CN117024817A - Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof - Google Patents
Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof Download PDFInfo
- Publication number
- CN117024817A CN117024817A CN202311212602.9A CN202311212602A CN117024817A CN 117024817 A CN117024817 A CN 117024817A CN 202311212602 A CN202311212602 A CN 202311212602A CN 117024817 A CN117024817 A CN 117024817A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- shape memory
- composite material
- heating
- hyperbranched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 96
- 239000004642 Polyimide Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 22
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 22
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000010 aprotic solvent Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 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 11
- 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 10
- 238000007363 ring formation reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000002355 dual-layer Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 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 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 230000009477 glass transition Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 37
- 239000010408 film Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007334 memory performance Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000006386 memory function Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a double-layer gradient polyimide composite material capable of realizing three-section shape memory, and a preparation method and application thereof, and belongs to the technical field of photoelectrode materials. According to the invention, a three-dimensional cyclic thermosetting cross-linked network is formed through nucleophilic substitution, and thermal imidization is performed, so that the amino-terminated polyimide with low molecular weight has mechanical strength and toughness equivalent to those of high molecular weight, the thermoplastic polyimide with low molecular weight and paraformaldehyde are combined and cyclized to obtain higher mechanical properties, and the composite layer containing GO is stacked through a pure matrix layer, so that the two-layer composite material obtains two loss factor peaks and a wider transition temperature range, and therefore, three-section shape memory deformation can be performed, and the three-section shape memory deformation can be realized on the premise of excellent mechanical properties and high glass transition temperature, thereby being beneficial to the application of the composite material under complex working conditions.
Description
Technical Field
The invention relates to the technical field of photoelectrode materials, in particular to a double-layer gradient polyimide composite material capable of realizing three-section shape memory, and a preparation method and application thereof.
Background
It is known that the synthetic monomer, molecular weight and crosslinking degree have decisive effects on various properties of the polymer material, and that the desired property enhancement in some or even many aspects can be achieved by controlling the above influencing factors. Taking polyimide as an example, diamine and dianhydride monomers are different, and the glass transition temperature and shape memory performance of the synthesized polyimide are also greatly different; the effect of the degree of crosslinking is generally exhibited by the comparison of thermoset and thermoplastic polyimides, thermoset polyimides which tend to have a high degree of chemical crosslinking will have higher mechanical properties and a more excellent shape recovery effect; the molecular weight generally has larger influence on the mechanical property and the reworkability of polyimide, the tensile strength of the material with higher molecular weight is always higher until the critical value is reached, the strength and toughness of the material with lower molecular weight are extremely poor and even the film is difficult to form, the molecular weight of the common polyimide is basically tens of thousands or hundreds of thousands at present, and the defects of difficult dissolution, difficult reworking and the like of the material with high relative molecular weight can cause the problems of resource waste or environmental pollution to a certain extent, which is contrary to the requirements of the development of the environment-friendly science in the current world, so the problem of how to design the shape memory resistant material with high mechanical property under the condition of lower relative molecular weight is urgently needed to be solved.
Chinese patent CN108794752a discloses a thermosetting polyimide and its application in realizing complex 3D structures, the material has good repairing property, weldability and recyclable property, but does not have multi-section shape memory behavior, and cannot be applied to complex working conditions.
Disclosure of Invention
In view of the above, the invention aims to provide a double-layer gradient polyimide composite material capable of realizing three-section shape memory, and a preparation method and application thereof. The double-layer gradient polyimide composite material prepared by the invention has a three-section shape memory function.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a double-layer gradient polyimide composite material capable of realizing three-section shape memory, which comprises the following steps:
mixing 4,4' -diaminodiphenyl ether, bisphenol A dianhydride and an organic aprotic solvent for nucleophilic substitution reaction to obtain polyamic acid solution;
mixing the polyamic acid solution with toluene for thermal imidization to obtain polyimide;
mixing the polyimide, the paraformaldehyde and the organic aprotic solvent for a first hyperbranched reaction to obtain a hyperbranched product;
performing first curing on the hyperbranched product to obtain a PI-HDCN film;
mixing the polyimide, paraformaldehyde, graphene oxide dispersion liquid and an organic aprotic solvent for a second hyperbranched reaction to obtain a GO-containing hyperbranched polyimide composite material;
and coating the hyperbranched polyimide composite material containing GO on the surface of the PI-HDCN film, and sequentially performing second curing and cyclization to obtain the double-layer gradient polyimide composite material capable of realizing three-section shape memory.
Preferably, the mass percentage of GO in the hyperbranched polyimide containing GO is 1-5%.
Preferably, the temperature of the first hyperbranched reaction and the second hyperbranched reaction are independently 50-60 ℃ and the time is independently 0.5-1 h.
Preferably, the temperature of the first curing and the second curing are independently 80-90 ℃ and the time is independently 0.5-5 h.
Preferably, the cyclisation comprises the following process: heating to 100-120 ℃ for 1-2 h, then heating to 140-160 ℃ for 1-2 h, continuously heating to 200-220 ℃ for 1-2 h, then heating to 240-260 ℃ for 1-2 h, and finally heating to 280-300 ℃ for 1-2 h.
Preferably, the cyclisation comprises the following process: heating to 120 ℃ for 1h, then heating to 150 ℃ for 1h, continuously heating to 200 ℃ for 1h, then heating to 250 ℃ for 1h, and finally heating to 280 ℃ for 1h.
Preferably, the temperature of the thermal imidization is 210-240 ℃ and the time is 5-6 h.
Preferably, the molar ratio of 4,4' -diaminodiphenyl ether to bisphenol a dianhydride is 1:0.92 to 1.02:0.91.
the invention also provides a double-layer gradient polyimide composite material which is prepared by the preparation method and can realize three-section shape memory.
The invention also provides application of the double-layer gradient polyimide composite material capable of realizing three-section shape memory in shape memory deformation.
The invention provides a preparation method of a double-layer gradient polyimide composite material capable of realizing three-section shape memory, which comprises the following steps: mixing 4,4' -diaminodiphenyl ether, bisphenol A dianhydride and an organic aprotic solvent for nucleophilic substitution reaction to obtain polyamic acid solution; mixing the polyamic acid solution with toluene for thermal imidization to obtain polyimide; mixing the polyimide, the paraformaldehyde and the organic aprotic solvent for a first hyperbranched reaction to obtain a hyperbranched product; performing first curing on the hyperbranched product to obtain a PI-HDCN thin film (PI-PHT precursor); mixing the polyimide, paraformaldehyde, graphene oxide dispersion liquid and an organic aprotic solvent for a second hyperbranched reaction to obtain a GO-containing hyperbranched polyimide composite material; and coating the hyperbranched polyimide composite material containing GO on the surface of the PI-HDCN film, and sequentially performing second curing and cyclization to obtain the double-layer gradient polyimide composite material (PI-PHT) capable of realizing three-section shape memory.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a three-dimensional cyclic thermosetting cross-linked network is formed through nucleophilic substitution, and thermal imidization is performed, so that the amino-terminated polyimide with low molecular weight has mechanical strength and toughness equivalent to those of high molecular weight, the thermoplastic polyimide with low molecular weight and paraformaldehyde are combined and cyclized to obtain higher mechanical properties, and the composite layer containing GO is stacked through a pure matrix layer, so that the two-layer composite material obtains two loss factor peaks and a wider transition temperature range, and therefore, three-section shape memory deformation can be performed, and the three-section shape memory deformation can be realized on the premise of excellent mechanical properties and high glass transition temperature, thereby being beneficial to the application of the composite material under complex working conditions.
Drawings
FIG. 1 is a schematic diagram of a reaction for preparing polyimide according to the present invention;
FIG. 2 is a schematic illustration of the reaction of a first cure and cyclisation;
FIG. 3 is a graph of thermal mechanical performance test of the dual-layer gradient polyimide composites prepared in examples and comparative examples, where (a) is storage modulus and (b) is dissipation factor;
FIG. 4 shows the two-stage shape memory properties of the dual-layer gradient polyimide composites prepared in examples and comparative examples, wherein (a) is PI-PHT-01, (b) is PI-PHT-03, (c) is PI-PHT-05, (d) is PI-PHT-13, (e) is PI-PHT-15, and (f) is PI-PHT-35;
FIG. 5 is a three-stage shape memory fixing and recovering process of the dual-layer gradient polyimide composite material prepared in example 3;
FIG. 6 is a three-stage shape memory test chart of the dual-layer gradient polyimide composites prepared in examples 1 to 3.
Detailed Description
The invention provides a preparation method of a double-layer gradient polyimide composite material capable of realizing three-section shape memory, which comprises the following steps:
mixing 4,4' -diaminodiphenyl ether, bisphenol A dianhydride and an organic aprotic solvent for nucleophilic substitution reaction to obtain polyamic acid solution;
mixing the polyamic acid solution with toluene for thermal imidization to obtain polyimide;
mixing the polyimide, the paraformaldehyde and the organic aprotic solvent for a first hyperbranched reaction to obtain a hyperbranched product;
performing first curing on the hyperbranched product to obtain a PI-HDCN film;
mixing the polyimide, paraformaldehyde, graphene oxide dispersion liquid and an organic aprotic solvent for a second hyperbranched reaction to obtain a GO-containing hyperbranched polyimide composite material;
and coating the hyperbranched polyimide composite material containing GO on the surface of the PI-HDCN film, and sequentially performing second curing and cyclization to obtain the double-layer gradient polyimide composite material capable of realizing three-section shape memory.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The invention mixes 4,4' -diaminodiphenyl ether, bisphenol A dianhydride and organic aprotic solvent for nucleophilic substitution reaction to obtain polyamide acid solution (PAA).
In the present invention, the molar ratio of 4,4' -diaminodiphenyl ether (ODA) to bisphenol a dianhydride (BPADA) is preferably 1:0.92 to 1.02:0.91.
in the present invention, the organic aprotic solvent is preferably N-methyl-2-pyrrolidone (NMP).
In the present invention, the ratio of the amount of the 4,4' -diaminodiphenyl ether to the organic aprotic solvent is preferably 1.0g: 25-30 mL.
In the present invention, the nucleophilic substitution reaction is preferably carried out under nitrogen or ice water bath conditions, and the time of the nucleophilic substitution reaction is not particularly limited in the present invention, and the nucleophilic substitution reaction may be carried out completely.
The preparation method comprises the steps of pouring the 4,4' -diaminodiphenyl ether into a three-neck flask with an overhead stirrer, adding N-methyl-2-pyrrolidone into the three-neck flask, waiting for complete dissolution of ODA, adding the bisphenol A dianhydride into the three-neck flask in an average three batches under the conditions of nitrogen atmosphere and ice water bath, and mechanically stirring to ensure complete nucleophilic substitution reaction to obtain the polyamic acid solution.
After the polyamic acid solution is obtained, the polyamic acid solution is mixed with toluene for thermal imidization to obtain polyimide.
In the present invention, the temperature of the thermal imidization is preferably 210 to 240℃and the time is preferably 5 to 6 hours.
In the present invention, toluene is preferably added to the polyamic acid solution, and the resulting mixture is heated using an electric heating mantle while the thermal imidization is performed by removing water from PAA by azeotropic, condensation reflux in a combination of a Dean-Stark apparatus and a bulb condenser.
In the invention, after the thermal imidization is completed, the invention preferably waits for the temperature to naturally reduce to room temperature, the mixture after the water is discharged is poured into the stirred industrial alcohol to separate out a precipitate, the precipitate is washed, filtered and then dried in an oven, and finally the obtained powder is the polyimide, and the polyimide is amino-terminated low molecular weight polyimide (marked as PI-NH 2 Or NH 2 -PI-NH 2 )。
In the present invention, a reaction scheme for preparing the polyimide is shown in fig. 1.
After polyimide is obtained, the polyimide, paraformaldehyde and an organic aprotic solvent are mixed for a first hyperbranched reaction to obtain a hyperbranched product.
In the present invention, the molar ratio of polyimide to paraformaldehyde is preferably 1:3.5 to 1:4.
In the present invention, the organic aprotic solvent is preferably N-methyl-2-pyrrolidone (NMP).
In the invention, polyimide is preferably dissolved in NMP to obtain polyimide solution for standby, the paraformaldehyde is dissolved in a single-neck flask containing NMP, distilled water is then added, the solution is placed in an oil bath pot and is continuously magnetically stirred until the solution becomes transparent, the paraformaldehyde solution is obtained, the polyimide solution is added into the single-neck flask when the temperature of the paraformaldehyde solution is reduced to 50-60 ℃, and the magnetic stirring is continued, so that the first hyperbranched reaction is carried out.
In the present invention, the temperature of the first hyperbranched reaction is preferably 50 to 60 ℃ and the time is preferably 0.5 to 1h.
After the hyperbranched product is obtained, the hyperbranched product is subjected to first curing to obtain the PI-HDCN film (PI-HDCN film, namely, a pure polyimide layer, and does not contain GO).
In the present invention, the temperature of the first curing is preferably 80 to 90 ℃ and the time is preferably 0.5 to 5 hours, and the first curing functions to remove the solvent.
In the present invention, the first curing is preferably performed in an oven.
The present invention preferably naturally casts the hyperbranched product on a pre-cleaned horizontal glass plate for the first curing.
After polyimide is obtained, the polyimide, paraformaldehyde, graphene oxide dispersion liquid and an organic aprotic solvent are mixed for a second hyperbranched reaction, and the hyperbranched polyimide composite material containing GO is obtained.
In the present invention, the graphene oxide dispersion liquid has the function of uniformly dispersing Graphene Oxide (GO) in a polyimide matrix.
In the present invention, the mass percentage of GO in the GO-containing hyperbranched polyimide is preferably 1 to 5%, more preferably 3%.
In the present invention, the molar ratio of polyimide to paraformaldehyde is preferably 1:3.5 to 1:4.
In the present invention, the temperature of the second hyperbranched reaction is preferably 50 to 60 ℃ and the time is preferably 0.5 to 1h.
In the present invention, the organic aprotic solvent is preferably consistent with the above scheme, and will not be described herein.
Preferably, the polyimide is dissolved in NMP to obtain polyimide solution for standby, the paraformaldehyde is dissolved in a single-neck flask containing NMP, distilled water is added, the solution is placed in an oil bath pot and is continuously magnetically stirred until the solution becomes transparent, the paraformaldehyde solution is obtained, when the temperature of the paraformaldehyde solution is reduced to 50-60 ℃, the graphene oxide dispersion liquid and the polyimide solution are added into the single-neck flask, and the magnetic stirring is continued, so that the second hyperbranched reaction is carried out.
The method comprises the steps of coating the hyperbranched polyimide composite material containing GO on the surface of the PI-HDCN film, sequentially carrying out second curing and cyclization to obtain the double-layer gradient polyimide composite material capable of realizing three-section shape memory (namely PI-PHT or PI-PHT-XY, wherein XY represents the mass percentage of different GO in two layers, X is 0, namely the first layer does not contain GO, and PHT represents a high-crosslinking network structure obtained after amino and aldehyde groups react).
In the present invention, the temperature of the second curing is preferably 80 to 90℃and the time is preferably 0.5 to 5 hours, and the second curing functions to remove the solvent.
In the present invention, the cyclization preferably includes the following processes: heating to 100-120 ℃ for 1-2 h, then heating to 140-160 ℃ for 1-2 h, continuously heating to 200-220 ℃ for 1-2 h, then heating to 240-260 ℃ for 1-2 h, and finally heating to 280-300 ℃ for 1-2 h, more preferably comprising the following steps: heating to 120 ℃ for 1h, then heating to 150 ℃ for 1h, continuously heating to 200 ℃ for 1h, then heating to 250 ℃ for 1h, and finally heating to 280 ℃ for 1h.
The present invention preferably naturally casts the GO-containing hyperbranched polyimide on the surface of the PI-HDCN film for the second curing and cyclization.
In the present invention, the second curing is preferably performed in an oven.
In the present invention, the cyclization is preferably carried out in a forced air drying oven.
In the present invention, the reaction scheme of the second curing and cyclizing is shown in FIG. 2.
The invention also provides a double-layer gradient polyimide composite material which is prepared by the preparation method and can realize three-section shape memory.
The invention also provides application of the double-layer gradient polyimide composite material capable of realizing three-section shape memory in shape memory deformation.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of PI-PHT-01
ODA (10 mmol,2.0 g) was first poured into a 100mL three-necked flask equipped with an overhead stirrer, which contained NMP solution (the total NMP required was 60g calculated as 10% solids). After waiting for the ODA to dissolve completely, BPADA (9.2 mmol,4.3 g) was weighed and added in three portions over 1h under nitrogen and ice water bath conditions, and mechanical stirring was performed for 12h to ensure that the reaction was complete to give a polyamic acid solution (PAA). Subsequently, 6g of toluene (one tenth of the NMP mass) was added to the PAA and the mixture was heated to 230℃using an electric heating mantle while the thermal imidization was carried out by removing the water from the PAA by high Wen Gongfei, condensed reflux in a combined Dean-Stark apparatus and bulb condenser, which process required a duration of 5 hours. And (3) cooling to room temperature, pouring the mixture after the water is discharged into rapidly stirred industrial alcohol to precipitate. The precipitate is washed and filtered for many times, and then dried in an oven for 2 hours, and finally the obtained powder is the amino-terminated low molecular weight polyimide, and the powder is dissolved in NMP to obtain polyimide solution for standby. Subsequently 0.875mmol of paraformaldehyde was dissolved in a single-necked flask containing 5mL of NMP, then 0.1mL of distilled water was added, and the mixture was placed in an oil bath at 80 ℃ with continuous magnetic stirring for 0.5h until the solution became clear. And adding polyimide solution into the single-neck flask when the temperature is reduced to 50 ℃, continuing to magnetically stir for 0.5h, naturally casting the mixed solution on a horizontal glass plate which is cleaned in advance, and removing solvent in an oven at 80 ℃ to cure for 1h to obtain a pure polyimide layer. Then repeating the steps, adding polyimide solution and mixed solution containing GO dispersion liquid into a single-neck flask when the temperature is reduced to 50 ℃, directly paving the completely reacted mixed solution on the cured film, continuously removing the solvent for 5 hours, waiting for complete curing to obtain a polyimide-GO composite layer (excluding a pure polyimide layer), wherein the addition amount of GO enables the mass fraction of GO in the polyimide-GO composite layer to be 1%, then transferring into a blast drying box for cyclization, and adopting a sectional programming heating strategy to prevent bubbles: the double-layer PI-PHT-01 composite material is finally obtained by heat preservation at 120 ℃ for 1h, heat preservation at 150 ℃ for 1h, heat preservation at 200 ℃ for 1h, heat preservation at 250 ℃ for 1h and heat preservation at 280 ℃ for 1h, and has two glass transition temperatures: 162.3 ℃ and 190.3 ℃; the shape memory fixation rate is 99.57%, and the shape recovery rate is 45.4%; three-section shape memory can be realized.
Example 2
Preparation of PI-PHT-03
The same as in example 1, except that the addition amount of GO in the preparation of the polyimide-GO composite layer was such that the mass fraction of GO in the polyimide-GO composite layer was 3%.
The double-layer PI-PHT-03 composite material is obtained, and has two glass transition temperatures: 164.7 ℃ and 192.6 ℃; the shape memory fixation rate is 99.42% and the shape recovery rate is 61.1%; three-section shape memory can be realized.
Example 3
Preparation of PI-PHT-05
The same as in example 1, except that the addition amount of GO in the preparation of the polyimide-GO composite layer was such that the mass fraction of GO in the polyimide-GO composite layer was 5%.
The double-layer PI-PHT-05 composite material is obtained, and has two glass transition temperatures: 163.8 ℃ and 193.3 ℃; shape memory fixation rate is 99.22% and shape recovery rate is 72.8%; three-section shape memory can be realized.
Comparative example 1
Preparation of PI-PHT-13
ODA (10 mmol,2.0 g) was first poured into a 100mL three-necked flask equipped with an overhead stirrer, which contained NMP solution (the total NMP required was 60g calculated as 10% solids). After waiting for the ODA to dissolve completely, BPADA (9.2 mmol,4.3 g) was weighed and added in two portions over 1h under nitrogen and ice water bath conditions, and mechanical stirring was carried out for 12h to ensure that the reaction was complete to give a polyamic acid solution (PAA). Subsequently, 6g of toluene (one tenth of the NMP mass) was added to the PAA and the mixture was heated to 230℃using an electric heating mantle while the thermal imidization was carried out by removing the water from the PAA by high Wen Gongfei, condensed reflux in a combined Dean-Stark apparatus and bulb condenser, which process required a duration of 5 hours. And (3) cooling to room temperature, pouring the mixture after the water is discharged into rapidly stirred industrial alcohol to precipitate. The precipitate is washed and filtered for many times, and then dried in an oven for 2 hours, and finally the obtained powder is the amino-terminated low molecular weight polyimide, and the powder is dissolved in NMP to obtain polyimide solution for standby. Subsequently 0.875mmol of paraformaldehyde was dissolved in a single-necked flask containing 5mL of NMP, then 0.1mL of distilled water was added, and the mixture was placed in an oil bath at 80 ℃ with continuous magnetic stirring for 0.5h until the solution became clear. Adding polyimide solution and first GO dispersion liquid into a single-neck flask when the temperature is reduced to 50 ℃, continuing to magnetically stir for 0.5h, naturally casting the mixed solution on a pre-cleaned horizontal glass plate, and removing solvent in an oven at 80 ℃ for curing to obtain a first polyimide-GO composite layer, wherein the mass fraction of GO in the first polyimide-GO composite layer is 1% due to the addition of GO in the first GO dispersion liquid. Then repeating the steps, adding a mixed solution of a polyimide solution and a second GO dispersion liquid into a single-neck flask when the temperature is reduced to 50 ℃, directly paving the completely reacted mixed solution on the cured film, continuously removing the solvent for 5 hours, waiting for complete curing to obtain a second polyimide-GO composite layer (excluding the first polyimide-GO composite layer), wherein the addition amount of GO in the second GO dispersion liquid enables the mass percent of GO in the second polyimide-GO composite layer to be 3%, then moving into a blast drying box for cyclization, and adopting a sectional programming heating strategy to prevent air bubbles: the double-layer PI-PHT-13 composite material is obtained by heat preservation at 120 ℃ for 1h, 150 ℃ for 1h, 200 ℃ for 1h, 250 ℃ for 1h and 280 ℃ for 1h, and has a glass transition temperature: 202.5 ℃; the shape memory fixation rate is 99.09%, and the shape recovery rate is 91.3%; three-section shape memory cannot be achieved.
Comparative example 2
Preparation of PI-PHT-15
The same as comparative example 1, except that the addition amount of GO in the second GO dispersion was such that the mass fraction of GO in the second polyimide-GO composite layer was 5%.
Obtaining the double-layer PI-PHT-15 composite material with a glass transition temperature: 202.5 ℃; the shape memory fixation rate is 98.78%, and the shape recovery rate is 93.2%; three-section shape memory cannot be achieved.
Comparative example 3
Preparation of PI-PHT-35
The same as comparative example 1, except that the addition amount of GO in the first GO dispersion was such that the mass fraction of GO in the first polyimide-GO composite layer was 3%, and the addition amount of GO in the second GO dispersion was such that the mass fraction of GO in the second polyimide-GO composite layer was 5%.
The obtained double-layer PI-PHT-35 composite material has a glass transition temperature: 201.8 ℃; the shape memory fixation rate is 98.38%, and the shape recovery rate is 93.9%; three-section shape memory cannot be achieved.
FIG. 3 is a graph showing the thermal mechanical properties of the two-layer gradient polyimide composites prepared in examples and comparative examples, where (a) is the storage modulus and (b) is the loss factor in FIG. 3, and it can be seen that one layer of pure polyimide film and one layer of the two-layer composite containing the GO composite film exhibit the conditions for achieving three-stage shape memory: a broader glass transition temperature range and two loss factor peaks; and the storage modulus and the loss factor of the double-layer composite material with the GO composite film are not the phenomenon.
FIG. 4 shows two-stage shape memory properties of the dual-layer gradient polyimide composite materials prepared in examples and comparative examples, wherein (a) is PI-PHT-01, (b) is PI-PHT-03, (c) is PI-PHT-05, (d) is PI-PHT-13, (e) is PI-PHT-15, and (f) is PI-PHT-35, and the composite material prepared in the invention has two-stage shape memory properties.
FIG. 5 is a three-stage shape memory fixing and recovering process of the dual-layer gradient polyimide composite material prepared in example 3, wherein S 0 Is the initial material; s is S 1 Is the first fixed programming of the material at 210 ℃, S 2 Is a second fixed programming at 180 ℃; s is S 1R The first stage of recovery automatically occurs after reheating to 180 ℃, and S 1 Comparing; s is S 0R Is a second recovery after heating to 210 ℃, and S 0 By comparison, the double-layer gradient polyimide composite material prepared by the invention has a three-section shape memory function.
FIG. 6 is a graph showing the three-stage shape memory performance test of the bilayer gradient polyimide composites prepared in examples 1-3, wherein (a) is PI-PHT-01, (b) is PI-PHT-03, and (c) is PI-PHT-05. It is understood that the bilayer composite consisting of a layer of pure polyimide and a layer of composite film containing GO can achieve the three-stage shape memory performance, consistent with the conclusion obtained in FIG. 5. Among them, PI-PHT-05 prepared in example 3 had the best performance.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the double-layer gradient polyimide composite material capable of realizing three-section shape memory is characterized by comprising the following steps of:
mixing 4,4' -diaminodiphenyl ether, bisphenol A type dianhydride and an organic aprotic solvent for nucleophilic substitution reaction to obtain polyamic acid solution;
mixing the polyamic acid solution with toluene for thermal imidization to obtain polyimide;
mixing the polyimide, the paraformaldehyde and the organic aprotic solvent for a first hyperbranched reaction to obtain a hyperbranched product;
performing first curing on the hyperbranched product to obtain a PI-HDCN film;
mixing the polyimide, paraformaldehyde, graphene oxide dispersion liquid and an organic aprotic solvent for a second hyperbranched reaction to obtain a GO-containing hyperbranched polyimide composite material;
and coating the hyperbranched polyimide composite material containing GO on the surface of the PI-HDCN film, and sequentially performing second curing and cyclization to obtain the double-layer gradient polyimide composite material capable of realizing three-section shape memory.
2. The preparation method of claim 1, wherein the mass percentage of GO in the hyperbranched polyimide containing GO is 1-5%.
3. The method of claim 1, wherein the first and second hyperbranched reactions are independently at a temperature of 50 to 60 ℃ for a time of 0.5 to 1h.
4. The method of claim 1, wherein the first and second curing are independently at a temperature of 80 to 90 ℃ for a time of 0.5 to 5 hours.
5. The method of claim 1, wherein the cyclizing comprises the following steps: heating to 100-120 ℃ for 1-2 h, then heating to 140-160 ℃ for 1-2 h, continuously heating to 200-220 ℃ for 1-2 h, then heating to 240-260 ℃ for 1-2 h, and finally heating to 280-300 ℃ for 1-2 h.
6. The method of preparation according to claim 1 or 5, wherein the cyclisation comprises the following process: heating to 120 ℃ for 1h, then heating to 150 ℃ for 1h, continuously heating to 200 ℃ for 1h, then heating to 250 ℃ for 1h, and finally heating to 280 ℃ for 1h.
7. The process according to claim 1, wherein the thermal imidization is carried out at a temperature of 210 to 240 ℃ for a time of 5 to 6 hours.
8. The method of claim 1, wherein the molar ratio of 4,4' -diaminodiphenyl ether to bisphenol a dianhydride is 1:0.92 to 1.02:0.91.
9. the dual-layer gradient polyimide composite material capable of realizing three-section shape memory, which is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the three-section shape memory enabled two-layer gradient polyimide composite material of claim 9 in shape memory deformation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311212602.9A CN117024817A (en) | 2023-09-20 | 2023-09-20 | Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311212602.9A CN117024817A (en) | 2023-09-20 | 2023-09-20 | Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117024817A true CN117024817A (en) | 2023-11-10 |
Family
ID=88643364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311212602.9A Pending CN117024817A (en) | 2023-09-20 | 2023-09-20 | Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117024817A (en) |
-
2023
- 2023-09-20 CN CN202311212602.9A patent/CN117024817A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5560250B2 (en) | Two-stage curing polyimide oligomer | |
| CN101343362B (en) | Polyimide resin, its midbody, preparation method and application thereof | |
| CN105295792A (en) | High-performance polyimide crosslinked and modified epoxy resin and preparation method thereof | |
| US10815390B2 (en) | Polyimide resin composition and varnish produced from terminal-modified imide oligomer prepared using 2-phenyl-4,4′-diaminodiphenyl ether and thermoplastic aromatic polyimide prepared using oxydiphthalic acid, polyimide resin composition molded article and prepreg having excellent heat resistance and mechanical characteristic, and fiber-reinforced composite material thereof | |
| CN108641665B (en) | Polyimide adhesive and preparation method thereof | |
| CN111019129A (en) | Low-thermal expansion coefficient soluble polyimide resin powder and preparation method thereof | |
| CN115305046B (en) | Polyimide core strip adhesive with high Wen Gaoke solubility resistance and preparation method thereof | |
| JPWO2008096441A1 (en) | Thermosetting resin composition containing compound having carbon-carbon triple bond, low temperature curing method and product thereof | |
| JP2003526704A (en) | High-performance resin composition for press-fitting and transfer molding and method for producing the same | |
| JP5435207B2 (en) | Terminal-modified imide oligomer | |
| CN101602856A (en) | Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes | |
| CN106279688B (en) | Thermoset polyimide resin and its preparation method and application | |
| CN117024817A (en) | Double-layer gradient polyimide composite material capable of realizing three-section shape memory and preparation method and application thereof | |
| JPH04213325A (en) | Polyimide resin prepared by addition reaction | |
| JP3448167B2 (en) | Polyimide resin coating film, method for forming coating film, and method for producing polyimide resin paint | |
| CN110498923A (en) | A kind of easily molded polyimide resin of superhigh temperature resistant and the preparation method and application thereof | |
| CN115449099A (en) | Preparation method, product and application of hollow glass bead composite polyimide film coated with polyimide precursor | |
| JP5210269B2 (en) | Imide oligomer blend composition | |
| JPH03185066A (en) | Thermosetting resin composition | |
| JP7496547B2 (en) | Imide oligomer, varnish, cured product thereof, and prepreg and fiber-reinforced composite material using the same | |
| JP2003292619A (en) | Polyimide resin-based composition, process for producing prepreg using the same and method for curing resin | |
| JPH03179026A (en) | Thermosetting resin composition, resin sheet, prepreg, and laminate | |
| CN116041702A (en) | Shape memory polyimide molding powder, preparation method and application thereof, and shape memory polyimide three-dimensional block material | |
| JP2024012127A (en) | Repairable and recyclable polyimide polymer resin, and repair method and recycling method of the same | |
| CN118344588A (en) | High-temperature-resistant low-viscosity high-solubility polyisoimide resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |