CN108559197A - A kind of preparation method of weather-proof bamboo-plastic composite material - Google Patents
A kind of preparation method of weather-proof bamboo-plastic composite material Download PDFInfo
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- CN108559197A CN108559197A CN201711363170.6A CN201711363170A CN108559197A CN 108559197 A CN108559197 A CN 108559197A CN 201711363170 A CN201711363170 A CN 201711363170A CN 108559197 A CN108559197 A CN 108559197A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- 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
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The present invention relates to a kind of preparation methods of weather-proof bamboo-plastic composite material, belong to bamboo moulding material technical field.The present invention is by teos hydrolysis and forms Sol-gel Coated to bamboo powder material surface, make the gradual coated filling of bamboo powder material surface groove, shallow trench is filled out negative smooth, effectively reduce contact area and the time of contact of bamboo powder material surface and oxygen, simultaneously because colloidal sol dries out, and the moieties volatilization in gel, the colloidal sol drying shelling of formation is coated, the mechanical property of material is effectively increased；And the present invention passes through teos hydrolysis coating modification, payload of the silicon dioxide gel in bamboo powder material surface, it is effectively combined with polyvinyl chloride, the particles filled amorphous regions in PVC macromolecular chain of inorganic silicon dioxide, reduce the transmission of heat, the thermal decomposition of macromolecular chain is inhibited to a certain extent, to be effectively improved to the heatproof air aging performance of bamboo-plastic composite material, is further modified the weatherability of bamboo-plastic composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of weather-proof bamboo-plastic composite material, belong to bamboo moulding material technical field.
Background technology
Wood plastic composite（It is with plant fiber（Such as wood powder, bamboo powder, sugarcane fishing agriculture and forestry organic waste material）And thermoplastic
（Such as, it is primary raw material, it is a kind of multiple made of the methods of forming such as extrusion, injection molding, molding along with a small amount of additive, auxiliary agent
Condensation material.Its product can be used for replacing natural timber or bamboo wood, for producing furniture, interior/exterior decoration material and Building wood
Material etc..Since wood plastic composite will influence during use after the temperature difference of morning and evening, spring, summer, autumn and winter, use outdoors
It also suffers and long-term expose to the sun and rain and bear different extraneous loads etc..These unavoidable factors in use can be made
It seriously fades at the surface of wood plastic composite, especially some dark materials, the defects of dimensional contraction, these defects are certain
The performance of wood plastic composite is reduced in degree.Bamboo fibre has the good reputation of plant glass fibre, is the carrying knot of bamboo
Structure unit, mechanical property is extremely excellent, has the great potential of manufacture high-performance fiber enhancing composite material.It crosses over more than 20 years,
Bamboo-plastic composite material research is interior at the international level to be carried out extensively.Important components of the BPC as WPC, at long-term family
During outer use, especially in the higher region of some temperature and humidities, the surface of material can fade, cracks, go mouldy
Deng, under serious conditions occur mechanical property failure to influence its normal use.Therefore, the quality of BPC weather resistances is wide to its
General application plays an important role.
Perhaps people have got used to the colour fading of common wood based panel, but in certain application scenarios, wood plastic composite
It fades but very unwelcome.It is especially used for the bed board of exterior finish, with the erosion of sunlight middle-ultraviolet lamp, temperature height to be more
It replaces and rainwater soaks, wood-plastic composite performance appearance color and performance be all hindered.In order to subtract
This few phenomenon, improves the fade resistance of material, uses directly addition modified nanoparticles or will be changed with application technology of spraying
Property nano granule suspension loads to bamboo powder surface, can effectively improve the ageing-resistant performance of bamboo-plastic composite material.However bamboo wood
It is mainly made of bamboo fibre and parenchyma cell, the two structure and chemical composition are there are significant difference so bamboo-plastic combined under how changing
The weather resistance of material is particularly important.
Invention content
The technical problems to be solved by the invention：Easy generation weather stain and weather resistance for bamboo-plastic composite material compared with
The problem of difference, provides a kind of preparation method of weather-proof bamboo-plastic composite material.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
（1）Take moso bamboo and clean dry, air-flow crushing is simultaneously ground up, sieved, and obtains abrasive flour and drying, obtain dry bamboo powder, then by
Mass ratio 1:1, dry bamboo powder is stirred with silane resin acceptor kh-550 ethanol solution, standing is cooled to room temperature, and obtains modification
Bamboo powder and vacuum freeze drying must dry modified bamboo powder；
（2）In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, matrix liquid is stirred to obtain, matrix liquid is set
In conical flask, 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, after being added dropwise to complete, insulation reaction, standing is cooled to
Room temperature obtains modified gel liquid；
（3）In mass ratio 1:10, soybean protein and deionized water are stirred, pH to 6.0~6.5 is adjusted, obtains mixed liquor, it will
Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid, in mass ratio 1：
1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray-drying installation, is spray-dried, collects
Dry particle；
（4）It counts in parts by weight, weighs 45~50 parts of polyvinyl chloride, 10~15 parts of dry particles, 3~5 parts of polyvinyl chloride respectively
Heat stabilizer C-101, nano-calcium carbonate and 2~3 parts of alumina silicate are placed in double screw extruder, extrusion process, collect extruded stock
And compression moulding, you can be prepared into a kind of weather-proof bamboo-plastic composite material.
Step（3）The pepsin additive amount is 50U/g.
Step（3）Inlet temperature is 85~90 DEG C to the spray drying condition in order to control, and outlet temperature is 55~60 DEG C,
Inlet amount is 15mL/min.
Step（4）The double screw extruder extrusion process temperature is 165~170 DEG C.
Compared with other methods, advantageous effects are the present invention：
（1）The present invention is by teos hydrolysis and forms Sol-gel Coated to bamboo powder material surface, makes bamboo powder material surface ditch
Slot gradual coated filling, shallow trench are filled out negative smooth, effectively reduce bamboo powder material surface and the contact area of oxygen and contact
Time, simultaneously because colloidal sol dry out and gel in moieties volatilization, coat formation colloidal sol drying shelling, have
Effect improves the mechanical property of material；
（2）The present invention forms silicon dioxide gel by teos hydrolysis and is loaded to bamboo powder particle surface and and polyvinyl chloride
Effectively compound and coating modification effect is formed, at this moment since silicon dioxide gel is in the payload of bamboo powder material surface, with
Polyvinyl chloride effectively combines, at this moment the particles filled nothing in PVC macromolecular chain of the inorganic silicon dioxide of better stability
Sizing region, can partly reduce the transmission of heat, inhibit the thermal decomposition of macromolecular chain to a certain extent, multiple to be moulded to bamboo
The heatproof air aging performance of condensation material effectively improves, further the weatherability of modified bamboo-plastic composite material.
Specific implementation mode
It takes moso bamboo and cleans and dry, air-flow crushing and ground 200 mesh sieve, and obtain abrasive flour and are placed at 35~40 DEG C and do
It is dry to moisture content be 20%, obtain dry bamboo powder, then in mass ratio 1:1, dry bamboo powder and mass fraction 10% is silane coupled
Agent KH-550 ethanol solutions, which are placed at 100 DEG C, is stirred 10~15min, and standing is cooled to room temperature, and obtains modified bamboo powder and vacuum
Freeze-drying must dry modified bamboo powder；In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, is stirred
Matrix liquid is placed in conical flask by matrix liquid, and 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, and speed is added dropwise in control hydrochloric acid
Rate is 2mL/min, and after being added dropwise to complete, then 25~30min of insulation reaction at 45~55 DEG C, standing are cooled to room temperature, and must be changed
Property coagulant liquid；In mass ratio 1:10, soybean protein and deionized water are stirred, pH to 6.0~6.5 is adjusted with glacial acetic acid,
It obtains mixed liquor pepsin is added in mixed liquor by enzyme additive amount 50U/g, after heat preservation enzymolysis, heating is boiled, and is stood cold
But to room temperature, enzymolysis liquid, in mass ratio 1 are obtained：1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray
In mist drying device, control inlet temperature is 85~90 DEG C, and outlet temperature is 55~60 DEG C, inlet amount 15mL/min, to be painted
After the completion of mist drying, dry particle is collected to obtain；Count in parts by weight, weigh respectively 45~50 parts of polyvinyl chloride, 10~15 parts it is dry
Dry particle, 3~5 parts of polychloroethylene heat stabilizer C-101, nano-calcium carbonate and 2~3 parts of alumina silicate are placed in double screw extruder
In, 10~15min of extrusion process at 165~170 DEG C, control rotor speed is 55~60r/min, after the completion of to be extruded, is received
Collection extruded stock is placed in compression moulding on 165~170,5~10MPa hot presses, you can is prepared into a kind of weather-proof bamboo-plastic combined
Material.
Example 1
It takes moso bamboo and cleans and dry, air-flow crushing and ground 200 mesh sieve, and obtain abrasive flour and are placed at 35 DEG C and dry to aqueous
Rate is 20%, obtains dry bamboo powder, then in mass ratio 1:1, by dry bamboo powder and 10% silane resin acceptor kh-550 of mass fraction
Ethanol solution, which is placed at 100 DEG C, is stirred 10min, and standing is cooled to room temperature, and obtains modified bamboo powder and vacuum freeze drying, obtains dry
Dry modified bamboo powder；In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, matrix liquid is stirred to obtain, by matrix
Liquid is placed in conical flask, and 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, and control hydrochloric acid drop rate is 2mL/min, is waited for
After being added dropwise to complete, then the insulation reaction 25min at 45 DEG C, standing are cooled to room temperature, and obtain modified gel liquid；In mass ratio 1:10,
Soybean protein and deionized water are stirred, pH to 6.0 is adjusted with glacial acetic acid, obtains mixed liquor, it, will by enzyme additive amount 50U/g
Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid, in mass ratio 1：
1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray-drying installation, control inlet temperature is
85 DEG C, outlet temperature is 55 DEG C, inlet amount 15mL/min, after the completion of to be spray dried, collects to obtain dry particle；By weight
Number meter, weighs 45 parts of polyvinyl chloride, 10 parts of dry particles, 3 parts of polychloroethylene heat stabilizer C-101, nano-calcium carbonate and 2 respectively
Part alumina silicate is placed in double screw extruder, and the extrusion process 10min at 165 DEG C, control rotor speed is 55r/min, waits squeezing
It after the completion of going out, collects extruded stock and is placed in compression moulding on 165,5MPa hot presses, you can it is multiple to be prepared into a kind of weather-proof bamboo modeling
Condensation material.
Example 2
It takes moso bamboo and cleans and dry, air-flow crushing and ground 200 mesh sieve, and obtain abrasive flour and are placed at 37 DEG C and dry to aqueous
Rate is 20%, obtains dry bamboo powder, then in mass ratio 1:1, by dry bamboo powder and 10% silane resin acceptor kh-550 of mass fraction
Ethanol solution, which is placed at 100 DEG C, is stirred 12min, and standing is cooled to room temperature, and obtains modified bamboo powder and vacuum freeze drying, obtains dry
Dry modified bamboo powder；In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, matrix liquid is stirred to obtain, by matrix
Liquid is placed in conical flask, and 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, and control hydrochloric acid drop rate is 2mL/min, is waited for
After being added dropwise to complete, then the insulation reaction 27min at 47 DEG C, standing are cooled to room temperature, and obtain modified gel liquid；In mass ratio 1:10,
Soybean protein and deionized water are stirred, pH to 6.2 is adjusted with glacial acetic acid, obtains mixed liquor, it, will by enzyme additive amount 50U/g
Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid, in mass ratio 1：
1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray-drying installation, control inlet temperature is
87 DEG C, outlet temperature is 57 DEG C, inlet amount 15mL/min, after the completion of to be spray dried, collects to obtain dry particle；By weight
Number meter, weighs 47 parts of polyvinyl chloride, 12 parts of dry particles, 4 parts of polychloroethylene heat stabilizer C-101, nano-calcium carbonate and 2 respectively
Part alumina silicate is placed in double screw extruder, and the extrusion process 12min at 167 DEG C, control rotor speed is 57r/min, waits squeezing
It after the completion of going out, collects extruded stock and is placed in compression moulding on 167,7MPa hot presses, you can it is multiple to be prepared into a kind of weather-proof bamboo modeling
Condensation material.
Example 3
It takes moso bamboo and cleans and dry, air-flow crushing and ground 200 mesh sieve, and obtain abrasive flour and are placed at 40 DEG C and dry to aqueous
Rate is 20%, obtains dry bamboo powder, then in mass ratio 1:1, by dry bamboo powder and 10% silane resin acceptor kh-550 of mass fraction
Ethanol solution, which is placed at 100 DEG C, is stirred 15min, and standing is cooled to room temperature, and obtains modified bamboo powder and vacuum freeze drying, obtains dry
Dry modified bamboo powder；In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, matrix liquid is stirred to obtain, by matrix
Liquid is placed in conical flask, and 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, and control hydrochloric acid drop rate is 2mL/min, is waited for
After being added dropwise to complete, then the insulation reaction 30min at 55 DEG C, standing are cooled to room temperature, and obtain modified gel liquid；In mass ratio 1:10,
Soybean protein and deionized water are stirred, pH to 6.5 is adjusted with glacial acetic acid, obtains mixed liquor, it, will by enzyme additive amount 50U/g
Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid, in mass ratio 1：
1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray-drying installation, control inlet temperature is
90 DEG C, outlet temperature is 60 DEG C, inlet amount 15mL/min, after the completion of to be spray dried, collects to obtain dry particle；By weight
Number meter, weighs 50 parts of polyvinyl chloride, 15 parts of dry particles, 5 parts of polychloroethylene heat stabilizer C-101, nano-calcium carbonate and 3 respectively
Part alumina silicate is placed in double screw extruder, and the extrusion process 15min at 170 DEG C, control rotor speed is 60r/min, waits squeezing
It after the completion of going out, collects extruded stock and is placed in compression moulding on 170,10MPa hot presses, you can it is multiple to be prepared into a kind of weather-proof bamboo modeling
Condensation material.
Sample preparation：Using German LeicaSM2000 types slip slice BPC planks thickness direction cut this hair preparation
Bamboo-plastic composite material, thickness is 250 μm or so of thin slice.The size of each sample is 4.5mm × 3.5mm × 0.3mm, quality
For 8mg or so.It is preserved in 103 ± 2 °C of dry 4h for use.
By sample after xenon lamp accelerated ageing 100h, surface color is held essentially constant.Xenon lamp accelerated ageing 200h, contains
The surfaces BPC of organic light stabilizer GW-327 and business nano-ZnO are seriously faded.And example 1 prepared by the present invention, 2,3 through xenon
Just there is significant discolouration phenomena in lamp accelerated ageing 300h, and it is excellent weather-proof to illustrate that the bamboo-plastic composite material for preparing of the present invention has
Performance.
Claims (4)
1. a kind of preparation method of weather-proof bamboo-plastic composite material, it is characterised in that specifically preparation process is：
（1）Take moso bamboo and clean dry, air-flow crushing is simultaneously ground up, sieved, and obtains abrasive flour and drying, obtain dry bamboo powder, then by
Mass ratio 1:1, dry bamboo powder is stirred with silane resin acceptor kh-550 ethanol solution, standing is cooled to room temperature, and obtains modification
Bamboo powder and vacuum freeze drying must dry modified bamboo powder；
（2）In mass ratio 1:10, ethyl orthosilicate is added in absolute ethyl alcohol, matrix liquid is stirred to obtain, matrix liquid is set
In conical flask, 1% hydrochloric acid of mass fraction is added dropwise in matrix liquid, after being added dropwise to complete, insulation reaction, standing is cooled to
Room temperature obtains modified gel liquid；
（3）In mass ratio 1:10, soybean protein and deionized water are stirred, pH to 6.0~6.5 is adjusted, obtains mixed liquor, it will
Pepsin is added in mixed liquor, and after heat preservation enzymolysis, heating is boiled, and standing is cooled to room temperature, and obtains enzymolysis liquid, in mass ratio 1：
1：1, dry modified bamboo powder, enzymolysis liquid and coagulant liquid are stirred and are placed in spray-drying installation, is spray-dried, collects
Dry particle；
（4）It counts in parts by weight, weighs 45~50 parts of polyvinyl chloride, 10~15 parts of dry particles, 3~5 parts of polyvinyl chloride respectively
Heat stabilizer C-101, nano-calcium carbonate and 2~3 parts of alumina silicate are placed in double screw extruder, extrusion process, collect extruded stock
And compression moulding, you can be prepared into a kind of weather-proof bamboo-plastic composite material.
2. a kind of preparation method of weather-proof bamboo-plastic composite material according to claim 1, it is characterised in that：Step（3）
The pepsin additive amount is 50U/g.
3. a kind of preparation method of weather-proof bamboo-plastic composite material according to claim 1, it is characterised in that：Step（3）
Inlet temperature is 85~90 DEG C to the spray drying condition in order to control, and outlet temperature is 55~60 DEG C, inlet amount 15mL/
min。
4. a kind of preparation method of weather-proof bamboo-plastic composite material according to claim 1, it is characterised in that：Step（4）
The double screw extruder extrusion process temperature is 165~170 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535585A (en) * | 2018-10-10 | 2019-03-29 | 安徽省科晟生态木装饰材料有限公司 | A kind of bamboo carbon fibre reinforced resin material |
| CN111635599A (en) * | 2020-05-28 | 2020-09-08 | 宁德市缔锋新材料科技有限公司 | Preparation method of bamboo-plastic composite material |
| CN113954278A (en) * | 2021-09-23 | 2022-01-21 | 界首市汇珠渔具有限公司 | Production process of bamboo-plastic fishing rod |
| CN114736491A (en) * | 2022-03-10 | 2022-07-12 | 江苏景宏新材料科技有限公司 | Degradable heat shrinkable film, degradable heat shrinkable multilayer film and preparation method thereof |
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| CN103087400A (en) * | 2011-10-27 | 2013-05-08 | 上海杰事杰新材料(集团)股份有限公司 | Wood-plastic composite material and preparation method thereof |
| CN103319818A (en) * | 2013-07-16 | 2013-09-25 | 福建剑源木塑科技有限公司 | Preparation method of polyvinyl chloride bamboo-plastic product produced by utilization of bamboo powder |
| CN104086920A (en) * | 2014-07-18 | 2014-10-08 | 东北林业大学 | Flame-retardant smoke-suppression type PVC-based wood-plastic composite material and preparation method thereof |
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| DE4408855A1 (en) * | 1994-03-16 | 1995-09-21 | Rawema Industrieanlagen Gmbh | Solid or foamed plastic using biomass as filler |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535585A (en) * | 2018-10-10 | 2019-03-29 | 安徽省科晟生态木装饰材料有限公司 | A kind of bamboo carbon fibre reinforced resin material |
| CN111635599A (en) * | 2020-05-28 | 2020-09-08 | 宁德市缔锋新材料科技有限公司 | Preparation method of bamboo-plastic composite material |
| CN113954278A (en) * | 2021-09-23 | 2022-01-21 | 界首市汇珠渔具有限公司 | Production process of bamboo-plastic fishing rod |
| CN113954278B (en) * | 2021-09-23 | 2023-08-11 | 界首市汇珠渔具有限公司 | Production process of bamboo-plastic fishing rod |
| CN114736491A (en) * | 2022-03-10 | 2022-07-12 | 江苏景宏新材料科技有限公司 | Degradable heat shrinkable film, degradable heat shrinkable multilayer film and preparation method thereof |
| CN114736491B (en) * | 2022-03-10 | 2023-10-13 | 江苏景宏新材料科技有限公司 | Degradable heat-shrinkable film, degradable heat-shrinkable multilayer film and preparation method thereof |
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