CN108504031A - A kind of preparation method of graphene oxide/phenolic resin film - Google Patents
A kind of preparation method of graphene oxide/phenolic resin film Download PDFInfo
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- CN108504031A CN108504031A CN201810396592.1A CN201810396592A CN108504031A CN 108504031 A CN108504031 A CN 108504031A CN 201810396592 A CN201810396592 A CN 201810396592A CN 108504031 A CN108504031 A CN 108504031A
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- phenolic resin
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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
- C08K9/00—Use of pretreated 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention discloses a kind of preparation methods of graphene oxide/phenolic resin film, including following preparation process：(1) graphene oxide suspension is prepared；(2) water soluble phenol resin is prepared；(3) graphene/phenolic resin composite is prepared.The present invention solves the defects of big traditional phenolic resin brittleness, the easy moisture absorption, poor toughness, electric conductivity difference and poor heat resistance using graphene oxide phenol-formaldehyde resin modified；The addition of graphene oxide improves the heat resistance and toughness of phenolic resin；Dispersibility of the graphene in phenolic resin can preferably be improved by preparing graphene nanometer sheet based on N methyl pyrrolidones, play the role of enhancing its excellent properties；By high-temperature heat treatment with better electric conductivity.
Description
Technical field
The present invention relates to a kind of composite material and preparation method thereof more particularly to a kind of graphene oxide/phenolic resin films
Preparation method.
Background technology
Phenolic resin has had more than 100 years history as one of three big synthetic resin, with its excellent adhesiveness
Energy, excellent heat resistance, good anti-flammability, remarkable mechanical property can be used as coating, binder, composite resin
The fields such as matrix, electronics and the fire-retardant original paper material of electronic engineering, machinery, space flight and aviation are widely used, especially phenolic aldehyde
Resin composite materials, purposes is super extensively, especially in the tips such as aerospace industry high-tech sector.Phenolic resin can pass through phenolic aldehyde
Substance carries out polycondensation in the presence of a catalyst and obtains, and the most commonly used is phenol and formaldehyde to be made for raw material.Phenolic aldehyde
Resin can be divided into two major classes, and one kind is thermoplastic phenolic resin, and frequently with acid as catalyst, when machine-shaping needs that solidification is added
Agent is two step resin；Another kind of is heat cured phenolic resin, to be added alkali as a catalyst in building-up process, in strand
Containing the methylol active group that can further react, curing agent need not be added in its machine-shaping, is single-step resin.
Development due to the extensive use of phenolic resin, and in terms of high and new technology, also proposed more phenolic resin
The shortcomings of high requirement, phenolic resin brittleness is bigger, and shrinking percentage is high, and thermal conductivity is poor limits pure phenolic resin
Many applications, so various phenol-formaldehyde resin modifieds are more and more concerned.Modification mode also has very much, can be divided into macromolecule at present and change
Property, inorganic filler is modified, the methods of nano material composite modified.
Graphene is a kind of New Two Dimensional material for the honeycomb structure being made of single layer sp2 hydbridized carbon atoms, has and is permitted
Mostly excellent performance.It has been found since 2004, graphene just becomes a big research hotspot of scientific circles.To graphene
Physicochemical properties while studied, emerge one after another with the relevant composite material of graphene.On nano science direction,
Graphene is also used to prepare receiving for relevant nanocomposite, especially graphene/metal or graphene/metal oxide
Nano composite material.Due to the excellent properties of graphene, these nanocomposites are in novel energy, bio-sensing, catalysis, optics
There are wide Research Prospects in the fields such as material.Due to the bulk effect that graphene shows, skin effect, quantum size,
The superior characteristic such as tensile strength and elasticity modulus, graphene are expected to, realization acquisition mechanics compound with macromolecule resin material
While performance boost, high-ductility, conduction, the heat conductivility etc. of conventional resins material are also improved.Based on the excellent heat conduction of graphene,
Electric conductivity is widely used in phenolic resin.
Application No. is the patents of invention of CN201410396902.1 to disclose a kind of preparation of graphene phenol-formaldehyde resin modified
Method, including：A phenol, formaldehyde, basic catalyst hybrid reaction) are obtained into phenolic resin；B) by step A) obtained phenolic resin
Graphene phenol-formaldehyde resin modified is obtained with graphene hybrid reaction.The present invention changes phenolic resin by using graphene
Property, the intensity and electric conductivity of phenolic resin are substantially increased, the resin impact strength after solidification improves 60% or more, bending
Intensity improves 40% or more, while imparting the phenolic resin electric conductivity after solidification, has widened the application field of phenolic resin,
It is easy to operate simultaneously, it is easy to industrialized production.
Application No. is the patents of invention of CN201710137863.7 to disclose a kind of preparation of graphene phenol-formaldehyde resin modified
Method, by with impregnated phenolic resin add a certain amount of grapheme material in conventional graphite improve resin the capacity of heat transmission and
Heat resistance, and for the problem of grapheme material and phenolic compatible difference, surface modification is carried out using silane coupling agent
Interface that mode both reduces can gap, compatibility of the graphene in resin is improved with this；It is big for impregnating resin viscosity,
Graphene is difficult to the problem of disperseing by the way of twice dispersing to improve the degree of scatter of graphene, improves the efficiency of material.
It is well known, however, that the dispersibility of graphene is not fine, graphene is added in phenolic resin and is easy to generate
Agglomeration may influence the heat resistance of phenolic resin, flame retardant property etc..How its nanoscale in resin matrix is realized
It is dispersed into the hot spot of research.This can effectively be solved the problems, such as by preparing graphene oxide by stripping graphite oxide.
Invention content
The present invention is directed to overcome the deficiencies of the prior art and provide one kind to improve graphene dispersibility in phenolic resin
Graphene phenol-formaldehyde resin modified preparation method.
To realize the present invention purpose the technical solution adopted is that：A kind of preparation side of graphene oxide/phenolic resin film
Method, it is characterised in that including following preparation process：
(1) graphene oxide suspension is prepared
It takes graphene oxide to pour into N-Methyl pyrrolidone, is ultrasonically treated after mixing, stand, take supernatant
Obtained supernatant is placed at 70~180 DEG C and is heat-treated by liquid, obtains solid powder, the solid powder second that then will be obtained
Alcohol washs, then is placed in 2~4h of heat treatment, same step at 50~100 DEG C and is washed twice again with ethyl alcohol, obtains required oxidation stone
Black alkene/phenolic resin suspension；
(2) water soluble phenol resin is prepared
Suitable phenol and formaldehyde Hybrid Heating are taken, NaOH is added after being warming up to 50~55 DEG C, heated at constant temperature is for a period of time
Obtain bright rufous water soluble phenol resin；
(3) graphene/phenolic resin composite is prepared
A certain amount of water soluble phenol resin is weighed, above-mentioned graphene oxide suspension one section of magnetic agitation at room temperature is added
Then time places it in and removes solvent in vacuum drying chamber, dried object is finally ground into fine powder with mortar, in hot press
In 160 DEG C, 0.06MPa conditions depress to thin slice.
Further, the graphite oxide powder solution concentration described in step (1) is 1~25mg/mL, the graphene oxide
A diameter of 1~2 μm of piece, the ultrasonic time are 1~72h.
Further, the molar ratio of phenol and the formaldehyde described in step (2) is 1: (2~5), the NaOH additive amounts
It is the 1~8% of phenol and formaldehyde pure material gross mass, the heated at constant temperature time is 60~180min.
Further, the magnetic agitation time described in step (3) be 10~70min, the vacuum drying temperature be 30~
80℃。
Application effect：Compared with prior art, the present invention haing the following advantages：(1) graphene oxide phenol-formaldehyde resin modified
Solves the defects of big traditional phenolic resin brittleness, the easy moisture absorption, poor toughness, electric conductivity difference and poor heat resistance.(2) graphite oxide
The addition of alkene improves the heat resistance and toughness of phenolic resin.(3) preparing graphene nanometer sheet based on N-Methyl pyrrolidone can
Preferably to improve dispersibility of the graphene in phenolic resin, play the role of enhancing its excellent properties.(4) it is warmed by height
Processing is with better electric conductivity.
Specific implementation mode
With reference to specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after having read the present invention, various equivalences of the those skilled in the art to the present invention
It is as defined in the appended claims that the modification of form falls within the application.
Embodiment 1
A kind of preparation method of graphene oxide/phenolic resin film, including following preparation process：
(1) graphene oxide suspension is prepared
It takes graphene oxide to pour into N-Methyl pyrrolidone, is ultrasonically treated after mixing, stand, take supernatant
Obtained supernatant is placed at 100 DEG C and is heat-treated by liquid, obtains solid powder, then washes obtained solid powder with ethyl alcohol
It washs, then is placed at 73 DEG C and is heat-treated 3h, same step is washed twice with ethyl alcohol again, obtains required graphene oxide/phenolic aldehyde tree
Fat suspension；
(2) water soluble phenol resin is prepared
Suitable phenol and formaldehyde Hybrid Heating are taken, NaOH is added after being warming up to 53 DEG C, heated at constant temperature obtains for a period of time
Bright rufous water soluble phenol resin；
(3) graphene/phenolic resin composite is prepared
A certain amount of water soluble phenol resin is weighed, above-mentioned graphene oxide suspension one section of magnetic agitation at room temperature is added
Then time places it in and removes solvent in vacuum drying chamber, dried object is finally ground into fine powder with mortar, in hot press
In 160 DEG C, 0.06MPa conditions depress to thin slice.
Embodiment 2
A kind of preparation method of graphene oxide/phenolic resin film, including following preparation process：
(1) graphene oxide suspension is prepared
It takes graphene oxide to pour into N-Methyl pyrrolidone, is ultrasonically treated after mixing, stand, take supernatant
Obtained supernatant is placed at 100 DEG C and is heat-treated by liquid, obtains solid powder, then washes obtained solid powder with ethyl alcohol
It washs, then is placed at 70 DEG C and is heat-treated 3h, same step is washed twice with ethyl alcohol again, obtains required graphene oxide/phenolic aldehyde tree
Fat suspension；
(2) water soluble phenol resin is prepared
Suitable phenol and formaldehyde Hybrid Heating are taken, NaOH is added after being warming up to 52 DEG C, heated at constant temperature obtains for a period of time
Bright rufous water soluble phenol resin；
(3) graphene/phenolic resin composite is prepared
A certain amount of water soluble phenol resin is weighed, above-mentioned graphene oxide suspension one section of magnetic agitation at room temperature is added
Then time places it in and removes solvent in vacuum drying chamber, dried object is finally ground into fine powder with mortar, in hot press
In 160 DEG C, 0.06MPa conditions depress to thin slice.
Two specific implementation modes of the present invention are above are only, but the design concept of the present invention is not limited thereto, all profits
The change for carrying out unsubstantiality to the present invention with this design, should all belong to the behavior for invading the scope of protection of the invention.In every case it is
Without departing from the content of technical solution of the present invention, according to the technical essence of the invention to any type of letter made by above example
Single modification, equivalent variations and remodeling, still fall within the protection domain of technical solution of the present invention.
Claims (4)
1. a kind of preparation method of graphene oxide/phenolic resin film, it is characterised in that including following preparation process：
(1) graphene oxide suspension is prepared
It takes graphene oxide to pour into N-Methyl pyrrolidone, is ultrasonically treated after mixing, stand, take supernatant, it will
Obtained supernatant is placed at 70~180 DEG C and is heat-treated, and obtains solid powder, then washes obtained solid powder with ethyl alcohol
It washs, then is placed in 2~4h of heat treatment, same step at 50~100 DEG C and is washed twice again with ethyl alcohol, obtain required graphite oxide
Alkene/phenolic resin suspension；
(2) water soluble phenol resin is prepared
Suitable phenol and formaldehyde Hybrid Heating are taken, NaOH is added after being warming up to 50~55 DEG C, heated at constant temperature obtains for a period of time
Bright rufous water soluble phenol resin；
(3) graphene/phenolic resin composite is prepared
Weigh a certain amount of water soluble phenol resin, be added above-mentioned graphene oxide suspension at room temperature one section of magnetic agitation when
Between, then place it in and remove solvent in vacuum drying chamber, dried object is finally ground into fine powder with mortar, in hot press in
160 DEG C, 0.06MPa conditions depress to thin slice.
2. a kind of preparation method of graphene oxide/phenolic resin according to claim 1, it is characterised in that step (1)
Described in graphite oxide powder solution concentration be 1~25mg/mL, a diameter of 1~2 μm of the graphene oxide sheet, the ultrasound
Time is 1~72h.
3. a kind of preparation method of graphene oxide/phenolic resin film according to claim 1, it is characterised in that step
(2) molar ratio of phenol described in and the formaldehyde is 1: (2~5), the NaOH additive amounts are that phenol and formaldehyde pure material are total
The 1~8% of quality, the heated at constant temperature time are 60~180min.
4. a kind of preparation method of graphene oxide/phenolic resin film according to claim 1, it is characterised in that step
(3) magnetic agitation time described in is 10~70min, and the vacuum drying temperature is 30~80 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810396592.1A CN108504031A (en) | 2018-04-20 | 2018-04-20 | A kind of preparation method of graphene oxide/phenolic resin film |
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| CN201810396592.1A CN108504031A (en) | 2018-04-20 | 2018-04-20 | A kind of preparation method of graphene oxide/phenolic resin film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467874A (en) * | 2018-10-18 | 2019-03-15 | 上海欧亚合成材料有限公司 | A kind of graphene oxide modified phenolic molding compound and preparation method thereof |
| CN110194880A (en) * | 2019-05-16 | 2019-09-03 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of Ni-coated graphite alkene reinforced resin based composites and preparation method thereof with electromagnetic shielding performance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467874A (en) * | 2018-10-18 | 2019-03-15 | 上海欧亚合成材料有限公司 | A kind of graphene oxide modified phenolic molding compound and preparation method thereof |
| CN109467874B (en) * | 2018-10-18 | 2021-08-10 | 上海欧亚合成材料股份有限公司 | Graphene oxide modified phenolic molding compound and preparation method thereof |
| CN110194880A (en) * | 2019-05-16 | 2019-09-03 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of Ni-coated graphite alkene reinforced resin based composites and preparation method thereof with electromagnetic shielding performance |
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