CN106084705B - A kind of high intensity antistatic composite material sheet material and preparation method thereof - Google Patents

A kind of high intensity antistatic composite material sheet material and preparation method thereof Download PDF

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CN106084705B
CN106084705B CN201610401903.XA CN201610401903A CN106084705B CN 106084705 B CN106084705 B CN 106084705B CN 201610401903 A CN201610401903 A CN 201610401903A CN 106084705 B CN106084705 B CN 106084705B
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copper powder
glass
glass fabric
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CN106084705A (en
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徐致伟
宋小雨
王静
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YANGZHOU RUNYOU COMPOSITE CO Ltd
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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    • 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
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    • C08K3/02—Elements
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

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Abstract

A kind of high intensity antistatic composite material sheet material is made up of composite outer structural layer and Conductive Core, between upper and lower outer structural layer, outer structural layer is combined Conductive Core by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, modified graphene, glass fabric；Conductive Core is combined by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat.The present invention manufactures convenient, traditional composite material moulded technique can be used to its production and processing without improving, mechanization degree is higher in production process, and required labour is less, and production cost is low, with good mechanical property, electric conductivity and antistatic performance, can be long-term use of at relatively high temperatures, rigidity is big, creep resistant, indeformable, designability is strong.There is high intensity and the occasion of antistatic performance simultaneously available for sheet material used in some needs such as petrochemical industry, metallurgy.

Description

A kind of high intensity antistatic composite material sheet material and preparation method thereof
Technical field
The invention discloses a kind of composite board, more particularly to a kind of high intensity antistatic composite material sheet material and Its production method.
Background technology
Thermosetting resin based composites are to utilize thermosetting resin, including unsaturated polyester resin, epoxy resin etc. are made For matrix material（Absolute majority is accounted for unsaturated polyester resin）, addition curing agent, accelerator, and strengthen with fiber, whisker etc. Material, a kind of composite made by certain processing technology.It has strong designability, anti-corrosion, machine-shaping convenient The advantages that, the fields such as building, municipal administration, traffic, packaging can be widely applied to by the composite board of its making.Though but such as This, thermosetting resin based composites are such as some in petrochemical industry, metallurgy in use there is also some obvious deficiencies Occasion is in use, generally require sheet material used or its product while have high intensity and antistatic performance, in order to avoid deformation or produce Electrostatic spark is given birth to, blast is may even happen that under serious conditions.The sheet material made using conventional thermosetting polymer matrix composites Can have certain antistatic property and strength character, but tend not to realize high intensity and highly antistatic simultaneously.Therefore, send out Bright one kind both has high intensity, and the highly anlistatig composite board of and can is very necessary.
The content of the invention
It is an object of the invention to overcome the shortcomings of conventional thermosetting polymer matrix composites, there is provided one kind has high-strength Degree, antistatic, indeformable composite sheet material and its production method.
A kind of high intensity antistatic composite material sheet material, following scheme is taken to realize：
A kind of high intensity antistatic composite material sheet material is made up of composite outer structural layer and Conductive Core, Conductive Core Between upper and lower composite outer structural layer.
Composite outer structural layer is by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, modified graphene, glass Glass fiber cloth is combined.
Conductive Core is by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl liquid Nitrile rubber, dibutyl phthalate and glass mat are combined.
Described unsaturated polyester resin is metaphenylene unsaturated polyester resin.
Described modified graphene is triethylene tetramine modified graphene.
Described glass fabric is that substance is 200g/m2Or 400g/m2One kind in alkali-free glass fiber cloth.
The described copper powder that organises is silane coupler modified copper powder, and average grain diameter is 5-25 μm；Described is silane coupled Agent is 3- aminopropyl triethoxysilane coupling agents.
Described glass mat is that substance is 300g/m2、600g/m2Or 900g/m2One kind in glass mat.
A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 10-20 parts by weight, ultrasonic disperse 1- 2h, the triethylene tetramine of 0.2-0.4 parts by weight and the Dicyclohexylcarbodiimide of 0.1-0.5 parts by weight are then added, is surpassed again Sonication 10-20min, after reacting 40-50h at 120-130 DEG C, the ethanol of 3-5 parts by weight is added, stands 48-60h, is filtered, After gained washing of precipitate, 36-48h is dried in vacuo at 55-65 DEG C, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 10-20% mass percentage concentrations is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, really Protect dilute sulfuric acid liquid level and exceed copper powder 10-20cm, be ultrasonically treated 30-60min, after then standing 24-48h, be ultrasonically treated 30- again 60min, sulfuric acid liquid is filtered to remove, then rinses copper powder to neutrality, drying with running water；
（3）The ethanol of 30-50 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 20-30 weights The drying copper powder of part is measured, after ultrasonic disperse 20-30min, supersonic generator 30min is closed, then opens supersonic generator, Again after ultrasonic disperse 20-30min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, organised Copper powder；
（4）By weight 100:0.6-1.2:0.6-0.8:0.1-0.3:60-80 weigh respectively unsaturated polyester resin, Methyl ethyl ketone peroxide, cobalt naphthenate, modified graphene and glass fabric, and by unsaturated polyester resin, methyl ethyl ketone peroxide, Cobalt naphthenate and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight, Ran Hou are uniformly brushed The glass fabric of half parts by weight is laid thereon, then pours into the resin sizing material of 1/3rd parts by weight, is next proceeded to The glass fabric of half parts by weight is laid, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In glass fiber cloth；
（6）By weight 100:0.8-1.2:0.6-1.0:10-20:0.3-0.5:1-3:50-70 weighs unsaturation respectively Polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate And glass mat, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl liquid fourth Nitrile rubber and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core of 1/3rd parts by weight Glue is coated uniformly on its surface, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating Conductive Core glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the table of glass mat again Face；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd weight are uniformly brushed on its surface Part step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into three/ The resin sizing material of one parts by weight, next proceed to lay half parts by weight glass fabric, finally by residue three/ The resin sizing material of one parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 40-60 DEG C, 3-5min is preheated, is then slowly forced into 1-5MPa, and keep 60- at this pressure 90min；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 4-6:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer For 1:1；The glass fabric substance used in upper and lower composite outer structural layer can be with identical or different, but in upper composite wood Expect that the glass fabric inside outer structural layer and used in inside lower composite outer structural layer is same substance.
A kind of high intensity antistatic composite material sheet material of the present invention, manufactures convenient, traditional composite material moulded life Production. art can be used to its production and processing without improving, and mechanization degree is higher in production process, and required labour is less, raw It is low to produce cost, there is good mechanical property, electric conductivity and antistatic performance, high intensity, can make for a long time at relatively high temperatures With rigidity is big, and creep resistant is indeformable, and designability is strong.
Brief description of the drawings
Below with reference to accompanying drawing, the invention will be further described.
Fig. 1 is a kind of high intensity antistatic composite material plate construction schematic diagram.
1- composite outer structural layers, 2- Conductive Cores, 3- unsaturated polyester resins, 4- methyl ethyl ketone peroxides, 5- cycloalkanes Sour cobalt, 6- modified graphenes, 7- glass fabrics, 8- organise copper powder, 9- carboxyl end of the liquid acrylonitrile-butadiene rubber, 10- O-phthalics Dibutyl phthalate, 11- glass mats.
Embodiment
Referring to the drawings 1, a kind of high intensity antistatic composite material sheet material is by composite outer structural layer 1 and Conductive Core 2 Form, Conductive Core 2 is between upper and lower composite outer structural layer 1.
Composite outer structural layer 1 is by unsaturated polyester resin 3, methyl ethyl ketone peroxide 4, cobalt naphthenate 5, modified graphene 6th, glass fabric 7 is combined.
Conductive Core 2 is by unsaturated polyester resin 3, methyl ethyl ketone peroxide 4, cobalt naphthenate 5, organise copper powder 8, end carboxyl LNBR 9, dibutyl phthalate 10 and glass mat 11 are combined.
Described unsaturated polyester resin is metaphenylene unsaturated polyester resin.
Described modified graphene is triethylene tetramine modified graphene.
Described glass fabric is that substance is 200g/m2Or 400g/m2One kind in alkali-free glass fiber cloth.
The described copper powder that organises is silane coupler modified copper powder, and average grain diameter is 5-25 μm；Described is silane coupled Agent is 3- aminopropyl triethoxysilane coupling agents.
Described glass mat is that substance is 300g/m2、600g/m2Or 900g/m2One kind in glass mat..
Embodiment 1：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 15 parts by weight, ultrasonic disperse 1.5h, Then the triethylene tetramine of 0.3 parts by weight and the Dicyclohexylcarbodiimide of 0.3 parts by weight are added, is ultrasonically treated 15min again, After reacting 45h at 125 DEG C, the ethanol of 4 parts by weight is added, stands 54h, filtering is true at 60 DEG C after gained washing of precipitate Sky dries 42h, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 15% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 15cm, is ultrasonically treated 45min, after then standing 36h, is ultrasonically treated 45min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 40 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 25 parts by weight Copper powder is dried, after ultrasonic disperse 25min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 25min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 15 μm）；
（4）By weight 100:0.9:0.7:0.2:70 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 200g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:1:0.8:15:0.4:2:60 weigh respectively unsaturated polyester resin, methyl ethyl ketone peroxide, Cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 600g/ m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber and Dibutyl phthalate is well mixed, and obtains Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 200g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 50 DEG C, 4min is preheated, is then slowly forced into 3MPa, and keep 75min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 5:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is identical.
Embodiment 2：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 10 parts by weight, ultrasonic disperse 1h, so The triethylene tetramine of 0.2 parts by weight and the Dicyclohexylcarbodiimide of 0.1 parts by weight are added afterwards, are ultrasonically treated 10min again, After reacting 40h at 120 DEG C, the ethanol of 3 parts by weight is added, stands 48h, is filtered, after gained washing of precipitate, the vacuum at 55 DEG C 36h is dried, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 10% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 10cm, is ultrasonically treated 30min, after then standing 24h, is ultrasonically treated 30min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 30 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 20 parts by weight Copper powder is dried, after ultrasonic disperse 20min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 20min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 5 μm）；
（4）By weight 100:0.6:0.6:0.1:60 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 200g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:0.8:0.6:10:0.3:1:50 weigh unsaturated polyester resin, peroxidating first and second respectively Ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 300g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 200g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 40 DEG C, 3min is preheated, is then slowly forced into 1MPa, and keep 60min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 4:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is identical.
Embodiment 3：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 20 parts by weight, ultrasonic disperse 2h, then The triethylene tetramine of 0.4 parts by weight and the Dicyclohexylcarbodiimide of 0.5 parts by weight are added, is ultrasonically treated 20min again, After reacting 50h at 130 DEG C, the ethanol of 5 parts by weight is added, stands 60h, is filtered, after gained washing of precipitate, the vacuum at 65 DEG C 48h is dried, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 20% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 20cm, is ultrasonically treated 60min, after then standing 48h, is ultrasonically treated 60min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 50 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 30 parts by weight Copper powder is dried, after ultrasonic disperse 30min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 30min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 25 μm）；
（4）By weight 100:1.2:0.8:0.3:80 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 400g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:1.2:1.0:20:0.5:3:70 weigh unsaturated polyester resin, peroxidating first and second respectively Ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 900g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 400g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 60 DEG C, 5min is preheated, is then slowly forced into 5MPa, and keep 90min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 6:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is identical.
Embodiment 4：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 10 parts by weight, ultrasonic disperse 1.5h, so The triethylene tetramine of 0.4 parts by weight and the Dicyclohexylcarbodiimide of 0.1 parts by weight are added afterwards, are ultrasonically treated 15min again, After reacting 40h at 130 DEG C, the ethanol of 4 parts by weight is added, stands 60h, is filtered, after gained washing of precipitate, the vacuum at 55 DEG C 42h is dried, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 20% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 10cm, is ultrasonically treated 45min, after then standing 48h, is ultrasonically treated 30min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 40 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 30 parts by weight Copper powder is dried, after ultrasonic disperse 20min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 25min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 25 μm）；
（4）By weight 100:0.6:0.7:0.3:60 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 400g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:1.2:0.6:15:0.5:1:60 weigh unsaturated polyester resin, peroxidating first and second respectively Ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 900g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 200g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 50 DEG C, 5min is preheated, is then slowly forced into 1MPa, and keep 75min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 6:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is different, but in upper composite outer structural layer Glass fabric used in inside portion and lower composite outer structural layer is same substance.
Embodiment 5：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 15 parts by weight, ultrasonic disperse 2h, then The triethylene tetramine of 0.2 parts by weight and the Dicyclohexylcarbodiimide of 0.3 parts by weight are added, is ultrasonically treated 20min again, After reacting 45h at 120 DEG C, the ethanol of 5 parts by weight is added, stands 48h, is filtered, after gained washing of precipitate, the vacuum at 60 DEG C 48h is dried, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 10% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 15cm, is ultrasonically treated 60min, after then standing 24h, is ultrasonically treated 45min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 50 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 20 parts by weight Copper powder is dried, after ultrasonic disperse 25min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 30min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 5 μm）；
（4）By weight 100:0.9:0.8:0.1:70 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 400g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:0.8:0.8:20:0.3:2:60 weigh unsaturated polyester resin, peroxidating first and second respectively Ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 300g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 200g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 60 DEG C, 3min is preheated, is then slowly forced into 3MPa, and keep 90min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 4:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is different, but in upper composite outer structural layer Glass fabric used in inside portion and lower composite outer structural layer is same substance.
Embodiment 6：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 20 parts by weight, ultrasonic disperse 1h, then The triethylene tetramine of 0.3 parts by weight and the Dicyclohexylcarbodiimide of 0.5 parts by weight are added, is ultrasonically treated 10min again, After reacting 50h at 125 DEG C, the ethanol of 3 parts by weight is added, stands 54h, is filtered, after gained washing of precipitate, the vacuum at 65 DEG C 36h is dried, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 15% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 20cm, is ultrasonically treated 30min, after then standing 36h, is ultrasonically treated 60min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 30 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 25 parts by weight Copper powder is dried, after ultrasonic disperse 30min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 20min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 15 μm）；
（4）By weight 100:1.2:0.6:0.2:80 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, cycloalkanes respectively Sour cobalt, modified graphene and glass fabric（Substance is 200g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, ring Alkanoic acid cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:1.0:1.0:10:0.4:3:50 weigh unsaturated polyester resin, peroxidating first and second respectively Ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 600g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 400g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 40 DEG C, 4min is preheated, is then slowly forced into 5MPa, and keep 60min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 5:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer is 1:1, the glass fabric substance used in upper and lower composite outer structural layer is different, but in upper composite outer structural layer Glass fabric used in inside portion and lower composite outer structural layer is same substance.
Embodiment 7：A kind of preparation method of high intensity antistatic composite material sheet material, its preparation process are：
（1）The graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 13 parts by weight, ultrasonic disperse 1.2h, Then the triethylene tetramine of 0.25 parts by weight and the Dicyclohexylcarbodiimide of 0.4 parts by weight are added, is ultrasonically treated again 18min, after reacting 46h at 128 DEG C, the ethanol of 3.5 parts by weight is added, stands 50h, is filtered, after gained washing of precipitate, 40h is dried in vacuo at 58 DEG C, obtains modified graphene；
（2）The dilution heat of sulfuric acid of 16% mass percentage concentration is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 12cm, is ultrasonically treated 50min, after then standing 28h, is ultrasonically treated 50min again, is filtered to remove Sulfuric acid liquid, copper powder then is rinsed to neutrality, drying with running water；
（3）The ethanol of 35 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 23 parts by weight Copper powder is dried, after ultrasonic disperse 23min, supersonic generator 30min is closed, then opens supersonic generator, it is ultrasonic again After scattered 28min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper powder that organises（Average grain Footpath is 20 μm）；
（4）By weight 100:0.7:0.7:0.13:75 weigh unsaturated polyester resin, methyl ethyl ketone peroxide, ring respectively Alkanoic acid cobalt, modified graphene and glass fabric（Substance is 200g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, Cobalt naphthenate and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
（5）In the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then at it It is upper to lay the glass fabric of half parts by weight, then the resin sizing material of 1/3rd parts by weight is poured into, next proceed to spread The glass fabric of half parts by weight is put, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass In fiber cloth；
（6）By weight 100:0.9:0.9:13:0.35:1.3:57 weigh unsaturated polyester resin, peroxidating first respectively Ethyl ketone, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass mat（Substance 600g/m2）, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
（7）Treat step（5）When middle resin sizing material reaches gel state, by the above-mentioned Conductive Core glue of 1/3rd parts by weight Its surface is coated uniformly on, then lays the glass mat of half parts by weight, 1/3rd parts by weight of re-coating are led Battery core layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
（8）Repeat step（4）, weigh and sample and prepare resin sizing material, glass fabric substance is 200g/m2；
（9）Treat step（7）When middle Conductive Core glue reaches gel state, 1/3rd parts by weight are uniformly brushed on its surface Step（8）The resin sizing material of preparation, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd The resin sizing material of parts by weight, next proceed to lay the glass fabric of half parts by weight, finally by residue 1/3rd The resin sizing material of parts by weight is uniformly brushed on glass fabric；
（10）Treat step（9）When the resin sizing material of the middle the superiors reaches gel state, the top cover of molding die is covered, is closed Mould, and temperature is raised to 48 DEG C, 3.5min is preheated, is then slowly forced into 4MPa, and keep 80min at this pressure；
（11）Thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material plate is made Material；
（12）During a kind of high intensity antistatic composite material board making, composite outer structural layer and Conductive Core The total weight ratio of various raw materials used is 4.6:1, the total weight ratio of various raw materials used in upper and lower composite outer structural layer For 1:1, the glass fabric substance used in upper and lower composite outer structural layer is identical.
It is as follows below by way of the effect of the detection proof embodiment of the present invention 1, its testing result：
Tensile strength：53.21MPa stretch modulus：2.35GPa；Bending strength：85.16MPa bending modulus： 2.76GPa hardness Barcol：46 Ba Keer, electrical conductivity：8.68×10-4S/m。
Above-mentioned test result shows that a kind of high intensity antistatic composite material sheet material comprehensive mechanical property of the invention is good, Antistatic property is good.

Claims (6)

1. a kind of preparation method of high intensity antistatic composite material sheet material, it is characterised in that by composite outer structural layer and lead Battery core layer is formed, and Conductive Core is between upper and lower composite outer structural layer；Composite outer structural layer is by unsaturated polyester (UP) Resin, methyl ethyl ketone peroxide, cobalt naphthenate, modified graphene, glass fabric are combined；Conductive Core is by unsaturated polyester (UP) Resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass Glass fibrofelt is combined；Its preparation process is：
(1) graphene of 1 parts by weight is weighed, is added in the dimethylformamide of 10-20 parts by weight, ultrasonic disperse 1-2h, so The triethylene tetramine of 0.2-0.4 parts by weight and the Dicyclohexylcarbodiimide of 0.1-0.5 parts by weight are added afterwards, are ultrasonically treated again 10-20min, after reacting 40-50h at 120-130 DEG C, the ethanol of 3-5 parts by weight is added, stand 48-60h, filtering, by gained After washing of precipitate, 36-48h is dried in vacuo at 55-65 DEG C, obtains modified graphene；
(2) dilution heat of sulfuric acid of 10-20% mass percentage concentrations is prepared, copper powder is fully immersed in dilution heat of sulfuric acid, it is ensured that Dilute sulfuric acid liquid level exceeds copper powder 10-20cm, is ultrasonically treated 30-60min, after then standing 24-48h, is ultrasonically treated 30- again 60min, sulfuric acid liquid is filtered to remove, then rinses copper powder to neutrality, drying with running water；
(3) ethanol of 30-50 parts by weight and the silane coupler of 1 parts by weight are weighed respectively, after mixing, weigh 20-30 parts by weight Drying copper powder, after ultrasonic disperse 20-30min, close supersonic generator 30min, then open supersonic generator, again After ultrasonic disperse 20-30min, filtering, unnecessary solvent is removed, the copper powder after processing is dried, screening, obtain the copper that organises Powder；
(4) unsaturated polyester resin, peroxidating are weighed respectively by weight 100: 0.6-1.2: 0.6-0.8: 0.1-0.3: 60-80 MEK, cobalt naphthenate, modified graphene and glass fabric, and by unsaturated polyester resin, methyl ethyl ketone peroxide, aphthenic acids Cobalt and modified graphene are sufficiently mixed uniformly, obtain resin sizing material；
(5) in the bottom of molding die die cavity, the above-mentioned resin sizing material of 1/3rd parts by weight is uniformly brushed, then on its upper berth The glass fabric of half parts by weight is put, then pours into the resin sizing material of 1/3rd parts by weight, next proceeds to lay two The glass fabric of/mono- parts by weight, then the resin sizing material of remaining 1/3rd parts by weight is uniformly brushed in glass fibre On cloth；
(6) unsaturated polyester (UP) is weighed respectively by weight 100: 0.8-1.2: 0.6-1.0: 10-20: 0.3-0.5: 1-3: 50-70 Resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, carboxyl end of the liquid acrylonitrile-butadiene rubber, dibutyl phthalate and glass Glass fibrofelt, and by unsaturated polyester resin, methyl ethyl ketone peroxide, cobalt naphthenate, the copper powder that organises, end carboxyl nitrile (HTBN) rubber Glue and dibutyl phthalate are well mixed, and obtain Conductive Core glue；
(7) it is when resin sizing material reaches gel state in step (5), the above-mentioned Conductive Core glue of 1/3rd parts by weight is uniform Glass mat coated in its surface, then lay half parts by weight, it is coated with the conductive core of 1/3rd parts by weight Layer glue, the Conductive Core glue of remaining 1/3rd parts by weight is finally coated uniformly on to the surface of glass mat again；
(8) repeat step (4), weigh and sample and prepare resin sizing material；
(9) when Conductive Core glue reaches gel state in step (7), 1/3rd parts by weight steps are uniformly brushed on its surface (8) resin sizing material prepared, the glass fabric of half parts by weight is then being laid thereon, then pour into 1/3rd weight The resin sizing material of part, next proceed to lay the glass fabric of half parts by weight, finally by remaining 1/3rd weight The resin sizing material of part is uniformly brushed on glass fabric；
(10) when the resin sizing material of the superiors in step (9) reaches gel state, the top cover of molding die is covered, matched moulds, and Temperature is raised to 40-60 DEG C, 3-5min is preheated, is then slowly forced into 1-5MPa, and keep 60-90min at this pressure；
(11) thermal source is closed, mould is naturally cooled to room temperature, molds, a kind of high intensity antistatic composite material sheet material is made；
(12) during a kind of high intensity antistatic composite material board making, used in composite outer structural layer and Conductive Core The total weight ratio of various raw materials be 4-6: 1, the total weight ratio of the various raw materials used in upper and lower composite outer structural layer is 1: 1；The glass fabric used in upper composite outer structural layer and the glass fabric used in lower composite outer structural layer Substance can be with identical or different, but the glass fabric inside upper composite outer structural layer is same substance, under it is compound Glass fabric used in inside material outer structural layer is same substance.
A kind of 2. preparation method of high intensity antistatic composite material sheet material according to claim 1, it is characterised in that institute The unsaturated polyester resin stated is metaphenylene unsaturated polyester resin.
A kind of 3. preparation method of high intensity antistatic composite material sheet material according to claim 1, it is characterised in that institute The modified graphene stated is triethylene tetramine modified graphene.
A kind of 4. preparation method of high intensity antistatic composite material sheet material according to claim 1, it is characterised in that institute The glass fabric stated is that substance is 200g/m2Or 400g/m2One kind in alkali-free glass fiber cloth.
A kind of 5. preparation method of high intensity antistatic composite material sheet material according to claim 1, it is characterised in that institute The copper powder that organises stated is silane coupler modified copper powder, and average grain diameter is 5-25 μm；Described silane coupler is 3- ammonia third Ethyl triethoxy silicane alkane coupling agent.
A kind of 6. preparation method of high intensity antistatic composite material sheet material according to claim 1, it is characterised in that institute The glass mat stated is that substance is 300g/m2、600g/m2Or 900g/m2One kind in glass mat.
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CN109707138B (en) * 2019-02-28 2024-04-05 周志茹 Multilayer-structure antistatic environment-friendly epoxy resin terrace and preparation method thereof
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