CN113861421A - 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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- CN113861421A CN113861421A CN202111322416.1A CN202111322416A CN113861421A CN 113861421 A CN113861421 A CN 113861421A CN 202111322416 A CN202111322416 A CN 202111322416A CN 113861421 A CN113861421 A CN 113861421A
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- epoxy resin
- toughening agent
- polyimide
- phenolic hydroxyl
- type epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 105
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 105
- 239000012745 toughening agent Substances 0.000 title claims abstract description 77
- 239000004642 Polyimide Substances 0.000 title claims abstract description 58
- 229920001721 polyimide Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- 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
- 239000002244 precipitate Substances 0.000 claims description 39
- 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 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- 150000004985 diamines Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- -1 3, 4-dicarboxyphenyl Chemical group 0.000 claims description 9
- 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 7
- 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 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 claims description 4
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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 claims description 4
- 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000005462 imide group Chemical group 0.000 abstract 1
- 238000010125 resin casting Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-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
- 239000004005 microsphere Substances 0.000 description 3
- 238000005086 pumping Methods 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
- 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 description 2
- 102100035915 D site-binding protein Human genes 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 101000873522 Homo sapiens D site-binding protein Proteins 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000001294 propane 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
- 238000004154 testing of material Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920001187 thermosetting polymer 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
- VHUWVCAJOXIARC-UHFFFAOYSA-N 4-[4-[4-(3,4-dicarboxyphenoxy)phenyl]sulfonylphenoxy]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=C(C(C(O)=O)=CC=3)C(O)=O)=CC=2)C=C1 VHUWVCAJOXIARC-UHFFFAOYSA-N 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
- 238000012661 block copolymerization Methods 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
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 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
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin 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
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-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Epoxy Resins (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention 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 and a structural chain segment without phenolic hydroxyl, wherein the structural chain segment containing phenolic hydroxyl can participate in the curing reaction of epoxy resin, and the toughening agent is introduced into an epoxy resin cross-linking network through a chemical bond, so that the compatibility and the interface bonding 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 keep good mechanical properties and heat resistance, and is applied to a high-temperature-resistant multi-functional group epoxy resin system. The preparation method comprises the steps of respectively preparing a polyamic acid solution containing phenolic hydroxyl and a polyamic acid solution without phenolic hydroxyl, mixing the two polyamic acid solutions, stirring, and then converting the polyamic acid into polyimide by a chemical imidization or thermal imidization mode to obtain the polyimide type epoxy resin toughening agent.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a polyimide type epoxy resin toughening agent and a preparation method thereof.
Background
The four-functional-group epoxy resin is a high-temperature-resistant thermosetting resin, has good corrosion resistance, dielectric property and mechanical property, and can be widely applied to multiple fields of electromechanical devices, transportation, sports equipment, pressure vessels, structural reinforcement and the like as an excellent matrix material. However, due to the highly crosslinked three-dimensional network structure, this type of epoxy resin has the disadvantage of poor toughness, limiting its further applications.
The toughening method of the existing epoxy resin 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 destroy the rigid structure of the epoxy resin, the toughening effect is achieved through effective stress transfer between the microspheres and the epoxy resin, but the mechanical property of the modified epoxy resin is obviously reduced.
CN102516717A uses a thermoplastic elastomer as a toughening agent to modify epoxy resin, the thermoplastic elastomer, a compatilizer and an auxiliary agent are uniformly mixed, and then the mixture is added into the epoxy resin for thermosetting, but the toughening agent and the epoxy resin have poor compatibility due to the weak polarity of the elastomer.
In CN105623265A, researchers modify epoxy resin with polyether polyol and its derivatives, by first compounding polyether polyol/polyether ketone/polyether sulfone, and then adding the compounded polyether polyol/polyether ketone/polyether sulfone into an epoxy system, the heat resistance of epoxy resin is better maintained, but because polyether polyol does not participate in the curing reaction of epoxy resin, the compatibility between the toughening agent and epoxy resin is poor.
In view of the above problems, the present applicant has studied a polyimide type epoxy resin toughening agent and a method for preparing the same. The toughening agent is a block type polyimide polymer and consists of a structural chain segment containing phenolic hydroxyl and a structural chain segment without phenolic hydroxyl, wherein the chain segment containing phenolic hydroxyl can participate in the curing reaction of the epoxy resin, and the toughening agent is introduced into a cross-linking network through a chemical bond, so that the compatibility and the interface bonding force of the toughening agent and the epoxy resin are improved; in addition, the main chain of the toughening agent contains rigid groups such as benzene rings, imide structures and the like, so that the epoxy resin can be toughened and the good mechanical strength of the epoxy resin can be maintained.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polyimide type epoxy resin toughening agent and a preparation method thereof, and solves the problems that the toughening agent is poor in compatibility with epoxy resin and the epoxy resin is not toughened and strengthened.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyimide-type epoxy toughener (CPEI) which is a block-type polyimide copolymer consisting of a structural segment containing phenolic hydroxyl groups and a structural segment not containing phenolic hydroxyl groups, having the following structural formula:
(A-B)m (P1)
in 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,
n1Is any integer of 5 to 300; n is1More preferably an integer of 10 to 50.
In the formula (P1), the segment B has a repeating unit represented by the following formula (II):
in the formula (II), R2Representations O, S,
R is O, S,
n2Is an integer of 5 to 300. From the viewpoint of comprehensive properties of the material, n2More preferably 20 to 100.
A preparation method of a polyimide type epoxy resin toughening agent comprises the following steps:
step 1, adding diamine containing phenolic hydroxyl and N-methyl pyrrolidone into a completely dried reaction vessel, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, then adding dianhydride in proportion, and stirring and reacting under the protection of nitrogen to obtain polyamic acid solution containing phenolic hydroxyl.
And 2, adding diamine without phenolic hydroxyl and N-methyl pyrrolidone into another reaction vessel, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, then adding dianhydride in proportion, and stirring for reaction under the protection of nitrogen to obtain the polyamic acid solution without phenolic hydroxyl.
And 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 in proportion, specifically in proportion that the molar ratio of the diamine containing phenolic hydroxyl groups to the dianhydride is 1: 1.02-1.05; and stirring for reaction under the protection of nitrogen, specifically stirring for reaction for 2-6 hours at-5-20 ℃ under the protection of nitrogen to obtain the phenolic hydroxyl group-containing polyamic acid solution.
Still further, the phenolic hydroxyl group-containing diamine monomer in step 1 includes one or more of 3,3' -dihydroxybenzidine (HAB), 3' -diamino-4, 4' -dihydroxydiphenyl sulfone (BAS), 3' -dihydroxy-4, 4' -diaminodiphenylmethane (3H4ADPM), 3' -diamino-4, 4' -dihydroxydiphenyl sulfide (3A4HDPES), and 3,3' -diamino-4, 4' -dihydroxydiphenyl ether (3A4 HDPE).
Further, the dianhydride is added in the step 2 in proportion, specifically in proportion that the molar ratio of the diamine without phenolic hydroxyl groups to the dianhydride is 1.02-1.05: 1; and stirring and reacting under the protection of nitrogen, specifically stirring and reacting for 2-6 hours at-5-20 ℃ under the protection of nitrogen to obtain the polyamic acid solution without phenolic hydroxyl.
Further, the diamine monomer having no phenolic hydroxyl group in step 2 includes one or more of 4,4' -diaminodiphenyl ether (ODA), 3, 4' -diaminodiphenyl ether (34ODA), 4' -diaminodiphenyl sulfide (DADPES), 4' -diaminodiphenyl sulfone (DADPS), and 4,4' -Diaminobenzophenone (DABP).
Still further, the dianhydride monomer in step 1-2 includes one or more of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 4,4 '-diphenyl ether dianhydride (ODPA), 3', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA), 3', 4,4 '-tetracarboxylic acid 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 for 8-20 hours; the chemical imidization means adding a chemical imidization reagent into the mixed solution, continuing to react, separating and purifying to obtain the polyimide type epoxy resin toughening agent, wherein the chemical imidization reagent is acetic anhydride/pyridine mixed solution or acetic anhydride/triethylamine mixed solution; the thermal imidization refers to firstly precipitating the polyamic acid in ethanol, and placing the polyamic acid powder in a drying oven for thermal imidization to obtain a polyimide product, wherein the thermal imidization temperature is 250 ℃/2h and 300 ℃/2 h.
Further, the polyimide-type epoxy resin toughening agent is obtained after separation and purification in the step 3, and specifically, the mixed solution obtained through reaction is poured into absolute ethyl alcohol, yellow filiform precipitate is obtained through precipitation, the precipitate is repeatedly washed for a plurality of times through the absolute ethyl alcohol, unreacted reaction monomers and solvents are removed, the obtained product is placed in a vacuum oven, drying is carried out for 12-20 hours at the temperature of 60 ℃ until the weight is constant, and white powder obtained through crushing is the target product polyimide-type epoxy resin toughening agent (CPEI).
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyimide type epoxy resin toughening agent CPEI is block copolymerization type polyimide, has rigid structures such as an imide structure and a benzene ring 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 and a structural chain segment without phenolic hydroxyl, wherein the chain segment containing phenolic hydroxyl can participate in the curing reaction of epoxy resin to form a covalent bond, and a linear polyimide molecular chain is introduced into an epoxy resin cross-linked network, so that the impact resistance of the epoxy resin is remarkably improved.
(3) The polyimide type epoxy resin toughening agent is a block polymer, and the interface action between the toughening agent and an epoxy resin matrix can be effectively regulated and controlled by regulating and controlling the proportion of a segment containing phenolic hydroxyl 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 of difficult uniform dispersion in the processing process.
(5) The polyimide type epoxy resin toughening agent is copolymerized 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 an SEM photograph of a fracture toughness test of an epoxy resin casting modified with a CPEI of a polyimide type toughening agent of the present invention, 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 those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The structure and performance tests involved in the following examples were performed as follows:
(1) fracture toughness: according to ASTM5045 test standard, the test is carried out by using XPV-25C type optical microscope and WDW-20E type microcomputer electronic control universal material testing machine.
(2) Impact strength: according to the test standard GB/T1843, an XJUY-5.5 type cantilever beam impact tester is adopted for testing.
(3) Bending strength: according to the standard GB/T2567, a WDW-20E type microcomputer electronic control universal material testing machine is adopted for testing.
(4) The section appearance is as follows: observed by using 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 defined amount of N-methylpyrrolidone, and 5 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl]Propanedianhydride (BPADA) is stirred to be completely dissolved, and is reacted for 2 hours at the constant temperature of-5 ℃ under the protection of nitrogen in the whole process, at the same time, 36 parts of 4,4' -diaminodiphenyl ether (ODA) are dissolved in a certain amount of N-methyl pyrrolidone, and then 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] are added in portions]Propanedianhydride (BPADA), stirred until completely dissolved, reacted at-5 ℃ for 2 hours, again under nitrogen, then mixed, stirred for a further 2 hours, then admixed with 90 parts of acetic anhydride and 28 parts of pyridineThe solution was mixed and the reaction was continued for 8 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 12 hours at the temperature of 60 ℃ until the weight of the precipitate is constant, and crushing the precipitate to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure of the polyimide type epoxy resin toughening agent, n is1Is 20, n2Is 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 5.7 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] sulfone are added in portions]Propanedianhydride (BPADA) is stirred to be completely dissolved, and is reacted for 3 hours at the constant temperature of 5 ℃ under the protection of nitrogen in the whole process, at the same time, 40 parts of 4,4' -diaminodiphenyl ether (ODA) is dissolved in a certain amount of N-methyl pyrrolidone, and then 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] is added in portions]And (3) stirring to completely dissolve the propylene dianhydride (BPADA), reacting at the constant temperature of 5 ℃ for 2 hours under the protection of nitrogen, mixing the two solutions, continuing stirring for 3 hours, adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, and continuing the reaction for 10 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 14 hours at the temperature of 60 ℃ to constant weight, and crushing the precipitate to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure, n is1Is 10, n2Is 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 certain amount of N-methylpyrrolidone, and 5.5 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] are added in portions]The preparation method comprises stirring to dissolve completely the propane dianhydride (BPADA), reacting at 5 deg.C for 4 hr under nitrogen protection, and dissolving 42 parts of 4,4' -diaminodiphenyl ether (ODA) in certain amountTo N-methylpyrrolidone, 100 parts of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl group was added in portions]And (3) stirring to completely dissolve the propane dianhydride (BPADA), reacting at 5 ℃ for 4 hours under the protection of nitrogen, mixing the two solutions, and continuing stirring 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 for 12 hours at the temperature of 60 ℃ to constant weight, then carrying out thermal imidization according to the temperature rising program of 250 ℃/2h +300 ℃/2h to obtain polyimide floccule, and crushing to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure, n is n1Is 5, n2Is 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 stirred until complete dissolution, the mixture is reacted at a constant temperature of 20 ℃ for 2 hours under nitrogen protection, at the same time, 67 parts of 3, 4' -diaminodiphenyl ether (34ODA) are dissolved in a certain amount of N-methylpyrrolidone, 100 parts of 4,4' -diphenyl ether dianhydride (ODPA) are added in batches and stirred until complete dissolution, the mixture is reacted at a constant temperature of 20 ℃ for 2 hours under nitrogen protection, then the two solutions are mixed and stirred for 2 hours, 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, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 12 hours at the temperature of 60 ℃ to constant weight, and crushing the precipitate to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure, n is1Is 10, n2Is 90.
Example 5
Preparation of polyimide type epoxy resin toughener (CPEI toughener): 6.1 parts of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone (BAS) are dissolved in a defined amount of N-methylpyrrolidone and then 7.1 parts of it are added in portions4,4' -diphenyl ether dianhydride (ODPA), stirring to completely dissolve, reacting at 0 ℃ for 4 hours under the protection of nitrogen, dissolving 76 parts of 4,4' -diaminodiphenyl sulfone (DADPS) in a certain amount of N-methyl pyrrolidone, adding 100 parts of 4,4' -diphenyl ether dianhydride (ODPA) in batches, stirring to completely dissolve, reacting at 0 ℃ for 4 hours under the protection of nitrogen, mixing the two solutions, continuing to stir for 4 hours, adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, and continuing to react for 12 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 20 hours at the temperature of 60 ℃ to constant weight, and crushing the precipitate to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure, n is1Is 20, n2Is 80.
Example 6
Preparation of polyimide type epoxy resin toughener (CPEI toughener): dissolving 4.4 parts of 3,3' -dihydroxy-4, 4' -diaminodiphenylmethane (3H4ADPM) in a certain amount of N-methylpyrrolidone, then adding 5.4 parts of 3,3', 4,4' -tetracarboxylic acid benzophenone dianhydride (BTDA) in portions, stirring until complete dissolution, reacting at 3 ℃ for 3 hours under nitrogen protection, while dissolving 70 parts of 4,4' -diaminodiphenyl sulfide (DADPES) in a certain amount of N-methylpyrrolidone, then adding 100 parts of 3,3', 4,4' -tetracarboxylic acid benzophenone dianhydride (BTDA) in portions, stirring until complete dissolution, reacting at 3 ℃ for 3 hours under nitrogen protection, then mixing the two solutions, continuing stirring for 3 hours, then adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, the reaction was continued for 20 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 18 hours at the temperature of 60 ℃ to constant weight, and crushing the precipitate to obtain a product, namely a target product, wherein in the molecular structure, n is n1Is 10, n2Is 80.
Example 7
Preparation of polyimide type epoxy resin toughener (CPEI toughener): dissolving 4.2 parts of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfide (3A4HDPES) in a certain amount of N-methylpyrrolidone, then adding 5.7 parts of 3,3', 4,4' -tetracarboxylic acid diphenyl Sulfide Dianhydride (SDPA) in batches, stirring until the 3,3', 4,4' -tetracarboxylic acid diphenyl Sulfide Dianhydride (SDPA) is completely dissolved, reacting at the constant temperature of 5 ℃ for 3 hours under the protection of nitrogen gas all the time, meanwhile, dissolving 69 parts of 4,4 '-diaminodiphenyl sulfide (DADPES) in a certain amount of N-methylpyrrolidone, then adding 100 parts of 3,3', 4,4 '-tetracarboxylic acid diphenyl Sulfide Dianhydride (SDPA) in batches, stirring until the 4,4' -diaminodiphenyl sulfide dianhydride is completely dissolved, reacting at the constant temperature of 5 ℃ for 2 hours under the protection of nitrogen gas also, then mixing the two solutions, continuing to stir for 3 hours, then adding a mixed solution of 90 parts of acetic anhydride and 28 parts of pyridine, the reaction was continued for 10 hours. Pouring the mixed solution into a large amount of absolute ethyl alcohol, carrying out suction filtration to obtain light yellow flocculent precipitate, washing the precipitate for a plurality of times by using the absolute ethyl alcohol, placing the precipitate in a vacuum oven, drying the precipitate for 15 hours at the temperature of 60 ℃ to constant weight, and crushing the precipitate to obtain a product, namely the target product, namely the polyimide type epoxy resin toughening agent, wherein in the molecular structure, n is1Is 10, n2Is 80.
Example 8
Preparation of polyimide type epoxy resin toughener (CPEI toughener): dissolving 2.8 parts of 3,3' -diamino-4, 4' -dihydroxydiphenyl ether (3A4HDPE) in a certain amount of N-methylpyrrolidone, then adding 5.7 parts of 2,2 ' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride (6FDA) in portions, stirring until completely dissolved, reacting at 5 ℃ for 3 hours under nitrogen protection, while adding 49 parts of 4,4' -Diaminobenzophenone (DABP) in a certain amount of N-methylpyrrolidone, then adding 100 parts of 2,2 ' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride (6FDA) in portions, stirring until completely dissolved, reacting at 5 ℃ for 2 hours under nitrogen protection, then mixing the two solutions, continuing stirring for 6 hours, 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, carrying out suction filtration to obtain light yellow flocculent precipitate, and washing the precipitate with absolute ethyl alcoholSeveral times, placing in a vacuum oven, drying at 60 deg.C for 12 hr to constant weight, pulverizing to obtain the target product polyimide type epoxy resin toughening agent, wherein in its molecular structure, n is1Is 10, n2Is 80.
The phenolic hydroxyl group-containing diamine monomer in the above examples may be a mixture of 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 can also be any mixture of 4,4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone and 4,4' -diaminobenzophenone; the dianhydride monomer may be any mixture of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4,4 '-diphenyl ether dianhydride, 3', 4,4 '-tetracarboxylic acid benzophenone dianhydride, 3', 4,4 '-tetracarboxylic acid diphenyl sulfide dianhydride, and 2, 2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride.
Application example 1
100 parts of tetrafunctional group epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the example 1 and 36 parts of curing agent diethyl toluene diamine are added, the mixture is uniformly stirred and poured into a preheated specific mold, the vacuum pumping is carried out to remove bubbles, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃ to obtain the toughened epoxy resin, and the fracture toughness, the impact strength and the bending strength of the toughened epoxy resin are tested, and the results are shown in Table 1.
Application example 2
100 parts of tetrafunctional group epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the example 2 and 36 parts of curing agent diethyl toluene diamine are added, the mixture is uniformly stirred and poured into a preheated specific mold, the vacuum pumping is carried out to remove bubbles, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃ to obtain the toughened epoxy resin, and the fracture toughness, the impact strength and the bending strength of the toughened epoxy resin are tested, and the results are shown in the table 1.
Application example 3
100 parts of tetrafunctional group epoxy resin TGDDM is heated to 120 ℃, 6.6 parts of the toughening agent prepared in the embodiment 3 and 36 parts of curing agent diethyl toluene diamine are added, the mixture is uniformly stirred and poured into a preheated specific mold, the vacuum pumping is carried out to remove bubbles, the mixture is cured for 2 hours at 150 ℃ and cured for 2 hours at 180 ℃ to obtain the toughened epoxy resin, and the fracture toughness, the impact strength and the bending strength of the toughened epoxy resin are tested, and the results are shown in Table 1.
Blank comparison
Heating 100 parts of tetrafunctional group epoxy resin TGDDM to 120 ℃, adding 36 parts of curing agent diethyl toluene diamine, uniformly stirring, pouring into a preheated specific mold, vacuumizing to remove bubbles, curing at 150 ℃ for 2 hours and at 180 ℃ for 2 hours to obtain an epoxy resin casting body serving as a blank sample.
Table 1 comparison of individual properties of CPEI toughening modified epoxy resin and unmodified epoxy resin with different molecular structures
| Toughening agent modified epoxy resin | Fracture toughness/MN/m3/2 | Impact Strength/KJ/m2 | 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 |
From the experimental results shown in table 1, it can be seen that the toughness of the epoxy resin material modified by the CPEI toughening agent with different molecular structures is significantly improved, the fracture toughness is improved by 4.8-65% compared with that of the pure resin, the impact strength is improved by 218%, and when the polyimide toughening agent in example 3 is used, the bending strength is improved.
As can be seen from figure 1, the section of the pure epoxy resin casting body is flat and smooth and is brittle fracture, as can be seen from figure 2, the toughening agent is microphase separated and uniformly dispersed in the epoxy resin matrix, the section is relatively rough and has more cracks, the crack can be effectively prevented from expanding under the action of stress, and the separated toughening agent is communicated with the epoxy resin casting body to absorb fracture energy through plastic deformation, so that the fracture toughness of the material is improved.
According to the technical scheme provided by the invention, the block type polyimide copolymer with controllable molecular weight and composition is applied to toughening modification of epoxy resin, the toughening effect is obvious, good bending strength is kept, the problems of poor compatibility of a toughening agent and the epoxy resin and no enhancement of epoxy resin toughening 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 transportation.
Claims (9)
1. The polyimide type epoxy resin toughening agent is characterized in that the polyimide type epoxy resin toughening agent is a block type polyimide copolymer, the block type polyimide copolymer consists of a structural chain segment containing phenolic hydroxyl and a structural chain segment without phenolic hydroxyl, and the structural formula is as follows:
(A-B)m (P1)
in 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,
n1Is any integer of 5 to 300;
in the formula (P1), the segment B has a repeating unit represented by the following formula (II):
in the formula (II), R2Representations O, S,
R is O, S,
n2Is an 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 and N-methyl pyrrolidone into a completely dried reaction vessel, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, then adding dianhydride in proportion, and stirring and reacting under the protection of nitrogen to obtain polyamic acid solution containing phenolic hydroxyl.
And 2, adding diamine without phenolic hydroxyl and N-methyl pyrrolidone into another reaction vessel, introducing inert gas, stirring until the diamine and the N-methyl pyrrolidone are completely dissolved, then adding dianhydride in proportion, and stirring for reaction under the protection of nitrogen to obtain the polyamic acid solution without phenolic hydroxyl.
And 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 proportion in the step 1, specifically, the molar ratio of the diamine containing phenolic hydroxyl groups to the dianhydride is 1: 1.02-1.05; and stirring for reaction under the protection of nitrogen, specifically stirring for reaction for 2-6 hours at the temperature of-5-20 ℃ under the protection of nitrogen to obtain the polyamic acid solution containing phenolic hydroxyl.
4. The method of claim 2, wherein the phenolic hydroxyl group-containing diamine monomer in step 1 comprises one or more selected from the group consisting of 3,3' -dihydroxybiphenyl, 3' -diamino-4, 4' -dihydroxydiphenylsulfone, 3' -dihydroxy-4, 4' -diaminodiphenylmethane, 3' -diamino-4, 4' -dihydroxydiphenylsulfide, and 3,3' -diamino-4, 4' -dihydroxydiphenylether.
5. The method for preparing the polyimide type epoxy resin toughening agent according to claim 2, wherein the dianhydride is added in proportion in the step 2, specifically, the molar ratio of the diamine without phenolic hydroxyl group to the dianhydride is 1.02-1.05: 1; and 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 to obtain the polyamic acid solution without phenolic hydroxyl.
6. The method of preparing a polyimide-type epoxy resin toughening agent according to claim 2, characterized in that: the diamine monomer without phenolic hydroxyl group in step 2 comprises one or more of 4,4' -diaminodiphenyl ether, 3, 4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfone and 4,4' -diaminobenzophenone.
7. The method of preparing a polyimide type epoxy resin toughening agent according to claim 2, wherein the dianhydride monomer in the step 1-2 comprises one or more of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 4,4 '-diphenyl ether dianhydride, 3', 4,4 '-tetracarboxylic acid benzophenone dianhydride, 3', 4,4 '-tetracarboxylic acid diphenyl sulfide dianhydride, and 2, 2' -bis (3, 4-dicarboxyphenyl) hexafluoromethane dianhydride.
8. The method for preparing a polyimide type epoxy resin toughening agent according to claim 2, wherein the stirring in the step 3 is continued, specifically, is continued for 2 to 6 hours; the continuous reaction is carried out for 8-20 hours; the chemical imidization means adding a chemical imidization reagent into the mixed solution, continuing to react, separating and purifying to obtain the polyimide type epoxy resin toughening agent, wherein the chemical imidization reagent is acetic anhydride/pyridine mixed solution or acetic anhydride/triethylamine mixed solution; the thermal imidization refers to firstly precipitating the polyamic acid in ethanol, and placing the polyamic acid powder in a drying oven for thermal imidization to obtain a polyimide product, wherein the thermal imidization temperature is 250 ℃/2h and 300 ℃/2 h.
9. The preparation method of 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, and specifically, the mixed solution obtained by the reaction is poured into absolute ethyl alcohol, light yellow filiform precipitate is obtained through precipitation, the precipitate is repeatedly washed for several times by the absolute ethyl alcohol, unreacted reaction monomers and solvents are removed, the mixture is placed in a vacuum oven, the mixture is dried for 12-20 hours at 60 ℃ to constant weight, and the obtained white powder is ground to obtain the target product polyimide-type epoxy resin toughening agent.
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| CN114853981A (en) * | 2022-05-26 | 2022-08-05 | 洛阳双瑞防腐工程技术有限公司 | Water-soluble polyimide modified epoxy resin and synthesis method thereof, water-based epoxy heat-resistant anticorrosive paint and preparation method thereof |
| CN114874441A (en) * | 2022-07-12 | 2022-08-09 | 明士(北京)新材料开发有限公司 | Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof |
| CN115536816A (en) * | 2022-10-28 | 2022-12-30 | 中国科学院兰州化学物理研究所 | Thermosetting epoxy resin shape memory polymer and preparation method thereof |
| CN115536816B (en) * | 2022-10-28 | 2024-02-20 | 中国科学院兰州化学物理研究所 | Thermosetting epoxy resin shape memory polymer and preparation method thereof |
| CN116333321A (en) * | 2023-03-08 | 2023-06-27 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Polyimide modified low-temperature-resistant epoxy resin containing POSS structure and preparation method thereof |
| CN116333321B (en) * | 2023-03-08 | 2024-05-14 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Polyimide modified low-temperature-resistant epoxy resin containing POSS structure and preparation method thereof |
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| CN113861421B (en) | 2023-12-01 |
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