CN108608550A - A kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board and preparation method thereof - Google Patents

A kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board and preparation method thereof Download PDF

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CN108608550A
CN108608550A CN201810416526.6A CN201810416526A CN108608550A CN 108608550 A CN108608550 A CN 108608550A CN 201810416526 A CN201810416526 A CN 201810416526A CN 108608550 A CN108608550 A CN 108608550A
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flame retardant
agricultural crop
crop straw
bamboo charcoal
coarse fodder
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李建州
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE 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
    • B27N1/00—Pretreatment of moulding material
    • B27N1/02—Mixing the material with binding agent
    • B27N1/0209—Methods, e.g. characterised by the composition of the agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/10—Moulding of mats
    • B27N3/12—Moulding of mats from fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/18—Auxiliary operations, e.g. preheating, humidifying, cutting-off
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE 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
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/18—Auxiliary operations, e.g. preheating, humidifying, cutting-off
    • B27N3/183—Forming the mat-edges, e.g. by cutting
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Housing For Livestock And Birds (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

The present invention relates to a kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre boards and preparation method thereof, which is prepared by following methods：1) straw cutting, crushing, screening are taken, it is so modified and dry that dry fines and dry coarse fodder through sodium hydroxide solution；2) loaded on bamboo charcoal ZnO/CuO composite materials are prepared；3) loaded on bamboo charcoal ZnO/CuO composite materials and eight Boratexes are added in urea-formaldehyde resin adhesive and prepare fines glue；Loaded on bamboo charcoal ZnO/CuO composite materials and nano-calcium carbonate are added in urea-formaldehyde resin adhesive and prepare coarse fodder glue；4) dry fines is mixed into obtain thin mixture with fines glue；Dry coarse fodder is mixed into obtain thick mixture with coarse fodder glue；Using thick mixture as sandwich layer, thin mixture be surface layer mated formation, precompressed, it is hot-forming, post-process to obtain the final product.Gained fiberboard has good mechanical property, water resistant moisture resistance and anti-corrosive antibacterial, and burst size of methanal is low, flame retardant property is good, is suitble to promote the use of.

Description

A kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board and preparation method thereof
Technical field
The invention belongs to straw fiber board technical fields, and in particular to a kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board And preparation method thereof.
Background technology
China is a large agricultural country, and agricultural straw resource is very abundant.Stalk is ripe crops cauline leaf (fringe) portion It is surplus after harvesting seed to be often referred to wheat, rice, corn, potato, oil plant, cotton, sugarcane and other crops for the general name divided Remaining part point is a kind of inexpensive, multiduty renewable biological source.Main chemical compositions content (the fiber of agricultural crop straw Element, hemicellulose and lignin) it is similar to timber, it can be used for substituting timber manufacture wood-based plate completely；According to statistics, every two mu of agricultures The stalk in field is equivalent to one mu of forest land, 1 year wood increments.Agricultural crop straw is used for wood-based panel industry, is to solve mesh Contradictory effective way between preceding wood supply deficiency and plank demand are big, while can also turn waste into wealth, avoid stalk resource Waste and crop straw burning caused by environmental pollution, increase farmers' income.
Existing artificial board of straw according to when preparing whether there is or not using adhesive to be divided into have glue wood-based plate and glue-free artificial board, In, for glue-free artificial board also in theoretical research and experiment development, there is no realize large-scale industrial production.There is glue artificial Plate according to use the difference of adhesive type be divided into adhesive made of synthetic resin artificial board of straw, inorganic adhesive artificial board of straw and Biological adhesive artificial board of straw.Wherein, inorganic adhesive artificial board of straw is using inorganic matter as adhesive, and there are at the beginning of gluing The defects of beginning intensity is low, hardening time is long, water resistance is poor；Biological adhesive artificial board of straw is with natural polymer As the main component of adhesive, there is also larger defects in the indexs such as water resistance, bonding strength, therefore application at present Widest or adhesive made of synthetic resin artificial board of straw.
The common adhesive made of synthetic resin of artificial board of straw mainly has phenolic resin adhesive, urea-formaldehyde resin adhesive, different Cyanate adhesive and other modified resin adhesives.Since isocyanates gluing agent low output is of high cost, in identical people It makes under plate production capacity, the cost of isocyanates gluing agent is approximately 10 times of urea-formaldehyde resin adhesive or more, it is difficult to promote the big rule of realization Mould is industrially used.Currently, 85% or more the country of China wood-based plate processing adhesive dosage be urea-formaldehyde resin adhesive or its Modified product, due to the advantages that its raw material is easy to get, preparation process is simple, of low cost and adhesive property is good, ambient temperature curable, In the following quite a long time, Lauxite will occupy the mainstream market of industry of artificial boards.
But contain unreacted free formaldehyde in urea-formaldehyde resin adhesive, it is easily cracked in the curing process；Using urea Urea formaldehyde adhesive prepares artificial board of straw, in process of production and during later stage use, continual can discharge free Formaldehyde causes the formaldehyde pollution of production and use occasion.Meanwhile agricultural crop straw belongs to combustible material, wood-based plate after molding It with larger heat release rate, also easily burns, is also easy to produce fire hazard；And urea-formaldehyde resin adhesive can be discharged by thermal decomposition Go out more formaldehyde；Agricultural crop straw itself belongs to biological material, perishable to go mouldy.Therefore, relative moderate cost is being kept On the basis of develop low burst size of methanal agricultural crop straw anti-corrosive antibacterial fire-retardation artificial board, be a problem to be solved.
Invention content
The object of the present invention is to provide a kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of low cost, burst size of methanal Be kept low for a long time, flame retardant property it is good.
Second object of the present invention is to provide a kind of preparation of above-mentioned agricultural crop straw anti-corrosive antibacterial flame retardant fibre board Method.
To achieve the goals above, the technical solution adopted in the present invention is：
A kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board, is prepared by method comprising the following steps：
1) it is 20-40mm to take agricultural crop straw to be cut to length, crushes and sieves, obtains draw ratio<5 fiber fines and length Diameter is than the fiber coarse fodder for 5-15；Fiber fines and fiber coarse fodder are immersed into the hydrogen-oxygen that mass concentration is 4.0%-5.0% respectively Change in sodium solution, 50-60min is kept the temperature under the conditions of 60 DEG C -65 DEG C, rear taking-up washing, drying to water content are no more than 6%, obtain dry Dry fines and dry coarse fodder, it is spare；
2) according to Zn2+With Cu2+Molar ratio be (2.0-2.5):1 ratio, by zinc nitrate, copper nitrate system soluble in water At mixed sols, after addition bamboo charcoal powder is uniformly dispersed in mixed sols, adds urea liquid and be uniformly mixed, then by system It is warming up to 130-140 DEG C of heat preservation 3-4h and carries out hydro-thermal reaction, after reaction through filtering, drying and obtaining solids, by obtained solid Object calcines 3-4h under the conditions of 400-450 DEG C, and cooling is simultaneously ground, and loaded on bamboo charcoal ZnO/CuO composite materials are obtained；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain fines glue, wherein contained in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive The mass ratio of resin is (1.2-1.4):(2.0-2.4):50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain coarse fodder glue, wherein institute in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive Resiniferous mass ratio is (0.6-0.7):(2.0-2.5):50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 10%-12% is obtained and carefully mixed Close material；Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 6%-8% obtains thick mixture；With Thick mixture is sandwich layer, thin mixture is after surface layer is mated formation, through precompressed, hot-forming and post-processing to get the farming Object stalk anti-corrosive antibacterial flame retardant fibre board.
In step 1), the agricultural crop straw is any one or combination in wheat straw, rice straw；The agricultural crop straw Water content is no more than 10%.Preferably, it is (3-4) that the agricultural crop straw, which is the mass ratio of wheat stalk and rice straw,:(6- 7) stalk mixture.
In step 1), the crushing refers to being crushed to 3-8mm.
In step 1), fiber fines accounts for the 20%-25% of stalk fibre total amount, and surplus is fiber coarse fodder.
In step 2), the addition quality of bamboo charcoal powder is 1.8-2.0 times of zinc nitrate and copper nitrate quality sum.Bamboo charcoal used Powder is submicron order bamboo charcoal powder, average particle size 500nm.
In step 2), the dosage of urea is Zn2+、Cu2+1.8-2.0 times of moles total number.
In step 2), the grinding is ground using super grinder, gained loaded on bamboo charcoal ZnO/CuO composite materials Granularity be 400-600nm.
In step 4), the pressure of the precompressed is 1.2-1.4MPa, time 20-25s.The decrement of precompressed is that slab is thick The 30%-40% of degree.
In step 4), the pressure of the hot pressing is 2.5-3.0MPa, and temperature is 150-160 DEG C, time 10-20min.
In step 4), the post-processing refers to that carry out successively primary is sawed in, drying, buck, sanding, secondary saw.
In step 4), the density of gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is 700-1000kg/m3, thickness is 8-25mm.The moisture content of gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is no more than 6%.
A kind of preparation method of above-mentioned agricultural crop straw anti-corrosive antibacterial flame retardant fibre board, includes the following steps：
1) it is 20-40mm to take agricultural crop straw to be cut to length, crushes and sieves, obtains draw ratio<5 fiber fines and length Diameter is than the fiber coarse fodder for 5-15；Fiber fines and fiber coarse fodder are immersed into the hydrogen-oxygen that mass concentration is 4.0%-5.0% respectively Change in sodium solution, 50-60min is kept the temperature under the conditions of 60 DEG C -65 DEG C, rear taking-up washing, drying to water content are no more than 6%, obtain dry Dry fines and dry coarse fodder, it is spare；
2) according to Zn2+With Cu2+Molar ratio be (2.0-2.5):1 ratio, by zinc nitrate, copper nitrate system soluble in water At mixed sols, after addition bamboo charcoal powder is uniformly dispersed in mixed sols, adds urea liquid and be uniformly mixed, then by system It is warming up to 130-140 DEG C of heat preservation 3-4h and carries out hydro-thermal reaction, after reaction through filtering, drying and obtaining solids, by obtained solid Object calcines 3-4h under the conditions of 400-450 DEG C, and cooling is simultaneously ground, and loaded on bamboo charcoal ZnO/CuO composite materials are obtained；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain fines glue, wherein contained in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive The mass ratio of resin is (1.2-1.4):(2.0-2.4):50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain coarse fodder glue, wherein institute in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive Resiniferous mass ratio is (0.6-0.7):(2.0-2.5):50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 10%-12% is obtained and carefully mixed Close material；Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 6%-8% obtains thick mixture；With Thick mixture is sandwich layer, thin mixture is after surface layer is mated formation, through precompressed, hot-forming and post-processing to get the farming Object stalk anti-corrosive antibacterial flame retardant fibre board.
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present invention, is added homemade bamboo charcoal in urea-formaldehyde resin adhesive Loading ZnO/CuO composite materials, wherein CuO can prevent rot fungi from immersing fibrolamellar as mould inhibitor；ZnO as antiseptic, With significant antibacterial sterilization capability；On the one hand bamboo charcoal is used as ZnO and CuO as the strong sorbing material with bigger serface Carrier, make its active ingredient making sheet, storage during not easily run off, active ingredient is slowly released in fibrous plate in It puts, reaches long-acting mould proof, antibacterial purpose；On the other hand it is dispersed in urea-formaldehyde resin adhesive and finally with glue and is dispersed in In fibrous plate, the formaldehyde to dissociate in urea-formaldehyde resin adhesive can be effectively adsorbed, and inhaled during subsequent fiber plate use Formaldehyde is strapped in the porous structure of bamboo charcoal, first is greatly decreased by the attached free formaldehyde because of adhesive season cracking slow release The burst size of aldehyde.
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present invention, is mated formation as surface layer using thin mixture, is suppressed, carefully Mixture has been mixed into loaded on bamboo charcoal ZnO/CuO composite materials and eight Boratexes based on fiber fines in adhesive used, and eight Boratex belongs to boron-containing compound, has stronger resistance for domestomycetes, mould and worm ant etc. and kills effect.Eight boric acid simultaneously Sodium belongs to containing boron-based flame retardant, melted by heat, and the glassy protective film of generation is covered in plate surface, burning things which may cause a fire disaster and oxygen can be isolated Gas reduces the release of the thermal discharge and imflammable gas of material combustion to prevent continuing for burning；Eight Boratexes are heated Dehydration occurs, absorbs a large amount of heat, the vapor of generation dilutes combustable gas concentration, with cellulose etc. together heat point Promote when solution at charcoal, to fire-retardant.Eight Boratexes and loaded on bamboo charcoal ZnO/CuO composite materials are mixed into glue according to rational proportioning Prepare thin mixture in glutinous agent, fiber fines thin layer formed in fiberboard tow sides, not only have long-term anti-corrosion, it is mothproof, Antibacterial effect, moreover it is possible to form the surface layer flame-retardant layer of tow sides, surface is not easy to light and easily only puts out open fire, has good resistance Fuel efficiency fruit.
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present invention, is mated formation as sandwich layer using thick mixture, is suppressed, slightly Mixture has been mixed into a small amount of loaded on bamboo charcoal ZnO/CuO composite materials and nanometer based on fiber coarse fodder in adhesive used Calcium carbonate, nano-calcium carbonate is as inorganic filler, and on the one hand the mechanical mechanics property of energy reinforcing fiber plank, improves its quiet Qu Qiang Degree, elasticity modulus and internal bond strength, while its expansion rate of water absorption is reduced, there is good water resistant moisture resistance；On the other hand, it receives Rice calcium carbonate belongs to inorganic combustion inhibitor, can be effectively increased the ignitor firing time of plank inner core, reduces heat release rate and total release heat, To prevent to burn.Nano-calcium carbonate and loaded on bamboo charcoal ZnO/CuO composite materials are mixed into according to rational proportioning in adhesive Thick mixture is prepared, fiberboard sandwich layer is used to prepare so that fibrous plate is with long-term anti-corrosion, mothproof, antibacterial effect On the basis of, there is good mechanical mechanics property and flame retardant effect.
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present invention passes through surface layer, the type of sandwich layer additive, dosage Rationally adjustment, surface layer resin added is big, and loaded on bamboo charcoal ZnO/CuO composite material additive amounts are more, by the synergistic effect of eight Boratexes, Based on anti-corrosion, mothproof, antibacterial, fire retardation, separation layer is formed；Meanwhile loaded on bamboo charcoal ZnO/CuO composite material adsorbing fibers The free formaldehyde of intralamellar part release, and the reaction of formaldehyde degradation by photocatalytic oxidation process occurs on surface layer, prevent Form aldehyde release.Sandwich layer resin added Small, loaded on bamboo charcoal ZnO/CuO composite material additive amounts are small, while cost is reduced, by the synergistic effect of nano-calcium carbonate, To improve based on mechanical property and fire retardation, core stiffening effect is formed.Inside and outside mutual cooperation, coordinative role, in low cost On the basis of, so that various additives is cooperated, gives full play to its effect, gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board Middle additive amount is few, at low cost, has long-acting anti-corrosion, mothproof, antibacterial, fire retardation and good water resistant moisture resistance, first Aldehyde burst size is few, meets the requirement of environmental protection, is suitble to promote the use of.
Specific implementation mode
The present invention is described further With reference to embodiment.
In specific implementation mode, the agricultural crop straw is that the mass ratio of wheat stalk and rice straw is 3:7 stalk Mixture；Wheat straw (wheat stalk) used and rice straw (rice straw) are purchased from Henan peasant household, using preceding drying to aqueous Amount is 10%.Bamboo charcoal powder used is submicron order bamboo charcoal powder, average particle size 500nm.The specification of nano-calcium carbonate used is 100nm。
In specific implementation mode, the temperature of the drying is 75-80 DEG C.
In specific implementation mode, urea-formaldehyde resin adhesive used is commercial goods (unmodified), and viscosity (applies 4 glasss, 25 DEG C) For 18-20s, solid content 50%.
Embodiment 1
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present embodiment, is prepared by following methods：
1) it is 20-40mm to take stalk mixture to be cut to length, is sieved after being crushed to 3-8mm with stalk crasher, obtains length Diameter ratio<5 fiber fines and draw ratio is the fiber coarse fodder of 5-15；Wherein, fiber fines accounts for the 20% of stalk fibre total amount, remaining Amount is fiber coarse fodder；
Fiber fines and fiber coarse fodder are immersed respectively in the sodium hydroxide solution that mass concentration is 5.0%, 60 DEG C of conditions Lower heat preservation 60min, rear to take out, after being washed to neutrality, drying to water content is 6%, obtains dry fines and dry coarse fodder, spare；
2) according to Zn2+With Cu2+Molar ratio be 2.0:1 ratio, by zinc nitrate, copper nitrate is soluble in water that mixing is made Colloidal sol, a concentration of 1.0mol/L of copper nitrate in mixed sols；Bamboo charcoal powder, the addition quality of bamboo charcoal powder are added in mixed sols For zinc nitrate and 1.8 times of copper nitrate quality sum, urea liquid is added after being uniformly dispersed, the dosage of urea is Zn2+、Cu2+ System is warming up to 130 DEG C of heat preservation 4h after mixing and carries out hydro-thermal reaction, passed through after reaction by 1.8 times of moles total number Obtained solid object under the conditions of 400 DEG C is calcined 4h, is ground through super grinder after cooling, obtain bamboo charcoal by filter, dry solids Loading ZnO/CuO composite materials, granularity 400-600nm；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain fines glue, wherein contained in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive The mass ratio of resin is 1.2:2.0:50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain coarse fodder glue, wherein institute in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive Resiniferous mass ratio is 0.6:2.1:50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 10% obtains thin mixture； Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 6% obtains thick mixture；With thick mixture It is that surface layer carries out slab of continuously mating formation to obtain for sandwich layer, thin mixture, gained slab carries out precompressed, hot-forming and rear place successively Reason, wherein the pressure of precompressed is 1.2MPa, and time 25s, the decrement of precompressed is the 30% of slab thickness；The pressure of hot pressing For 2.5MPa, temperature is 150 DEG C, time 20min；It is described post-processing refer to the primary saw side carried out successively, drying, buck, Sanding, secondary saw side are to get the agricultural crop straw anti-corrosive antibacterial flame retardant fibre board；
The density of gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is 850kg/m3, thickness 10mm, moisture content is 6%.
Embodiment 2
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present embodiment, is prepared by following methods：
1) it is 20-40mm to take stalk mixture to be cut to length, is sieved after being crushed to 3-8mm with stalk crasher, obtains length Diameter ratio<5 fiber fines and draw ratio is the fiber coarse fodder of 5-15；Wherein, fiber fines accounts for the 23% of stalk fibre total amount, remaining Amount is fiber coarse fodder；
Fiber fines and fiber coarse fodder are immersed respectively in the sodium hydroxide solution that mass concentration is 5.0%, 65 DEG C of conditions Lower heat preservation 50min, rear to take out, after being washed to neutrality, drying to water content is 6%, obtains dry fines and dry coarse fodder, spare；
2) according to Zn2+With Cu2+Molar ratio be 2.2:1 ratio, by zinc nitrate, copper nitrate is soluble in water that mixing is made Colloidal sol, a concentration of 1.0mol/L of copper nitrate in mixed sols；Bamboo charcoal powder, the addition quality of bamboo charcoal powder are added in mixed sols For zinc nitrate and 1.9 times of copper nitrate quality sum, urea liquid is added after being uniformly dispersed, the dosage of urea is Zn2+、Cu2+ System is warming up to 140 DEG C of heat preservation 3h after mixing and carries out hydro-thermal reaction, passed through after reaction by 1.9 times of moles total number Obtained solid object under the conditions of 450 DEG C is calcined 3h, is ground through super grinder after cooling, obtain bamboo charcoal by filter, dry solids Loading ZnO/CuO composite materials, granularity 400-600nm；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain fines glue, wherein contained in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive The mass ratio of resin is 1.3:2.2:50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain coarse fodder glue, wherein institute in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive Resiniferous mass ratio is 0.65:2.3:50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 11% obtains thin mixture； Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 7% obtains thick mixture；With thick mixture It is that surface layer carries out slab of continuously mating formation to obtain for sandwich layer, thin mixture, gained slab carries out precompressed, hot-forming and rear place successively Reason, wherein the pressure of precompressed is 1.3MPa, and time 25s, the decrement of precompressed is the 35% of slab thickness；The pressure of hot pressing For 2.7MPa, temperature is 155 DEG C, time 15min；It is described post-processing refer to the primary saw side carried out successively, drying, buck, Sanding, secondary saw side are to get the agricultural crop straw anti-corrosive antibacterial flame retardant fibre board；
The density of gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is 850kg/m3, thickness 10mm, moisture content is 6%.
Embodiment 3
The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present embodiment, is prepared by following methods：
1) it is 20-40mm to take stalk mixture to be cut to length, is sieved after being crushed to 3-8mm with stalk crasher, obtains length Diameter ratio<5 fiber fines and draw ratio is the fiber coarse fodder of 5-15；Wherein, fiber fines accounts for the 25% of stalk fibre total amount, remaining Amount is fiber coarse fodder；
Fiber fines and fiber coarse fodder are immersed respectively in the sodium hydroxide solution that mass concentration is 5.0%, 65 DEG C of conditions Lower heat preservation 50min, rear to take out, after being washed to neutrality, drying to water content is 6%, obtains dry fines and dry coarse fodder, spare；
2) according to Zn2+With Cu2+Molar ratio be 2.5:1 ratio, by zinc nitrate, copper nitrate is soluble in water that mixing is made Colloidal sol, a concentration of 1.0mol/L of copper nitrate in mixed sols；Bamboo charcoal powder, the addition quality of bamboo charcoal powder are added in mixed sols For zinc nitrate and 2.0 times of copper nitrate quality sum, urea liquid is added after being uniformly dispersed, the dosage of urea is Zn2+、Cu2+ System is warming up to 135 DEG C of heat preservation 3.5h after mixing and carries out hydro-thermal reaction, passed through after reaction by 2.0 times of moles total number Obtained solid object under the conditions of 430 DEG C is calcined 3.5h, grinds, obtain through super grinder after cooling by filtering, dry solids Loaded on bamboo charcoal ZnO/CuO composite materials, granularity 400-600nm；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain fines glue, wherein contained in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive The mass ratio of resin is 1.4:2.4:50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, It is uniformly mixed to obtain coarse fodder glue, wherein institute in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive Resiniferous mass ratio is 0.7:2.5:50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 12% obtains thin mixture； Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 8% obtains thick mixture；With thick mixture It is that surface layer carries out slab of continuously mating formation to obtain for sandwich layer, thin mixture, gained slab carries out precompressed, hot-forming and rear place successively Reason, wherein the pressure of precompressed is 1.4MPa, and time 20s, the decrement of precompressed is the 40% of slab thickness；The pressure of hot pressing For 3.0MPa, temperature is 150 DEG C, time 10min；It is described post-processing refer to the primary saw side carried out successively, drying, buck, Sanding, secondary saw side are to get the agricultural crop straw anti-corrosive antibacterial flame retardant fibre board；
The density of gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is 850kg/m3, thickness 10mm, moisture content is 6%.
Experimental example 1
This experimental example carries out the physical and mechanical property of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by embodiment 1-3 Detection, the results are shown in Table 1.Comparative example in table 1 is that (adhesive used is urea-formaldehyde resin adhesive to commercially available common rice straw fiber plate Glutinous agent).
Wherein, the detection methods such as static bending strength, elasticity modulus, internal bond strength refer to standard GB/T/T11718- 2009。
The detection method of expansion rate of water absorption refers to standard GB/T/T17657-1999 for 24 hours.
The physical and mechanical property testing result of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by 1 embodiment 1-3 of table
Detection project Embodiment 1 Embodiment 2 Embodiment 3 Comparative example
Practical measurement density, kg/m3 852 850 853 880
Practical measurement moisture content, % 6.0 5.9 6.0 6.7
Static bending strength, MPa 32.6 33.0 33.5 29.4
Elasticity modulus, MPa 3389 3407 3423 3058
Internal bond strength, MPa 0.92 0.93 1.01 0.86
Expansion rate of water absorption for 24 hours, % 7.7 7.6 7.0 9.3
As it can be seen from table 1 compared with comparative example, agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by embodiment 1-3 Static bending strength, elasticity modulus and internal bond strength have raising by a relatively large margin, respectively reach 33.5MPa, 3423MPa and 1.01MPa illustrates that agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by the present invention has good mechanical property.Embodiment 1- The expansion rate of water absorption for 24 hours of 3 gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre boards is only 7.0%, and water resistance is good, testing result Show that gained agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the invention has good water resistant humidity resistance.
Experimental example 2
This experimental example carries out the environmental protection flame retardant performance of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by embodiment 1-3 Detection, the results are shown in Table 2.Wherein, comparative example is the same as experimental example 1.
The environmental protection flame retardant energy testing result of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by 2 embodiment 1-3 of table
From table 2 it can be seen that the burst size of methanal of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by embodiment 1-3 is equal No more than 0.17mg/L, it is E0 grades, belongs to and may be directly applied to indoor environment-friendly type decoration finishing material；Obtained by embodiment 1-3 The limit oxygen index of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is not less than 30.8%, is nonflammable material.The experimental results showed that The agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the present invention has good flame retardant property, and burst size of methanal is low, belongs to environmental protection The fibrous plate of type.
Experimental example 3
This experimental example carries out the anti-corrosive antibacterial performance of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by embodiment 1-3 It checks and surveys, the results are shown in Table 3.Wherein, comparative example is the same as experimental example 1.
Wherein, rotproofness laboratory reference standard GB/T/T13942.1-2009, whiterot fungi select Corilus versicolor Quel., brown rot Select gloeophyllum trabeum；The rotproofness of plank is characterized using mass loss rate.
Antibiotic property laboratory reference professional standard QB/T2591-2003, strain used are staphylococcus aureus and large intestine bar Bacterium judges fungistatic effect using antibacterial circle diameter size.
The anti-corrosive antibacterial energy testing result of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board obtained by 3 embodiment 1-3 of table
From table 3 it can be seen that agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is in whiterot fungi rotproofness obtained by embodiment 1-3 Mass loss rate in experiment is no more than 9.0%, and the mass loss rate in the experiment of brown rot fungus rotproofness is no more than 8.5%, Belong to strong corrosion resistant grade；With the comparison of the antibacterial circle diameter size of comparative example it is found that embodiment 1-3 institutes in being tested by antibiotic property The antibiotic property for obtaining agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is largely increased, to staphylococcus aureus and Escherichia coli With apparent biocidal property.The experimental results showed that agricultural crop straw anti-corrosive antibacterial flame retardant fibre board of the invention is with excellent Anti-corrosive antibacterial.

Claims (9)

1. a kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board, it is characterised in that：By method comprising the following steps preparation At：
1) it is 20-40mm to take agricultural crop straw to be cut to length, crushes and sieves, obtains draw ratio<5 fiber fines and draw ratio For the fiber coarse fodder of 5-15；Fiber fines and fiber coarse fodder are immersed into the sodium hydroxide that mass concentration is 4.0%-5.0% respectively In solution, 50-60min is kept the temperature under the conditions of 60 DEG C -65 DEG C, it is rear to take out washing, drying to water content no more than 6%, it must dry thin Material and dry coarse fodder, it is spare；
2) according to Zn2+With Cu2+Molar ratio be (2.0-2.5):1 ratio, by zinc nitrate, copper nitrate is soluble in water that mixing is made Colloidal sol after addition bamboo charcoal powder is uniformly dispersed in mixed sols, adds urea liquid and is uniformly mixed, be then warming up to system 130-140 DEG C of heat preservation 3-4h carries out hydro-thermal reaction and obtained solid object exists after reaction through filtering, drying and obtaining solids 3-4h is calcined under the conditions of 400-450 DEG C, cooling is simultaneously ground, and loaded on bamboo charcoal ZnO/CuO composite materials are obtained；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, mixing It is uniform to obtain fines glue, wherein institute is resinous in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive Mass ratio be (1.2-1.4):(2.0-2.4):50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, mixing It is uniform to obtain coarse fodder glue, wherein contained tree in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive The mass ratio of fat is (0.6-0.7):(2.0-2.5):50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 10%-12% is obtained and carefully mixed Material；Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 6%-8% obtains thick mixture；With thick Mixture is sandwich layer, thin mixture is after surface layer is mated formation, through precompressed, hot-forming and post-processing to get the crops Stalk anti-corrosive antibacterial flame retardant fibre board.
2. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 1), institute It is wheat straw, any one or combination in rice straw to state agricultural crop straw；The water content of the agricultural crop straw is no more than 10%.
3. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 2, it is characterised in that：It is fine in step 1) Dimension fines accounts for the 20%-25% of stalk fibre total amount, and surplus is fiber coarse fodder.
4. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 2), bamboo The addition quality of powdered carbon is 1.8-2.0 times of zinc nitrate and copper nitrate quality sum.
5. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 2), urine The dosage of element is Zn2+、Cu2+1.8-2.0 times of moles total number.
6. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 4), institute The pressure for stating precompressed is 1.2-1.4MPa, time 20-25s.
7. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 4), institute The pressure for stating hot pressing is 2.5-3.0MPa, and temperature is 150-160 DEG C, time 10-20min.
8. agricultural crop straw anti-corrosive antibacterial flame retardant fibre board according to claim 1, it is characterised in that：In step 4), institute The density for obtaining agricultural crop straw anti-corrosive antibacterial flame retardant fibre board is 700-1000kg/m3, thickness 8-25mm.
9. a kind of preparation method of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board as described in any one of claim 1-8, It is characterized in that：Include the following steps：
1) it is 20-40mm to take agricultural crop straw to be cut to length, crushes and sieves, obtains draw ratio<5 fiber fines and draw ratio For the fiber coarse fodder of 5-15；Fiber fines and fiber coarse fodder are immersed into the sodium hydroxide that mass concentration is 4.0%-5.0% respectively In solution, 50-60min is kept the temperature under the conditions of 60 DEG C -65 DEG C, it is rear to take out washing, drying to water content no more than 6%, it must dry thin Material and dry coarse fodder, it is spare；
2) according to Zn2+With Cu2+Molar ratio be (2.0-2.5):1 ratio, by zinc nitrate, copper nitrate is soluble in water that mixing is made Colloidal sol after addition bamboo charcoal powder is uniformly dispersed in mixed sols, adds urea liquid and is uniformly mixed, be then warming up to system 130-140 DEG C of heat preservation 3-4h carries out hydro-thermal reaction and obtained solid object exists after reaction through filtering, drying and obtaining solids 3-4h is calcined under the conditions of 400-450 DEG C, cooling is simultaneously ground, and loaded on bamboo charcoal ZnO/CuO composite materials are obtained；
3) loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) and eight Boratexes are added in urea-formaldehyde resin adhesive, mixing It is uniform to obtain fines glue, wherein institute is resinous in loaded on bamboo charcoal ZnO/CuO composite materials, eight Boratexes and urea-formaldehyde resin adhesive Mass ratio be (1.2-1.4):(2.0-2.4):50；
Loaded on bamboo charcoal ZnO/CuO composite materials obtained by step 2) are added with nano-calcium carbonate in urea-formaldehyde resin adhesive, mixing It is uniform to obtain coarse fodder glue, wherein contained tree in loaded on bamboo charcoal ZnO/CuO composite materials, nano-calcium carbonate and urea-formaldehyde resin adhesive The mass ratio of fat is (0.6-0.7):(2.0-2.5):50；
4) dry fines obtained by step 1) is mixed with fines glue obtained by step 3), resin added 10%-12% is obtained and carefully mixed Material；Dry coarse fodder obtained by step 1) is mixed with coarse fodder glue obtained by step 3), resin added 6%-8% obtains thick mixture；With thick Mixture is sandwich layer, thin mixture is after surface layer is mated formation, through precompressed, hot-forming and post-processing to get the crops Stalk anti-corrosive antibacterial flame retardant fibre board.
CN201810416526.6A 2018-05-03 2018-05-03 A kind of agricultural crop straw anti-corrosive antibacterial flame retardant fibre board and preparation method thereof Pending CN108608550A (en)

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