CN108047570A - A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof - Google Patents

A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof Download PDF

Info

Publication number
CN108047570A
CN108047570A CN201810045590.8A CN201810045590A CN108047570A CN 108047570 A CN108047570 A CN 108047570A CN 201810045590 A CN201810045590 A CN 201810045590A CN 108047570 A CN108047570 A CN 108047570A
Authority
CN
China
Prior art keywords
plastic composite
wood plastic
weather
wood
assembly type
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
CN201810045590.8A
Other languages
Chinese (zh)
Inventor
费鹏
陆丹羽
刘胜
汤林枭
陈天衡
刘玉娟
蔡杰
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.)
Minnan Normal University
Original Assignee
Minnan Normal 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 Minnan Normal University filed Critical Minnan Normal University
Priority to CN201810045590.8A priority Critical patent/CN108047570A/en
Publication of CN108047570A publication Critical patent/CN108047570A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
    • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of weather-proof wood plastic composites of LBL self-assembly type and preparation method thereof, using wood powder and polypropylene as primary raw material, dioctyl phthalate is plasticiser, ethylene vinyl acetate copolymer is bulking agent, azodicarbonamide is foaming agent, talcum powder and zinc stearate are lubricant, wood plastic composite are prepared by twin-screw extrusion shaping, with H2Ti2O5•H2O nanotubes are modified it as nanometer light absorber and with γ aminopropyl triethoxysilanes, by wood plastic composite in nanotube/γ aminopropyl triethoxysilanes dispersion liquid and kayexalate solution alternate immersion several times, by H by the way of LBL self-assembly2Ti2O5•H2O nanotubes are coated on surface of wood-plastic composite material in the form of nanometer film so that it obtains preferable weather resistance, can effectively prevent that use occurs photooxidation oxidation and is destroyed wood plastic composite in the process outdoors.

Description

A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof
Technical field
The invention belongs to the technical field of comprehensive utilization of agriculture and forestry by-product, and in particular to applied to outdoor building decoration material A kind of weather-proof wood plastic composite of LBL self-assembly type in material field and preparation method thereof.
Background technology
Since the 1990s, wood plastic composite has welcome the epoch of explosive growth, more than past 20 Nian Zhong, world wood plastic composite market are rapidly developed with annual double-digit growth rate, year ends 2016, global wood and plastic composite Demand is expected more than 3,000,000 tons, and total value is up to 6,000,000,000 dollars or so.
Wood plastic composite is one kind with the low values biomass fiber such as wood powder, sawdust, husk, agricultural crop straw, bagasse A kind of composite material being process for matrix, mixed plastic.It combines the advantages of plant fiber and plastics both sides, while Some inherent defects of the two are overcome, such as：There is an appearance of wood materials, while knot without timber, twill, it can also lead to It crosses overlay film or adds the product that a variety of colors and decorative pattern is made in colorant；Good physical performance, it is bigger than plastic hardness, than the ruler of timber Very little stability is good；Be molded with easy processing as plastics, while to as timber, there is secondary operation type, can use bolt, Nail is fixed；Be not afraid of damage by worms, be corrosion-resistant, water absorption rate it is low, weatherability is strong, and service life is long；Disposal molding, without using gluing Agent, without formaldehyde；Maintenance cost is low and belongs to green material, can recycle use.
The most important effect of wood plastic composite is to substitute solid wood to be applied to industry-by-industry, is wanted to structure and performance It is most widely used in terms of asking than relatively low building decorative product, the 75% of wood-plastic composite material products are accounted about, outdoor products are mainly wrapped Seat, trestle, bed board, wallboard, railing, hedge etc. are included, interior products mainly include door bar line, skirting, decorative panel etc..
Although wood plastic composite has many advantages in building decoration area than conventional wooden, with the development of the times With the raising of people's demand, there are many problems outdoors and in indoor application.On the one hand, weather stain, which has become, works as One of key issue present in preceding open air wood-plastic products use.The same with other high molecular materials, wood plastic product makes outdoors Used time, sunlight, oxygen and water grading factors in outdoor natural environment can all damage to its apparent property and mechanical property, The destruction of apparent property is primarily referred to as material and colour fading and xanthochromia occurs, and shows in mechanical property it is brittleness increase, impact strength It reduces.The ageing failure problem of material seriously affects and restricts the performance and the market competitiveness of wood-plastic products, and then interferes wood moulding The development of industry.Therefore, how to improve the weatherability of wood plastic composite has become one of focus of research, anti-aging type wood moulding Product becomes letter product leaved for development.
Agine mechaism, influence factor etc. from high molecular material, it can be found that photooxidation aoxidizes（It is especially ultraviolet Light）It is the most important reason of wood plastic composite aging, addition light stabilizer is that improve high molecular material weatherability the most frequently used, most Convenient and most economical method, but traditional light stabilizer more or less there are problems that, can not meet today's society pair The needs of wood plastic composite, such as：
1. ultra-violet absorber can absorb the ultraviolet light with high-energy, then by modes such as fluorescence, phosphorescence, heat by this portion Point energy transfer is gone out, and high molecular material is avoided to absorb ultraviolet light and degrade, and is current most common light stabilizer, mainly Species has salicylic acid esters, benzophenone, benzotriazole and triazines etc..But ultra-violet absorber may be from purple It decomposes under the action of outer light, gradually exhausts, high molecular material is made to lose weather resistance.Meanwhile to the absorption of ultraviolet light It is limit, it is necessary to preferable effect could be generated under certain concentration；It needs certain absorption depth simultaneously, therefore, It is limited for some relatively thin material effects.
All it is to protect macromolecule by shifting the energy of ultraviolet light 2. excited state quenchers are similar with ultra-violet absorber Material is not degraded.The complex compound or salt of nickelous are current most widely used excited state quenchers, but it is in high temperature（300 ℃）Under can decompose, generation nickel sulfide generation environment pollution.
3. photomask agent is the substance that refers to fully absorb or reflect ultraviolet light, it can prevent ultraviolet light across and into Material molecule chain break is caused inside high molecular material, similar to having added barrier together between ultraviolet light and high molecular material, Mainly there are carbon black, zinc oxide and some pigment.Photomask agent is different to the protective effect of different high molecular materials, because its Different from the extinction spectrum of high molecular material, the ultraviolet light harmless to a kind of high molecular material may degrade another material； In addition, light shield may react in itself with certain family macromolecule material.Such as, iron oxide is a kind of common photomask agent, but its Polyvinyl chloride can be catalyzed（PVC）Oxygenolysis.In addition, photomask agent is typically a kind of pigment, has dyeability, this is significantly Limit its application range.
4. hindered amine as light stabilizer can prevent the process of photooxidation chain reaction, by hydroperoxide decomposition, chain is captured The free radical that formula reaction generates transfers excited energy so as to cut off chain reaction, prevents high molecular material by oxygenolysis. But since hindered amine as light stabilizer is in alkalescence, in PVC, polymethyl methacrylate（PMMA）, makrolon（PC）Deng containing acidity Application in the high molecular material of component is extremely restricted.
New inorganic nano material is developed, is current one for improving the weatherability of wood plastic composite and weatherability A research hotspot, nano-TiO2Typical Representative exactly therein.Rutile type nano TiO2By huge surface area and it can surpass The ultraviolet light partly penetrated in polymer surface is fallen in more interface scatterings；In addition it is possible to portion is sponged by electron transition Divide ultraviolet light, this provides theoretical foundation as light stabilizer for it to improve the weatherability of wood plastic composite.
But these inorganic nano materials are typically compound with fiber-base composite materials in the form of blending, for composite wood Material reaches preferable weather resistance, it is desirable that inorganic nano material has relatively high additive amount so that product cost is excessively high；Separately Outside, the addition of inorganic nano light stabilizer is likely to decrease wood-fibred and synthesizes the compatibility between high molecular material, causes multiple Condensation material mechanical property deteriorates.
The content of the invention
It is an object of the present invention to it easy to aging weather-proof is asked for current wood plastic composite is existing in application process Topic, and traditional light stabilizer also exposes many disadvantages, such as organic light stabilizer cannot it is long-acting it is anti-aging, have certain environment dirty The problems such as dye, dosage is larger, cost is higher, TiO by blending method incorporation composite material, causing for inorganic nano weather resisting agent2 And nanometer tubing light absorber efficiency of light absorption it is relatively low the problem of, a kind of weather-proof wood plastic composite of LBL self-assembly type is provided And preparation method thereof.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, comprises the following steps：
1）20-30 parts of wood powders are crossed into 100-150 mesh sieves, it is dry, the titanate coupling agent of wood powder weight 2-4% is then added in, in 80-90 DEG C is stirred to react 3-5h, then proceedes to stirring and is cooled to room temperature, obtains modified wood powder；
2）By step 1）Obtained modified wood powder, 60-100 parts of polypropylene, 2-5 parts of dioctyl phthalates, 8-12 parts of second After alkene-vinyl acetate copolymer, 1-3 part azodicarbonamide, 2-8 parts of talcum powder and 1-3 parts of zinc stearate mixing, in 130- It is stirred 10-20 minutes at 160 DEG C, obtains mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, through mould shape, cooling, traction and cutting, obtains wood Plastic composite materials；
4）Wood plastic composite is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained pre- Treated wood plastic composite, the pretreatment cause wood-fibred surface portion to hydrolyze, expose more hydroxyls and carboxyl, from And it is easier to adsorb polyelectrolyte；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：The salt of titania powder and rare earth element is added in In NaOH solution, in N2After 1.5-2.5 h are stirred in atmosphere, emulsion is poured into reaction kettle, then in 90-150 DEG C Lower reaction 8-30 h, then cool down reaction kettle, remove supernatant liquor and obtain reaction intermediate, finally add into intermediate product Acid liquid simultaneously stirs acidifying so that the pH value of whole system is maintained at 1.5-3 and continues to stir 18-24 h, then filters, collects Sediment is simultaneously washed with deionized to neutrality, then by drying precipitate, obtains rare earth doped H2Ti2O5•H2O receives Mitron；
6）By 0.2-0.3 parts of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane With 9 parts of absolute ethyl alcohol blending constituent dispersion liquids, sonic oscillation 15-25 min obtain nanotube/gamma-aminopropyl-triethoxy-silane Dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid （Polyelectrolyte solution with whole electricity）With kayexalate solution（Electronegative polyelectrolyte solution）If middle alternate immersion Dry time, 20-25 min are impregnated every time, then dries, obtains the weather-proof wood plastic composite of LBL self-assembly type.
Step 1）, the wood powder dry 18-24h at 90-110 DEG C.
Step 3）, double screw extruder extrusion molding process, each section of heating temperature T1-T10 is respectively 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 10-15 revs/min, and material pressure is 1.5-2.0 MPA。
Step 5）, the TiO2The total amount of the salt of powder and rare earth element and the amount ratio of NaOH solution are 1g:20-25 mL。
Step 5）, the concentration of the NaOH solution is 5-10M.
Step 5）, the acid solution is the hydrochloric acid solution of 1-1.5mol/L.
Step 5), the sediment at 70-80 DEG C it is dry at least 24 it is small when.
Step 7）, the wood plastic composite is in nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid and polystyrene The number of alternate immersion is 3-10 times in sodium sulfonate solution.
Step 7）, 15-20 min are washed with deionized after each immersion of the wood plastic composite and carry out again next time It impregnates.
The present invention is modified wood powder using titanate coupling agent, with modified wood powder and is gathered using above technical scheme Propylene is primary raw material, and dioctyl phthalate is plasticiser, and vinyl-vinyl acetate copolymer is bulking agent, azo two Formamide is foaming agent, and talcum powder and zinc stearate are lubricant, and wood and plastic composite is prepared by twin-screw extrusion one-pass molding Material, H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes and by the rare earth doped area in nanotube, to reduce its taboo Bandwidth enhances its light absorpting ability, with rare earth doped H2Ti2O5•H2O nanotubes as nanometer light absorber, and It is modified with gamma-aminopropyl-triethoxy-silane nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid is made, Then using kayexalate solution as electronegative polyelectrolyte solution, with nanotube/gamma-aminopropyl-triethoxy-silane Dispersion liquid is the polyelectrolyte solution of positively charged, will treated wood plastic composite in nanotube/gamma-aminopropyl-triethoxy In silane dispersion fluid and kayexalate solution alternate immersion several times, by rare earth element by the way of LBL self-assembly The H of doping2Ti2O5•H2O nanotubes are coated on surface of wood-plastic composite material in the form of nanometer film so that it obtains preferable resistance to Wait performance, prepared weather-proof surface of wood-plastic composite material alternately cladding nanotube/gamma-aminopropyl-triethoxy-silane layer and Kayexalate layer.
The present invention has the following advantages：
1st, compared with traditional wood plastic composite, H2Ti2O5•H2O nanotubes are due to stronger absorption photon（Especially Ultraviolet light）Ability, can effectively prevent wood plastic composite from photooxidation oxidation occurs during use outdoors and is destroyed；
2nd, H is used with simple2Ti2O5•H2O nanotubes are compared, the present invention by into nanotube rare earth doped element reducing Its energy gap enhances its absorbing ability.
2nd, compared with traditional inorganic nano light stabilizer, H of the invention2Ti2O5•H2O nanotubes light stabilizer be not with The form incorporation composite material of blending, but by LBL self-assembly, composite material surface is attached in the form of nanometer film, is received The usage amount of rice light stabilizer is low, helps to reduce product cost, and enhances product weather resistance；In addition, this product will not Because with the poor compatibility of wood-fibred and plastics material mechanical performance is caused to deteriorate.
3rd, compared with traditional organic light stabilizer, rare earth doped H2Ti2O3•H2O nanotubes will not occur point Solution has long-acting weather resistance, does not pollute the environment simultaneously.
Specific embodiment
A kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, comprises the following steps：
1）20-30 parts of wood powders are crossed into 100-150 mesh sieves, dry 18-24h, then adds in wood powder weight 2-4% at 90-110 DEG C Titanate coupling agent, be stirred to react 3-5h in 80-90 DEG C, then proceed to stirring be cooled to room temperature, obtain modified wood powder；
2）By step 1）Obtained modified wood powder, 60-100 parts of polypropylene, 2-5 parts of dioctyl phthalates, 8-12 parts of second After alkene-vinyl acetate copolymer, 1-3 part azodicarbonamide, 2-8 parts of talcum powder and 1-3 parts of zinc stearate mixing, in 130- It is stirred 10-20 minutes at 160 DEG C, obtains mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, each section of heating temperature T1-T10 is respectively 120 DEG C, and 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 10-15 revs/min, material It presses as 1.5-2.0 MPA, then through mould shape, cooling, traction and cutting, obtains wood plastic composite；
4）Wood plastic composite is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained pre- Treated wood plastic composite, the pretreatment cause wood-fibred surface portion to hydrolyze, expose more hydroxyls and carboxyl, from And it is easier to adsorb polyelectrolyte；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：The salt of titania powder and rare earth element is added in into concentration For in 5-10M NaOH solutions（ TiO2The total amount of the salt of powder and rare earth element and the amount ratio of NaOH solution are 1g:20-25 mL）, in N2After 1.5-2.5 h are stirred in atmosphere, emulsion is poured into reaction kettle, is then reacted at 90-150 DEG C 8-30 h, then cool down reaction kettle, remove supernatant liquor and obtain reaction intermediate, 1- is finally added into intermediate product The hydrochloric acid solution of 1.5mol/L simultaneously stirs acidifying so that and the pH value of whole system is maintained at 1.5-3 and continues to stir 18-24 h, Then filter, collect sediment and be washed with deionized to neutrality, then drying at least 24 is small at 70-80 DEG C by sediment When, obtain rare earth doped H2Ti2O5•H2O nanotubes；
6）By 0.2-0.3 parts of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane With 9 parts of absolute ethyl alcohol blending constituent dispersion liquids, then sonic oscillation 15-25 min stir 1.5-2.5h, obtain nanometer at normal temperatures Pipe/gamma-aminopropyl-triethoxy-silane dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid With alternate immersion in kayexalate solution, 20-25 min are impregnated every time, are all washed with deionized after impregnating every time 15-20 min remove the polyelectrolyte of composite material surface physical absorption, alternate immersion 3-10 times in total, then in 70-80 DEG C Drying, then dries, obtains the weather-proof wood plastic composite of LBL self-assembly type.
Embodiment 1
A kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, comprises the following steps：
1）20 parts of wood powders are crossed into 100 mesh sieves, it is dry at 90 DEG C then to add in the titanate coupling agent of wood powder weight 2% for 24 hours, in 80 DEG C are stirred to react 5h, then proceed to stirring and are cooled to room temperature, obtain modified wood powder；
2）By step 1）Obtained modified wood powder, 60 parts of polypropylene, 2 parts of dioctyl phthalates, 8 parts of ethane-acetic acid ethyenyls After ester copolymer, 1 part of azodicarbonamide, 2 parts of talcum powder and 1 part of zinc stearate mixing, stir 20 minutes, obtain at 130 DEG C To mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, each section of heating temperature T1-T10 is respectively 120 DEG C, and 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 10 revs/min, and material pressure is 1.5MPA then through mould shape, cooling, traction and cutting, obtains wood plastic composite；
4）Wood plastic composite is positioned in the NaOH solution of 1M, 35 min are impregnated at 65 DEG C, obtains pretreated wood Plastic composite materials, the pretreatment cause wood-fibred surface portion to hydrolyze, expose more hydroxyls and carboxyl, so as to be easier to inhale Agglomeration electrolyte；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：By titania powder and Ce (NO3)2•6H2O adds in concentration For in 5M NaOH solutions（ TiO2Powder and Ce (NO3)2•6H2The total amount of O and the amount ratio of NaOH solution are 1g:20mL）, in N2 After being stirred 1.5h in atmosphere, emulsion is poured into reaction kettle, 30 h are then reacted at 90 DEG C, then by reaction kettle Cooling removes supernatant liquor and obtains reaction intermediate, and hydrochloric acid solution and the stirring of 1mol/L is finally added into intermediate product Acidifying so that the pH value of whole system is maintained at 1.5 and continues to stir 18h, then filters, and collects sediment and uses deionized water Washing when then drying at least 24 is small at 70 DEG C by sediment, obtains rare earth doped H to neutrality2Ti2O5•H2O receives Mitron；
6）By 0.2 part of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 Then part absolute ethyl alcohol blending constituent dispersion liquid, sonic oscillation 15min stir 1.5 h, obtain nanotube/γ-ammonia third at normal temperatures Ethyl triethoxy silicane alkane dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid With alternate immersion in kayexalate solution, 20min is impregnated every time, and 15 are all washed with deionized after impregnating every time Min, removes the polyelectrolyte of composite material surface physical absorption, and alternate immersion 3 times in total then in 70 DEG C of drying, are then dried It is dry, obtain the weather-proof wood plastic composite of LBL self-assembly type.
Embodiment 2
A kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, comprises the following steps：
1）30 parts of wood powders are crossed into 150 mesh sieves, the titanate coupling agent of dry 18h, then addition wood powder weight 4% at 110 DEG C, 3h is stirred to react in 90 DEG C, stirring is then proceeded to and is cooled to room temperature, obtain modified wood powder；
2）By step 1）Obtained modified wood powder, 100 parts of polypropylene, 5 parts of dioctyl phthalates, 12 parts of ethylene-acetates After vinyl ester copolymers, 3 parts of azodicarbonamides, 8 parts of talcum powder and 3 parts of zinc stearate mixing, 10 points are stirred at 160 DEG C Clock obtains mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, each section of heating temperature T1-T10 is respectively 120 DEG C, and 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 15 revs/min, and material pressure is 2.0 MPA then through mould shape, cooling, traction and cutting, obtain wood plastic composite；
4）Wood plastic composite is positioned in the NaOH solution of 1-1.5M, 25 min are impregnated at 75 DEG C, after obtaining pretreatment Wood plastic composite, which causes wood-fibred surface portion to hydrolyze, exposes more hydroxyls and carboxyl, so as to more holding Easily absorption polyelectrolyte；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：By titania powder and Ce (NO3)2•6H2O adds in concentration For in 10M NaOH solutions（ TiO2Powder and Ce (NO3)2•6H2The total amount of O and the amount ratio of NaOH solution are 1g:25 mL）, In N2After 2.5 h are stirred in atmosphere, emulsion is poured into reaction kettle, 8h is then reacted at 150 DEG C, it then will be anti- Kettle is answered to cool down, supernatant liquor is removed and obtains reaction intermediate, the hydrochloric acid solution of 1.5mol/L is finally added into intermediate product And stir acidifying so that the pH value of whole system is maintained at 3 and continues to stir 18 h, then filters, and collects sediment and spends Ion water washing when then drying at least 24 is small at 80 DEG C by sediment, obtains rare earth doped H to neutrality2Ti2O5• H2O nanotubes；
6）By 0.3 part of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 Then part absolute ethyl alcohol blending constituent dispersion liquid, 25 min of sonic oscillation stir 2.5h, obtain nanotube/γ-ammonia third at normal temperatures Ethyl triethoxy silicane alkane dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid With alternate immersion in kayexalate solution, 25 min are impregnated every time, 20 are all washed with deionized after impregnating every time Min, removes the polyelectrolyte of composite material surface physical absorption, and alternate immersion 10 times in total then in 80 DEG C of drying, are then dried It is dry, obtain the weather-proof wood plastic composite of LBL self-assembly type.
Embodiment 3
A kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, comprises the following steps：
1）25 parts of wood powders are crossed into 120 mesh sieves, for 24 hours, the titanate esters for then adding in wood powder weight 2-4% are coupled for drying at 103 DEG C Agent is stirred to react 4 h in 85 DEG C, then proceedes to stirring and is cooled to room temperature, obtains modified wood powder；
2）By step 1）Obtained modified wood powder, 80 parts of polypropylene, 3.5 parts of dioctyl phthalates, 10 parts of ethylene-acetate second After enoate copolymer, 2 parts of azodicarbonamides, 5 parts of talcum powder and 2 parts of zinc stearate mixing, stirred 15 minutes at 145 DEG C, Obtain mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, each section of heating temperature T1-T10 is respectively 120 DEG C, and 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 15 revs/min, and material pressure is 1.75 MPA then through mould shape, cooling, traction and cutting, obtain wood plastic composite；
4）Wood plastic composite is positioned in the NaOH solution of 1.25 M, 30 min is impregnated at 70 DEG C, after obtaining pretreatment Wood plastic composite, which causes wood-fibred surface portion to hydrolyze, exposes more hydroxyls and carboxyl, so as to more holding Easily absorption polyelectrolyte；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：By titania powder and Ce (NO3)2•6H2O adds in concentration For in 7.5 M NaOH solutions（ TiO2Powder and Ce (NO3)2•6H2The total amount of O and the amount ratio of NaOH solution are 1g: 25 mL）, in N2After being stirred 2h in atmosphere, emulsion is poured into reaction kettle, 18 h are then reacted at 120 DEG C, then will Reaction kettle cools down, and removes supernatant liquor and obtains reaction intermediate, the last hydrochloric acid that 1.25 mol/L are added into intermediate product Solution ＆ stir is acidified so that the pH value of whole system is maintained at 2.5 and continues to stir 18 h, then filters, collects sediment And be washed with deionized to neutrality, when then by sediment, drying at least 24 is small at 75 DEG C, obtain rare earth doped H2Ti2O5•H2O nanotubes；
6）By 0.25 part of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 Then part absolute ethyl alcohol blending constituent dispersion liquid, 20 min of sonic oscillation stir 2.0 h, obtain nanotube/γ-ammonia at normal temperatures Propyl-triethoxysilicane dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid With alternate immersion in kayexalate solution, 20 min are impregnated every time, 15 are all washed with deionized after impregnating every time Min, removes the polyelectrolyte of composite material surface physical absorption, and alternate immersion 5 times in total then in 75 DEG C of drying, are then dried It is dry, obtain the weather-proof wood plastic composite of LBL self-assembly type.

Claims (10)

1. a kind of preparation method of the weather-proof wood plastic composite of LBL self-assembly type, it is characterised in that：It comprises the following steps：
1）20-30 parts of wood powders are crossed into 100-150 mesh sieves, it is dry, the titanate coupling agent of wood powder weight 2-4% is then added in, in 80-90 DEG C is stirred to react 3-5h, is subsequently cooled to room temperature, obtains modified wood powder；
2）By step 1）Obtained modified wood powder, 60-100 parts of polypropylene, 2-5 parts of dioctyl phthalates, 8-12 parts of second After alkene-vinyl acetate copolymer, 1-3 part azodicarbonamide, 2-8 parts of talcum powder and 1-3 parts of zinc stearate mixing, in 130- It is stirred 10-20 minutes at 160 DEG C, obtains mixed material；
3）Said mixture material is placed in extrusion molding in double screw extruder, obtains wood plastic composite；
4）Wood plastic composite is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained pre- Treated wood plastic composite；
5）Prepare rare earth doped H2Ti2O5•H2O nanotubes：The salt of titania powder and rare earth element is added in into NaOH In solution, in N2After 1.5-2.5 h are stirred in atmosphere, emulsion is poured into reaction kettle, it is then anti-at 90-150 DEG C 8-30 h are answered, then cool down reaction kettle, supernatant liquor is removed and obtains reaction intermediate, acid is finally added into intermediate product Liquid simultaneously stirs acidifying so that the pH value of whole system is maintained at 1.5-3 and continues to stir 18-24 h, then filters, collects precipitation Object is simultaneously washed with deionized to neutrality, then by drying precipitate, obtains rare earth doped H2Ti2O5•H2O nanotubes；
6）By 0.2-0.3 parts of rare earth doped H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane With 9 parts of absolute ethyl alcohol blending constituent dispersion liquids, sonic oscillation 15-25 min obtain nanotube/gamma-aminopropyl-triethoxy-silane Dispersion liquid；
7）By step 4）Pretreated wood plastic composite is in above-mentioned nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid With alternate immersion in kayexalate solution several times, 20-25 min are impregnated every time, are then dried, are obtained layer by layer from group The weather-proof wood plastic composite of dress type.
2. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 1）, the wood powder dry 18-24h at 90-110 DEG C.
3. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 3）, double screw extruder extrusion molding process, each section of heating temperature T1-T10 is respectively 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 140 DEG C and 120 DEG C, engine speed is 10-15 revs/min, and material pressure is 1.5- 2.0 MPA。
4. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 5）, the TiO2The total amount of the salt of powder and rare earth element and the amount ratio of NaOH solution are 1g:20-25 mL.
5. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 5）, the concentration of the NaOH solution is 5-10M.
6. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 5）, the acid solution is the hydrochloric acid solution of 1-1.5mol/L.
7. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 5), the sediment at 70-80 DEG C it is dry at least 24 it is small when.
8. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 7）, the wood plastic composite is in nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid and polystyrolsulfon acid The number of alternate immersion is 3-10 times in sodium solution.
9. a kind of preparation method of weather-proof wood plastic composite of LBL self-assembly type according to claim 1, feature exist In：Step 7）, 15-20 min are washed with deionized after each immersion of the wood plastic composite and are impregnated next time again.
10. the weather-proof wood plastic composite of LBL self-assembly type obtained according to any preparation methods of claim 1-9.
CN201810045590.8A 2018-01-17 2018-01-17 A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof Pending CN108047570A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810045590.8A CN108047570A (en) 2018-01-17 2018-01-17 A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810045590.8A CN108047570A (en) 2018-01-17 2018-01-17 A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108047570A true CN108047570A (en) 2018-05-18

Family

ID=62126835

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810045590.8A Pending CN108047570A (en) 2018-01-17 2018-01-17 A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108047570A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102140255A (en) * 2011-04-14 2011-08-03 浙江工商大学 Hot-press type wood plastic composite for toy and preparation method thereof
CN103102585A (en) * 2011-11-15 2013-05-15 天津德昊超微新材料有限公司 Special material for wood plastic extrusion foaming and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102140255A (en) * 2011-04-14 2011-08-03 浙江工商大学 Hot-press type wood plastic composite for toy and preparation method thereof
CN103102585A (en) * 2011-11-15 2013-05-15 天津德昊超微新材料有限公司 Special material for wood plastic extrusion foaming and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PENG FEI ET AL.: "Synthesis of H2Ti2O3•H2O nanotubes and their effects on the flame retardancy of bamboo fiber/high-density polyethylene composites", 《COMPOSITES: PART A》 *
沈青: "《分子酸碱化学》", 31 March 2012, 上海科学技术文献出版社 *
潘海峰: "棉织物和软质聚氨酯泡沫的层层自组装阻燃涂层的设计及其性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Similar Documents

Publication Publication Date Title
CN103289172B (en) Hardly-deformable polyethylene wood-plastic composite and preparation method
CN107400294A (en) Bio-based degradable material and preparation method thereof, application
CN103992589B (en) A kind of wood plastic building mould utilizing recovery waste material to produce and preparation method thereof
CN103554850A (en) Environment-friendly type anti-cracking corrosion-resistant waterproof material and preparation method thereof
CN103993697B (en) Formula of wood-plastic bathroom plate and production method
CN108329585A (en) A kind of novel weathering resistant type wood plastic composite and preparation method thereof
CN108822440A (en) A kind of flame-retardant wood-plastic plate and preparation method thereof
CN114231013B (en) Environment-friendly plastic building template material and preparation method thereof
CN105086245A (en) PVC (polyvinyl chloride) plastic wood board and preparation method thereof
CN109096643A (en) A kind of novel green fire-resistant waterproof wood plastic composite and preparation method thereof
CN105086246A (en) Flame-retardant modified pvc (polyvinyl chloride) decorative material
CN108276600A (en) Weather-proof wood plastic composite of LBL self-assembly type of nucleocapsid and preparation method thereof
CN108047570A (en) A kind of weather-proof wood plastic composite of LBL self-assembly type and preparation method thereof
CN113502100A (en) Self-cleaning high-weather-resistance temperature-sensitive color-changing coating and preparation method thereof
CN108164826A (en) A kind of weather-proof wood plastic composite and preparation method thereof
CN108219187A (en) A kind of weather-proof wood plastic composite of self assembly type and preparation method thereof
CN115109351B (en) Wood powder filled PVC composite material for picture frame and preparation method thereof
CN109181143A (en) A kind of high-intensity shielding type wood moulding door-window section bar
CN108192130A (en) A kind of fire-retardant bamboo-plastic composite material of self assembly type and preparation method thereof
CN105111616A (en) Wood-plastic decorative building material
CN106675068A (en) Biomass composite material, preparation method thereof and fence
CN111234115A (en) Synthesis method of ACR (acrylic resin) with high impact strength
CN104804451A (en) Light wood-plastic compound material for outdoor use
CN110283468A (en) A kind of preparation method of the compound plastic-wood material of high durable
CN1105040A (en) Agriculture film

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

Application publication date: 20180518

RJ01 Rejection of invention patent application after publication