CN107501853B - 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 PDFInfo
- Publication number
- CN107501853B CN107501853B CN201710651693.4A CN201710651693A CN107501853B CN 107501853 B CN107501853 B CN 107501853B CN 201710651693 A CN201710651693 A CN 201710651693A CN 107501853 B CN107501853 B CN 107501853B
- Authority
- CN
- China
- Prior art keywords
- rgo
- nano
- sio
- functionalization
- fsio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of functionalization redox graphene phenol-formaldehyde resin modifieds and preparation method thereof, use nano-particles self assemble technology first, utilize Nano-meter SiO_22It is restored by GO functionalization, and to GO, forms functionalization rGO.Pass through Nano-meter SiO_2 in control hybrid material2With the ratio of GO, the factors such as concentration, the dosage of reducing agent so that hybrid material guarantee dispersibility while, play synergistic effect, effectively improve the heat resistance of phenolic resin.The introducing of nano material can not only improve the heat resistance of resin, while the comprehensive performances such as mechanical property that can also improve resin, be conducive to expand its application range, have good development prospect in the research application aspect of modified resin base ablation resistant material.
Description
Technical field
The present invention relates to a kind of functionalization redox graphene phenol-formaldehyde resin modifieds and preparation method thereof, belong to polymer
The technical field of based composites.
Background technique
Exploration of the progress and the mankind of science to the outer space, makes people to the heat resistance and ablation property of ablative composite material
More stringent requirements are proposed.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, craftsmanship 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 be modified to phenolic resin.
The modification of phenolic resin can be carried out by block phenolic hydroxyl group and introduction other components two ways, wherein introducing is received
Rice material carries out heat resistance modified being the apparent method of modifying of common effect.
Graphene is a kind of tightly packed carbonaceous new material at single 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
Ideal reinforcement.Graphene oxide (GO) is the intermediate product that chemical method prepares graphene, surface contain hydroxyl, carboxyl,
The a large amount of active function groups such as epoxy group, make it have certain activity.The GO and redox graphene (rGO) of sheet are logical
It crosses absorption heat and forms barrier obstruction heat propagation, so, more and more it is used in the modification of phenolic resin.Xuwei Hua Qi
Research in Master's thesis " graphene oxide/Phenolic Resin In situ Composites preparation and performance " (Guilin University of Technology, 2013)
Show that GO is added in phenolic resin by way of in-situ polymerization, the hot property of compound resin can be significantly improved.There is document
It records, the heat resistance of rGO is better than GO, but since active group is reduced disappearance, so dispersion of the rGO in resin is compared with GO
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 be unformed white powder, have special interface performance and bulk effect.
Nano-meter SiO_22It is spherical rigid nanoparticle, large specific surface area, adsorption capacity are strong, size is small, in the side such as thermal resistance, resistance, fusing point
Face shows specific function compared with conventional material.In addition Nano-meter SiO_22There is stronger binding ability with polymer, it can be to polymerization
The physico-chemical property of object matrix generates special role.By SiO2It is introduced into phenolic resin, heat-resisting, the intensity of phenolic resin can be improved
Etc. performances.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 dispersion of SiClx is not obvious the raising of phenolic resin heat resistance.
Patent CN201410721476.4 uses nano silica and graphene oxide hybrid material modified organic silicon tree
Rouge improves the heat resistance of organic siliconresin.It is pointed out, since the huge surface area of graphene and strong Van der Waals force are not easy it
In dispersing in resin matrix, and it is lower with the interaction force of matrix resin.And use two or more nanoparticle
The mode of hydridization can make nanoparticle and resin matrix have fabulous compatibility and interface performance.However, its use it is miscellaneous
Changing particle is Nano-meter SiO_22With GO, as previously mentioned, GO is obvious without rGO effect in terms of improving heat resistance.
Summary of the invention
It is an object of the invention to be directed to the above-mentioned problems in the prior art, a kind of functionalization oxygen reduction fossil is provided
Black alkene phenol-formaldehyde resin modified, first by SiO2Hydridization is carried out with rGO, and functionalization SiO is made2- rGO hybrid material (i.e. 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 the present invention also provides the preparation method of functionalization redox graphene phenol-formaldehyde resin modified, solve
Nanoparticle is easily reunited in preparation process, is not easy evenly dispersed problem in phenolic resin glue, improves phenolic aldehyde tree
Ablation property, the heat resistance of rouge.
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
Material) it is filler, phenolic resin is modified, the raw material including following parts by weight: 100 parts of phenolic resin, FSiO2-rGO
0.5~1 part.
Further, the phenolic resin be thermosetting property alcohol resite, technical indicator: free phenol 13~15%, Gu
57~62 % of body content, 138~145 mPas of viscosity, s/160 DEG C of gel time 100~120.
Further, the FSiO2- rGO, preparing raw material includes Nano-meter SiO_22And GO；The Nano-meter SiO_22It is spherical
Grain, partial size are 80~100nm；The GO with a thickness of 0.9~1.5nm, lamella diameter is 2~5 μm, 1~2 layer of the number of plies.
Further, the FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide, 30min is impregnated at 90 DEG C, carry out at surface
Reason, is washed after immersion, dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring,
Being added dropwise to the concentration of gamma-aminopropyl-triethoxy-silane in the solution is 5.0wt%, then proceedes to 1~2h of stirring, makes its hydrolysis,
Prepare hydrolyzed silane solution；
3) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22, 50~70 DEG C of water-baths add
30~60min is reacted in thermal agitation, then filters, and collects Nano-meter SiO_22After filter cake distilled water flushing to neutrality, in 50~100 DEG C
Drying；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min, is configured to point of 1.2~1.5mg/mL
Dispersion liquid, and adjusting pH with glacial acetic acid is 4.0~6.0；
5) the GO aqueous solution that concentration is 1~3mg/mL is added drop-wise in the dispersion liquid of step 4), makes GO and Nano-meter SiO_22's
Mass ratio is 1:5~9, ultrasound 60min after being added dropwise to complete, and is filtered and with 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 aqueous solution, pH then is adjusted with the NaOH aqueous solution of 1M
After being 12.0,80 DEG C of reaction 3h, filter and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2- rGO powder；
7) second alcohol and water is mixed according to volume ratio 9:1, adjusting pH with glacial acetic acid is 4.0~5.0, is then dripped while stirring
Add phenyl silane modifying agent, being added dropwise to the concentration of phenyl silane modifying agent in the solution is 5.0wt%, continues 1~2h of stirring, makes
Modifying agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder, 50~70 DEG C of heating water bath stirrings are anti-
Answer 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, in step 1), the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1 in the mixed liquor.
Preferably, 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, in step 5), GO and Nano-meter SiO_22Mass ratio be 1:7.
Preferably, in step 5), rate of addition is 1~2 drop/s.
Preferably, SiO described in step 6)2- GO and NaBH4Mass ratio be 1:2.
Preferably, in step 7), phenyl silane modifying agent is phenyltrimethoxysila,e, phenyl triethoxysilane or two
Phenyidimethoxysilane.
Preferably, SiO described in step 8)2The mass ratio of phenyl silane modifying agent in-rGO powder and step 7) solution
For 100:2.
Preferably, step 3), 7), 8) in, mixing speed be 100 turns/min.
A kind of preparation method of functionalization redox graphene phenol-formaldehyde resin modified, step include:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 10~50mg/mL is configured to ethyl alcohol, and ultrasonic 30min is obtained
FSiO2The alcohol dispersion liquid of-rGO；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes according to the ratio with phenolic resin, 600~
1000r/min 20~30min of magnetic agitation, then 20~40min of ultrasonic disperse, then 1000~1500rpm/min magnetic agitation
40~50min, stirring and ultrasonic procedure are kept for 20~30 DEG C of system temperature, obtain mixed liquor；
(3) by step (2) mixed liquor, it is that 0.01MPa vacuum defoamation handles 10~20min in vacuum degree, obtains uniformly mixed
Resin slurry, i.e. functionalization graphene phenol-formaldehyde resin modified.
The functionalization graphene phenol-formaldehyde resin modified, curing method are as follows: slurry is poured into mold, 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, phenolic resin sample is obtained.
To efficiently solve dispersibility, the compatibility of the heat resistance and nanoparticle of phenolic resin in resin matrix, this
Invention uses nano-particles self assemble technology first, utilizes Nano-meter SiO_22It is restored by GO functionalization, and to GO, forms function
RGO can be changed.Pass through Nano-meter SiO_2 in control hybrid material2With the ratio of GO, the factors such as concentration, the dosage of reducing agent, so that hydridization
Material plays synergistic effect, effectively improves the heat resistance of phenolic resin while guaranteeing dispersibility.The introducing of nano material is not
It is only capable of improving the heat resistance of resin, while the comprehensive performances such as mechanical property that can also improve resin, is conducive to expand its application
Range has good development prospect in the research application aspect of modified resin base ablation resistant material.
Beneficial effects of the present invention:
1. the graphene using functionalization is heat resistance modified to phenolic resin progress, method is simple, and effect is obvious.
2. using Nano-meter SiO_22Hydridization is carried out with rGO, improves dispersion of the nano particle in resin matrix, resistance to thermal effect
Fruit is good.
3. improving heat resistance the GO reduction treatment in hybrid material.
4. SiO2Make heat resistance best with the rational proportion of rGO.
Specific embodiment
Below by embodiment further description technical solution of the present invention.These descriptions are not to make to the content of present invention
It is further to limit.It is all that equivalent replacement made by the content of present invention or is correspondingly improved, still fall within protection scope of the present invention
Within.
It is raw materials used in following embodiments:
Phenolic resin be thermosetting property alcohol-soluble phenolic resin, technical indicator: free phenol 13~15%, solid content 57~
62 %, 138~145 mPas of viscosity, s/160 DEG C of gel time 100~120；
Nano-meter SiO_22For spheric granules, partial size is 80~100nm；
GO with a thickness of 0.9~1.5nm, lamella diameter is 2~5 μm, 1~2 layer of the number of plies.
One, FSiO is prepared2-rGO
Embodiment 1
A kind of FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1)
In, 30min is impregnated at 90 DEG C, is surface-treated, is washed after immersion, it is dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring,
Being added dropwise to the concentration of gamma-aminopropyl-triethoxy-silane in the solution is 5.0wt%, then proceedes to stirring 2h, makes its hydrolysis, makes
Standby hydrolyzed silane solution；
3) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22(Nano-meter SiO_22With silane
The mass ratio of gamma-aminopropyl-triethoxy-silane is 100:2 in hydrolyzate), 50 DEG C of heating water baths stir (100 turns/min) reactions
Then 60min is filtered, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, dried in 100 DEG C；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min is configured to the dispersion liquid of 1.2mg/mL,
Adjusting pH with glacial acetic acid is 6.0；
5) the GO aqueous solution that concentration is 2mg/mL is added drop-wise in the dispersion liquid of step 4), GO: Nano-meter SiO_22Mass ratio 1:
5, rate of addition is 1 ~ 2 drop/s, ultrasound 60min after being added dropwise to complete, and filters and uses distilled water flushing filter cake to neutrality, freeze and do
It is dry, obtain SiO2- GO powder；
6) by SiO2- GO powder is added to 2.6mol/L NaBH4In aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:
2, using the NaOH aqueous solution of 1M to adjust pH is 12.0, reacts 3 h at 80 DEG C, suction filtration and with distilled water flushing filter cake to neutrality,
Freeze-drying, obtains SiO2- rGO powder；
7) by second alcohol and water according to volume ratio 9:1 mix, with glacial acetic acid adjust pH be 4.0, then side stirring (100 turns/
Min) phenyltrimethoxysila,e modifying agent is added dropwise in side, and being added dropwise to the concentration of phenyltrimethoxysila,e in the solution is
5.0wt% continues to stir 2h, makes modifying agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder (SiO2- rGO powder and step 7) are molten
The mass ratio of phenyltrimethoxysila,e modifying agent is 100:2 in liquid), 50 DEG C of heating water baths stir (100 turns/min) reactions
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 FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1)
In, 30min is impregnated at 90 DEG C, is surface-treated, is washed after immersion, it is dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring,
Being added dropwise to the concentration of gamma-aminopropyl-triethoxy-silane in the solution is 5.0wt%, then proceedes to stirring 1h, makes its complete water
Solution, prepares hydrolyzed silane solution；
3) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22(Nano-meter SiO_22With silane
The mass ratio of gamma-aminopropyl-triethoxy-silane is 100:2 in hydrolyzate), 70 DEG C of heating water baths stir (100 turns/min) reactions
Then 30min is filtered, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, dried in 50 DEG C；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min is configured to the dispersion liquid of 1.5mg/mL,
Adjusting pH with glacial acetic acid is 5.0；
5) the GO aqueous solution that concentration is 2mg/mL is added drop-wise in the dispersion liquid of step 4), GO: Nano-meter SiO_22Mass ratio 1:
9, rate of addition is 1 ~ 2 drop/s, ultrasound 60min after being added dropwise to complete, and filters and uses distilled water flushing filter cake to neutrality, freeze and do
It is dry, obtain SiO2- GO powder；
6) by SiO2- GO powder is added to 2.6mol/L NaBH4In aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:
2, using the NaOH aqueous solution of 1M to adjust pH is 12.0, reacts 3 h at 80 DEG C, suction filtration and with distilled water flushing filter cake to neutrality,
Freeze-drying, obtains SiO2- rGO powder；
7) by second alcohol and water according to volume ratio 9:1 mix, with glacial acetic acid adjust pH be 5.0, then side stirring (100 turns/
Min) phenyl triethoxysilane modifying agent is added dropwise in side, and being added dropwise to the concentration of phenyl triethoxysilane in the solution is
5.0wt% continues to stir 1h, makes modifying agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder (SiO2- rGO powder and step 7) are molten
The mass ratio of phenyl triethoxysilane modifying agent is 100:2 in liquid), 70 DEG C of heating water baths stir (100 turns/min) reactions
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 FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1)
In, 30min is impregnated at 90 DEG C, is surface-treated, is washed after immersion, it is dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring,
Being added dropwise to the concentration of gamma-aminopropyl-triethoxy-silane in the solution is 5.0wt%, then proceedes to stirring 1.5h, makes its complete water
Solution, prepares hydrolyzed silane solution；
3) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22(Nano-meter SiO_22With silane
The mass ratio of gamma-aminopropyl-triethoxy-silane is 100:2 in hydrolyzate), 60 DEG C of heating water baths stir (100 turns/min) reactions
Then 50min is filtered, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, dried in 80 DEG C；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min is configured to the dispersion liquid of 1.4mg/mL,
Adjusting pH with glacial acetic acid is 4.0；
5) the GO aqueous solution that concentration is 1mg/mL is added drop-wise in the dispersion liquid of step 4), GO: Nano-meter SiO_22Mass ratio 1:
7, rate of addition is 1~2 drop/s, ultrasound 60min after being added dropwise to complete, and filters and uses distilled water flushing filter cake to neutrality, freeze and do
It is dry, obtain SiO2- GO powder；
6) by SiO2- GO powder is added to 2.6mol/L NaBH4In aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:
2, using the NaOH aqueous solution of 1M to adjust pH is 12.0, reacts 3 h at 80 DEG C, suction filtration and with distilled water flushing filter cake to neutrality,
Freeze-drying, obtains SiO2- rGO powder；
7) by second alcohol and water according to volume ratio 9:1 mix, with glacial acetic acid adjust pH be 4.5, then side stirring (100 turns/
Min) dimethoxydiphenylsilane modifying agent is added dropwise in side, and being added dropwise to the concentration of dimethoxydiphenylsilane in the solution is
5.0wt% continues to stir 1.5h, makes modifying agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder (SiO2- rGO powder and step 7) are molten
The mass ratio of dimethoxydiphenylsilane modifying agent is 100:2 in liquid), 60 DEG C of heating water baths stir (100 turns/min) reactions
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 FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide (volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1)
In, 30min is impregnated at 90 DEG C, is surface-treated, is washed after immersion, it is dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring,
Being added dropwise to the concentration of gamma-aminopropyl-triethoxy-silane in the solution is 5.0wt%, then proceedes to stirring 1.5h, makes its complete water
Solution, prepares hydrolyzed silane solution；
3) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22(Nano-meter SiO_22With silane
The mass ratio of gamma-aminopropyl-triethoxy-silane is 100:2 in hydrolyzate), 60 DEG C of heating water baths stir (100 turns/min) reactions
Then 50min is filtered, collect Nano-meter SiO_22After filter cake distilled water flushing to neutrality, dried in 80 DEG C；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min is configured to the dispersion liquid of 1.5mg/mL,
Adjusting pH with glacial acetic acid is 4.0；
5) the GO aqueous solution that concentration is 2mg/mL is added drop-wise in the dispersion liquid of step 4), GO: Nano-meter SiO_22Mass ratio 1:
7, rate of addition is 1~2 drop/s, ultrasound 60min after being added dropwise to complete, and filters and uses distilled water flushing filter cake to neutrality, freeze and do
It is dry, obtain SiO2- GO powder；
6) by SiO2- GO powder is added to 2.6mol/L NaBH4In aqueous solution, SiO2- GO and NaBH4Mass ratio be 1:
2, using the NaOH aqueous solution of 1M to adjust pH is 12.0, reacts 3 h at 80 DEG C, suction filtration and with distilled water flushing filter cake to neutrality,
Freeze-drying, obtains SiO2- rGO powder；
7) by second alcohol and water according to volume ratio 9:1 mix, with glacial acetic acid adjust pH be 5.0, then side stirring (100 turns/
Min) phenyl triethoxysilane modifying agent is added dropwise in side, and being added dropwise to the concentration of phenyl triethoxysilane in the solution is
5.0wt% continues to stir 1.5h, makes modifying agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder (SiO2- rGO powder and step 7) are molten
The mass ratio of phenyl triethoxysilane modifying agent is 100:2 in liquid), 60 DEG C of heating water baths stir (100 turns/min) reactions
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
For step with embodiment 1, parameter is different: changing the step SiO in 4) dispersion liquid2Concentration, pH value, GO is water-soluble in step 5)
Liquid concentration, GO and Nano-meter SiO_22Mass ratio, step 7) silane modifier, is specifically shown in Table 1.Wherein comparative example 6, step 4) use 1M
NaOH solution adjust pH value be 10.0.
FSiO prepared by Examples 1 to 4 and comparative example 1~62The analysis of-rGO assembling effect:
To examine FSiO2The assembling effect of-rGO hybrid material, by the FSiO of preparation2- rGO is dispersed with the concentration of 1mg/mL
In ethyl alcohol, ultrasonic disperse 30min stands 30min, observes delamination.Three kinds of situations of assembling effect point:
I grades: good, black is presented in hybrid material, does not separate；
II grades: preferably, black is presented in hybrid material, is slightly separated；
III level: it is poor, lamination, top black rGO, lower part white SiO is presented2。
Dispersion:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 0.3mg/mL is configured to ethyl alcohol, and ultrasonic 30min obtains FSiO2-
The alcohol dispersion liquid of rGO；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes, 800r/min according to the ratio with phenolic resin
Magnetic agitation 25min, then ultrasonic disperse 30min, then 1200rpm/min magnetic agitation 45min, stirring and ultrasonic procedure are kept
20 ~ 30 DEG C of system temperature, obtain mixed liquor；
(3) by step (2) mixed liquor, vacuum defoamation handles 15min, and vacuum degree 0.01MPa obtains uniformly mixed resin
Slurry, i.e. functionalization graphene phenol-formaldehyde resin modified.
Functionalization graphene phenol-formaldehyde resin modified slurry is poured into mold, is put into 120 DEG C of constant temperature 2h in baking oven, then heat up
To 150 DEG C constant temperature 2 hours, be finally warming up to 170 DEG C of isothermal curings 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.
1 FSiO of table2The main raw materials in proportion of-rGO is compared with performance
Two, 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, FSiO2-rGO 1
Part.
Specific step is as follows:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 10mg/mL is configured to ethyl alcohol, and ultrasonic 30min obtains FSiO2-rGO
Alcohol dispersion liquid；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes, 600r/min according to the ratio with phenolic resin
Magnetic agitation 20min, then ultrasonic disperse 40min, then 1000rpm/min magnetic agitation 40min, stirring and ultrasonic procedure are kept
20~30 DEG C of system temperature, obtain mixed liquor；
(3) by step (2) mixed liquor, vacuum defoamation handles 10min, and vacuum degree 0.01MPa obtains uniformly mixed resin
Slurry, 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.
Specific step is as follows:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 50mg/mL is configured to ethyl alcohol, and ultrasonic 30min obtains FSiO2-rGO
Alcohol dispersion liquid；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes, 1000r/ according to the ratio with phenolic resin
Min magnetic agitation 30min, then ultrasonic disperse 20min, then 1500rpm/min magnetic agitation 50min, stirring and ultrasonic procedure
It is kept for 20~30 DEG C of system temperature, obtains mixed liquor；
(3) by step (2) mixed liquor, vacuum defoamation handles 20min, and vacuum degree 0.01MPa obtains uniformly mixed resin
Slurry, 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.
Specific step is as follows:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 30mg/mL is configured to ethyl alcohol, and ultrasonic 30min obtains FSiO2-rGO
Alcohol dispersion liquid；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes, 800r/min according to the ratio with phenolic resin
Magnetic agitation 25min, then ultrasonic disperse 30min, then 1200rpm/min magnetic agitation 45min, stirring and ultrasonic procedure are kept
20 ~ 30 DEG C of system temperature, obtain mixed liquor；
(3) by step (2) mixed liquor, vacuum defoamation handles 15min, and vacuum degree 0.01MPa obtains uniformly mixed resin
Slurry, i.e. functionalization graphene phenol-formaldehyde resin modified.
Comparative example 7
With embodiment 5, step (2) is different only, step (2) are as follows: makes step (1) for raw material proportioning and other conditions
Standby FSiO2The alcohol dispersion liquid of-rGO mixes according to the ratio with phenolic resin, and 600r/min magnetic agitation 20min must be mixed
Liquid.
Comparative example 8
With embodiment 5, step (2) is different only, step (2) are as follows: makes step (1) for raw material proportioning and other conditions
Standby FSiO2The alcohol dispersion liquid of-rGO, mixes according to the ratio with phenolic resin, and ultrasonic disperse 40min obtains mixed liquor.
Comparative example 9
Raw material proportioning and other conditions with embodiment 5, the difference is that: FSiO2- rGO replaces with SiO2-GO。
Comparative example 10
By unmodified phenolic resin curing, method are as follows: slurry is poured into mold, 120 DEG C of constant temperature 2h in baking oven are put into, then
It is warming up to 150 DEG C of constant temperature 2 hours, is finally warming up to 170 DEG C of isothermal curings 1 hour, obtain phenolic resin sample.
Comparative example 11
Raw material proportioning and other conditions with embodiment 5, the difference is that: FSiO2- rGO replaces with rGO.
The functionalization graphene phenol-formaldehyde resin modified of embodiment 5~7 is solidified, method are as follows: slurry is poured into mold, is put
Enter 120 DEG C of constant temperature 2h in baking oven, then be warming up to 150 DEG C of constant temperature 2h, is finally warming up to 170 DEG C of isothermal curing 1h, obtains phenolic aldehyde tree
Rouge sample.
The method that the dispersion of comparative example 7 and 8 uses embodiment 1, the results are shown in Table 2.
In order to evaluate the thermal behavior of 7~11 phenol-formaldehyde resin modified of embodiment 5~7 and comparative example, use in a nitrogen atmosphere
Thermogravimetric analyzer carries out heat analysis test, Range of measuring temp are as follows: room temperature ~ 800 DEG C, heating rate: 10 DEG C/min.Quality is taken to damage
Temperature corresponding to 5%, mass loss 10% and maximum thermal decomposition is lost as index, is denoted as T respectively5%、T10%And TdmaxIt embodies and is modified
The thermal behavior of phenolic resin.Take 800 DEG C of charcoal residual rates as its Heat-tolerant index.Data are as shown in table 2.
Phenolic resin heat analysis result after table 2 solidifies
。
Claims (9)
1. a kind of functionalization redox graphene phenol-formaldehyde resin modified, it is characterised in that: be with FSiO2- rGO is filler, to phenol
Urea formaldehyde is modified, and the parts by weight of the phenolic resin are 100 parts, FSiO2The parts by weight of-rGO are 0.5~1 part；
The FSiO2The preparation method of-rGO, step include:
1) by Nano-meter SiO_22It is put into the mixed liquor of the concentrated sulfuric acid and hydrogen peroxide, impregnates 30min at 90 DEG C, be surface-treated, soak
It is washed after bubble, it is dry；
2) second alcohol and water is mixed according to volume ratio 9:1, gamma-aminopropyl-triethoxy-silane is then added dropwise while stirring, be 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) step 1) treated Nano-meter SiO_2 is added in the hydrolyzed silane solution prepared to step 22, 50~70 DEG C of heating water baths stir
30~60min of reaction is mixed, is then filtered, Nano-meter SiO_2 is collected2After filter cake distilled water flushing to neutrality, dried in 50~100 DEG C
It is dry；
4) by the processed Nano-meter SiO_2 of step 3)2It is added to the water, ultrasonic 30min is configured to the dispersion liquid of 1.2~1.5mg/mL,
And adjusting pH with glacial acetic acid is 4.0~6.0；
5) the GO aqueous solution that concentration is 1~3mg/mL is added drop-wise in the dispersion liquid of step 4), makes GO and Nano-meter SiO_22Mass ratio
For 1:5~9, ultrasound 60min after being added dropwise to complete is filtered and with distilled water flushing filter cake to neutrality, is freeze-dried, is obtained SiO2-GO
Powder；
6) by SiO2- GO powder is added to 2.6mol/L NaBH4In aqueous solution, then adjusting pH with the NaOH aqueous solution of 1M is
After 12.0,80 DEG C of reaction 3h, filter and use distilled water flushing filter cake to neutrality, be freeze-dried, obtain SiO2- rGO powder；
7) second alcohol and water is mixed according to volume ratio 9:1, adjusting pH with glacial acetic acid is 4.0~5.0, and benzene is then added dropwise while stirring
Base silane modifying agent, being added dropwise to the concentration of phenyl silane modifying agent in the solution is 5.0wt%, continues 1~2h of stirring, makes to be modified
Agent complete hydrolysis；
8) SiO that step 6) obtains is added into the solution of step 7)2- rGO powder, 50~70 DEG C of heating water baths are stirred to react 30
~60min, then filter and use distilled water flushing filter cake to neutrality, it is last 50~100 DEG C dry, obtain FSiO2-rGO。
2. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: the phenolic aldehyde
Resin be thermosetting property alcohol resite, technical indicator: free phenol 13~15%, 57~62 % of solid content, viscosity 138~
145 mPas, s/160 DEG C of gel time 100~120.
3. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: described
FSiO2- rGO, preparing raw material includes Nano-meter SiO_22And GO；The Nano-meter SiO_22For spheric granules, partial size is 80~100nm；It is described
GO with a thickness of 0.9~1.5nm, lamella diameter is 2~5 μm, 1~2 layer of the number of plies.
4. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: step 1)
In, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1 in the mixed liquor；
Processed Nano-meter SiO_2 described in step 3)2With the mass ratio of gamma-aminopropyl-triethoxy-silane in hydrolyzed silane solution
For 100:2；
In step 5), GO and Nano-meter SiO_22Mass ratio be 1:7；
SiO described in step 6)2- GO and NaBH4Mass ratio be 1:2；
SiO described in step 8)2The mass ratio of phenyl silane modifying agent is 100:2 in-rGO powder and step 7) solution.
5. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: step 5)
In, rate of addition is 1~2 drop/s.
6. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: step 7)
In, phenyl silane modifying agent is phenyltrimethoxysila,e, phenyl triethoxysilane or dimethoxydiphenylsilane.
7. functionalization redox graphene phenol-formaldehyde resin modified according to claim 1, it is characterised in that: step 3),
7), 8) in, mixing speed is 100 turns/min.
8. the preparation method of functionalization redox graphene phenol-formaldehyde resin modified described in a kind of claim 1, which is characterized in that
Step includes:
(1) FSiO is weighed2- rGO powder, the dispersion liquid of 10~50mg/mL is configured to ethyl alcohol, and ultrasonic 30min obtains FSiO2-rGO
Alcohol dispersion liquid；
(2) FSiO for preparing step (1)2The alcohol dispersion liquid of-rGO mixes, 600~1000r/ according to the ratio with phenolic resin
Min 20~30min of magnetic agitation, then 20~40min of ultrasonic disperse, then 1000~1500rpm/min magnetic agitation 40~
50min, stirring and ultrasonic procedure are kept for 20~30 DEG C of system temperature, obtain mixed liquor；
(3) by step (2) mixed liquor, it is that 0.01MPa vacuum defoamation handles 10~20min in vacuum degree, obtains uniformly mixed tree
Rouge slurry, i.e. functionalization redox graphene phenol-formaldehyde resin modified.
9. preparation method according to claim 8, it is characterised in that: the modified phenol of the functionalization redox graphene
Urea formaldehyde, curing method are as follows: functionalization redox graphene phenol-formaldehyde resin modified slurry is poured into mold, 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, functionalization reduction-oxidation is obtained
Graphene phenol-formaldehyde resin modified sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710651693.4A CN107501853B (en) | 2017-08-02 | 2017-08-02 | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710651693.4A CN107501853B (en) | 2017-08-02 | 2017-08-02 | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107501853A CN107501853A (en) | 2017-12-22 |
| CN107501853B true CN107501853B (en) | 2019-07-09 |
Family
ID=60689835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710651693.4A Expired - Fee Related CN107501853B (en) | 2017-08-02 | 2017-08-02 | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107501853B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108115151B (en) * | 2017-12-25 | 2020-01-14 | 哈尔滨工业大学 | In-situ reduction preparation method of nano-silver modified reduced graphene oxide hybrid structure |
| CN108711521B (en) * | 2018-04-03 | 2020-05-12 | 北京玻钢院复合材料有限公司 | Preparation method of modified phenolic resin electrode material |
| CN108504031A (en) * | 2018-04-20 | 2018-09-07 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of preparation method of graphene oxide/phenolic resin film |
| CN115975424B (en) * | 2022-12-13 | 2024-01-19 | 广东电网有限责任公司 | Conductive filler and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627994A (en) * | 2015-02-06 | 2015-05-20 | 中国科学院山西煤炭化学研究所 | Preparation method of reduced graphene oxide/phenol formaldehyde resin-base activated carbon in-situ composite material |
| 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 |
| CN106952675A (en) * | 2017-03-22 | 2017-07-14 | 西北大学 | Graphene-based organic carrier and preparation method thereof, electric slurry and preparation method thereof |
-
2017
- 2017-08-02 CN CN201710651693.4A patent/CN107501853B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627994A (en) * | 2015-02-06 | 2015-05-20 | 中国科学院山西煤炭化学研究所 | Preparation method of reduced graphene oxide/phenol formaldehyde resin-base activated carbon in-situ composite material |
| 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 |
| CN106952675A (en) * | 2017-03-22 | 2017-07-14 | 西北大学 | Graphene-based organic carrier and preparation method thereof, electric slurry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107501853A (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501853B (en) | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof | |
| CN103788413B (en) | The method of graphene oxide chemically modified mineral filler, products obtained therefrom and application | |
| CN103317734B (en) | Method for preparing radar wave-absorbing composite material based on carbon nanometer film | |
| CN105271212B (en) | A kind of graphene aerogel material and preparation method thereof | |
| CN106189066B (en) | Phenolic resin/silicon dioxide composite aerogel material and preparation method thereof | |
| CN104371274B (en) | Modified alumina composite material, copper-coated substrate and preparation method of copper-coated substrate | |
| CN103599705B (en) | The method of organic/inorganic hybrid membrane is prepared in a kind of ultrasonic immersing | |
| CN110797494B (en) | Diaphragm functional coating material for lithium ion battery and preparation method thereof | |
| CN108178930B (en) | Silicone rubber nanocomposite for electromagnetic shielding and preparation method thereof | |
| CN103435828B (en) | Graphene oxide silicon dioxide compound/polymer hybridization proton exchange membrane of sulfonation and preparation method thereof | |
| CN107915853A (en) | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application | |
| CN105778133A (en) | Carbon nanotube/graphene oxide nanoribbon-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN107032321A (en) | The hollow carbon sphere material of a kind of nitrogen-phosphor codoping and shell with classification macropore meso-hole structure and its preparation method and application | |
| CN106832757A (en) | A kind of composite of Graphene phenol-formaldehyde resin modified and preparation method thereof, application | |
| CN103467920B (en) | Method for improving mechanical property and heat resistance property of epoxy resin | |
| CN105694358A (en) | Sulfonated polyether ether ketone-sulfonated oxidized graphene hybrid membrane and preparation and application thereof | |
| CN106747431A (en) | A kind of Graphene ceramic composite powder and preparation method thereof | |
| CN104231624A (en) | Modified cyanate resin heat-conducting composite material and preparation method thereof | |
| CN102912626A (en) | Preparation method of fiber surface sizing agent based on carbon nanotube/graphene oxide/POSS (Polysilsesquioxane) monomer | |
| CN105107392A (en) | Multiwalled carbon nanotube surface-embedded modified polyvinylidene fluoride (PVDF) membrane and preparation method thereof | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film | |
| CN109705407A (en) | A kind of production method of graphene rubber concentrate feed and graphene rubber | |
| CN110385048A (en) | A kind of porous carbon nanosheet mixed substrate membrane containing nano-grade molecular sieve of two dimension and preparation method thereof | |
| CN110408071A (en) | A kind of constant pressure and dry phenolic aldehyde aeroge and preparation method thereof | |
| CN106898802A (en) | A kind of high-performing car hydrogen fuel cell composite nano-powder material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190709 Termination date: 20200802 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |