CN107501853A - A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof - Google Patents

A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof Download PDF

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CN107501853A
CN107501853A CN201710651693.4A CN201710651693A CN107501853A CN 107501853 A CN107501853 A CN 107501853A CN 201710651693 A CN201710651693 A CN 201710651693A CN 107501853 A CN107501853 A CN 107501853A
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CN107501853B (en
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葛曷
葛曷一
张文博
姚亚琳
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University of Jinan
Beijing Composite Material Co Ltd
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Beijing Composite Material Co Ltd
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The present invention relates to a kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof, first using nano-particles self assemble technology, Nano-meter SiO_2 is utilized2Reduced by GO functionalization, and to GO, form functionalization rGO.By controlling Nano-meter SiO_2 in hybrid material2With GO ratio, the factor such as the concentration of reducing agent, dosage so that hybrid material plays cooperative effect while ensureing dispersed, effectively improves the heat resistance of phenolic resin.The introducing of nano material can not only improve the heat resistance of resin, while can also improve the combination properties such as the mechanical property of resin, be advantageous to expand its application, have good development prospect in the research application aspect of modified resin base ablation resistant material.

Description

A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof
Technical field
The present invention relates to a kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof, belong to polymer The technical field of based composites.
Background technology
Exploration of the progress and the mankind of science to the outer space, make heat resistance and ablation property of the people to ablative composite material Propose higher requirement.Phenolic resin (PF) has excellent heat resistance and good process industrial art performance, is widely used as The main base of ablation resistant material.But the heat resistance of phenolic resin, manufacturability and mechanical property are still difficult to meet current space The demand of boat ablation resistant material.In order to further improve the performance of ablator, it is necessary to which phenolic resin is modified.
The modification of phenolic resin can be carried out by blocking phenolic hydroxyl group and introducing other components two ways, wherein, introducing is received Rice material carry out it is heat resistance modified be conventional positive effect method of modifying.
Graphene is a kind of tightly packed carbonaceous new material into individual layer bi-dimensional cellular shape lattice structure of carbon atom.Due to it Unique structure, the features such as showing excellent thermal stability, mechanical property, electric conductivity, be to prepare advanced composite material Preferable reinforcement.Graphene oxide（GO）The intermediate product that chemical method prepares graphene, its surface contain hydroxyl, carboxyl, The substantial amounts of active function groups such as epoxy radicals, make it have certain activity.The GO and redox graphene (rGO) of sheet are logical Cross absorption heat and form barrier obstruction heat propagation, so, more and more it is used in the modification of phenolic resin.Xuwei Hua Qi Master's thesis《Graphene oxide/Phenolic Resin In situ Composites prepare and performance》Studied in (Guilin University of Technology, 2013) Show, GO is added in phenolic resin by way of in-situ polymerization, can significantly improve the hot property of compound resin.There is document To record, rGO heat resistance is better than GO, but because active group is reduced disappearance, so rGO is scattered compared with GO in resin It is difficult.In existing research, the method that rGO is directly used for the improved heat resistance of resin is rarely reported.
Silica (SiO2) nano particle is unformed white powder, there is special interface performance and bulk effect. Nano-meter SiO_22It is spherical rigid nano-particle, specific surface area is big, adsorption capacity is strong, size is small, in the side such as thermal resistance, resistance, fusing point Face shows specific function compared with conventional material.Other Nano-meter SiO_22There is stronger binding ability with polymer, can be to polymerization The physico-chemical property of thing matrix produces special role.By SiO2It is introduced into phenolic resin, heat-resisting, the intensity of phenolic resin can be improved Etc. performance.Patent CN104961872A discloses a kind of preparation method of nano-silicon dioxide modified phenolic resin, in synthesis phenol Silica is added during urea formaldehyde, nano-silicon dioxide modified phenolic resin is obtained by situ aggregation method.Due to dioxy The scattering problem of SiClx, its raising to phenolic resin heat resistance and unobvious.
Patent CN201410721476.4 uses nano silicon and graphene oxide hybrid material modified organic silicon tree Fat, improve the heat resistance of organic siliconresin.It is pointed out, because the huge surface area of graphene and strong Van der Waals force are not easy it In scattered and relatively low with the interaction force of matrix resin in resin matrix.And use two or more nano-particle The mode of hydridization can make nano-particle and resin matrix have fabulous compatibility and interface performance.However, its use it is miscellaneous It is Nano-meter SiO_2 to change particle2With GO, as it was previously stated, GO does not have rGO positive effects in terms of heat resistance is improved.
The content of the invention
It is an object of the invention to for the above-mentioned problems in the prior art, there is provided a kind of functionalization oxygen reduction fossil Black alkene phenol-formaldehyde resin modified, first by SiO2Hydridization is carried out with rGO, and functionalization SiO is made2- rGO hybrid materials（That is FSiO2- rGO）, then phenolic resin is carried out with it heat resistance modified, dispersion effect of the nano particle in resin matrix can be improved, it is modified The heat resistance of phenolic resin significantly improves afterwards.
Meanwhile present invention also offers the preparation method of functionalization redox graphene phenol-formaldehyde resin modified, solve Nano-particle is easily reunited in preparation process, is not easy the problem of dispersed in phenolic resin glue, improves phenolic aldehyde tree Ablation property, the heat resistance of fat.
Technical solution of the present invention is as follows：
A kind of functionalization redox graphene phenol-formaldehyde resin modified, is with FSiO2- rGO (functionalization SiO2- rGO hydridization materials Material) it is filler, phenolic resin is modified, includes the raw material of following parts by weight：100 parts of phenolic resin, FSiO2-rGO 0.5 ~1 part.
Further, the phenolic resin is thermosetting alcohol resite, its technical indicator：Free phenol 13~15%, Gu The % of body content 57~62, the mPas of viscosity 138~145, s/160 DEG C of gel time 100~120.
Further, the FSiO2- rGO, preparing raw material include Nano-meter SiO_22And GO；The Nano-meter SiO_22For spherical Grain, particle diameter is 80~100nm；The thickness of the GO is 0.9~1.5nm, a diameter of 2~5 μm of lamella, 1~2 layer of the number of plies.
Further, the FSiO2- rGO preparation method, step include：
1）By Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide, soaks 30min at 90 DEG C, be surface-treated, Wash, dry after immersion；
2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to 1~2h of stirring, make its hydrolysis, prepares Hydrolyzed silane solution；
3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2, 50~70 DEG C of heating water baths stir 30~60min of reaction is mixed, is then filtered, collects Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 50~100 DEG C of bakings It is dry；
4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.2~1.5mg/mL dispersion liquid, And it is 4.0~6.0 to adjust pH with glacial acetic acid；
5）The GO aqueous solution that concentration is 1~3mg/mL is added drop-wise to step 4）Dispersion liquid in, make GO and Nano-meter SiO_22Quality Than for 1:5~9, it is added dropwise to complete rear ultrasonic 60min, filters and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2- GO powder；
6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, then it is with 1M NaOH aqueous solution regulation pH 12.0,80 DEG C reaction 3h after, filter and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2- rGO powder；
7）By second alcohol and water according to volume ratio 9:1 mixing, it is 4.0~5.0 with glacial acetic acid regulation pH, benzene is then added dropwise while stirring Base silane modifying agent, it is 5.0wt% to be added dropwise to the concentration of phenyl silane modifying agent in the solution, continues 1~2h of stirring, makes modification Agent complete hydrolysis；
8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder, 50~70 DEG C of heating water bath stirring reactions 30 ~60min, then filter and use distilled water flushing filter cake to neutrality, it is last 50~100 DEG C dry, obtain FSiO2-rGO。
Preferably, step 1）In, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3 in the mixed liquor:1.
Preferably, the Nano-meter SiO_2 described in step 3)2With the matter of gamma-aminopropyl-triethoxy-silane in hydrolyzed silane solution Amount is than being 100:2.
Preferably, step 5）In, GO and Nano-meter SiO_22Mass ratio be 1:7.
Preferably, step 5）In, rate of addition is 1~2 drop/s.
Preferably, the SiO described in step 6)2- GO and NaBH4Mass ratio be 1:2.
Preferably, step 7）In, phenyl silane modifying agent is phenyltrimethoxysila,e, phenyl triethoxysilane or two Phenyidimethoxysilane.
Preferably, the SiO described in step 8)2- rGO powder and step 7）The mass ratio of phenyl silane modifying agent in solution For 100: 2.
Preferably, step 3）、7）、8）In, mixing speed is 100 turns/min.
A kind of preparation method of functionalization redox graphene phenol-formaldehyde resin modified, step include：
（1）Weigh FSiO2- rGO powder, 10~50mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2- RGO alcohol dispersion liquid；
（2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 600~1000r/ Min 20~30min of magnetic agitation, then 20~40min of ultrasonic disperse, then 1000~1500rpm/min magnetic agitations 40~ 50min, stirring and ultrasonic procedure keep 20~30 DEG C of system temperature, obtain mixed liquor；
（3）By step（2）Mixed liquor, it is that 0.01MPa vacuum defoamations handle 10~20min in vacuum, obtains well mixed tree Fat slurry, i.e. functionalization graphene phenol-formaldehyde resin modified.
Described functionalization graphene phenol-formaldehyde resin modified, curing are：Slurry is poured into mould, is put into baking oven 120 DEG C of constant temperature 2h, then 150 DEG C of constant temperature 2h are warming up to, 170 DEG C of isothermal curing 1h are finally warming up to, obtain phenolic resin sample.
To efficiently solve dispersiveness, the compatibility of the heat resistance of phenolic resin and nano-particle in resin matrix, this Invention uses nano-particles self assemble technology first, utilizes Nano-meter SiO_22Reduced by GO functionalization, and to GO, form work( RGO can be changed.By controlling Nano-meter SiO_2 in hybrid material2With GO ratio, the factor such as the concentration of reducing agent, dosage so that hydridization Material plays cooperative effect while ensureing dispersed, effectively improves the heat resistance of phenolic resin.The introducing of nano material is not It is only capable of improving the heat resistance of resin, while can also improves the combination properties such as the mechanical property of resin, is advantageous to expand its application Scope, there is good development prospect in the research application aspect of modified resin base ablation resistant material.
Beneficial effects of the present invention：
1. heat resistance modified to phenolic resin progress using the graphene of functionalization, method is simple, positive effect.
2. use Nano-meter SiO_22Hydridization is carried out with rGO, nano particle is improved and disperses in resin matrix, resistance to thermal effect Fruit is good.
3. by the GO reduction treatments in hybrid material, improve heat resistance.
4. SiO2Make it that heat resistance is optimal with rGO rational proportion.
Embodiment
Below by embodiment further description technical solution of the present invention.These descriptions are not that present invention is made It is further to limit.All equivalent substitutions made to present invention, or be correspondingly improved, still fall within protection scope of the present invention Within.
It is raw materials used in following embodiments：
Phenolic resin is thermosetting alcohol-soluble phenolic resin, its technical indicator：Free phenol 13~15%, the % of solids content 57~62, The mPas of viscosity 138~145, s/160 DEG C of gel time 100~120；
Nano-meter SiO_22For spheric granules, particle diameter is 80~100nm；
GO thickness is 0.9~1.5nm, a diameter of 2~5 μm of lamella, 1~2 layer of the number of plies.
First, FSiO is prepared2-rGO
Embodiment 1
A kind of FSiO2- rGO preparation method, step include：
1）By Nano-meter SiO_22It is put into the concentrated sulfuric acid and hydrogen peroxide（The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1）Mixed liquor in, 30min is soaked at 90 DEG C, is surface-treated, is washed after immersion, is dried；
2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to stir 2h, make its hydrolysis, prepare silicon Alkane hydrolyzate；
3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2（Nano-meter SiO_22With silane hydrolyzate The mass ratio of gamma-aminopropyl-triethoxy-silane is 100 in liquid:2）, 50 DEG C of heating water bath stirrings（100 turns/min）Reaction 60min, then filter, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 100 DEG C of drying；
4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.2mg/mL dispersion liquid, uses ice Vinegar acid for adjusting pH is 6.0；
5）The GO aqueous solution that concentration is 2mg/mL is added drop-wise to step 4）Dispersion liquid in, GO:Nano-meter SiO_22Mass ratio 1:5, drop Acceleration is 1 ~ 2 drop/s, is added dropwise to complete rear ultrasonic 60min, filters and uses distilled water flushing filter cake to neutrality, is freeze-dried, obtains SiO2- GO powder；
6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:2, adopt It is that 3 h are reacted at 12.0,80 DEG C with 1M NaOH aqueous solution regulation pH, filters and use distilled water flushing filter cake to neutrality, freeze Dry, obtain SiO2- rGO powder；
7）By second alcohol and water according to volume ratio 9:1 mixing, it is 4.0 with glacial acetic acid regulation pH, then side is stirred（100 turns/min）Side Phenyltrimethoxysila,e modifying agent is added dropwise, it is 5.0wt% to be added dropwise to the concentration of phenyltrimethoxysila,e in the solution, is continued 2h is stirred, makes modifying agent complete hydrolysis；
8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder（SiO2- rGO powder and step 7）In solution The mass ratio of phenyltrimethoxysila,e modifying agent is 100: 2）, 50 DEG C of heating water bath stirrings（100 turns/min）React 60min, Then filter and use distilled water flushing filter cake to neutrality, it is last 100 DEG C dry, obtain FSiO2-rGO。
Embodiment 2
A kind of FSiO2- rGO preparation method, step include：
1）By Nano-meter SiO_22It is put into the concentrated sulfuric acid and hydrogen peroxide（The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1）Mixed liquor in, 30min is soaked at 90 DEG C, is surface-treated, is washed after immersion, is dried；
2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to stir 1h, make its complete hydrolysis, make Standby hydrolyzed silane solution；
3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2（Nano-meter SiO_22With silane hydrolyzate The mass ratio of gamma-aminopropyl-triethoxy-silane is 100 in liquid:2）, 70 DEG C of heating water bath stirrings（100 turns/min）Reaction 30min, then filter, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 50 DEG C of drying；
4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.5mg/mL dispersion liquid, uses ice Vinegar acid for adjusting pH is 5.0；
5）The GO aqueous solution that concentration is 2mg/mL is added drop-wise to step 4）Dispersion liquid in, GO:Nano-meter SiO_22Mass ratio 1:9, drop Acceleration is 1 ~ 2 drop/s, is added dropwise to complete rear ultrasonic 60min, filters and uses distilled water flushing filter cake to neutrality, is freeze-dried, obtains SiO2- GO powder；
6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:2, adopt It is that 3 h are reacted at 12.0,80 DEG C with 1M NaOH aqueous solution regulation pH, filters and use distilled water flushing filter cake to neutrality, freeze Dry, obtain SiO2- rGO powder；
7）By second alcohol and water according to volume ratio 9:1 mixing, it is 5.0 with glacial acetic acid regulation pH, then side is stirred（100 turns/min）Side Phenyl triethoxysilane modifying agent is added dropwise, it is 5.0wt% to be added dropwise to the concentration of phenyl triethoxysilane in the solution, is continued 1h is stirred, makes modifying agent complete hydrolysis；
8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder（SiO2- rGO powder and step 7）In solution The mass ratio of phenyl triethoxysilane modifying agent is 100: 2）, 70 DEG C of heating water bath stirrings（100 turns/min）React 30min, Then filter and use distilled water flushing filter cake to neutrality, it is last 100 DEG C dry, obtain FSiO2-rGO。
Embodiment 3
A kind of FSiO2- rGO preparation method, step include：
1）By Nano-meter SiO_22It is put into the concentrated sulfuric acid and hydrogen peroxide（The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1）Mixed liquor in, 30min is soaked at 90 DEG C, is surface-treated, is washed after immersion, is dried；
2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to stir 1.5h, make its complete hydrolysis, Prepare hydrolyzed silane solution；
3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2（Nano-meter SiO_22With silane hydrolyzate The mass ratio of gamma-aminopropyl-triethoxy-silane is 100 in liquid:2）, 60 DEG C of heating water bath stirrings（100 turns/min）Reaction 50min, then filter, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 80 DEG C of drying；
4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.4mg/mL dispersion liquid, uses ice Vinegar acid for adjusting pH is 4.0；
5）The GO aqueous solution that concentration is 1mg/mL is added drop-wise to step 4）Dispersion liquid in, GO:Nano-meter SiO_22Mass ratio 1:7, drop Acceleration is 1~2 drop/s, is added dropwise to complete rear ultrasonic 60min, filters and uses distilled water flushing filter cake to neutrality, is freeze-dried, obtains SiO2- GO powder；
6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:2, adopt It is that 3 h are reacted at 12.0,80 DEG C with 1M NaOH aqueous solution regulation pH, filters and use distilled water flushing filter cake to neutrality, freeze Dry, obtain SiO2- rGO powder；
7）By second alcohol and water according to volume ratio 9:1 mixing, it is 4.5 with glacial acetic acid regulation pH, then side is stirred（100 turns/min）Side Dimethoxydiphenylsilane modifying agent is added dropwise, it is 5.0wt% to be added dropwise to the concentration of dimethoxydiphenylsilane in the solution, Continue to stir 1.5h, make modifying agent complete hydrolysis；
8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder（SiO2- rGO powder and step 7）In solution The mass ratio of dimethoxydiphenylsilane modifying agent is 100: 2）, 60 DEG C of heating water bath stirrings（100 turns/min）Reaction 50min, then filter and use distilled water flushing filter cake to neutrality, it is last 80 DEG C dry, obtain FSiO2-rGO。
Embodiment 4
A kind of FSiO2- rGO preparation method, step include：
1）By Nano-meter SiO_22It is put into the concentrated sulfuric acid and hydrogen peroxide（The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1）Mixed liquor in, 30min is soaked at 90 DEG C, is surface-treated, is washed after immersion, is dried；
2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to stir 1.5h, make its complete hydrolysis, Prepare hydrolyzed silane solution；
3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2（Nano-meter SiO_22With silane hydrolyzate The mass ratio of gamma-aminopropyl-triethoxy-silane is 100 in liquid:2）, 60 DEG C of heating water bath stirrings（100 turns/min）Reaction 50min, then filter, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 80 DEG C of drying；
4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.5mg/mL dispersion liquid, uses ice Vinegar acid for adjusting pH is 4.0；
5）The GO aqueous solution that concentration is 2mg/mL is added drop-wise to step 4）Dispersion liquid in, GO:Nano-meter SiO_22Mass ratio 1:7, drop Acceleration is 1~2 drop/s, is added dropwise to complete rear ultrasonic 60min, filters and uses distilled water flushing filter cake to neutrality, is freeze-dried, obtains SiO2- GO powder；
6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:2, adopt It is that 3 h are reacted at 12.0,80 DEG C with 1M NaOH aqueous solution regulation pH, filters and use distilled water flushing filter cake to neutrality, freeze Dry, obtain SiO2- rGO powder；
7）By second alcohol and water according to volume ratio 9:1 mixing, it is 5.0 with glacial acetic acid regulation pH, then side is stirred（100 turns/min）Side Phenyl triethoxysilane modifying agent is added dropwise, it is 5.0wt% to be added dropwise to the concentration of phenyl triethoxysilane in the solution, is continued 1.5h is stirred, makes modifying agent complete hydrolysis；
8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder（SiO2- rGO powder and step 7）In solution The mass ratio of phenyl triethoxysilane modifying agent is 100: 2）, 60 DEG C of heating water bath stirrings（100 turns/min）React 50min, Then filter and use distilled water flushing filter cake to neutrality, it is last 80 DEG C dry, obtain FSiO2-rGO。
Comparative example 1~6
Step is different with embodiment 1, parameter：Change step 4）SiO in dispersion liquid2Concentration, pH value, step 5）The middle GO aqueous solution is dense Degree, GO and Nano-meter SiO_22Mass ratio, step 7）Silane modifier, specifically it is shown in Table 1.Wherein comparative example 6, step 4）Using 1M's NaOH solution regulation pH value is 10.0.
FSiO prepared by embodiment 1~4 and comparative example 1~62- rGO assembling effects are analyzed：
To examine FSiO2The assembling effect of-rGO hybrid materials, by the FSiO of preparation2- rGO is scattered in second with 1mg/mL concentration In alcohol, ultrasonic disperse 30min, 30min is stood, observe delamination.Three kinds of situations of assembling effect point：
I levels：Good, black is presented in hybrid material, does not separate；
II levels：Preferably, black is presented in hybrid material, is slightly separated；
III level：Difference, lamination, top black rGO, bottom white SiO is presented2。
Deployment conditions：
(1) FSiO is weighed2- rGO powder, 0.3mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2-rGO Alcohol dispersion liquid；
（2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 800r/min magnetic force 25min, then ultrasonic disperse 30min, then 1200rpm/min magnetic agitation 45min are stirred, stirring and ultrasonic procedure keep system 20 ~ 30 DEG C of temperature, obtains mixed liquor；
（3）By step（2）Mixed liquor, vacuum defoamation processing 15min, vacuum 0.01MPa, obtains well mixed paste resin Body, i.e. functionalization graphene phenol-formaldehyde resin modified.
Functionalization graphene phenol-formaldehyde resin modified slurry is poured into mould, is put into 120 DEG C of constant temperature 2h in baking oven, then heat up To 150 DEG C of constant temperature 2 hours, 170 DEG C of isothermal curings are finally warming up to 1 hour, obtain phenolic resin sample.The phenolic aldehyde that will be cured Resin samples break it is disconnected, with scanning electron microscopic observation cross-section morphology.It the results are shown in Table 1.
The FSiO of table 12- rGO main raw materials in proportion and performance comparision
2nd, functionalization graphene phenol-formaldehyde resin modified is prepared
Embodiment 5
A kind of preparation method of functionalization graphene phenol-formaldehyde resin modified, raw material：100 parts of phenolic resin, FSiO21 part of-rGO.
Comprise the following steps that：
（1）Weigh FSiO2- rGO powder, 10mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2- rGO's Alcohol dispersion liquid；
（2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 600r/min magnetic force 20min, then ultrasonic disperse 40min, then 1000rpm/min magnetic agitation 40min are stirred, stirring and ultrasonic procedure keep system 20~30 DEG C of temperature, obtains mixed liquor；
（3）By step（2）Mixed liquor, vacuum defoamation processing 10min, vacuum 0.01MPa, obtains well mixed paste resin Body, i.e. functionalization graphene phenol-formaldehyde resin modified.
Embodiment 6
A kind of preparation method of functionalization graphene phenol-formaldehyde resin modified, raw material：100 parts of phenolic resin, FSiO2-rGO 0.5 Part.
Comprise the following steps that：
（1）Weigh FSiO2- rGO powder, 50mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2- rGO's Alcohol dispersion liquid；
（2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 1000r/min magnetic Power stirs 30min, then ultrasonic disperse 20min, then 1500rpm/min magnetic agitation 50min, stirring and ultrasonic procedure keeping body It is 20~30 DEG C of temperature, obtains mixed liquor；
（3）By step（2）Mixed liquor, vacuum defoamation processing 20min, vacuum 0.01MPa, obtains well mixed paste resin Body, i.e. functionalization graphene phenol-formaldehyde resin modified.
Embodiment 7
A kind of preparation method of functionalization graphene phenol-formaldehyde resin modified, raw material：100 parts of phenolic resin, FSiO2-rGO 0.7 Part.
Comprise the following steps that：
（1）Weigh FSiO2- rGO powder, 30mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2- rGO's Alcohol dispersion liquid；
（2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 800r/min magnetic force 25min, then ultrasonic disperse 30min, then 1200rpm/min magnetic agitation 45min are stirred, stirring and ultrasonic procedure keep system 20 ~ 30 DEG C of temperature, obtains mixed liquor；
（3）By step（2）Mixed liquor, vacuum defoamation processing 15min, vacuum 0.01MPa, obtains well mixed paste resin Body, i.e. functionalization graphene phenol-formaldehyde resin modified.
Comparative example 7
Raw material proportioning and other conditions are with embodiment 5, and step (2) is different only, step（2）For：By step（1）Prepare FSiO2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 600r/min magnetic agitation 20min, obtain mixed liquor.
Comparative example 8
Raw material proportioning and other conditions are with embodiment 5, and step (2) is different only, step（2）For：By step（1）Prepare FSiO2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, ultrasonic disperse 40min, obtain mixed liquor.
Comparative example 9
With embodiment 5, difference is for raw material proportioning and other conditions：FSiO2- rGO replaces with SiO2-GO。
Comparative example 10
By unmodified phenolic resin curing, method is：Slurry is poured into mould, is put into 120 DEG C of constant temperature 2h in baking oven, then heat up To 150 DEG C of constant temperature 2 hours, 170 DEG C of isothermal curings are finally warming up to 1 hour, obtain phenolic resin sample.
Comparative example 11
With embodiment 5, difference is for raw material proportioning and other conditions：FSiO2- rGO replaces with rGO.
The functionalization graphene phenol-formaldehyde resin modified of embodiment 5~7 is solidified, method is：Slurry is poured into mould, put Enter 120 DEG C of constant temperature 2h in baking oven, then be warming up to 150 DEG C of constant temperature 2h, be finally warming up to 170 DEG C of isothermal curing 1h, obtain phenolic aldehyde tree Fat sample.
The method that the deployment conditions of comparative example 7 and 8 use embodiment 1, as a result as shown in table 2.
In order to evaluate the thermal behavior of embodiment 5~7 and the phenol-formaldehyde resin modified of comparative example 7~11, use in a nitrogen atmosphere Thermogravimetric analyzer carries out heat analysis test, and Range of measuring temp is：Room temperature ~ 800 DEG C, heating rate：10℃/min.Quality is taken to damage Lose 5%, mass loss 10% and maximum thermally decomposes corresponding temperature as index, be designated as T respectively5%、T10%And TdmaxEmbody and be modified The thermal behavior of phenolic resin.800 DEG C of charcoal residual rates are taken as its Heat-tolerant index.Data are as shown in table 2.
Phenolic resin heat analysis result after table 2 solidifies
。

Claims (10)

  1. A kind of 1. functionalization redox graphene phenol-formaldehyde resin modified, it is characterised in that：It is with FSiO2- rGO is filler, to phenol Urea formaldehyde is modified, and includes the raw material of following parts by weight：100 parts of phenolic resin, FSiO20.5~1 part of-rGO.
  2. 2. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that：The phenolic aldehyde Resin is thermosetting alcohol resite, its technical indicator：Free phenol 13~15%, the % of solids content 57~62, viscosity 138~ 145 mPas, s/160 DEG C of gel time 100~120.
  3. 3. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that：It is described FSiO2- rGO, preparing raw material include Nano-meter SiO_22And GO；The Nano-meter SiO_22For spheric granules, particle diameter is 80~100nm；It is described GO thickness is 0.9~1.5nm, a diameter of 2~5 μm of lamella, 1~2 layer of the number of plies.
  4. 4. the functionalization redox graphene phenol-formaldehyde resin modified according to claim 1 or 3, it is characterised in that：It is described FSiO2- rGO preparation method, step include：
    1）By Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide, soaks 30min at 90 DEG C, be surface-treated, soaks Wash, dry after bubble；
    2）By second alcohol and water according to volume ratio 9:1 mixing, is then added dropwise gamma-aminopropyl-triethoxy-silane while stirring, is added dropwise It is 5.0wt% to the concentration of gamma-aminopropyl-triethoxy-silane in the solution, then proceedes to 1~2h of stirring, make its hydrolysis, prepares Hydrolyzed silane solution；
    3）To step 2）Step 1 is added in the hydrolyzed silane solution of preparation）Nano-meter SiO_2 after processing2, 50~70 DEG C of heating water baths stir 30~60min of reaction is mixed, is then filtered, collects Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 50~100 DEG C of bakings It is dry；
    4）By step 3）Treated Nano-meter SiO_22It is added to the water, ultrasonic 30min, is configured to 1.2~1.5mg/mL dispersion liquid, And it is 4.0~6.0 to adjust pH with glacial acetic acid；
    5）The GO aqueous solution that concentration is 1~3mg/mL is added drop-wise to step 4）Dispersion liquid in, make GO and Nano-meter SiO_22Mass ratio For 1:5~9, it is added dropwise to complete rear ultrasonic 60min, filters and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2-GO Powder；
    6）By SiO2- GO powder is added to 2.6mol/L NaBH4In the aqueous solution, then it is with 1M NaOH aqueous solution regulation pH 12.0,80 DEG C reaction 3h after, filter and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2- rGO powder；
    7）By second alcohol and water according to volume ratio 9:1 mixing, it is 4.0~5.0 with glacial acetic acid regulation pH, benzene is then added dropwise while stirring Base silane modifying agent, it is 5.0wt% to be added dropwise to the concentration of phenyl silane modifying agent in the solution, continues 1~2h of stirring, makes modification Agent complete hydrolysis；
    8）To step 7）Solution in add step 6）Obtained SiO2- rGO powder, 50~70 DEG C of heating water bath stirring reactions 30 ~60min, then filter and use distilled water flushing filter cake to neutrality, it is last 50~100 DEG C dry, obtain FSiO2-rGO。
  5. 5. functionalization redox graphene phenol-formaldehyde resin modified according to claim 4, it is characterised in that：Step 1） In, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3 in the mixed liquor:1；
    Preferably, the SiO described in step 3)2With the SiO described in step 3)2With the ethoxy of γ-aminopropyl three in hydrolyzed silane solution The mass ratio of base silane is 100:2；
    Preferably, step 5）In, GO and Nano-meter SiO_22Mass ratio be 1:7；
    Preferably, the SiO described in step 6)2- GO and NaBH4Mass ratio be 1:2；
    Preferably, the SiO described in step 8)2- rGO powder and step 7）The mass ratio of phenyl silane modifying agent is in solution 100: 2。
  6. 6. functionalization redox graphene phenol-formaldehyde resin modified according to claim 4, it is characterised in that：Step 5） In, rate of addition is 1~2 drop/s.
  7. 7. functionalization redox graphene phenol-formaldehyde resin modified according to claim 4, it is characterised in that：Step 7） In, phenyl silane modifying agent is phenyltrimethoxysila,e, phenyl triethoxysilane or dimethoxydiphenylsilane.
  8. 8. functionalization redox graphene phenol-formaldehyde resin modified according to claim 4, it is characterised in that：Step 3）、 7）、8）In, mixing speed is 100 turns/min.
  9. A kind of 9. preparation method of functionalization redox graphene phenol-formaldehyde resin modified described in claim 1, it is characterised in that Step includes：
    （1）Weigh FSiO2- rGO powder, 10~50mg/mL dispersion liquid is configured to ethanol, ultrasonic 30min, obtains FSiO2-rGO Alcohol dispersion liquid；
    （2）By step（1）The FSiO of preparation2- rGO alcohol dispersion liquid, mixed with phenolic resin by proportioning, 600~1000r/ Min 20~30min of magnetic agitation, then 20~40min of ultrasonic disperse, then 1000~1500rpm/min magnetic agitations 40~ 50min, stirring and ultrasonic procedure keep 20~30 DEG C of system temperature, obtain mixed liquor；
    （3）By step（2）Mixed liquor, it is that 0.01MPa vacuum defoamations handle 10~20min in vacuum, obtains well mixed tree Fat slurry, i.e. functionalization graphene phenol-formaldehyde resin modified.
  10. 10. preparation method according to claim 9, it is characterised in that：Described functionalization graphene phenol-formaldehyde resin modified, Curing is：Slurry is poured into mould, is put into 120 DEG C of constant temperature 2h in baking oven, then is warming up to 150 DEG C of constant temperature 2h, is finally risen Temperature obtains phenolic resin sample to 170 DEG C of isothermal curing 1h.
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CN108711521A (en) * 2018-04-03 2018-10-26 北京玻钢院复合材料有限公司 The preparation method of phenol-formaldehyde resin modified electrode material
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CN105542228A (en) * 2016-01-31 2016-05-04 华南理工大学 Preparation method of functionalized nano-silica based on graphene
CN106520040A (en) * 2016-10-20 2017-03-22 西安交通大学 Preparation method for modified graphene oxide, MGO-SiO2 nano-hybrid material and MGO-SiO2 modified phenolic resin hot melting adhesive film
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