CN115302600A - Modified solid wood floor and manufacturing method thereof - Google Patents

Modified solid wood floor and manufacturing method thereof Download PDF

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Publication number
CN115302600A
CN115302600A CN202211061424.XA CN202211061424A CN115302600A CN 115302600 A CN115302600 A CN 115302600A CN 202211061424 A CN202211061424 A CN 202211061424A CN 115302600 A CN115302600 A CN 115302600A
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China
Prior art keywords
jin
particle
small
solid wood
size
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Chinese (zh)
Inventor
程凡
杨亮庆
欧阳倩雯
佘学彬
仲利涛
莫德旺
刘颖
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Guangdong Nature Home Technology Research Co ltd
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Guangdong Nature Home Technology Research Co ltd
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Priority to CN202211061424.XA priority Critical patent/CN115302600A/en
Publication of CN115302600A publication Critical patent/CN115302600A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/12—Impregnating by coating the surface of the wood with an impregnating paste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/50—Mixtures of different organic impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

Abstract

The invention is suitable for the technical field of floors, and provides a manufacturing method of a modified solid wood floor, which comprises the following steps: preparing a small-particle-size polyurethane dispersion; modifying and synthesizing small-particle-size styrene-acrylic emulsion by using small-particle-size polyurethane dispersoid; dipping the board by using a styrene-acrylic emulsion with small particle size, and then shaping and drying the board; preparing expandable modified epoxy resin; and (3) coating the expandable modified epoxy resin on the plate, heating and foaming the plate, and cutting the redundant foamed part. The invention also provides a modified solid wood floor. The modified solid wood floor manufactured by the invention has the advantages of no formaldehyde, good water resistance, good sealing and filling properties, yellowing resistance, no influence on the adhesive force of the surface coating, and capability of having certain functional processing modification, and meeting the use requirements.

Description

Modified solid wood floor and manufacturing method thereof
Technical Field
The invention belongs to the technical field of floors, and particularly relates to a modified solid wood floor and a manufacturing method thereof.
Background
Currently, there are three major types of flooring substrates on the market: fiberboard (wood fibers glued together), plywood (wood veneers glued together), and solid wood, with solid wood flooring being the most popular with consumers. The raw materials used by the solid wood floor at present mainly use the two-winged-bean hardwood, the material density is high, the porosity is small, moisture is not easy to enter the interior, the stability of the product is high, especially, the wood floor can keep an undeformed stable state for a long time in a geothermal environment, but the hardwood resource is limited, the growth period of the tree is long, the price of the solid wood floor product is far higher than that of a common strengthened floor and a composite floor, and therefore, the significance of how to meet the required performance standard by adopting a density increasing and filling mode for cheap solid wood is important.
Some methods for impregnation modification exist in the market at present, but all have the defects, such as water glass impregnation is adopted, the water resistance is poor, the water glass is easy to deform due to high water or humidity, and the coating on the surface is damaged; the resin containing formaldehyde is adopted for impregnation, so that the formaldehyde can be released, and the health of a user is harmed; the MDI and the like are adopted for dipping, so that the paint is difficult to brush and has poor yellowing resistance, and cannot be commercially applied; the plastic resin is adopted for impregnation, the viscosity of the plastic resin is high, and the plastic resin is difficult to inject into the wood whether the pressure impregnation or the vacuum impregnation is adopted.
Disclosure of Invention
The embodiment of the invention aims to provide a manufacturing method of a modified solid wood floor, aiming at solving the problems in the prior art.
The embodiment of the invention is realized in such a way that the manufacturing method of the modified solid wood floor comprises the following steps:
preparing a small-particle-size polyurethane dispersion;
modifying and synthesizing small-particle-size styrene-acrylic emulsion by using small-particle-size polyurethane dispersoid;
dipping the plate by using styrene-acrylic emulsion with small particle size, and then shaping and drying the plate;
preparing expandable modified epoxy resin;
and (3) coating the expandable modified epoxy resin on the plate, heating and foaming the plate, and cutting the redundant foamed part.
Preferably, the method specifically comprises the following steps:
mixing polybutylene adipate or polycaprolactone diol, polycarbonate diol or polycaprolactone polyol, polytetrahydrofuran diol or polycaprolactone polyol, adding IPDI or TDI, and a catalyst, heating to react, adding a chain extender 2-2 dimethylolpropionic acid or 1,4-butanediol or resorcinol dihydroxyethyl ether solution dissolved in N-methylpyrrolidone or acetone into the reaction kettle, continuing to react, cooling, adding one or more of hydroxyethyl methacrylate, caprolactam, cyclohexanone amine and methyl ethyl ketone amine for end capping, cooling after reacting, adding one or more of triethylamine, sodium hydroxide and sodium acetate, and finally adding deionized water for emulsifying to obtain a small-particle-size polyurethane dispersion;
mixing one or more of butyl acrylate, ethyl acrylate and isooctyl acrylate, styrene, methyl methacrylate or acrylonitrile to obtain a mixed solution, adding part of the mixed solution, part of an initiator potassium persulfate and a composite emulsifier into a reaction kettle, heating and stirring, then adding a small-particle-size polyurethane dispersion and an aluminum sol solution, continuing to react, slowly dripping the rest of the mixed solution, the initiator, acrylic acid or alpha-methacrylic acid, N-N hydroxymethyl acrylamide and aluminum chloride into the solution, carrying out heat preservation reflux reaction after dripping is finished, cooling to room temperature, and filtering and discharging to obtain a small-particle-size styrene-acrylic emulsion;
placing the plate in a treatment tank, carrying out vacuum treatment, then pressurizing and dipping the small-particle-size styrene-acrylic emulsion into the plate, carrying out vacuum treatment again after dipping, pressurizing the treated plate, and shaping and drying the plate;
heating low-molecular-weight low-viscosity epoxy resin, adding modifier chloroprene-hydroxyethyl methacrylate copolymer, polypropylene glycol diglycidyl ether and boron trifluoride diethyl etherate, stirring to prepare a component A, mixing a curing agent, a filling agent and foamed microspheres to prepare a component B to obtain expandable modified epoxy resin, and mixing the component A and the component B for brushing when in use;
and brushing the mixed expandable modified epoxy resin on the dried board, heating and foaming the board, and cutting the redundant foaming material to obtain the modified solid wood floor.
Preferably, the small particle size polyurethane dispersion has an average particle size distribution between 0.001 and 0.07 μm.
Preferably, the catalyst is one or more of dibutyltin dilaurate, N-dimethylcyclohexylamine, N-dimethylbenzylamine and N-ethylmorpholine.
Preferably, the stirring speed of the reaction kettle is 100-200r/min.
Preferably, the composite emulsifier is formed by compounding NP-10, OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine and polyol fatty acid ester.
Preferably, the low molecular weight and low viscosity epoxy resin is at least two of EPON 8132, EPlKOTE817, dimer acid modified epoxy resin EPD-171, 128 epoxy resin and E51 epoxy resin.
Preferably, the curing agent is one or more of a polythiol curing agent, a T31 curing agent, a 650 curing agent, a 593 curing agent, hexamethyl tetrahydrophthalic anhydride, a modified thiourea curing agent, an anhydride curing agent and polyether polyol.
Preferably, the filler is one of silicon powder, calcium carbonate, kaolin and talcum powder;
the foaming microspheres are thermoplastic hollow polymer microspheres and consist of a thermoplastic polymer shell and liquid alkane gas sealed in, and the foaming temperature is 80-120 ℃.
Another object of the embodiments of the present invention is to provide a modified solid wood floor, which is manufactured by the above manufacturing method.
According to the modified solid wood floor provided by the embodiment of the invention, the board is impregnated by the polyurethane modified styrene-acrylic emulsion, and the board is coated by the expandable modified epoxy resin, so that the density of cheap solid wood is increased in a filling manner, and the performance requirements of no formaldehyde, good water resistance, good sealing and filling performance, yellowing resistance, no influence on the adhesive force of surface coating and the like are met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The embodiment of the invention provides a method for manufacturing a modified solid wood floor, which comprises the steps of firstly synthesizing a small-particle-size polyurethane dispersoid, then synthesizing a small-particle-size styrene-acrylic emulsion by modifying polyurethane, then taking the modified styrene-acrylic emulsion as an aqueous impregnation liquid, impregnating the aqueous impregnation liquid into a plate by adopting a vacuum and high-pressure impregnation process, then shaping and drying the plate, accelerating the crosslinking and curing of the internal emulsion, simultaneously preventing the plate from bending and deforming, preparing expandable modified epoxy resin, coating the upper part and the lower part of the floor after slotting, heating, finally cleaning expanded edge substances, and carrying out subsequent veneering or coating treatment;
synthesizing small-particle-size polyurethane modified styrene-acrylic emulsion, namely introducing aqueous polyurethane dispersion with special particle size as a part of the seed emulsion at the stage of the seed emulsion, continuously synthesizing the styrene-acrylic emulsion, adding a proper amount of self-crosslinking substance and penetrant at the final cooling stage of the styrene-acrylic emulsion, so that the emulsion can better enter gaps in the board through pressurization and vacuum impregnation under the condition of small overall particle size, and self-crosslinking is carried out in the board to form a large, waterproof and reticular irreversible filler;
the polyurethane dispersion is small in particle size, low in viscosity and designable in molecular structure, the types and the proportion of soft and hard monomers can be changed, and a hydrophilic chain extender with a special functional group can be introduced, but the price is high, the solid content is low, the curing shrinkage is large, the styrene-acrylic emulsion with the small particle size has very good water resistance, the styrene-acrylic emulsion is often used for exterior wall coatings, yellowing resistance and water resistance, the single use or direct mixing is not ideal, the viscosity of the single styrene-acrylic emulsion is relatively high, the temperature is slightly high, the creep property of the single styrene-acrylic emulsion is certain in viscosity, the single use of the waterborne polyurethane can cause water evaporation in the drying process to generate shrinkage due to the low solid content besides the high price, so that the interior cannot be well filled, the left holes enable water vapor to enter, the deformation is finally caused, the direct mixing is easy to demulsify and stratify, the two are not so compatible, the combination of the polyurethane dispersion and the styrene-acrylic emulsion in the molecular layer is realized by adopting a core-shell polymerization mode, an IPN interpenetrating structure is formed, more hard monomers can also reduce the overall creep property and improve the adhesion strength, and reduce the overall cost;
however, as the water-based filling resin, structural shrinkage occurs along with the evaporation of moisture, the shrinkage process causes the closed holes to generate gaps again, and provides conditions for the entry of moisture, so that expandable modified epoxy resin is selected for coating, resin substances can permeate into the holes with certain thickness on the surface layer of the board after coating, and the holes are blocked by heating treatment and then rapidly foamed, so that a substance similar to a rubber pad is formed, the holes are sealed with certain expansion pressure, and redundant foamed substances are cut off by machine treatment, at the moment, the board forms a very stable structure, water vapor can not enter easily, deformation can not occur, and water resistance and yellowing resistance are achieved, and subsequent UV paint or veneering treatment is not affected (the expandable modified epoxy resin is subjected to toughening modification, so that toughness is improved, foaming and brittle fracture are avoided, the light resistance of the epoxy resin is reduced, pulverization is avoided after a long time, special foaming microspheres are added into the water-based filling resin, and the water-based sealing structure similar to the rubber pad is rapidly foamed under a high-frequency heating condition, and a micropore blocking effect is achieved;
the specific manufacturing method comprises the following steps (raw materials in parts by mass):
(1) Preparation of polyurethane dispersions of specific particle size:
mixing 10-100 parts of polybutylene adipate or polycaprolactone diol, polycarbonate diol or polycaprolactone polyol and polytetrahydrofuran diol or polycaprolactone polyol according to the proportion of 40-70% to 20-30% to 10-20%, adding the mixture into a reaction kettle, adding 10-200 parts of IPDI or TDI and 0.01-0.2 part of catalyst, heating to 80-120 ℃, maintaining the temperature for reaction for 1-2 hours, adding 3-10 parts of chain extender 2-2 dimethylolpropionic acid or 1,4-butanediol or resorcinol dihydroxyethyl ether solution dissolved in 20-40 parts of N-methylpyrrolidone or acetone into the reaction kettle, continuing the reaction for 1-3 hours, cooling to 40-60 ℃, adding 1-10 parts of hydroxyethyl methacrylate or caprolactam or cyclohexanone amine or methyl ethyl ketone amine for end capping, cooling to 40-45 ℃ after the reaction for 1-3 hours, adding 1-8 parts of triethylamine or sodium hydroxide or sodium acetate, and finally adding 30-200 parts of deionized water for emulsification;
the polyurethane dispersions of specific particle size have a distribution of average particle sizes of between 0.001 and 0.07. Mu.m.
The catalyst is one or more of dibutyltin dilaurate, N-dimethyl cyclohexylamine, N-dimethyl benzylamine and N-ethyl morpholine.
A stirring component is arranged in the reaction kettle, the stirring component is one or a combination of a paddle type structure, a propulsion type structure, a turbine type structure, an anchor type structure and a frame type structure, and the speed of the stirring component is set to be 100-200r/min;
(2) Polyurethane modification synthesis of styrene-acrylic emulsion with small particle size:
weighing monomers, namely 10-50 parts of butyl acrylate or ethyl acrylate or isooctyl acrylate, 10-80 parts of styrene, 10-50 parts of methyl methacrylate or acrylonitrile, weighing 1-10 parts of initiator potassium persulfate and 2-20 parts of composite emulsifier, firstly adding 30% of monomers, 30% of initiator potassium persulfate and composite emulsifier into a reaction kettle, heating to 80-90 ℃, stirring for 1 hour at a speed of 100-500r/min, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20-50 parts of aluminum sol solution with the concentration of 20-40%, continuing to react for 30min-1 hour, then slowly adding the rest monomers, initiator, 20-100 parts of acrylic acid or alpha-methacrylic acid, 10-20 parts of N-N hydroxymethyl acrylamide and 2-10 parts of aluminum chloride into the solution dropwise, keeping the temperature and refluxing for 1-1.5 hours at 85-95 ℃ after the dropwise addition is finished, and then filtering the small-particle-size styrene-acrylate emulsion after the temperature is reduced to obtain room temperature styrene-acrylate emulsion;
the composite emulsifier is compounded by NP-10, OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine and polyol fatty acid ester;
(3) Impregnation process for treating plate
Placing the plate to be treated in a treatment tank, setting the vacuum to be 0.01-0.15Mpa, treating for 0.5-1h under the condition, after the vacuum treatment, carrying out liquid medicine impregnation on the plate by adopting a high-pressure impregnation mode on the small-particle-size styrene-acrylic emulsion in the step (2), setting the pressure to be 0.1-0.5Mpa, treating for 1-4h, after the high-pressure treatment, releasing the pressure to the normal pressure by adopting a slow hydraulic mode, standing for 2h under the normal pressure, carrying out vacuum treatment again, setting the vacuum to be 0.01-0.5Mpa, treating for 1-2h, releasing the pressure after the treatment, recovering impregnation liquid, and allowing the plate to enter the next procedure;
(4) Plate shaping and drying treatment
Placing the treated plate on a steel plate operating platform which can be locked by screws and applies certain pressure, controlling the temperature, humidity and time curve of a drying kiln, controlling the initial temperature to be 40-50 ℃, the humidity to be 50-80%, the treatment time to be 3-10h, the second-stage treatment temperature to be 50-70 ℃, the humidity to be 30-50%, the treatment time to be 3-12 h, slowly cooling to room temperature after the treatment is finished, and standing for 48h to wait for the next process;
(5) Preparation of expandable modified epoxy resin:
mixing two kinds of epoxy resin with low molecular weight and low viscosity according to the proportion of 1:3-5, heating to 60-70 ℃, then adding 1-10 parts of modifier chloroprene-hydroxyethyl methacrylate copolymer, 1-10 parts of polypropylene glycol diglycidyl ether and 0.01-0.1 part of boron trifluoride diethyl etherate, and stirring for 1-3h at the temperature by adopting the speed of 100-500r/min to prepare a component A;
the low molecular weight and low viscosity epoxy resin is two of Hansen EPON 8132, hansen EPlKOTE817, dimer acid modified EPD-171, 128 epoxy resin and E51 epoxy resin;
mixing 10-20 parts of curing agent, 10-100 parts of filler and 3-10 parts of foaming microspheres to prepare a component B;
the curing agent is one or more of polythiol curing agent, T31 curing agent, 650 curing agent, 593 curing agent, hexamethyl tetrahydrophthalic anhydride, modified thiourea curing agent, anhydride curing agent and polyether polyol.
The filler is one of silicon powder, calcium carbonate, kaolin and talcum powder;
the foaming microspheres are thermoplastic hollow polymer microspheres and consist of a thermoplastic polymer shell and liquid alkane gas sealed in, and the foaming temperature is 80-120 ℃;
when in use, the two are directly mixed and then coated;
(6) Coating and post-processing the plate: putting the plate treated in the step (4) into a machine, mixing the component A and the component B in the step (5), adding the mixture into the machine, and automatically carrying out flow line painting, wherein the painting glue applying amount is controlled to be 50-150g/m 2 And simultaneously heating a plurality of plates by a high-frequency heater in a high-frequency manner for 20-80s, rapidly foaming the plates, and then automatically cutting redundant foaming materials in subsequent processes.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
The manufacturing method of the modified solid wood floor comprises the following steps:
(1) Mixing 100 jin of polybutylene adipate glycol, 20% of polycarbonate glycol and 10% of polytetrahydrofuran glycol according to the proportion of 70% to 20% to 10%, adding the mixture into a reaction kettle, adding 10 jin of TDI and 0.01 jin of dibutyltin dilaurate, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of 2-2 dimethylolpropionic acid solution of a chain extender, which is dissolved in 20 jin of N-methyl pyrrolidone, into the reaction kettle, continuously reacting for 3 hours, cooling to 50 ℃, adding 1 jin of hydroxyethyl methacrylate for end sealing, cooling to 40 ℃ after reacting for 2 hours, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of composite emulsifier (NP-10, OP-10 and sodium dodecyl sulfate are mixed), adding 30% of monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 80 ℃, keeping the speed of 100r/min, stirring for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with the concentration of 20%, continuing to react for 30min, adding the rest monomers, the initiator and 20 jin of acrylic acid in the next 2h, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride slowly dripping into the solution, preserving heat and refluxing at 85 ℃ for 1.5h after dripping, cooling to room temperature, and filtering and discharging;
(3) Placing the plate to be treated in a treatment tank, setting the vacuum to be 0.08MPa, treating for 1h under the condition, soaking the plate with the emulsion filtered and discharged in the step (2) in a high-pressure soaking mode after vacuum treatment, setting the pressure to be 0.5MPa, treating for 4h, releasing the pressure to normal pressure in a slow hydraulic mode after high-pressure treatment, placing for 2h under normal pressure, performing vacuum treatment again, setting the vacuum to be 0.03MPa, treating for 2h, releasing the pressure and recovering impregnation liquid after treatment, and allowing the plate to enter the next process;
(4) Placing all the processed plates on a steel plate operating platform which can be locked by screws and can apply certain pressure, controlling the temperature, humidity and time curve of a drying kiln, controlling the initial temperature to be 50 ℃, the humidity to be 60%, the processing time to be 3h, controlling the second-stage processing temperature to be 50 ℃, the humidity to be 30%, the processing time to be 3h, slowly cooling to room temperature after the processing is finished, placing for 48h, and waiting for the next process;
(5) Mixing two epoxy resins E51 with low molecular weight and low viscosity and two dimer acid modified epoxy resins EPD-171 according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, and stirring for 2 hours at the temperature by adopting the speed of 500r/min to prepare a component A; mixing 10 jin of T31 curing agent, 30 jin of calcium carbonate and 10 jin of foaming microspheres to prepare a component B;
(6) Putting the plate treated in the step (4) into a machine, mixing the component A and the component B in the step (5), adding the mixture into the machine, and automatically carrying out flow line coating, wherein the coating glue application amount is controlled to be 100g/m 2 And simultaneously carrying out high-frequency heating on a plurality of plates by a high-frequency heating machine, wherein the heating treatment time is 30s, and the plates are rapidly foamed and then enter the subsequent process to automatically carry out cutting treatment on redundant foaming materials.
Example 2
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 10 jin of polycaprolactone diol, polycaprolactone polyol and polytetrahydrofuran diol according to the proportion of 50% to 30% to 20%, adding the mixture into a reaction kettle, adding 50 jin of IPDI and 0.1 jin of N, N-dimethyl cyclohexylamine, heating to 100 ℃, maintaining the temperature for reaction for 2 hours, adding 3 jin of chain extender 1,4-butanediol solution dissolved in 30 jin of acetone into the reaction kettle for continuous reaction for 2 hours, cooling to 45 ℃, adding 3 jin of caprolactam for end capping, cooling to 40 ℃ after reaction for 2 hours, adding 3 jin of sodium hydroxide, and finally adding 100 jin of deionized water for emulsification;
(2) Weighing monomers (20 jin of ethyl acrylate, 10 jin of styrene and 10 jin of acrylonitrile), initiators (3 jin of initiators potassium persulfate) and 10 jin of compound emulsifiers (sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine and polyol fatty acid ester), adding 30% of monomers, initiators and compound emulsifiers into a reaction kettle, heating to 80 ℃, keeping the rotation speed at 200r/min, stirring for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 30 jin of aluminum sol solution with the concentration of 25%, continuing to react for 45min, adding the rest monomers, initiators and 30 jin of alpha-methacrylic acid, 15 jin of N-N hydroxymethyl acrylamide and 3 jin of aluminum chloride into the solution slowly in the next 2h, keeping the temperature and performing reflux reaction for 1h at 95 ℃ after the dropwise addition is finished, cooling to room temperature, and filtering and discharging;
(3) Placing the plate to be treated in a treatment tank, setting the vacuum to be 0.01Mpa, treating for 1h under the condition, soaking the plate with the emulsion filtered and discharged in the step (2) in a high-pressure soaking mode after vacuum treatment, setting the pressure to be 0.1Mpa, treating for 4h, releasing pressure to normal pressure in a slow hydraulic mode after high-pressure treatment, placing for 2h under normal pressure, then performing vacuum treatment once again, setting the vacuum to be 0.01Mpa, treating for 2h, releasing pressure and recovering impregnation liquid after treatment, and enabling the plate to enter the next procedure;
(4) Placing all the processed plates on a steel plate operating platform which can be locked by screws and can apply certain pressure, controlling the temperature, humidity and time curve of a drying kiln, controlling the initial temperature to be 40 ℃, the humidity to be 50%, the processing time to be 3h, controlling the second-stage processing temperature to be 50 ℃, the humidity to be 30%, the processing time to be 3h, slowly cooling to room temperature after the processing is finished, placing for 48h, and waiting for the next process;
(5) Mixing two epoxy resins EPON 8132 with low molecular weight and low viscosity and EPlKOTE817 according to the proportion of 1:5, heating to 65 ℃, then adding 1 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 1 jin of polypropylene glycol diglycidyl ether and 0.05 jin of boron trifluoride diethyl etherate, and stirring for 1h at the temperature by adopting the speed of 100r/min to prepare a component A; 15 jin of 650 curing agent, 593 curing agent, 10 jin of silicon powder and 3 jin of foaming microspheres are mixed to prepare a component B;
(6) Putting the plate treated in the step (4) into a machine, mixing the component A and the component B in the step (5), adding the mixture into the machine, and automatically carrying out flow line coating, wherein the coating amount is controlled to be 50g/m 2 And simultaneously carrying out high-frequency heating on a plurality of plates by a high-frequency heating machine, wherein the heating treatment time is 20s, and the plates are rapidly foamed and then enter the subsequent process to automatically carry out cutting treatment on redundant foaming materials.
Example 3
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 50 jin of polybutylene adipate polyol, 50 jin of polycaprolactone polyol and 15% of polytetrahydrofuran diol according to the proportion of 60% to 25% to 15%, adding 200 jin of TDI and 0.2 jin of N, N-dimethylbenzylamine, heating to 120 ℃, maintaining the temperature for reaction for 1.5h, adding 8 jin of chain extender resorcinol dihydroxyethyl ether solution dissolved in 40 jin of N-methyl pyrrolidone into the reaction kettle, continuing the reaction for 2h, cooling to 60 ℃, adding 5 jin of cyclohexanone amine for end capping, cooling to 40 ℃ after the reaction for 3h, adding 8 jin of sodium acetate, and finally adding 150 jin of deionized water for emulsification;
(2) Weighing monomers (30 jin of isooctyl acrylate, 80 jin of styrene and 50 jin of methyl methacrylate), an initiator (8 jin of initiator potassium persulfate) and 10 jin of composite emulsifier (NP-10 and sodium dodecyl sulfate are mixed), adding 30% of monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 90 ℃, keeping the speed of 500r/min, stirring for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and an aluminum sol solution with the concentration of 50 jin of 40%, continuing to react for 1h, slowly dripping the rest monomers, the initiator and 40 jin of acrylic acid, 15 jin of N-hydroxymethyl acrylamide and 10 jin of aluminum chloride into the solution in the next 2h, preserving heat at 90 ℃, carrying out reflux reaction for 1h after dripping, cooling to room temperature, filtering and discharging;
(3) Placing a plate to be treated in a treatment tank, setting vacuum to be 0.15Mpa, treating for 0.5h under the condition, soaking the plate with the emulsion filtered and discharged in the step (2) in a high-pressure soaking mode after vacuum treatment, setting the pressure to be 0.3Mpa, treating for 1h, releasing pressure to normal pressure in a slow hydraulic mode after high-pressure treatment, placing for 2h under normal pressure, performing vacuum treatment again, setting the vacuum to be 0.5Mpa, treating for 1h, releasing pressure and recovering impregnation liquid after treatment is finished, and enabling the plate to enter the next procedure;
(4) Placing all the treated plates on a steel plate operation table which can be locked by screws and can apply certain pressure, controlling the temperature, humidity and time curve of a drying kiln, controlling the initial temperature to be 45 ℃, the humidity to be 60%, the treatment time to be 5h, controlling the second-stage treatment temperature to be 70 ℃, the humidity to be 50%, and the treatment time to be 12h, slowly cooling to room temperature after the treatment is finished, and waiting for the next process after the plates are placed for 48 h;
(5) Mixing two epoxy resin dimer acid modified epoxy resins EPD-171 and 128 epoxy resins with low molecular weight and low viscosity according to the proportion of 1:4, heating to 70 ℃, then adding 10 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 10 jin of polypropylene glycol diglycidyl ether and 0.1 jin of boron trifluoride diethyl etherate, and stirring for 2 hours at the temperature by adopting the speed of 300r/min to prepare a component A; mixing 20 jin of hexamethyl tetrahydrophthalic anhydride, a modified thiourea curing agent, 100 jin of kaolin and 5 jin of foaming microspheres to prepare a component B;
(6) Putting the plate treated in the step (4) into a machine, mixing the component A and the component B in the step (5), adding the mixture into the machine, and automatically carrying out flow line coating, wherein the coating amount is controlled to be 150g/m 2 Simultaneously high-frequency heating a plurality of plates by a high-frequency heating machine for 8 timesAnd 0s, rapidly foaming the plate, and then performing subsequent processes to automatically cut redundant foaming materials.
Example 4
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 100 jin of polybutylene adipate glycol, 30% of polycarbonate diol and 10% of polycaprolactone polyol according to the proportion of 60% to 30% to 10%, adding the mixture into a reaction kettle, adding 10 jin of TDI and 0.01 jin of N-ethylmorpholine, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of a chain extender 2-2 dimethylolpropionic acid solution dissolved in 20 jin of N-methylpyrrolidone into the reaction kettle for continuous reaction for 3 hours, cooling to 50 ℃, adding 1 jin of methyl ethyl ketone amine for end sealing, cooling to 40 ℃ after reaction for 2 hours, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of a composite emulsifier (formed by mixing sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and N-dodecyl dimethylamine), adding 30% of the monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with a concentration of 20%, continuing to react for 30min, slowly dripping the rest monomers, the initiator and 20 jin of acrylic acid, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride into the solution in the next 2h, preserving heat and carrying out reflux reaction at 85 ℃ for 1.5h after dripping, cooling to room temperature, and filtering and discharging;
(3) Same as the step of the example 1;
(4) Same as the step of the example 1;
(5) Mixing two epoxy resins of low molecular weight and low viscosity, namely Vast EPON 8132 and Vast EPlKOTE817 according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, and stirring for 2 hours at the temperature by adopting the speed of 500r/min to prepare a component A; mixing 10 jin of anhydride curing agent, 30 jin of talcum powder and 10 jin of foaming microsphere to prepare component B;
(6) The procedure was the same as in example 1.
Example 5
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 100 jin of polycaprolactone diol, polycarbonate diol and polytetrahydrofuran diol according to the proportion of 60 percent to 30 percent to 10 percent, adding the mixture into a reaction kettle, adding 10 jin of TDI, 0.01 jin of dibutyltin dilaurate and N, N-dimethyl cyclohexylamine, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of 2-2 dimethylolpropionic acid solution of a chain extender 2-2 dissolved in 20 jin of N-methyl pyrrolidone into the reaction kettle, continuing the reaction for 3 hours, cooling to 50 ℃, adding 1 jin of methyl ethyl ketone amine for end capping, cooling to 40 ℃ after the reaction for 2 hours, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of a composite emulsifier (OP-10, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate) which are mixed together), adding 30% of the monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with a concentration of 20%, continuing to react for 30min, adding the rest monomers, the initiator and 20 jin of acrylic acid in the next 2h, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride slowly dropwise into the solution, preserving heat and refluxing at 85 ℃ for 1.5h after dropwise adding, cooling to room temperature, and filtering and discharging;
(3) Same as the step of the example 1;
(4) Same as the step of the example 1;
(5) Mixing 128 epoxy resin with low molecular weight and low viscosity and E51 epoxy resin according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, stirring for 2h at the temperature by adopting the speed of 500r/min, and preparing a component A; mixing 10 jin of polyether polyol, 30 jin of calcium carbonate and 10 jin of foaming microspheres to prepare a component B;
(6) The procedure was the same as in example 1.
Example 6
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 100 jin of poly (butylene adipate) glycol, polycarbonate glycol and polytetrahydrofuran glycol according to the proportion of 60% to 30% to 10%, adding the mixture into a reaction kettle, adding 10 jin of TDI and 0.01 jin of N, N-dimethylcyclohexylamine and N, N-dimethylbenzylamine, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of a chain extender 2-2 dimethylolpropionic acid solution dissolved in 20 jin of N-methyl pyrrolidone into the reaction kettle for continuous reaction for 3 hours, cooling to 50 ℃, adding 1 jin of methyl ethyl ketone amine for end capping, cooling to 40 ℃ after reaction for 2 hours, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of composite emulsifier (NP-10, sodium dodecyl sulfate and polyol fatty acid ester are mixed), adding 30% of monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with a concentration of 20%, continuing to react for 30min, adding the rest monomers, the initiator and 20 jin of acrylic acid in the next 2h, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride slowly dripping into the solution, preserving heat and refluxing at 85 ℃ for 1.5h after dripping, cooling to room temperature, and filtering and discharging;
(3) Same as the step of the example 1;
(4) Same as the step of the example 1;
(5) Mixing two epoxy resins of Hansen EPON 8132 and E51 with low molecular weight and low viscosity according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, stirring for 2h at the temperature by adopting the speed of 500r/min, and preparing a component A; mixing 10 jin of polythiol curing agent, 30 jin of calcium carbonate and 10 jin of foaming microspheres to prepare a component B;
(6) The procedure was the same as in example 1.
Example 7
A modified solid wood floor is manufactured by the following steps:
(1) Mixing 100 jin of polycaprolactone diol, polycaprolactone polyol and polytetrahydrofuran diol according to the proportion of 70 percent to 20 percent to 10 percent, adding the mixture into a reaction kettle, adding 10 jin of TDI, 0.01 jin of dibutyltin dilaurate and N-ethylmorpholine, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of 2-2 dimethylolpropionic acid solution of a chain extender dissolved in 20 jin of N-methyl pyrrolidone into the reaction kettle, continuing to react for 3 hours, cooling to 50 ℃, adding 1 jin of hydroxyethyl methacrylate for end capping, cooling to 40 ℃ after reacting for 2 hours, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of compound emulsifier (OP-10 and polyol fatty acid ester are mixed), adding 30% of the monomers, the initiator and the compound emulsifier into a reaction kettle, heating to 80 ℃, keeping the speed of 100r/min, stirring for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with the concentration of 20%, continuing to react for 30min, adding the rest monomers, the initiator and 20 jin of acrylic acid, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride into the solution slowly dropwise, keeping the temperature at 85 ℃ after dropwise adding, carrying out reflux reaction for 1.5h, cooling to room temperature, filtering and discharging;
(3) Same as the step of the example 1;
(4) Same as the step of the example 1;
(5) Mixing two types of American vast EPON 8132 and 128 epoxy resin with low molecular weight and low viscosity according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, stirring for 2h at the temperature by adopting the speed of 500r/min, and preparing a component A; mixing 593 curing agent of 10 jin, hexamethyl tetrahydrophthalic anhydride, 30 jin of kaolin and 10 jin of foaming microspheres to prepare component B;
(6) The procedure was the same as in example 1.
Example 8
The manufacturing method of the modified solid wood floor comprises the following steps:
(1) Mixing 100 jin of polycaprolactone diol, polycarbonate diol and polycaprolactone polyol according to the proportion of 70% to 20% to 10%, adding the mixture into a reaction kettle, adding 10 jin of TDI, 0.01 jin of dibutyltin dilaurate, N-dimethylcyclohexylamine and N, N-dimethylbenzylamine, heating to 80 ℃, maintaining the temperature for reaction for 2 hours, adding 10 jin of 2-2 dimethylolpropionic acid solution of a chain extender dissolved in 20 jin of N-methyl pyrrolidone into the reaction kettle, continuing the reaction for 3 hours, cooling to 50 ℃, adding 1 jin of hydroxyethyl methacrylate for end capping, after the reaction for 2 hours, cooling to 40 ℃, adding 5 jin of triethylamine, and finally adding 200 jin of deionized water for emulsification;
(2) Weighing monomers (10 jin of butyl acrylate, 50 jin of styrene and 10 jin of methyl methacrylate), an initiator (5 jin of initiator potassium persulfate) and 2 jin of a composite emulsifier (NP-10, N-dodecyl dimethylamine and polyol fatty acid ester are mixed), adding 30% of the monomers, the initiator and the composite emulsifier into a reaction kettle, heating to 80 ℃, stirring at a speed of 100r/min for 1h, then adding the small-particle-size polyurethane dispersion synthesized in the step (1) and 20 jin of aluminum sol solution with a concentration of 20%, continuing to react for 30min, adding the rest of the monomers, the initiator and 20 jin of acrylic acid, 20 jin of N-hydroxymethyl acrylamide and 2 jin of aluminum chloride slowly dropwise into the solution, preserving heat, refluxing at 85 ℃ for 1.5h after dropwise addition, cooling to room temperature, and filtering and discharging;
(3) Same as the step of the example 1;
(4) Same as the step of the example 1;
(5) Mixing two types of American vast EPON 8132 and E51 epoxy resin with low molecular weight and low viscosity according to the proportion of 1:3, heating to 60 ℃, then adding 2 jin of modifier chloroprene-hydroxyethyl methacrylate copolymer, 5 jin of polypropylene glycol diglycidyl ether and 0.01 jin of boron trifluoride diethyl etherate, stirring for 2h at the temperature by adopting the speed of 500r/min, and preparing a component A; mixing 10 jin of modified thiourea curing agent, anhydride curing agent, 30 jin of kaolin and 10 jin of foaming microspheres to prepare a component B;
(6) The procedure was the same as in example 1.
Comparative example 1
The MDI is adopted to impregnate the board, wherein the treatment process and the impregnation process of the board are the same as those of the example 1 (step 3 and step 4, the emulsion in the step 3 is replaced by MDI with equal mass).
Comparative example 2
The board is impregnated by the waterborne polyurethane, wherein the treatment process and the impregnation process of the board are the same as those of the embodiment 1 (step 3 and step 4, the emulsion in the step 3 is replaced by the waterborne polyurethane with equal mass).
Comparative example 3
The plate is impregnated by the styrene-acrylic emulsion, wherein the treatment process and the impregnation process of the plate are the same as those of the plate in the example 1 (step 3 and step 4, the emulsion in the step 3 is replaced by the styrene-acrylic emulsion with equal mass).
And (3) performance testing:
the solid wood floors treated in example 1 and comparative examples 1 to 3 were subjected to a performance test;
the formaldehyde detection is carried out according to GB/T17657-2013, the moisture-proof dimensional stability detection is carried out according to an industry standard 'moisture absorption dimensional stability detection standard of wood and wood-based materials' (LY/T3222-2020), the heat-proof dimensional stability detection is carried out according to an industry standard 'wood floor for floor heating' LY/T1700-2018, the yellowing resistance detection is carried out according to GB/T23983-2009, and the paint film adhesion, surface wear resistance, paint film hardness and paint film surface pollution resistance detection are carried out according to GB15036-2018;
the modified solid wood flooring made in example 1 was subjected to a performance test, and the results are shown in table 1:
TABLE 1
Figure BDA0003826395710000181
Figure BDA0003826395710000191
As can be seen from Table 1, the modified solid wood floor manufactured by the embodiment of the invention has excellent performances, and meets the use requirements;
the treated plate of comparative example 1 was subjected to performance tests, and the results are shown in table 2:
TABLE 2
Figure BDA0003826395710000192
As can be seen from table 2, when MDI is used for impregnation, the problem of plate yellowing caused by the structure of MDI is serious, and the adhesive force of a paint film is also influenced to a certain extent, new products can be developed only by adopting a solid wood sticker or film mode, paint application cannot be directly brushed, and besides, MDI has active performance, impregnation liquid cannot be used for multiple times, so that waste is serious, and cost is high;
the board treated in comparative example 2 was subjected to a performance test, and the results are shown in table 3:
TABLE 3
Figure BDA0003826395710000201
As can be seen from Table 3, when the aqueous polyurethane is adopted for impregnation, the solid content is low, the moisture content is high, the post-treatment moisture is difficult, the treatment cost is high, and if the polyurethane with high solid content is adopted, the viscosity is too high, so that the wood impregnation amount is limited, and the effect is poor;
the board treated in comparative example 3 was subjected to a performance test, and the results are shown in table 4:
TABLE 4
Figure BDA0003826395710000202
Figure BDA0003826395710000211
As can be seen from Table 4, when the styrene-acrylic emulsion is adopted for impregnation, the overall effect is good, but the styrene-acrylic emulsion has certain creep property and contains a plurality of soft monomers, so that the surface wear resistance is slightly poor, and meanwhile, the hardness of a paint film just reaches H and cannot be directly used.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The manufacturing method of the modified solid wood floor is characterized by comprising the following steps:
preparing a small-particle-size polyurethane dispersion;
modifying and synthesizing small-particle-size styrene-acrylic emulsion by using small-particle-size polyurethane dispersoid;
dipping the board by using a styrene-acrylic emulsion with small particle size, and then shaping and drying the board;
preparing expandable modified epoxy resin;
and (3) coating the expandable modified epoxy resin on the plate, heating and foaming the plate, and cutting the redundant foamed part.
2. The method for manufacturing a modified solid wood floor according to claim 1, comprising the following steps:
mixing polybutylene adipate or polycaprolactone diol, polycarbonate diol or polycaprolactone polyol, polytetrahydrofuran diol or polycaprolactone polyol, adding IPDI or TDI, and a catalyst, heating to react, adding a chain extender 2-2 dimethylolpropionic acid or 1,4-butanediol or resorcinol dihydroxyethyl ether solution dissolved in N-methylpyrrolidone or acetone into the reaction kettle, continuing to react, cooling, adding one or more of hydroxyethyl methacrylate, caprolactam, cyclohexanone amine and methyl ethyl ketone amine for end capping, cooling after reacting, adding one or more of triethylamine, sodium hydroxide and sodium acetate, and finally adding deionized water for emulsifying to obtain a small-particle-size polyurethane dispersion;
mixing one or more of butyl acrylate, ethyl acrylate and isooctyl acrylate, styrene, methyl methacrylate or acrylonitrile to obtain a mixed solution, adding part of the mixed solution, part of an initiator potassium persulfate and a composite emulsifier into a reaction kettle, heating and stirring, then adding a small-particle-size polyurethane dispersion and an aluminum sol solution, continuing to react, slowly dripping the rest of the mixed solution, the initiator, acrylic acid or alpha-methacrylic acid, N-N hydroxymethyl acrylamide and aluminum chloride into the solution, carrying out heat preservation reflux reaction after dripping is finished, cooling to room temperature, and filtering and discharging to obtain a small-particle-size styrene-acrylic emulsion;
placing the plate in a treatment tank, carrying out vacuum treatment, then pressurizing and dipping the small-particle-size styrene-acrylic emulsion into the plate, carrying out vacuum treatment again after dipping, pressurizing the treated plate, and shaping and drying the plate;
heating low-molecular-weight low-viscosity epoxy resin, adding modifier chloroprene-hydroxyethyl methacrylate copolymer, polypropylene glycol diglycidyl ether and boron trifluoride diethyl etherate, stirring to prepare a component A, mixing a curing agent, a filling agent and foamed microspheres to prepare a component B to obtain expandable modified epoxy resin, and mixing the component A and the component B for brushing when in use;
and brushing the mixed expandable modified epoxy resin on the dried board, heating and foaming the board, and cutting the redundant foaming material to obtain the modified solid wood floor.
3. The method of claim 2, wherein the small-particle polyurethane dispersion has an average particle size distribution of 0.001-0.07 μm.
4. The method of claim 2, wherein the catalyst is one or more of dibutyl tin dilaurate, N-dimethylcyclohexylamine, N-dimethylbenzylamine, and N-ethylmorpholine.
5. The method of claim 2, wherein the stirring speed of the reaction vessel is 100-200r/min.
6. The method of claim 2, wherein the compound emulsifier is selected from the group consisting of NP-10, OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine, and polyol fatty acid ester.
7. The method of claim 2, wherein the low molecular weight and low viscosity epoxy resin is at least two of EPON 8132, EPlKOTE817, dimer acid modified epoxy EPD-171, 128 epoxy, and E51 epoxy.
8. The method of claim 2, wherein the curing agent is one or more of a polythiol curing agent, a T31 curing agent, a 650 curing agent, a 593 curing agent, hexamethyltetrahydrophthalic anhydride, a modified thiourea curing agent, an anhydride curing agent, and a polyether polyol.
9. The method for manufacturing a modified solid wood floor as claimed in claim 2, wherein the filler is one of silica powder, calcium carbonate, kaolin and talc;
the foaming microspheres are thermoplastic hollow polymer microspheres and consist of a thermoplastic polymer shell and liquid alkane gas sealed in, and the foaming temperature is 80-120 ℃.
10. A modified solid wood flooring, characterized by being manufactured by the method of manufacturing a modified solid wood flooring according to any one of claims 1 to 9.
CN202211061424.XA 2022-09-01 2022-09-01 Modified solid wood floor and manufacturing method thereof Pending CN115302600A (en)

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CN1438257A (en) * 2003-03-06 2003-08-27 华南理工大学 Acrylic polyurethane copolymer emulsion, its preparation method and use
CN101974141A (en) * 2010-09-19 2011-02-16 广州市香港科大霍英东研究院 Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD)
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