CN108192130A - A kind of fire-retardant bamboo-plastic composite material of self assembly type and preparation method thereof - Google Patents

A kind of fire-retardant bamboo-plastic composite material of self assembly type and preparation method thereof Download PDF

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CN108192130A
CN108192130A CN201810046113.3A CN201810046113A CN108192130A CN 108192130 A CN108192130 A CN 108192130A CN 201810046113 A CN201810046113 A CN 201810046113A CN 108192130 A CN108192130 A CN 108192130A
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bamboo
composite material
plastic composite
fire
assembly type
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费鹏
白榕
陈斌
刘玉娟
刘琪
李璐
陈晨昕
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Minnan Normal University
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    • 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
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Abstract

The invention discloses a kind of fire-retardant bamboo-plastic composite materials of self assembly type and preparation method thereof, using bamboo powder and high density polyethylene (HDPE) as primary raw material, silane coupling agent is coupling agent, ethylene vinyl acetate copolymer is bulking agent, azodicarbonamide is foaming agent, polyethylene wax and zinc stearate are lubricant, and bamboo-plastic composite material is prepared by twin-screw extrusion disposal molding；H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes simultaneously are modified it with γ aminopropyl triethoxysilanes nanotube/γ aminopropyl triethoxysilane dispersion liquids are made, then by treated, bamboo-plastic composite material alternate immersion in nanotube/γ aminopropyl triethoxysilanes dispersion liquid and kayexalate solution several times, obtains the fire-retardant bamboo-plastic composite material of self assembly type.Product of the present invention, H2Ti2O5•H2O nanotubes are that composite material surface is attached in the form of nanometer film, can reach good flame retardant effect using the nano-meter flame retardants of lower content, help to reduce product cost.

Description

A kind of fire-retardant bamboo-plastic composite material of 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 be led to applied to building and ornament materials A kind of fire-retardant bamboo-plastic composite material of self assembly type in domain and preparation method thereof.
Background technology
In China while forest resourceies scarcity, China is also the country that global bamboo wood type is most abundant, distribution is most wide, is had The title of " bamboo kingdom ".According to statistics, the shared bamboo kind more than 70 in the whole world belongs to, more than 1000 kinds, and just has 37 categories known to China, and more than 500 Kind.There are bamboo wood distribution in major part province of China, city and autonomous region, are concentrated mainly on southern each province, the Yellow River and the Yangtze river basin, to dissipate Based on raw bamboo, the Changjiang river to Nanling one with for mixing bamboo grove area, South China based on Cluster Bamboo, southwest using high mangosteen as It is main.According to the 8th national forest assessment as a result, to the end of the year 2013, China's bamboo grove area is 6,010,000 hectares, bamboo grove face Product, bamboo wood accumulation, bamboo product yield and export volume rank first in the world.Meanwhile bamboo belongs to the fast-growing seed of forest, under normal circumstances, 3-4 can become a useful person utilization, and its texture straight, hardness are high, are very suitable for preparing bamboo-plastic composite material.To sum up, this The bamboo resource of a little rich reserves to solve the current timber supply and demand contradiction in China, promotes forestry industry upgrading and transformation to provide one Practical way.The potentiality and advantage of bamboo timber resource are fully excavated, are had to the research for further deepening bamboo-plastic composite material important Meaning.The most important effect of bamboo-plastic composite material is to substitute solid wood to be applied to industry-by-industry, to structure and performance requirement It is most widely used in terms of than relatively low building decorative product, the 75% of bamboo-plastic composite material product is accounted about, product mainly includes door Line, skirting, decorative panel etc..
The main component of bamboo-plastic composite material is bamboo fibre and synthetic resin, belongs to the low material of poor heat resistance, ignition point Material, heat is high after burning, and plastics can generate a large amount of dense smokes after combustion, severe jamming fire occur after escape and rescue Help action.The fire hazard caused by bamboo plastic decorating material is also the problem of public extremely pays close attention in recent years.With China city The continuous quickening of change process, urban population density constantly increase, and the probability that fire occurs loses with caused by and also improves year by year.It is public An Bu Fires Department count, and national fire 31.2 ten thousand of being informed of a case altogether in 2016 dies 1582 people, hinders 1065 people, direct property loss 37.2 hundred million yuan.At present, world's every country all pays much attention to disaster caused by fire, also to the fire line of indoor building material Certain requirement can be proposed.
By add in fire retardant improve bamboo-plastic composite material flame retardant property, have the characteristics that it is simple, effective, economical, but Traditional fire retardant exposes the problem of more and more.Halogenated flame retardant almost can be described as most effective fire retardant, fire-retardant effect Rate is height, and additive amount is low, and global year total dosage was once reaching 300,000 tons or more, but halogenated flame retardant can generate largely in burning Cigarette and toxic, corrosive gas, environment and human body can be damaged, this does not conform to current health and environmental protection concept；Gold Belong to hydroxide flame retardant and mainly include magnesium hydroxide (MTH) and aluminium hydroxide (ATH), be the halogen-free flameproof of usage amount maximum Agent.But to reach good flame retardant effect, the additive amount of this based flame retardant need it is very big, generally reach 50 wt% with On, this serious deterioration mechanical property of high molecular material；The age that boron flame retardant occurs, 18 beginnings of the century just weaved very early The fire-retardant aspect of product has application, but it is easily hydrolyzed, less about its report.
Since the 1980s, nanometer technology has obtained vigorous growth, and sepiolite, montmorillonite, graphene, carbon are received Mitron etc. is all applied in flame retardant area, and these inorganic nano fire retardants are typically compound with fiber base in the form of blending Material cladding, in order to reach preferable flame retardant property, it is desirable that inorganic nano fire retardant has relatively high additive amount so that product Cost is excessively high；In addition, the addition of inorganic nano fire retardant be likely to decrease bamboo fibre and synthesize high molecular material between it is compatible Property, composite materials property is caused to deteriorate.
Therefore, the flame retardant property of bamboo-plastic composite material how is improved under the premise of control cost, is still tradesman It is badly in need of the problem solved.
Invention content
It is an object of the present invention to for current bamboo-plastic composite material in application process existing incendive problem with And conventional flame retardant the defects of exposing, a kind of fire-retardant bamboo-plastic composite material of self assembly type and preparation method thereof is provided.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, includes the following steps：
1）20-30 parts of bamboo powders are crossed into 100-150 mesh sieve, it is dry, the silane coupling agent of bamboo powder weight 2-4% is then added in, in 80- 90 DEG C are stirred to react 3-5h, then proceed to stirring and are cooled to room temperature, and obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 60-100 parts of high density polyethylene (HDPE)s, 1-3 parts of azodicarbonamides, 8-12 parts of second After alkene-vinyl acetate copolymer, 2-8 part polyethylene wax and 1-3 parts of zinc stearate mixing, 10- is stirred at 100-120 DEG C 20 minutes, obtain mixed material；
3）Said mixture material is placed in double screw extruder and is squeezed out, through mould shape, cooling, traction and cutting, obtains bamboo Plastic composite materials；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained To pretreated bamboo-plastic composite material, which makes the hydrolysis of bamboo fibre surface portion so as to be easier absorption polyelectrolyte；
5）H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes：By TiO2Powder is added in NaOH solution, in N2It is stirred in atmosphere After mixing mixing 1.5-2.5 h, emulsion is poured into reaction kettle, 8-30 h are then reacted at 90-150 DEG C, it then will reaction Kettle is placed under normal temperature condition and cools down, and removes upper strata clarification lye and obtains reaction intermediate, acid is finally added into intermediate product Liquid simultaneously stirs acidification 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 H2Ti2O5•H2O nanotubes；
6）By 0.2-0.3 parts of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohols Blending constituent dispersion liquid, sonic oscillation 15-25 min, then stirs 1.5-2.5h at normal temperatures, obtains nanotube/γ-aminopropyl Triethoxysilane dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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 self assembly type Fire-retardant bamboo-plastic composite material.
Step 1）, the bamboo 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 TiO2Powder and the amount ratio of NaOH solution are 1g:20-25 mL.
Step 5）, a concentration of 5-10M of the NaOH solution.
Step 5）, the acid solution is the hydrochloric acid solution of 1-1.5mol/L.
Step 5), the sediment are at least 24 hours dry at 70-80 DEG C.
Step 7）, the bamboo-plastic composite material 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 all washed with deionized after each immersion of the bamboo-plastic composite material, remove composite wood Expect the polyelectrolyte of surface physics absorption, then impregnated next time.
The present invention is using above technical scheme, and using bamboo powder and high density polyethylene (HDPE) as primary raw material, silane coupling agent is even Join agent, vinyl-vinyl acetate copolymer is bulking agent, and azodicarbonamide is foaming agent, and polyethylene wax and zinc stearate are Lubricant prepares bamboo-plastic composite material by twin-screw extrusion disposal molding；H is prepared by hydrothermal synthesis method2Ti2O5•H2O Nanotube simultaneously is modified it with gamma-aminopropyl-triethoxy-silane nanotube/gamma-aminopropyl-triethoxy-silane is made Dispersion liquid, then using kayexalate solution as electronegative polyelectrolyte solution, with nanotube/three second of γ-aminopropyl Oxysilane dispersion liquid is positively charged polyelectrolyte solution, will treated bamboo-plastic composite material in nanotube/γ-aminopropyl Alternate immersion several times, will by the way of LBL self-assembly in triethoxysilane dispersion liquid and kayexalate solution H2Ti2O5•H2O nanotubes are coated on bamboo-plastic composite material surface in the form of nanometer film so that it obtains preferable anti-flammability Can, prepared flame retardant type bamboo-plastic composite material surface alternately coats nanotube/gamma-aminopropyl-triethoxy-silane layer and polyphenyl Vinyl sulfonic acid sodium layer.
The present invention has the following advantages：
1st, compared with traditional bamboo-plastic composite material, H2Ti2O5•H2The tubular structure of O nanotubes and huge specific surface area can With the heat release of absorption and bond material in the reactive intermediate for thermally decomposing with being generated in combustion process, reduction combustion process With smoke amount, the flame retardant property of bamboo-plastic composite material is improved；In addition, due to H2Ti2O5•H2The high major diameter of O nanotubes itself Than being able to maintain that the physical arrangement of composite material, preventing the mass-and heat-transfer in combustion process so that the burning of composite material is not filled Point, a large amount of charcoal particle packings further prevent oxygen and heat from being oozed to matrix in composite material surface, the layer of charcoal for forming densification Thoroughly, matrix while is also prevented to burn the cigarette generated to material surface release, so as to reduce the Heat liberation unit of composite material.
2nd, compared with halogenated flame retardant, product of the present invention is nontoxic, and poisonous and harmful substance will not be discharged in combustion process, The problems such as will not causing environmental pollution.
3rd, compared with magnesium hydroxide and aluminium hydroxide fire retardant, product of the present invention is because the fire retardant utilized is nanometer material Material, grain size very little, specific surface area is very big, and usage amount is relatively low with regard to that can reach good flame retardant effect.
4th, compared with traditional inorganic nano fire retardant, product of the present invention is not the incorporation composite material in the form of blending, But composite material surface is attached in the form of nanometer film, the amount of the nano-meter flame retardants used is very low, helps to reduce product Cost；In addition, product of the present invention will not cause material mechanical performance to deteriorate because of the poor compatibility with bamboo fibre and plastics.
The present invention is main material production bamboo-plastic composite material using bamboo powder and high density polyethylene (HDPE), can also use wood The plant sources fiber and polypropylene, polyvinyl chloride etc. such as powder, agricultural crop straw powder plastics are main material production composite material.
Specific embodiment
A kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, includes the following steps：
1）20-30 parts of bamboo powders are crossed into 100-150 mesh sieve, dry 18-24h, then adds in bamboo powder weight 2-4% at 90-110 DEG C Silane coupling agent, be stirred to react 3-5h in 80-90 DEG C, then proceed to stirring and be cooled to room temperature, obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 60-100 parts of high density polyethylene (HDPE)s, 1-3 parts of azodicarbonamides, 8-12 parts of second After alkene-vinyl acetate copolymer, 2-8 part polyethylene wax and 1-3 parts of zinc stearate mixing, 10- is stirred at 100-120 DEG C 20 minutes, obtain mixed material；
3）Said mixture material is placed in double screw extruder and is extruded into, 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, Material pressure is 1.5-2.0 MPA, then through mould shape, cooling, traction and cutting, obtains bamboo-plastic composite material；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained To pretreated bamboo-plastic composite material, which makes the hydrolysis of bamboo fibre surface portion so as to be easier absorption polyelectrolyte；
5）H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes：By TiO2Powder is added in 5-10M NaOH solutions, described TiO2Powder and the amount ratio of NaOH solution are 1g:20-25 mL, in N2After 1.5-2.5 h are stirred in atmosphere, by emulsion It pours into reaction kettle, 8-30 h is then reacted at 90-150 DEG C, then reaction kettle is placed under normal temperature condition and is cooled down, remove Upper strata clarification lye obtains reaction intermediate, and the hydrochloric acid solution of 1-1.5mol/L is finally added into intermediate product and stirs acid Change so that the pH value of whole system be maintained at 1.5-3 and continue stir 18-24 h, then filter, collect sediment and spend from Then sediment at 70-80 DEG C is dried at least 24 hours to neutrality, obtains H by sub- water washing2Ti2O5•H2O nanotubes；
6）By 0.2-0.3 parts of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohols Blending constituent dispersion liquid, sonic oscillation 15-25 min, then stirs 1.5-2.5h at normal temperatures, obtains nanotube/γ-aminopropyl Triethoxysilane dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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, obtains the fire-retardant bamboo-plastic composite material of self assembly type.
Embodiment 1
A kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, includes the following steps：
1）25 parts of bamboo powders are crossed into 120 mesh sieve, it is dry at 103 DEG C then to add in the silane coupling agent of bamboo powder weight 3% for 24 hours, in 85 DEG C are stirred to react 4h, then proceed to stirring and are cooled to room temperature, and obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 80 parts of high density polyethylene (HDPE)s, 2 parts of azodicarbonamides, 10 parts of ethylene-acetates After vinyl ester copolymers, 5 parts of polyethylene waxes and 2 parts of zinc stearate mixing, stirred 15 minutes at 110 DEG C, obtain mixed material；
3）Said mixture material is placed in double screw extruder and is extruded into, 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 15 revs/min, material It presses as 1.5MPA, then through mould shape, cooling, traction and cutting, obtains bamboo-plastic composite material；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1.25M, 30 min are impregnated at 70 DEG C, are pre-processed Bamboo-plastic composite material afterwards, the pretreatment make the hydrolysis of bamboo fibre surface portion so as to be easier absorption polyelectrolyte；
5）H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes：By TiO2Powder is added in 7.5M NaOH solutions, in N2Gas After 2 h are stirred in atmosphere, emulsion is poured into reaction kettle, 18 h are then reacted at 120 DEG C, are then placed in reaction kettle It is cooled down under normal temperature condition, removes upper strata clarification lye and obtain reaction intermediate, 1.25mol/L is finally added into intermediate product Hydrochloric acid solution and stir acidification so that the pH value of whole system be maintained at 2.0 and continue stir 20 h, then filter, collect Sediment is simultaneously washed with deionized to neutrality, and then sediment is dried at least 24 hours at 75 DEG C, obtains H2Ti2O5• H2O nanotubes；
6）By 0.2 part of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohol mixing Into dispersion liquid, then 15 min of sonic oscillation stirs 2.5h at normal temperatures, obtain nanotube/gamma-aminopropyl-triethoxy silicon Alkane dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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 3 times in total then in 70 DEG C of drying, obtain certainly Packaging fire-retardant bamboo-plastic composite material.
Embodiment 2
A kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, includes the following steps：
1）20 parts of bamboo powders are sieved with 100 mesh sieve, the silane coupling agent for then adding in bamboo powder weight 2% for 24 hours are dried at 90 DEG C, in 80 DEG C 5h is stirred to react, then proceedes to stirring and be cooled to room temperature, obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 60 parts of high density polyethylene (HDPE)s, 1 part of azodicarbonamide, 8 parts of ethylene-acetate second After enoate copolymer, 2 parts of polyethylene waxes and 1 part of zinc stearate mixing, stirred 20 minutes at 100 DEG C, obtain mixed material；
3）Said mixture material is placed in double screw extruder and is extruded into, 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 revs/min, material It presses as 1.5MPA, then through mould shape, cooling, traction and cutting, obtains bamboo-plastic composite material；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1M, 35 min are impregnated at 65 DEG C, after obtaining pretreatment Bamboo-plastic composite material, the pretreatment make bamboo fibre surface portion hydrolysis so as to be easier absorption polyelectrolyte；
5）H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes：By TiO2Powder is added in 5M NaOH solutions, in N2Atmosphere In be stirred 1.5 h after, emulsion is poured into reaction kettle, 30 h are then reacted at 90 DEG C, are then placed in reaction kettle It is cooled down under normal temperature condition, removes upper strata clarification lye and obtain reaction intermediate, finally add 1mol/L's into intermediate product Hydrochloric acid solution simultaneously stirs acidification so that the pH value of whole system is maintained at 1.5 and continues to stir 18 h, then filters, and it is heavy to collect Starch is simultaneously washed with deionized to neutrality, and then sediment is dried at least 24 hours at 70 DEG C, obtains H2Ti2O5•H2O Nanotube；
6）By 0.3 part of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohol mixing Into dispersion liquid, then 25 min of sonic oscillation stirs 1.5h at normal temperatures, obtain nanotube/gamma-aminopropyl-triethoxy silicon Alkane dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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 75 DEG C of drying, obtain certainly Packaging fire-retardant bamboo-plastic composite material.
Embodiment 3
A kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, includes the following steps：
1）30 parts of bamboo powders are crossed into 150 mesh sieve, the silane coupling agent of dry 18h, then addition bamboo powder weight 4% at 110 DEG C, in 90 DEG C are stirred to react 3h, then proceed to stirring and are cooled to room temperature, and obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 100 parts of high density polyethylene (HDPE)s, 3 parts of azodicarbonamides, 12 parts of ethylene-acetates After vinyl ester copolymers, 8 parts of polyethylene waxes and 3 parts of zinc stearate mixing, stirred 10 minutes at 120 DEG C, obtain mixture Material；
3）Said mixture material is placed in double screw extruder and is extruded into, 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 15 revs/min, material It presses as 2.0 MPA, then through mould shape, cooling, traction and cutting, obtains bamboo-plastic composite material；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1.5M, 25min is impregnated at 75 DEG C, after obtaining pretreatment Bamboo-plastic composite material, the pretreatment make bamboo fibre surface portion hydrolysis so as to be easier absorption polyelectrolyte；
5）H is prepared by hydrothermal synthesis method2Ti2O5•H2O nanotubes：By TiO2Powder is added in 10M NaOH solutions, in N2Atmosphere In be stirred 2.5 h after, emulsion is poured into reaction kettle, 8 h are then reacted at 150 DEG C, are then placed in reaction kettle It is cooled down under normal temperature condition, removes upper strata clarification lye and obtain reaction intermediate, 1.5mol/L is finally added into intermediate product Hydrochloric acid solution and stir acidification so that the pH value of whole system is maintained at 3 and continues to stir 24 h, then filters, it is heavy to collect Starch is simultaneously washed with deionized to neutrality, and then sediment is dried at least 24 hours at 80 DEG C, obtains H2Ti2O5•H2O Nanotube；
6）By 0.25 part of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohol mixing Into dispersion liquid, then 20 min of sonic oscillation stirs 2 h, obtains nanotube/gamma-aminopropyl-triethoxy-silane at normal temperatures Dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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, in total alternate immersion 5, then in 80 DEG C of drying, obtains from group The fire-retardant bamboo-plastic composite material of dress type.

Claims (10)

1. a kind of preparation method of the fire-retardant bamboo-plastic composite material of self assembly type, it is characterised in that：It includes the following steps：
1）20-30 parts of bamboo powders are crossed into 100-150 mesh sieve, it is dry, the silane coupling agent of bamboo powder weight 2-4% is then added in, in 80- 90 DEG C are stirred to react 3-5h, are subsequently cooled to room temperature, obtain modified bamboo powder；
2）By step 1）Obtained modification bamboo powder, 60-100 parts of high density polyethylene (HDPE)s, 1-3 parts of azodicarbonamides, 8-12 parts of second After alkene-vinyl acetate copolymer, 2-8 part polyethylene wax and 1-3 parts of zinc stearate mixing, 10- is stirred at 100-120 DEG C 20 minutes, obtain mixed material；
3）Said mixture material is placed in extrusion molding in double screw extruder, obtains bamboo-plastic composite material；
4）Above-mentioned bamboo-plastic composite material is positioned in the NaOH solution of 1-1.5M, 25-35 min are impregnated at 65-75 DEG C, are obtained To pretreated bamboo-plastic composite material；
5）Prepare H2Ti2O5•H2O nanotubes：By TiO2Powder is added in NaOH solution, in N21.5-2.5 is stirred in atmosphere After h, emulsion is poured into reaction kettle, 8-30 h are then reacted at 90-150 DEG C, are then cooled down reaction kettle, in removing Layer clear liquid obtains reaction intermediate, and acid solution is finally added into intermediate product and stirs acidification so that the pH value of whole system It 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 will Drying precipitate obtains H2Ti2O5•H2O nanotubes；
6）By 0.2-0.3 parts of H2Ti2O5•H2O nanotubes, 0.5 part of gamma-aminopropyl-triethoxy-silane and 9 parts of absolute ethyl alcohols mix Dispersion liquid is synthesized, sonic oscillation 15-25 min obtain nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid；
7）By step 4）Pretreated bamboo-plastic composite material 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 self assembly type Fire-retardant bamboo-plastic composite material.
2. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that：Step Rapid 1）, the bamboo powder dry 18-24h at 90-110 DEG C.
3. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that： 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, and 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 fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that： Step 5）, the TiO2Powder and the amount ratio of NaOH solution are 1g:20-25 mL.
5. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that：Step Rapid 5）, a concentration of 5-10M of the NaOH solution.
6. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that：Step Rapid 5）, the acid solution is the hydrochloric acid solution of 1-1.5mol/L.
7. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 3, it is characterised in that：Step It is rapid 5), the sediment is dry at least 24 hours at 70-80 DEG C.
8. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that：Step Rapid 7）, the bamboo-plastic composite material is in nanotube/gamma-aminopropyl-triethoxy-silane dispersion liquid and kayexalate solution The number of middle alternate immersion is 3-10 times.
9. a kind of preparation method of fire-retardant bamboo-plastic composite material of self assembly type according to claim 1, it is characterised in that： Step 7）, 15-20 min are washed with deionized after each immersion of the bamboo-plastic composite material and are impregnated next time again.
10. the fire-retardant bamboo-plastic composite material of self assembly type obtained according to any preparation methods of claim 1-9.
CN201810046113.3A 2018-01-17 2018-01-17 A kind of fire-retardant bamboo-plastic composite material of self assembly type and preparation method thereof Pending CN108192130A (en)

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CN109734987A (en) * 2019-01-15 2019-05-10 广东金特环保股份有限公司 A kind of bamboo fibre microcellular foam material and its manufacturing method
CN115124776A (en) * 2022-05-30 2022-09-30 湖南协成管业科技有限公司 Natural bamboo fiber modified PE or PP composite material and preparation method thereof
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