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

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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
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Prior art keywords
titanium dioxide
solution
veneer
added
preparation
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刘玉
朱晓冬
王巍聪
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Northeast Forestry University
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Northeast Forestry University
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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
    • 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

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  • 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

The invention discloses a kind of modifying titanium dioxide composite materials, veneer, wood-based plate and preparation method thereof, belong to artificial board technology field.Composite material preparation includes that Butyl Phthalate will be added in dehydrated alcohol, and heating water bath simultaneously stirs；It takes hydrogenperoxide steam generator to be added and stirs to get solution A 3；It takes dehydrated alcohol to be added in the beaker equipped with deionized water, obtains solution B, solution B is added drop-wise in solution A 3, liquor ferri trichloridi is added after stirring and is stirred for, stands, obtain the nano titanic oxide sol presoma modified with iron ion；It by the sol precursor with magnetic stirrer, pours into reaction kettle, is taken out after reacting 5.5-6.5h under the conditions of certain temperature, after filtering, be dried to obtain the modified nano titanium dioxide powder of iron ion.Veneer preparation includes that veneer is put into citric acid solution to impregnate, and sodium hypophosphite is added, using suspension C impregnation etc..The utilization rate of catalysis light source can be improved in the present invention.

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. a kind of modifying titanium dioxide composite material and preparation method thereof, which is characterized in that comprising steps of
Dehydrated alcohol is added in beaker at room temperature, is placed on the balancer of magnetic stirring apparatus, is 550-650 with revolving speed It is added Butyl Phthalate under conditions of rev/min, the volume ratio of the Butyl Phthalate and the dehydrated alcohol is 1: 5, obtains solution A 1；
Beaker equipped with the 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, obtains solution A 2；
According to the ratio for being 3.5: 3 with the volume ratio of the Butyl Phthalate, taking mass concentration is the hydrogenperoxide steam generator of 29-31% It is added in the solution A 2, and stirs 28-32min with electronic agitator motor, obtain solution A 3；
According to the ratio for being 1: 1 with the 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 the deionized water and the Butyl Phthalate is 1: 1；
The solution B is slowly dropped in the solution A 3,85-95min is stirred with electronic agitator motor, is added later The liquor ferri trichloridi of 0.95-1.05mol/l, the ferric chloride solution of addition and the volume ratio of the Butyl Phthalate are 1: 6, It is further continued for stirring 55-65min with electronic agitator motor；After stirring, the solution stirred is removed, at room temperature 7.5-8.5h is stood, the nano titanic oxide sol presoma modified with iron ion is obtained；
The magnetic stirrer 9.5- for being 550-650 revs/min with revolving speed by the nano titanic oxide sol presoma Then 10.5min pours into the 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.
2. modifying titanium dioxide composite material, which is characterized in that be prepared for preparation method described in accordance with the claim 1.
3. a kind of modifying titanium dioxide veneer preparation method, which is characterized in that comprising steps of
Veneer is put into ultrasonic immersing 18-22min in the citric acid solution of mass concentration 1-15%, is added and the 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 modified nano titanium dioxide powder of the iron ion for taking claim 1 to be prepared, is put into distilled water, shape The suspension C for being 0.95-1.05% at mass concentration；
By the suspension C under conditions of ultrasonic power 550-650w after ultrasonic disperse 28-32min, described in after drying Veneer, which is immersed in the suspension C, impregnates 28-32min, takes out the veneer after dipping, 60 DEG C of -80 DEG C of bakings It does to equilibrium moisture content, obtains modifying titanium dioxide veneer.
4. modifying titanium dioxide veneer preparation method according to claim 3, it is characterised in that:
The mass concentration of the citric acid solution is 3%.
5. a kind of modifying titanium dioxide veneer, which is characterized in that for according to preparation method as claimed in claim 3 preparation and ?.
6. a kind of modifying titanium dioxide preparation method of artificial board, which is characterized in that comprising steps of
The modifying titanium dioxide veneer that claim 3 is prepared as decoration panel, select five layers of glued board as Substrate；
Calculate plate unit area resin added and curing agent content, resin added 66.6g/m2, curing agent is mass concentration 19- 21% ammonium chloride solution, curing agent additive amount are 0.1%；
Adhesive is configured after calculating, applies adhesive on the modifying titanium dioxide veneer, uses hot press by institute later It states decoration panel to overlay on the substrate, hot pressing temperature is 118-122 DEG C, hot pressing time 58-62s, hot pressing pressure 4Mpa.
7. a kind of modifying titanium dioxide wood-based plate, which is characterized in that for according to preparation method as claimed in claim 6 preparation and ?.
CN201810991729.8A 2018-08-28 2018-08-28 Modifying titanium dioxide composite material, veneer, wood-based plate and preparation method thereof Pending CN109129775A (en)

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