CN116987362B - Benzoxazine resin-based graphene film material and preparation method and application thereof - Google Patents
Benzoxazine resin-based graphene film material and preparation method and application thereof Download PDFInfo
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- CN116987362B CN116987362B CN202311254546.5A CN202311254546A CN116987362B CN 116987362 B CN116987362 B CN 116987362B CN 202311254546 A CN202311254546 A CN 202311254546A CN 116987362 B CN116987362 B CN 116987362B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000017525 heat dissipation Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 26
- ZQSIJRDFPHDXIC-UHFFFAOYSA-N daidzein Chemical compound C1=CC(O)=CC=C1C1=COC2=CC(O)=CC=C2C1=O ZQSIJRDFPHDXIC-UHFFFAOYSA-N 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 235000007240 daidzein Nutrition 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- 238000001338 self-assembly Methods 0.000 claims description 8
- FKKJJPMGAWGYPN-UHFFFAOYSA-N thiophen-2-ylmethanamine Chemical compound NCC1=CC=CS1 FKKJJPMGAWGYPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 150000001993 dienes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- -1 thienyl benzoxazine Chemical compound 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000007142 ring opening reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000005130 benzoxazines Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000021615 conjugation Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CGACGSHTSCXSSO-UHFFFAOYSA-N 2h-1,3-benzoxazine Chemical compound C1=CC=C2C=NCOC2=C1 CGACGSHTSCXSSO-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical group C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
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- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a benzoxazine resin-based graphene film material, a preparation method and application thereof, wherein the film material is formed by benzoxazine containing thienyl and graphene; the thienyl group-containing benzoxazine structure is shown below. According to the thienyl benzoxazine/graphene-containing film system, graphene and benzoxazine are self-assembled through the conjugate physical effect, and then DA (DA) reaction between conjugated diene on a thiophene ring and substituted olefin on graphene is further combined, so that the orientation degree of a film material is improved, excellent thermal conductivity and electrical conductivity are provided for the material, and meanwhile the defects of poor toughness and the like of a traditional benzoxazine polymer are overcome. The preparation method disclosed by the invention is simple in preparation process, low in equipment requirement and suitable for large-scale production, and the prepared graphene film material can be used for heat dissipation of electronic elements or batteries of new energy automobiles.
Description
Technical Field
The invention belongs to composite material films, and particularly relates to a benzoxazine resin-based graphene film material, and a preparation method and application thereof.
Background
The high-performance polymer has excellent thermal stability and good mechanical properties, and has extremely wide application prospects in the fields of new energy automobiles, aerospace, electronic packaging, paint adhesives and the like. Among a plurality of high polymer materials, benzoxazine is used as a novel thermosetting resin, and has the characteristics of near zero shrinkage during curing, flexible molecular design, low dielectric constant, excellent thermal oxygen stability, excellent mechanical property and the like, so that the benzoxazine gradually becomes an excellent substitute for the traditional phenolic resin. Polybenzoxazines are generally prepared by ring-opening polymerization of heterocyclic six-membered 1, 3-benzoxazine monomers. Most commonly synthesized from Mannich condensation reactions of phenol, primary amines and formaldehyde. Due to its particular molecular design flexibility, a wide variety of starting materials are available for the synthesis of benzoxazines.
The yield of soybeans in crops is great, and soybean germs contain 41.7% of daidzein. The daidzein has biological activities such as antioxidation, antibiosis, antioxidation and the like, and is widely applied to foods and medicines. In addition, daidzein has 2 phenolic hydroxyl groups and has high designability as a phenolic source. In addition to phenolic hydroxyl groups, special phthalimidine structures may improve polymerization reactivity.
Graphene is a perfect two-dimensional (2D) carbon material, consisting of sp 2 The hybridized carbon atoms are mutually connected to form a monoatomic layer, the carbon atoms are distributed in a two-dimensional hexagonal lattice shape in the graphene sheet layer, and the whole graphene sheet layer is in a soft sheet layer structure. Has huge length-width ratio and specific surface area, and is widely used for preparing the difunctional material with good heat conduction, electric conduction and electromagnetic interference shielding performance. In the prior art, the pure reduced graphene film is generally fragile, the strain becomes low during fracture, the mechanical property of the composite material can only be slightly improved by adopting the traditional blending method of the composite material, and the graphene content in the composite material is low, so that the performances of heat conduction, electric conductivity and the like of the composite material are generally greatly reduced.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a benzoxazine resin-based graphene film material, which is prepared by synthesizing a novel benzoxazine resin containing a thienyl group by adopting a biological-based raw material, and overcomes the defects of poor toughness and the like of the traditional benzoxazine polymer material according to structural arrangement of a composite material and interaction between the benzoxazine and graphene, and has high heat conduction and flame retardance.
The invention also provides a preparation method and application of the benzoxazine resin-based graphene film material.
The technical scheme is as follows: in order to achieve the above purpose, the benzoxazine resin-based graphene film material is formed by thienyl group-containing benzoxazine and graphene, wherein the mass ratio of the graphene to the thienyl group-containing benzoxazine is 1:5-2:1, and the thienyl group-containing benzoxazine has the structure shown as follows:
。
wherein the graphene is single-layer graphene.
The preparation method of the benzoxazine resin-based graphene film material comprises the following steps:
(1) Adding an organic solvent into daidzein, 2-thiophenemethylamine and paraformaldehyde, filtering reactants after heating reaction, washing filtrate, and spin-evaporating and drying to obtain a solid product, namely the thienyl-containing benzoxazine;
(2) Mixing and stirring the prepared thienyl-containing benzoxazine and graphene dispersion liquid, wherein the mass ratio of the graphene to the thienyl-containing benzoxazine is 1:5-2:1, then carrying out vacuum filtration and self-assembly on the mixed liquid, and finally carrying out heating and solidification to obtain the target product benzoxazine resin-based graphene film material.
Wherein, the mol ratio of daidzein, paraformaldehyde and 2-thiophenemethanamine in the step (1) is 4:15-17:8.
preferably, the mol ratio of daidzein, paraformaldehyde and 2-thiophenemethanamine is 4:17:8.
wherein the organic solvent in the step (1) is selected from any one of toluene, xylene or dioxane.
Wherein the heating reaction temperature in the step (1) is 80-130 ℃ for 6-10 hours.
Preferably, the synthesis process of the benzoxazine monomer in the step (1) is as follows:
wherein, in the step (2), the thienyl-containing benzoxazine and the graphene dispersion liquid are stirred and reacted for 10-20h at room temperature.
Wherein, the graphene dispersion liquid in the step (2) is diluted by N-methyl pyrrolidone, and the diluted graphene dispersion liquid is subjected to ultrasonic treatment for 20-60 min; before vacuum filtration, the graphene and benzoxazine mixed solution is subjected to ultrasonic treatment for 5-10 min.
And (2) mixing the prepared thienyl-containing benzoxazine with graphene according to different mass proportions, uniformly dispersing, preparing a film by vacuum-assisted self-assembly, and finally heating, solidifying and polymerizing to obtain a target product.
And (3) performing vacuum filtration self-assembly in the step (2) to obtain a film by suction filtration in a Buchner core funnel, and drying the film obtained by the suction filtration in a vacuum drying oven.
Preferably, the graphene dispersion liquid in the step (2) is a single-layer graphene dispersion liquid, and the single-layer graphene dispersion liquid is diluted before being mixed with the benzoxazine, wherein the dilution ratio is 0.1-1 mg/mL.
The specific heating process of heating and curing in the step (2) is as follows: sequentially heating to 140-150deg.C for 1-2h, 160-170deg.C for 1-2h, 180-190 deg.C for 1-2h, 200-210 deg.C for 1-2h, 220-230 deg.C for 1-2h, and 240-250 deg.C for 1-2h.
Preferably, the specific heating process of the heating curing is as follows: sequentially heating to 140 ℃ for 1h, 160 ℃ for 1h, 180 ℃ for 1h, 200 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h.
The benzoxazine resin-based graphene film material is applied to electronic components and battery heat dissipation materials.
Preferably, the heat sink can be used for heat dissipation of electronic components or batteries of new energy automobiles.
The preparation process of the benzoxazine/graphene composite film provided by the invention has the advantages of simplicity and controllability, low production cost, strong interlayer binding force and the like. The graphene and the benzoxazine are assembled through the conjugated physical effect, and then are further combined through DA reaction between conjugated diene on the thiophene ring and substituted olefin on the graphene, so that the interlayer bonding force of the graphene is strong. Due to the addition of the graphene, the thermal performance of the benzoxazine resin and the performances such as toughness, electric conduction and thermal conduction of the benzoxazine resin are greatly improved.
The invention adopts the bio-based benzoxazine/graphene composite material for the first time, wherein the bio-based raw material is adopted to synthesize the novel benzoxazine resin containing the thienyl group, and the defects of poor toughness and the like of the traditional benzoxazine polymer material are overcome according to the structural arrangement of the composite material and the interaction between the benzoxazine and the graphene. The composite material prepared by the invention adopts a novel resin structure (benzoxazine monomer), the conjugation effect brought by pi-pi conjugation structure is combined with the interaction between conjugated diene on a thiophene ring and substituted olefin on graphene, and the composite material formed by self-assembly of the thiophene group-containing resin and graphene has a continuous phase structure, is assembled through various functions and has excellent heat conduction.
The novel resin structure (benzoxazine monomer) prepared by the invention has the DA reaction between conjugated diene on thiophene ring and substituted olefin on graphene, and the reaction mechanism is as follows:
the ultrathin film with the graphene/benzoxazine layer structure is prepared by a very simple process, has toughness similar to paper and has high heat conduction and flame retardance. The benzoxazine with a brand new structure is prepared, and the interface performance is improved through the P-P conjugation of the benzoxazine and graphene; the dangling vinyl groups at the defect positions on the thiophene and the graphene can undergo DA reaction, and the interfacial strength is further increased through covalent interaction. Meanwhile, the benzoxazine with the specific structure can repair defects on the surface of graphene and further enhance the performance. The invention improves the orientation degree through the layer-by-layer assembled structure, and is beneficial to improving the heat conduction and flame retardance.
The pure benzoxazine monomer synthesized in the invention is very brittle after being solidified, cannot be bent and has very low intrinsic heat conductivity; and the pure graphene film is also very easy to crack. The film of the invention has a layer-by-layer stacked structure observed under SEM, has toughness similar to paper, and has obviously improved heat conductivity. In addition, the raw material proportion of the benzoxazine and the graphene in the synthesis, the temperature at which the filtration is finished and the drying is finished, and the mixing and stirring time of the graphene and the benzoxazine monomer can influence the effect of the product, and the effect of adjusting each reaction condition is inferior to that of the method. In particular, the ratio of the benzoxazine monomer to the graphene in the invention can have a significant effect on the heat conduction performance due to too much or too little benzoxazine monomer.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. according to the invention, the bio-based benzoxazine and the graphene are assembled to prepare the film, and the graphene is connected with benzoxazine molecules between layers while being stacked and assembled layer by layer, so that the graphene can play a stable role in the benzoxazine, has good orientation degree and has excellent heat conduction performance. The cured film material has toughness similar to paper, and the defect of poor toughness of the benzoxazine polymer is overcome. Meanwhile, the whole preparation process is prepared by vacuum filtration, the process is simple, the requirement on equipment is low, and the method is suitable for large-scale production.
2. According to the thienyl benzoxazine/graphene-containing film system, graphene and benzoxazine are self-assembled through the conjugate physical effect, and then DA (DA) reaction between conjugated diene on a thiophene ring and substituted olefin on graphene is further combined, so that the orientation degree of a film material is improved, excellent thermal conductivity and electrical conductivity are provided for the material, and meanwhile the defects of poor toughness and the like of a traditional benzoxazine polymer are overcome. The film prepared by the invention has high heat conductivity, flame retardant capability and better electric conduction performance, and simultaneously has ultrathin thickness (about 55 mu m). The heat dissipation device has wide application prospect in the fields of heat dissipation of electric flexible electronic devices, integrated circuits and the like, and is particularly used for heat dissipation of electronic components and batteries of new energy automobiles.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of benzoxazine obtained in example 1;
FIG. 2 is an infrared spectrum of benzoxazine obtained in example 1;
FIG. 3 is a DSC of the benzoxazine obtained in example 1;
FIG. 4 is a TGA graph of benzoxazines obtained in example 1;
FIG. 5 shows the effect and SEM of the film obtained in example 1.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
The graphene is single-layer graphene (the purity of the graphene is more than 99wt%, the thickness is 0.5-3nm, the sheet diameter is 0.5-5 mu m, the single-layer rate is more than 98%), and the graphene is purchased from the carbon-rich graphene science and technology company in Suzhou, in particular to a purchased graphene N-methylpyrrolidone dispersion liquid, and the graphene concentration is 1mg/mL.
Example 1
Preparing a benzoxazine resin-based graphene film material:
1. 1g (0.004 mol) of daidzein, 0.52g (0.017 mol) of paraformaldehyde, 0.89g (0.008 mol) of 2-thiophenemethylamine were charged into the flask at room temperature, 50 mL of xylene was added thereto, and stirred and reacted at 130℃for 6 hours. After stopping the reaction, the reaction product was filtered, the filtrate was washed and then distilled off in a rotary manner, and the benzoxazine monomer was obtained by drying in a vacuum drying oven at 50 ℃ for one day in a yield of about 83%.
2. N-methylpyrrolidone was added to 20mL of the graphene dispersion (1 mg/mL) at room temperature to dilute it to 100mL (0.2 mg/mL), and after 30min of ultrasonic dispersion was uniform, 100mg of the benzoxazine monomer (prepared in step 1) was added and stirred at room temperature for 20h. After stirring, carrying out ultrasonic treatment on the solution for 10min, carrying out vacuum-assisted self-assembly on the solution in a Buchner sand core funnel, carrying out suction filtration for 10h, drying the film obtained after the suction filtration in a vacuum drying oven at 80 ℃ for 20h, and finally carrying out heating, ring-opening, curing and polymerization on the film to obtain the benzoxazine resin-based graphene film material as the target product. The specific heating process of the heating ring-opening curing polymerization is as follows: sequentially heating to 140 ℃ for 1h, 160 ℃ for 1h, 180 ℃ for 1h, 200 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h.
FIG. 1 is a nuclear magnetic resonance spectrum of the benzoxazine monomer prepared in step 1, wherein the characteristic peaks of the oxazine ring are about 5.03ppm and 4.11ppm of chemical shift. 1 H NMR (400 MHz, CDCl 3 ), ppm:δ = 8.12 (d, 1H, H d ), 7.89 (s, 1H, H e ), 7.32 (m, 3H, H g and H h ), 7.23 (d, 1H, H f ), 7,01 (m, 1H, H i ), 6.95 (m, 5H, H l , H k and H j ), 5.03 (s, 2H, H a ), 4.96 (s, 2H, H a’ ), 4.24 (s, 2H, H b ), 4.16 (m, 4H, H c and H c’ ), 4.11 (s, 2H, H b’ )。
FIG. 2 is an infrared spectrum of the benzoxazine monomer prepared in step 1, wherein 918 and 1235 cm -1 Is a characteristic peak of oxazine ring.
FIG. 3 is a DSC graph obtained by differential scanning calorimetry of the benzoxazine monomer prepared in step 1, and it can be seen that the thermal ring-opening polymerization initiation temperature of the monomer is about 190 ℃, and the exothermic peak of polymerization appears at 226 ℃.
Fig. 4 is a TGA profile of the benzoxazine monomer prepared in step 2 after curing (the curing mode is the same as the method in step 2, except that no graphene is added), the 5% thermal weight loss temperature is 326 ℃, and the carbon residue rate at 800 ℃ is 62.8%.
The benzoxazine resin-based graphene film prepared by the embodiment has the electrical conductivity of about 1.64S/cm and the thermal conductivity of about 27W/mK. And the thermal conductivity of the polybenzoxazine resin without graphene is only 0.18W/mK.
Fig. 5 shows that the film prepared in step 2 has a layer-by-layer stacked structure observed under SEM, has toughness similar to paper, and has significantly improved thermal conductivity.
Example 2
Preparing a benzoxazine resin-based graphene film material:
1. 1g (0.004 mol) of daidzein, 0.52g (0.017 mol) of paraformaldehyde, 0.89g (0.008 mol) of 2-thiophenemethylamine were charged into the flask at room temperature, 50 mL toluene was added thereto, and stirred and reacted at 120℃for 8 hours. After stopping the reaction, the reaction product was filtered, the filtrate was washed and then distilled off in a rotary manner, and the benzoxazine monomer was obtained by drying in a vacuum drying oven at 50 ℃ for one day in a yield of about 78%.
2. N-methylpyrrolidone was added to 20mL of the graphene dispersion (1 mg/mL) at room temperature to dilute it into 200mL (0.1 mg/mL), and after ultrasonic dispersion was carried out for 30min, 100mg of the benzoxazine monomer (prepared in step 1) was added and stirred at room temperature for 20h. After stirring, carrying out ultrasonic treatment on the solution for 10min, carrying out vacuum-assisted self-assembly on the solution in a Buchner sand core funnel for 10h, drying the film obtained after the completion of the suction filtration in a vacuum drying oven at 80 ℃ for 20h, and finally carrying out heating, ring-opening, solidification and polymerization to obtain a target product. The specific heating process of the heating ring-opening curing polymerization is as follows: sequentially heating to 140 ℃ for 1h, 160 ℃ for 1h, 180 ℃ for 1h, 200 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h.
The benzoxazine resin-based graphene film prepared by the embodiment has the electrical conductivity of about 1.61S/cm and the thermal conductivity of about 25W/mK.
Example 3
1. 1g (0.004 mol) of daidzein, 0.52g (0.017 mol) of paraformaldehyde and 0.89g (0.008 mol) of 2-thiophenemethylamine were charged into the flask at room temperature, 50 ml of 1, 4-dioxane was added thereto, and stirred and reacted at 110℃for 13 hours. After stopping the reaction, the reaction product was filtered, the filtrate was washed and then distilled off in a rotary manner, and the benzoxazine monomer was obtained by drying in a vacuum drying oven at 50 ℃ for one day in a yield of about 87%.
2. N-methylpyrrolidone was added to 20mL of the graphene dispersion (1 mg/mL) at room temperature to dilute it to 100mL (0.2 mg/mL), and after ultrasonic dispersion for 20min, 20mg of the benzoxazine monomer (prepared in step 1) was added and stirred at room temperature for 20h. After stirring, carrying out ultrasonic treatment on the solution for 15min, carrying out vacuum-assisted self-assembly on the solution in a Buchner sand core funnel, carrying out suction filtration for 10h, drying the film obtained after the suction filtration in a vacuum drying oven at 80 ℃ for 20h, and finally carrying out heating, ring-opening, solidification and polymerization to obtain a target product. The specific heating process of the heating ring-opening curing polymerization is as follows: sequentially heating to 140 ℃ for 1h, 160 ℃ for 1h, 180 ℃ for 1h, 200 ℃ for 1h, 220 ℃ for 1h, and 240 ℃ for 1h.
The benzoxazine resin-based graphene film prepared by the embodiment has the electrical conductivity of about 1.80S/cm and the thermal conductivity of about 29W/mK.
Example 4
Example 4 the same procedure as in example 3 was followed except that N-methylpyrrolidone was added to 20mL of a graphene dispersion (1 mg/mL) to dilute it to 100mL (0.2 mg/mL), and after stirring it for 30 minutes with ultrasound, 10mg of a benzoxazine monomer was added to conduct a reaction. The benzoxazine resin-based graphene film prepared by the embodiment has the electrical conductivity of about 2.1S/cm and the thermal conductivity of about 27W/mK.
Comparative example 1
Comparative example 1 the same preparation as in example 1 was used, except that no additional step 2 was used: benzoxazine monomers. Comparative example 1 the pure graphene film prepared was split to different degrees due to the not tight bonding, and performance test could not be performed.
Comparative example 2
Comparative example 2 the same preparation as in example 1 was used, except that no additional step 2 was used: and (3) graphene. Comparative example 2 the pure benzoxazine monomer prepared was very brittle, inflexible and very low in intrinsic thermal conductivity, with a thermal conductivity of only 0.18W/mK after curing.
Comparative example 3
Comparative example 3 the same preparation method as in example 1 was used, except that the mass ratio of graphene to benzoxazine monomer was 1:6, the thermal conductivity of the prepared film is 1.3W/mK.
Comparative example 4
Comparative example 4 the same preparation method as in example 1 was used, except that the mass ratio of graphene to benzoxazine monomer was 3:1, the film formation is difficult due to the reduced amount of the monomer.
Claims (10)
1. The benzoxazine resin-based graphene film material is characterized by being formed by benzoxazine containing thienyl and graphene, wherein the mass ratio of the graphene to the benzoxazine containing thienyl is 1:5-2:1, and the benzoxazine containing thienyl has the structure shown as follows:
。
2. the benzoxazine resin-based graphene film material according to claim 1, wherein the graphene is a single-layer graphene.
3. A method for preparing the benzoxazine resin-based graphene film material according to claim 1, which is characterized by comprising the following steps:
(1) Adding an organic solvent into daidzein, 2-thiophenemethylamine and paraformaldehyde, filtering reactants after heating reaction, washing filtrate, and spin-evaporating and drying to obtain a solid product, namely the thienyl-containing benzoxazine;
(2) Mixing and stirring the prepared thienyl-containing benzoxazine and graphene dispersion liquid, wherein the mass ratio of the graphene to the thienyl-containing benzoxazine is 1:5-2:1, then carrying out vacuum filtration and self-assembly on the mixed liquid, and finally carrying out heating and solidification to obtain the target product benzoxazine resin-based graphene film material.
4. A process according to claim 3, wherein the molar ratio of daidzein, paraformaldehyde, 2-thiophenemethanamine in step (1) is 4:15-17:8, 8; the organic solvent is selected from any one of toluene, xylene or dioxane.
5. A process according to claim 3, wherein the heating reaction temperature in step (1) is 80-130 ℃ for a period of 6-10 hours.
6. The method according to claim 3, wherein the thienyl group containing benzoxazine in the step (2) and the graphene dispersion are stirred and reacted for 10-20 hours at room temperature.
7. The method according to claim 3, wherein the graphene dispersion in the step (2) is diluted with N-methylpyrrolidone, and the diluted graphene dispersion is sonicated for 20 to 60 minutes; before vacuum filtration, the graphene and benzoxazine mixed solution is subjected to ultrasonic treatment for 5-10 min.
8. A method according to claim 3, wherein the vacuum filtration in step (2) is self-assembled by suction filtration in a buchner sand core funnel, and the film obtained after the completion of the suction filtration is dried in a vacuum drying oven.
9. A production method according to claim 3, wherein the specific temperature-raising process of the temperature-raising solidification in step (2) is as follows: sequentially heating to 140-150deg.C for 1-2h, 160-170deg.C for 1-2h, 180-190 deg.C for 1-2h, 200-210 deg.C for 1-2h, 220-230 deg.C for 1-2h, and 240-250 deg.C for 1-2h.
10. Use of the benzoxazine resin-based graphene film material according to claim 1 in electronic components and battery heat dissipation materials.
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| CN108997548A (en) * | 2018-09-06 | 2018-12-14 | 西南石油大学 | A kind of photolytic activity benzoxazine resin and preparation method thereof |
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