CN108102290B - Graphene grafted modified phenolic resin material and preparation method thereof - Google Patents
Graphene grafted modified phenolic resin material and preparation method thereof Download PDFInfo
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 159
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000005011 phenolic resin Substances 0.000 claims abstract description 122
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 118
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000007265 chloromethylation reaction Methods 0.000 claims description 34
- 150000001540 azides Chemical class 0.000 claims description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- -1 chloromethyl alkyl ether Chemical class 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical group [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- RRSXICBKOPODSP-UHFFFAOYSA-N 1,4-bis(chloromethoxy)butane Chemical group ClCOCCCCOCCl RRSXICBKOPODSP-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000007517 lewis acids Chemical group 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- UXGJIYZFPDSEBM-UHFFFAOYSA-N phenol;azide Chemical compound [N-]=[N+]=[N-].OC1=CC=CC=C1 UXGJIYZFPDSEBM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- TZLVRPLSVNESQC-UHFFFAOYSA-N potassium azide Chemical compound [K+].[N-]=[N+]=[N-] TZLVRPLSVNESQC-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002464 physical blending Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene grafted modified phenolic resin material and a preparation method thereof. According to the invention, the phenolic resin is grafted to the graphene by a chemical grafting method, so that the problems of easy agglomeration of the graphene and the interface between the graphene and the phenolic resin are solved, and the obtained material has excellent mechanical properties and thermal stability.
Description
Technical Field
The invention belongs to the field of phenolic resin materials, and particularly relates to a graphene grafted modified phenolic resin material and a preparation method thereof.
Background
Among the three commonly used thermosetting resins, phenolic resin has the advantages of easy obtainment of raw materials for preparation, simple production process and equipment, relatively low price, good thermal stability, high heat resistance, strong mechanical property and the like of the product size, and becomes an indispensable functional material which is widely applied in industry. However, with the continuous development of the current industrial application, the traditional phenolic resin can not meet the use requirements of some fields such as aviation field, and the modification of the phenolic resin is urgently needed. Therefore, it is a hot point of research to use phenolic resin as a matrix material and other reinforcing materials to prepare phenolic resin matrix composite materials by a certain method so as to improve certain properties of the phenolic resin matrix composite materials.
At present, most reports are found about graphene/phenolic resin composite materials prepared mainly by a physical blending method, for example, chinese patent CN 10469367B discloses a preparation method of a graphene-containing phenolic resin-based composite material, which comprises adding phenolic resin into a graphene oxide solution, heating and stirring to be semisolid under ultrasonic dispersion, and drying to obtain a modified phenolic resin. The graphene oxide/phenolic resin composite material prepared by using a physical blending method not only needs to solve the problems of compatibility and interface between phenolic resin and graphene oxide, but also has limited performance improvement due to more defects on the surface of the graphene oxide.
In order to overcome the problems of compatibility and interface, some add surfactants, such as graphene solution containing surfactants, to the phenolic resin material in the synthesis process of graphene modified phenolic resin disclosed in chinese patents CN 104292745A and CN 104231539 a, to avoid the aggregation of graphene, but the amount of the added surfactant is high, which may limit the improvement of the material performance to a certain extent. In addition, graphene oxide and a surfactant are added in the phenolic resin synthesis to solve the problem of uneven mixing of graphene oxide in the phenolic resin, for example, in chinese patent CN 104403066A, graphene oxide and a larger amount of surfactant are added in the phenolic resin synthesis.
We have also found that there are very few reports of preparing composites by physically blending unmodified graphene as a reinforcing material with a phenolic resin matrix material, and the analytical reasons may be that unmodified graphene is less dispersible and compatible in the matrix material than graphene oxide.
Thus, there is a need for a way to link or mix the phenolic resin and the (unmodified) graphene such that the performance of the phenolic resin is improved while avoiding the problem of poor compatibility between the (unmodified) graphene and the phenolic resin.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the graphene/phenolic resin material obtained by grafting the phenolic resin to the graphene by adopting a chemical grafting method not only can effectively avoid the problems, but also greatly improves the thermal conductivity and the mechanical property of the material, thereby completing the invention.
The object of the present invention is to provide the following:
(1) a preparation method of a graphene grafted modified phenolic resin material comprises the following steps:
step 1, preparing chloromethylation phenolic resin;
step 2, preparing azide phenolic resin;
and 3, mixing the azide phenolic resin with the graphene, reacting, and separating to obtain the modified phenolic resin material after the reaction is finished.
In a preferred embodiment, in step 1, a phenolic resin and a chloromethylating reagent are reacted in solvent I to give a chloromethylated phenolic resin, wherein,
the chloromethylating reagent is selected from chloromethyl alkyl ether, such as ClCH2O(CH2)nCH3Or (ClCH)2O)2(CH2)nWherein n is 1-6, preferably 1, 4-dichloromethoxybutane;
a catalyst is also added in the preparation process of the chloromethylated phenolic resin, and the catalyst is selected from Lewis acid; the weight ratio of the catalyst to the phenolic resin to the chloromethylation reagent is 1: (1.5-4): (10-20).
In a preferred embodiment, in the step 2, the chloromethylated phenolic resin and the azide are reacted in the solvent II to obtain the azido phenolic resin, and the molar ratio of the chloromethylated phenolic resin to the azide is 1 (1.5-4).
In a preferred embodiment, in step 3, the graphene is selected from unmodified graphene;
the mass ratio of the azido phenolic resin to the graphene is 1 (0.001-0.1), preferably 1 (0.005-0.05), and more preferably 1 (0.005-0.02).
(2) The graphene grafted modified phenolic resin material comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, of graphene,
according to the graphene grafted modified phenolic resin material and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
1) the novel chloromethylation reagent is adopted in the preparation process of the azido phenolic resin, and is extremely toxic and carcinogenic compared with the traditional chloromethylation reagent (chloromethyl ether or bischloromethyl ether), and the novel green chloromethylation reagent is more environment-friendly, so that the damage to a user is greatly reduced, the pollution to the environment is reduced, and the azido phenolic resin has good environment friendliness;
2) compared with the existing physical mixing, the phenolic resin is grafted to the graphene by a chemical grafting method, so that the graphene is uniformly dispersed in the phenolic resin, and the problems that the graphene is easy to agglomerate and the interface exists between the graphene and the phenolic resin are solved;
3) other auxiliary agents are not added in the synthesis process of the modified phenolic resin material, so that the cost is reduced, and the influence of the auxiliary agents on the performance of products is avoided;
4) at 1000 ℃, the carbon residue content of the phenolic resin is 44.6%, the final carbon residue content of the graphene grafted modified phenolic resin material is 54.2%, and the thermal stability of the phenolic resin added with unmodified graphene is obviously improved;
5) the grafted graphene is not modified, so that the damage of a re-modification process to the molecular structure of the graphene is reduced, the graphene plays a greater role in the phenolic resin, and the mechanical property of the phenolic resin can be better improved.
Drawings
Fig. 1 is a scanning electron micrograph of a graphene material;
FIG. 2 is a scanning electron micrograph of the graphene grafted modified phenolic resin material prepared in example 3;
FIG. 3 is an infrared spectrum of the phenolic resin in comparative example 1 and the graphene graft modified phenolic resin material prepared in example 3;
FIG. 4 is an XRD pattern of the phenolic resin, unmodified graphene and the material synthesized in example 3 in comparative example 1 of the present invention;
FIG. 5 is a thermogravimetric plot of the phenolic resin of comparative example 1 and the material synthesized in example 3 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention aims to provide a preparation method of a graphene grafted modified phenolic resin material, which comprises the following steps:
step 1, preparing chloromethylation phenolic resin;
step 2, preparing azide phenolic resin;
and 3, mixing the azide phenolic resin with the graphene, reacting, and separating to obtain the modified phenolic resin material after the reaction is finished.
In the step 1, phenolic resin and a chloromethylation reagent react in a solvent I to obtain chloromethylated phenolic resin.
The phenol resin in the present invention is a generic term for a resinous polymer obtained by polycondensation of phenol and aldehyde in the presence of an acidic or basic catalyst, and may be, for example, a resin synthesized from phenol and formaldehyde.
In a preferred embodiment, the chloromethylating agent is selected from the group consisting of chloromethylated alkyl ethers, such as ClCH2O(CH2)nCH3Or (ClCH)2O)2(CH2)nWherein n is 1 to 6, preferably 1, 4-dichloromethoxybutane. At present, the most usedThe method is widely characterized in that formaldehyde, trioxymethylene, paraformaldehyde and hydrochloric acid are matched to be used as chloromethylation reagents, so that the toxicity is low, the price is low, the reaction time is long, and the yield is not high; ClCH2OCH3And (ClCH)2)2O can also replace HCHO-HCl to be used as a chloromethylation reagent, has high activity and good reaction selectivity, but is extremely toxic, corrosive and difficult to store and transport; and ClCH2Si(CH3)3、ClSi(CH3)2HCHO and the like can also be used as chloromethylation reagents, and have the advantages of no toxicity, high yield, good reaction selectivity, difficult preparation, high price and limited application range. The long-carbon-chain chloromethyl alkyl ether selected in the invention has the advantages of high boiling point, high activity and safe and effective use, makes up the defects of the chloromethylation reagents, and is a better choice for the chloromethylation reagents.
In a preferred embodiment, the solvent i is selected from any one or more of acetone, methanol, ethanol, isopropanol or n-butanol, preferably acetone.
In a preferred embodiment, a catalyst is further added during the preparation of the chloromethylated phenolic resin, and the catalyst is selected from Lewis acid, preferably selected from any one or more of zinc chloride, stannic chloride, ferric chloride, aluminum chloride or copper chloride.
The reaction mechanism of the phenolic resin and the chloromethylation reagent in the step 1 may be: first, an alkyl carbonium ion (e.g., one produced under catalysis of a Lewis acid)+CH2OCH2CH2CH2CH2OCH2Cl) on a benzene ring, then carrying out nucleophilic substitution reaction on free chloride ions, and breaking ether bonds to obtain the chloromethylated phenolic resin, wherein the total reaction formula is as follows:
the catalyst is used for promoting the chloromethylation reagent to form a carbonium ion so as to perform electrophilic substitution reaction on a benzene ring of a phenolic resin molecule, for example, tin tetrachloride is used as the catalyst, 1, 4-dichloromethoxybutane is used as the chloromethylation reagent, and the catalytic reaction is as follows:
SnCl4+ClCH2OCH2CH2CH2CH2OCH2Cl→+CH2OCH2CH2CH2OCH2Cl+SnCl5 -
in a preferred embodiment, the weight ratio of the catalyst, phenolic resin and chloromethylating agent is 1: (1.5-4): (10-20). The catalyst dosage influences the methylation rate of the phenolic resin, the catalyst dosage is less, the generation rate of the alkyl carbonium ions is low, and further the chloromethylation rate is low, but if the catalyst dosage is too much (exceeds the proportion), the concentration of the alkyl carbonium ions is rapidly increased in a short time, so that the chloromethylation reaction rate is too high, the cross-linking reaction among phenolic resin macromolecules can be promoted, the cross-linking is a dechlorination process, and the chloromethylation degree of the phenolic resin is reduced on the contrary at the moment.
In a further preferred embodiment, the chloromethylating reagent is added dropwise to the reaction system. The reaction rate can be controlled by the dropwise adding mode, and the phenomenon that the whole chloromethylation reaction rate is too high due to the generation of a large amount of alkyl carbonium ions is avoided, so that the cross-linking reaction caused by chloromethylation of a large amount of benzene rings on the macromolecules of the phenolic resin is avoided.
In a preferred embodiment, the ratio of the total weight of the phenolic resin, the catalyst and the chloromethylation reagent to the volume of the solvent I is 1 (2.5-4.0), and in this range, the solvent I can sufficiently dissolve the reaction raw materials, and the concentration of the raw materials is not too small, so that the chloromethylation reaction can be carried out at a high speed.
In a preferred embodiment, the temperature of the chloromethylation reagent is gradually increased in the dropping process, and the chloromethylation reaction of the phenolic resin is carried out for 4-10 h at 45-65 ℃, preferably for 5-8 h at 50-60 ℃.
In a preferred embodiment, after the reaction in step 1 is completed, the temperature is reduced to room temperature, a large amount of water is added into the reaction system, so that the chloromethylated phenolic resin is separated out from the organic solvent, and the chloromethylated phenolic resin is obtained by centrifugation or filtration, washing with water and drying.
In the step 2, reacting the chloromethylated phenolic resin with the azide in a solvent II to obtain the azide phenolic resin.
In a preferred embodiment, the azide compound is selected from sodium azide, potassium azide or acyl azide, preferably sodium azide.
In a preferred embodiment, the solvent II is selected from any one or more of N, N-dimethylformamide, N-dimethylacetamide, toluene, p-xylene and ethylbenzene, and is preferably N, N-dimethylformamide.
In a preferred embodiment, after the azide compound is added into the solvent II, the chloromethylated phenolic resin is added in a dropwise manner, and stirring is carried out during the dropwise addition process and the reaction process, so that the azide reaction is accelerated.
In a preferred embodiment, the molar ratio of the chloromethylated phenolic resin to the azide compound is 1 (1.5-4). The azide compound is excessive relative to the chloromethylated phenolic resin, so that the azide reaction is fully performed, and the reaction rate and the yield are improved.
In a preferred embodiment, the chloromethylated phenolic resin and the azide react at the temperature of 40-65 ℃ for 12-48 h.
In a preferred embodiment, the product is isolated after the reaction is complete. If the solvent II is water-soluble, a large amount of deionized water can be added into the reaction solution, stirred, kept stand, separated from solid matters, washed by the deionized water and dried to obtain the azide phenolic resin.
In the step 3, the azide phenolic resin and the graphene are mixed in a solvent III for reaction, and the modified phenolic resin material is obtained by separation after the reaction is finished.
In a preferred embodiment, the graphene is selected from unmodified graphene. Graphene which is widely used for material modification at present is graphene oxide, a large number of oxygen-containing functional groups are contained on the graphene oxide, the dispersibility of the graphene oxide in a solvent is better than that of unmodified graphene, however, the introduction of the oxygen-containing functional groups destroys the regular lattice structure of the graphene, and the irreversible change causes the conductivity of the graphene oxide to be poor and has loss in physical and chemical properties.
The unmodified graphene consists of benzene six-membered rings without any unstable bonds, has high chemical stability and excellent mechanical properties, but has weak interaction with other media, and strong van der Waals force exists between graphene sheets, so that aggregation is easily generated. The azide phenolic resin is reacted with graphene, so that the phenolic resin is grafted to the graphene, the mechanical property and the thermal property of the phenolic resin are enhanced, and the problem that the compatibility of unmodified graphene and the phenolic resin is poor is solved.
In a preferred embodiment, the solvent iii is selected from any one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, nitrobenzene, ethylene glycol or dimethyl sulfoxide, and the solvent iii is a high boiling point solvent to satisfy the reaction of the phenol azide resin and graphene at a higher temperature.
In a preferred embodiment, the mass ratio of the azido phenolic resin to the graphene is 1 (0.001-0.1), preferably 1 (0.005-0.05), and more preferably 1 (0.005-0.02).
In a preferred embodiment, in order to make the azide phenolic resin and the graphene fully contact in the solvent III, the mixed system is subjected to ultrasonic dispersion, preferably by using 40-120 KHz ultrasonic waves for 15-40 min.
In a preferred embodiment, the azide phenolic resin and the graphene react at the temperature of 140-200 ℃ for 15-30 h, preferably at the temperature of 160-180 ℃ for 18-24 h.
In a preferred embodiment, the reaction is carried out under an inert atmosphere, which is nitrogen or argon, preferably nitrogen.
In a preferred embodiment, after the reaction is completed, the reaction solution is cooled and separated to obtain a solid material, and the solid material is washed and dried to obtain a final product. The separation mode comprises filtration or centrifugation, preferably at 5000-9000 rpm for 5-15 min. The cleaning solvent is selected from water, ethanol or acetone.
In step 1 of the present invention, the chloromethylation reagent can be prepared as follows: mixing alcohol, formaldehyde and a catalyst, reacting, and performing aftertreatment to obtain a product. The alcohol is the corresponding alcohol after the chloromethylation reagent, namely the long carbon chain chloromethyl alkyl ether is dechlorinated, namely ClCH2O(CH2)nCH3Corresponding to HO (CH)2)nCH3，(ClCH2O)2(CH2)nCorresponding to HOCH2(CH2)n- 2CH2OH。
In a preferred embodiment, the formaldehyde has a (mass/volume) concentration of 35% to 40%.
In a preferred embodiment, the catalyst is selected from the group consisting of thionyl chloride (SOCl)2) Phosgene (COCl)2) And phosphorus trichloride (PCl)3) Preferably, phosphorus trichloride.
In a preferred embodiment, the volume ratio of the alcohol, formaldehyde and catalyst is 100: (220-400): (120-200), and the molar ratio is 10: (25-50): (10-25).
In a preferred embodiment, since the reaction is exothermic, the addition of a catalyst such as phosphorus trichloride also gives off a large amount of heat, and the catalyst is selected to be added dropwise slowly with stirring, to facilitate control of the reaction temperature. Preferably, the reaction system is reacted in an ice-water bath.
In a preferred embodiment, the reaction system is reacted for 2-5 hours at a temperature of 10-25 ℃. The reaction for preparing the chloromethylation reagent is a homogeneous reaction, while the reaction product is not water-soluble, and the product is continuously separated out from a water phase reaction system along with the reaction, so that the synthesis reaction is favorably carried out, the separation of the product is convenient, and the purity of the product is high.
In a preferred embodiment, the post-treatment comprises standing for layering, separating supernatant, drying the supernatant with a drying agent, and distilling under reduced pressure to obtain the chloromethylation reagent, wherein the drying agent is selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate or anhydrous copper sulfate.
Another aspect of the present invention is to provide a graphene graft modified phenolic resin material, preferably prepared according to the above preparation method, the material comprising the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 2 parts by weight of graphene.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
The main raw materials and sources thereof in the invention are as follows: phenol resin (model: PF6808, Shandong Shengquan chemical Co., Ltd.); unmodified graphene (graphene prepared by mechanical exfoliation, commercially available); graphene oxide (modified graphene oxide prepared by Hummers method, homemade).
Example 1
Dissolving 7g of phenolic resin in 250mL of acetone, adding 4g of anhydrous zinc chloride, dropwise adding 78g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 50 ℃ for 10 hours, adding a large amount of deionized water into the reaction solution, stirring, standing, performing suction filtration, washing with deionized water for multiple times, and performing vacuum drying to obtain chloromethylated phenolic resin;
dissolving 0.163g of sodium azide in N, N-dimethylformamide, dropwise adding 4g of chloromethylated phenolic resin (the molar ratio of the chloromethylated phenolic resin to the sodium azide is 1:2.5) while stirring, reacting for 36 hours at 40 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing, and drying in vacuum to obtain the azido phenolic resin;
ultrasonically dispersing 0.005g of graphene and 1g of azide phenolic resin in N-methyl pyrrolidone for 15min at 80KHz, heating to 160 ℃, reacting in nitrogen for 24h, separating at the rotating speed of 7500rpm by a centrifugal machine when the temperature is reduced to room temperature, centrifuging for 10min, cleaning by acetone, and drying to obtain the final product.
Example 2
Respectively adding 30mL of 1, 4-butanediol and 80mL of 37% formaldehyde solution into a reactor, dropwise adding 60mL of phosphorus trichloride while stirring, reacting for 4 hours at 10 ℃, standing the reaction mixed solution for 24 hours, separating supernatant after layering, drying the supernatant with anhydrous magnesium sulfate, and distilling under reduced pressure to obtain 1, 4-dichloromethoxybutane;
dissolving 5g of phenolic resin in 190mL of acetone, adding 3g of anhydrous zinc chloride, dropwise adding 60g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 60 ℃ for 5 hours, adding a large amount of deionized water into the reaction solution, stirring, standing, performing suction filtration, washing with deionized water for multiple times, and drying to obtain chloromethylated phenolic resin;
dissolving 0.09g of sodium azide in N, N-dimethylformamide, dropwise adding 2g of chloromethylated phenolic resin (the molar ratio of the chloromethylated phenolic resin to the sodium azide is 1:2.7) while stirring, reacting for 24 hours at 50 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing and drying to obtain the azido phenolic resin;
adding 0.01g of graphene and 1g of azide phenolic resin into N-methyl pyrrolidone, performing ultrasonic dispersion for 30min at 40KHz, heating to 180 ℃, reacting in nitrogen for 24h, cooling to room temperature, separating at 6000rpm by using a centrifugal machine, centrifuging for 15min, cleaning by using acetone, and drying to obtain a final product.
Example 3
Adding 60mL of 1, 4-butanediol and 150mL of 37% formaldehyde solution into a reactor respectively, dropwise adding 100mL of phosphorus trichloride while stirring, reacting for 3h at 15 ℃, standing the reaction mixed solution for 24h, separating supernatant after layering, drying the supernatant with anhydrous magnesium sulfate, and distilling under reduced pressure to obtain 1, 4-dichloromethoxybutane;
dissolving 6.8g of phenolic resin in 136mL of acetone, adding 3.9g of anhydrous zinc chloride, dropwise adding 42g of 1, 4-dichloromethoxybutane under stirring, reacting at the constant temperature of 55 ℃ for 6 hours, adding a large amount of deionized water into the reaction solution, stirring, standing, performing suction filtration, washing with deionized water for multiple times, and drying to obtain chloromethylated phenolic resin;
dissolving 0.073g of sodium azide in N, N-dimethylformamide, dropwise adding 1g of chloromethylated phenolic resin (the molar ratio of the chloromethylated phenolic resin to the sodium azide is 1:4) while stirring, reacting for 12 hours at 45 ℃, then adding a large amount of deionized water, stirring, standing, filtering, washing and drying to obtain the azido phenolic resin;
ultrasonically dispersing 0.02g of graphene and 1g of azide phenolic resin in N-methylpyrrolidone, ultrasonically dispersing for 20min at 60KHz, heating to 160 ℃, reacting for 18h in nitrogen, separating at a rotating speed of 5500rpm by using a centrifugal machine when the temperature is reduced to room temperature, centrifuging for 15min, cleaning by using acetone, and drying to obtain a final product, wherein a scanning electron microscope picture is shown in figure 2. Fig. 1 is a scanning electron microscope image of graphene, and fig. 2 is a scanning electron microscope image of the composite material. It can be seen that dispersed graphene is not seen on the surface of the grafted composite material, and the surface morphology of the graphene is greatly changed probably after the phenolic resin is grafted on the surface of the graphene. The thickness of the sheet layer on the surface of the composite material is obviously increased compared with that of graphene.
Comparative example 1
Phenolic resin not grafted with graphene.
Comparative example 2
The preparation was carried out as in example 1, with the only difference that the unmodified graphene was exchanged for graphene oxide.
Examples of the experiments
Electron scanning microscope: model S4800 scanning electron microscope manufactured by HITACHI, Japan.
Infrared spectrum analysis: spectrumone type Fourier transform infrared spectrometer manufactured by PE corporation of America.
X-ray diffraction with a scanning interval of 5-80 degrees with a D8advance X-ray diffractometer manufactured by Japan chemical and electric appliances, using a Cu target K α ray, a graphite monochromator, a tube current of 100mA, a tube voltage of 50KV, and a scanning speed of 5 °/min.
TG test: TG209F3 model thermogravimetric analyzer manufactured by Shanghai electronic technology Limited company with a temperature rise rate of 5 ℃/min.
And (3) testing mechanical properties: the microcomputer controlled electronic universal tester produced by Shenzhen Kaiqiang mechanical Limited has a drafting rate of 5 mm/min.
Experimental example 1 Infrared Spectroscopy
The phenol resin in comparative example 1 and the graphene grafted modified phenol resin material prepared in example 3 were subjected to infrared analysis, and the results are shown in fig. 3. In this figure, the characteristic peaks of the phenolic resin in comparative example 1 are as follows: 3336cm-1Is a stretching vibration of the associated hydroxyl group; 2922cm-1Is an asymmetric stretching vibration absorption peak of aliphatic-CH 2-; 1601cm-1～1458cm-1C ═ C stretching vibration peak specific to benzene ring skeleton; 1235cm-1The stretching vibration peak of oxygen on the phenolic hydroxyl and carbon on the benzene ring appears; 813cm-1、758cm-1The corresponding-CH out-of-plane bending vibration peaks of the tri-substituted benzene and the di-substituted benzene are stronger, which indicates that the products of the di-substituted benzene and the tri-substituted benzene are more. After the azide reaction, the reaction solution is at 2100cm-1The right and left parts of the complex present with-N3But the azide peak of the grafted product disappeared and was 1274cm-1A new small peak appears, and is supposed to be an absorption peak of carbon-nitrogen bonds generated by grafting the phenolic resin and the graphene.
Experimental example 2 XRD analysis
The phenolic resin material in the comparative example 1, the unmodified graphene and the material synthesized in the example 3 are subjected to XRD tests, and the XRD spectrum is shown in figure 4.
As can be seen from fig. 4, the XRD pattern of the phenolic resin is 17.8 °, 25.3 °, 31.1 ° and 44.5 ° diffraction peaks, the XRD pattern of the unmodified graphene is 26.5 ° diffraction peaks, and the XRD pattern of the material synthesized in example 3 has diffraction peaks at 17.8 ° and 26.5 ° simultaneously, which indicates that the graphene graft modified phenolic resin material is synthesized in example 3.
Experimental example 3 thermal stability
The thermal stability of phenolic resin materials has a large impact on their processing and use properties. The phenolic resin of comparative example 1 and the material synthesized in example 3 were subjected to TG curve measurement.
As shown in fig. 5, it can be seen from the following figure that the thermal decomposition temperature of the phenolic resin is 100 ℃ when the weight loss rate is 5%, while the thermal weight loss rate of the graphene/phenolic resin material is only 1.9%, and the thermal decomposition temperature is 166 ℃ when the thermal weight loss rate reaches 5%, and the difference between the two is 66 ℃. The weight loss rate of the phenolic resin is slow between 100 ℃ and 330 ℃, but is faster than that of the graphene/phenolic resin material between 166 ℃ and 460 ℃. The phenol formaldehyde resin has obvious thermal weight loss phenomenon between 330 ℃ and 800 ℃, and the corresponding graphene/phenol formaldehyde resin material has obvious thermal weight loss phenomenon between 460 ℃ and 800 ℃. It can also be seen that the graphene/phenolic resin material has a higher carbon residue rate than phenolic resin, and the weight loss rate of the graphene/phenolic resin material in the whole process is obviously much lower than that of phenolic resin. These show that the thermal stability of the material can be greatly improved after the phenolic resin is grafted on the surface of graphene. This is also much better than the thermal properties of graphene/phenolic resin materials prepared by physical blending as described in the literature. At 1000 ℃, the carbon residue of the phenolic resin is 44.6%, while the final carbon residue of the material synthesized in example 3 is 54.2%, and the thermal stability of the phenolic resin added with unmodified graphene is remarkably improved.
Experimental example 4 mechanical Properties
The materials prepared in examples 1 to 3 and comparative example 2 and the phenolic resin in comparative example 1 were subjected to mechanical property measurement, and the results are shown in table 1.
As can be seen from table 1, the breaking strength of the graphene-grafted phenolic resin material gradually increases with the increase of the content of graphene (within a mass ratio of graphene to phenol azide resin being 0.5-2: 100), and the breaking strength of the graphene-grafted phenolic resin material is significantly improved compared with that of a phenolic resin not grafted with graphene, and the breaking strength of the phenolic resin is significantly enhanced by unmodified graphene compared with graphene oxide.
TABLE 1 mechanical Properties data
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (18)
1. A preparation method of a graphene grafted modified phenolic resin material comprises the following steps:
step 1, preparing chloromethylation phenolic resin;
step 2, preparing azide phenolic resin;
and 3, mixing the azide phenolic resin with the graphene, reacting, and separating to obtain the modified phenolic resin material after the reaction is finished.
2. The process according to claim 1, wherein in step 1, a phenol resin and a chloromethylating reagent are reacted in a solvent I to obtain a chloromethylated phenol resin,
the chloromethylation reagent is selected from chloromethyl alkyl ether;
the solvent I is selected from any one or more of acetone, methanol, ethanol, isopropanol or n-butanol.
3. The method of claim 2, wherein the chloromethylating reagent is selected from the group consisting of ClCH2O(CH2)nCH3Or (ClCH)2O)2(CH2)nWherein n is 1-6;
the solvent I is acetone.
4. The method according to claim 3, wherein the chloromethylating reagent is 1, 4-dichloromethoxybutane.
5. The method according to claim 2, wherein in step 1, a catalyst is further added during the preparation of the chloromethylated phenolic resin, and the catalyst is selected from lewis acids;
the weight ratio of the catalyst to the phenolic resin to the chloromethylation reagent is 1 (1.5-4) to 10-20;
the volume ratio of the total weight of the phenolic resin, the catalyst and the chloromethylation reagent to the solvent I is 1 (2.5-4.0);
adding a chloromethylation reagent into the reaction system in a dropwise manner, and gradually heating in the dropwise process;
the reaction system is reacted for 4 to 10 hours at a temperature of 45 to 65 ℃.
6. The preparation method according to claim 5, wherein the catalyst is selected from any one or more of zinc chloride, stannic chloride, ferric chloride, aluminum chloride or copper chloride;
the reaction system is reacted for 5 to 8 hours at 50 to 60 ℃.
7. The preparation method according to claim 1, wherein in step 2, chloromethylated phenolic resin and azide are reacted in a solvent II to obtain azide phenolic resin; wherein,
the azide is selected from sodium azide, potassium azide or acyl azide;
the solvent II is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, toluene, p-xylene and ethylbenzene.
8. The method according to claim 7, wherein the azide compound is sodium azide;
the solvent II is N, N-dimethylformamide.
9. The preparation method of claim 7, wherein in the step 2, the molar ratio of the chloromethylated phenolic resin to the azide compound is 1 (1.5-4);
reacting the chloromethylated phenolic resin with the azide at the temperature of 40-65 ℃ for 12-48 h.
10. The preparation method according to claim 1, wherein in step 3, the phenol azide resin and the graphene are mixed in a solvent III,
the graphene is selected from unmodified graphene;
the solvent III is selected from any one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, nitrobenzene, ethylene glycol or dimethyl sulfoxide;
the mass ratio of the azide phenolic resin to the graphene is 1 (0.001-0.1);
the azide phenolic resin and the graphene react for 15-30 h at the temperature of 140-200 ℃.
11. The preparation method of the graphene material, wherein the mass ratio of the azide phenolic resin to the graphene is 1 (0.005-0.05);
the azide phenolic resin and the graphene react for 18-24 hours at the temperature of 160-180 ℃.
12. The preparation method of the graphene composite material, wherein the mass ratio of the azide phenolic resin to the graphene is 1 (0.005-0.02).
13. The method according to claim 10, wherein in step 3, the reaction is carried out under an inert atmosphere, which is nitrogen or argon;
the separation mode is selected from filtration or centrifugation;
and cleaning the modified phenolic resin material after separation, wherein the cleaning solvent is any one or more of water, ethanol or acetone.
14. The method of claim 13, wherein the inert atmosphere is nitrogen;
the separation method is centrifugation.
15. The method according to claim 2, wherein the chloromethylation reagent is prepared as follows: mixing alcohol, formaldehyde and a catalyst, reacting, and post-treating to obtain a product, wherein,
the concentration (mass/volume) of the formaldehyde is 35-40%; and/or
The molar ratio of the alcohol to the formaldehyde to the catalyst is 10 (25-50) to 10-25; and/or
Reacting the alcohol and formaldehyde at 10-25 ℃ for 2-5 h; and/or
The post-treatment comprises standing, separating, and drying the supernatant with a drying agent selected from anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium sulfate or anhydrous copper sulfate.
16. The graphene grafted and modified phenolic resin material is obtained by the preparation method of any one of claims 1 to 15, and is characterized by comprising the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.1-10 parts by weight of graphene.
17. The material of claim 16, wherein the material comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.5-5 parts by weight of graphene.
18. The material of claim 17, wherein the material comprises the following components in parts by weight:
100 parts by weight of a phenolic resin,
0.5-2 parts of graphene.
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