CN108714954A - Carbon-fibre reinforced epoxy resin stalk composite board and preparation method thereof - Google Patents

Carbon-fibre reinforced epoxy resin stalk composite board and preparation method thereof Download PDF

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Publication number
CN108714954A
CN108714954A CN201810409058.XA CN201810409058A CN108714954A CN 108714954 A CN108714954 A CN 108714954A CN 201810409058 A CN201810409058 A CN 201810409058A CN 108714954 A CN108714954 A CN 108714954A
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carbon
epoxy resin
fibre reinforced
reinforced epoxy
stalk
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洪家敏
洪振龙
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Xinyang Meili Zhenhao Straw New Material Technology Co Ltd
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Xinyang Meili Zhenhao Straw New Material Technology Co Ltd
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Priority to CN201810409058.XA priority Critical patent/CN108714954A/en
Publication of CN108714954A publication Critical patent/CN108714954A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27DWORKING VENEER OR PLYWOOD
    • B27D1/00Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08Manufacture of shaped articles; Presses specially designed therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08Moulding or pressing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00Compositions of lignin-containing materials
    • C08L97/02Lignocellulosic material, e.g. wood, straw or bagasse
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00Adhesives based on homopolymers or copolymers 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/16Halogen-containing compounds
    • C08K2003/166Magnesium halide, e.g. magnesium chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/222Magnesia, i.e. magnesium oxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045Sulfates
    • C08K2003/3063Magnesium sulfate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/322Ammonium phosphate
    • C08K2003/323Ammonium polyphosphate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Forests & Forestry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of preparation method of carbon-fibre reinforced epoxy resin stalk composite board, this method includes first mixing stalk particle with carbon-fibre reinforced epoxy resin pour mass, then cold pressing treatment of mating formation is carried out after being mixed with diaminodiphenylsulfone curing agent, finally use water-soluble fire-resisting adhesive that the polylith obtained blank plate of cold pressing of mating formation is carried out adhering and pressing processing, to obtain carbon-fibre reinforced epoxy resin stalk composite board.The carbon-fibre reinforced epoxy resin stalk composite board has higher internal bond strength, higher bending strength and preferable flame retardant property.

Description

Carbon-fibre reinforced epoxy resin stalk composite board and preparation method thereof
Technical field
The present invention relates to a kind of wood-based plate and preparation method thereof, especially a kind of carbon-fibre reinforced epoxy resin stalk is compound Plate and preparation method thereof.
Background technology
Artificial straw composite plate is because with investment of production is few, low energy consumption, cost is few, to the not high spy of quality requirements of raw materials Point becomes the important component of wood-based plate.Wherein, what China produced every year can be used as what wood-based plate raw material used Agricultural crop straw yield is about 600,000,000 tons or more, but due to technology restriction, straw circulating reuse ratio is not high always.Existing skill In art, starts to be applied to the fields such as furniture, packaging using agricultural crop straw as the wood-based plate that part raw material manufacture, therefore, expand Grande culture object stalk is one of the effective way realized stalk resource and recycled using scale as wood-based plate raw material.But It is that the structural strength and fire protecting performance of existing artificial board of straw be not high, causes artificial board of straw service life shorter and fire-retardant Performance is insufficient.
In order to solve the above problems, people are seeking always a kind of ideal technical solution.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of carbon-fibre reinforced epoxy resin stalk composite boards And preparation method thereof.
To achieve the goals above, the technical solution adopted in the present invention is:A kind of carbon-fibre reinforced epoxy resin stalk The preparation method of composite plate, includes the following steps:
It mixes according to the mass ratio of stalk particle and carbon-fibre reinforced epoxy resin pour mass and is(5~9):(0.4~0.7)'s Ratio is added the carbon-fibre reinforced epoxy resin pour mass into the stalk particle and is mixed, and premix is formed;
Cold pressing addition into the premix of mating formation accounts for the carbon-fibre reinforced epoxy resin cast weight 3%~5.3% Diaminodiphenylsulfone curing agent is warming up to 50 DEG C~95 DEG C stirrings and obtains mixture in 0.5 hour~1.5 hours, by the mixing Material is mated formation on forming belt, and slab woollen is formed;Cold pressing treatment is carried out to the slab woollen and obtains blank plate;
Blank plate described in polylith is stacked bonding by adhering and pressing using water-soluble fire-resisting adhesive, at cold moudling, drying Carbon-fibre reinforced epoxy resin stalk composite board is made after reason.
Based on above-mentioned, the carbon-fibre reinforced epoxy resin pour mass is through the following steps that obtained:
It weighs 300g~500g acyl chlorides carbon nano tubes to be placed in vacuum drying oven, 30 DEG C~50 DEG C drying 2h~4h are subsequently placed in In reaction kettle, and 8L~10L thionyl chlorides and the N of 300mL~500mL is added, N '-dimethyl formamide forms mixed liquor;It will Mixed liquor is heated to 50 DEG C~70 DEG C heat preservation 18h~for 24 hours, is evaporated under reduced pressure, the thionyl chloride is steamed, temperature after reaction It is cooled to room temperature and 8L~10L anhydrous tetrahydro furans stirring 0.5h~2h is added into the reaction kettle, through filtering, grinding, vacuum It is dried to obtain acyl chlorides carbon nano tube;
It weighs acyl chlorides carbon nano tube described in 300g~500g and is placed in addition 8L~10L ethylenediamines in reaction kettle, lead to nitrogen and carry out Stirring at normal temperature 1.5h~2h is then heated to 80 DEG C~110 DEG C heat preservation 55h~72h, and temperature, which is cooled to room temperature, is added 8L~10L Anhydrous tetrahydro furan stirs 1h~2h, and product obtains aminated carbon nano tube through filtering, grinding, vacuum drying;
It is carried out at vacuum drying after the aminated carbon nano tube is mixed 50 DEG C~60 DEG C stirring 10h~12h with epoxy resin Reason, obtains the carbon-fibre reinforced epoxy resin pour mass.
Based on above-mentioned, the water-soluble fire-resisting adhesive is through the following steps that obtained:
According to mass parts, weigh first 1~2 part of magnesium sulfate, 0.2~1 part of magnesium chloride, 2~8 parts of water, 0.5~1 part of polyvinyl alcohol, 0.1~0.5 part of boron phenol mixture, 0.5~1.5 part of magnesia, 0.05~0.2 part of phosphate, 0.05~0.2 part of ammonium polyphosphate, first 0.5~2.0 part of sour calcium;Then it carries out the magnesium chloride, the polyethylene alcohol and water to be mixed to prepare base soln, by the base Plinth solution and the magnesium sulfate, the boron phenol mixture, the magnesia, the phosphate, the ammonium polyphosphate and the formic acid Calcium is mixed, and the water-soluble fire-resisting adhesive is made.
Based on above-mentioned, the phosphate be diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium monohydrogen phosphate, one kind in calcium phosphate or Several combinations.
Based on above-mentioned, a diameter of 0.5mm~50mm of the stalk particle, the stalk particle be by crush straw, Wheat straw or corn stalk are simultaneously sieved.
The present invention also provides a kind of preparation methods of carbon-fibre reinforced epoxy resin stalk composite board, it is by above-mentioned preparation Made from method.
It is measured according to method as defined in GB/T 17657-2013:The carbon-fibre reinforced epoxy resin straw prepared by this method The density of stalk composite board is 400~1000 Kg/m3;Static bending strength in normal state >=18 megapascal/millimeter;The elasticity of flexure Modulus >=2200 megapascal/millimeter;Internal bond strength average value >=0.95 megapascal/millimeter;Surface bonding strength average value >=1.3 Megapascal/millimeter.It is strong with higher bending strength and interior combination to be indicated above the carbon-fibre reinforced epoxy resin stalk composite board Degree.
Burning examination is carried out to the carbon-fibre reinforced epoxy resin stalk composite board according to method as defined in GB 8624-2012 It tests, can reach B1 grades, therefore the carbon-fibre reinforced epoxy resin stalk composite board has preferable flame retardant property.
The carbon-fibre reinforced epoxy resin stalk composite board is according to GB 18580-2001《Indoor decorating and refurnishing materials people Form aldehyde release in plate and its product is made to limit the quantity》The condensed steam water and climate box method of defined measure, can reach E1 grades and its with Upper standard, therefore the carbon-fibre reinforced epoxy resin answers stalk plywood with good environmental-protecting performance.
Compared with prior art, carbon-fibre reinforced epoxy resin stalk made from preparation method provided by the present invention is compound Plate has the following advantages:Raw material of the carbon-fibre reinforced epoxy resin stalk composite board using agricultural crop straw as artificial composite plank Source further solves the not high problem of China's agricultural crop straw recovery utilization rate while instead of primary timber.Into One step, stalk particle is wrapped up by using carbon-fibre reinforced epoxy resin pour mass, utilizes amine functional groups and epoxy group The ring-opening reaction of generation simultaneously participates in the interface enhancing between the cross-linked network structure and carbon fiber and resin matrix of resin matrix, The caking property between stalk particle, carbon fiber and resin matrix is improved, multiple dimensioned collaboration enhancing, toughening are realized, to carry The high interlayer shear and shock resistance of stalk composite board.
Further, each raw material magnesia in the water-soluble fire-resisting adhesive, magnesium chloride, tertiary sodium phosphate, poly- second Enol and ammonium polyphosphate etc. have fire retardation, and the carbon-fibre reinforced epoxy resin stalk composite board knot is made after repressed molding Structure is stablized, and has flame retardant property, can substitute existing wooden flake board, can be directly used for hotel, market, The building fields such as school, family.
Specific implementation mode
Below with specific embodiment, it is multiple to further explain carbon-fibre reinforced epoxy resin stalk provided by the invention The preparation method of plywood.
Embodiment 1
The present embodiment provides a kind of preparation methods of carbon-fibre reinforced epoxy resin stalk composite board, include the following steps:
Mixing is 5 according to the mass ratio of stalk particle and carbon-fibre reinforced epoxy resin pour mass:0.4 ratio is to the straw The carbon-fibre reinforced epoxy resin pour mass is added in stalk particle to be mixed, and premix is formed;
Cold pressing addition into the premix of mating formation accounts for the diamino of the carbon-fibre reinforced epoxy resin cast weight 3% Diphenyl sulfone curing agent is warming up to 50 DEG C of stirrings and obtains mixture in 1.5 hours, the mixture is mated formation on forming belt, is formed Slab woollen;Cold pressing treatment is carried out to the slab woollen, obtains blank plate;
Blank plate described in polylith is stacked bonding by adhering and pressing using water-soluble fire-resisting adhesive, at cold moudling, drying Carbon-fibre reinforced epoxy resin stalk composite board is made after reason.
Wherein, the carbon-fibre reinforced epoxy resin pour mass is through the following steps that obtained:
It weighs 500g acyl chlorides carbon nano tubes to be placed in vacuum drying oven, 50 DEG C of drying 4h are subsequently placed in reaction kettle, and be added The N of 10L thionyl chlorides and 500mL, N '-dimethyl formamide form mixed liquor;Mixed liquor is heated to 50 DEG C of heat preservation 18h, instead Vacuum distillation steams thionyl chloride after answering, and is cooled to room temperature and 10L anhydrous tetrahydro furans stirring 2h is added into reaction kettle, Acyl chlorides carbon nano tube is obtained through filtering, grinding, vacuum drying;
It weighs acyl chlorides carbon nano tube described in 500g and is placed in addition 10L ethylenediamines in reaction kettle, lead to nitrogen and carry out stirring at normal temperature 2h, Be then heated to 80 DEG C heat preservation 55h, be cooled to room temperature be added 10L anhydrous tetrahydro furans stirring 1h, product through filtering, grinding, very Sky is dried to obtain aminated carbon nano tube;
Progress vacuum drying treatment obtains the carbon after the aminated carbon nano tube is mixed 60 DEG C of stirring 12h with epoxy resin Fiber reinforced epoxy resin pour mass.
The water-soluble fire-resisting adhesive is through the following steps that obtained:
According to mass parts, 1 part of magnesium sulfate, 0.2 part of magnesium chloride, 2 parts of water, 0.5 part of polyvinyl alcohol, boron phenol mixture 0.1 are weighed first Part, 0.5 part of magnesia, 0.05 part of diammonium hydrogen phosphate, 0.2 part of ammonium polyphosphate, 0.5 part of calcium formate;Then by the magnesium chloride, institute It states polyethylene alcohol and water to carry out being mixed to prepare base soln, by the base soln and the magnesium sulfate, the boron phenol mixture, institute It states magnesia, the phosphate, the ammonium polyphosphate and the calcium formate to be mixed, the water-soluble fire-resisting is made and coheres Agent.
Below to the carbon-fibre reinforced epoxy resin stalk composite board finished product made from preparation method provided in this embodiment It makes a service test.
It burns to the carbon-fibre reinforced epoxy resin stalk composite board according to method as defined in GB 8624-2012 Experiment, result are:The W/s of fire growth rate index≤25;The MJ of total heat release in 600s≤3.5;Flame is laterally spread Length<Sample edge;The mm of flame cusp height≤50;Flue gas generating rate index≤1m2/s2;Total smoke-producing amount≤50 in 600 s m 2;Density flaming droplet/particle:Without density flaming droplet/particle in 600 s;Whether filter paper is ignited:Filter paper is not ignited; Produce smoke toxicity:Reach ZA2Grade, meets B-s1 as defined in GB 8624-2012, d0, t1 grade standard.
In addition, the density of carbon-fibre reinforced epoxy resin stalk composite board obtained by this method is 650 Kg/m3;It is described Static bending strength >=18 megapascal/the millimeter of carbon-fibre reinforced epoxy resin stalk composite board in normal state;The modulus of elasticity in static bending >=2200 megapascal/millimeter;Internal bond strength average value >=0.95 megapascal/millimeter;Surface bonding strength average value >=1.3 million Pa/millimeter.
Embodiment 2
The present embodiment provides it is a kind of prepare carbon-fibre reinforced epoxy resin stalk composite board and method, it is different from embodiment 1 It is:This approach includes the following steps:
Mixing is 9 according to the weight ratio of stalk particle and carbon-fibre reinforced epoxy resin pour mass:0.7 ratio is to the straw The carbon-fibre reinforced epoxy resin pour mass is added in stalk particle to be mixed, and premix is formed;
Cold pressing addition into the premix of mating formation accounts for the diamino of the carbon-fibre reinforced epoxy resin cast weight 4% Diphenyl sulfone curing agent is warming up to 95 DEG C of stirrings and obtains mixture in 0.5 hour, the mixture is mated formation on forming belt, is formed Slab woollen;Cold pressing treatment is carried out to the slab woollen, obtains blank plate;
Blank plate described in polylith is stacked bonding by adhering and pressing using water-soluble fire-resisting adhesive, at cold moudling, drying The carbon-fibre reinforced epoxy resin stalk composite board is made after reason.
Below to the carbon-fibre reinforced epoxy resin stalk composite board finished product made from preparation method provided in this embodiment It makes a service test.
It burns to the carbon-fibre reinforced epoxy resin stalk composite board according to method as defined in GB 8624-2012 Experiment, result are:The W/s of fire growth rate index≤25;The MJ of total heat release in 600s≤3.5;Flame is laterally spread Length<Sample edge;The mm of flame cusp height≤50;Flue gas generating rate index≤1m2/s2;Total smoke-producing amount≤50 in 600 s m2;Density flaming droplet/particle:Without density flaming droplet/particle in 600 s;Whether filter paper is ignited:Filter paper is not ignited; Produce smoke toxicity:Reach ZA2Grade, meets B-s1 as defined in GB 8624-2012, d0, t1 grade standard.
In addition, the density of the carbon-fibre reinforced epoxy resin stalk composite board is 680 Kg/m3;The fibre reinforced Static bending strength >=18.3 megapascal/the millimeter of epoxy resin stalk composite board in normal state;The modulus of elasticity in static bending >=2,180,000,000 Pa/millimeter;Internal bond strength average value >=1.2 megapascal/millimeter;Surface bonding strength average value >=1.2 megapascal/millimeter.
Embodiment 3
The present embodiment provides a kind of methods preparing carbon-fibre reinforced epoxy resin stalk composite board, as different from Example 1: Carbon-fibre reinforced epoxy resin pour mass is through the following steps that obtained described in the embodiment:
It weighs 300g acyl chlorides carbon nano tubes to be placed in vacuum drying oven, 30 DEG C of drying 2h are subsequently placed in reaction kettle, and 8L is added The N of thionyl chloride and 300mL, N '-dimethyl formamide form mixed liquor;Mixed liquor is heated to 70 DEG C of heat preservation 18h, reaction knot Vacuum distillation steams thionyl chloride after beam, is cooled to room temperature and 8L anhydrous tetrahydro furans stirring 2h is added into reaction kettle, pass through Filter, grinding, vacuum drying obtain acyl chlorides carbon nano tube;
It weighs acyl chlorides carbon nano tube described in 500g and is placed in addition 8L ethylenediamines in reaction kettle, lead to nitrogen and carry out stirring at normal temperature 1.5h is then heated to 80 DEG C of heat preservation 55h, is cooled to room temperature and 8L anhydrous tetrahydro furans stirring 2h is added, product is through filtering, grinding Mill, vacuum drying obtain aminated carbon nano tube;
Progress vacuum drying treatment obtains the carbon after the aminated carbon nano tube is mixed 50 DEG C of stirring 12h with epoxy resin Fiber reinforced epoxy resin pour mass.
Below to the carbon-fibre reinforced epoxy resin stalk composite board finished product made from preparation method provided in this embodiment It makes a service test.
It burns to the carbon-fibre reinforced epoxy resin stalk composite board according to method as defined in GB 8624-2012 Experiment, result are:The W/s of fire growth rate index≤25;The MJ of total heat release in 600s≤3.5;Flame is laterally spread Length<Sample edge;The mm of flame cusp height≤50;Flue gas generating rate index≤1m2/s2;Total smoke-producing amount≤50 in 600 s m2;Density flaming droplet/particle:Without density flaming droplet/particle in 600 s;Whether filter paper is ignited:Filter paper is not ignited; Produce smoke toxicity:Reach ZA2Grade, meets B-s1 as defined in GB 8624-2012, d0, t1 grade standard.
In addition, the density of the carbon-fibre reinforced epoxy resin stalk composite board is 700Kg/m3;The fibre reinforced Static bending strength >=18.1 megapascal/the millimeter of epoxy resin stalk composite board in normal state;The modulus of elasticity in static bending >=2,230,000,000 Pa/millimeter;Internal bond strength average value >=1.5 megapascal/millimeter;Surface bonding strength average value >=1.3 megapascal/millimeter.
Finally it should be noted that:The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof;To the greatest extent Invention is explained in detail with reference to preferred embodiment for pipe, those of ordinary skills in the art should understand that:Still It can modify to the specific implementation mode of the present invention or equivalent replacement is carried out to some technical characteristics;Without departing from this hair The spirit of bright technical solution should all cover within the scope of the technical scheme claimed by the invention.

Claims (6)

1. a kind of preparation method of carbon-fibre reinforced epoxy resin stalk composite board, includes the following steps:
It mixes according to the mass ratio of stalk particle and carbon-fibre reinforced epoxy resin pour mass and is(5~9):(0.4~0.7)'s Ratio is added the carbon-fibre reinforced epoxy resin pour mass into the stalk particle and is mixed, and premix is formed;
Cold pressing addition into the premix of mating formation accounts for the carbon-fibre reinforced epoxy resin cast weight 3%~5.3% Diaminodiphenylsulfone curing agent is warming up to 50 DEG C~95 DEG C stirrings and obtains mixture in 0.5 hour~1.5 hours, by the mixing Material is mated formation on forming belt, and slab woollen is formed;Cold pressing treatment is carried out to the slab woollen and obtains blank plate;
Blank plate described in polylith is stacked bonding by adhering and pressing using water-soluble fire-resisting adhesive, at cold moudling, drying Carbon-fibre reinforced epoxy resin stalk composite board is made after reason.
2. preparation method according to claim 1, which is characterized in that the carbon-fibre reinforced epoxy resin pour mass is logical It crosses made from following steps:
It weighs 300g~500g acyl chlorides carbon nano tubes to be placed in vacuum drying oven, 30 DEG C~50 DEG C drying 2h~4h are subsequently placed in In reaction kettle, and 8L~10L thionyl chlorides and the N of 300mL~500mL is added, N '-dimethyl formamide forms mixed liquor;It will Mixed liquor is heated to 50 DEG C~70 DEG C heat preservation 18h~for 24 hours, is evaporated under reduced pressure, the thionyl chloride is steamed, temperature after reaction It is cooled to room temperature and 8L~10L anhydrous tetrahydro furans stirring 0.5h~2h is added into the reaction kettle, through filtering, grinding, vacuum It is dried to obtain acyl chlorides carbon nano tube;
It weighs acyl chlorides carbon nano tube described in 300g~500g and is placed in addition 8L~10L ethylenediamines in reaction kettle, lead to nitrogen and carry out Stirring at normal temperature 1.5h~2h is then heated to 80 DEG C~110 DEG C heat preservation 55h~72h, and temperature, which is cooled to room temperature, is added 8L~10L Anhydrous tetrahydro furan stirs 1h~2h, and product obtains aminated carbon nano tube through filtering, grinding, vacuum drying;
It is carried out at vacuum drying after the aminated carbon nano tube is mixed 50 DEG C~60 DEG C stirring 10h~12h with epoxy resin Reason, obtains the carbon-fibre reinforced epoxy resin pour mass.
3. preparation method according to claim 1 or 2, which is characterized in that the water-soluble fire-resisting adhesive be by with Made from lower step:
According to mass parts, weigh first 1~2 part of magnesium sulfate, 0.2~1 part of magnesium chloride, 2~8 parts of water, 0.5~1 part of polyvinyl alcohol, 0.1~0.5 part of boron phenol mixture, 0.5~1.5 part of magnesia, 0.05~0.2 part of phosphate, 0.05~0.2 part of ammonium polyphosphate, first 0.5~2.0 part of sour calcium;Then it carries out the magnesium chloride, the polyethylene alcohol and water to be mixed to prepare base soln, by the base Plinth solution and the magnesium sulfate, the boron phenol mixture, the magnesia, the phosphate, the ammonium polyphosphate and the formic acid Calcium is mixed, and the water-soluble fire-resisting adhesive is made.
4. preparation method according to claim 3, which is characterized in that the phosphate is diammonium hydrogen phosphate, biphosphate The combination of one or more of ammonium, calcium monohydrogen phosphate, calcium phosphate.
5. preparation method according to claim 4, which is characterized in that a diameter of 0.5mm~50mm of the stalk particle, The stalk particle is by crushing straw, wheat straw or corn stalk and being sieved to obtain.
6. a kind of carbon-fibre reinforced epoxy resin stalk composite board, which is characterized in that it is by any one of Claims 1 to 5 institute Made from the preparation method stated.
CN201810409058.XA 2018-05-02 2018-05-02 Carbon-fibre reinforced epoxy resin stalk composite board and preparation method thereof Pending CN108714954A (en)

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Application publication date: 20181030