is beneficial for the forward progress of the cyclization reaction.

[0122] Furthermore, after adding the azeotropic dehydrating agent and the cyclization catalyst, heating is started until the temperature reaches T1, which is preferably 80°C-150°C. After the reaction system is maintained at the T1 temperature for 1 hour to 12 hours, the azeotropic dehydrating agent is removed.

[0123] T1 can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, etc.

[0124] The holding time at temperature T1 is 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, and 12 hours.

[0125] Further, after removing the azeotropic dehydrating agent, the temperature of the reaction system is lowered to T2, which is preferably 60℃-80℃. Then, room temperature water with a mass twice that of the material is prepared and the material is slowly poured into the system while stirring, thereby obtaining the imide dicarboxylic acid.

[0126] The precipitant is methanol, ethanol, or deionized water.

[0127] The amount of precipitant added is twice the mass of the remaining reactants.

[0128] T2 can be 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, etc.

[0129] In some embodiments, a primary diamine and trimellitic anhydride are added to an organic solvent and stirred at room temperature for 0.5 to 2 hours to construct a reaction system. An azeotropic dehydrating agent and a cyclization catalyst are added to the reaction system, and the mixture is heated to T1 for reflux and water separation. After reacting for 1 to 12 hours, the azeotropic dehydrating agent is separated, and the mixture is cooled to T2. A precipitating agent is added dropwise while stirring to precipitate a solid product. The product is then filtered, dried, and an imide dicarboxylic acid is obtained.

[0130] In step three, the molar ratio of the imide dicarboxylic acid to the diol is 1:(0.6-1.5). For example, it can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0131] The amount of catalyst used is 4%-6% of the mass of the reactants.

[0132] The diol is selected from one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecyldiol, dodecyldiol, tridedecyldiol, tetradedecyldiol, pentadecyldiol, hexadecyldiol, heptadecadiol, octadecyldiol, ethylene glycol mono-, diethylene glycol di-, triethylene glycol tri-, tetraethylene glycol tetra-, and benzyldimethyl alcohol, preferably diethylene glycol or ethylene glycol.

[0133] In this application, the long-chain diols, due to their relatively long molecular chains, result in polyesterimide macromolecules with relatively good toughness. Simultaneously, the presence of imide structures in the molecular chains of the synthesized polyesterimide contributes to its good heat resistance. Therefore, the polyesterimide synthesized in this application possesses not only good toughness but also good heat resistance.

[0134] The catalyst is selected from one or more of sulfuric acid, phosphoric acid, methanesulfonic acid, methylbenzenesulfonic acid, strong acid H-type cation exchange resin, and TP-284.

[0135] Further, after the imide dicarboxylic acid and diol are added to the system consisting of the catalyst and organic solvent, heating is started until the temperature reaches T3, which is preferably 80°C-130°C. After the reaction system is maintained at the T3 temperature for 1 hour to 5 hours, the organic solvent is removed.

[0136] T3 can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 122℃, 124℃, 125℃, 126℃, 128℃, 130℃, etc.

[0137] The organic solvent is selected from one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone, and 1,4-dioxane.

[0138] Furthermore, the organic solvent is removed by gradually increasing the temperature, with the temperature not exceeding 260°C.

[0139] Preferably, toluene is removed when the temperature is raised to 140°C-146°C, and more preferably, DMF is removed when the temperature is raised to above 147°C.

[0140] In some embodiments, an imide dicarboxylic acid and a diol are added to a system consisting of a catalyst and an organic solvent, heated to T3, and refluxed to separate the solvent. After reacting for 1 to 5 hours, the organic solvent is separated and recycled. Toluene is recovered by heating to 140°C-146°C, and DMF is recovered by heating to above 147°C. The maximum temperature does not exceed 260°C, thus obtaining a long-chain macromolecular polyesterimide.

[0141] This application provides an epoxy-polyesterimide matrix resin, comprising polyesterimide, epoxy resin, and curing agent.

[0142] This application provides an epoxy-polyester imide matrix resin, which is composed of polyester imide, epoxy resin and curing agent.

[0143] The mass ratio of the epoxy resin, polyesterimide and curing agent is 100:(5-30):(30-90).

[0144] This application provides a method for preparing an epoxy-polyester imide matrix resin, comprising the following steps:

[0145] Polyester imide, epoxy resin, and curing agent are mixed evenly to obtain the epoxy-polyester imide matrix resin.

[0146] Furthermore, this application provides a method for preparing an epoxy-polyesterimide matrix resin, comprising the following steps:

[0147] Step 1: Mix the aforementioned polyesterimide with epoxy resin to obtain mixture one;

[0148] Step 2: Add curing agent to the first mixture and mix evenly to obtain the epoxy-polyesterimide matrix resin.

[0149] In step one, the polyesterimide and epoxy resin are mixed and heated to T4, and then melt-blended until homogeneous to obtain mixture one.

[0150] T4 is 80℃-150℃, for example, it can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, etc.

[0151] The mass ratio of the epoxy resin, polyesterimide and curing agent is 100:(5-30):(30-90).

[0152] Specifically, the mass ratio of epoxy resin to polyesterimide is 100:(5-30), for example, it can be 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28, 100:29, 100:30, etc.

[0153] Specifically, the mass ratio of epoxy resin to curing agent is 100:(30-90). For example, it can be 100:30, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75, 100:80, 100:85, or 100:90.

[0154] The epoxy resin is selected from bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol AF diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, hydroquinone diglycidyl ether type epoxy resin, resorcinol diglycidyl ether type epoxy resin, catechol diglycidyl ether type epoxy resin, tert-butylhydroquinone diglycidyl ether type epoxy resin, methylhydroquinone diglycidyl ether type epoxy resin, tetrabromobisphenol A diglycidyl ether type epoxy resin, terephthalic acid diglycidyl ether type epoxy resin, isophthalic acid diglycidyl ether type epoxy resin, catechol diglycidyl ether type epoxy resin, phthalic acid diglycidyl ether type epoxy resin, naphthol diglycidyl ether type epoxy resin, naphthalic acid diglycidyl ester type epoxy resin, hydrogenated bisphenol A diglycidyl ether type epoxy resin, etc. The epoxy resin comprises one or more of the following: oil ether type epoxy resin, tetrahydrophthalic anhydride glycidyl ether type epoxy resin, methyltetrahydrophthalic anhydride glycidyl ether type epoxy resin, hexahydrophthalic anhydride glycidyl ether type epoxy resin, nadic anhydride glycidyl ether type epoxy resin, methylnadic anhydride glycidyl ether type epoxy resin, alicyclic epoxy resin, phenol-formaldehyde resin glycidyl ether type epoxy resin, o-cresol-formaldehyde resin glycidyl ether type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate epoxy resin, organotitanium epoxy resin, organosilicon epoxy resin, organophosphorus epoxy resin, dimer acid diglycidyl ether epoxy resin, and bisphenol A-formaldehyde resin glycidyl ether type epoxy resin, preferably bisphenol A diglycidyl ether type epoxy resin or bisphenol F diglycidyl ether type epoxy resin.

[0155] In some embodiments, the epoxy resin is N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane epoxy resin and bisphenol A diglycidyl ether type epoxy resin, with a mass ratio of 1:1-2.

[0156] The curing agent is selected from dicyandiamide, modified dicyandiamide, DMP-30, N,N-dimethyl-p-aminopyridine, methylimidazole, 2-ethyl-4-methylimidazole, 80 anhydride, tung oil anhydride, maleic anhydride, methylnedic anhydride, nedic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenylsuccinic anhydride, ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptahydratediamine, octanediamine, nonanediamine, decanediamine, undecyldiamine, tridecyldiamine, tetradecyldiamine, pentadecyldiamine, hexadecyldiamine, heptadecanyldiamine, octadecyldiamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, methyl-m-phenylenediamine, methyl-p-phenylenediamine, methyl 2,4,6-Trimethyl-m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-di... Aminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 2,6-bis(4-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)benzonitrile, 3,5-bis(4-aminophenoxy)benzoic acid, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(2-trifluoromethyl-4-aminophenoxy) Benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,6-bis(4-aminophenoxy)toluene, 2,5-bis(4-aminophenoxy)toluene, 3,5-bis(2-trifluoromethyl-4-aminophenoxy)benzoic acid, 2,6-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,5-bis(2-trifluoromethyl-4-aminophenoxy)toluene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)diphenylmethane, 4,4'-bis(3-aminophenoxy)diphenylmethane, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfone, 4,4'-bis(4-aminophenoxy)diphenyl sulfide, 4,4'-bis(3-aminophenoxy)diphenyl sulfide Ethers, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl sulfide, 4,4'-bis(4-aminophenoxy)diphenyl ether, 4,4'-bis(3-aminophenoxy)diphenyl ether, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl ether, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(2-trifluoromethyl)biphenyl -4-Aminophenoxy)biphenyl, pyromellitic dianhydride, 3,3',4,4'-tetracarboxylic diphenyl ether dianhydride, 3,3',4,4'-tetracarboxybenzophenone dianhydride, 3,3',4,4'-tetracarboxybiphenyl dianhydride, 3,3',4,4'-tetracarboxylic diphenyl sulfone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,6-bis(3,4-dicarboxyphenoxy)toluene dianhydride, 1,4-bis(3,4- One or more of the following: dicarboxyphenoxy phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)-3,3'5,5'-tetramethyldiphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, tetrabromophthalic anhydride, tetrafluorophthalic anhydride, 4-chlorophthalic anhydride, 3-chlorophthalic anhydride, 4-bromophthalic anhydride, 3-bromophthalic anhydride, 4-fluorophthalic anhydride, and 3-fluorophthalic anhydride, preferably m-phenylenediamine or decanediamine.

[0157] This application provides an application of epoxy-polyesterimide matrix resin in aerospace, electronics, and shipbuilding.

[0158] Example

[0159] The materials and test methods used in the embodiments of this application are described in a general and / or specific manner. In the following embodiments, unless otherwise specified, % means wt%, i.e., weight percentage. Reagents or instruments used, unless otherwise specified, are all commercially available conventional reagent products.

[0160] Example 1: Preparation of Polyester Imide

[0161] Example 1-1

[0162] Preparation of imide dicarboxylic acids

[0163] 17.2 g (0.1 mol) of 1,10-decanediamine (DAD), 500 g of N,N-dimethylformamide (DMF), and 38.4 g (0.2 mol) of trimellitic anhydride (TMA) were added to a reactor. After stirring at room temperature for 1.5 hours, 300 g of toluene (Tol) and 6.5 g of methylbenzenesulfonic acid (PTSA) were added. The mixture was heated under reflux at 95°C-140°C for 10 hours to remove water. 300 g of toluene was separated, cooled to room temperature, and 500 g of methanol was added dropwise while stirring. A solid product precipitated, was filtered, and dried at 230°C for 4 hours to obtain 51.9 g of imide dicarboxylic acid (theoretical amount 52.0 g), denoted as DTA-1. The yield was 99.8%, the melting point was 228.52°C, and the Fourier transform infrared spectrum is shown below. Figure 1 As shown, the DSC spectrum is as follows Figure 2 As shown.

[0164] Preparation of polyesterimide

[0165] A mixture of 52.0 g (0.1 mol) of DTA-1, 62.6 g of N,N-dimethylacetamide (DMAc), and 62.6 g of toluene, 10.6 g (0.1 mol) of diethylene glycol (DEG), and 5.2 g of TP-284 catalyst (Zhejiang Yingruiyun New Material Technology Co., Ltd.) was added to a reactor. After heating and refluxing for 5 hours, the reaction temperature was gradually increased (from room temperature to 124 °C). The organic solvent was separated and recycled, with the temperature not exceeding 260 °C, yielding 58.5 g of polyesterimide (theoretical amount 59.0 g), denoted as PDTAD-1. The yield was 99.2%. The Fourier transform infrared spectrum is shown below. Figure 3 As shown; the parameters of polyesterimide are shown in Table 1 and Table 2.

[0166] The polyester imides in Examples 1-2 to 1-6 differ from those in Example 1-1 only in the type of diamine. Their parameters are shown in Table 1 and Table 2.

[0167] The polyester imides of Examples 1-7 differ from those of Examples 1-6 only in the type of diamine. Their parameters are shown in Table 1 and Table 2.

[0168] The polyesterimides in Examples 1-8 to 1-9 differ from those in Example 1-1 only in the type of diol. Their parameters are shown in Table 1 and Table 2.

[0169] The polyesterimide in Examples 1-10 differs from that in Examples 1-1 only in the type of azeotropic dehydrating agent. Its parameters are shown in Table 1 and Table 2.

[0170] The polyesterimide in Examples 1-11 differs from that in Examples 1-1 only in the type of cyclization catalyst. Its parameters are shown in Table 1 and Table 2.

[0171] The polyesterimides of Examples 1-12 differ from those of Examples 1-1 only in that no azeotropic dehydrating agent or cyclization catalyst is added. Their parameters are shown in Table 1 and Table 2.

[0172] Example 2: Preparation of epoxy-polyesterimide matrix resin

[0173] Example 2-1

[0174] 50.0 g of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane epoxy resin, 50.0 g of bisphenol A diglycidyl ether epoxy resin, 5.0 g of PDTAD-1 polyester imide, and 30.0 g of 2-ethyl-4-methylimidazolium curing agent were mixed evenly to obtain 135.0 g of epoxy-polyester imide matrix resin, denoted as J-1.

[0175] The only difference between Examples 2-2 to 2-12 and Example 2-1 is the type of polyesterimide. Their parameters are shown in Tables 1 and 2.

[0176] Example 3

[0177] The only difference between Examples 3-1 to 3-12 is the epoxy-polyesterimide matrix resin.

[0178] Appropriate amounts of the epoxy-polyesterimide matrix resin prepared in Example 2 were taken and uniformly coated onto standard stainless steel test pieces. These pieces were then stacked, clamped, and placed in a forced-air oven for curing. The temperature was raised from room temperature to 90°C and held for 1 hour. Then, the temperature was raised to 160°C and held for 2 hours. Finally, the temperature was raised to 190°C and held for 1 hour, after which the pieces were allowed to cool naturally to room temperature. Tensile shear strength tests were performed using an electronic tensile testing machine under room temperature (25°C) and high temperature (200°C) conditions. The results are shown in Table 3.

[0179] Appropriate amounts of the epoxy-polyesterimide matrix resin prepared in Example 2 were taken and uniformly impregnated onto glass cloth. Standard stainless steel test pieces were stacked and clamped together, and then placed in a forced-air oven for curing. The temperature was raised from room temperature to 90°C, held for 1 hour, then raised to 160°C, held for 2 hours, then raised to 190°C, held for 1 hour, and finally allowed to cool naturally to room temperature. Tensile shear strength tests were performed using an electronic tensile testing machine under room temperature (25°C) and high temperature (200°C) conditions. The results are shown in Table 3.

[0180] The elongation at break of epoxy-polyesterimide matrix resin was tested using a universal testing machine. The specific operation is as follows:

[0181] 1. Turn on the universal testing machine and preheat for 15 minutes. Secure the upper and lower bolts, install the elongation test clamping device, open the test method for elongation at break, and zero the software load and stroke, and calibrate the load.

[0182] 2. Hold the sample in place so that it is on the vertical plane of the upper and lower clamps. Fine-tune the position of the upper clamp so that the sample is completely vertical but not under any force.

[0183] 3. Use vernier calipers to measure the distance between the upper and lower clamps at this time, and record it as the standard distance L0.

[0184] 4. Zero the stroke, press the start button to start the test, stop the test when the sample fails, and read the stroke L1 at this time.

[0185] 5. Calculate the elongation at break: ε = L1 / L0 x 100%

[0186] Table 1. Parameters for each embodiment

[0187]

[0188] Table 2

[0189]

[0190]

[0191]

[0192] Table 3 Performance data of epoxy-polyesterimide matrix resin

[0193]

[0194] In summary, the polyester imide of this application has a high weight-average molecular weight and a Mw / Mn value close to 1. The epoxy-polyester imide matrix resin synthesized using it has good high-temperature resistance and excellent flexibility.

[0195] Although the embodiments of this application have been described above in conjunction with the accompanying drawings, this application is not limited to the specific embodiments and application fields described above. The specific embodiments described above are merely illustrative and instructive, not restrictive. Those skilled in the art can make many other forms based on the guidance of this specification and without departing from the scope of protection of the claims of this application, and these are all within the scope of protection of this application.

Claims

1. A polyesterimide, wherein, It has the following structure: Where n is 1-100; R1 is ethylene or -C2H4-O-C2H4-; R2 is a straight-chain alkylene group having 5-12 carbon atoms or , Among them, R3 and R4 are each an alkylene group having 1-6 carbon atoms; The weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) of the polyesterimide is 1.01-1.3; The weight-average molecular weight of the polyesterimide is 20,000 g / mol to 49,000 g / mol.

2. A method for preparing the polyesterimide according to claim 1, wherein, Includes the following steps: The diamine and trimellitic anhydride were added to an organic solvent and stirred to react. An azeotropic dehydrating agent and a cyclization catalyst were added to the above reaction. After removing the azeotropic dehydrating agent, a precipitating agent was added dropwise while stirring to obtain an imide dicarboxylic acid. The imide dicarboxylic acid and diol are added to a catalyst and an organic solvent, and then the organic solvent is removed to obtain polyester imide; The primary diamine is an aliphatic diamine or an aromatic diamine; The azeotropic dehydrating agent is toluene or benzene; The cyclization catalyst is methylbenzenesulfonic acid or methylsulfonic acid.

3. The preparation method according to claim 2, wherein, The molar ratio of the diamine to trimellitic anhydride is 1:(2-2.5).

4. The preparation method according to claim 2, wherein, The primary amine is m-phenylenediamine or 1,10-decanediamine; The diol is diethylene glycol or ethylene glycol.

5. The preparation method according to claim 2, wherein, After adding the azeotropic dehydrating agent and the cyclization catalyst, heating is started until the temperature reaches T1, which is 80℃-150℃. The reaction system is maintained at the T1 temperature for 1 hour to 12 hours, and then the azeotropic dehydrating agent is removed.

6. The preparation method according to claim 2, wherein, After removing the azeotropic dehydrating agent, the temperature of the reaction system is lowered to T2, which is 60℃-80℃. Then, room temperature water with a mass twice that of the material is prepared and the material is slowly poured into the mixture while stirring, thereby obtaining the imide dicarboxylic acid.

7. The preparation method according to claim 2, wherein, The molar ratio of the imide dicarboxylic acid to the diol is 1:(0.6-1.5).

8. The preparation method according to claim 2, wherein, The catalyst is selected from one or more of sulfuric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid, strongly acidic H-type cation exchange resin, and TP-284; and / or The precipitant is methanol, ethanol, or deionized water.

9. The preparation method according to claim 2, wherein, After the imide dicarboxylic acid and diol are added to the system consisting of a catalyst and an organic solvent, the mixture is heated until the temperature reaches T3, which is 80°C-130°C. The reaction system is maintained at the T3 temperature for 1-5 hours, after which the organic solvent is removed.

10. The preparation method according to claim 2, wherein, The organic solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,4-dioxane.

11. The preparation method according to claim 2, wherein, The organic solvent is removed by gradually increasing the temperature, which shall not exceed 260°C.

12. An epoxy-polyesterimide matrix resin, wherein, It includes the polyesterimide, epoxy resin, and curing agent as described in claim 1.

13. The epoxy-polyesterimide matrix resin according to claim 12, wherein, The mass ratio of the epoxy resin, polyesterimide and curing agent is 100:(5-30):(30-90).

14. A method for preparing an epoxy-polyesterimide matrix resin, wherein, Includes the following steps: The polyester imide described in claim 1, epoxy resin, and curing agent are mixed evenly to obtain the epoxy-polyester imide matrix resin.

15. The application of the epoxy-polyesterimide matrix resin of claim 12 or 13 or the epoxy-polyesterimide matrix resin prepared according to claim 14 in aerospace, electronics, and shipbuilding.

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