CN107973888A - A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof - Google Patents
A kind of functional graphene oxide/full bio-based benzoxazine colophony composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of functional graphene oxide/benzoxazine colophony composite material and preparation method thereof, the present invention first provides a kind of low viscosity full bio-based benzoxazine, it is obtained by bio-based phenolic monomers, chaff amine and paraformaldehyde polymerisation, wherein the bio-based phenolic monomers are anacardol or laccol.The full bio-based benzoxazine monomer can keep the characteristic of low viscosity at normal temperatures, easy to industrially be processed further and synthesize, have higher economic value.And functional graphene oxide/benzoxazine colophony composite material is obtained based on the full bio-based benzoxazine of the low viscosity is compound, gained composite materials property and thermal property are greatly improved compared to pure benzoxazine colophony, are with a wide range of applications.
Description
Technical field
The present invention relates to technical field of composite materials is belonged to, it is related to a kind of functional graphene oxide/full bio-based benzo
Oxazine resin composite materials and preparation method thereof, more particularly, to the full life that two kinds of low viscosities are synthesized with anacardol and laccol
Thing base benzoxazine monomer (CFa and UFa), and with the compound obtained functionalization graphite oxide of KH570 functional graphene oxides
Alkene/benzoxazine colophony composite material and preparation method thereof.
Background technology
Benzoxazine colophony as a kind of polymer of novel high-performance, there is volume zero to shrink, cure after without byproduct,
The features such as heat endurance is high, glass transition temperature is high, surface energy is low, water absorption rate is low, leads in aerospace, electronics and environment
Domain has obtained extensive utilization.In general, benzoxazine is to pass through Mannich by phenols intermediate, amine intermediate and formaldehyde
Prepared by reaction.Therefore the benzoxazine colophony of different performance can be designed based on different types of phenols and amine.It is many
The benzoxazine monomer of species is developed into by conventional art can meet some key performance criterias, such as excellent mechanics
Processing characteristics of performance, fire resistance and tolerance interval class etc..
However, be mostly petroleum base nonrenewable resources currently used for the raw material for synthesizing benzoxazine, or by oil and
Prepared by its derivative aromatic bisphenols or diamines, since raw material molecule is rigid, for solid or have at room temperature
Higher viscosity, therefore to industrial production and be processed further bringing inconvenience, which greatly limits them
Application.Therefore, the exploitation of low viscosity and the benzoxazine with good thermodynamic property is one very attractive
Problem.On the other hand, prepared from renewable resource bio-based benzoxazine colophony economically with all have in ecology it is important
Meaning, solves the problems, such as the preparation of the full bio-based benzoxazine of low viscosity and the green bio based composites of excellent in mechanical performance,
The dependence to petroleum base and its derivative raw material can be not only reduced, will also greatly promote that environmentally protective, high-performance is biological
The development of based composites.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned deficiency existing in the prior art, there is provided a kind of low viscosity
Full bio-based benzoxazine and preparation method thereof, and it is excellent based on the full bio-based benzoxazine of the low viscosity mechanical property to be prepared
Different green bio based composites.
In order to solve the above technical problems, technical solution provided by the invention is：
There is provided a kind of low viscosity full bio-based benzoxazine, it is by bio-based phenolic monomers, chaff amine and paraformaldehyde not
Polymerisation obtains under conditions of addition solvent, wherein the bio-based phenolic monomers are anacardol or laccol.
Preferably, the bio-based phenolic monomers, chaff amine and paraformaldehyde molar ratio are 1-1.2：1-1.2：0.1-
0.2。
By such scheme, the paraformaldehyde number-average molecular weight is 300-600.
The present invention also provides the preparation method of the full bio-based benzoxazine of above-mentioned low viscosity, comprise the following steps that：By biology
Base phenolic monomers, chaff amine and paraformaldehyde mix in proportion, and are warming up to 110-120 DEG C of reaction 2-3h, will be anti-after having reacted
Answer product to be dissolved in chloroform, obtained solution is filtered, is extracted with sodium hydroxide solution, and gained subnatant distilled water will be extracted
Cleaning to neutrality, then vacuum distillation removes solvent, and products therefrom purifies to obtain the full bio-based benzo of low viscosity using column chromatography
Oxazine.
Present invention additionally comprises the Polybenzoxazine resin cured according to the full bio-based benzoxazine of above-mentioned low viscosity, institute
Stating curing is：Cure 1h respectively in 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C successively.
Present invention additionally comprises based on the full bio-based benzoxazine of above-mentioned low viscosity with functional graphene oxide is compound obtains
Functional graphene oxide/full bio-based benzoxazine colophony composite material.
The preparation method of above-mentioned functional graphene oxide/full bio-based benzoxazine colophony composite material, specific steps
It is as follows：
1) preparation of graphene oxide (GO)：Graphene oxide (GO) is prepared with improved Hummers methods；
2) preparation of functional graphene oxide (KGO)：Graphene oxide obtained by step 1) is added in absolute ethyl alcohol, is surpassed
Sound is uniformly dispersed to obtain the graphene dispersing solution that concentration is 0.5-1.5mg/mL, adjusts graphene dispersing solution pH value to 3-4, then
γ-methacryloxypropyl trimethoxy silane (KH570) is added under agitation, is heated to 60-65 DEG C of reaction 20-
25h, carries out centrifuge washing with absolute ethyl alcohol and deionized water to gained reaction solution respectively after reaction, then ultrasonic disperse in
KH570 functional graphene oxides (KGO) dispersion liquid is obtained in deionized water, finally by KH570 functional graphene oxides point
Dispersion liquid is dried in vacuo to obtain KH570 functional graphene oxides (KGO)；
3) preparation of the full bio-based benzoxazine of low viscosity：By bio-based phenolic monomers, chaff amine and paraformaldehyde in proportion
It is uniformly mixed, is warming up to 110-120 DEG C of reaction 2-3h, reaction product is dissolved in chloroform after having reacted, obtained solution is filtered,
Extracted with sodium hydroxide solution, and extraction gained subnatant cleaned to neutrality, then vacuum distillation with distilled water and removes solvent,
Products therefrom purifies to obtain the full bio-based benzoxazine of low viscosity using column chromatography；
4) preparation of functional graphene oxide/full bio-based benzoxazine colophony composite material：It is prepared by step 2)
The full bio-based benzoxazine 0.1-0.5 in mass ratio of low viscosity that KH570 functional graphene oxides are prepared with step 3)：100
It is uniformly mixed, and ultrasonic disperse obtains mixed solution, and the vacuum drying of gained mixed solution, curing then are obtained functionalization oxidation
Graphene/full bio-based benzoxazine colophony composite material.
By such scheme, the improved Hummers methods of step 1) prepare graphene oxide and concretely comprise the following steps：By natural scale stone
Pour into three-necked flask after ink powder, the concentrated sulfuric acid, concentrated phosphoric acid and potassium permanganate mixing, at room temperature mechanical agitation 30min, then will
Three-necked flask is put into water-bath, and constant temperature stirs 12h at 50 DEG C, then stops heating, continues mechanical agitation, and frozen water is mixed
Compound is slowly added into three-necked flask, then adds H2O2Solution, the reaction was continued 1h stand overnight, add HCl solution, stir
The mixed liquor taken out after uniformly in three-necked flask is poured into beaker, carries out repeatedly centrifugation washing to mixed liquor with distilled water, until
Upper solution is in neutrality, and then carrying out ultrasonic disperse to it obtains graphene oxide dispersion, by graphene oxide dispersion
Vacuum drying obtains solid graphene oxide (GO).
Preferably, the volume ratio of the step 2) KH570 and graphene oxide dispersion is 1：10-15.
By such scheme, the step 4) vacuum drying temperature is 90-100 DEG C, drying time 4-6h.
By such scheme, the step 4) condition of cure is：Successively in 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C points
1h is not cured.
For the present invention in order to prepare the full bio-based benzoxazine of low viscosity, it is raw material to select anacardol, laccol, chaff amine, used
Raw material anacardol, laccol, chaff amine belong to natural reproducible resource, and anacardol is extracted from cashew nut liquid, and laccol is the master of raw lacquer
Component is wanted, and chaff amine derives from plant waste such as cane suger, bagasse, rice husk, maize cob etc..Anacardol is in phenolic aldehyde ring
There are a kind of chain alkyl side chain thus make prepared benzoxazine viscosity low, laccol has the similar adjacent benzene two of two kinds of activity
Hydroxyl group, one of which phenolic hydroxy group can be used for the formation of benzoxazine ring, and another kind may participate in catalysis benzoxazine
Ring-opening reaction, thus improve with reactions such as the chaff amine with greater activity the crosslink density of benzoxazine colophony, it is prepared
Polybenzoxazine resin there is the glass transition temperature of higher, the mechanical property of higher and low water imbibition.
After the present invention uses the full bio-based benzoxazine monomer UFa of Material synthesis such as bio-based phenolic monomers, chaff amine, into one
Walk synthesis KH570 functional graphene oxides/bio-based benzoxazine colophony composite material due to the use of silane coupling agent at
Manage graphene oxide so that KGO has preferably dispersiveness relative to GO in bio-based benzoxazine colophony matrix.In addition,
Interacted between KGO and bio-based benzoxazine colophony matrix, form intermolecular hydrogen bonding and ester bond, therefore to biology
Hot property, mechanical property and the chemical reagent-resistant performance of base benzoxazine colophony have more obvious improvement result.
The beneficial effects of the present invention are：1st, the present invention is entirely biological with Material synthesis such as bio-based laccol, anacardol, chaff amine
Base benzoxazine monomer (CFa and UFa), raw material is environmentally protective, and whole preparation process is easy to operate, preparation condition temperature
With product yield is higher, and the full bio-based benzoxazine monomer can keep the characteristic of low viscosity at normal temperatures, easy to work
It is processed further and synthesizes in industry, there is higher economic value.2nd, it is provided by the invention to be based on full bio-based benzoxazine list
Body (CFa and UFa) is heating and curing and can obtain benzoxazine colophony, the side of laccol type benzoxazine colophony in resin curing process
More double bonds take part in extra cross-linking reaction in the alkyl fatty chain of base, further increase the crosslink density of solidfied material,
So that gained benzoxazine colophony has good mechanical property and heat resistance.3rd, KH570 functions provided by the present invention
Change graphene oxide/bio-based benzoxazine colophony composite material and handle graphene oxide due to the use of silane coupling agent so that
KGO has preferably dispersiveness, and KGO and bio-based benzoxazine colophony base relative to GO in benzoxazine colophony matrix
Interaction occurs between body and forms intermolecular hydrogen bonding and ester bond, therefore gained composite materials property is compared with thermal property
It is greatly improved, is with a wide range of applications in pure benzoxazine colophony.
Brief description of the drawings
Fig. 1 is organism-based raw material laccol (Urushiol) used and anacardol (Cardanol) in the embodiment of the present invention 1 and 2
Chemical structural drawing；
Fig. 2 is the synthetic reaction formula of the full bio-based benzoxazine UFa and CFa of low viscosity prepared by Examples 1 and 2；
Fig. 3 is the infrared spectrogram of the full bio-based benzoxazine UFa and CFa of low viscosity prepared by Examples 1 and 2；
Fig. 4 is the full bio-based benzoxazine UFa's of low viscosity prepared by embodiment 11H NMR spectras；
Fig. 5 is the full bio-based benzoxazine CFa's of low viscosity prepared by embodiment 21H NMR spectras；
Fig. 6 be the full bio-based benzoxazine UFa and CFa of low viscosity prepared by Examples 1 and 2 at room temperature and handstand shape
Photo under state；
Fig. 7 is the full bio-based benzoxazine resin PCFa (a) of low viscosity and PUFa prepared by Examples 1 and 2
(b) outside drawing；
Fig. 8 is the full bio-based benzoxazine resin PCFa (c) of low viscosity and PUFa prepared by Examples 1 and 2
(d) section SEM figures；
Fig. 9 is the storage modulu of the full bio-based benzoxazine resin PCFa and PUFa of low viscosity prepared by Examples 1 and 2
Scheme (a) and tan δ figures (b)；
Low viscosity full bio-based benzoxazine resin PUFas and PCFa of the Figure 10 prepared by Examples 1 and 2 is in N2Atmosphere
Under TGA curve maps；
Figure 11 is the FTIR spectrograms of the GO and KGO prepared by embodiment 3；
Figure 12 is connecing for full bio-based benzoxazine resin PCFa and the PUFa film of low viscosity prepared by Examples 1 and 2
Feeler photo；
Figure 13 is the XRD spectrum of the GO and KGO prepared by embodiment 3；
Figure 14 is at 25 DEG C, and the PUFa prepared by Examples 1 and 2 and PCFa are placed in distilled water in the suction of 0-30 days
Water rate curve；
Figure 15 is at 25 DEG C, and the PUFa prepared by Examples 1 and 2 and PCFa are placed in 10%HCl solution in 0-30
It water absorption rate curve；
Figure 16 is at 25 DEG C, and the PUFa prepared by Examples 1 and 2 and PCFa are placed in 10%NaOH solution in 0-30
It water absorption rate curve；
The SEM that Figure 17 is the GO (a) and KGO (b) prepared by embodiment 3 schemes；
Figure 18 is the SEM figures of the KGO/PUFa composite materials prepared by embodiment 3-5, wherein (a) is PUFa-
KGO0.1%；(b) it is PUFa-KGO0.3%；(c) it is PUFa-KGO0.5%；
Figure 19 is the SEM figures of the KGO/PCFa composite materials prepared by embodiment 6-8, wherein (a) is PCFa-
KGO0.1%；(b) it is PCFa-KGO0.3%；(c) it is PCFa-KGO0.5%.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
A kind of preparation of the full bio-based benzoxazine UFa of low viscosity, it is prepared as follows：
Laccol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Stirred evenly into 250mL three-neck flasks, be warming up to the lower reaction 2h of 110 DEG C of stirrings, reaction product is dissolved in chloroform after having reacted,
By obtained solution filter, with sodium hydroxide solution (25wt%) extract, and will extraction gained subnatant with distilled water clean to
Neutrality, then vacuum distillation remove solvent, and products obtained therefrom is dried, is further purified using column chromatography, obtained at room temperature
The full bio-based benzoxazine (UFa) of rufous.
The full bio-based benzoxazine UFa of above-mentioned preparation is taken to be placed in 100 DEG C of vacuum drying chamber dry 4h, then true
Cure as follows in empty drying box：140 DEG C (1h), 160 DEG C (1h), 180 DEG C (1h), 200 DEG C (1h), 220 DEG C (1h), Gu
Cooled to room temperature after the completion of change, obtains bio-based benzoxazine colophony material (being named as PUFa).
The chemical structural drawing of laccol used in the present embodiment (Urushiol) is as shown in Figure 1, synthetic reaction formula such as Fig. 2 of UFa
It is shown.
Full bio-based benzoxazine UFa infrared spectrograms manufactured in the present embodiment as shown in figure 3,1H NMR spectras such as Fig. 4
It is shown.
Photo under the photos and handstand state of UFa manufactured in the present embodiment at room temperature is as shown in Figure 6, it is seen that its viscosity
Relatively low, after tested, the viscosity of UFa manufactured in the present embodiment is 0.863Pa.s.Fig. 7 is the outer of PUFa (b) manufactured in the present embodiment
See figure, it is seen that PUFa flexibilities are higher, and it is 447MPa to measure prepared PUFa Young's modulus, and glass transition temperature is 143 DEG C,
The temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 395 DEG C and 427 DEG C, the carbon yield at 800 DEG C is 39%.
Fig. 8 is that the section SEM of PUFa (d) manufactured in the present embodiment schemes, it is observed that smooth surface, display brittleness is broken
The feature split.The storage modulu figure (a) of PUFa and tan δ figures (b) are as shown in Figure 9, it is known that its storage modulu under the conditions of 25 DEG C is
510.7MPa.PUFa is in N2TGA curve maps under atmosphere are as shown in Figure 10, it is known that the temperature T of PUFa weightlessness 5%5With weightlessness 10%
Temperature T10Respectively 395 DEG C and 427 DEG C.In addition carbon yields of the PUFa at 800 DEG C has higher heat surely for 39%, PUFa
The reason for qualitative is probably which increases polyphenyl since side base alkyl fatty chain of the laccol than anacardol has more double-strands
The more crosslinking points of Bing oxazine resins.Figure 12 is water droplet in the contact angle photo of PUFa films, water droplet connecing on PUFa films
Feeler is 86 °, shows that PUFa has stronger hydrophobicity.Figure 14-16 is respectively that PUFa manufactured in the present embodiment is placed in distillation
In the water absorption rate curve of 0-30 days in water, 10%HCl solution and 10%NaOH solution, it is known that it is in distilled water, HCl solution (matter
Measure fraction for 10%) and NaOH solution (mass fraction 10%) in immersion 30 days after water absorption rate be respectively 0.15%, 0.16%
With 1.03%, it is seen that PUFa has relatively low water absorption rate in acid, alkali and distilled water, has good acid-fast alkali-proof performance.
Embodiment 2
A kind of preparation of the full bio-based benzoxazine CFa of low viscosity, it is prepared as follows：
Anacardol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Enter into 250mL three-neck flasks and stir evenly, be warming up to the lower reaction 3h of 110 DEG C of stirrings, reaction product is dissolved in chlorine after having reacted
It is imitative, obtained solution is filtered, is extracted with sodium hydroxide solution, and extraction gained subnatant is cleaned to neutrality with distilled water,
Then vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography at room temperature, obtains rufous
Full bio-based benzoxazine (CFa).
The full bio-based benzoxazine CFa of above-mentioned preparation is taken to be placed in 100 DEG C of vacuum drying chamber dry 6h, then true
Cure as follows in empty drying box：140 DEG C (1h), 160 DEG C (1h), 180 DEG C (1h), 200 DEG C (1h), 220 DEG C (1h), Gu
Cooled to room temperature after the completion of change, obtains full bio-based benzoxazine colophony (being named as PCFa).
The chemical structural drawing of anacardol used in the present embodiment (Cardanol) is as shown in Figure 1, the synthetic reaction formula such as figure of CFa
Shown in 2.Full bio-based benzoxazine CFa infrared spectrograms manufactured in the present embodiment as shown in figure 3,1H NMR spectras such as Fig. 5 institutes
Show.
Photo under the photos and handstand state of CFa manufactured in the present embodiment at room temperature is as shown in Figure 6, it is seen that its viscosity
Relatively low, after tested, the CFa viscosity prepared by the present embodiment is 0.052Pa.s.Fig. 7 is the outer of PCFa (a) manufactured in the present embodiment
See figure, it is seen that PCFa flexibilities are higher, and it is 160MPa to measure prepared PCFa Young's modulus, and glass transition temperature is 85 DEG C,
The temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 372 DEG C and 399 DEG C, the carbon yield at 800 DEG C is 33%.
Fig. 8 be PCFa (c) manufactured in the present embodiment section SEM scheme, from figure can clearly observe threadiness and
Plastic deformation, because the introducing of long side chain causes these threadinesss and plastic deformation to absorb energy when hitting, so that
Good toughness is shown, in addition, for UFa, more double bonds have participated in extra reaction in alkyl fatty chain, this also increases
The crosslinking points of Polybenzoxazine resin, cause PUFa to have the crosslink density of higher than PCFa.The storage modulu figure (a) of PCFa
It is as shown in Figure 9 with tan δ figures (b), it is known that its storage modulu under the conditions of 25 DEG C is 203.2MPa.PCFa is in N2TGA under atmosphere
Curve map is as shown in Figure 10, it is known that the temperature T of PCFa weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 372 DEG C and 399 DEG C.
In addition, carbon yields of the PCFa at 800 DEG C is 33%, illustrate that PUFa has higher heat endurance, it may be possible to due to laccol ratio
The side base alkyl fatty chain of anacardol has more double-strands, and which increases the more crosslinking points of Polybenzoxazine resin.Cause
This, the crosslink density of PUFa can also be better than PCFa apparently higher than PCFa, the heat endurance of PUFa.Figure 12 is water droplet in PCFa films
Contact angle photo, contact angle of the water droplet on PCFa films be 68 °, show that PUFa has stronger hydrophobicity.Figure 14-16 points
PCFa manufactured in the present embodiment Wei be placed in distilled water, 10%HCl solution and 10%NaOH solution in the water suction of 0-30 days
Rate curve, its immersion 30 day in distilled water, HCl solution (mass fraction 10%) and NaOH solution (mass fraction 10%)
Water absorption rate is respectively 0.21%, 0.23% and 0.66% afterwards, illustrates that PCFa has relatively low water suction in acid, alkali and distilled water
Rate, has good acid-fast alkali-proof performance.
Embodiment 3
A kind of full bio-based benzoxazine UFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PUFa-KGO), it is prepared as follows：
Laccol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Stirred evenly into 250mL three-neck flasks, be warming up to the lower reaction 2h of 120 DEG C of stirrings, reaction product is dissolved in chloroform after having reacted,
By obtained solution filter, with sodium hydroxide solution (25wt%) extract, and will extraction gained subnatant with distilled water clean to
Neutrality, then vacuum distillation remove solvent, and products therefrom is dried, is further purified using column chromatography, obtained at room temperature
The full bio-based benzoxazine (UFa) of brownish black.
Graphene oxide (GO), specific method are prepared with improved Hummers methods：By natural flake graphite powder 2g, dense sulphur
Poured into after sour 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min, this
Shi Fanying releases big calorimetric, and solution is in blackish green, and then three-necked flask is put into water-bath, stirs 12h in 50 DEG C of constant temperature, fills
Divide reaction, stop heating, continue mechanical agitation, solution is in lilac at this time, will shift to an earlier date ready mixture of ice and water 267mL and delay
Slow to add in three-necked flask, solution can become aubergine at this time, then add the H that mass fraction is 2mL 30%2O2Solution, it is molten
Liquid can become golden yellow, the reaction was continued 1h, stand overnight, add the HCl solution that mass fraction is 10%, taken after stirring evenly
The mixed liquor gone out in three-necked flask is poured into beaker, carries out repeatedly centrifugation washing to mixed liquor with the distilled water prepared, until
Upper solution is in neutrality, and then carrying out ultrasonic disperse to it can obtain graphene oxide dispersion, and graphene oxide is disperseed
Liquid can obtain solid graphene oxide (GO) after being placed in 60 DEG C of vacuum drying chamber fully drying.
The graphene oxide of 0.1g is added in 100mL absolute ethyl alcohols, uniform dispersion liquid is formed after ultrasonic disperse, then
With the pH value of 10wt%HCl solution adjusting dispersion liquid to 3-4, then by γ-methacryloxy third of 10mL purity 95%
Base trimethoxy silane (KH570) is added slowly with stirring in graphene oxide dispersion, and is fully reacted at 60 DEG C
24h, then multiple centrifuge washing is carried out to gained mixed solution with absolute ethyl alcohol and deionized water respectively, then by solid ultrasound point
Dissipate and KH570 functional graphene oxides (KGO) dispersion liquid is obtained in deionized water, finally by KH570 functionalization graphite oxides
Alkene dispersion liquid can obtain solid KH570 functional graphene oxides after being placed in 60 DEG C of vacuum drying chamber fully drying
(KGO)。
The KGO and full bio-based benzoxazine UFa of above-mentioned preparation are taken according to 0.1：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic disperse 1h, obtains dispersed mixed solution, and the mixed solution prepared then is placed in 100 DEG C
Dry 5h, then cures as follows in vacuum drying chamber in vacuum drying chamber：140℃(1h)、160℃(1h)、180℃
(1h), 200 DEG C (1h), 220 DEG C (1h), cooled to room temperature after the completion of curing, obtains functional graphene oxide/full biology
Base benzoxazine colophony composite material (being named as PUFa-KGO0.1%).
After tested, PUFa-KGO0.1% Young's modulus manufactured in the present embodiment is 710MPa, and glass transition temperature is
157 DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 438 DEG C and 451 DEG C, the carbon yield at 800 DEG C is
43%.Figure 11 is the FTIR spectrograms of GO manufactured in the present embodiment and KGO, comparing function graphene oxide and graphene oxide
Knowable to infrared spectrogram, 1053cm-1And 1225cm-1C-O stretching vibration peaks at place disappear and in 1089cm-1Place occur Si-
The stretching vibration peak of O-Si and Si-O-C, this is primarily due to a silicone hydroxyl part and the oxygen that silane coupling agent hydrolysis produces
Graphite alkene reacts, what another part alkoxy hydrolytic condensation was formed.In addition, in 2923cm-1And 2846cm-1Go out
Showing new absworption peak, the two absworption peaks correspond respectively to the stretching vibration of the methyl and methylene in silane coupling agent,
1627cm-1The C=C flexural vibrations peaks enhancing at place, is primarily due to KH570 and introduces new C=C with graphite oxide alkene reaction,
Cause the increase of C=C quantity.These changes of infrared spectrogram all demonstrate graphene oxide, and there occurs anti-with silane coupling agent
Should.Figure 13 is the XRD spectrum of GO and KGO, and as seen from the figure, GO a sharp diffraction maximum, the spy with GO nearby occurs at 10.9 °
It is consistent to levy diffraction maximum, it was demonstrated that GO has successfully been prepared by native graphite.According to Bragg equation 2dSin θ=n λ, Ke Yiji
Calculate the prepared corresponding interlamellar spacing d=0.811nm of GO.After functionalization being carried out with KH570 to GO, the diffraction maximum of KGO
Deviate to the left, nearby diffraction maximum occur at 10.3 °.According to Bragg equation 2dSin θ=n λ, can calculate prepared
The corresponding interlamellar spacing d=0.858nm of KGO.It follows that the interlamellar spacing of KGO is greater than the interlamellar spacing of GO, this is primarily due to
On KGO molecules after success grafted silane coupling agent, cause the distance increase of the piece interlayer of GO, it was demonstrated that silane coupling agent is successfully right
GO is modified.The SEM that Figure 17 is GO (a) and KGO (b) schemes, it can be seen that the surface of GO and KGO all has obvious pleat
Wrinkle pattern, but the fold on GO surfaces is some larger, and surface globality is also more stronger.And after coupling agent modified
KGO surfaces globality is poor, and fold becomes small and more, its surface is divided into many parts, this is because after coupling agent modified
KGO surfaces have macromolecular chain, and the π for hindering graphene oxide layer is stacked, this feature also causes KGO to have in resin matrix
There is more preferable dispersiveness.
Embodiment 4
A kind of full bio-based benzoxazine UFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PUFa-KGO), it is prepared as follows：
Laccol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.005mol, number-average molecular weight 600) are added
Stirred evenly into 250mL three-neck flasks, be warming up to the lower reaction 3h of 120 DEG C of stirrings, reaction product is dissolved in chloroform after having reacted,
Obtained solution is filtered, is extracted with sodium hydroxide solution, and extraction gained subnatant is cleaned to neutrality with distilled water, then
Vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography, obtained rufous and give birth to entirely at room temperature
Thing base benzoxazine (UFa).
Graphene oxide (GO), specific method are prepared with improved Hummers methods：By natural flake graphite powder 2g, dense sulphur
Poured into after sour 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min, this
Shi Fanying releases big calorimetric, and solution is in blackish green, and then three-necked flask is put into water-bath, stirs 12h in 50 DEG C of constant temperature, fills
Divide reaction.Stop heating, continue mechanical agitation, solution is in lilac at this time.Ready mixture of ice and water 267mL will be shifted to an earlier date to delay
Slow to add in three-necked flask, solution can become aubergine at this time, then add the H that mass fraction is 2mL 30%2O2, solution meeting
Become golden yellow, the reaction was continued 1h is stood overnight.It is 10%HCl to add mass fraction, and three-necked flask is taken out after stirring evenly
In mixed liquor pour into beaker, repeatedly centrifugation washing is carried out to mixed liquor with the distilled water prepared, until upper solution is in
Neutrality, then carries out ultrasonic disperse to it and can obtain graphene oxide dispersion, graphene oxide dispersion is placed in 60 DEG C
Vacuum drying chamber in it is fully dry after can obtain solid graphene oxide (GO).
The graphene oxide of 0.1g is added in 100mL absolute ethyl alcohols, uniform dispersion liquid is formed after ultrasonic disperse, then
With hydrochloric acid solution adjust dispersion liquid pH value arrive 3-4, then by 10mL purity for 95% γ-methacryloxypropyl three
Methoxy silane (KH570) is added slowly with stirring in graphene oxide dispersion, and the fully reaction 25h at 65 DEG C,
Multiple centrifuge washing is carried out to obtained mixed solution with absolute ethyl alcohol and deionized water respectively again, then ultrasonic disperse in go from
KH570 functional graphene oxides (KGO) dispersion liquid is obtained in sub- water, finally by KH570 functional graphene oxide dispersion liquids
After fully drying is placed in vacuum drying chamber can obtain solid KH570 functional graphene oxides (KGO).
The KGO and full bio-based benzoxazine UFa of above-mentioned preparation are taken according to 0.3：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic disperse 1h, obtains dispersed mixed solution, and the mixed solution prepared then is placed in 100 DEG C
Dry 6h, then cures as follows in vacuum drying chamber in vacuum drying chamber：140℃(1h)、160℃(1h)、180℃
(1h), 200 DEG C (1h), 220 DEG C (1h), cooled to room temperature after the completion of curing, obtains functional graphene oxide/full biology
Base benzoxazine colophony composite material (being named as PUFa-KGO0.3%).
After tested, PUFa-KGO0.3% Young's modulus manufactured in the present embodiment is 962MPa, and glass transition temperature is
159 DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 440 DEG C and 452 DEG C, the carbon yield at 800 DEG C is
44%.
Embodiment 5
A kind of full bio-based benzoxazine UFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PUFa-KGO), it is prepared as follows：
Laccol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Stirred evenly into 250mL three-neck flasks, be warming up to the lower reaction 2h of 110 DEG C of stirrings, reaction product is dissolved in chloroform after having reacted,
Obtained solution is filtered, is extracted with sodium hydroxide solution, and extraction gained subnatant is cleaned to neutrality with distilled water, then
Vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography, obtained rufous and give birth to entirely at room temperature
Thing base benzoxazine (UFa).
Graphene oxide (GO), specific method are prepared with improved Hummers methods：By natural flake graphite powder 2g, dense sulphur
Poured into after sour 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min, this
Shi Fanying releases big calorimetric, and solution is in blackish green, and then three-necked flask is put into water-bath, stirs 12h in 50 DEG C of constant temperature, fills
Divide reaction.Stop heating, continue mechanical agitation, solution is in lilac at this time.Ready mixture of ice and water 267mL will be shifted to an earlier date to delay
Slow to add in three-necked flask, solution can become aubergine at this time, then add the H that mass fraction is 2mL 30%2O2, solution meeting
Become golden yellow the reaction was continued 1h, stand overnight.It is 10%HCl to add mass fraction, and three-necked flask is taken out after stirring evenly
In mixed liquor pour into beaker, repeatedly centrifugation washing is carried out to mixed liquor with the distilled water prepared, until upper solution is in
Neutrality, then carries out ultrasonic disperse to it and can obtain graphene oxide dispersion, graphene oxide dispersion is placed in 60 DEG C
Vacuum drying chamber in it is fully dry after can obtain solid graphene oxide (GO).
The graphene oxide of 0.1g is added in 150mL absolute ethyl alcohols, uniform dispersion liquid is formed after ultrasonic disperse, then
With hydrochloric acid solution adjust dispersion liquid pH value arrive 3-4, then by 10mL purity for 95% γ-methacryloxypropyl three
Methoxy silane (KH570) is added slowly with stirring in graphene oxide dispersion, and the fully reaction 24h at 60 DEG C,
Multiple centrifuge washing is carried out to obtained mixed solution with absolute ethyl alcohol and deionized water respectively again, removes unreacted KH570,
And solution is in neutrality, then it is scattered to obtain KH570 functional graphene oxides (KGO) in deionized water for ultrasonic disperse
Liquid, can obtain after KH570 functional graphene oxide dispersion liquids are finally placed in 60 DEG C of vacuum drying chamber fully drying
Solid KH570 functional graphene oxides (KGO).
The KGO and full bio-based benzoxazine UFa of above-mentioned preparation are taken according to 0.5：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic 1h, obtains dispersed mixed solution, then the mixed solution prepared is placed in 100 DEG C of vacuum
Dry 6h, then cures as follows in vacuum drying chamber in drying box：140℃(1h)、160℃(1h)、180℃
(1h), 200 DEG C (1h), 220 DEG C (1h), cooled to room temperature after the completion of curing, obtains functional graphene oxide/full biology
Base benzoxazine colophony composite material (being named as PUFa-KGO0.5%).
After tested, PUFa-KGO0.5% Young's modulus manufactured in the present embodiment is 848MPa, and glass transition temperature is
165 DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 442 DEG C and 454 DEG C, the carbon yield at 800 DEG C is
45%.
Figure 18 is the SEM figures of KGO/PUFa composite materials prepared by embodiment 3-5, wherein (a) is PUFa-KGO0.1%；
(b) it is PUFa-KGO0.3%；(c) it is PUFa-KGO0.5%, it is seen that with the increase of KGO contents, the section of composite material becomes
Must be more and more coarse, the micropore quantity on section is also gradually increasing, this is that KGO is uniformly dispersed, is crosslinked in laccol type benzo
Caused by good covalent attachment being formd in oxazine resin matrix and with laccol type benzoxazine colophony matrix.When material is subject to
During external forces, micropore can also absorb substantial amounts of energy, prevent stress concentration, prevent the extension of crackle, so as to improve
The mechanical property of material.
Embodiment 6
A kind of full bio-based benzoxazine CFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PCFa-KGO), it is prepared as follows：
Anacardol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.005mol, number-average molecular weight 600) are added
Enter into 250mL three-neck flasks and stir evenly, be warming up to the lower reaction 2h of 110 DEG C of stirrings, reaction product is dissolved in chlorine after having reacted
It is imitative, obtained solution is filtered, is extracted with sodium hydroxide solution (25wt%), and extraction gained subnatant is cleaned with distilled water
To neutrality, then vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography, obtained at room temperature
To the full bio-based benzoxazine (CFa) of rufous.
Graphene oxide (GO), specific method are prepared with improved Hummers methods：By natural flake graphite powder 2g, dense sulphur
Poured into after sour 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min, this
Shi Fanying releases big calorimetric, and solution is in blackish green, and then three-necked flask is put into water-bath, stirs 12h in 50 DEG C of constant temperature, fills
Divide reaction.Stop heating, continue mechanical agitation, solution is in lilac at this time.Ready mixture of ice and water 267mL will be shifted to an earlier date to delay
Slow to add in three-necked flask, solution can become aubergine at this time, then add the H that mass fraction is 2mL 30%2O2, solution meeting
Become golden yellow, the reaction was continued 1h is stood overnight.It is 10%HCl to add mass fraction, and three-necked flask is taken out after stirring evenly
In mixed liquor pour into beaker, repeatedly centrifugation washing is carried out to mixed liquor with the distilled water prepared, until upper solution is in
Neutrality, then carries out ultrasonic disperse to it and can obtain graphene oxide dispersion, graphene oxide dispersion is placed in 60 DEG C
Vacuum drying chamber in it is fully dry after can obtain solid graphene oxide (GO).
The graphene oxide of 0.1g is added in 150mL absolute ethyl alcohols, uniform dispersion liquid is formed after ultrasonic disperse, then
With the pH value of hydrochloric acid solution adjusting dispersion liquid to 3-4, then by 10mL γ-methacryloxypropyl trimethoxy silane
(KH570) it is added slowly with stirring in graphene oxide dispersion, and the fully reaction 20h, then with anhydrous second at 60 DEG C
Alcohol and deionized water carry out multiple centrifuge washing to obtained mixed solution, remove unreacted KH570, and make it that solution is in
Property, then ultrasonic disperse obtains KH570 functional graphene oxides (KGO) dispersion liquid in deionized water, finally by KH570 work(
Can change after graphene oxide dispersion is placed in 60 DEG C of vacuum drying chamber fully drying can obtain solid KH570 functionalization
Graphene oxide (KGO).
The KGO and full bio-based benzoxazine CFa of above-mentioned preparation are taken according to 0.1：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic 1h, obtains dispersed mixed solution, then the mixed solution prepared is placed in 100 DEG C of vacuum
Dry 4h, then cures as follows in vacuum drying chamber in drying box：140℃(1h)、160℃(1h)、180℃
(1h), 200 DEG C (1h), 220 DEG C (1h), cooled to room temperature after the completion of curing, obtains functional graphene oxide/full biology
Base benzoxazine colophony composite material (being named as PCFa-KGO0.1%).
After tested, PCFa-KGO0.1% Young's modulus manufactured in the present embodiment is 378MPa, glass transition temperature 98
DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 399 DEG C and 425 DEG C, the carbon yield at 800 DEG C is
39%.
Embodiment 7
A kind of full bio-based benzoxazine CFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PCFa-KGO), it is prepared as follows：
Anacardol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Enter into 250mL three-neck flasks and stir evenly, be warming up to the lower reaction 2h of 120 DEG C of stirrings, reaction product is dissolved in chlorine after having reacted
It is imitative, obtained solution is filtered, is extracted with sodium hydroxide solution, and extraction gained subnatant is cleaned to neutrality with distilled water,
Then vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography at room temperature, obtains rufous
Full bio-based benzoxazine (CFa).
Graphene oxide (GO), specific method are prepared with improved Hummers methods：By natural flake graphite powder 2g, dense sulphur
Poured into after sour 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min, this
Shi Fanying releases big calorimetric, and solution is in blackish green, and then three-necked flask is put into water-bath, stirs 12h in 50 DEG C of constant temperature, fills
Divide reaction, then stop heating, continuation mechanical agitation, solution is in lilac at this time.Ready mixture of ice and water will be shifted to an earlier date
267mL is slowly added into three-necked flask, and solution can become aubergine at this time, then adds the H that mass fraction is 2mL 30%2O2,
Solution can become golden yellow, the reaction was continued 1h, stand overnight.It is 10%HCl to add mass fraction, and three are taken out after stirring evenly
Mixed liquor in mouth flask is poured into beaker, repeatedly centrifugation washing is carried out to mixed liquor with the distilled water prepared, until upper strata
Solution is in neutrality, and then carrying out ultrasonic disperse to it can obtain graphene oxide dispersion, and graphene oxide dispersion is put
In 60 DEG C of vacuum drying chamber solid graphene oxide (GO) can be obtained after abundant drying.
The graphene oxide of 0.1g is added in 100mL absolute ethyl alcohols, uniform dispersion liquid is formed after ultrasonic disperse, then
With the pH value of 10%HCl solution adjusting dispersion liquid to 3-4, then by 10mL γ-methacryloxypropyl trimethoxy silicon
Alkane (KH570) is added slowly with stirring in graphene oxide dispersion, and the fully reaction 23h at 65 DEG C.Again with anhydrous
Ethanol and deionized water carry out multiple centrifuge washing to obtained mixed solution, remove unreacted KH570, and make it that solution is in
It is neutral.Then carry out ultrasonic disperse and can obtain KH570 functional graphene oxides (KGO) dispersion liquid, by KH570 functionalization oxygen
Graphite alkene dispersion liquid can obtain solid KH570 functionalization oxidation stone after being placed in 60 DEG C of vacuum drying chamber fully drying
Black alkene (KGO).
The KGO and full bio-based benzoxazine CFa of above-mentioned preparation are taken according to 0.3：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic 1h, obtains dispersed mixed solution, then the mixed solution prepared is placed in 100 DEG C of vacuum
It is dry in drying box, then cure as follows in vacuum drying chamber：140℃(1h)、160℃(1h)、180℃(1h)、
200 DEG C (1h), 220 DEG C (1h), cooled to room temperature after the completion of curing, obtains composite material and (is named as PCFa-
KGO0.3%).
After tested, the PCFa-KGO0.3% Young's modulus prepared by the present embodiment is 570MPa, and glass transition temperature is
107 DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 427 DEG C and 444 DEG C, the carbon yield at 800 DEG C is
41%.
Embodiment 8
A kind of full bio-based benzoxazine CFa and its KH570 functional graphene oxide of low viscosity/full bio-based Ben Bing Evil
The preparation of piperazine resin composite materials (PCFa-KGO), it is prepared as follows：
Anacardol (0.05mol), chaff amine (0.05mol) and paraformaldehyde (0.01mol, number-average molecular weight 300) are added
Enter into 250mL three-neck flasks and stir evenly, be warming up to the lower reaction 2h of 110 DEG C of stirrings, reaction product is dissolved in chlorine after having reacted
It is imitative, obtained solution is filtered, is extracted with sodium hydroxide solution, and extraction gained subnatant is cleaned to neutrality with distilled water,
Then vacuum distillation removes solvent, and products therefrom is dried, is further purified using column chromatography at room temperature, obtains rufous
Full bio-based benzoxazine (CFa).
Graphene oxide (GO) is prepared with improved Hummers methods, specific method is：By natural flake graphite powder 2g, dense
Poured into after sulfuric acid 220mL, concentrated phosphoric acid 27mL and potassium permanganate 12g mixing in three-necked flask, at room temperature mechanical agitation 30min,
Big calorimetric is released in reaction at this time, and solution is in blackish green, and then three-necked flask is put into water-bath, and 12h are stirred in 50 DEG C of constant temperature,
Fully reaction.Stop heating, continue mechanical agitation, solution is in lilac at this time.Ready mixture of ice and water 267mL will be shifted to an earlier date
It is slowly added into three-necked flask, solution can become aubergine at this time, then add the H that mass fraction is 2mL 30%2O2, solution
It can become golden yellow, the reaction was continued 1h is stood overnight.It is 10%HCl to add mass fraction, and three mouthfuls of burnings are taken out after stirring evenly
Mixed liquor in bottle is poured into beaker, repeatedly centrifugation washing is carried out to mixed liquor with the distilled water prepared, until upper solution
It is in neutrality, then carrying out ultrasonic disperse to it can obtain graphene oxide dispersion, and graphene oxide dispersion is placed in 60
DEG C vacuum drying chamber in it is fully dry after can obtain solid graphene oxide (GO).
The graphene oxide of 0.1g is added in 100mL absolute ethyl alcohols, it is 1mg/mL's that concentration is obtained after ultrasonic disperse
Graphene dispersing solution, adds the pH value of suitable 10%HCl solution adjusting dispersion liquid to 3-4, it is in faintly acid to make it, then will
γ-methacryloxypropyl trimethoxy silane (KH570) that 10mL purity is 95% is added slowly with stirring oxygen
In graphite alkene dispersion liquid, and it is heated at 60 DEG C fully reacting 24h, then respectively with absolute ethyl alcohol and deionized water to obtaining
Mixed solution carries out multiple centrifuge washing, removes unreacted KH570, and solution is in neutrality, and then ultrasonic disperse is in going
KH570 functional graphene oxides (KGO) dispersion liquid is obtained in ionized water, finally disperses KH570 functional graphene oxides
Liquid can obtain solid KH570 functional graphene oxides (KGO) after being placed in 60 DEG C of vacuum drying chamber fully drying.
The KGO and full bio-based benzoxazine CFa of above-mentioned preparation are taken according to 0.5：100 mass ratio mixing, in room temperature
Lower stirring 2h, ultrasonic disperse 1h, obtains dispersed mixed solution, and the mixed solution prepared then is placed in 100 DEG C
It is dry in vacuum drying chamber, then cure as follows in vacuum drying chamber：140℃(1h)、160℃(1h)、180℃
(1h), 200 DEG C (1h), 220 DEG C (1h), cooled to room temperature obtains composite material and (is named as PCFa- after completion cures
KGO0.5%).
After tested, PCFa-KGO0.5% Young's modulus obtained by the present embodiment is 487MPa, glass transition temperature 115
DEG C, the temperature T of weightlessness 5%5With the temperature T of weightlessness 10%10Respectively 460 DEG C and 475 DEG C, PCFa-KGO0.5% is at 800 DEG C
Carbon yield be 46%.
Figure 19 is the SEM figures of the KGO/PCFa composite materials prepared by embodiment 6-8, wherein (a) is PCFa-
KGO0.1%；(b) it is PCFa-KGO0.3%；(c) it is PCFa-KGO0.5%, as seen from the figure, it is seen that with the increasing of KGO contents
Add, the section of composite material becomes more and more coarse, and the micropore quantity on section is also gradually increasing, this is that KGO equably divides
Dissipate, be crosslinked in cashew nut phenolic benzoxazine colophony matrix and formd with cashew nut phenolic benzoxazine colophony matrix good
Caused by covalent attachment.When material is subject to external forces, micropore can also absorb substantial amounts of energy, prevent stress concentration, resistance
The extension of crack arrest line, so as to improve the mechanical property of material.
Thus illustrate, the full bio-based benzoxazine UFa and CFa of low viscosity prepared by the present invention, at room temperature with liquid
Form exists, and is conducive to industrial processes production.And KH570 functional graphene oxides/full bio-based benzene prepared by the present invention
And oxazine resin composite materials (PUFa-KGO and PCFa-KGO) Young's modulus and Good Heat-resistance, there is good mechanicalness
Energy and thermo-chemical stability.
The claimed scope of the invention is by affiliated claims and its equivalent thereof.It is each cited by the present invention
Raw material, and bound, the section value of each raw material of the present invention, and the bound of technological parameter (such as temperature, time), area
Between value can realize the present invention, embodiment numerous to list herein.The above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope, various changes and modifications of the present invention are possible, these changes
Change and improvement is both fallen within the range of claimed invention.
Claims (8)
1. a kind of full bio-based benzoxazine of low viscosity, it is characterised in that it is by bio-based phenolic monomers, chaff amine and paraformaldehyde
Polymerisation obtains under conditions of solvent is not added, wherein the bio-based phenolic monomers are anacardol or laccol.
2. the full bio-based benzoxazine of low viscosity according to claim 1, it is characterised in that the bio-based phenols list
Body, chaff amine and paraformaldehyde molar ratio are 1-1.2：1-1.2：0.1-0.2.
3. the preparation method of the full bio-based benzoxazine of low viscosity described in a kind of claim 1 or 2, it is characterised in that specific
Step is as follows：Bio-based phenolic monomers, chaff amine and paraformaldehyde are mixed in proportion, are warming up to 110-120 DEG C of reaction 2-
3h, is dissolved in chloroform after having reacted by reaction product, and obtained solution is filtered, is extracted with sodium hydroxide solution, and will extract institute
Obtain subnatant to be cleaned to neutrality with distilled water, be then evaporated under reduced pressure and remove solvent, products therefrom purifies to obtain low using column chromatography
The full bio-based benzoxazine of viscosity.
4. the Polybenzoxazine resin that the full bio-based benzoxazine of low viscosity described in a kind of claim 1 or 2 cures, its
It is characterized in that, the curing is：Cure 1h respectively in 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C successively.
5. a kind of full bio-based benzoxazine of low viscosity described in claim 1 or 2 with functional graphene oxide is compound obtains
Functional graphene oxide/full bio-based benzoxazine colophony composite material.
A kind of 6. preparation of functional graphene oxide/full bio-based benzoxazine colophony composite material described in claim 5
Method, it is characterised in that comprise the following steps that：
1) preparation of graphene oxide：Graphene oxide is prepared with improved Hummers methods；
2) preparation of functional graphene oxide：Graphene oxide obtained by step 1) is added in absolute ethyl alcohol, ultrasonic disperse is equal
It is even to obtain the graphene dispersing solution that concentration is 0.5-1.5mg/mL, graphene dispersing solution pH value is adjusted to 3-4, then in stirring bar
γ-methacryloxypropyl trimethoxy silane is added under part, is heated to 60-65 DEG C of reaction 20-25h, after reaction
Centrifuge washing is carried out to gained reaction solution with absolute ethyl alcohol and deionized water respectively, then ultrasonic disperse obtains in deionized water
KH570 functional graphene oxide dispersion liquids, KH570 functional graphene oxide dispersion liquids finally be dried in vacuo to obtain
KH570 functional graphene oxides；
3) preparation of the full bio-based benzoxazine of low viscosity：Bio-based phenolic monomers, chaff amine are mixed in proportion with paraformaldehyde
Uniformly, 110-120 DEG C of reaction 2-3h is warming up to, reaction product is then dissolved in chloroform, obtained solution is filtered, and use hydrogen-oxygen
Change sodium solution extraction, extraction gained subnatant is cleaned to neutrality, then vacuum distillation with distilled water and removes solvent, products therefrom
Purify to obtain the full bio-based benzoxazine of low viscosity using column chromatography；
4) preparation of functional graphene oxide/full bio-based benzoxazine colophony composite material：KH570 prepared by step 2)
The full bio-based benzoxazine 0.1-0.5 in mass ratio of low viscosity that functional graphene oxide is prepared with step 3)：100 mixing are equal
It is even, and ultrasonic disperse obtains mixed solution, and the vacuum drying of gained mixed solution, curing then are obtained functionalization graphite oxide
Alkene/full bio-based benzoxazine colophony composite material.
7. preparation method according to claim 6, it is characterised in that the step 4) vacuum drying temperature is 90-100
DEG C, drying time 4-6h.
8. preparation method according to claim 6, it is characterised in that the step 4) condition of cure is：Successively in 140
DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C cure 1h respectively.
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