CN105601979A - Method for preparing phenolic foam containing expanded graphite - Google Patents
Method for preparing phenolic foam containing expanded graphite Download PDFInfo
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- CN105601979A CN105601979A CN201610061425.2A CN201610061425A CN105601979A CN 105601979 A CN105601979 A CN 105601979A CN 201610061425 A CN201610061425 A CN 201610061425A CN 105601979 A CN105601979 A CN 105601979A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a method for preparing phenolic foam containing expanded graphite. According to the method, firstly, polyacrylic acid is adopted to modify expanded graphite; secondly, gamma-epoxy propoxy propyl trimethoxy silane is adopted to modify expanded graphite so that silane modified expanded graphite alkene can be prepared; finally, phenolic resin containing expanded graphite is prepared through reaction between phenol and paraformaldehyde, and phenolic foam is further prepared. By means of the method, the defects that the mechanical property of phenolic foam is poor, fragility is large, and dreg falling occurs frequently can be effectively improved, the mechanical property of phenolic foam is improved, and phenolic foam has a wider application prospect range.
Description
Technical field
The present invention relates to polymeric foamed material, especially relate to a kind of modified expanded graphite that adopts and prepare phenolic aldehyde treeFat is also made the method for phenol formaldehyde foam.
Background technology
Phenol formaldehyde foam is as one of most widely used flame resistant heat insulation material, and phenol formaldehyde foam has the property of a lot of excellencesCan, for example high temperature resistant, heat-resisting, Stability Analysis of Structures, low cigarette, difficult combustion. the raw material source of phenol formaldehyde foam is abundant,Production technology is simple, with low cost, and phenol formaldehyde foam cost is only equivalent to 2/3rds of polyurethane foam. PhenolThe quality of aldehyde foam is light, but specific strength is very large, and size is more stable, even can under the condition of-30 DEG C, growPhase is used, and size changing rate is now only 1%, and phenol formaldehyde foam can be for a long time at the high temperature bar of 150 DEG CUnder part, using. phenol formaldehyde foam Related product purposes is very extensive, is used to many fields.
Though phenol formaldehyde foam has the performance of many excellences, but phenol formaldehyde foam also exists some defects, and phenolic aldehyde is being usedIn the time of the fields such as building, pipeline, chemical industry, aviation, phenol formaldehyde foam is as a kind of structural material, by forceThe mechanical property aspects such as degree, toughness are all weak, and easily fall slag dry linting, for phenol formaldehyde foam in mechanical propertyOn deficiency, need to carry out study on the modification to the mechanical property of phenol formaldehyde foam.
At present, inoganic particle modified phenol formaldehyde foam is a kind of conventional method of modifying, in order to change phenol formaldehyde foamFoam structure, adds inorganic particulate in phenolic resins and improves foam structure by foaming.
Expanded graphite is obtained through high-temperature expansion by expansible graphite, has loose structure, porous surface,Form bending, the long-pending expansion in expansion rear surface, surface can be improved, absorption affinity strengthens. because this special structure,Can be chimeric voluntarily between expanded graphite, increase like this its flexibility, resilience and plasticity, expansion stoneChina ink is because surface area expands, and nucleating point increases, and as heterogeneous nucleation agent, reduces to form abscess needed certainlyBy energy, abscess increased, abscess-size reduces, and foam structure is more even, thereby improves phenol formaldehyde foamPerformance.
Summary of the invention
The problems referred to above that exist for prior art, the applicant provides the phenolic aldehyde bubble of a kind of utilization containing expanded graphiteThe preparation method of foam. The inventive method can effectively be improved phenol formaldehyde foam poor mechanical property, and fragility great Yi falls slagShortcoming, improve the mechanical property of phenol formaldehyde foam, make the application prospect widely that has of phenol formaldehyde foam.
Technical scheme of the present invention is as follows:
A preparation method who contains the phenol formaldehyde foam of expanded graphite, the method comprises the steps:
(1) by polyacrylic acid, N, N '-dicyclohexylcarbodiimide joins the tetrahydrofuran solution of expanded graphiteIn, after ultrasonic mixing 0.5～2h, at N2Protection, under the condition of 50～70 DEG C, magnetic agitation 4～12h, producesThing cleans 2～5 times with oxolane and is dried, and makes polyacrylic acid modified expanded graphite;
(2) the polyacrylic acid modified expanded graphite, the N that step (1) are made, N '-dicyclohexyl carbon two AsiasAmine is dispersed in the anhydrous tetrahydro furan of 50～100mL, and ultrasonic dispersion 1h, then at N2Under protective condition,Dispersion liquid is dropwise added in γ-glycidoxypropyltrime,hoxysilane, under 60～80 DEG C of conditions, stir4～8h, centrifugal, the dry expanded graphite alkene that makes the grafting of γ-glycidoxypropyltrime,hoxysilane;
(3) the expanded graphite alkene of γ-glycidoxypropyltrime,hoxysilane grafting step (2) being madeJoin in phenol, sonic oscillation 0.5～3h, then adds solid polyformaldehyde powder, catalyst n aOHThe aqueous solution reacts 1～1.5h at 70～80 DEG C, then at 80～85 DEG C, reacts 1～1.5h, then at 90～100 DEG CLower reaction 2.5～3.5h; Finally cool to 80～85 DEG C with the speed of 1～5 DEG C/min, and add urea as firstAldehyde agent for capturing reaction 10～15min, then be cooled to 70 DEG C ,-0.07～0.10MPa with the speed of 1～5 DEG C/minCondition under vacuum dehydration, after be cooled to room temperature with the speed of 1～5 DEG C/min again, and add Al (OH)3, addEntering ethylene glycol, to make the viscosity of resin be 2000～5000mPa.s, makes the phenolic resins containing expanded graphite;
(4) phenolic resins containing expanded graphite step (3) being made is with Tween 80, carrene, hardAfter bubble silicone oil is uniformly mixed, then in mixture, add curing agent p-methyl benzenesulfonic acid, stir, put into mouldIn tool and be placed in the constant temperature oven 0.5h～1h of 70～80 DEG C, then place at ambient temperature 1～2 day,Make the described phenol formaldehyde foam containing expanded graphite.
In described step (1), the particle diameter of expanded graphite is 100～500 orders; The oxolane of described expanded graphiteThe mass concentration of solution is 0.1～5%.
Polyacrylic acid, N in described step (1), the oxolane of N '-dicyclohexylcarbodiimide and expanded graphiteThe mass ratio of solution is 1:1:200～500.
Polyacrylic acid modified expanded graphite, N in described step (2), the quality of N '-dicyclohexylcarbodiimideThan being 1:1～2.
Polyacrylic acid modified expanded graphite and γ-glycidoxypropyltrime,hoxysilane in described step (2)Mass ratio be 1:25～75.
The expanded graphite of the middle γ-glycidoxypropyltrime,hoxysilane grafting of described step (3) and phenolMass ratio is 0.1～2:100.
In described step (3), the mol ratio of phenol and paraformaldehyde powder is 0.5～1:1; Described NaOH is water-solubleThe mass concentration of liquid is 10～30%, and consumption is 0.8～5% of phenol quality.
In described step (3), amount of urea is 1～5% of paraformaldehyde powder quality, described Al (OH)3ConsumptionFor 5～15% of phenol usage.
The middle carrene consumption of described step (4) is containing 5～7% of the phenolic resins quality of expanded graphite; DescribedTween 80 consumption is containing 3～4% of the phenolic resins quality of expanded graphite; The described silicon oil dosage of hard bubbling is swollen for containing1～3% of the phenolic resins quality of swollen graphite; Described p-methyl benzenesulfonic acid consumption is the phenolic resins containing expanded graphite10～20% of quality.
The technique effect that the present invention is useful is:
(1) the inventive method select expanded graphite as modified particle, expanded graphite by expansible graphite at heightAt warm 900 DEG C, expand and make, after overexpansion, between graphite flake layer, spacing increases, and forms quasiflake graphite,Therefore expanded graphite has larger specific area, by particle large this specific area for phenol formaldehyde foamIn the middle of modification, can make the nucleating point in foam increase, thereby the abscess quantity forming is increased, foamIt is less more even that size becomes, and therefore has better mechanical property. And the wide material sources of expanded graphite, becomeThis is lower, and preparation technology is simple, has broad application prospects and business with expanded graphite modified phenol formaldehyde foamBe worth.
(2) the inventive method is being used γ-glycidoxypropyltrime,hoxysilane graft modification expanded graphiteBefore, first process expanded graphite with polyacrylic acid, solution expanded graphite and silane coupler grafting time are long,The unconspicuous problem of reaction effect, has obviously shortened the reaction time, has improved reaction efficiency.
(3) the inventive method is selected paraformaldehyde pressed powder in the preparation process of phenolic resins, has avoidedAfter tradition formalin precursor reactant, need the problem of long-time dehydration, saved the energy, shortened the time; SelectUrea is as formaldehyde catching agent, and cost is lower, adds aluminium hydroxide as a kind of packing agent, improves phenolic aldehyde bubbleThe fire resistance of foam, finally, by the viscosity of the phenolic resins that spent glycol regulated make, makes phenolic aldehyde treeFat viscosity reaches the concentration range of suitable foaming.
Brief description of the drawings
Fig. 1 is that the phenol formaldehyde foam in embodiment 1 amplifies the image of 50 times under the microscope.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is specifically described.
Embodiment 1
A preparation method who contains the phenol formaldehyde foam of expanded graphite, the method comprises the steps:
(1) by 100mg polyacrylic acid, 100mgN, N '-dicyclohexylcarbodiimide joins 50ml qualityConcentration is (particle diameter of expanded graphite is 100 orders) in 0.1% expanded graphite tetrahydrofuran solution, ultrasonic mixingAfter 0.5h, at N2Protection, under the condition of 60 DEG C, magnetic agitation 4h, product cleans 3 times with oxolane and doesDry, make polyacrylic acid modified expanded graphite;
(2) the polyacrylic acid modified expanded graphite, the 100mgN that 100mg step (1) are made, N '-bis-Carbodicyclo hexylimide is dispersed in the anhydrous tetrahydro furan of 100mL, and ultrasonic dispersion 1h, then at N2Under protective condition, dispersion liquid is dropwise added in 2.8g γ-glycidoxypropyltrime,hoxysilane, at 60 DEG CUnder condition, stir 4h, centrifugal, the dry expansion that makes the grafting of γ-glycidoxypropyltrime,hoxysilaneGraphene;
(3) the expansion stone of γ-glycidoxypropyltrime,hoxysilane grafting 0.4g step (2) being madeChina ink alkene joins in 100g phenol, and sonic oscillation 1h, then adds 52g solid polyformaldehyde powder, 5gMass concentration is 10% the NaOH aqueous solution, at 70 DEG C, reacts 1h, then at 80 DEG C, reacts 1h,At 100 DEG C, react 2.5h again; Finally cool to 80 DEG C with the speed of 5 DEG C/min, and add 1g urea to doFor formaldehyde catching agent reaction 10min, then be cooled to 70 DEG C, the condition of-0.07MPa with the speed of 5 DEG C/minLower vacuum dehydration, after be cooled to room temperature with the speed of 1 DEG C/min again, and add 5gAl (OH)3, add second twoIt is 4000mPa.s that alcohol makes the viscosity of resin, makes the phenolic resins containing expanded graphite;
(4) phenolic resins containing expanded graphite 100g step (3) being made, with 3g Tween 80,5gCarrene, the 1g silicone oil that hard bubbles stirs 1min with the speed of 2000r/min, then in mixture, adds 10gCuring agent p-methyl benzenesulfonic acid, stirs 0.5min with the speed of 1000r/min, stirs, and puts into mould alsoBe placed in the constant temperature oven 0.5h of 80 DEG C, then place at ambient temperature 1 day, can make described containing expandingThe phenol formaldehyde foam of graphite. Image when gained phenolic resin foam amplifies 50 times under the microscope as shown in Figure 1(carry out microscopic analysis in order to prepare foam sample, foam need be coated with the gold of 1.5-2.5 layer in inert gas).
As seen from Figure 1, the present invention makes phenolic resin foam abscess structure more uniformly.
Embodiment 2
A preparation method who contains the phenol formaldehyde foam of expanded graphite, the method comprises the steps:
(1) by 100mg polyacrylic acid, 100mgN, N '-dicyclohexylcarbodiimide joins 50ml qualityConcentration is (particle diameter of expanded graphite is 200 orders) in 5% expanded graphite tetrahydrofuran solution, ultrasonic mixingAfter 2h, at N2Protection, under the condition of 50 DEG C, magnetic agitation 10h, product cleans 2 times with oxolane and doesDry, make polyacrylic acid modified expanded graphite;
(2) the polyacrylic acid modified expanded graphite, the 150mgN that 100mg step (1) are made, N '-bis-Carbodicyclo hexylimide is dispersed in the anhydrous tetrahydro furan of 100mL, and ultrasonic dispersion 1h, then at N2Under protective condition, dispersion liquid is dropwise added in 7.5g γ-glycidoxypropyltrime,hoxysilane, at 60 DEG CUnder condition, stir 4h, centrifugal, the dry expansion that makes the grafting of γ-glycidoxypropyltrime,hoxysilaneGraphene;
(3) the expansion stone of γ-glycidoxypropyltrime,hoxysilane grafting 1g step (2) being madeChina ink alkene joins in 100g phenol, and sonic oscillation 3h, then adds 80g solid polyformaldehyde powder, 4gMass concentration is 30% the NaOH aqueous solution, at 75 DEG C, reacts 1h, then at 80 DEG C, reacts 1.5h,At 90 DEG C, react 3.5h again; Finally cool to 80 DEG C with the speed of 1 DEG C/min, and add the conduct of 4g ureaFormaldehyde catching agent reaction 15min, then be cooled to 70 DEG C with the speed of 5 DEG C/min, true under the condition of 0.05MPaEmpty dehydration, after be cooled to room temperature with the speed of 5 DEG C/min again, and add 15gAl (OH)3, add ethylene glycolMaking the viscosity of resin is 2000mPa.s, makes the phenolic resins containing expanded graphite;
(4) phenolic resins containing expanded graphite 100g step (3) being made, with 4g Tween 80,7gCarrene, the 3g silicone oil that hard bubbles stirs 1min with the speed of 2000r/min, then in mixture, adds 20gCuring agent p-methyl benzenesulfonic acid, stirs 0.5min with the speed of 1000r/min, stirs, and puts into mould alsoBe placed in the constant temperature oven 1h of 75 DEG C, then place at ambient temperature 1 day, can make described containing expansion stoneThe phenol formaldehyde foam of China ink.
Embodiment 3
A preparation method who contains the phenol formaldehyde foam of expanded graphite, the method comprises the steps:
(1) by 100mg polyacrylic acid, 100mgN, N '-dicyclohexylcarbodiimide joins 50ml qualityConcentration is (particle diameter of expanded graphite is 500 orders) in 0.5% expanded graphite tetrahydrofuran solution, ultrasonic mixingAfter 1h, at N2Protection, under the condition of 70 DEG C, magnetic agitation 8h, product cleans 5 times with oxolane and doesDry, make polyacrylic acid modified expanded graphite;
(2) the polyacrylic acid modified expanded graphite, the 200mgN that 100mg step (1) are made, N '-bis-Carbodicyclo hexylimide is dispersed in the anhydrous tetrahydro furan of 100mL, and ultrasonic dispersion 1h, then at N2Under protective condition, dispersion liquid is dropwise added in 5g γ-glycidoxypropyltrime,hoxysilane, at 60 DEG CUnder condition, stir 4h, centrifugal, the dry expansion that makes the grafting of γ-glycidoxypropyltrime,hoxysilaneGraphene;
(3) the expansion stone of γ-glycidoxypropyltrime,hoxysilane grafting 0.8g step (2) being madeChina ink alkene joins in 100g phenol, and sonic oscillation 1h, then adds 65g solid polyformaldehyde powder, 3gMass concentration is 15% the NaOH aqueous solution, at 80 DEG C, reacts 1h, then at 85 DEG C, reacts 1.5h,At 90 DEG C, react 3h again; Finally cool to 85 DEG C with the speed of 1 DEG C/min, and add the conduct of 3g ureaFormaldehyde catching agent reaction 15min, then be cooled to 70 DEG C with the speed of 5 DEG C/min, true under the condition of 0.1MPaEmpty dehydration, after be cooled to room temperature with the speed of 5 DEG C/min again, and add 10gAl (OH)3, add ethylene glycolMaking the viscosity of resin is 3000mPa.s, makes the phenolic resins containing expanded graphite;
(4) phenolic resins containing expanded graphite 100g step (3) being made, with 3.5g Tween 80,7gCarrene, the 2g silicone oil that hard bubbles stirs 1min with the speed of 2000r/min, then in mixture, adds 15gCuring agent p-methyl benzenesulfonic acid, stirs 0.5min with the speed of 1000r/min, stirs, and puts into mould alsoBe placed in the constant temperature oven 0.5h of 80 DEG C, then place at ambient temperature 1 day, can make described containing expandingThe phenol formaldehyde foam of graphite.
Claims (9)
1. a preparation method who contains the phenol formaldehyde foam of expanded graphite, is characterized in that the method comprises following stepRapid:
(1) by polyacrylic acid, N, N '-dicyclohexylcarbodiimide joins the tetrahydrofuran solution of expanded graphiteIn, after ultrasonic mixing 0.5～2h, at N2Protection, under the condition of 50～70 DEG C, magnetic agitation 4～12h, producesThing cleans 2～5 times with oxolane and is dried, and makes polyacrylic acid modified expanded graphite;
(2) the polyacrylic acid modified expanded graphite, the N that step (1) are made, N '-dicyclohexyl carbon two AsiasAmine is dispersed in the anhydrous tetrahydro furan of 50～100mL, and ultrasonic dispersion 1h, then at N2Under protective condition,Dispersion liquid is dropwise added in γ-glycidoxypropyltrime,hoxysilane, under 60～80 DEG C of conditions, stir4～8h, centrifugal, the dry expanded graphite alkene that makes the grafting of γ-glycidoxypropyltrime,hoxysilane;
(3) the expanded graphite alkene of γ-glycidoxypropyltrime,hoxysilane grafting step (2) being madeJoin in phenol, sonic oscillation 0.5～3h, then adds solid polyformaldehyde powder, catalyst n aOHThe aqueous solution reacts 1～1.5h at 70～80 DEG C, then at 80～85 DEG C, reacts 1～1.5h, then at 90～100 DEG CLower reaction 2.5～3.5h; Finally cool to 80～85 DEG C with the speed of 1～5 DEG C/min, and add urea as firstAldehyde agent for capturing reaction 10～15min, then be cooled to 70 DEG C ,-0.07～0.10MPa with the speed of 1～5 DEG C/minCondition under vacuum dehydration, after be cooled to room temperature with the speed of 1～5 DEG C/min again, and add Al (OH)3, addEntering ethylene glycol, to make the viscosity of resin be 2000～5000mPa.s, makes the phenolic resins containing expanded graphite;
(4) phenolic resins containing expanded graphite step (3) being made is with Tween 80, carrene, hardAfter bubble silicone oil is uniformly mixed, then in mixture, add curing agent p-methyl benzenesulfonic acid, stir, put into mouldIn tool and be placed in the constant temperature oven 0.5h～1h of 70～80 DEG C, then place at ambient temperature 1～2 day,Make the described phenol formaldehyde foam containing expanded graphite.
2. preparation method according to claim 1, is characterized in that expanded graphite in described step (1)Particle diameter be 100～500 orders; The mass concentration of the tetrahydrofuran solution of described expanded graphite is 0.1～5%.
3. preparation method according to claim 1, it is characterized in that polyacrylic acid in described step (1),N, the mass ratio of the tetrahydrofuran solution of N '-dicyclohexylcarbodiimide and expanded graphite is 1:1:200～500.
4. preparation method according to claim 1, is characterized in that polyacrylic acid in described step (2)The expanded graphite of modification, N, the mass ratio of N '-dicyclohexylcarbodiimide is 1:1～2.
5. preparation method according to claim 1, is characterized in that polyacrylic acid in described step (2)The mass ratio of modified expanded graphite and γ-glycidoxypropyltrime,hoxysilane is 1:25～75.
6. preparation method according to claim 1, is characterized in that γ-epoxy third in described step (3)The expanded graphite of oxygen base propyl trimethoxy silicane grafting and the mass ratio of phenol are 0.1～2:100.
7. preparation method according to claim 1, is characterized in that in described step (3) that phenol is with manyThe mol ratio of polyformaldehyde powder is 0.5～1:1; The mass concentration of the described NaOH aqueous solution is 10～30%, usesAmount is 0.8～5% of phenol quality.
8. preparation method according to claim 1, is characterized in that amount of urea in described step (3)For 1～5% of paraformaldehyde powder quality, described Al (OH)3Consumption is 5～15% of phenol usage.
9. preparation method according to claim 1, is characterized in that carrene in described step (4)Consumption is containing 5～7% of the phenolic resins quality of expanded graphite; Described Tween 80 consumption is to contain expanded graphite3～4% of phenolic resins quality; The described silicon oil dosage of hard bubbling is containing the phenolic resins quality of expanded graphite1～3%; Described p-methyl benzenesulfonic acid consumption is containing 10～20% of the phenolic resins quality of expanded graphite.
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| CN115044181A (en) * | 2022-03-28 | 2022-09-13 | 中建工程产业技术研究院有限公司 | Glass fiber composite material and preparation and recovery method thereof |
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| CN106009490A (en) * | 2016-07-08 | 2016-10-12 | 江南大学 | Heterogeneous nucleating agent toughening-modified phenolic resin foam and preparation method thereof |
| CN106009490B (en) * | 2016-07-08 | 2018-06-19 | 江南大学 | A kind of phenolic resin foam of heterogeneous nucleation agent toughening modifying and preparation method thereof |
| CN106966379A (en) * | 2017-03-15 | 2017-07-21 | 江南大学 | A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material |
| CN106966379B (en) * | 2017-03-15 | 2019-03-01 | 江南大学 | A kind of preparation method of the modification phenolic resin-based carbon foam of graphene/silicon dioxide hybrid material |
| CN109200327A (en) * | 2018-07-06 | 2019-01-15 | 苏州盖德精细材料有限公司 | A kind of novel high-performance medical dressing and preparation method thereof |
| CN109200327B (en) * | 2018-07-06 | 2021-07-09 | 苏州盖德精细材料有限公司 | Novel high-performance medical dressing and preparation method thereof |
| CN114060781A (en) * | 2021-09-30 | 2022-02-18 | 深圳市联域光电股份有限公司 | Aluminum alloy heat dissipation cavity structure containing heat storage body for LED lamp and preparation method thereof |
| CN115044181A (en) * | 2022-03-28 | 2022-09-13 | 中建工程产业技术研究院有限公司 | Glass fiber composite material and preparation and recovery method thereof |
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