CN114213998A - Inorganic flame retardant, mildew-proof flame-retardant aldehyde-free adhesive, preparation method and application of mildew-proof flame-retardant aldehyde-free adhesive, and preparation method of mildew-proof flame-retardant aldehyde-free adhesive - Google Patents
Inorganic flame retardant, mildew-proof flame-retardant aldehyde-free adhesive, preparation method and application of mildew-proof flame-retardant aldehyde-free adhesive, and preparation method of mildew-proof flame-retardant aldehyde-free adhesive Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining 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
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
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- 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
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention provides an inorganic flame retardant, a mildew-proof flame-retardant aldehyde-free adhesive, a preparation method and application thereof, and a preparation method of the mildew-proof flame-retardant aldehyde-free adhesive board, and relates to the technical field of flame-retardant materials. The inorganic flame retardant provided by the invention comprises, by weight, 35-50 parts of aluminum hydroxide, 8-15 parts of ferric oxide, 5-10 parts of magnesium oxide, 5-10 parts of calcium oxide, 15-30 parts of II-type ammonium polyphosphate, 15-30 parts of zinc borate, 10-20 parts of expanded vermiculite and 5-10 parts of silicon micropowder. The inorganic flame retardant provided by the invention has the advantages of less addition amount in the board, good flame retardant property, less smoke release amount and lower cost, and is suitable for large-scale popularization and application. In addition, the inorganic flame retardant provided by the invention has a mildew-proof effect.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to an inorganic flame retardant, a mildew-proof flame-retardant aldehyde-free adhesive, a preparation method and application thereof, and a preparation method of a mildew-proof flame-retardant aldehyde-free plywood.
Background
The artificial board is a plate or a molded product which is pressed by taking wood or other non-wood plants as raw materials, separating the raw materials into various unit materials through certain mechanical processing, and applying or not applying an adhesive and other additives. The artificial board mainly comprises three types of plywood, shaving board and fiber board, wherein the plywood has the best strength and volume stability and is the most widely applied in practical application. Plywood is a three-layer or multi-layer plate material made up by using wood segments and making them be rotary-cut into single board or sliced into thin wood and using adhesive to make them be glued together, and usually using odd number of layers of single board and making the fibre directions of adjacent layers of single board be mutually perpendicular.
In recent years, with the continuous increase of the yield of plywood and the continuous improvement of people's fire protection consciousness, various flame retardant boards appear on the market, and the production process mainly comprises two production processes: wet flame retardant and dry flame retardant. The wet-method flame retardance has the problems of complex production process, difficult standard reaching of physical and chemical performance indexes (bonding strength and dipping stripping), easy moisture absorption and mildewing of finished product board surfaces, corrosion of light steel keels and iron nails and the like; although the dry process can better solve some problems brought by the wet process, in order to achieve a certain flame retardant effect, the existing flame retardant is usually added in a large amount (the addition amount is more than 40%), the production cost is generally higher, and the physicochemical property indexes are not easy to reach the standard, especially the bonding strength.
Disclosure of Invention
The invention aims to provide an inorganic flame retardant, a mildew-proof flame-retardant aldehyde-free adhesive, a preparation method and application thereof, and a preparation method of the mildew-proof flame-retardant aldehyde-free adhesive board.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an inorganic flame retardant which is prepared from the following raw materials, by weight, 35-50 parts of aluminum hydroxide, 8-15 parts of ferric oxide, 5-10 parts of magnesium oxide, 5-10 parts of calcium oxide, 15-30 parts of II-type ammonium polyphosphate, 15-30 parts of zinc borate, 10-20 parts of expanded vermiculite and 5-10 parts of silicon micropowder.
Preferably, the average polymerization degree of the type II ammonium polyphosphate is more than or equal to 1000; the content of N is more than or equal to 14 wt%; p2O5The content is more than or equal to 71wt percent.
The invention provides a mildew-proof flame-retardant aldehyde-free adhesive, which is prepared from the following raw materials, by weight, 100 parts of a lignin aldehyde-free adhesive, 15-25 parts of flour, 25-35 parts of an inorganic flame retardant, 0.5-2.0 parts of a silane coupling agent and 0.1-0.5 part of a mildew preventive; the inorganic flame retardant is the inorganic flame retardant in the technical scheme.
Preferably, the lignin formaldehyde-free adhesive has a viscosity of 40 to 100 mPas; the pH value is 11.5-12.5; the solid content is 33-38 wt%.
The invention provides a preparation method of the mildew-proof flame-retardant formaldehyde-free adhesive, which comprises the following steps:
mixing lignin formaldehyde-free adhesive, silane coupling agent and mildew preventive to obtain a mixture;
and mixing the mixture, an inorganic flame retardant and flour to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
The invention provides application of the mildew-proof flame-retardant aldehyde-free glue in the technical scheme or the mildew-proof flame-retardant aldehyde-free glue prepared by the preparation method in the technical scheme in preparation of a plate.
Preferably, the panel comprises plywood.
The invention provides a preparation method of a mildew-proof flame-retardant formaldehyde-free plywood, which comprises the following steps:
sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; gluing the two surfaces of the middle plate 3 and the middle plate 5; the middle plate 2 is coated with glue on one surface in contact with the upper surface anticorrosion scientific wood veneer 1; one side of the middle plate 6, which is in contact with the lower surface layer anti-corrosion scientific and technological veneer 7, is coated with glue; the adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in the technical scheme or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in the technical scheme;
and sequentially carrying out cold pressing and hot pressing on the plate blank to obtain the mildew-proof flame-retardant aldehyde-free plywood.
Preferably, the unit area gluing amount of each surface of the double-sided gluing is 200-280 g/m2。
Preferably, the single-sided gluing amount per unit area is 160-200 g/m2。
The invention provides an inorganic flame retardant which is prepared from the following raw materials, by weight, 35-50 parts of aluminum hydroxide, 8-15 parts of ferric oxide, 5-10 parts of magnesium oxide, 5-10 parts of calcium oxide, 15-30 parts of II-type ammonium polyphosphate, 15-30 parts of zinc borate, 10-20 parts of expanded vermiculite and 5-10 parts of silicon micropowder. In the invention, the aluminum hydroxide is heated and decomposed to form a metal oxide protective layer, and simultaneously, the water vapor is released to reduce the combustion temperature and dilute the oxygen in the air so as to slow down the combustion process; iron sesquioxide can promote the formation of carbon; the calcium oxide and the magnesium oxide have the heat radiation blocking effect, so that the thermal decomposition of the material is inhibited, the combustion can be prevented, and certain mildew-proof and antibacterial effects are achieved; the ammonium polyphosphate II can promote the dehydration and carbon formation of the plate and reduce the smoke; the zinc borate forms a glass state protective layer in the combustion process, so that the heat transfer is blocked, and the combustion process is slowed down; the expanded vermiculite can be rapidly expanded at high temperature, so that carbonization is promoted, and the release of smoke is reduced; the silicon micropowder can promote the generation of a large amount of water vapor and slow down the combustion degree. The inorganic flame retardant provided by the invention has the advantages of less addition amount in the board, good flame retardant property, less smoke release amount and lower cost, and is suitable for large-scale popularization and application. In addition, the inorganic flame retardant provided by the invention has a mildew-proof effect.
The invention also provides a mildew-proof flame-retardant aldehyde-free adhesive, and the mildew-proof flame-retardant aldehyde-free plywood prepared from the mildew-proof flame-retardant aldehyde-free adhesive reaches level 0 in mildew resistance and level B in flame retardance1The adhesive strength reaches more than 0.9MPa at-C level and the other performances reach the standard requirements.
The invention also provides a preparation method of the mildew-proof flame-retardant formaldehyde-free plywood, and the preparation method is simple and convenient in process, is formed in one step, and saves the production cost.
Detailed Description
The invention provides an inorganic flame retardant which is prepared from the following raw materials, by weight, 35-50 parts of aluminum hydroxide, 8-15 parts of ferric oxide, 5-10 parts of magnesium oxide, 5-10 parts of calcium oxide, 15-30 parts of II-type ammonium polyphosphate, 15-30 parts of zinc borate, 10-20 parts of expanded vermiculite and 5-10 parts of silicon micropowder.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 35-50 parts by weight of aluminum hydroxide, preferably 40-45 parts by weight. In the present invention, the particle size of the aluminum hydroxide is preferably 20 to 75 μm, and more preferably 50 μm.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 8-15 parts of ferric oxide, preferably 8-12 parts by weight of aluminum hydroxide. In the present invention, the ferric oxide is preferably industrial grade ferric oxide.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 5-10 parts by weight of magnesium oxide, preferably 7-8 parts by weight of aluminum hydroxide. In the present invention, the magnesium oxide is preferably nano magnesium oxide; the particle size of the nano magnesium oxide is preferably 10-200 nm, and more preferably 80-100 nm.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 5-10 parts by weight of calcium oxide, preferably 7-8 parts by weight of aluminum hydroxide. In the present invention, the calcium oxide is preferably nano calcium oxide; the particle size of the nano calcium oxide is preferably 10-200 nm, and more preferably 80-100 nm.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 15-30 parts by weight of II-type ammonium polyphosphate, preferably 22-25 parts by weight of aluminum hydroxide. In the invention, the average polymerization degree of the II-type ammonium polyphosphate is preferably not less than 1000, and more preferably 1200-2000; the content of N is preferably not less than 14 wt%, and more preferably 14.2-14.4 wt%; p2O5The content is preferably not less than 71 wt%, more preferably 72 to 73 wt%.
In the invention, the raw materials for preparing the inorganic flame retardant comprise, by weight, 15-30 parts of zinc borate, preferably 18-23 parts of aluminum hydroxide. In the present invention, the zinc borate is preferably technical grade zinc borate.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 10-20 parts of expanded vermiculite, preferably 14-16 parts by weight of aluminum hydroxide. In the present invention, the expanded vermiculite is preferably a silicate mixture; the particle size of the expanded vermiculite is preferably 20-75 μm, and more preferably 50 μm. In a specific embodiment of the invention, the exfoliated vermiculite is that sold by the mineral products of Huabang.
In the invention, the raw materials for preparing the inorganic flame retardant comprise 5-10 parts by weight of silica micropowder, preferably 7-8 parts by weight of aluminum hydroxide. In the invention, the main component of the silicon micropowder is silicon dioxide; the content of silicon dioxide in the silicon micro powder is preferably more than or equal to 97 wt%; the particle size of the silicon micro powder is preferably 10-20 μm, and more preferably 16 μm.
In the present invention, the preparation method of the inorganic flame retardant preferably includes: mixing aluminum hydroxide, ferric oxide, magnesium oxide, calcium oxide, II-type ammonium polyphosphate, zinc borate, expanded vermiculite and silica micropowder to obtain the inorganic flame retardant. In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 1000-2000 r/min, and more preferably 1200-1700 r/min; the mixing time is preferably 10-30 min, and more preferably 13-22 min.
The invention provides a mildew-proof flame-retardant aldehyde-free adhesive, which is prepared from the following raw materials, by weight, 100 parts of a lignin aldehyde-free adhesive, 15-25 parts of flour, 25-35 parts of an inorganic flame retardant, 0.5-2.0 parts of a silane coupling agent and 0.1-0.5 part of a mildew preventive; the inorganic flame retardant is the inorganic flame retardant in the technical scheme.
According to the invention, the raw materials for preparing the mildew-proof flame-retardant formaldehyde-free adhesive comprise 100 parts by weight of lignin formaldehyde-free adhesive. In the invention, the viscosity of the lignin aldehyde-free adhesive is preferably 40-100 mPa & s, and more preferably 56-80 mPa & s; the pH value is preferably 11.5-12.5, and more preferably 12.2; the solid content is preferably 33 to 38 wt%, more preferably 35 to 37 wt%.
In the invention, the raw materials for preparing the mildew-proof flame-retardant formaldehyde-free adhesive comprise 15-25 parts of flour, preferably 18-22 parts of the flour, based on the weight parts of the lignin formaldehyde-free adhesive.
In the invention, the raw materials for preparing the mildew-proof flame-retardant aldehyde-free adhesive comprise 25-35 parts of inorganic flame retardant, preferably 28-32 parts of lignin aldehyde-free adhesive by weight. In the invention, the inorganic flame retardant is the inorganic flame retardant described in the above technical scheme.
In the invention, the raw materials for preparing the mildew-proof flame-retardant aldehyde-free adhesive comprise 0.5-2.0 parts of silane coupling agent, preferably 1.0-1.5 parts by weight of lignin aldehyde-free adhesive. In the present invention, the silane coupling agent is preferably KH-560. The strength of the mildew-proof flame-retardant aldehyde-free plywood can be improved by adopting the silane coupling agent.
In the invention, the raw materials for preparing the mildew-proof flame-retardant aldehyde-free adhesive comprise 0.1-0.5 part of mildew preventive, preferably 0.2-0.4 part of mildew preventive based on the weight parts of the lignin aldehyde-free adhesive. In the present invention, the mildewcide is preferably a cason mildewcide. In an embodiment of the present invention, the mildew preventive is Kathon sold by Shanghai Nissi chemical technology Co., Ltd, product number KS25 (isothiazolinone), and the effective component is 5-chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one.
The invention also provides a preparation method of the mildew-proof flame-retardant formaldehyde-free adhesive, which comprises the following steps:
mixing lignin formaldehyde-free adhesive, silane coupling agent and mildew preventive to obtain a mixture;
and mixing the mixture, an inorganic flame retardant and flour to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
According to the invention, the lignin formaldehyde-free adhesive, the silane coupling agent and the mildew preventive are mixed to obtain a mixture. In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 500-1000 r/min, and more preferably 800 r/min; the mixing time is preferably 3-10 min, and more preferably 5-9 min.
After the mixture is obtained, the mixture is mixed with the inorganic flame retardant and the flour to obtain the mildew-proof flame-retardant formaldehyde-free glue. In the present invention, the mixing is preferably performed under stirring conditions; the stirring speed is preferably 1000-1500 r/min, and more preferably 1200-1400 r/min; the mixing time is preferably 5-15 min, and more preferably 7-11 min.
The invention also provides application of the mildew-proof flame-retardant aldehyde-free glue in the technical scheme or the mildew-proof flame-retardant aldehyde-free glue prepared by the preparation method in the technical scheme in preparation of plates. In the present invention, the panel preferably comprises plywood.
The invention also provides a preparation method of the mildew-proof flame-retardant formaldehyde-free plywood, taking the preparation of seven-layer plywood as an example, when the upper and lower surface layers are additionally pasted with the anticorrosion technical wood, the preparation method comprises the following steps:
sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; gluing the two surfaces of the middle plate 3 and the middle plate 5; the middle plate 2 is coated with glue on one surface in contact with the upper surface anticorrosion scientific wood veneer 1; one side of the middle plate 6, which is in contact with the lower surface layer anti-corrosion scientific and technological veneer 7, is coated with glue; the adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in the technical scheme or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in the technical scheme;
and sequentially carrying out cold pressing and hot pressing on the plate blank to obtain the mildew-proof flame-retardant aldehyde-free plywood.
The method comprises the steps of sequentially assembling an upper surface anticorrosion scientific and technological veneer 1, a middle plate 2, a middle plate 3, a middle plate 4, a middle plate 5, a middle plate 6 and a lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank. In the invention, the upper surface layer anticorrosion technical wood veneer 1 and the lower surface layer anticorrosion technical wood veneer 7 are technical wood veneers subjected to anticorrosion treatment, and are preferably technical wood veneers which are subjected to mildew-proof treatment by adding 0.3 wt% of kason serving as a mildew-proof agent in a secondary glue spreading process. In the invention, the thicknesses of the upper surface layer anticorrosion technical wood veneer 1 and the lower surface layer anticorrosion technical wood veneer 7 are independently 30-45 threads, and more preferably 36-42 threads. In the present invention, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5 and the middle plate 6 are preferably eucalyptus, poplar or pine; the thickness of median plate 2, median plate 3, median plate 4, median plate 5 and median plate 6 is independent preferred 2.6 ~ 3.2mm, more preferred 2.6 ~ 3.0 mm.
In the invention, the two surfaces of the middle plate 3 and the middle plate 5 are coated with glue; the unit area gluing amount of each surface of the double-sided gluing is preferably 200-280 g/m2More preferably 230 to 260g/m2. In the invention, one side of the middle plate 2, which is in contact with the upper surface anticorrosion scientific and technological veneer 1, is coated with glue; the unit area gluing amount of the single-sided gluing is preferably 160-200 g/m2More preferably 170 to 190g/m2. In the invention, one side of the middle plate 6, which is in contact with the lower surface layer anti-corrosion scientific and technological veneer 7, is coated with glue; the unit area gluing amount of the single-sided gluing is preferably 160-200 g/m2More preferably 170 to 190g/m2。
In the present invention, the assembly is preferably performed in a manner of criss-cross assembly according to the texture from top to bottom.
After the board blank is obtained, the board blank is sequentially subjected to cold pressing and hot pressing to obtain the mildew-proof flame-retardant aldehyde-free plywood. In the invention, the unit pressure of the cold pressing is preferably 0.6-0.8 MPa, and more preferably 0.6-0.7 MPa; the cold pressing time is preferably 30-50 min, and more preferably 35-46 min. In the present invention, the temperature of the hot pressing is preferably 125 ℃; the unit pressure of the hot pressing is preferably 0.6-0.9 MPa, and more preferably 0.7-0.8 MPa; the time for hot pressing is preferably 500-600 s, and more preferably 540-600 s.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples and comparative examples employ the preparation of starting materials:
aluminum hydroxide: the average particle size is 50 μm;
magnesium oxide: the average particle size is 80 nm;
calcium oxide: the average particle size is 80 nm;
form II ammonium polyphosphate: an average degree of polymerization of 1500, an N content of 14.3 wt.%, P2O5The content was 72.5 wt%;
expanded vermiculite: the average particle size is 50 μm;
silicon micropowder: the content of silica was 97.5 wt%, and the average particle diameter was 16 μm;
lignin formaldehyde-free adhesives: viscosity of 56 mPas; the pH value is 12.2; the solids content was 35 wt%;
silane coupling agent: KH-560;
mildew preventive: KS25 sold by Shanghai Ri Qian chemical technology Co., Ltd;
example 1
Firstly, preparing inorganic flame retardant
According to the weight portion, 40 portions of aluminum hydroxide, 10 portions of ferric oxide, 5 portions of magnesium oxide, 5 portions of calcium oxide, 20 portions of II-type ammonium polyphosphate, 20 portions of zinc borate, 10 portions of expanded vermiculite and 5 portions of silicon micropowder are sequentially added into a stirring kettle, and the mixture is stirred for 22min under the condition of 1200r/min, so that the inorganic flame retardant is obtained.
Secondly, preparing the mildew-proof flame-retardant formaldehyde-free adhesive
1) Sequentially adding 100 parts by weight of lignin formaldehyde-free adhesive, 1.0 part by weight of silane coupling agent and 0.3 part by weight of mildew preventive into a stirrer, and stirring for 9min at the speed of 500r/min to obtain a mixture;
2) and adding 30 parts of the inorganic flame retardant and 20 parts of flour into the mixture, and stirring for 11min at the speed of 1200r/min to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
Thirdly, preparing the mildew-proof flame-retardant formaldehyde-free plywood with low cost and high performance
Taking the preparation of seven-layer plywood as an example, the upper and lower surface layers are additionally pasted with anti-corrosion technical wood: sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; the middle plate 3 and the middle plate 5 are coated with glue on two sides, and the coating weight per unit area of each side is 250g/m2(ii) a The middle plate 2 is coated with glue on one side in contact with the upper surface anticorrosion scientific and technological veneer 1, and the glue coating amount per unit area is 180g/m2(ii) a The middle plate 6 is coated with glue on one side in contact with the lower surface layer anticorrosive scientific wood veneer 7, and the glue coating amount per unit area is 180g/m2(ii) a The adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in the technical scheme or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in the technical scheme; the assembly mode is that the assembly is carried out in a criss-cross mode from top to bottom according to textures; the upper surface anticorrosion technical veneer 1 and the lower surface anticorrosion technical veneer 7 are technical veneers which are added with 0.3 wt% of kason serving as a mildew preventive in the secondary glue distribution process for mildew prevention treatment; the thickness of the upper surface layer anticorrosive technical veneer 1 and the lower surface layer anticorrosive technical veneer 7 is 36 threads; the middle plate 2, the middle plate 3,The middle plate 4, the middle plate 5 and the middle plate 6 are eucalyptus; the thickness of middle plate 2, middle plate 3, middle plate 4, middle plate 5 and middle plate 6 is 3.0 mm.
And (3) cold-pressing the plate blank for 40min under the unit pressure of 0.7MPa, and then hot-pressing for 540s at the temperature of 125 ℃ under the unit pressure of 0.7MPa to obtain the mildew-proof flame-retardant aldehyde-free plywood.
Example 2
Firstly, preparing inorganic flame retardant
According to the weight parts, 45 parts of aluminum hydroxide, 8 parts of ferric oxide, 7 parts of magnesium oxide, 7 parts of calcium oxide, 25 parts of II-type ammonium polyphosphate, 23 parts of zinc borate, 14 parts of expanded vermiculite and 7 parts of silicon micropowder are sequentially added into a stirring kettle, and the mixture is stirred for 15min under the condition of 1500r/min to obtain the inorganic flame retardant.
Secondly, preparing the mildew-proof flame-retardant formaldehyde-free adhesive
1) Sequentially adding 100 parts by weight of lignin formaldehyde-free adhesive, 1.2 parts by weight of silane coupling agent and 0.4 part by weight of mildew preventive into a stirrer, and stirring for 5min at the speed of 800r/min to obtain a mixture;
2) and adding 28 parts of the inorganic flame retardant and 22 parts of flour into the mixture, and stirring for 9min under the condition of 1300r/min to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
Thirdly, preparing the mildew-proof flame-retardant formaldehyde-free plywood with low cost and high performance
Taking the preparation of seven-layer plywood as an example, the upper and lower surface layers are additionally pasted with anti-corrosion technical wood: sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; the middle plate 3 and the middle plate 5 are coated with glue on two sides, and the coating weight per unit area of each side is 240g/m2(ii) a The middle plate 2 is coated with glue on one side in contact with the upper surface anticorrosion scientific and technological veneer 1, and the glue coating amount per unit area is 190g/m2(ii) a The middle plate 6 is coated with glue on one side in contact with the lower surface layer anticorrosive scientific wood veneer 7, and the coating amount per unit area is 190g/m2(ii) a The adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in the technical scheme or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in the technical scheme; the assembly is carried out in a manner ofAssembling the blank in a crisscross manner according to the texture from top to bottom; the upper surface anticorrosion technical veneer 1 and the lower surface anticorrosion technical veneer 7 are technical veneers which are added with 0.3 wt% of kason serving as a mildew preventive in the secondary glue distribution process for mildew prevention treatment; the thickness of the upper surface layer anticorrosive technical veneer 1 and the lower surface layer anticorrosive technical veneer 7 is 42 threads; the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5 and the middle plate 6 are eucalyptus; the thickness of middle plate 2, middle plate 3, middle plate 4, middle plate 5 and middle plate 6 is 3.2 mm.
And (3) cold-pressing the plate blank for 35min under the unit pressure of 0.8MPa, and then hot-pressing the plate blank for 500s at the temperature of 125 ℃ under the unit pressure of 0.8MPa to obtain the mildew-proof flame-retardant aldehyde-free plywood.
Example 3
Firstly, preparing inorganic flame retardant
According to the weight parts, 43 parts of aluminum hydroxide, 12 parts of ferric oxide, 8 parts of magnesium oxide, 8 parts of calcium oxide, 22 parts of II-type ammonium polyphosphate, 18 parts of zinc borate, 16 parts of expanded vermiculite and 8 parts of silicon micropowder are sequentially added into a stirring kettle, and the mixture is stirred for 13min under the condition of 1700r/min to obtain the inorganic flame retardant.
Secondly, preparing the mildew-proof flame-retardant formaldehyde-free adhesive
1) Sequentially adding 100 parts by weight of lignin formaldehyde-free adhesive, 1.5 parts by weight of silane coupling agent and 0.4 part by weight of mildew preventive into a stirrer, and stirring for 7min at the speed of 700r/min to obtain a mixture;
2) and adding 32 parts of the inorganic flame retardant and 18 parts of flour into the mixture, and stirring for 7min at the speed of 1400r/min to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
Thirdly, preparing the mildew-proof flame-retardant formaldehyde-free plywood with low cost and high performance
Taking the preparation of seven-layer plywood as an example, the upper and lower surface layers are additionally pasted with anti-corrosion technical wood: sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; the middle plate 3 and the middle plate 5 are coated with glue on two sides, and the coating weight per unit area of each side is 260g/m2(ii) a The middle plate 2 is coated with glue on one side in contact with the upper surface anticorrosion scientific wood veneer 1, and the glue coating amount per unit area is 170g/m2(ii) a In the middle ofThe single surface of the plate 6, which is in contact with the lower surface layer anticorrosion scientific wood veneer 7, is coated with glue, and the coating amount per unit area is 170g/m2(ii) a The adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in the technical scheme or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in the technical scheme; the assembly mode is that the assembly is carried out in a criss-cross mode from top to bottom according to textures; the upper surface anticorrosion technical veneer 1 and the lower surface anticorrosion technical veneer 7 are technical veneers which are added with 0.3 wt% of kason serving as a mildew preventive in the secondary glue distribution process for mildew prevention treatment; the thickness of the upper surface layer anticorrosive technical veneer 1 and the lower surface layer anticorrosive technical veneer 7 is 32 threads; the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5 and the middle plate 6 are eucalyptus; the thickness of middle plate 2, middle plate 3, middle plate 4, middle plate 5 and middle plate 6 is 2.8 mm.
And (3) cold-pressing the plate blank for 46min under the unit pressure of 0.6MPa, and then hot-pressing for 600s at the temperature of 125 ℃ under the unit pressure of 0.8MPa to obtain the mildew-proof flame-retardant aldehyde-free plywood.
Comparative example 1
The same as example 1 except that aluminum hydroxide, iron oxide, magnesium oxide and calcium oxide were not added to prepare the inorganic flame retardant in the first step.
Comparative example 2
The same as example 1 except that the inorganic flame retardant was prepared without adding ammonium polyphosphate form II and exfoliated vermiculite in the first step.
Comparative example 3
The method is basically the same as the example 1, except that the silane coupling agent and the mildew preventive are not added when the mildew-proof flame-retardant formaldehyde-free glue is prepared in the step two.
Comparative example 4
The same as example 1 except that the preparation raw materials of the inorganic flame retardant were modified to "43 parts of aluminum hydroxide, 22 parts of type II ammonium polyphosphate and 18 parts of zinc borate".
Comparative example 5
The process is basically the same as example 1, except that the preparation raw materials of the inorganic flame retardant are modified to 43 parts of aluminum hydroxide, 22 parts of type II ammonium polyphosphate and 18 parts of zinc borate, and the using amount of the inorganic flame retardant is adjusted from 30 parts to 50 parts when the mildewproof flame-retardant aldehyde-free adhesive is prepared in the second step.
Test example
The properties of the plywood sheets prepared in examples 1 to 3 and comparative examples 1 to 5 are shown in table 1.
TABLE 1 Properties of the plywood sheets prepared in examples 1 to 3 and comparative examples 1 to 5
In Table 1, the burning behavior index THR600sMJ is the total heat released over 600 s; smoke generation characteristic index SMOGRA/(m)2/s2) Generating a rate index for the flue gas; TSP600s/m2Test 600s total smoke generation.
As can be seen from table 1, comparative example 1 compares to example 1: all indexes of the flame retardant are reduced without adding four metal oxides, wherein the total heat release within 600s is increased from 12.7MJ to 16.5MJ and becomes unqualified, because in the combustion process, less water vapor released by thermal decomposition of aluminum hydroxide is generated, the combustion temperature is not reduced, and oxygen in air is not diluted, so that the combustion process is slowed down and the synergistic protection effect of the metal oxide protective layer is realized; the mildew-proof performance is reduced from 0 grade to 1 grade, because of the lack of nano-scale magnesium oxide and calcium oxide, which have certain mildew-proof effect.
Comparative example 2 compared to example 1: the absence of the ammonium polyphosphate II and the expanded vermiculite leads to the remarkable deterioration of the combustion performance and the smoke generation characteristic, particularly the smoke generation characteristic, because the ammonium polyphosphate II and the expanded vermiculite can inhibit and reduce the release of smoke to a certain extent.
Comparative example 3 compared to example 1: silane coupling agent and mildew preventive are not added, so that the bonding strength and mildew resistance of the II-type adhesive are obviously poor, and the data in the table show that the silane coupling agent has an obvious effect on the strength improvement of the flame-retardant adhesive and influences the combustion performance and the smoke generation characteristic to a certain extent, because the combustion performance and the smoke generation characteristic are greatly influenced by the strength.
Comparative examples 4 and 5 compared to example 1: the inorganic flame retardant provided by the invention is replaced by the flame retardant mainly comprising aluminum hydroxide, II-type ammonium polyphosphate and zinc borate, and the results show that: when the flame retardant is added in the same proportion for performance index test, the combustion performance and the smoke production characteristic are both unqualified, and the mildew resistance is grade 1; when the addition ratio of the flame retardant is increased to 50 parts, the bonding strength of class II is obviously reduced, although the combustion performance is qualified, the smoke generation characteristic is still not qualified, and the mildew resistance is grade 1. Therefore, the inorganic flame retardant provided by the invention has the advantages of less addition amount, good flame retardant property, less smoke release amount, low cost and certain mildew-proof function.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The inorganic flame retardant is characterized by comprising, by weight, 35-50 parts of aluminum hydroxide, 8-15 parts of ferric oxide, 5-10 parts of magnesium oxide, 5-10 parts of calcium oxide, 15-30 parts of II-type ammonium polyphosphate, 15-30 parts of zinc borate, 10-20 parts of expanded vermiculite and 5-10 parts of silicon micropowder.
2. The inorganic flame retardant of claim 1, wherein the average degree of polymerization of the type II ammonium polyphosphate is not less than 1000; the content of N is more than or equal to 14 wt%; p2O5The content is more than or equal to 71wt percent.
3. The mildew-proof flame-retardant formaldehyde-free adhesive is characterized by comprising, by weight, 100 parts of lignin formaldehyde-free adhesive, 15-25 parts of flour, 25-35 parts of inorganic flame retardant, 0.5-2.0 parts of silane coupling agent and 0.1-0.5 part of mildew preventive; the inorganic flame retardant is the inorganic flame retardant described in claim 1 or 2.
4. The mould-proof flame-retardant aldehyde-free adhesive according to claim 3, wherein the viscosity of the lignin aldehyde-free adhesive is 40-100 mPa-s; the pH value is 11.5-12.5; the solid content is 33-38 wt%.
5. The preparation method of the mildewproof flame-retardant aldehyde-free glue as claimed in any one of claims 3 to 4, which comprises the following steps:
mixing lignin formaldehyde-free adhesive, silane coupling agent and mildew preventive to obtain a mixture;
and mixing the mixture, an inorganic flame retardant and flour to obtain the mildew-proof flame-retardant formaldehyde-free adhesive.
6. The application of the mildewproof flame-retardant aldehyde-free glue prepared by any one of claims 3 to 4 or the mildewproof flame-retardant aldehyde-free glue prepared by the preparation method of claim 5 in preparing plates.
7. Use according to claim 6, wherein the board comprises plywood.
8. The preparation method of the mildew-proof flame-retardant formaldehyde-free plywood is characterized by comprising the following steps of:
sequentially assembling the upper surface anticorrosion scientific and technological veneer 1, the middle plate 2, the middle plate 3, the middle plate 4, the middle plate 5, the middle plate 6 and the lower surface anticorrosion scientific and technological veneer 7 from top to bottom to obtain a plate blank; gluing the two surfaces of the middle plate 3 and the middle plate 5; the middle plate 2 is coated with glue on one surface in contact with the upper surface anticorrosion scientific wood veneer 1; one side of the middle plate 6, which is in contact with the lower surface layer anti-corrosion scientific and technological veneer 7, is coated with glue; the adhesive used for the double-sided coating and the single-sided coating is the mildew-proof flame-retardant aldehyde-free adhesive in any one of claims 3 to 4 or the mildew-proof flame-retardant aldehyde-free adhesive prepared by the preparation method in claim 5;
and sequentially carrying out cold pressing and hot pressing on the plate blank to obtain the mildew-proof flame-retardant aldehyde-free plywood.
9. The method according to claim 8, wherein the reaction mixture is heated to a temperature in the reaction mixtureThe unit area gluing amount of each surface of the double-sided gluing is 200-280 g/m2。
10. The preparation method of claim 8, wherein the single-sided glue coating amount per unit area is 160-200 g/m2。
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