CN108102290A - A kind of graphene graft modification phenolic resin material and preparation method thereof - Google Patents
A kind of graphene graft modification phenolic resin material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene graft modification phenolic resin materials and preparation method thereof, the preparation method includes preparing Azide phenolic resin using chloromethylation phenolic resin and azido compound, Azide phenolic resin is grafted on graphene again, so as to obtain graphene graft modification phenolic resin material.Phenolic resin is grafted on graphene by the present invention by chemical grafting method, and solving graphene, easily with interface problem existing for phenolic resin, obtained material has excellent mechanical property and thermal stability for reunion and graphene.
Description
Technical field
The invention belongs to phenolic resin material field, more particularly to a kind of graphene graft modification phenolic resin material and its
Preparation method.
Background technology
In common three big thermosetting resins, phenolic resin is readily available except the raw material of preparation, production technology and
Equipment is simple, outside price is relatively cheap, the size of product also have good thermal stability, higher heat resistance, compared with
The advantages that strong mechanical property, have become it is industrial extensively using and indispensable functional material.But with the present age
The continuous development of commercial Application, traditional phenolic resin cannot meet the requirement of some fields such as aviation field, compel
That cuts needs to be modified phenolic resin.Therefore, pass through using phenolic resin as basis material and other reinforcing materials certain
Method phenolic resin-base composite is made with improve its some performance become research hot spot.
At present, it is multiple to be seen in the more graphene/phenolic resin mainly prepared using the method for physical blending of report
Condensation material, as 10469367 B of Chinese patent CN disclose a kind of preparation of the phenolic resin-base composite containing graphene
Method, adds in phenolic resin into graphene oxide solution, and under ultrasonic disperse, heating stirring to semisolid, drying is to changing
Property phenolic resin.Preparing graphene oxide/phenolic resin composite using the method for physical blending not only needs to solve phenolic aldehyde
The problem of compatibility between resin and graphene oxide and interface, and due to graphene oxide surface existing defects compared with
It is more, so performance raising is limited.
To overcome the problems, such as compatibility and interface, someone is using addition surfactant, such as Chinese patent CN
In graphene phenol-formaldehyde resin modified building-up process disclosed in 104231539 A of 104292745 A and CN into phenolic resin material
The graphene solution containing surfactant is added, is reunited to avoid graphene, but point of the surfactant wherein added in
Amount is higher, may generate a degree of limitation to the improvement of material property.Also oxidation is added in phenolic resin synthesis
Graphene and surfactant mixed with to solve the problems, such as graphene oxide in phenolic resin it is non-uniform, such as Chinese patent CN
104403066 A add in graphene oxide and the surfactant of larger dose in phenolic resin synthesis.
It was also found that unmodified graphene is rarely used to be carried out for reinforcing material and phenolic resin as matrix resin material
Physical blending prepares the report of composite material, analysis reason may be unmodified graphene than graphene oxide in matrix material
Dispersiveness and compatibility are all worse in material.
The connection there is an urgent need for a kind of phenolic resin and (unmodified) graphene or hybrid mode are so that phenolic resin as a result,
Performance be improved, while avoid the problem that (unmodified) graphene and phenolic compatible are bad.
The content of the invention
To solve the above-mentioned problems, present inventor has performed sharp study, it turns out that：It will using chemical grafting method
Phenolic resin is grafted to the graphene/phenolic resin material obtained on graphene, not only can effectively avoid the above problem, Er Qiecai
Material also improves a lot in thermal conductivity and mechanical property, thereby completing the present invention.
It is an object of the invention to provide following aspect：
(1) a kind of preparation method of graphene graft modification phenolic resin material, comprises the following steps：
Step 1, chloromethylation phenolic resin is prepared；
Step 2, Azide phenolic resin is prepared；
Step 3, Azide phenolic resin with graphene is mixed, is reacted, isolated modified phenol after the completion of reaction
Urea formaldehyde material.
In a preferred embodiment, in step 1, phenolic resin and chloromethylation reagents are reacted in solvent I,
Chloromethylation phenolic resin is obtained, wherein,
The chloromethylation reagents are selected from chloromethyl alkyl ether, such as ClCH2O(CH2)nCH3Or (ClCH2O)2(CH2)n, wherein
N=1~6 are preferably Isosorbide-5-Nitrae-dichloro methyl butyl ether；
Chloromethylation phenolic resin is additionally added catalyst during preparing, the catalyst is selected from lewis acid；It is described to urge
The weight ratio of agent, phenolic resin and chloromethylation reagents is 1：(1.5~4)：(10~20).
In a preferred embodiment, in step 2, by chloromethylation phenolic resin and azido compound in solvent II
Middle reaction, obtains Azide phenolic resin, and the molar ratio of chloromethylation phenolic resin and azido compound is 1:(1.5~4).
In a preferred embodiment, in step 3, the graphene is selected from unmodified graphene；
The mass ratio of the Azide phenolic resin and the graphene is 1:(0.001~0.1) is preferably 1:(0.005
~0.05), it is more preferably 1:(0.005~0.02).
(2) a kind of graphene graft modification phenolic resin material includes the component of following weight proportion：
100 parts by weight of phenolic resin,
0.1~5 parts by weight of graphene are preferably 0.5~2 parts by weight,
A kind of graphene graft modification phenolic resin material provided according to the present invention and preparation method thereof has with following
Beneficial effect：
1) using new chloromethylation reagents, relatively traditional chloromethane in the preparation process of Azide phenolic resin of the present invention
Base reagent (chloromethyl ether or bischlormethyl ether) has severe toxicity, and carcinogenic, and novel green chloromethylation reagents are more environmentally-friendly, so as to greatly
Ground alleviates the injury to user, reduces the pollution to environment, has good environment friendly；
2) compared with existing physical mixed, phenolic resin is grafted on graphene by chemical grafting method, is made
Graphene uniformly disperses in phenolic resin, solves graphene easily reunion and graphene and interface existing for phenolic resin
Problem；
3) other auxiliary agents are not added in phenol-formaldehyde resin modified material synthesis processes, while cost is reduced, avoid auxiliary agent
Influence to properties of product；
4) at 1000 DEG C, the carbon left of phenolic resin is 44.6%, and graphene graft modification phenolic resin material is most
Whole carbon left is 54.2%, and the thermal stability for adding the phenolic resin after unmodified graphene is obviously improved；
5) graphene of grafting is unmodified, reduces destruction of the process modified again for the molecular structure of graphene,
Graphene is made to play greater role in phenolic resin, can more preferably improve the mechanical property of phenolic resin.
Description of the drawings
Fig. 1 is the stereoscan photograph of grapheme material；
Fig. 2 is the stereoscan photograph of graphene graft modification phenolic resin material prepared by embodiment 3；
Fig. 3 is the infrared of the graphene graft modification phenolic resin material that phenolic resin is prepared with embodiment 3 in comparative example 1
Spectrogram；
Fig. 4 is the XRD of the material that phenolic resin, unmodified graphene and embodiment 3 synthesize in comparative example 1 of the present invention
Collection of illustrative plates；
Fig. 5 is the thermal gravimetric analysis curve figure of the material that phenolic resin and embodiment 3 synthesize in comparative example 1 of the present invention.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
To be clear, clear and definite.
The object of the present invention is to provide a kind of preparation method of graphene graft modification phenolic resin material, including following step
Suddenly：
Step 1, chloromethylation phenolic resin is prepared；
Step 2, Azide phenolic resin is prepared；
Step 3, Azide phenolic resin with graphene is mixed, is reacted, isolated modified phenol after the completion of reaction
Urea formaldehyde material.
In step 1, phenolic resin and chloromethylation reagents in solvent I are reacted, obtain chloromethylation phenolic resin.
Phenolic resin refers to that phenol gathers with the aldehyde resinousness that polycondensation forms in the presence of an acidic or basic catalyst in the present invention
The general name of object is closed, may be, for example, the resin that phenol is synthesized with formaldehyde.
In a preferred embodiment, the chloromethylation reagents are selected from chloromethyl alkyl ether, such as ClCH2O(CH2)nCH3Or (ClCH2O)2(CH2)n, wherein n=1~6 are preferably Isosorbide-5-Nitrae-dichloro methyl butyl ether.At present, it is most popular to be
Chloromethylation reagents are done in formaldehyde, metaformaldehyde and paraformaldehyde and hydrochloric acid cooperation, and toxicity is smaller, price is low, but the reaction time
Long, yield is not high；ClCH2OCH3(ClCH2)2O can also replace HCHO-HCl as chloromethylation reagents, active high, anti-
Should be selectively good, but have severe toxicity, be corrosive and store transport difficult；And ClCH2Si(CH3)3、ClSi(CH3)2- HCHO etc.
It can be used as chloromethylation reagents, it is nontoxic, yield is high, good reaction selectivity, but difficult and price is prepared, it limits using model
It encloses.The Long carbon chain chloromethyl alkyl ether boiling point selected in the present invention is high, active high, safe to use effective, compensates for above-mentioned each chlorine
The shortcomings that methylating reagent is the preferable selection of chloromethylation reagents.
In a preferred embodiment, the solvent I is appointed in acetone, methanol, ethyl alcohol, isopropanol or n-butanol
Meaning is one or more, is preferably acetone.
In a preferred embodiment, chloromethylation phenolic resin is additionally added catalyst during preparing, described to urge
Agent is selected from lewis acid, is preferably selected from any one in zinc chloride, butter of tin, iron chloride, aluminium chloride or copper chloride or more
Kind.
The reaction mechanism of phenolic resin and chloromethylation reagents may be in step 1：It is acted on first in Louis acid catalysis
Lower generation alkyl carbonium ion is (such as+CH2OCH2CH2CH2CH2OCH2Cl then) the electrophilic substitution reaction on phenyl ring dissociates
Chlorion carries out nucleophilic substitution, makes ether bond rupture, obtains chloromethylation phenolic resin, net reaction is：
Catalyst is used to that chloromethylation reagents to be promoted to form carbonium ion and then carry out parent to the phenyl ring of phenolic resin molecule
Electric substitution reaction such as using butter of tin as catalyst, makees chloromethylation reagents, catalytic reaction with Isosorbide-5-Nitrae-dichloro methyl butyl ether
For：
SnCl4+ClCH2OCH2CH2CH2CH2OCH2Cl→+CH2OCH2CH2CH2OCH2Cl+SnCl5 -
In a preferred embodiment, the weight ratio of the catalyst, phenolic resin and chloromethylation reagents is 1：
(1.5~4)：(10~20).Catalyst amount influence phenolic resin the rate that methylates, catalyst amount is few, alkyl carbon just from
Son generates that rate is low, and then chloromethylation rate is low, if but catalyst amount it is excessive (being more than said ratio), alkyl in the short time
Carbonium ion concentration increases sharply, and the rate for causing chloromethylation is too fast, can promote to hand between phenolic resin macromolecular
Connection reaction is crosslinked to lose chlorine process, and the chloromethylation degree of phenolic resin reduces instead at this time.
In further preferred embodiment, chloromethylation reagents add in reaction system by the way of being added dropwise.It is added dropwise
Mode can control reaction rate, avoids the generation of a large amount of alkyl carbonium ions and causes entire chloromethylation rate too fast, from
And the cross-linking reaction that the phenyl ring in phenolic resin macromolecular is avoided largely to be occurred by chloromethylation.
In a preferred embodiment, the total weight of the phenolic resin, catalyst and chloromethylation reagents and institute
The ratio between volume of solvent I is stated as 1:(2.5~4.0), within this range, solvent I can fully dissolve reaction raw materials, while raw material is dense
Degree is unlikely to too small, ensures that chloromethylation is carried out with faster rate.
In a preferred embodiment, gradually heating, the chloromethane of phenolic resin during chloromethylation reagents are added dropwise
Glycosylation reaction reacts 4~10h at 45~65 DEG C, and 5~8h is reacted preferably at 50~60 DEG C.
In a preferred embodiment, after the completion of being reacted in step 1, room temperature is down to, is added in into reaction system big
Water is measured, chloromethylation phenolic resin is made to be precipitated from organic solvent, centrifuges or filters, chloromethylation is drying to obtain after being washed with water
Phenolic resin.
In step 2, chloromethylation phenolic resin and azido compound in solvent II are reacted, obtain Azide phenolic aldehyde tree
Fat.
In a preferred embodiment, the azido compound is selected from sodium azide, potassium azide or acid azide
Compound is preferably sodium azide.
In a preferred embodiment, the solvent II is selected from n,N-Dimethylformamide, N, N- dimethylacetamides
Any one or more in amine, toluene, paraxylene, ethylbenzene is preferably n,N-Dimethylformamide.
In a preferred embodiment, after azido compound being added in solvent II, chloromethylation phenolic resin uses
Dropwise addition mode adds in, and is added dropwise in process and reaction process with stirring, accelerates the progress of azido reaction.
In a preferred embodiment, the molar ratio of chloromethylation phenolic resin and azido compound is 1:(1.5~
4).Azido compound is excessive compared with chloromethylation phenolic resin so that azido reaction fully carries out, improve reaction rate and
Yield.
In a preferred embodiment, chloromethylation phenolic resin and azido compound are anti-at 40~65 DEG C of temperature
It should be 12~48h.
In a preferred embodiment, after the completion of reaction, product is separated.If solvent II is water solubility, can
Substantial amounts of deionized water is added in into reaction solution and is stirred, stands, separate solid matter, it is dry after being washed with deionized, it obtains
To Azide phenolic resin.
In step 3, Azide phenolic resin with graphene in solvent II I is mixed, is reacted, divided after the completion of reaction
From obtaining phenol-formaldehyde resin modified material.
In a preferred embodiment, the graphene is selected from unmodified graphene.Current relatively broad use
It is graphene oxide in the graphene of material modification, thereon containing substantial amounts of oxygen-containing functional group, dispersiveness in a solvent is more not
Modified graphene is good, however the introducing of oxygen-containing functional group destroys the regular lattice structure of graphene, this irreversible
Variation is so that the electric conductivity of graphene oxide is poor, and there are the losses in terms of physics, chemical property.
Unmodified graphene is made of the benzene hexatomic ring for being free of any labile bond, and chemical stability is high, mechanical property
Can be excellent but weaker with the interaction of other media, and graphene film interlayer has stronger Van der Waals force, easily generates poly-
Collection.By Azide phenolic resin and graphite alkene reaction, phenolic resin is made to be grafted on graphene, so as in enhancing phenolic resin power
The problem of unmodified graphene and bad phenolic compatible being avoided while learning performance and hot property.
In a preferred embodiment, the solvent III be selected from N-Methyl pyrrolidone, n,N-Dimethylformamide,
Any one or more in n,N-dimethylacetamide, nitrobenzene, ethylene glycol or dimethyl sulfoxide (DMSO), the solvent III is height boiling
Point solvent, to meet the reaction of Azide phenolic resin and graphene under higher temperature.
In a preferred embodiment, the mass ratio of the Azide phenolic resin and the graphene is 1:
(0.001~0.1) is preferably 1:(0.005~0.05), more preferably 1:(0.005~0.02).
In a preferred embodiment, for Azide phenolic resin is made to be come into full contact with graphene in solvent III,
Ultrasonic disperse is carried out to mixed system, it is preferred to use the ultrasonic wave of 40~120KHz, 15~40min of ultrasound.
In a preferred embodiment, Azide phenolic resin and graphene react 15 at 140~200 DEG C of temperature
~30h, preferably at 160~180 DEG C react 18~for 24 hours.
In a preferred embodiment, reaction carry out under an inert atmosphere, the inert atmosphere be nitrogen or argon gas,
Preferably nitrogen.
In a preferred embodiment, after the completion of reaction, cooled down to reaction solution, separated, obtain solid material,
Solid material is cleaned, is dried, obtains final products.The separate mode includes filtering or centrifugation, preferably 5000~
Under 9000rpm, 5~15min is centrifuged.Solvent for cleaning is selected from water, ethyl alcohol or acetone.
In step 1 of the present invention, the chloromethylation reagents can be prepared as follows：Alcohol, formaldehyde and catalyst are mixed
After reacted, it is post-treated, obtain product.The alcohol removes chloromethyl for chloromethylation reagents, that is, Long carbon chain chloromethyl alkyl ether
Corresponding alcohol, i.e. ClCH afterwards2O(CH2)nCH3Corresponding to HO (CH2)nCH3, (ClCH2O)2(CH2)nCorresponding to HOCH2(CH2)n- 2CH2OH。
In a preferred embodiment, (mass/volume) concentration of the formaldehyde is 35%~40%.
In a preferred embodiment, the catalyst is selected from thionyl chloride (SOCl2), phosgene (COCl2) and trichlorine
Change phosphorus (PCl3), it is preferably phosphorus trichloride.
In a preferred embodiment, the volume ratio of the alcohol, formaldehyde and catalyst is 100：(220~400)：
(120~200), molar ratio 10：(25~50)：(10~25).
In a preferred embodiment, since this reaction is exothermic reaction, the addition of catalyst such as phosphorus trichloride is same
Sample can release big calorimetric, thus selecting catalyst is under stiring, is slowly added dropwise, convenient for controlling reaction temperature.Preferably, reactant
It lies in ice-water bath and reacts.
In a preferred embodiment, reaction system reacts 2~5h at 10~25 DEG C of temperature.Prepare chloromethylation
The reaction of reagent is homogeneous reaction, and reaction product is non-aqueous, and with the progress of reaction, product is constantly from aqueous phase reactions body
It is precipitated in system, is not only advantageous to the progress of synthetic reaction, and convenient for the separation of product, product purity height.
In a preferred embodiment, the post processing includes stratification, supernatant is separated, with drier to upper
Clear liquid is dried, and through vacuum distillation, obtains chloromethylation reagents, wherein, the drier is selected from anhydrous magnesium sulfate, anhydrous sulphur
Sour sodium, dead plaster or anhydrous cupric sulfate.
Another aspect of the present invention is to provide a kind of graphene graft modification phenolic resin material, preferably according to above-mentioned preparation
Method is made, and the material includes the component of following weight proportion：
100 parts by weight of phenolic resin,
0.1~10 parts by weight of graphene, preferably 0.5~5 parts by weight, more preferably 0.5~2 parts by weight.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of invention forms any restrictions.
Primary raw material and its source are in the present invention：Phenolic resin (model：PF6808, Shandong holy well chemical industry share are limited
Company)；Unmodified graphene (graphene prepared by mechanical stripping method, commercially available)；Graphene oxide (improves Hummers methods
The graphene oxide of preparation, self-control).
Embodiment 1
7g phenolic resin is dissolved in 250mL acetone, adds in 4g anhydrous zinc chlorides, stirs lower dropwise addition 78g1,4- dichloros
Methyl butyl ether adds in substantial amounts of deionized water into reaction solution at 50 DEG C after isothermal reaction 10h, stirs, and stands, and filters, and uses
Deionized water is repeatedly washed, and vacuum drying obtains chloromethylation phenolic resin；
0.163g sodium azide is dissolved in n,N-Dimethylformamide, stirs lower dropwise addition 4g chloromethylation phenolic resin
(the molar ratio 1 of chloromethylation phenolic resin and sodium azide:2.5) 36h, is reacted at 40 DEG C, then adds in substantial amounts of deionization
Water stirs, and stands, and filters, and washs, and vacuum drying obtains Azide phenolic resin；
0.005g graphenes and 1g Azide phenolic resin ultrasonic disperses is ultrasonic under N-Methyl pyrrolidone, 80KHz
Scattered 15min is heated to 160 DEG C and is reacted in nitrogen for 24 hours, separates rotating speed with centrifuge when temperature is down to room temperature
7500rpm, centrifuge 10min, after cleaned with acetone, drying obtain final products.
Embodiment 2
30mL 1,4-butanediol and 80mL37% formalins are separately added into reactor, stir lower dropwise addition 60mL tri-
Phosphorus chloride reacts 4h at 10 DEG C, and reaction mixture is stood for 24 hours, supernatant is separated after being layered, by supernatant with anhydrous sulphur
Sour magnesium is dried, and vacuum distillation obtains Isosorbide-5-Nitrae-dichloro methyl butyl ether；
5g phenolic resin is dissolved in 190mL acetone, adds in 3g anhydrous zinc chlorides, stirs lower dropwise addition 60g1,4- dichloros
Methyl butyl ether adds in substantial amounts of deionized water into reaction solution at 60 DEG C after isothermal reaction 5h, stirs, and stands, and filters, spends
Ionized water repeatedly washs, and chloromethylation phenolic resin is obtained after dry；
0.09g sodium azide is dissolved in n,N-Dimethylformamide, stirs lower dropwise addition 2g chloromethylation phenolic resin
(the molar ratio 1 of chloromethylation phenolic resin and sodium azide:2.7), react for 24 hours at 50 DEG C, then add in substantial amounts of deionization
Water stirs, and stands, and filters, and washs, dry, obtains Azide phenolic resin；
0.01g graphenes and 1g Azide phenolic resin are added in N-Methyl pyrrolidone, ultrasonic disperse under 40KHz
30min is heated to 180 DEG C and is reacted in nitrogen for 24 hours, separates rotating speed 6000rpm with centrifuge when temperature is down to room temperature, from
Heart 15min, is cleaned with acetone, is dried to obtain final products.
Embodiment 3
60mL 1,4-butanediol and 150mL37% formalins are separately added into reactor, stir lower dropwise addition 100mL
Phosphorus trichloride reacts 3h at 15 DEG C, and reaction mixture is stood for 24 hours, supernatant is separated after being layered, by supernatant with anhydrous
Magnesium sulfate is dried, and vacuum distillation obtains Isosorbide-5-Nitrae-dichloro methyl butyl ether；
6.8g phenolic resin is dissolved in 136mL acetone, adds in 3.9g anhydrous zinc chlorides, stirs lower dropwise addition 42g1,4-
Dichloro methyl butyl ether adds in substantial amounts of deionized water into reaction solution at 55 DEG C after isothermal reaction 6h, stirs, and stands, and filters,
It is repeatedly washed with deionized water, chloromethylation phenolic resin is obtained after dry；
0.073g sodium azide is dissolved in n,N-Dimethylformamide, stirs lower dropwise addition 1g chloromethylation phenolic resin
(the molar ratio 1 of chloromethylation phenolic resin and sodium azide:4) 12h, is reacted at 45 DEG C, then adds in substantial amounts of deionized water,
Stirring is stood, and is filtered, and is washed, dry, obtains Azide phenolic resin；
It is ultrasonic under 60KHz by 0.02g graphenes and 1g Azide phenolic resin ultrasonic disperses in N-Methyl pyrrolidone
Scattered 20min, is heated to 160 DEG C and 18h is reacted in nitrogen, separates rotating speed with centrifuge when temperature is down to room temperature
5500rpm, centrifuge 15min, after cleaned with acetone, drying obtain final products, scanning electron microscope (SEM) photograph is as shown in Figure 2.Fig. 1 is
The scanning electron microscope (SEM) photograph of graphene, Fig. 2 are the scanning electron microscope (SEM) photograph of composite material.It can be seen that the table of the composite material after grafting
Scattered graphene is not seen in face, it may be possible to after phenolic resin is grafted on graphene surface so that graphene surface pattern is sent out
Larger change is given birth to.Composite material surface lamellar spacing substantially increases compared with graphene.
Comparative example 1
The phenolic resin of non-grafted graphene.
Comparative example 2
If prepared by embodiment 1, differ only in and unmodified graphene is changed to graphene oxide.
Experimental example
Electronic scanner microscope：The S4800 type electronic scanner microscopes of Japanese HITACHI companies production.
Infrared spectrum analysis：The Spectrumone type Fourier Transform Infrared Spectrometer of PE companies of U.S. production.
X-ray diffraction：The D8advance type X-ray diffractometers of Rigaku Electric company production, 2 θ=5 of sweep interval
~80 °, using Cu target K alpha rays, graphite monochromator, tube current 100mA, tube voltage 50KV, sweep speed be set as 5 °/
min。
TG is tested：The TG209F3 type thermogravimetric analyzers of resistance to excellent (Shanghai) Electronic Science and Technology Co., Ltd. production, heating rate 5
℃/min。
Mechanics Performance Testing：The omnipotent test machine of microcomputer controlled electronic of Kai Qiang Machinery Co., Ltd.s of Shenzhen production, drawing-off
Rate is 5mm/min.
1 infrared spectrum analysis of experimental example
Graphene graft modification phenolic resin material prepared by phenolic resin in comparative example 1 and embodiment 3 carries out infrared
Analysis, the results are shown in Figure 3.In the figure, the characteristic peak of phenolic resin is as follows in comparative example 1：3336cm-1It is associate hydrogen bond
Stretching vibration；2922cm-1It is the asymmetric stretching vibration absworption peak of aliphatic-CH2-；1601cm-1~1458cm-1For phenyl ring bone
The distinctive C=C stretching vibration peaks of frame；1235cm-1Place occurs that the stretching vibration peak of oxygen and carbon on phenyl ring on phenolic hydroxyl group；
813cm-1、758cm-1Corresponding is trisubstituted benzene, disubstituted benzenes-CH out-of-plane bending vibrations peak, and peak is stronger, illustrates two substitutions
The product of benzene and trisubstituted benzene is more.In 2100cm after azido reaction-1Appearance-N at left and right3Infrared absorption peak, but be grafted
Product nitrine peak afterwards disappears and in 1274cm-1There is a new small peak in place, thus it is speculated that is phenolic resin and graphene grafting
The absworption peak of the carbon nitrogen carbon key of generation.
2 XRD analysis of experimental example
The material that phenolic resin material, unmodified graphene and embodiment 3 synthesize in comparative example 1 is subjected to XRD surveys
Examination, XRD spectra are as shown in Figure 4.
As shown in Figure 4,2 θ are by crystal face diffraction at 17.8 °, 25.3 °, 31.1 ° and 44.5 ° in the XRD spectrum of phenolic resin
Peak, in the XRD spectrum of unmodified graphene 2 θ at 26.5 ° by crystallographic plane diffraction peak, and the material that embodiment 3 synthesizes
There is crystallographic plane diffraction peak at 17.8 ° and 26.5 ° simultaneously in XRD spectrum, illustrate that embodiment 3 has synthesized graphene graft modification phenolic aldehyde
Resin material.
3 thermal stability of experimental example
The thermal stability of phenolic resin material processes it and performance has large effect.By phenol in comparative example 1
The material that urea formaldehyde and embodiment 3 synthesize measures TG curves.
As shown in figure 5, as can be seen that heat decomposition temperature of the phenolic resin when weight-loss ratio is 5% is 100 from figure below
DEG C, and the thermal weight loss rate of graphene/phenolic resin material is only 1.9% at this time, heat decomposition temperature is when thermal weight loss rate reaches 5%
166 DEG C, the two differs 66 DEG C.Although phenolic resin weight loss rate is slow between 100 DEG C~330 DEG C, than graphene/phenol
Weight loss rate of the urea formaldehyde material between 166 DEG C~460 DEG C is fast.Phenolic resin occurs substantially between 330 DEG C~800 DEG C
Thermal weight loss phenomenon, corresponding graphene/phenolic resin material but apparent heat will just occurs between 460 DEG C~800 DEG C
Weightlessness.It is also seen that graphene/phenolic resin material has higher carbon yield than phenolic resin, stone in whole process
The weight-loss ratio of black alkene/phenolic resin material is many significantly lower than phenolic resin.These all show that phenolic resin is grafted to graphene
The thermal stability of raising material that can be largely after surface.This method using physical blending recorded with document
The hot property of graphene/phenolic resin material of preparation is compared to also well very much.At 1000 DEG C, the carbon left of phenolic resin is
44.6%, and the final carbon left for the material that embodiment 3 synthesizes is 54.2%, adds the phenolic aldehyde tree after unmodified graphene
The thermal stability of fat is obviously improved.
4 mechanical property of experimental example
Material and the phenolic resin of comparative example 1 prepared by Examples 1 to 3, comparative example 2 carries out mechanics performance determining,
The results are shown in Table 1.
As shown in Table 1, the fracture strength of graphene grafting phenolic resin material gradually increases with the increase of graphene content
Greatly (in graphene and Azide phenolic resin mass ratio=0.5~2:In the range of 100), and graphene grafting phenolic resin material
Compared with the phenolic resin of non-grafted graphene, fracture strength is significantly improved, and unmodified graphene is compared to oxidation stone
Black alkene becomes apparent from the enhancing of phenolic resin fracture strength.
1 mechanical performance data of table
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencings, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
1. a kind of preparation method of graphene graft modification phenolic resin material, comprises the following steps：
Step 1, chloromethylation phenolic resin is prepared；
Step 2, Azide phenolic resin is prepared；
Step 3, Azide phenolic resin with graphene is mixed, is reacted, isolated modified phenolic resin after the completion of reaction
Fat material.
2. preparation method according to claim 1, which is characterized in that in step 1, by phenolic resin and chloromethylation reagents
It is reacted in solvent I, obtains chloromethylation phenolic resin, wherein,
The chloromethylation reagents are selected from chloromethyl alkyl ether, such as ClCH2O(CH2)nCH3Or (ClCH2O)2(CH2)n, wherein n=1
~6, it is preferably Isosorbide-5-Nitrae-dichloro methyl butyl ether；And/or
The solvent I in acetone, methanol, ethyl alcohol, isopropanol or n-butanol any one or more, be preferably acetone.
3. preparation method according to claim 2, which is characterized in that in step 1, chloromethylation phenolic resin prepares process
In be additionally added catalyst, the catalyst is selected from lewis acid, is preferably zinc chloride, butter of tin, iron chloride, aluminium chloride or chlorine
Change any one or more in copper；And/or
The weight ratio of the catalyst, phenolic resin and chloromethylation reagents is 1:(1.5~4):(10~20)；And/or
The ratio between the total weight of the phenolic resin, catalyst and chloromethylation reagents and the volume of the solvent I are 1:(2.5~
4.0)；And/or
Chloromethylation reagents add in reaction system by the way of being added dropwise, gradually heating during being added dropwise；And/or
Reaction system reacts 4~10h at 45~65 DEG C, and 5~8h is reacted preferably at 50~60 DEG C.
4. preparation method according to claim 1, which is characterized in that in step 2, by chloromethylation phenolic resin and nitrine
Compound is reacted in solvent II, obtains Azide phenolic resin；Wherein,
The azido compound is selected from sodium azide, potassium azide or acyl azide, is preferably sodium azide；And/or
The solvent II is arbitrary in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, toluene, paraxylene, ethylbenzene
One or more are preferably n,N-Dimethylformamide.
5. preparation method according to claim 4, which is characterized in that in step 2, chloromethylation phenolic resin and Azide
The molar ratio for closing object is 1:(1.5~4)；And/or
The reaction at 40~65 DEG C of temperature of chloromethylation phenolic resin and azido compound is 12~48h.
6. preparation method according to claim 1, which is characterized in that in step 3, Azide phenolic resin exists with graphene
It is mixed in solvent II I,
The graphene is selected from unmodified graphene；And/or
The solvent III is selected from N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, nitrobenzene, second
Any one or more in glycol or dimethyl sulfoxide (DMSO)；And/or
The mass ratio of the Azide phenolic resin and the graphene is 1:(0.001~0.1) is preferably 1:(0.005~
0.05), it is more preferably 1:(0.005~0.02)；And/or
Azide phenolic resin and graphene react 15~30h at 140~200 DEG C of temperature, anti-preferably at 160~180 DEG C
Answer 18~for 24 hours.
7. preparation method according to claim 6, which is characterized in that in step 3, reaction carries out under an inert atmosphere, institute
Inert atmosphere is stated as nitrogen or argon gas, more preferably nitrogen；And/or
Separate mode is selected from filtering or centrifugation, preferably centrifuges；And/or
Phenol-formaldehyde resin modified material is cleaned after separation, cleaning solvent is any one or more in water, ethyl alcohol or acetone.
8. the preparation method according to Claims 2 or 3, which is characterized in that the chloromethylation reagents can be as follows
It prepares：It is reacted after alcohol, formaldehyde and catalyst are mixed, it is post-treated, product is obtained, wherein,
(mass/volume) concentration of the formaldehyde is 35%~40%；And/or
The molar ratio of the alcohol, formaldehyde and catalyst is 10:(25~50):(10~25)；And/or
The alcohol and formaldehyde react 2~5h at 10~25 DEG C；And/or
The post processing includes standing, and separation is dried supernatant liquor with drier, and the drier is selected from anhydrous slufuric acid
Magnesium, anhydrous sodium sulfate, dead plaster or anhydrous cupric sulfate.
9. a kind of graphene graft modification phenolic resin material is preferably obtained according to one of claim 1 to 8 preparation method
It arrives, which is characterized in that the material includes the component of following weight proportion：
100 parts by weight of phenolic resin,
0.1~10 parts by weight of graphene.
10. material according to claim 9, which is characterized in that the material includes the component of following weight proportion：
100 parts by weight of phenolic resin,
0.5~5 parts by weight of graphene are preferably 0.5~2 parts by weight.
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| CN112707381A (en) * | 2020-12-30 | 2021-04-27 | 高立雅 | Preparation method and application of nitrogen-rich hollow carbon sphere modified graphene positive electrode active material |
| CN112707381B (en) * | 2020-12-30 | 2022-09-13 | 新乡市中天新能源科技股份有限公司 | Preparation method and application of nitrogen-rich hollow carbon sphere modified graphene positive electrode active material |
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