Manufacturing process of smoke-suppression and fire-retardant plywood

Abstract

The present application relates to a kind of manufacturing process of smoke suppression flame-retardant plywood, including eucalyptus veneer, plywood core and the multi-layer structure of organic phosphorus flame-retardant environment-friendly amino resin flame-retardant adhesive eucalyptus board layer, organic phosphorus flame-retardant environment-friendly amino resin flame-retardant adhesive eucalyptus board layer is prepared by evenly coating organic phosphorus flame-retardant environment-friendly amino resin flame-retardant coating on the eucalyptus board, and the multi-layer structure is that flame-retardant adhesive coating is inserted between eucalyptus veneer and board core;Through process, the smoke suppression and flame-retardant performance of wood-based panel are greatly improved, glue well, combustion performance reaches B1 level and above, formaldehyde emission reaches E NF Class, smoke toxicity t1 level, and bonding strength ≥0.1 MPa.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of furniture wood board, in particular to the field of smoke-suppressing and flame-retardant fine woodworking board. BACKGROUND

[0002] Fine woodworking board refers to a special plywood made by splicing wood strips or using hollow board as core board, covering two or more layers of plywood on both sides, and then being pressed by glue, which is widely used in furniture manufacturing, sewing machine table board, carriage, ship production and construction industry, etc.

[0003] Wood materials such as artificial boards are flammable or combustible materials, and a large number of artificial boards are used for indoor decoration and decoration, which increases the risk of indoor fire.

[0004] Most of the flame retardants used in the market are substitutes for plastic or fiber material flame retardant treatment, and the development of environmentally friendly, low-toxicity, high-efficiency and multifunctional wood processing flame retardants is a major development direction of future flame retardants. Comprehensive application and related research of phosphorus-based flame retardants in wood materials found that water-based phosphorus-containing flame retardants contain conductive ions (such as ammonium ions, chloride ions, etc. electrochemical reaction), acidic substances (chemical reaction with metal after contact), oxidizing agents (oxidation under certain conditions), which will affect the water resistance, mechanical properties of wood materials, and cause problems such as moisture absorption, halogen return and metal corrosion, which need to be reasonably controlled and treated during use. While having flame retardant properties, there is little research on physical and mechanical properties, moisture absorption, and anti-corrosion metal properties, and the environmental friendliness of artificial board flame retardants is not considered, and there is a lack of research and evaluation of health and safety in the industry, and green and environmentally friendly flame retardants for wood processing are urgently needed. Therefore, for the application of water-based phosphorus-containing flame retardants in wood, it is necessary to continuously optimize the technology and application scheme in practice to improve the flame retardant performance and sustainability of the material.

[0005] Flame-retardant adhesive is an adhesive that can maintain structural stability at high temperatures, and is widely used in construction, aerospace, electronics, automobiles and other fields. The simplest method for preparing flame-retardant adhesive is to blend flame retardants (such as nanomaterials, metal oxides, nitrogen and phosphorus co-doping, etc.) with adhesive, and the main research trend is to enhance the adhesion performance, improve the flame-retardant efficiency, and reduce the toxicity of flame-retardant adhesive. SUMMARY

[0006] The technical purpose of the present application is to solve the problems in the background art, and to provide a manufacturing process of smoke-suppressing and flame-retardant fine woodworking board.

[0007] The above technical purpose of the present application is achieved by the following technical scheme:

[0008] A manufacturing process of smoke-suppression and flame-retardant fine wood board, comprising eucalyptus veneer, fine wood board core and organic phosphorus flame-retardant environment-friendly amino resin flame-retardant adhesive eucalyptus board layer of multi-layer structure;

[0009] The organic phosphorus flame-retardant environment-friendly amino resin flame-retardant adhesive eucalyptus board layer is prepared by uniformly coating the organic phosphorus flame-retardant environment-friendly amino resin flame-retardant agent on the eucalyptus board, and the preparation process of the organic phosphorus flame-retardant environment-friendly amino resin flame-retardant agent is that: the adhesive is uniformly mixed by mixing a certain mass ratio of phosphorus-containing flame-retardant adhesive A and biomass-based phosphorus cross-linking flame-retardant B, and the mixed solution of the flame-retardant A and B is mixed and stirred uniformly with the water dispersion in deionized water to obtain the organic phosphorus flame-retardant environment-friendly amino resin flame-retardant agent.

[0010] Acetaminophen hexakisaminocyclotriphosphazene is used as one of the main reactants for synthesizing rosin-based phosphazene cross-linking flame retardant because acetaminophen hexakisaminocyclotriphosphazene has a very stable molecular structure, and the amino, phosphazene and other structures are used to react with the rosin-based flame retardant modifier, and the branched structure of the active sites such as amino and phosphazene is used to synthesize rosin-based phosphazene cross-linking flame retardant with excellent performance; the phosphorus / nitrogen / silicon multi-flame-retardant element compound is dissolved in deionized water as an organic framework system for complexation reaction, MgCl2 fully dissolved in the aqueous solution is slowly added to the ligand system, and then a single metal complex is prepared under constant temperature conditions by using hydrothermal reaction. In the process of preparing the single metal complex, other metal precursors with different valence states are gradually added, the accurate spatial arrangement of the organic column in the complex flame retardant is used as an additional metal chelating site, the metal ions are inserted into the uncoordinated P / N atoms, and the reaction process is controlled by the small molecule step-by-step cross-linking and molecular weight method, so that a new type of multi-metal complex flame retardant modifier is obtained. The branched phosphorus compound such as tetrahydroxymethyl phosphonium chloride is used as a chemical structure active site with the above-mentioned multi-metal complex flame retardant modifier, an organic phosphorus intermediate and a flame retardant low-toxicity technology system are formed by rapid complexation technology, and a multi-metal complex phosphorus cross-linking flame retardant is prepared. Finally, the rosin-based biomass-based phosphorus cross-linking flame retardant and the multi-metal complex phosphorus cross-linking flame retardant are prepared into a smoke-suppression and low-toxicity biomass-based phosphorus-containing flame retardant in different proportions by ultrasonic dispersion compatibility.

[0011] The present application has the advantages that the prepared water-soluble rosin-based biomass-based flame-retardant modifier is used to prepare a multi-metal complex phosphorus cross-linking flame retardant after being combined with a metal complex, and then the multi-metal complex phosphorus cross-linking flame retardant is compounded into a compounded flame retardant containing water-soluble rosin-based phosphorus cross-linking flame retardant with smoke-suppression and low-toxicity effects, and the prepared flame retardant can be applied to prepare a wood-based board material with better flame-retardant performance; in combination with an adhesive, the flame retardant has the advantages of environmental protection, smoke suppression, low toxicity, flame retardation, no pollution and the like.

[0012] As preferred, the mass ratio of the phosphorus-containing flame-retardant adhesive A and the biomass-based phosphorus flame-retardant cross-linking agent B is (2:1)-(8:1);In the water dispersion coating water solution mixed system of A, B and water dispersion coating, the mass fraction of the A, B mixed solution is 2-5 parts, the mass fraction of the water dispersion coating is 15-30 parts, and the rest is deionized water;The three are mixed and stirred uniformly at 40-60℃.

[0013] The present application has the advantage that the formation of water dispersion is due to the interaction force between the molecules or particles and water molecules, which makes the solid substance uniformly dispersed in water. These interaction forces include static attraction, dissolution, adsorption, hydrophobicity, etc. Through these forces, solid particles or molecules can be stably suspended in water to form a water dispersion. Water dispersion can uniformly disperse solid substances in water to form a uniform dispersion system. This helps to improve the effective utilization rate and reaction rate of the substance.

[0014] As preferred, the phosphorus-containing flame-retardant adhesive A is prepared from melamine, rosin-based phosphonitrile cross-linking flame retardant, urea and formaldehyde. The preparation process is as follows: 30-70 parts of melamine, 15-25 parts of formaldehyde and 15-25 parts of urea are respectively added to a reaction kettle for dimerization reaction, 5-15 parts of rosin-based phosphonitrile cross-linking flame retardant is added as a primer after reaction for 60-90 min, and the reaction is continued for 60-90 min to obtain the phosphorus-containing flame-retardant adhesive A.

[0015] As preferred, the rosin-based phosphonitrile cross-linking flame retardant is prepared by esterification of acyl chloride rosin acid, propylene pimaric acid and phosphorus dihydric alcohol with triethanolamine as catalyst, then adding ethanol aqueous solution, stirring uniformly, then adding p-acetamidophenol hexamino cyclotriphosphazene, stirring for a period of time, and then stopping the reaction to obtain the rosin-based phosphonitrile cross-linking flame retardant. The mass fraction of rosin acid, propylene pimaric acid, phosphorus dihydric alcohol and p-acetamidophenol hexamino cyclotriphosphazene is 25 parts, 35 parts, 20 parts and 20 parts respectively.

[0016] As preferred, the biomass-based phosphorus cross-linking flame retardant B is a metal complex biomass-based phosphorus cross-linking flame retardant.

[0017] As preferred, the preparation process of the metal complex biomass-based phosphorus cross-linking flame retardant is as follows: the rosin-based biomass-based flame-retardant modifier is prepared by mixing and stirring phosphorus dihydric alcohol and rosin acid compound, then stirring and mixing in ethanol aqueous solution for 40-60 min, then adding tetramethylammonium chloride phosphorus branched phosphorus compound and stirring and mixing for 40-60 min to obtain water-soluble rosin-based phosphorus cross-linking flame retardant. The mass fraction of rosin-based biomass-based flame-retardant modifier and tetramethylammonium chloride phosphorus branched phosphorus compound is 15-30 parts, and the rest is ethanol aqueous solution.

[0018] As preferred, 5-10 parts of phosphorus / nitrogen / silicon multi-flame-retardant element compound is dissolved in deionized water and stirred uniformly as an organic framework system of complex reaction, and a multi-metal complex is prepared by complexing MgCl2 aqueous solution 15-30 parts and Fe, Cu metal precursor solution 3-6 parts at 50-80 DEG C constant temperature and fully dissolved in deionized water, metal ions are inserted into uncoordinated P / N atoms to form a multi-metal complex flame-retardant modifier, and finally water-soluble rosin-based phosphorus cross-linking flame retardant 15-30 parts, multi-metal complex flame-retardant modifier 5-10 parts and tetrahydroxy phosphorus chloride 5-10 parts are quickly complexed in an aqueous solution to obtain a metal complex biomass-based phosphorus cross-linking flame retardant B.

[0019] As preferred, the multi-layer structure of the smoke-suppression flame-retardant plywood is that the outer layer is two layers of eucalyptus veneer, and the middle is a plywood core, the outer upper and lower layers of the plywood core are coated with an organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant coating, and the eucalyptus veneer is bonded to the coating, and the bonded eucalyptus veneer is also coated with an organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant coating, as shown in Figure 2.

[0020] As preferred, the organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant agent is coated by roll coating, the coating thickness is 2-5 mm, and the glue amount is 200-380 g / m 2 After the flame-retardant glue is coated, pre-drying is completed, and then a dry heat method hot pressing process is performed, the veneer between the eucalyptus veneers is longitudinally and transversely layered, the hot pressing adopts a pressure of 0.1-0.4 MPa and a temperature of 100-160 DEG C, and finally the drying time is 30-90 min.

[0021] By the multi-layer wood board and the flame-retardant adhesive structure, and in cooperation with the specific hot pressing process, the obtained hot-pressed multi-layer wood board has high flatness, good gluing state and better mechanical properties.

[0022] In summary, the present application has the following advantages:

[0023] 1. By the multi-layer coating of the organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant coating, the smoke-suppression and flame-retardant properties of the plywood can be greatly improved;

[0024] 2. By the multi-layer wood board and the flame-retardant adhesive structure, and in cooperation with the specific hot pressing process, the obtained hot-pressed multi-layer wood board has high flatness, good gluing state and better mechanical properties;

[0025] 3. The fine wood board manufactured by the scheme, according to GB 8624-2012, the smoke suppression low-toxicity and difficult-to-burn single board type artificial board combustion performance reaches B1 (B) level, the test combustion rate growth index is less than 100W / s, the total heat release amount of 600s is less than 7.0MJ, the combustion performance is improved by more than 10% compared with the B1 (B) standard of GB 8624-2012, which is of great significance to solve the problem of unstable quality caused by product and test errors at present, and the smoke toxicity reaches the t1 level of GB / T 20285, the metal corrosion rate of galvanized parts is less than 15% by using the GB / T 34724-2017 standard detection method, and the formaldehyde emission amount reaches E NF level by using the GB / T 39600-2021 standard detection method, and the glue strength is greater than or equal to 0.7MPa (class II). BRIEF DESCRIPTION OF DRAWINGS

[0026] Fig. 1 is a manufacturing process flow chart of a smoke-suppression and difficult-to-burn fine wood board;

[0027] Fig. 2 is a multi-layer structure of a smoke-suppression and difficult-to-burn fine wood board;

[0028] Among them, 1, eucalyptus single board layer; 2, organic phosphorus flame-retardant environment-friendly amino resin flame-retardant coating; 3, fine wood board core layer. DETAILED DESCRIPTION

[0029] The following specific examples are only an explanation of the present application, which is not a limitation of the present application. Those skilled in the art can make modifications to the present examples without creative contribution after reading the present specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

[0030] It should be noted that, as a non-key component in the present scheme, the approximate optimal amount in the previous exploration process is directly selected for testing, but more details are not described. Example 1

[0031] (1) Preparation of phosphorus-containing flame-retardant adhesive A: after esterification of acyl chloride of rosin acid, propylene pimaric acid and phosphorus-containing dihydric alcohol with triethanolamine as catalyst, adding ethanol aqueous solution, stirring uniformly, then adding p-acetamidophenol hexamino cyclotriphosphazene, stirring for a period of time, and then generating rosin-based phosphazene cross-linked flame retardant after the reaction is completed; wherein rosin acid 25 parts, propylene pimaric acid 35 parts, phosphorus-containing dihydric alcohol and p-acetamidophenol hexamino cyclotriphosphazene each 20 parts;

[0032] Then the melamine, rosin-based phosphorus-containing flame retardant, urea and formaldehyde were prepared into a phosphorus-containing flame-retardant adhesive, the preparation process was that 45 parts, 22.5 parts, 22.5 parts of melamine, formaldehyde and urea were respectively added into a reaction kettle for dimerization reaction, 10 parts of rosin-based phosphorus-containing flame retardant was added as a primer after 60 minutes of reaction to continue reaction for 80 minutes to obtain the phosphorus-containing flame-retardant adhesive A;

[0033] (2) Preparation of biomass-based phosphorus-containing cross-linked flame retardant B: after the rosin-based biomass-based flame-retardant modifier was prepared by mixing and stirring the phosphorus-containing dihydric alcohol and rosin acid compound, the water-soluble rosin-based phosphorus-containing cross-linked flame retardant was prepared by mixing and stirring in the ethanol aqueous solution for 60 minutes, adding the four-hydroxymethyl phosphorus chloride branched phosphorus compound and mixing and stirring for 60 minutes; wherein the mass fraction of the rosin-based biomass-based flame-retardant modifier and the four-hydroxymethyl phosphorus chloride branched phosphorus compound was 20 parts, and the rest was the ethanol aqueous solution; then the phosphorus / nitrogen / silicon multi-flame-retardant element compound 8 parts was dissolved in deionized water to be uniformly stirred as an organic framework system for complex reaction, a multi-metal complex was prepared by complexing the MgCl2 aqueous solution 25 parts and the metal precursor solution of Fe and Cu 4.8 parts after hydrothermal reaction at 65℃ constant temperature and fully dissolving in deionized water, the metal ion was inserted into the un-coordinated P / N atoms to form a multi-metal complex flame-retardant modifier, finally the water-soluble rosin-based phosphorus-containing cross-linked flame retardant 20 parts, the multi-metal complex flame-retardant modifier 5 parts and the four-hydroxyl phosphorus chloride 7 parts were rapidly complexed in the aqueous solution to obtain the metal complex biomass-based phosphorus-containing cross-linked flame retardant B.

[0034] (3) Preparation of the organic phosphorus-containing flame-retardant environmentally-friendly amino resin flame-retardant: the A and B with a mass ratio of 2:1 were mixed and stirred uniformly, then mixed and stirred uniformly with the water dispersion coating, the mass fraction of the A and B mixed solution was 2 parts, and the mass fraction of the water dispersion coating was 15 parts.

[0035] (4) Coating and wood board hot pressing: the coating of (3) was uniformly coated on the wood board by rolling with a coating thickness of 2mm and a glue coating amount of 200g / m 2 ; after the flame-retardant adhesive was coated, the pre-drying was completed, then the dry heat method hot pressing process was carried out, the eucalyptus veneer was longitudinally and transversely arranged layer by layer, the hot pressing was carried out at a pressure of 0.1MPa and a temperature of 100℃, and finally the drying time was 30 minutes; the multi-layer structure of the wood board was that the outer layer was two eucalyptus veneers, the middle was a core of the wood board, the core of the wood board was coated with the organic phosphorus-containing flame-retardant environmentally-friendly amino resin flame-retardant coating on the upper and lower layers, the eucalyptus veneer was adhered to the coating, and the eucalyptus veneer and the eucalyptus veneer between the adhered eucalyptus veneer were also coated with the organic phosphorus-containing flame-retardant environmentally-friendly amino resin flame-retardant coating. Example 2

[0036] (1) Preparation of phosphorus-containing flame-retardant adhesive A: After the esterification of acyl chloride rosin acid, propylene pimaric acid, and phosphorus-containing dihydric alcohol is completed with triethanolamine as catalyst, ethanol aqueous solution is added and stirred uniformly, then p-acetylaminophenol hexamino cyclotriphosphazene is added, stirred for a period of time, and then the reaction is completed to generate rosin-based phosphazene cross-linked flame retardant; wherein the mass fractions of rosin acid, propylene pimaric acid, phosphorus-containing dihydric alcohol, and p-acetylaminophenol hexamino cyclotriphosphazene are 26 parts, 38 parts, 18 parts, and 18 parts, respectively;

[0037] Then, melamine, rosin-based phosphazene cross-linked flame retardant, and urea and formaldehyde are used to prepare a phosphorus-containing flame-retardant adhesive, and the preparation process is as follows: 46 parts of melamine, 22 parts of formaldehyde, and 22 parts of urea are added to a reaction kettle for dimerization reaction, 10 parts of rosin-based phosphazene cross-linked flame retardant is added as a primer after 60 minutes of reaction, and the reaction continues for 80 minutes to obtain the phosphorus-containing flame-retardant adhesive A.

[0038] (2) Preparation of biomass-based phosphorus cross-linked flame retardant B: After the rosin-based biomass-based flame-retardant modifier is prepared by mixing and stirring the phosphorus-containing dihydric alcohol and rosin acid compound, the mixture is stirred in ethanol aqueous solution for 60 minutes, then the four-hydroxymethyl phosphorus chloride branched phosphorus compound is added and stirred for 60 minutes to prepare the water-soluble rosin-based phosphorus cross-linked flame retardant; wherein the mass fractions of the rosin-based biomass-based flame-retardant modifier and the four-hydroxymethyl phosphorus chloride branched phosphorus compound are 20 parts, and the rest is ethanol aqueous solution; then, the phosphorus / nitrogen / silicon multi-flame-retardant element compound 8 parts is dissolved in deionized water and stirred uniformly as the organic framework system for complexation reaction, and the multi-metal complex is prepared by complexing the MgCl2 aqueous solution 25 parts fully dissolved in deionized water with the metal precursor solution of Fe and Cu 4.8 parts at 65°C constant temperature and hydrothermal reaction; the metal ion is inserted into the uncoordinated P / N atoms to form a multi-metal complex flame-retardant modifier; finally, the water-soluble rosin-based phosphorus cross-linked flame retardant 20 parts, the multi-metal complex flame-retardant modifier 5 parts, and the four-hydroxyl phosphorus chloride 7 parts are quickly complexed in the aqueous solution to obtain the metal complex biomass-based phosphorus cross-linked flame retardant B.

[0039] (3) Preparation of organic phosphorus flame-retardant environmentally friendly amino resin flame retardant: A and B with a mass ratio of 8:1 are mixed and stirred uniformly, then mixed and stirred uniformly with water dispersion paint, the mass fractions of A and B mixed solution are 5 parts, and the mass fraction of water dispersion paint is 30 parts.

[0040] (4) Coating and wood board hot pressing: the paint of (3) is uniformly coated on the wood board by rolling with a coating thickness of 5 mm, and the glue coating amount is 380 g / m 2; the eucalyptus veneer is longitudinally or transversely laid in layers, hot pressing is performed at a pressure of 0.4 MPa and a temperature of 160 DEG C, and finally drying is performed for 90 min; the multilayer structure of the wood board is that the outer layer is two eucalyptus veneers, the middle is a core of the wood-based board, the outer two layers of the core of the wood-based board are coated with the organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant coating, and the eucalyptus veneers are bonded to the coating; the bonded eucalyptus veneers and the eucalyptus veneers therebetween are also coated with the organic phosphorus flame-retardant environmentally-friendly amino resin flame-retardant coating. Example 3

[0041] (1) Preparation of the phosphorus-containing flame-retardant adhesive A: the rosin-based phosphazene cross-linking flame-retardant agent is prepared by esterification of acyl chloride rosin acid, propylene pimaric acid and phosphorus-containing dihydric alcohol with triethanolamine as a catalyst, then adding an ethanol aqueous solution, uniformly stirring, adding p-acetylaminophenol hexaaminocyclotriphosphazene, stirring for a period of time, and then stopping the reaction to obtain the rosin-based phosphazene cross-linking flame-retardant agent; wherein the mass fractions of the acyl chloride rosin acid, the propylene pimaric acid, the p-acetylaminophenol hexaaminocyclotriphosphazene and the phosphorus-containing dihydric alcohol are 25 parts, 35 parts, 20 parts and 20 parts, respectively;

[0042] Then, the melamine, the rosin-based phosphazene cross-linking flame-retardant agent, the urea and the formaldehyde are used to prepare the phosphorus-containing flame-retardant adhesive, the preparation process is that 45 parts of the melamine, 22.5 parts of the formaldehyde and 22.5 parts of the urea are respectively added into a reaction kettle for dimerization reaction, 10 parts of the rosin-based phosphazene cross-linking flame-retardant agent is added as a primer for continued reaction for 80 min after the reaction for 60 min, and then the phosphorus-containing flame-retardant adhesive A is obtained;

[0043] (2) Preparation of the biomass-based phosphorus cross-linking flame-retardant agent B: the rosin-based biomass-based flame-retardant modifier is prepared by mixing and stirring the phosphorus-containing dihydric alcohol and the rosin acid compound, then the water-soluble rosin-based phosphorus cross-linking flame-retardant agent is prepared by stirring and mixing in the ethanol aqueous solution for 60 min, adding 8 parts of the phosphorus / nitrogen / silicon multi-flame-retardant element compound dissolved in deionized water for uniform stirring as an organic framework system for complexation reaction, and then hydrothermally reacting at 65 DEG C for constant temperature and fully dissolving 25 parts of the MgCl2 aqueous solution and 5 parts of the metal precursor solution of Fe and Cu in deionized water to complex the multi-metal complex; the metal ion is inserted into the uncoordinated P / N atoms to form the multi-metal complex flame-retardant modifier; finally, the water-soluble rosin-based phosphorus cross-linking flame-retardant agent 20 parts, the multi-metal complex flame-retardant modifier 5 parts and the tetrahydroxyl chlorophosphonium 7 parts are quickly complexed in the aqueous solution to obtain the metal complex biomass-based phosphorus cross-linking flame-retardant agent B.

[0044] (3) Preparation of the organic phosphorus environmentally friendly amino resin flame retardant: 4.5:1 of A, B mixed and stirred uniformly, and then mixed with the water dispersion coating, and stirred uniformly, the mass fraction of the A, B mixed solution is 3 parts, and the mass fraction of the water dispersion coating is 21 parts.

[0045] (4) Coating coating and wood board hot pressing: the coating of (3) is uniformly coated on the wood board by rolling, the coating thickness is 3.5 mm, the glue coating amount is 305 g / m 2 ; after the flame retardant glue is coated, the pre-drying is completed, and then the dry hot method hot pressing process is performed, the eucalyptus veneer is longitudinally and transversely arranged layer by layer, the hot pressing adopts a pressure of 0.2 MPa and a temperature of 120 DEG C, and finally the drying time is 60 min; the multi-layer structure of the wood board is that the outer layer is two eucalyptus veneers, the middle is a core of the wood board, the core of the wood board is coated with an organic phosphorus environmentally friendly amino resin flame retardant coating on the upper and lower layers, and the eucalyptus veneer is bonded to the coating, and the bonded eucalyptus veneer is also coated with an organic phosphorus environmentally friendly amino resin flame retardant coating between the eucalyptus veneers. Example 4

[0046] (1) Preparation of the phosphorus-containing flame-retardant adhesive A: after the acyl chloride of the rosin acid, the acryl pimaric acid, and the phosphorus-containing dihydric alcohol are esterified with triethanolamine as a catalyst, the ethanol aqueous solution is mixed and stirred uniformly, then the p-acetamidophenol hexamino cyclotriphosphazene is added, and after stirring for a period of time, the reaction is completed to generate the rosin-based phosphazene cross-linked flame retardant; wherein the rosin acid is 25 parts, the acryl pimaric acid is 35 parts, the phosphorus-containing dihydric alcohol and the p-acetamidophenol hexamino cyclotriphosphazene are each 20 parts;

[0047] Then, the melamine, the rosin-based phosphazene cross-linked flame retardant, the urea, and the formaldehyde are used to prepare the phosphorus-containing flame-retardant adhesive, and the preparation process is that 45 parts, 22.5 parts, and 22.5 parts of the melamine, the formaldehyde, and the urea are respectively added to the reaction kettle for dimerization reaction, 10 parts of the rosin-based phosphazene cross-linked flame retardant is added as a primer after the reaction for 60 min, and the phosphorus-containing flame-retardant adhesive A is obtained after the reaction for 80 min.

[0048] (2) Preparation of biomass-based phosphorus cross-linked flame retardant B: After the rosin-based biomass-based flame-retardant modifier was prepared by mixing and stirring the phosphorus-containing dihydric alcohol and rosin acid compound, the mixture was stirred in an ethanol aqueous solution for 60 min, and then the branched phosphorus compound of tetrahydroxymethyl phosphorus chloride was added and stirred for 60 min to prepare the water-soluble rosin-based phosphorus cross-linked flame retardant; wherein the mass fractions of the rosin-based biomass-based flame-retardant modifier and the branched phosphorus compound of tetrahydroxymethyl phosphorus chloride were 20 parts, and the rest was the ethanol aqueous solution; then, 8 parts of the phosphorus / nitrogen / silicon multi-flame-retardant element compound was dissolved in deionized water to prepare an organic framework system for complex reaction, and a multi-metal complex was prepared by complexing 25 parts of MgCl2 aqueous solution and 5 parts of Fe and Cu metal precursor solution which were fully dissolved in deionized water at 65°C, so that the metal ions were inserted into the uncoordinated P / N atoms to form a multi-metal complex flame-retardant modifier; finally, 20 parts of the water-soluble rosin-based phosphorus cross-linked flame retardant, 5 parts of the multi-metal complex flame-retardant modifier, and 7 parts of tetrahydroxyl phosphorus chloride were rapidly complexed in the aqueous solution to obtain the metal complex biomass-based phosphorus cross-linked flame retardant B.

[0049] (3) Preparation of the organic phosphorus flame-retardant environmentally friendly amino resin flame retardant: A and B with a mass ratio of 3.8:1 were mixed and stirred uniformly, and then mixed and stirred uniformly with the water dispersion coating, the mass fractions of the A and B mixed solution were 4 parts, and the mass fraction of the water dispersion coating was 25 parts.

[0050] (4) Coating and wood board hot pressing: the coating of (3) was uniformly coated on the wood board by rolling with a coating thickness of 4 mm and a glue amount of 320 g / m 2 ; after the flame-retardant glue was coated, the pre-drying was completed, and then the dry hot pressing process was performed, the eucalyptus veneer was longitudinally and transversely arranged layer by layer, the hot pressing was performed at a pressure of 0.3 MPa and a temperature of 140°C, and finally the drying time was 60 min; the multi-layer structure of the wood board was that the outer layer was two eucalyptus veneers, the middle was a core of the cabinet board, the core of the cabinet board was coated with the organic phosphorus flame-retardant environmentally friendly amino resin flame-retardant coating on the upper and lower layers, and the eucalyptus veneer was bonded to the coating, and the eucalyptus veneer between the bonded eucalyptus veneers was also coated with the organic phosphorus flame-retardant environmentally friendly amino resin flame-retardant coating. Example 5

[0051] (1) Preparation of the phosphorus-containing flame-retardant adhesive A: after the rosin-based phosphazene cross-linked flame retardant was esterified by acyl chloride rosin acid, propylene pimaric acid, and phosphorus-containing dihydric alcohol with triethanolamine as a catalyst, the rosin acid, the propylene pimaric acid, and the phosphorus-containing dihydric alcohol were mixed and stirred uniformly in the ethanol aqueous solution, then para-acetylaminophenol hexaaminocyclotriphosphazene was added and stirred for a period of time, and then the rosin-based phosphazene cross-linked flame retardant was generated after the reaction was completed; wherein the rosin acid was 25 parts, the propylene pimaric acid was 35 parts, and the phosphorus-containing dihydric alcohol and the para-acetylaminophenol hexaaminocyclotriphosphazene were each 20 parts.

[0052] Then the melamine, rosin-based phosphorus-containing flame retardant, urea and formaldehyde were prepared into a phosphorus-containing flame-retardant adhesive, the preparation process was that 45 parts, 22.5 parts, 22.5 parts of melamine, formaldehyde and urea were respectively added into a reaction kettle for dimerization reaction, 10 parts of rosin-based phosphorus-containing flame retardant was added as a primer after 60 minutes of reaction to continue reaction for 80 minutes to obtain the phosphorus-containing flame-retardant adhesive A;

[0053] (2) Preparation of biomass-based phosphorus-containing cross-linked flame retardant B: after the rosin-based biomass-based flame-retardant modifier was prepared by mixing and stirring the phosphorus-containing dihydric alcohol and rosin acid compound, the mixture was stirred in an ethanol aqueous solution for 60 minutes, 8 parts of phosphorus / nitrogen / silicon multi-flame-retardant element compound was dissolved in deionized water and stirred uniformly as an organic framework system for complex reaction, a multi-metal complex was prepared by complexing 25 parts of MgCl2 aqueous solution and 5 parts of metal precursor solution of Fe and Cu which were fully dissolved in deionized water at 65℃ constant temperature by hydrothermal reaction, the metal ions were inserted into the uncoordinated P / N atoms to form a multi-metal complex flame-retardant modifier, finally the water-soluble rosin-based phosphorus-containing cross-linked flame retardant 20 parts, the multi-metal complex flame-retardant modifier 5 parts and the tetrahydroxy phosphorus chloride 7 parts were quickly complexed in the aqueous solution to obtain the metal complex biomass-based phosphorus-containing cross-linked flame retardant B.

[0054] (3) Preparation of organic phosphorus-containing environmentally friendly amino resin flame retardant: the A and B with a mass ratio of 6:1 were mixed and stirred uniformly, then mixed and stirred uniformly with a water dispersion coating, the mass fraction of the A and B mixed solution was 4.5 parts, and the mass fraction of the water dispersion coating was 24 parts.

[0055] (4) Coating and hot pressing of the wood board: the coating of (3) was uniformly coated on the wood board by rolling, the coating thickness was 2.5 mm, and the glue coating amount was 270 g / m 2 ; after the flame retardant glue was coated, the pre-drying was completed, then the dry heat method hot pressing process was carried out, the eucalyptus veneer was longitudinally and transversely arranged layer by layer, the hot pressing was carried out at a pressure of 0.4 MPa and a temperature of 135℃, and finally the drying time was 45 minutes; the multi-layer structure of the wood board was that the outer layer was two layers of eucalyptus veneer, the middle was a core of the wood board, the core of the wood board was coated with the organic phosphorus-containing environmentally friendly amino resin flame retardant coating on the upper and lower layers, and the eucalyptus veneer was adhered to the coating, and the eucalyptus veneer between the adhered eucalyptus veneers was also coated with the organic phosphorus-containing environmentally friendly amino resin flame retardant coating. Comparative Example 1

[0056] (1) Preparation of phosphorus-containing flame-retardant adhesive A: The preparation of rosin-based phosphazene cross-linked flame retardant is as follows: acyl chloride rosin acid, propylene pimaric acid, and phosphorus-containing dihydric alcohol are esterified with triethanolamine as catalyst, then ethanol aqueous solution is added and stirred uniformly, then p-acetylaminophenol hexamino cyclotriphosphazene is added, and stirred for a period of time, then the reaction is completed, and rosin-based phosphazene cross-linked flame retardant is generated; wherein rosin acid is 25 parts, propylene pimaric acid is 35 parts, and p-acetylaminophenol hexamino cyclotriphosphazene is 20 parts each;

[0057] Then, melamine, rosin-based phosphazene cross-linked flame retardant, urea and formaldehyde are used to prepare a phosphorus-containing flame-retardant adhesive, and the preparation process is as follows: 45 parts of melamine, 22.5 parts of formaldehyde and 22.5 parts of urea are added to the reaction kettle for dimerization reaction, 10 parts of rosin-based phosphazene cross-linked flame retardant is added as a primer after 60 minutes of reaction, and the reaction continues for 80 minutes to obtain the phosphorus-containing flame-retardant adhesive A.

[0058] (2) Coating and hot pressing of wood board: A coating is uniformly coated on the wood board by rolling, with a coating thickness of 3 mm and a glue coating amount of 300 g / m 2 ; After the coating of the flame-retardant adhesive is completely pre-dried, dry heat method hot pressing process is performed, with one layer of eucalyptus veneer being longitudinally arranged and one layer being transversely arranged layer by layer, hot pressing is performed at a pressure of 0.3 MPa and a temperature of 135℃, and finally drying is performed for 60 minutes; the multi-layer structure of the wood board is that the outer layer is two layers of eucalyptus veneer, the middle is a core of the wood-based board, the core of the wood-based board is coated with an organic phosphorus flame-retardant environmentally friendly amino resin flame-retardant coating on the upper and lower layers, and the eucalyptus veneer is adhered to the coating, and the eucalyptus veneer adhered to the eucalyptus veneer is also coated with an organic phosphorus flame-retardant environmentally friendly amino resin flame-retardant coating. Comparative Example 2

[0059] It is a conventional ordinary wood board on the market, without flame-retardant adhesive coating and special multi-layer structure.

[0060] The wood-based boards obtained in the above examples and comparative examples are detected for bonding strength, investigated for combustion performance of artificial board according to GB 8624-2012, investigated for smoke toxicity according to GB / T 20285, and detected for formaldehyde emission according to GB / T 39600-2021 standard detection method.

[0061] Among them, the combustion performance level refers to the combustion performance level of 5.1.2 of GB 8624-2012, which is A, B1 (B, C), B2 (D, E), and B3 respectively; the smoke toxicity level is divided into t0, t1, and t2, and the greater the danger and the lower the safety from t0 to t2, t1 represents reaching the quasi-safety level ZA3; the formaldehyde emission level in GB / T 39600-2021 is E1, E0, and E NF , among which E NFThe formaldehyde emission is preferably less than or equal to 0.025.

[0062] The test results are as follows:

[0063]

[0064] From the above data, it can be concluded that under the experimental conditions near Example 3, a better smoke-retardant and flame-retardant plywood with good performance can be obtained, the combustion performance reaches A level, the smoke toxicity level is t1, the bonding strength is 0.91 MPa, and the formaldehyde emission level is also in E NF level, while the flame retardancy is excellent, the bonding strength and the lower smoke toxicity are also considered; the smoke toxicity level of the examples is all t1, the combustion performance level is B1 level or above, the bonding strength is greater than or equal to 0.7 MPa, and the formaldehyde emission level is E NF level, which shows that the raw material components and the combination method of the multi-layer board structure of the present application can obviously improve the performance of the template; compared with the comparative examples, in the comparative example 1, only the A adhesive coating is used for coating, the multi-layer structure is retained, the bonding strength is 0.68 MPa, and other performances are poor; in the comparative example 2, there is no coating participation and no multi-layer structure of the wood board, not only the mechanical property bonding strength is low, but also the combustion performance and the smoke toxicity are obviously different from the examples.

Claims

1. A process for the manufacture of smoke-suppressing, fire-retardant wood-based panels, characterized in that The multi-layer structure comprises eucalyptus wood veneer, a core of blockboard and an environmentally friendly organic phosphorus flame-retardant amino resin flame-retardant adhesive layer of eucalyptus wood veneer. The environmentally friendly organic phosphorus flame-retardant amino resin flame-retardant adhesive layer of eucalyptus wood veneer is prepared by uniformly coating an environmentally friendly organic phosphorus flame-retardant amino resin flame-retardant adhesive layer on the eucalyptus wood veneer, and the preparation process of the environmentally friendly organic phosphorus flame-retardant amino resin flame-retardant adhesive is as follows: the adhesive is prepared by uniformly mixing a certain mass ratio of a phosphorus-containing flame-retardant adhesive A and a biomass-based phosphorus cross-linking flame-retardant B, and then mixing and stirring the mixed solution of A and B with a water dispersion in deionized water to obtain the environmentally friendly organic phosphorus flame-retardant amino resin flame-retardant adhesive. The phosphorus-containing flame-retardant adhesive A is prepared by using melamine, a rosin-based phosphazene cross-linking flame retardant, urea and formaldehyde, and the preparation process is as follows: 30-70 parts of melamine, 15-25 parts of formaldehyde and 15-25 parts of urea are respectively added to a reaction kettle for dimerization reaction, 5-15 parts of the rosin-based phosphazene cross-linking flame retardant is added as a primer after 60-90 minutes of reaction to continue the reaction for 60-90 minutes to obtain the phosphorus-containing flame-retardant adhesive A. The rosin-based phosphazene cross-linking flame retardant is prepared by esterification of acyl chloride rosin acid, propylene pimaric acid and phosphorus dihydric alcohol with triethanolamine as a catalyst, and then adding ethanol aqueous solution, stirring uniformly, adding p-acetylaminophenol hexaaminocyclotriphosphazene, stirring for a period of time, and then stopping the reaction to obtain the rosin-based phosphazene cross-linking flame retardant; wherein the mass fractions of the acyl chloride rosin acid, the propylene pimaric acid, the phosphorus dihydric alcohol and the p-acetylaminophenol hexaaminocyclotriphosphazene are 25 parts, 35 parts, 20 parts and 20 parts, respectively. The biomass-based phosphorus cross-linking flame retardant B is a metal complex biomass-based phosphorus cross-linking flame retardant. The preparation process of the metal complex biomass-based phosphorus cross-linking flame retardant is as follows: a rosin-based biomass-based flame-retardant modifier is prepared by mixing and stirring phosphorus dihydric alcohol and rosin acid compounds, and then stirring and mixing in an ethanol aqueous solution for 40-60 minutes, adding a branched phosphorus compound of tetramethyl chlorophosphonium phosphate for 40-60 minutes of stirring and mixing to obtain a water-soluble rosin-based phosphorus cross-linking flame retardant. The mass fractions of the rosin-based biomass-based flame-retardant modifier and the branched phosphorus compound of tetramethyl chlorophosphonium phosphate are 15-30 parts, and the rest is an ethanol aqueous solution. 5-10 parts of a phosphorus / nitrogen / silicon multi-flame-retardant element compound is dissolved in deionized water to prepare an organic framework system for complexation reaction, and a multi-metal complex is prepared by hydrothermal reaction at 50-80℃ constant temperature and complexation of 15-30 parts of MgCl2 aqueous solution fully dissolved in deionized water and 3-6 parts of metal precursor solutions of Fe and Cu, so that the metal ions are inserted into the uncoordinated P / N atoms to form a multi-metal complex flame-retardant modifier, and finally the metal complex biomass-based phosphorus cross-linking flame retardant B is obtained by rapid complexation of 15-30 parts of the water-soluble rosin-based phosphorus cross-linking flame retardant, 5-10 parts of the multi-metal complex flame-retardant modifier and 5-10 parts of the tetrahydroxy chlorophosphonium phosphate in an aqueous solution.

2. The manufacturing process of the smoke-suppressing and flame-retardant blockboard according to claim 1. The mass ratio of the phosphorus-containing flame-retardant adhesive A and the biomass-based phosphorus cross-linking flame retardant B is (2:1)-(8:1); in the water dispersion coating water solution mixed system of A, B and water, the mass fraction of the mixed solution of A and B is 2-5 parts, the mass fraction of the water dispersion coating is 15-30 parts, and the rest is deionized water; the three are mixed and stirred uniformly at 40-60°C.

3. The manufacturing process of the smoke-suppressing and flame-retardant blockboard according to claim 2, characterized in that: The multi-layer structure of the smoke-suppressing and flame-retardant blockboard is that the outer layer is two layers of eucalyptus veneer, and the middle layer is a blockboard core, the outer upper and lower layers of the blockboard core are coated with an organic phosphorus flame-retardant and environmentally friendly amino resin flame-retardant coating, and the eucalyptus veneer is bonded to the coating, and the bonded eucalyptus veneer and eucalyptus veneer are also coated with an organic phosphorus flame-retardant and environmentally friendly amino resin flame-retardant coating.

4. The manufacturing process of the smoke-suppressing and flame-retardant blockboard according to claim 3, characterized in that: The organic phosphorus flame-retardant environment-friendly amino resin flame-retardant agent is coated by roll coating, the coating thickness is 2-5 mm, and the coating amount is 200-380 g / m 2 ; After the flame-retardant adhesive glue is coated and pre-dried, the dry heat method hot pressing process is performed, the eucalyptus veneer is longitudinally and transversely layered and laid, the hot pressing adopts a pressure of 0.1-0.4 MPa and a temperature of 100-160°C, and finally the drying time is 30-90 min.

5. Smoke-suppressing, fire-retardant wood-based panels, characterized in that The manufacturing process of the smoke-suppressing and flame-retardant blockboard according to any one of claims 1-4 is prepared, and can be applied to prepare a blockboard with excellent properties, smoke suppression, flame retardance, and good mechanical properties.

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