CN108084307A - A kind of preparation method of graphene and its method of static conductive graphene EPS - Google Patents
A kind of preparation method of graphene and its method of static conductive graphene EPS Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
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Abstract
The present invention relates to a kind of methods of the preparation method and its static conductive graphene EPS of graphene：Intercalation is carried out to graphite with oxidation intercalator, High power microwavs continuous swelling is carried out to this intercalated graphite and ultrasonic stripping prepares single-layer graphene, graphene is modified, then it is polymerize again with styrene monomer, the graphene EPS moulding articles prepared after foaming can reach static conductive effect, and mechanical property also obtains larger raising；Consider process costs, can first prepare antistatic graphene EPS moulding articles, then equally reach static conductive effect in one layer graphene conductive coating of surface spraying again.Its sheet resistance is up to 104~106Ω, tensile strength reach B1 grades, can play a significant role in specific areas such as military project, electric power, automobiles up to 0.8 1.2Mpa, compression strength up to 0.4 0.5Mpa, flame retardant rating.
Description
Technical field
The present invention relates to a kind of preparation of graphene, graphene modification and graphene applied technical field, more particularly, to one
The preparation method of kind graphene and its preparation method of static conductive graphene EPS.
Background technology
Graphene be it is a kind of by the tightly packed two dimensional crystal material formed of carbon atom, it is excellent because it has unique structure
The performances such as different electricity, mechanics, optics, chemistry and calorifics become the hot spot of many people research.In the industrial applications of graphene
In, graphene of the number of plies at 1~2 layer can be referred to as single-layer graphene.
The downstream application of graphene is slowly not switched on market, especially in field of compound material.Graphene preparation has oxidation also
Former method and Physical etc., graphene is because of large specific surface area, and usual reactivity is all higher, especially the graphene after redox
Edge can also be left some active groups or inhibition group, so graphene should carry out appropriate modification, stone before downstream application
The modification of black alkene is related to change, grafting or surface package of group etc., therefore, the modification of graphene be graphene preparation and under
Critically important one ring of centre in trip application.
At present, in the method for graphene preparation of industrialization, the production capacity that Physical prepares graphene is limited, and is generally all existed
Ton/year, and the graphene stability produced is poor, and oxidation-reduction method prepares graphene process stabilizing, yield is higher, generally may be used
Up to 100 tons/year, it is suitble to a kind of preparation method of large-scale production, but the post processing cost of the spent acid after its redox is higher,
It is the principal element that cost can not be greatly lowered in graphene.
Oxidation-reduction method, which prepares graphene, mainly Brodie methods, Staudenmaier methods, Hummers methods, improvement
Hummers methods etc., Brodie methods, Staudenmaier methods are containing concentrated nitric acid, KClO3System can have been generated in reaction process
Poisonous gas and pollution it is more serious.Existing Hummers methods are improved in Hummers methods, are the concentrated sulfuric acid, nitrate, potassium permanganate body
System, 98% concentrated sulfuric acid are generally the 30-90 (mass ratio, similarly hereinafter) of graphite, and nitrate is the 1-5 of graphite, and potassium permanganate is graphite
1-10, while to use other strong oxidizers, such as hydrogen peroxide, hydrochloric acid, Strong oxdiative intercalator usage amount is big, seriously polluted；
Simultaneously in order to which reaction process is controlled to stablize, generally want first ice bath or step up thermotonus again after being reacted in low temperature；
In actual large-scale production process, Strong oxdiative intercalator usage amount can increase oxidation-reduction method, and post processing cost is high, pollution is big, and
Real reaction activity is more difficult to control, and technology stability is poor, danger coefficient is big.It is few to be badly in need of a kind of oxidation intercalator dosage of exploitation,
The good graphene preparation method of technology stability.
EPS, that is, expandable polystyrene adds in foaming agent using polystyrene resin beads, while heating is softened,
Gas is generated, forms a kind of foamed plastics of rigid closed cell structure, EPS is mainly used in the packaging of product food, external wall
The fields such as heat preservation, but EPS product mechanical strengths are relatively low at present, limit the application of EPS manufactured goods, and in Militaryl package and electricity
Fields such as power, heavy industry, automobile, and require antistatic static conductive high field, the appearance of static conductive graphene EPS at a time when its
When.
The content of the invention
The purpose of the present invention is that the mono-layer graphite in view of the above shortcomings of the prior art, providing a kind of suboxides system
The manufacturing cost of graphene is greatly reduced in the preparation method of alkene, and environmentally friendly cost is greatly reduced.
It is a further object of the present invention to provide a kind of graphene method of modifying of suitable graphene industrialization downstream application, are
The industrial applications of graphene provide a kind of reliable way method.
It is a further object of the present invention to provide a kind of high intensity, high fire-retardance, static conductive graphene EPS moulding article,
And a kind of graphene conductive coating is provided, it is attached to antistatic graphene EPS surfaces to achieve the effect that surface static conductive, together
Shi Tigao coating adhesion grades, meanwhile, it can only be fabricated to leading for single side or multiaspect according to application field and engineer application needs
The graphene EPS moulding articles of electrostatic.
Technical scheme is as follows：
A kind of preparation method of static conductive graphene EPS, comprises the following steps：
(1) the oxidation intercalation of graphite：Using the graphite of 800~1200 mesh grain sizes as raw material, purity be more than 99%, by graphite with
Aoxidize intercalator mixing carry out intercalation, it is described oxidation intercalator be mass fraction be 90%-98% the concentrated sulfuric acid, nitrate, height
The mixture of potassium manganate, mass ratio are graphite：The concentrated sulfuric acid：Nitrate：Potassium permanganate=1：1~5：0.1~0.5：0.5~1；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling 20 to intercalated graphite
~200S, control control 200~300KW of output power carry out mono-layer graphite of the ultrasound stripping into the number of plies at 1~2 layer after discharging
Alkene；
(3) alcohol of graphene washes modification：The graphene that step (2) obtains is mixed into 1~5h, graphene with a certain amount of alcohol
Mass ratio with alcohol is 1：5~10, it carries out alcohol and washes modified filtration drying；
(4) preparation of static conductive graphene EPS, raw material and its mass percent system as needed for following suspension polymerization system
It is standby：
A kind of preparation method of surface static conductive graphene EPS, comprises the following steps：
A, graphene EPS moulding articles are first prepared, by following suspension polymerization system, are prepared by mass percentage：
B, graphene conductive coating is sprayed on EPS moulding articles again, the material quality of the graphene conductive coating
Percentage is：
Step (3)
Preferably, the nitrate is at least one of sodium nitrate, potassium nitrate；The alcohol is ethylene glycol, different molecular
At least one of polyethylene glycol of amount.
Preferably, the initiator is dibenzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide acetic acid butyl ester
At least one of；The dispersant be active calcium phosphate, EPS dispersant specials；The dispersion aids for sodium alkyl benzene sulfonate,
At least one of polyvinyl alcohol.
Preferably, the resin is epoxy resin, acrylic resin, alkyd resin, amino resins, polyester resin, poly- ammonia
At least one of ester resin, organic siliconresin, fluorocarbon resin and related compound resin.
Preferably, the wetting dispersing agent is at least one in BYK140, BYK161, BYK163, BYK168, BYK2000
Kind；The stabilizer is at least one of polyethylene wax, polyamide wax, aerosil；Adhesion promoter is even for silane
Join at least one of agent, titanate coupling agent, modified poly ester compound, modified propylene acid compound.
Preferably, the mixed solvent be ethyl alcohol, dimethylbenzene, trimethylbenzene, n-butanol, ethyl acetate, butyl acetate, the third two
At least one of alcohol methyl ether acetate.
The preparation process of the static conductive graphene EPS is：
(1) by mass percent styrene 28~32%, pure water 62~68.8%, modified graphene 0.5~1%, point
Powder 0.5~1.5%, dispersion aids 0.1~0.2% are added in reaction kettle, carry out pre-dispersed stirring 15min, mixing speed
Keep 100-150r/min；
(2) and then initiator 0.1~0.3% is added in, mixing speed keeps 150-200r/min, and starts to warm up；When anti-
When answering the material temperature in kettle to rise to 88~91 DEG C, when polymerisation 7~9 is small at this temperature；
(3) seal pot tank adds foaming agent pentane 2~3%, continues to heat up；When material in reactor temperature rises to 115~
At 125 DEG C, when constant temperature holding 6~8 is small；
(4) after hot stage, decrease temperature and pressure takes out material filtering, then dry graphene EPS beads；Finally,
Foaming is prepared into various graphene EPS moulding articles.
The preparation process of the surface static conductive graphene EPS is：
(1) graphene EPS moulding articles are prepared：By mass percent styrene 28~32%, pure water, modified graphene
0.05~0.15%, dispersant 0.4~1%, dispersion aids 0.05~0.1% are added in reaction kettle, carry out pre-dispersed stirring
15min, mixing speed keep 100-150r/min；
(2) and then initiator 0.05~0.2% is added in, mixing speed keeps 150-200r/min, and starts to warm up；When anti-
When answering the material temperature in kettle to rise to 88~91 DEG C, when polymerisation 6~8 is small at this temperature；
(3) seal pot tank adds foaming agent pentane 2~3%, continues to heat up；When material in reactor temperature rises to 115~
At 125 DEG C, when constant temperature holding 4~6.5 is small；
(4) after hot stage, decrease temperature and pressure takes out material filtering, dry graphene EPS beads；Then, foam
It is prepared into various graphene EPS moulding articles；
(5) finally, in graphene EPS molded article surface graphite spraying alkene electrically-conducting paints, done at a temperature of 60~80 DEG C
Dry 5~10h, 30~100um of coating layer thickness, up to the graphene EPS moulding articles of surface static conductive after drying.
The present invention is beneficial to be had technical effect that：
(1) a kind of preparation method method of new graphene is developed, graphene preparation technology route is ripe, is suitble to industry
Change big production；(2) preparation of this graphene significantly reduces the cost of existing preparation of industrialization and environmentally friendly cost；(3) provide
One kind is suitable for industrialized graphene method of modifying, and a kind of reliable way method is provided for the industrial applications of graphene；
(4) provide a kind of high intensity, high fire-retardance, static conductive graphene EPS beads preparation method and moulding article (5) provide one
The preparation method (6) of kind graphene conductive coating provides a kind of high intensity, high fire-retardance, the graphene EPS pearls of surface static conductive
The preparation method and moulding article (7) of grain are wanted in the fields such as Militaryl package and electric power, heavy industry, automobile, and to antistatic static conductive
High field is asked, provides a kind of static conductive graphene EPS moulding article materials；(8) the downstream application model of graphene has been widened
It encloses and the application range of graphene EPS.
A kind of preparation method of graphene of the present invention and its downstream application that the method for static conductive graphene EPS is graphene
And the application of graphene EPS opens a kind of new implemented method, it is easy to accomplish industrialization significantly reduces the system of graphene
Standby cost.Graphene through the applicant prepare and it is modified, polymerize with EPS made of graphene EPS moulding articles, can more improve
Graphene EPS product property indices, such as the advantages that high strength, high fire-retardance, static conductive.This static conductive graphene EPS
Moulding article density is 25~30kg/m3, sheet resistance is up to 104~106Ω, tensile strength reach 0.8-1.2Mpa, pressure resistance
Degree reaches B1 grades up to 0.4-0.5Mpa, flame retardant rating, can be applied to the fields such as Militaryl package and electric power, heavy industry, automobile, and to anti-quiet
Conductance electrostatic requires high field.
Description of the drawings
Fig. 1 is the tensile strength comparison diagram of embodiment provided by the invention；
Fig. 2 is the compression strength comparison diagram of embodiment provided by the invention；
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
(1) the oxidation intercalation of graphite：Using the graphite of 800 mesh grain sizes as raw material, purity 99%, by graphite and oxidation intercalator
Mixing carries out intercalation, and oxidation intercalator system is 90% concentrated sulfuric acid, sodium nitrate, potassium permanganate system, and mass ratio is graphite：Dense sulphur
Acid：Sodium nitrate：Potassium permanganate=1：1：0.1：0.5；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
20S, control control output power 300KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2000m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：By graphene and a certain amount of ethylene glycol mixing 1h, the matter of graphene and ethylene glycol
Amount is than being 1：5, it carries out alcohol and washes modified filtration drying；
(4) preparation of static conductive graphene EPS by following suspension polymerization system, is prepared by mass percentage：
By mass percent styrene 28%, pure water 68.8%, modified graphene 0.5%, dispersant active calcium phosphate
0.5%th, dispersion aids polyvinyl alcohol 0.1%, be added in reaction kettle, carry out pre-dispersed stirring 15min, mixing speed is kept
100r/min；Then initiator dibenzoyl peroxide 0.1% is added in, mixing speed keeps 150r/min, and starts to warm up；When
When material in reactor temperature rises to 88 DEG C, when polymerisation 9 is small at this temperature；Seal pot tank adds foaming agent pentane
2%, continue to heat up；When material in reactor temperature rises to 115 DEG C, when constant temperature holding 8 is small；After hot stage, cooling
Material filtering is taken out in decompression, then dry graphene EPS beads；Finally, foaming is prepared into various graphene EPS moldings systems
Product.This static conductive graphene EPS moulding articles density is 25kg/m3, sheet resistance is up to 106Ω, tensile strength reach
1.0Mpa, compression strength reach 0.45Mpa, and flame retardant rating reaches B1 grades.
Embodiment 2
(1) the oxidation intercalation of graphite：Using the graphite of 1100 mesh grain sizes as raw material, purity 99.9% inserts graphite and oxidation
Layer agent mixing carries out intercalation, and oxidation intercalator system is 95% concentrated sulfuric acid, potassium nitrate, potassium permanganate system, and mass ratio is graphite：
The concentrated sulfuric acid：Potassium nitrate：Potassium permanganate=1：5：0.5：1；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
200S, control control output power 200KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2500m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：Graphene is mixed with a certain amount of cetomacrogol 1000 (molecular weight 1000)
The mass ratio of 5h, graphene and polyethylene glycol is 1：10, it carries out alcohol and washes modified filtration drying；
(4) preparation of static conductive graphene EPS by following suspension polymerization system, is prepared by mass percentage：
By mass percent styrene 32%, pure water 62%, modified graphene 1%, dispersant active calcium phosphate
1.5%th, dispersion aids cetyl benzenesulfonic acid sodium, polyvinyl alcohol 0.2% is added in reaction kettle, carries out pre-dispersed stirring
15min, mixing speed keep 150r/min；Then initiator dibenzoyl peroxide 0.1%, the tertiary fourth of perbenzoic acid are added in
Ester 0.2%, mixing speed keeps 200r/min, and starts to warm up；When material in reactor temperature rises to 91 DEG C, in this temperature
When lower polymerisation 7 is small；Seal pot tank adds foaming agent pentane 3%, continues to heat up；When material in reactor temperature rises to 125
DEG C when, constant temperature keep 6 it is small when；After hot stage, decrease temperature and pressure takes out material filtering, then dry graphene EPS pearls
Grain；Finally, foaming is prepared into various graphene EPS moulding articles.This static conductive graphene EPS moulding articles density is 27kg/
m3, sheet resistance is up to 104Ω, tensile strength reach 1.1Mpa, and compression strength reaches 0.47Mpa, and flame retardant rating reaches B1 grades.
Embodiment 3
(1) the oxidation intercalation of graphite：Using the graphite of 1200 mesh grain sizes as raw material, purity 99.5% inserts graphite and oxidation
Layer agent mixing carries out intercalation, and oxidation intercalator system is 98% concentrated sulfuric acid, sodium nitrate, potassium nitrate, potassium permanganate system, mass ratio
For graphite：The concentrated sulfuric acid：Sodium nitrate：Potassium nitrate：Potassium permanganate=1：3：0.1：0.2：0.7；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
130S, control control output power 250KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2200m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：By graphene and a certain amount of ethylene glycol, Macrogol 6000 mixing 3h, graphite
The mass ratio of alkene and ethylene glycol, polyethylene glycol is 1：4：4, it carries out alcohol and washes modified filtration drying；
(4) preparation of static conductive graphene EPS by following suspension polymerization system, is prepared by mass percentage：
By mass percent styrene 30%, pure water 65.45%, modified graphene 0.8%, dispersant active calcium phosphate
0.9%th, dispersion aids neopelex 0.15% is added in reaction kettle, carries out pre-dispersed stirring 15min, stirring speed
Degree keeps 125r/min；Then initiator peroxide acetic acid butyl ester 0.2% is added in, mixing speed keeps 185r/min, and opens
Begin to heat up；When material in reactor temperature rises to 90 DEG C, when polymerisation 8 is small at this temperature；Seal pot tank adds foaming
Agent pentane 2.5% continues to heat up；When material in reactor temperature rises to 119 DEG C, when constant temperature holding 7 is small；Hot stage terminates
Afterwards, decrease temperature and pressure takes out material filtering, then dry graphene EPS beads；Finally, foaming is prepared into various graphene EPS
Moulding article.This static conductive graphene EPS moulding articles density is 28kg/m3, sheet resistance is up to 105Ω, tensile strength reach
1.2Mpa, compression strength reach 0.5Mpa, and flame retardant rating reaches B1 grades.
Embodiment 4
(1) the oxidation intercalation of graphite：Using the graphite of 800 mesh grain sizes as raw material, purity 99%, by graphite and oxidation intercalator
Mixing carries out intercalation, and oxidation intercalator system is 96% concentrated sulfuric acid, sodium nitrate, potassium permanganate system, and mass ratio is graphite：Dense sulphur
Acid：Sodium nitrate：Potassium permanganate=1：1：0.1：0.5；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
150S, control control output power 220KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2150m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：By graphene and a certain amount of ethylene glycol mixing 1h, the matter of graphene and ethylene glycol
Amount is than being 1：5, it carries out alcohol and washes modified filtration drying；
(4) preparation of surface static conductive graphene EPS：
A, graphene EPS is first prepared, by following suspension polymerization system, is prepared by mass percentage：
B, the preparation and spraying of graphene conductive coating：
By mass percent styrene 28%, pure water 69.45%, modified graphene 0.05%, dispersant activity phosphoric acid
Calcium 0.4%, dispersion aids polyvinyl alcohol 0.05% are added in reaction kettle, carry out pre-dispersed stirring 15min, and mixing speed is kept
100r/min；Then initiator peroxidized t-butyl perbenzoate 0.05% is added in, mixing speed keeps 150r/min, and starts to rise
Temperature；When material in reactor temperature rises to 88 DEG C, when polymerisation 8 is small at this temperature；Seal pot tank adds foaming agent penta
Alkane 2% continues to heat up；When material in reactor temperature rises to 115 DEG C, when constant temperature holding 6.5 is small；After hot stage,
Decrease temperature and pressure takes out material filtering, dry graphene EPS beads；Then, foaming is prepared into various graphene EPS moldings systems
Product.Finally, in this graphene EPS molded article surfaces graphite spraying alkene electrically-conducting paint, dry 10h, applies at a temperature of 60 DEG C
Layer thickness 30um, up to the graphene EPS moulding articles of surface static conductive after drying.
This surface static conductive graphene EPS moulding articles density is 25kg/m3, sheet resistance is up to 106Ω, tension are strong
For degree up to 0.8Mpa, compression strength reaches 0.4Mpa, and flame retardant rating reaches B1 grades,
Embodiment 5
(1) the oxidation intercalation of graphite：Using the graphite of 1000 mesh grain sizes as raw material, purity 99.9% inserts graphite and oxidation
Layer agent mixing carries out intercalation, and oxidation intercalator system is 94% concentrated sulfuric acid, potassium nitrate, potassium permanganate system, and mass ratio is graphite：
The concentrated sulfuric acid：Potassium nitrate：Potassium permanganate=1：5：0.5：1；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
150S, control control output power 200KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2420m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：Graphene is mixed with a certain amount of cetomacrogol 1000 (molecular weight 1000)
The mass ratio of 5h, graphene and polyethylene glycol is 1：10, it carries out alcohol and washes modified filtration drying；
(4) preparation of surface static conductive graphene EPS：
A, graphene EPS is first prepared, by following suspension polymerization system, is prepared by mass percentage：
B, the preparation and spraying of graphene conductive coating：
By mass percent styrene 32%, pure water 63.6%, modified graphene 0.1%, dispersant active calcium phosphate
1%th, dispersion aids neopelex 0.05%, polyvinyl alcohol 0.05% is added in reaction kettle, carries out pre-dispersed stir
15min is mixed, mixing speed keeps 150r/min；Then initiator dibenzoyl peroxide 0.1%, perbenzoic acid uncle are added in
Butyl ester 0.1%, mixing speed keeps 200r/min, and starts to warm up；It is warm herein when material in reactor temperature rises to 91 DEG C
When the lower polymerisation 6 of degree is small；Seal pot tank adds foaming agent pentane 3%, continues to heat up；When material in reactor temperature rises to
At 125 DEG C, when constant temperature holding 4 is small；After hot stage, decrease temperature and pressure takes out material filtering, dry graphene EPS pearls
Grain；Then, foaming is prepared into various graphene EPS moulding articles.Finally, sprayed in this graphene EPS molded article surfaces
Graphene conductive coating, dry 5h, coating layer thickness 100um at a temperature of 80 DEG C, up to the graphene of surface static conductive after drying
EPS moulding articles.
This surface static conductive graphene EPS moulding articles density is 30kg/m3, sheet resistance is up to 104Ω, tension are strong
For degree up to 0.91Mpa, compression strength reaches 0.42Mpa, and flame retardant rating reaches B1 grades,
Embodiment 6
(1) the oxidation intercalation of graphite：Using the graphite of 1200 mesh grain sizes as raw material, purity 99.5% inserts graphite and oxidation
Layer agent mixing carries out intercalation, and oxidation intercalator system is 97% concentrated sulfuric acid, sodium nitrate, potassium nitrate, potassium permanganate system, mass ratio
For graphite：The concentrated sulfuric acid：Sodium nitrate：Potassium nitrate：Potassium permanganate=1：3：0.1：0.2：0.7；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves carry out continuous swelling to intercalated graphite
170S, control control output power 250KW carry out the simple ultrasonic single-layer graphene removed into the number of plies at 1-2 layers after discharging, than
Surface area 2360m2/ g, lamellar spacing 0.33-1nm；
(3) alcohol of graphene washes modification：Graphene is mixed into 3h, graphite with a certain amount of ethylene glycol, polyethylene glycol 5000
The mass ratio of alkene and ethylene glycol, polyethylene glycol is 1：4：4, it carries out alcohol and washes modified filtration drying；
(4) preparation of surface static conductive graphene EPS：
A, graphene EPS is first prepared, by following suspension polymerization system, is prepared by mass percentage：
B, the preparation and spraying of graphene conductive coating：
By mass percent styrene 30%, pure water 66.57%, modified graphene 0.15%, dispersant activity phosphoric acid
Calcium 0.6%, dispersion aids polyvinyl alcohol 0.08% are added in reaction kettle, carry out pre-dispersed stirring 15min, and mixing speed is kept
130r/min；Then initiator peroxidized t-butyl perbenzoate 0.05%, peroxide acetic acid butyl ester 0.05%, stirring speed are added in
Degree keeps 165r/min, and starts to warm up；When material in reactor temperature rises to 89 DEG C, polymerisation 7 is small at this temperature
When；Seal pot tank adds foaming agent pentane 2.5%, continues to heat up；When material in reactor temperature rises to 121 DEG C, constant temperature is protected
Hold 5 it is small when；After hot stage, decrease temperature and pressure takes out material filtering, dry graphene EPS beads；Then, foaming system
It is standby to obtain various graphene EPS moulding articles.Finally, in this graphene EPS molded article surfaces graphite spraying alkene electrically-conducting paint,
Dry 7h, coating layer thickness 50um at a temperature of 70 DEG C, up to the graphene EPS moulding articles of surface static conductive after drying.
This surface static conductive graphene EPS moulding articles density is 27kg/m3, sheet resistance is up to 105Ω, tension are strong
For degree up to 0.85Mpa, compression strength reaches 0.43Mpa, and flame retardant rating reaches B1 grades.
Shown in the performance as Fig. 1 for the EPS modeling products that Examples 1 to 6 is prepared, 2.
After the graphene prepared in embodiment 2 and embodiment 6 is polymerize with commercially available graphene XFQ022 progress reaction kettles
The performance of the graphene EPS moulding articles of preparation is compared, and polymerization technique, graphene EPS moulding article preparation processes are all
Preparation process in embodiment 6, the results are shown in Table 1：
Table 1
Claims (9)
1. a kind of preparation method of static conductive graphene EPS, it is characterised in that comprise the following steps：
(1) the oxidation intercalation of graphite：Using the graphite of 800~1200 mesh grain sizes as raw material, purity is more than 99%, by graphite and oxidation
Intercalator mixing carry out intercalation, it is described oxidation intercalator be mass fraction be 90%-98% the concentrated sulfuric acid, nitrate, permanganic acid
The mixture of potassium, mass ratio are graphite：The concentrated sulfuric acid：Nitrate：Potassium permanganate=1：1~5：0.1~0.5：0.5~1；
(2) high-frequency microwave continuous swelling prepares graphene：915MHz high-frequency microwaves to intercalated graphite carry out continuous swelling 20~
200S, control control 200~300KW of output power carry out single-layer graphene of the ultrasound stripping into the number of plies at 1~2 layer after discharging；
(3) alcohol of graphene washes modification：The graphene that step (2) obtains is mixed into 1~5h, graphene and alcohol with a certain amount of alcohol
Mass ratio be 1：5~10, it carries out alcohol and washes modified filtration drying；
(4) preparation of static conductive graphene EPS, as needed for following suspension polymerization system prepared by raw material and its mass percent：
2. a kind of preparation method of surface static conductive graphene EPS, it is characterised in that comprise the following steps：
A, graphene EPS moulding articles are first prepared, by following suspension polymerization system, are prepared by mass percentage：
B, graphene conductive coating is sprayed on graphene EPS moulding articles again, the raw material matter of the graphene conductive coating
Measuring percentage is：
3. preparation method according to claim 1, it is characterised in that the nitrate for sodium nitrate, in potassium nitrate at least
It is a kind of；The alcohol is at least one of polyethylene glycol of ethylene glycol, different molecular weight.
4. preparation method according to claim 1 or 2, it is characterised in that the initiator is dibenzoyl peroxide, mistake
Aoxidize at least one of t-butyl perbenzoate, peroxide acetic acid butyl ester；The dispersant is active calcium phosphate, and EPS is special
Dispersant；The dispersion aids is at least one of sodium alkyl benzene sulfonate, polyvinyl alcohol.
5. preparation method according to claim 2, it is characterised in that the resin is epoxy resin, acrylic resin, alcohol
At least one in acid resin, amino resins, polyester resin, polyurethane resin, organic siliconresin, fluorocarbon resin and related compound resin
Kind.
6. preparation method according to claim 2, it is characterised in that the wetting dispersing agent for BYK140, BYK161,
At least one of BYK163, BYK168, BYK2000；The stabilizer is polyethylene wax, polyamide wax, aerosil
At least one of；Adhesion promoter is silane coupling agent, the acidifying of titanate coupling agent, modified poly ester compound, modified propylene
Close at least one of object.
7. preparation method according to claim 2, it is characterised in that the mixed solvent for ethyl alcohol, dimethylbenzene, trimethylbenzene,
At least one of n-butanol, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate.
8. preparation method according to claim 1, it is characterised in that the preparation process of the static conductive graphene EPS is：
(1) by mass percent styrene 28~32%, pure water 62~68.8%, modified graphene 0.5~1%, dispersant
0.5~1.5%, dispersion aids 0.1~0.2% is added in reaction kettle, carries out pre-dispersed stirring 15min, and mixing speed is kept
100-150r/min；
(2) and then initiator 0.1~0.3% is added in, mixing speed keeps 150-200r/min, and starts to warm up；Work as reaction kettle
When interior temperature of charge rises to 88~91 DEG C, when polymerisation 7~9 is small at this temperature；
(3) seal pot tank adds foaming agent pentane 2~3%, continues to heat up；When material in reactor temperature rises to 115~125 DEG C
When, when constant temperature holding 6~8 is small；
(4) after hot stage, decrease temperature and pressure takes out material filtering, then dry graphene EPS beads；Finally, foam
It is prepared into various graphene EPS moulding articles.
9. preparation method according to claim 2, it is characterised in that the preparation process of the surface static conductive graphene EPS
For：
(1) graphene EPS moulding articles are prepared：The step of by mass percent styrene 28~32%, pure water, claim 1
(3) graphene 0.05~0.15%, dispersant 0.4~1%, the dispersion aids 0.05~0.1% being prepared are added to reaction
In kettle, pre-dispersed stirring 15min is carried out, mixing speed keeps 100-150r/min；
(2) and then initiator 0.05~0.2% is added in, mixing speed keeps 150-200r/min, and starts to warm up；Work as reaction kettle
When interior temperature of charge rises to 88~91 DEG C, when polymerisation 6~8 is small at this temperature；
(3) seal pot tank adds foaming agent pentane 2~3%, continues to heat up；When material in reactor temperature rises to 115~125
DEG C when, constant temperature keep 4~6.5 it is small when；
(4) after hot stage, decrease temperature and pressure takes out material filtering, dry graphene EPS beads；Then, prepared by foaming
Obtain various graphene EPS moulding articles；
(5) finally, in graphene EPS molded article surface graphite spraying alkene electrically-conducting paints, dry 5 at a temperature of 60~80 DEG C~
10h, 30~100um of coating layer thickness, up to the graphene EPS moulding articles of surface static conductive after drying.
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| CN110922751A (en) * | 2019-12-12 | 2020-03-27 | 南通双晨新材料科技有限公司 | Preparation method of acid and alkali resistant nylon cable tie material |
| CN113416340A (en) * | 2021-07-29 | 2021-09-21 | 重庆中科建筑科技(集团)有限公司 | Preparation method of modified graphene EPS (expandable polystyrene) particles and mortar and modified graphene EPS mortar |
| CN116023672A (en) * | 2022-12-15 | 2023-04-28 | 江阴市星宇化工有限公司 | Composite filler of tricalcium phosphate special for polymerization and preparation method thereof |
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