CN113861421B - Polyimide type epoxy resin toughening agent and preparation method thereof - Google Patents
Polyimide type epoxy resin toughening agent and preparation method thereof Download PDFInfo
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- CN113861421B CN113861421B CN202111322416.1A CN202111322416A CN113861421B CN 113861421 B CN113861421 B CN 113861421B CN 202111322416 A CN202111322416 A CN 202111322416A CN 113861421 B CN113861421 B CN 113861421B
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- epoxy resin
- toughening agent
- phenolic hydroxyl
- type epoxy
- polyimide
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 108
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 108
- 239000012745 toughening agent Substances 0.000 title claims abstract description 84
- 239000004642 Polyimide Substances 0.000 title claims abstract description 72
- 229920001721 polyimide Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 41
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 150000004985 diamines Chemical class 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 claims description 3
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 3
- 238000001556 precipitation Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000005462 imide group Chemical group 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- -1 3, 4-dicarboxyphenyl Chemical group 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000010125 resin casting Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 4
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- UTYHQSKRFPHMQQ-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC(OC=2C=C(N)C(O)=CC=2)=C1 UTYHQSKRFPHMQQ-UHFFFAOYSA-N 0.000 description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- GFUCMNMXYOVTDJ-UHFFFAOYSA-N 2,4-diamino-6-butan-2-ylphenol Chemical compound CCC(C)C1=CC(N)=CC(N)=C1O GFUCMNMXYOVTDJ-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- 102100035915 D site-binding protein Human genes 0.000 description 2
- 101000873522 Homo sapiens D site-binding protein Proteins 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The application discloses a polyimide type epoxy resin toughening agent and a preparation method thereof, wherein the toughening agent is a block type polyimide polymer, and consists of a structural chain segment containing phenolic hydroxyl groups and a structural chain segment without phenolic hydroxyl groups, wherein the structural chain segment containing phenolic hydroxyl groups can participate in the curing reaction of epoxy resin, and the toughening agent is introduced into an epoxy resin crosslinking network through chemical bonds, so that the compatibility and interface binding force of the toughening agent and the epoxy resin are improved; on the other hand, the main chain of the epoxy resin contains rigid groups such as benzene rings, imide structures and the like, so that the epoxy resin can maintain good mechanical properties and heat resistance, and is applied to a high-temperature-resistant multifunctional epoxy resin system. The preparation method comprises the steps of respectively preparing a polyamic acid solution containing phenolic hydroxyl groups and a polyamic acid solution without phenolic hydroxyl groups, mixing the two polyamic acid solutions, stirring, and then converting the polyamic acid into polyimide through a chemical imidization or thermal imidization mode to obtain the polyimide type epoxy resin toughening agent.
Description
Technical Field
The application relates to the technical field of materials, in particular to a polyimide type epoxy resin toughening agent and a preparation method thereof.
Background
The tetrafunctional epoxy resin is a high temperature resistant thermosetting resin, has good corrosion resistance, dielectric property and mechanical property, and is widely used as an excellent matrix material in a plurality of fields such as electromechanical devices, transportation, sports equipment, pressure vessels, structural reinforcement and the like. However, due to the highly crosslinked three-dimensional network structure, such epoxy resins have the disadvantage of poor toughness, limiting their further application.
The toughening method of the epoxy resin at present mainly comprises rubber toughening, rigid particle toughening, thermoplastic resin toughening, core-shell particle toughening and the like.
CN102936396a adopts polymer microspheres as toughening materials to improve the toughness of epoxy resin, the addition of the microspheres can damage the rigid structure of the epoxy resin, and the toughening effect is achieved through effective stress transfer between the microspheres and the epoxy resin, but the mechanical properties of the modified epoxy resin are obviously reduced.
CN102516717a modifies epoxy resin with thermoplastic elastomer as toughening agent, and the thermoplastic elastomer, compatibilizer and auxiliary agent are mixed uniformly before being added into the epoxy resin for thermal curing, but the toughening agent has poor compatibility with the epoxy resin due to the weak polarity of the elastomer.
In CN105623265a, researchers use polyether polyol and its derivatives to modify epoxy resin, firstly, compound polyether polyol/polyether ketone/polyether sulfone, then add into epoxy system, better keep the heat resistance of epoxy resin, but because polyether polyol does not participate in the curing reaction of epoxy resin, the compatibility between toughening agent and epoxy resin is poor.
In order to solve the problems, the inventor researches a polyimide type epoxy resin toughening agent and a preparation method thereof. The toughening agent is a block polyimide polymer, and consists of a structural chain segment containing phenolic hydroxyl groups and a structural chain segment without phenolic hydroxyl groups, wherein the chain segment containing the phenolic hydroxyl groups can participate in the curing reaction of the epoxy resin, and the toughening agent is introduced into a crosslinked network through chemical bonds, so that the compatibility and interfacial binding force of the toughening agent and the epoxy resin are improved; in addition, the main chain of the toughening agent contains a benzene ring, an imide structure and other rigid groups, so that the toughening agent can maintain good mechanical strength of the epoxy resin while toughening.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide a polyimide type epoxy resin toughening agent and a preparation method thereof, which solve the problems of poor compatibility of the toughening agent and epoxy resin and unreinforced toughening of the epoxy resin.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a polyimide type epoxy resin toughening agent (CPEI), which is a block type polyimide copolymer, the block type polyimide copolymer is composed of a structural chain segment containing phenolic hydroxyl groups and a structural chain segment not containing the phenolic hydroxyl groups, and the structural formula is as follows:
(A-B) m (P1)
in the formula (P1), m is an integer greater than 4; wherein the segment A has a repeating unit represented by the following formula (I):
in formula (I), X comprises
R represents O, S,n 1 Is any integer from 5 to 300; n is n 1 Further preferably an integer of 10 to 50.
In formula (P1), segment B has a repeating unit represented by formula (II):
in the formula (II), R 2 Represent O, S,R is O, S>n 2 Is any integer of 5 to 300. From the material comprehensive performance consideration, n 2 Further preferably an integer of 20 to 100.
A preparation method of a polyimide type epoxy resin toughening agent comprises the following steps:
and step 1, adding diamine containing phenolic hydroxyl groups and N-methyl pyrrolidone into a completely dried reaction container, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, adding dianhydride according to a proportion, and stirring and reacting under the protection of nitrogen to obtain a polyamide acid solution containing the phenolic hydroxyl groups.
And 2, adding diamine without phenolic hydroxyl groups and N-methylpyrrolidone into another reaction container, introducing inert gas, stirring until the diamine and the N-methylpyrrolidone are completely dissolved, adding dianhydride according to a proportion, and stirring and reacting under the protection of nitrogen to obtain the polyamide acid solution without phenolic hydroxyl groups.
And step 3, mixing the two polyamic acid solutions obtained in the step 1 and the step 2, continuously stirring, then converting the polyamic acid into polyimide through chemical imidization or thermal imidization, and finally separating and purifying to obtain the polyimide type epoxy resin toughening agent.
Further, the dianhydride is added in the step 1 according to the proportion, specifically according to the molar ratio of the diamine containing phenolic hydroxyl to the dianhydride of 1:1.02-1.05; stirring and reacting under the protection of nitrogen, specifically stirring and reacting for 2-6 hours in an environment of-5-20 ℃ under the protection of nitrogen, and obtaining the polyamic acid solution containing phenolic hydroxyl.
Still further, the phenolic hydroxyl group-containing diamine monomer in the step 1 includes one or more of 3,3' -dihydroxybenzidine (HAB), 3' -diamino-4, 4' -dihydroxydiphenyl sulfone (BAS), 3' -dihydroxy-4, 4' -diaminodiphenyl methane (3H 4 ADPM), 3' -diamino-4, 4' -dihydroxydiphenyl sulfide (3 A4 HDPES) and 3,3' -diamino-4, 4' -dihydroxydiphenyl ether (3 A4 HDPE).
Further, the dianhydride is added in the step 2 according to the proportion, specifically according to the molar ratio of diamine without phenolic hydroxyl to dianhydride of 1.02-1.05:1; stirring and reacting under the protection of nitrogen, specifically stirring and reacting for 2-6 hours in an environment of-5-20 ℃ under the protection of nitrogen, and obtaining the polyamide acid solution without phenolic hydroxyl.
Still further, the diamine monomer having no phenolic hydroxyl group in the step 2 includes one or more of 4,4' -diaminodiphenyl ether (ODA), 3,4' -diaminodiphenyl ether (34 ODA), 4' -diaminodiphenyl sulfide (DADPES), 4' -diaminodiphenyl sulfone (DADPS) and 4,4' -Diaminobenzophenone (DABP).
Still further, the dianhydride monomer in the step 1-2 includes one or more of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 4 '-diphenyl ether dianhydride (ODPA), 3',4 '-tetracarboxylic benzophenone dianhydride (BTDA), 3',4 '-tetracarboxylic diphenyl Sulfide Dianhydride (SDPA), and 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride (6 FDA).
Further, the stirring in the step 3 is continued, specifically, the stirring is continued for 2 to 6 hours; the continuous reaction is carried out, specifically for 8-20 hours; the chemical imidization is to add a chemical imidization reagent into the mixed solution, continue the reaction, and obtain the polyimide type epoxy resin toughening agent after separation and purification, wherein the chemical imidization reagent is acetic anhydride/pyridine mixed solution or acetic anhydride/triethylamine mixed solution; the thermal imidization is to precipitate the polyamic acid in ethanol, and put the polyamic acid powder into an oven for thermal imidization to obtain a polyimide product, wherein the thermal imidization temperature is 250 ℃/2h and 300 ℃/2h.
And 3, separating and purifying to obtain the polyimide type epoxy resin toughening agent, namely pouring the mixed solution obtained by the reaction into absolute ethyl alcohol, precipitating to obtain yellow filiform precipitate, repeatedly washing the precipitate for a plurality of times by using the absolute ethyl alcohol, removing unreacted reaction monomers and solvents, placing the precipitate in a vacuum oven, drying at 60 ℃ for 12-20 hours to constant weight, and crushing to obtain white powder, namely the polyimide type epoxy resin toughening agent (CPEI) which is a target product.
Compared with the prior art, the application has the following beneficial effects:
(1) The polyimide type epoxy resin toughening agent CPEI is block type polyimide, has an imide structure, a benzene ring and other rigid structures in the structure, has good thermal stability, and can be used for toughening high-temperature epoxy resin.
(2) The polyimide type epoxy resin toughening agent is a block polymer and consists of a structural chain segment containing phenolic hydroxyl groups and a structural chain segment without phenolic hydroxyl groups, wherein the chain segment containing the phenolic hydroxyl groups can participate in the curing reaction of the epoxy resin to form covalent bonds, and linear polyimide molecular chains are introduced into an epoxy resin crosslinking network to obviously improve the shock resistance of the epoxy resin.
(3) The polyimide type epoxy resin toughening agent is a block polymer, and the interface effect between the toughening agent and the epoxy resin matrix can be effectively regulated and controlled by regulating and controlling the proportion of phenolic hydroxyl-containing chain segments in a molecular structure.
(4) The polyimide type epoxy resin toughening agent has good compatibility with epoxy resin, can be dissolved in the epoxy resin at a certain temperature, and avoids the problem that the polyimide type epoxy resin toughening agent is difficult to disperse uniformly in the processing process.
(5) The polyimide type epoxy resin toughening agent is a copolymerization type polyimide, the molecular weight and the molecular structure of the polyimide type epoxy resin toughening agent are controllable, and the synthesis process is simple.
Drawings
FIG. 1 is an SEM photograph of a cross section of an unmodified epoxy resin casting after fracture toughness testing.
FIG. 2 is a SEM photograph of a cross section of an epoxy resin casting modified with a polyimide-type toughening agent CPEI according to the present application after fracture toughness test, wherein the left image is a photograph of an epoxy resin casting having a CPEI content of 5% and the right image is a photograph of an epoxy resin casting having a CPEI content of 10%.
Detailed Description
In order to make the technical solution of the present application better understood by those skilled in the art, the technical solution of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
The structure and performance tests involved in the following embodiments were performed as follows:
(1) Fracture toughness: the test was performed according to ASTM5045 using an XPV-25C optical microscope and a WDW-20E micro-electro-mechanical control universal material tester.
(2) Impact strength: according to the standard GB/T1843 test standard, an XJUY-5.5 cantilever beam impact tester is adopted for testing.
(3) Flexural strength: according to the standard GB/T2567, a WDW-20E microcomputer electronic control universal material testing machine is adopted for testing.
(4) Profile morphology: and (3) observing by adopting a JSM-7001 type scanning electron microscope.
Example 1
Preparation of polyimide type epoxy resin toughening agent: 3 parts of 3,3' -dihydroxybenzidine (HAB) are dissolved in a certain amount of N-methylpyrrolidone, and then 5 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl group are added in portions]The preparation method comprises the steps of stirring the dianhydride (BPADA) until the dianhydride (BPADA) is completely dissolved, reacting for 2 hours at the constant temperature of-5 ℃ under the protection of nitrogen in the whole process, dissolving 36 parts of 4,4' -diaminodiphenyl ether (ODA) into a certain amount of N-methylpyrrolidone, and adding 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl in batches]The preparation method comprises the steps of stirring the dianhydride (BPADA) until the dianhydride (BPADA) is completely dissolved, reacting for 2 hours at the constant temperature of-5 ℃ under the protection of nitrogen, mixing the two solutions, continuously stirring for 2 hours, adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, and continuously reacting for 8 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, placing the precipitate in a vacuum oven, drying at 60 ℃ for 12 hours to constant weight, and pulverizing to obtain the polyimide type epoxy resin toughening agent which is the target product, wherein n is the molecular structure of the polyimide type epoxy resin toughening agent 1 Is 20, n 2 100.
Example 2
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 2.8 parts of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone (BAS) are dissolved in a defined amount of N-methylpyrrolidone, and then 5.7 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl are added in portions]The preparation method comprises the steps of stirring the dianhydride (BPADA) until the dianhydride is completely dissolved, reacting for 3 hours at the constant temperature of 5 ℃ under the protection of nitrogen in the whole process, dissolving 40 parts of 4,4' -diaminodiphenyl ether (ODA) into a certain amount of N-methylpyrrolidone, and adding 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) in batchesPhenyl group]The reaction was carried out at a constant temperature of 5℃for 2 hours under the protection of nitrogen gas, followed by mixing the two solutions, continuing to stir for 3 hours, and then adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, and continuing to react for 10 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, placing the precipitate in a vacuum oven, drying at 60 ℃ for 14 hours to constant weight, and pulverizing to obtain the polyimide type epoxy resin toughening agent which is the target product, wherein n is the molecular structure of the polyimide type epoxy resin toughening agent 1 Is 10, n 2 100.
Example 3
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 2.9 parts of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone (BAS) are dissolved in a defined amount of N-methylpyrrolidone, and then 5.5 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl are added in portions]The preparation method comprises the steps of stirring the dianhydride (BPADA) until the dianhydride (BPADA) is completely dissolved, reacting for 4 hours at the constant temperature of 5 ℃ under the protection of nitrogen in the whole process, dissolving 42 parts of 4,4' -diaminodiphenyl ether (ODA) into a certain amount of N-methylpyrrolidone, and adding 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl in batches]The malononide (BPADA) was stirred until it was completely dissolved, and reacted at a constant temperature of 5℃for 4 hours under the protection of nitrogen gas as well, and then the above two solutions were mixed and stirred for 2 hours under the same conditions to obtain a polyamic acid solution. Pouring the mixed solution into deionized water to obtain flocculent precipitate, placing the flocculent precipitate in a vacuum oven, drying at 60 ℃ for 12 hours to constant weight, then performing thermal imidization according to the temperature rise program of 250 ℃/2h+300 ℃/2h to obtain polyimide floccules, and crushing the polyimide floccules to obtain a product, namely the polyimide type epoxy resin toughener as a target product, wherein n is the molecular structure of the polyimide type epoxy resin toughener 1 Is 5, n 2 100.
Example 4
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 16 parts of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone (BAS) are dissolved in a certain amount of N-methylpyrrolidone, 19 parts of 4,4' -diphenyl ether dianhydride (ODPA) are added in batches and stirredTo complete dissolution, the reaction is carried out for 2 hours at a constant temperature of 20 ℃ under the protection of nitrogen in the whole process, meanwhile 67 parts of 3,4 '-diaminodiphenyl ether (34 ODA) is dissolved in a certain amount of N-methylpyrrolidone, then 100 parts of 4,4' -diphenyl ether dianhydride (ODPA) is added in batches, the mixture is stirred to complete dissolution, the reaction is carried out for 2 hours at a constant temperature of 20 ℃ under the protection of nitrogen, the two solutions are mixed, the stirring is continued for 2 hours, and then a mixed solution of 90 parts of acetic anhydride and 28 parts of triethylamine is added, and the reaction is continued for 8 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, placing the precipitate in a vacuum oven, drying at 60 ℃ for 12 hours to constant weight, and pulverizing to obtain the polyimide type epoxy resin toughening agent which is the target product, wherein n is the molecular structure of the polyimide type epoxy resin toughening agent 1 Is 10, n 2 90.
Example 5
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 6.1 parts of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone (BAS) is dissolved in a certain amount of N-methylpyrrolidone, 7.1 parts of 4,4' -diphenyl ether dianhydride (ODPA) is added in batches, stirred until the mixture is completely dissolved, the mixture is reacted at the constant temperature of 0 ℃ for 4 hours under the protection of nitrogen in the whole course, meanwhile, 76 parts of 4,4' -diamino-diphenyl sulfone (DADPS) is dissolved in a certain amount of N-methylpyrrolidone, 100 parts of 4,4' -diphenyl ether dianhydride (ODPA) is added in batches, the mixture is stirred until the mixture is completely dissolved, the mixture is reacted at the constant temperature of 0 ℃ for 4 hours under the protection of nitrogen, the mixture is continuously stirred for 4 hours, and then 90 parts of acetic anhydride and 28 parts of pyridine are added for continuous reaction for 12 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, placing the precipitate in a vacuum oven, drying at 60 ℃ for 20 hours to constant weight, and pulverizing to obtain the polyimide type epoxy resin toughening agent which is the target product, wherein n is the molecular structure of the polyimide type epoxy resin toughening agent 1 Is 20, n 2 80.
Example 6
Polyimide type epoxy resin toughening agent (CPEI toughening agent)Preparation: 4.4 parts of 3,3' -dihydroxy-4, 4' -diaminodiphenyl methane (3H 4 ADPM) is dissolved in a certain amount of N-methylpyrrolidone, then 5.4 parts of 3,3', 4' -tetracarboxylic benzophenone dianhydride (BTDA) is added in batches, stirred until complete dissolution, the reaction is carried out at a constant temperature of 3 ℃ for 3 hours, and at the same time, 70 parts of 4,4' -diaminodiphenyl sulfide (DADPES) is dissolved in a certain amount of N-methylpyrrolidone, then 100 parts of 3,3', 4' -tetracarboxylic benzophenone dianhydride (BTDA) is added in batches, stirred until complete dissolution is carried out, the reaction is carried out at a constant temperature of 3 ℃ for 3 hours under the same nitrogen protection, then the two solutions are mixed, stirred for 3 hours, then 90 parts of acetic anhydride and 28 parts of pyridine mixed solution are added, and the reaction is continued for 20 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, drying in a vacuum oven at 60deg.C for 18 hr to constant weight, and pulverizing to obtain the final product with molecular structure n 1 Is 10, n 2 80.
Example 7
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 4.2 parts of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfide (3A 4 HDPES) was dissolved in a certain amount of N-methylpyrrolidone, then 5.7 parts of 3,3', 4' -tetracarboxylic acid diphenyl Sulfide Dianhydride (SDPA) was added in portions, stirred until it was completely dissolved, reacted at a constant temperature of 5℃for 3 hours under nitrogen protection throughout, at the same time 69 parts of 4,4' -diaminodiphenyl sulfide (DADPES) was dissolved in a certain amount of N-methylpyrrolidone, then 100 parts of 3,3', 4' -tetracarboxylic acid diphenyl Sulfide Dianhydride (SDPA) was added in portions, stirred until it was completely dissolved, reacted at a constant temperature of 5℃for 2 hours under nitrogen protection as well, then the above two solutions were mixed, stirred for 3 hours again, then a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine was added, and the reaction was continued for 10 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, drying in a vacuum oven at 60deg.C for 15 hr to constant weight, and pulverizing to obtain productPolyimide type epoxy resin toughening agent as target product, and its molecular structure is n 1 Is 10, n 2 80.
Example 8
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 2.8 parts of 3,3' -diamino-4, 4' -dihydroxydiphenyl ether (3A 4 HDPE) is dissolved in a certain amount of N-methylpyrrolidone, then 5.7 parts of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride (6 FDA) is added in batches, stirred until complete dissolution, the reaction is carried out for 3 hours at a constant temperature of 5 ℃, the whole process is under the protection of nitrogen, meanwhile, 49 parts of 4,4' -Diaminobenzophenone (DABP) is dissolved in a certain amount of N-methylpyrrolidone, then 100 parts of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride (6 FDA) is added in batches, stirring is carried out until complete dissolution, the reaction is carried out for 2 hours at a constant temperature of 5 ℃ under the protection of nitrogen, then the two solutions are mixed, stirring is continued for 6 hours, and then a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine is added, and the reaction is continued for 10 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, filtering to obtain light yellow flocculent precipitate, washing the precipitate with absolute ethyl alcohol for several times, placing the precipitate in a vacuum oven, drying at 60 ℃ for 12 hours to constant weight, and pulverizing to obtain the polyimide type epoxy resin toughening agent which is the target product, wherein n is the molecular structure of the polyimide type epoxy resin toughening agent 1 Is 10, n 2 80.
The phenolic hydroxyl group-containing diamine monomer in the above-described examples may also be mixed with any of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 3 '-dihydroxy-4, 4' -diaminodiphenyl methane, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfide and 3,3 '-diamino-4, 4' -dihydroxydiphenyl ether; the diamine monomer without phenolic hydroxyl group can be any mixture of several of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone and 4,4' -diaminodiphenyl ketone; the dianhydride monomer can be any of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4 '-diphenyl ether dianhydride, 3',4 '-tetracarboxylic diphenyl ketone dianhydride, 3',4 '-tetracarboxylic diphenyl sulfide dianhydride and 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride.
Application example 1
100 parts of tetrafunctional epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the example 1 and 36 parts of the curing agent diethyl toluenediamine are added, the mixture is stirred uniformly and poured into a preheated specific die, air bubbles are removed through vacuumizing, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃, the toughened epoxy resin is obtained, and the fracture toughness, impact strength and bending strength of the toughened epoxy resin are tested, and the results are shown in Table 1.
Application example 2
100 parts of tetrafunctional epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the example 2 and 36 parts of the curing agent diethyl toluenediamine are added, the mixture is stirred uniformly and poured into a preheated specific die, air bubbles are removed through vacuumizing, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃, the toughened epoxy resin is obtained, and the fracture toughness, impact strength and bending strength of the toughened epoxy resin are tested, and the results are shown in Table 1.
Application example 3
100 parts of tetrafunctional epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the embodiment 3 and 36 parts of the curing agent diethyl toluenediamine are added, the mixture is stirred uniformly and poured into a preheated specific mold, air bubbles are removed through vacuumizing, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃, the toughened epoxy resin is obtained, and the fracture toughness, impact strength and bending strength of the toughened epoxy resin are tested, and the results are shown in table 1.
Blank comparison
100 parts of tetrafunctional epoxy resin TGDDM is heated to 120 ℃, 36 parts of curing agent diethyl toluenediamine is added, the mixture is stirred uniformly and poured into a preheated specific mould, the mould is vacuumized to remove bubbles, and the mixture is cured for 2 hours at 150 ℃ and for 2 hours at 180 ℃ to obtain an epoxy resin casting body which is used as a blank sample.
Table 1 comparison of various properties of CPEI toughened modified epoxy resins and unmodified epoxy resins of different molecular structures
| Toughening agent modified epoxy resin | Fracture toughness/MN/m 3/2 | Impact Strength/KJ/m 2 | Flexural Strength/MPa |
| Blank sample | 13.74 | 5.37 | 95.2 |
| Application example 1 | 14.43 | 12.26 | 82.4 |
| Application example 2 | 17.44 | 11.18 | 80.6 |
| Application example 3 | 22.71 | 17.10 | 102.8 |
As shown in the experimental results in Table 1, the toughness of the epoxy resin material modified by CPEI toughening agents with different molecular structures is obviously improved, the fracture toughness is improved by 4.8-65% compared with that of pure resin, the impact strength is improved by 108-218%, and when the polyimide toughening agent in the embodiment 3 is adopted, the bending strength is improved.
As can be seen from FIG. 1, the cross section of the pure epoxy resin casting body is flat and smooth and is brittle fracture, as can be seen from FIG. 2, the toughening agent is microphase separated in the epoxy resin matrix and is uniformly dispersed, the cross section is rough and has more cracks, the crack growth can be effectively prevented under the action of stress, and the separated toughening agent phase absorbs fracture energy through plastic deformation, so that the fracture toughness of the material is improved.
According to the technical scheme, the block type polyimide copolymer with controllable molecular weight and composition is applied to the toughening modification of the epoxy resin, the toughening effect is obvious, meanwhile, good bending strength is maintained, the problems that the compatibility of the toughening agent and the epoxy resin is poor and the toughening of the epoxy resin is not enhanced are solved, and the block type polyimide copolymer can be used as a composite material matrix, a coating and other materials and applied to the fields of aerospace and traffic.
Claims (9)
1. The polyimide type epoxy resin toughening agent is characterized by being a block type polyimide copolymer, wherein the block type polyimide copolymer consists of a structural chain segment containing phenolic hydroxyl groups and a structural chain segment not containing the phenolic hydroxyl groups, and the structural formula is as follows:
(A-B) m (P1)
in the formula (P1), m is an integer greater than 4; wherein the segment A has a repeating unit represented by the following formula (I):
in the formula (I), X represents
R representsn 1 Is 5 to 300;
in formula (P1), segment B has a repeating unit represented by formula (II):
in the formula (II), R 2 Represents O; r representsn 2 Is any integer of 5 to 300.
2. A method of preparing the polyimide type epoxy resin toughening agent according to claim 1, comprising the steps of:
step 1, adding diamine containing phenolic hydroxyl groups and N-methyl pyrrolidone into a completely dried reaction container, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, then adding dianhydride according to a proportion, and stirring and reacting under the protection of nitrogen to obtain a polyamide acid solution containing the phenolic hydroxyl groups;
step 2, adding diamine and N-methyl pyrrolidone which do not contain phenolic hydroxyl groups into another reaction container, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, adding dianhydride according to a proportion, and stirring and reacting under the protection of nitrogen to obtain a polyamide acid solution which does not contain phenolic hydroxyl groups;
and step 3, mixing the two polyamic acid solutions obtained in the step 1 and the step 2, continuously stirring, then converting the polyamic acid into polyimide through chemical imidization or thermal imidization, and finally separating and purifying to obtain the polyimide type epoxy resin toughening agent.
3. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, wherein the dianhydride is added in the step 1 according to a proportion, specifically according to a molar ratio of diamine containing phenolic hydroxyl groups to dianhydride of 1:1.02-1.05; stirring and reacting under the protection of nitrogen, specifically stirring and reacting for 2-6 hours at the temperature of-5-20 ℃ under the protection of nitrogen, and obtaining the polyamic acid solution containing phenolic hydroxyl.
4. The method for preparing a polyimide type epoxy resin toughening agent according to claim 2, wherein the phenolic hydroxyl group-containing diamine monomer in the step 1 is 3,3' -dihydroxybenzidine or 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone.
5. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, wherein dianhydride is added in the step 2 according to a proportion, specifically according to a molar ratio of diamine without phenolic hydroxyl groups to dianhydride of 1.02-1.05:1; stirring and reacting under the protection of nitrogen, specifically stirring and reacting for 2-6 hours at the temperature of-5-20 ℃ under the protection of nitrogen, and obtaining the polyamic acid solution without phenolic hydroxyl.
6. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, which is characterized in that: the diamine monomer which does not contain phenolic hydroxyl groups in the step 2 is 4,4' -diaminodiphenyl ether.
7. The method for preparing a polyimide type epoxy resin toughening agent according to claim 2, wherein the dianhydride monomer in the step 1-2 is 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride.
8. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, wherein the stirring in the step 3 is continued, in particular, the stirring is continued for 2 to 6 hours; continuing the reaction, specifically for 8-20 hours; the chemical imidization is to add a chemical imidization reagent into the mixed solution, continue the reaction, and obtain the polyimide type epoxy resin toughening agent after separation and purification, wherein the chemical imidization reagent is acetic anhydride/pyridine mixed solution or acetic anhydride/triethylamine mixed solution; the thermal imidization is to precipitate the polyamic acid in ethanol, and put the polyamic acid powder into an oven for thermal imidization to obtain a polyimide product, wherein the thermal imidization temperature is 250 ℃/2h and 300 ℃/2h.
9. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, wherein the polyimide type epoxy resin toughening agent is obtained after separation and purification in the step 3, specifically, the mixed solution obtained by the reaction is poured into absolute ethyl alcohol, light yellow filiform sediment is obtained by precipitation, the sediment is repeatedly washed for 3 times by the absolute ethyl alcohol, unreacted reaction monomers and solvents are removed, the sediment is placed in a vacuum oven, the vacuum oven is dried for 12-20 hours to constant weight at 60 ℃, and white powder obtained by crushing is the polyimide type epoxy resin toughening agent which is the target product.
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| KR20180000863A (en) * | 2016-06-24 | 2018-01-04 | 코오롱인더스트리 주식회사 | Polyamic acid rasin, polyimide films, and display device comprising thereof |
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| KR20180000863A (en) * | 2016-06-24 | 2018-01-04 | 코오롱인더스트리 주식회사 | Polyamic acid rasin, polyimide films, and display device comprising thereof |
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