[go: up one dir, main page]

CN109129775A - Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof - Google Patents

Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof Download PDF

Info

Publication number
CN109129775A
CN109129775A CN201810991729.8A CN201810991729A CN109129775A CN 109129775 A CN109129775 A CN 109129775A CN 201810991729 A CN201810991729 A CN 201810991729A CN 109129775 A CN109129775 A CN 109129775A
Authority
CN
China
Prior art keywords
solution
titanium dioxide
preparation
veneer
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810991729.8A
Other languages
Chinese (zh)
Inventor
刘玉
朱晓冬
王巍聪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeast Forestry University
Original Assignee
Northeast Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeast Forestry University filed Critical Northeast Forestry University
Priority to CN201810991729.8A priority Critical patent/CN109129775A/en
Publication of CN109129775A publication Critical patent/CN109129775A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
    • 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
    • B27K3/007—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising nanoparticles
    • 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
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/003—Treating of wood not provided for in groups B27K1/00, B27K3/00 by using electromagnetic radiation or mechanical waves
    • B27K5/0065—Ultrasonic treatment
    • 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
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/04—Combined bleaching or impregnating and drying of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/13—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/026—Wood layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/758—Odour absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • B32B2309/022—Temperature vs pressure profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • B32B2309/025—Temperature vs time profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/12—Pressure
    • B32B2309/125—Pressure vs time profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

本发明公开了一种改性二氧化钛复合材料、木单板、人造板及其制备方法，属于人造板技术领域。复合材料制备包括将无水乙醇中加入酞酸丁酯，水浴加热并搅拌；取过氧化氢溶液加入并搅拌得到溶液A3；取无水乙醇加入到装有去离子水的烧杯中，得到溶液B，将溶液B滴加到溶液A3中，搅拌后加入三氯化铁溶液再搅拌，静置，得到用铁离子改性的纳米二氧化钛溶胶前驱体；将该溶胶前驱体以磁力搅拌器搅拌，倒入反应釜内，在一定温度条件下反应5.5‑6.5h后取出，经过抽滤后，干燥得到铁离子改性的纳米二氧化钛粉末。木单板制备包括将木单板放入柠檬酸溶液中浸渍，加入次亚磷酸钠、采用混悬液C浸渍处理等。本发明可提高催化光源的利用率。The invention discloses a modified titanium dioxide composite material, a wood veneer, a man-made panel and a preparation method thereof, belonging to the technical field of man-made panels. The preparation of composite material includes adding butyl phthalate into absolute ethanol, heating and stirring in a water bath; adding hydrogen peroxide solution and stirring to obtain solution A3; taking absolute ethanol and adding it into a beaker containing deionized water to obtain solution B , add solution B dropwise to solution A3, add ferric chloride solution after stirring, stir again, and let stand to obtain a nano-titania sol precursor modified with iron ions; the sol precursor is stirred with a magnetic stirrer, poured Put it into the reaction kettle, take it out after reacting for 5.5-6.5 hours under a certain temperature condition, and after suction filtration, dry to obtain iron ion-modified nano titanium dioxide powder. The preparation of the wooden veneer includes dipping the wooden veneer in a citric acid solution, adding sodium hypophosphite, and immersing the wooden veneer with suspension C, and the like. The invention can improve the utilization rate of the catalytic light source.

Description

Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof
Technical field
The present invention relates to environment friendly artificial board technical fields, single more particularly to a kind of modifying titanium dioxide composite material, wood Plate, wood-based plate and preparation method thereof.
Background technique
Formaldehyde is indoor common polluted gas, is mostly derived from plate fitment and wood-based plate ornament materials, Long Term Contact meeting Great threat is generated to human health.Optically catalytic TiO 2 technology is a kind of new environmentally friendly processing technique, to packet Including the gas chromatography including formaldehyde has apparent degradation effect, using nano-titanium dioxide as photochemical catalyst, have compared with High chemical stability and photoelectric properties is obtained handling the advantage that wood-based plate organic pollutant toxic, difficult to degrade is shown The extensive concern of people, has broad application prospects.
Have in the prior art it is many about titanium dioxide as photochemical catalyst be used for control artificial board formaldehyde release grind Study carefully.For example, using artificial board decorative veneer, micro veneer, melamine impregnated base paper as object, by impregnating dopen Nano dioxy Change titanium (TiO2) doping melamine resin adehsive stick agent, explore 3 kinds of impregnation materials to the formaldehyde controlled release of face artificial board Ability, result of study show nano-TiO2Addition, reduction veneer that can be different degrees of, 3 kinds of micro veneer, impregnated paper materials The Form aldehyde release of face artificial board, with nano-TiO2The increase of additive amount, the burst size of methanal of face artificial board is under gradually The trend of drop.
But titanium dioxide as catalysis material there is also shortcoming, one of deficiency be its can only absorbing wavelength it is smaller Ultraviolet light, it is lower to the efficiency of solar energy utilization, however be actually needed degradation of formaldehyde application environment in, majority all in nature Under the conditions of light, ultraviolet light conditions are more harsh, thus the generally existing nature of titanium dioxide optical catalyst material in the prior art The not high technological deficiency of PARA FORMALDEHYDE PRILLS(91,95) degradation rate under the conditions of light.
Summary of the invention
(1) technical problem
In conclusion PARA FORMALDEHYDE PRILLS(91,95) degradation rate is not under the conditions of natural light as photochemical catalyst for titanium dioxide in the prior art Height becomes technical field technical problem urgently to be resolved.
(2) technical solution
The present invention provides a kind of modifying titanium dioxide composite material and preparation method thereofs, comprising:
Dehydrated alcohol is added in beaker at room temperature, is placed on the balancer of magnetic stirring apparatus, is 550- with revolving speed It is added Butyl Phthalate under conditions of 650 revs/min, the volume ratio of Butyl Phthalate and dehydrated alcohol is 1: 5, obtains solution A 1；
Beaker equipped with solution A 1 is put into temperature and is set as heating water bath in 49-51 DEG C of thermostat water bath, and uses electricity Dynamic agitator motor persistently stirs 28-32min (minute), obtains solution A 2；
According to the ratio for being 3.5: 3 with the volume ratio of Butyl Phthalate, taking mass concentration is the hydrogenperoxide steam generator of 29-31% It is added in solution A 2, and stirs 28-32min with electronic agitator motor, obtain solution A 3；
According to the ratio for being 1: 1 with Butyl Phthalate volume ratio, dehydrated alcohol is taken to be added in the beaker equipped with deionized water, Obtain solution B, the volume ratio of deionized water and Butyl Phthalate is 1: 1；
Solution B is slowly dropped in solution A 3,85-95min is stirred with electronic agitator motor, 0.95- is added later The liquor ferri trichloridi of 1.05mol/l, the ferric chloride solution of addition and the volume ratio of Butyl Phthalate are 1: 6, are further continued for electronic Agitator motor stirs 55-65min；After stirring, the solution stirred is removed, stands 7.5-8.5h at room temperature (hour) obtains the nano titanic oxide sol presoma modified with iron ion；
The magnetic stirrer 9.5- for being 550-650 revs/min with revolving speed by nano titanic oxide sol presoma Then 10.5min pours into nano titanic oxide sol presoma in reaction kettle, anti-under conditions of temperature is 175-185 DEG C It is taken out after answering 5.5-6.5h, after filtering, is dried to obtain the modified nano titanium dioxide powder of iron ion.
The present invention also provides a kind of modifying titanium dioxide composite material, for according to the preparation of above-mentioned composite material and preparation method thereof ?.
The present invention also provides a kind of modifying titanium dioxide veneer preparation methods, comprising steps of
Veneer is put into ultrasonic immersing 18-22min in the citric acid solution of mass concentration 1-15%, addition and citric acid The sodium hypophosphite that citric acid molar ratio in solution is 1: 1, it is spare after 60 DEG C of -80 DEG C of drying；
At room temperature, the nano titanium dioxide powder for taking above-mentioned iron ion modified, is put into distilled water, forming mass concentration is The suspension C of 0.95-1.05%；
By suspension C under conditions of ultrasonic power 550-650w (watt) after ultrasonic disperse 28-32min, after drying Veneer, which is immersed in suspension C, impregnates 28-32min, takes out veneer after dipping, and 60 DEG C -80 DEG C are dried to balance Moisture content obtains modifying titanium dioxide veneer.
Wherein, the mass concentration of citric acid solution is 3%.
The present invention also provides a kind of modifying titanium dioxide veneers, to be prepared according to above-mentioned veneer preparation method.
The present invention also provides a kind of modifying titanium dioxide preparation method of artificial board, comprising steps of
Using the modifying titanium dioxide veneer prepared through the above method as decoration panel, select five layers of glued board as base Material；
It calculates plate unit area resin added and curing agent content, resin added 66.6g/m2, curing agent is mass concentration The ammonium chloride solution of 19-21%, curing agent additive amount are 0.1%；
Adhesive is configured after calculating, adhesive is applied on modifying titanium dioxide veneer, will be adornd using hot press later Panel overlays on the substrate, and hot pressing temperature is 118-122 DEG C, hot pressing time 58-62s, hot pressing pressure 4Mpa.
The present invention also provides a kind of modifying titanium dioxide wood-based plates, to be prepared according to above-mentioned preparation method of artificial board.
(3) technical effect
Compared with the mode of the prior art, the present invention can reach following technical effect:
According to the modifying titanium dioxide composite material and preparation method thereof that aforementioned present invention provides, the modification dioxy being prepared Change titanium composite material, the experiment proved that, the titanium dioxide of Fe2O3 doping modification is not carried out according to the above-mentioned preparation method of the present invention Material is handled the formalin that initial concentration is 1.0mg/L, degradation rate is in 60 minutes under the conditions of natural light 36.35%, and the composite titania material after Fe2O3 doping modification is carried out according to the above-mentioned preparation method of the present invention, same Natural light under the conditions of, be Degradation Formaldehyde rate in the formalin of 1.0mg/L to initial concentration be 54.77%, it is seen that this The iron ion modifying titanium dioxide composite material that the preparation method of invention is prepared improves the formaldehyde drop under the conditions of natural light Solution rate, the photocatalysis efficiency for being doped with titanium dioxide after a certain amount of iron can be significantly improved.
Also, in modifying titanium dioxide veneer preparation method provided by the present invention, citric acid is first passed through to timber list Plate carries out esterification treatment, is dehydrated into after acid anhydride using the carboxylic acid group in citric acid and reacts into ester with the alcoholic extract hydroxyl group of wood-cellulose, increases Add the carboxyl-content on timber, make-the 0H of nano-titanium dioxide and the covalently bound cross-linked structure of wood formation, to improve Load effect of the nano-titanium dioxide on timber, while the iron ion doping modification of nano-titanium dioxide is attached to wood surface On, effective visible light light degradation layer can be formed, the utilization rate of catalysis light source is improved, preferably improves the first of artificial board with this Aldehyde discharges problem；
When citric acid concentration increases in a certain range, esterification rate can also be gradually increased until balance.Work as citric acid When concentration is 3%, the free carboxyl group amount retained on veneer is most, average out to 0.944mmol；When citric acid concentration is 1%, The free carboxyl group amount retained on veneer is minimum, average out to 0.421mmol.It can when therefore using 3% citric acid treatment veneer To adhere to most nano-titanium dioxides in subsequent experimental, to improve Degradation Formaldehyde rate.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
The invention proposes a kind of modifying titanium dioxide composite materials, veneer, wood-based plate and preparation method thereof.To make this The technical solution of invention is more obvious and easy to understand, and several specific embodiments are set forth below, and the present invention is described in further detail.
Embodiment 1
The embodiment of the present invention 1 provides a kind of modifying titanium dioxide composite material and preparation method thereof, comprising steps of
Dehydrated alcohol, is added in beaker by step S10 at room temperature, is placed on the balancer of magnetic stirring apparatus, to turn Butyl Phthalate is added under conditions of being 550-650 revs/min in speed, obtains solution A 1.
The volume ratio of Butyl Phthalate and dehydrated alcohol is 1: 5, the i.e. dehydrated alcohol of 5 volumes, the corresponding phthalandione that 1 volume is added Butyl ester.
Beaker equipped with solution A 1 is put into temperature and is set as heating water bath in 49-51 DEG C of thermostat water bath by step S11, And 28-32min is persistently stirred using electric mixer motor, obtain solution A 2.
Step S12, according to the ratio for being 3.5: 3 with the volume ratio of Butyl Phthalate, taking mass concentration is the peroxide of 29-31% Change hydrogen solution to be added in solution A 2, and stir 28-32min with electronic agitator motor, obtains solution A 3.
Step S13 takes dehydrated alcohol to be added to equipped with deionized water according to the ratio for being 1: 1 with Butyl Phthalate volume ratio Beaker in, obtain solution B.Wherein deionized water and the volume ratio of Butyl Phthalate are 1: 1.
Solution B is slowly dropped in solution A 3 by step S14, stirs 85-95min, Zhi Houjia with electronic agitator motor Enter the liquor ferri trichloridi of 0.95-1.05mol/1, the ferric chloride solution of addition and the volume ratio of Butyl Phthalate are 1: 6.
Step S15 is further continued for stirring 55-65min with electronic agitator motor；After stirring, remove stirred it is molten Liquid stands 7.5-8.5h at room temperature, obtains the nano titanic oxide sol presoma modified with iron ion.
Step S16, the magnetic stirrer for being 550-650 revs/min with revolving speed by nano titanic oxide sol presoma Then 9.5-10.5min pours into nano titanic oxide sol presoma in reaction kettle, the condition for being 175-185 DEG C in temperature It is taken out after lower reaction 5.5-6.5h, after filtering, is dried to obtain the modified nano titanium dioxide powder of iron ion.
Embodiment 2
The embodiment of the present invention 2 provides a preferred embodiment of modifying titanium dioxide composite material and preparation method thereof.At this In preferred embodiment, the method comprising the steps of:
Step S20 measures the dehydrated alcohol of 150ml with graduated cylinder at room temperature, is added in the beaker of 500ml, is placed on double On the balancer of digital display constant temperature blender with magnetic force, and shows under conditions of constant temperature blender with magnetic force revolving speed is 600 revs/min and add in even numbers Enter the Butyl Phthalate of 30ml.
The obtained beaker equipped with the mixed solution prepared of step S20 is put into temperature and is set as 50 DEG C by step S21 Digital display thermostat water bath in heating water bath, and be persistently stirred solution 30min using electric mixer motor.
Step S22 measures 30% hydrogenperoxide steam generator of 35ml with graduated cylinder and obtained mixed solution in step S21 is added In and with electronic agitator motor stir 30min, obtain solution A 3；
Step S23 measures 30ml dehydrated alcohol with graduated cylinder and is added in the beaker equipped with 30ml deionized water, obtains solution B；
Step S24, B solution is slowly dropped in A, stirs 1.5h with electronic agitator motor.
The liquor ferri trichloridi 5ml of 1mol/l is added after completing step S24 process, is further continued for using electric mixing by step S25 Mix device motor stirring 1h.
Step S26 removes the solution stirred after step S25, stands 8h at room temperature, obtains using iron The nano titanic oxide sol presoma of ion modification.
Step S27, the even numbers for being 600 revs/min by ferric trichloride modified nano titanic oxide sol presoma revolving speed Aobvious constant temperature blender with magnetic force stirs 10min, and ferric trichloride modified nano titanic oxide sol presoma is then poured into reaction It in kettle, is taken out after reaction 6h under conditions of temperature is 180 DEG C, after filtering, is dried to obtain the modified nanometer two of iron ion Titanium dioxide powder.
According to preparation method provided by the invention, doping iron ion modification nano-titanium dioxide is attached to wood surface, The utilization rate that catalysis light source can be improved, forms effective Visible Light Induced Photocatalytic layer, is doped with titanium dioxide after a certain amount of iron Photocatalysis efficiency can be significantly improved, and improve the Form aldehyde release problem of timber with this.
Embodiment 3
The embodiment of the present invention 3 provides a kind of modifying titanium dioxide veneer preparation method, and the method comprising the steps of:
Veneer is put into ultrasonic immersing 18-22min in the citric acid solution of mass concentration 1-15% by step S30, is added The sodium hypophosphite for being 1: 1 with the citric acid molar ratio in citric acid solution, progress first time drying, 60 DEG C -80 of drying temperature DEG C, it is spare after drying.Preferably, it is spare to be dried to equilibrium moisture content.
Esterification treatment is carried out to wood single-plate by citric acid, makes citric acid and veneer cellulose that esterification occur, Free carboxyl group content on timber is increased, and then is conducive to titanium dioxide nanoparticle and is attached on veneer, it can be using covalently In conjunction with making titanium dioxide form cross-linked structure on timber.
Step S31 prepares the modified nano titanium dioxide powder of iron ion.
It is specific the preparation method is the same as that of Example 1 or embodiment 2 described in, repeat no more.
Step S32, at room temperature, the nano titanium dioxide powder for taking iron ion modified are put into distilled water, and it is dense to form quality Degree is the suspension C of 0.95-1.05%.
Step S33 after ultrasonic disperse 28-32min, will dry suspension C under conditions of ultrasonic power 550-650w Veneer afterwards, which is immersed in suspension C, impregnates 28-32min.
Step S34 takes out veneer after dipping, carries out second and dries, and 60 DEG C -80 DEG C of drying temperature, drying To equilibrium moisture content, modifying titanium dioxide veneer is obtained.
Embodiment 4
One preferred embodiment of the offer modifying titanium dioxide veneer preparation method of the embodiment of the present invention 4.
In the preferred embodiment, comprising steps of
Veneer is put into ultrasonic immersing 20min in the citric acid solution that mass concentration is 3%, addition and citric acid by S40 Molar ratio be 1: 1 catalyst sodium hypophosphite, carry out 80 DEG C drying after it is spare.
When citric acid concentration is 3%, the free carboxyl group amount retained on veneer is most, average out to 0.944mmol.
S41 prepares the modified nano titanium dioxide powder of iron ion.The preparation process is repeated no more with embodiment 2.
S42 does impregnation to veneer using the modified nanometer titanium dioxide composite material of iron ion.
At room temperature, modified nano-titanium dioxide powder is taken to be put into distilled water, concentration 1%, ultrasonic power 600w's Under the conditions of after ultrasonic disperse 30min, the veneer of above-mentioned modification is immersed in the suspension of titanium dioxide and impregnates 30min, is impregnated After take out be dried to equilibrium moisture content under the conditions of 80 DEG C.
When veneer is dried after dipping modifying titanium dioxide, free carboxyl group of the drying temperature to the reservation on veneer And the combination of titanium dioxide has a certain impact, the free carboxyl group and dioxy retained on veneer when drying temperature is 80 DEG C It is preferable to change titanium combination effect.
In one timing of other conditions, optimised process should dry for 80 DEG C after 3% concentration citric acid treatment for veneer, then 80 DEG C of drying after modified nano-titanium dioxide impregnation, burst size of methanal average are 1.81mg/L, Degradation Formaldehyde rate It is 86.6%, effect is best.
Embodiment 5
Another embodiment of the offer modifying titanium dioxide veneer preparation method of the embodiment of the present invention 5.
In this embodiment, veneer is put into ultrasonic immersing in the citric acid solution that mass concentration is 7%, dipping is modified When veneer is dried after titanium dioxide, drying temperature is 60 DEG C, other implementation steps are repeated no more with embodiment 3.
When 7% concentration citric acid treatment veneer dipping post-baking temperature is 60 DEG C, burst size of methanal average is 2.76mg/ L, Degradation Formaldehyde rate are 79.6%, and effect is worst.
Embodiment 6
The embodiment of the present invention 6 provides a kind of modifying titanium dioxide preparation method of artificial board, and the method comprising the steps of:
Step S60, the modifying titanium dioxide veneer that embodiment 3 is prepared select five layers of gluing as decoration panel Plate is as substrate.
Step S61 calculates plate unit area resin added and curing agent content, resin added 66.6g/m2, curing agent is The ammonium chloride solution of mass concentration 19-21%, curing agent additive amount are 0.1%.That is the mass ratio of curing agent and adhesive is 0.1%.
Step S62 configures adhesive after calculating, and adhesive is applied on modifying titanium dioxide veneer, later using heat Press overlays decoration panel on substrate, and hot pressing temperature is 118-122 DEG C, hot pressing time 58-62s, hot pressing pressure 4Mpa.
Embodiment 7
One preferred embodiment of the offer modifying titanium dioxide preparation method of artificial board of the embodiment of the present invention 7.The preferred reality Apply example comprising steps of
Make finishing material pressing plate with the board using poplar board that embodiment 3 or 4 is prepared, selects five layers of glued board as substrate. Plate unit area resin added and curing agent content, resin added 66.6g/m are calculated first2, curing agent is the chlorine of concentration 20% Change ammonium salt solution, additive amount 0.1%.Adhesive is configured after calculating, and adhesive is applied on veneer.It will be adornd using hot press later Panel overlays on substrate, and hot pressing temperature is 120 DEG C, hot pressing time 60s, hot pressing pressure 4Mpa.
The prior art carrys out the inefficient of degradation of formaldehyde with titanium dioxide treatment wood-based plate.The present invention passes through citric acid first Esterification treatment is carried out to wood single-plate, makes citric acid and veneer cellulose that esterification occur, friendship can be formed on timber Join reticular structure, increases free carboxyl group content on timber, and then be conducive to titanium dioxide nanoparticle and be attached on veneer, mention Then doping iron ion modification nano-titanium dioxide is attached to wood surface by the adhesive force of high titanium dioxide, formed effective Light degradation layer improves the utilization rate of catalysis light source, further improves the Form aldehyde release problem of timber with this, more effectively degradation first Aldehyde reaches the research purpose for administering formaldehyde indoor pollution.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation Thought of the invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not It is interpreted as limitation of the present invention.

Claims (7)

1.一种改性二氧化钛复合材料制备方法，其特征在于，包括步骤：1. a modified titanium dioxide composite material preparation method, is characterized in that, comprises the steps: 在室温下将无水乙醇添加至烧杯中，放在磁力搅拌器的平衡台上，以转速为550-650转/分的条件下加入酞酸丁酯，所述酞酸丁酯与所述无水乙醇的体积比为1∶5，得到溶液A1；Add absolute ethanol to the beaker at room temperature, put it on the balance table of the magnetic stirrer, and add butyl phthalate at a speed of 550-650 r/min. The volume ratio of water ethanol is 1:5 to obtain solution A1; 将装有所述溶液A1的烧杯放入温度设为49-51℃的恒温水浴锅中水浴加热，并使用电动搅拌器电机持续搅拌28-32min，得到溶液A2；Put the beaker containing the solution A1 into a constant temperature water bath with a temperature of 49-51 ° C and heat it in a water bath, and use an electric stirrer motor to continuously stir for 28-32 min to obtain solution A2; 按照与所述酞酸丁酯的体积比为3.5∶3的比例，取质量浓度为29-31％的过氧化氢溶液加入到所述溶液A2中，并用电动搅拌器电机搅拌28-32min，得到溶液A3；According to the ratio of 3.5:3 with the volume ratio of the butyl phthalate, take the hydrogen peroxide solution with a mass concentration of 29-31% and add it to the solution A2, and stir with an electric stirrer motor for 28-32min to obtain solution A3; 按照与所述酞酸丁酯体积比为1∶1的比例，取无水乙醇加入到装有去离子水的烧杯中，得到溶液B，所述去离子水与所述酞酸丁酯的体积比为1∶1；According to the ratio of 1:1 by volume to the butyl phthalate, take absolute ethanol and add it to a beaker containing deionized water to obtain solution B. The volume of the deionized water and the butyl phthalate is The ratio is 1:1; 将所述溶液B缓慢滴加到所述溶液A3中，用电动搅拌器电机搅拌85-95min，之后加入0.95-1.05mol/l的三氯化铁溶液，加入的所述氯化铁溶液与所述酞酸丁酯的体积比为1∶6，再继续用电动搅拌器电机搅拌55-65min；搅拌结束后，取下搅拌完的溶液，在室温的条件下静置7.5-8.5h，得到用铁离子改性的纳米二氧化钛溶胶前驱体；The solution B was slowly added dropwise to the solution A3, stirred with an electric stirrer motor for 85-95min, then 0.95-1.05mol/l ferric chloride solution was added, and the added ferric chloride solution was mixed with the solution. The volume ratio of butyl phthalate is 1:6, and then continue to stir with an electric stirrer motor for 55-65min; after stirring, remove the stirred solution, and stand at room temperature for 7.5-8.5h to obtain a Fe ion-modified nano-titania sol precursor; 将所述纳米二氧化钛溶胶前驱体以转速为550-650转/分的磁力搅拌器搅拌9.5-10.5min，然后将所述纳米二氧化钛溶胶前驱体倒入反应釜内，在温度为175-185℃的条件下反应5.5-6.5h后取出，经过抽滤后，干燥得到铁离子改性的纳米二氧化钛粉末。Stir the nano-titania sol precursor for 9.5-10.5min with a magnetic stirrer with a rotational speed of 550-650 r/min, and then pour the nano-titania sol precursor into the reaction kettle at a temperature of 175-185 ° C. It is taken out after 5.5-6.5 hours of reaction under the conditions, and after suction filtration, the nano-titanium dioxide powder modified by iron ions is obtained by drying. 2.改性二氧化钛复合材料，其特征在于，为按照权利要求1所述的制备方法制备而得。2. The modified titanium dioxide composite material is characterized in that, it is prepared according to the preparation method of claim 1. 3.一种改性二氧化钛木单板制备方法，其特征在于，包括步骤：3. a method for preparing modified titanium dioxide wood veneer, is characterized in that, comprises the steps: 将木单板放入质量浓度1-15％的柠檬酸溶液中超声浸渍18-22min，加入与所述柠檬酸溶液中的柠檬酸摩尔比为1∶1的次亚磷酸钠，60℃-80℃烘干后备用；Put the wooden veneer into the citric acid solution with a mass concentration of 1-15% for ultrasonic immersion for 18-22min, add sodium hypophosphite with a molar ratio of 1:1 to the citric acid in the citric acid solution, 60 ℃-80 ℃ for drying after use; 室温下，取权利要求1制备而得的铁离子改性的纳米二氧化钛粉末，放入蒸馏水中，形成质量浓度为0.95-1.05％的混悬液C；At room temperature, take the iron ion-modified nano titanium dioxide powder prepared in claim 1, put it into distilled water, and form a suspension C with a mass concentration of 0.95-1.05%; 将所述混悬液C在超声功率550-650w的条件下超声分散28-32min后，将烘干后的所述木单板浸没于所述混悬液C中浸渍28-32min，浸渍结束后将所述木单板取出，60℃-80℃烘干至平衡含水率，得到改性二氧化钛木单板。After the suspension C is ultrasonically dispersed for 28-32min under the condition of ultrasonic power 550-650w, the dried wood veneer is immersed in the suspension C for 28-32min, and after the immersion is completed The wood veneer is taken out and dried at 60°C-80°C to equilibrium moisture content to obtain a modified titanium dioxide wood veneer. 4.根据权利要求3所述的改性二氧化钛木单板制备方法，其特征在于：4. modified titanium dioxide wood veneer preparation method according to claim 3 is characterized in that: 所述柠檬酸溶液的质量浓度为3％。The mass concentration of the citric acid solution is 3%. 5.一种改性二氧化钛木单板，其特征在于，为根据权利要求3所述的制备方法制备而得。5. A modified titanium dioxide wood veneer is characterized in that, it is prepared by the preparation method according to claim 3. 6.一种改性二氧化钛人造板制备方法，其特征在于，包括步骤：6. a method for preparing a modified titanium dioxide man-made panel, characterized in that, comprising the steps: 将权利要求3制备而得的所述改性二氧化钛木单板作为饰面板，选择五层胶合板作为基材；The modified titanium dioxide wood veneer prepared in claim 3 is used as a decorative panel, and five-layer plywood is selected as a base material; 计算板材单位面积施胶量及固化剂含量，施胶量为66.6g/m2，固化剂为质量浓度19-21％的氯化铵溶液，固化剂添加量为0.1％；Calculate the sizing amount and curing agent content per unit area of the board, the sizing amount is 66.6g/m 2 , the curing agent is an ammonium chloride solution with a mass concentration of 19-21%, and the curing agent addition is 0.1%; 计算好后配置胶黏剂，在所述改性二氧化钛木单板上涂胶黏剂，之后使用热压机将所述饰面板压贴在所述基材上，热压温度为118-122℃，热压时间为58-62s，热压压力为4Mpa。After calculating, configure the adhesive, apply the adhesive on the modified titanium dioxide wood veneer, and then use a hot press to press the decorative panel on the substrate, and the hot pressing temperature is 118-122 ° C , the hot pressing time is 58-62s, and the hot pressing pressure is 4Mpa. 7.一种改性二氧化钛人造板，其特征在于，为根据权利要求6所述的制备方法制备而得。7. A modified titanium dioxide man-made panel, characterized in that, it is prepared by the preparation method according to claim 6.
CN201810991729.8A 2018-08-28 2018-08-28 Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof Pending CN109129775A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810991729.8A CN109129775A (en) 2018-08-28 2018-08-28 Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810991729.8A CN109129775A (en) 2018-08-28 2018-08-28 Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109129775A true CN109129775A (en) 2019-01-04

Family

ID=64828700

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810991729.8A Pending CN109129775A (en) 2018-08-28 2018-08-28 Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109129775A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109623995A (en) * 2019-01-09 2019-04-16 中南林业科技大学 Light-induced mildew-proof bamboo product and preparation method thereof
CN110936453A (en) * 2019-12-16 2020-03-31 内蒙古农业大学 Treatment method for enhancing outdoor durability of heat-treated wood by nano material
CN114634761A (en) * 2021-04-23 2022-06-17 上海保立佳新材料有限公司 Outdoor textile coating adhesive and preparation method thereof
RU2831310C1 (en) * 2024-09-16 2024-12-04 Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный лесотехнический университет имени Г.Ф. Морозова" Method of making plywood

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1244457A (en) * 1998-08-10 2000-02-16 浙江省德清县莫干山竹胶板厂 Manufacture of faced bamboo board
CN1742582A (en) * 2005-09-29 2006-03-08 深圳清华大学研究院 Photocatalyst-type anti-biotic material preparing method
CN103433988A (en) * 2013-08-27 2013-12-11 东北林业大学 Method for performing functional improvement on wood by using polybasic carboxylic acid
CN104437490A (en) * 2014-10-18 2015-03-25 中山市创科科研技术服务有限公司 A kind of preparation method of iron-doped titanium dioxide nano sol
CN107139298A (en) * 2017-06-13 2017-09-08 浙江省林业科学研究院 A kind of manufacture method of bamboo material surface load nano-titanium dioxide material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1244457A (en) * 1998-08-10 2000-02-16 浙江省德清县莫干山竹胶板厂 Manufacture of faced bamboo board
CN1742582A (en) * 2005-09-29 2006-03-08 深圳清华大学研究院 Photocatalyst-type anti-biotic material preparing method
CN103433988A (en) * 2013-08-27 2013-12-11 东北林业大学 Method for performing functional improvement on wood by using polybasic carboxylic acid
CN104437490A (en) * 2014-10-18 2015-03-25 中山市创科科研技术服务有限公司 A kind of preparation method of iron-doped titanium dioxide nano sol
CN107139298A (en) * 2017-06-13 2017-09-08 浙江省林业科学研究院 A kind of manufacture method of bamboo material surface load nano-titanium dioxide material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
严捍东等: "《土木工程材料 第2版》", 31 August 2014, 上海：同济大学出版社 *
王成刚等: "《综合化学实验教程》", 28 February 2013, 武汉：华中师范大学出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109623995A (en) * 2019-01-09 2019-04-16 中南林业科技大学 Light-induced mildew-proof bamboo product and preparation method thereof
CN110936453A (en) * 2019-12-16 2020-03-31 内蒙古农业大学 Treatment method for enhancing outdoor durability of heat-treated wood by nano material
CN114634761A (en) * 2021-04-23 2022-06-17 上海保立佳新材料有限公司 Outdoor textile coating adhesive and preparation method thereof
CN114634761B (en) * 2021-04-23 2023-01-17 上海保立佳新材料有限公司 Outdoor textile coating adhesive and preparation method thereof
RU2831310C1 (en) * 2024-09-16 2024-12-04 Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный лесотехнический университет имени Г.Ф. Морозова" Method of making plywood

Similar Documents

Publication Publication Date Title
CN109129775A (en) Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof
CN100372812C (en) Preparation method of nanoporous silica airgel block
CN104562637B (en) Method for constructing surface of fabric with ultraviolet protection and wash-resistant special wetting functions
CN106943843A (en) A kind of waste gas adsorption runner body and preparation method thereof and equipment
CN104624243B (en) Preparation method of nanometer titanium dioxide/loofah sponge composite photocatalyst
CN107984561B (en) A kind of method for preparing environmental protection plywood with auxiliary heating and environmental protection plywood
CN106812017A (en) A kind of Graphene decorative panel and preparation method thereof
CN112252069B (en) A preparation method of multifunctional superhydrophobic formaldehyde-free wood-based panel
CN1511630A (en) Method for preparing porous ceramics supported high activity nano titanium dioxide
CN104893463A (en) Quick-dry fiber coating
CN113024168A (en) Stain-resistant wall-ground integrated veneer and preparation method thereof
Liu et al. Reversible photo-responsive smart wood with resistant to extreme weather
CN107694545A (en) A kind of preparation method that efficient heavy ion adsorbent can be recycled
CN105153766A (en) Quick-dry diatom ooze paint
CN114214875B (en) Negative ion impregnated paper and preparation method and application thereof
CN104532677A (en) Manufacturing method of melamine impregnated paper
CN108382024B (en) A kind of environmental and ecological plate and preparation method thereof
KR101543543B1 (en) A composition of sheet for protection of wood
CN109676726A (en) A kind of method of modifying of bamboo and wood modifying agent, preparation method and fast-growing bamboo and wood
CN109049219A (en) A kind of wicker modification processing method for braiding
CN108355695A (en) A kind of special diatom ooze and preparation method having the interior purifying formaldehyde for turning light
CN117601204A (en) A decorative veneer that can continuously release negative oxygen ions and its preparation process
CN106493826A (en) A kind of preparation method of anti-bacterial fibre plate
CN101905472B (en) Method for modifying poplar fiber with silicon-boron sol
CN101811001B (en) Method for preparing organic-inorganic compound mesoporous film and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190104