CN104497471B - A kind of method that subcritical water extrusion prepares wood plastic composite - Google Patents
A kind of method that subcritical water extrusion prepares wood plastic composite Download PDFInfo
- Publication number
- CN104497471B CN104497471B CN201410697662.9A CN201410697662A CN104497471B CN 104497471 B CN104497471 B CN 104497471B CN 201410697662 A CN201410697662 A CN 201410697662A CN 104497471 B CN104497471 B CN 104497471B
- Authority
- CN
- China
- Prior art keywords
- wood
- extrusion
- reaction
- plastic composite
- subcritical water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of method that subcritical water extrusion prepares wood plastic composite, belong to high polymer material Reaction extrusion research field.Thermoplastic macromolecule material that reactant gross mass percentage composition is 40%~80% will be accounted for, wood powder that reactant gross mass percentage composition is 60%~15% is accounted for and accounts for the interfacial reaction auxiliary agent that reactant gross mass is 0%~10% and mix, mixture carries out melting extrusion blending reaction in the double screw extruder with subcritical water extrusion reaction condition and certain rotating speed, product is extruded through cooling down, granulating, dry, then through mill mill, tabletting, wood plastic composite is made.The present invention is the further improvement on the basis of original twin-screw extrusion blending method prepares wood plastic composite.The present invention further enhances the reaction of plastics and wood-fibred surface, and blending and course of reaction are easy to control, and yield is high, energy consumption is low, pollution is small, be easy to scale, obtained wood plastic composite excellent in mechanical performance.
Description
Technical field
The invention belongs to high polymer material Reaction extrusion research field, it is related to a kind of subcritical water extrusion preparation wood moulding and answers
The method of condensation material；It is further changing of being carried out on the basis of original twin-screw extrusion blending method prepares wood plastic composite
Enter, i.e., melt blending is carried out in the double screw extruder with subcritical water extrusion reaction condition and certain screw speed and is squeezed
Go out reaction.
Technical background
Timber is unique reproducible material in four big raw material (timber, cement, steel, plastics) in the world, while again
It is Ecosystem environmental protection material.Society is more and more for the demand of Wood products, but timber resources is mainly derived from the forest reserves,
With the development of modern social economy, society also increasingly payes attention to the ecological functions of the forest reserves, and which results in timber money
The anxiety in source, so the utilization rate and reuse ratio that improve timber just seem particularly significant.
With a large amount of consumption gone from bad to worse with petroleum resources of environment, renewable resource string is being lived and produced
The research of middle application is received more and more attention, and degradable plant fiber is used as into the filler of composite not only
Living resources can be made rationally to be applied, can also make the usage amount of the non-renewable petroleum resources of reduction.Wood plastic composite is one
Plant without using any toxic chemical substance and durable in use, environmental protection composite, with water-fast, corrosion-resistant, mechanical property
The features such as energy and dimensional stability are good.
But wood plastic composite also has some technical problems during preparation, because wood fibre is in
Now stronger polarity, and polymer is presented nonpolar, the difference between both polarity causes the compatibility between two kinds of materials
It is poor, interface is generally occurred in when material is destroyed, therefore the improvement of interface compatibility and interface adhesion is to improve wood
The key of plastic composite materials mechanical property.
The fine structure of woody plant cells includes fiber, conduit, parenchyma cell etc..Its structure is that research xylplant is fine
The key of dimension.Microfibre is the most basic unit for constituting cellulose cell wall skeleton, and hemicellulose, lignin are then fine
" filler " and " adhesive " between fiber (and fiber).During being pre-processed to string these " fillers "
" adhesive " will partly or entirely be dissolved, will be loose between microfibre so that the microfibre in plant cell
It is exposed.It is more thorough that these " fillers " and " adhesive " dissolve, and it is more clear that its microfibre exposes.
In the recombination process of wood plastic composite, because most of thermoplastic is nonpolar, with hydrophobicity
Group, and wood-fibred surface has the functional groups such as substantial amounts of polar hydroxyl groups and phenolic hydroxyl group, and these groups have very strong
Hydrophily, so, the fusion between interface is difficult to realize between timber and plastics.Furthermore, due to being readily formed between hydroxyl
Hydrogen bond so that there is very strong Hyarogen-bonding between wood-fibred, cause scattered inequality of the wood-fibred in thermoplastic.
Wood plastic composite is that the thermoplasticity that wood-fibred disperses as dispersed phase using thermoplastic as continuous phase is answered
Interface between condensation material, two-phase is combined into an entirety often through the method for physics or chemistry, make its simultaneously with
The characteristic of timber and plastics.The physical modification method of enhancing wood plastic composite interface binding power mainly has：Heat treating process, radiation
The methods such as facture, surface-discharge processing, steam gas explosion method.Physical treatment method is although simple and practical, but effect but differs
It is fixed obvious.Chemical method is then that the hydroxy number of wood surface is reduced by chemically reacting, reduction polymer and wood surface
Between the effect of repelling each other, improve the bonding force at interface, or can be set up physically or chemically between wood-fibred and polymer
The combination of key.Main method has：Compatilizer method, modification by coupling, surface grafting method, etherificate, acetylation etc..Wherein modification by coupling
It is a kind of relatively effective method.
Heat treating process is the processing most common processing method of wood fibre.Modification and preceding place for wood plant fibre
Contain in reason, wood fibre and combine water and free water, this is unfavorable to recombination process, is lost in Blending Processes due to the rise of temperature
Water, so as to produce space and internal defect in the composite.The hydroxyl on wood-fibred surface can be caused by heat treatment
Content decreases, and is conducive to the bonding of wood-fibred and polymeric matrix.But can also make cell wall structure unstable, and it is high
Temperature can make string occur anisotropic shrinkage, rupture the destruction for resulting even in cell membrane.So for different types of
The temperature for the heat treatment that wood-fibred is used also is differed.
Radiation treatment method be it is a kind of by outside energy come so that the technology favorably changed occurs in structure for material.Using
Gamma radiation source is radiated, and before processing need to add some additives, can so obtain more preferable treatment effect.
Discharge process method includes cold plasma discharge, corona discharge, sputtering discharge etc..Cold plasma discharge processing master
Free radical is triggered to produce the effect such as polymerization, chemical modification.Sputtering discharge processing mainly causes the change in terms of timberphysics,
Roughness increase on such as surface etc., to strengthen the adhesive property between interface.The effect of Corona discharge Treatment is mainly raising
The surface energy of high polymer material, improves the compatibility with fiber molecule surface.
Alkali process is a kind of processing method of traditional chemical modification wood-fibred, is widely used in very much the table of natural fiber
Face is handled, and typically uses the sodium hydroxide solution of low concentration.Alkali process can dissolve the pectin of fiber surface, half fibre
Dimension, lignin and some other low molecule impurity, but not change the chemical constitution of cellulose, it can make it that fiber surface is coarse,
Enhance and surface is effectively contacted between plastic substrate.But alkali pretreatment require appointed condition it is more harsh, than if desired for
Stainless steel, corrosion resistant equipment, while needing to consume substantial amounts of alkali so that operating cost is greatly increased.
There is commonly used acid in acid treatment：Sulfuric acid, acetic acid, hydrochloric acid etc..Concentrated acid can make cellulose effectively be degraded,
But acid, it is necessary to special consersion unit, and needs to design preferable recovery process with corrosivity and toxicity.Although diluted acid is located in advance
Reason has solved some drawbacks of strong acid treatment, but the subsequent technique of its acid treatment is not only time-consuming but also energy consumption is big, economy effect
Beneficial low, environmental pollution is serious.
Surface grafting method is that alkenes organic monomer is grafted into wood-fibred surface to bond between wood-fibred and polymer to increase
A kind of method of property.The polymer of some vinyl monomers on lignose surface grafting, can improve the suction of timber well
Wellability, cohesive aqueous and its with plastic material.
Steam gas explosion method is a kind of physical modification method of relatively new wood fibre, and its processing procedure is discarded without reclaiming
The problem of thing, there is high efficiency, high intensity, low energy consumption, low stain, low cost.It can destroy again in fiber simultaneously
Part xylan, to separating halfway lignin formation catabolite.It is by causing the change of wood fibre microstructure
So that the cell membrane of xylplant ruptures, the hemicellulose in string can be removed, so that in string
Microfibre content increase, specific surface area increase.Meanwhile, gas explosion method can remove water-soluble substances and tree in string
Lipid material, so as to change the microstructure and chemical reactivity of fiber.
Gas explosion method is usually under 0.69~4.83MPa pressure, fiber to be heated into 160~260 DEG C with steam, then
Normal pressure is decompressed in even several seconds a few minutes suddenly so that the gas in the instant water vaporization in cell, space is swollen rapidly
It is swollen, generate " explosion " effect so that part lignin is separated, destroy the protection of lignin and hemicellulose to cellulose and make
With so that cellulosic molecule is exposed, and is conducive to the interaction of wood-fibred and thermoplastic.
Super/subcritical fluids have a physical and chemical performance of uniqueness, such as excellent solvability, higher ion concentration,
Relatively low viscosity, higher diffusion coefficient and heat transfer coefficient.Super/subcritical fluids mainly include：The compound of water, alcohols
(methanol, ethanol, propyl alcohol), CO2Super/subcritical state Deng, these materials reported be used for biomass liquefying, handle organic
Waste water, solid refuse, waste old etc., are widely used.
Cansell F etc. are by the research to supercritical water, and the performance to the water of critical zone has carried out specific description, recognized
It is a kind of in critical zone physics, a kind of adjustable fluid of chemical property for water, with huge potentiality, and is a kind of environment
Friendly reaction medium.The density of supercritical water can increased dramatically with the rise of pressure, it is possible to increase the solvation energy of water
Power, can strengthen the dissolubility to biomass material.Masaru Watanabe etc. summarize organic matter in super/subcritical water
Response characteristic, the property such as ionic product, the dielectric constant of water can also connect with the change of the external conditions such as temperature, pressure
Continuous change, so, super/subcritical water is not only good reaction medium and solvent, or soda acid co-catalyst.Cellulose,
Under conditions of super/subcritical water different degrees of hydrolysis can occur for hemicellulose and lignin etc..
The content of the invention
A kind of subcritical water extrusion preparation wood moulding is provided and answered the invention aims to improve the deficiencies in the prior art
The method of condensation material.
The technical scheme is that：Wood plastic composite method is prepared in original double screw extruder melt blending
On the basis of, by now with wood and plastic composite preparation method for material be swelled with subcritical water, gas explosion handles the method for wood powder and is combined,
Propose in subcritical water as under solvent and reaction-ability medium existence condition, melting extrusion is carried out to wood powder and thermoplastic and is total to
Mixed reaction so that the lignin and hemicellulose material on wood powder surface can be partly dissolved or liquefy, and to microfibre therein
Formation is swelled and separated, so as to improve thermoplastic and the interfacial reaction of microfibre in wood powder, improve interface binding power, carry
The mechanical property of high wood plastic composite.
The present invention concrete technical scheme be：A kind of method that subcritical water extrusion prepares wood plastic composite, its is specific
Step is：
A. by account for reactant gross mass percentage composition be 40%~80% thermoplastic macromolecule material, account for reaction-ure mixture
Wood powder that percentage composition is 15%~60% and account for the interfacial reaction reagent that reaction-ure mixture is 0%~10% and mix；
B., said mixture is added to melting extrusion in the double screw extruder of certain rotating speed in the lump, while in twin-screw
Injection water in the middle part of the machine barrel of extruder, makes its melting extrusion Blending Processes be under the state of subcritical water；
C. reaction product deviates from volatile matter through vacuum, cools down, granulates, dries, and then through mill mill, tabletting, is made
Wood plastic composite.
It is preferred that described thermoplastic macromolecule material is ABS (acrylonitrile-butadiene-styrene copolymer), PS, AS, PE
At least one of or PP.
It is preferred that above-mentioned wood powder is one kind in Eucalyptus wood powder or poplar wood powder, bamboo powder etc. can also be used；The size of wood powder
Size is generally 40 mesh between 120 mesh.
It is preferred that above-mentioned interfacial reaction reagent is：Silane coupling agent, maleic anhydride, stearic acid, maleic anhydride grafting
ABS, maleic anhydride grafting PS, maleic anhydride grafting AS or maleic anhydride graft PP, maleic anhydride are grafted any one in PE.
It is preferred that the melting extrusion reaction temperature in above-mentioned step B is 150~260 DEG C；It is preferred that described certain in the same direction
The screw speed of double screw extruder is 50~200r/min.
It is preferred that the condition of melting extrusion Blending Processes Subcritical water is in above-mentioned steps B：150~260 DEG C of temperature；Typically
Pressure 0.4MPa~3.7MPa of subcritical water.
Melting extrusion reaction prepare wood plastic composite technological process and extruder screw rod structure figure referring to Fig. 1 and Fig. 2.
This experiment screw extruder used is co-rotating twin screw extruder group of the second order to quadravalence, by conveying screwing element, is pinched
Close screwing element, compression screwing element and left-hand thread element mixing composition, when subcritical water extrusion reaction is operated, B inlets
It is connected with microprocessor pump drive and pressure gauge.The control of extruder reaction temperature is in 150~260 DEG C, the control of extruder screw rotating speed
In 50rpm~200rpm；The mixture of wood powder and thermoplastic is added by C charge doors, is injected while being measured in B inlets
Water, speed and the reaction temperature control that inlet pressure is injected by water；Reaction product is opened through cooling, granulation and then through mill
White silk, cooling, tabletting, are made wood plastic composite.
Beneficial effect：
1. with it is simple wood plastic composite prepared using double screw extruder compared with, due to subcritical water as solvent and
The presence of reaction medium, reduces the viscosity of reaction system, enhances the molten of water ion and hemicellulose in wood powder and lignin
Solution, reaction, promote its microfibre to be swelled and reacted with interfacial reaction reagent or plastics continuous phase, enhance wood moulding and answer
The interface binding power of condensation material, improves the material mechanical performance of wood plastic composite.
2. compared with steam gas explosion method, due to being carried out in the double screw extruder of continous way, will extrusion blending with
Promote interfacial reaction to become one, technical process serialization, yield are high, energy consumption is low, be easy to maximization, scale.
3. extrusion blending, interfacial reaction degree and sub-critical water extraction can be according to screw speed, screw slenderness ratio, screw rods
Structure combining form and reaction temperature are controlled, and process conditions are easy to optimization, and the wood moulding that can obtain higher force performance is answered
Condensation material.
4. compared with method of chemical treatment, the inventive method aftertreatment technology is simple, operator's labor intensity is small, contact
Pollution less, environmental pollution it is low.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is capital equipment of the invention：- 20mm Assembled Twin Screw Extruder Screw figure；Wherein A discharges for gas
Mouthful, B is water inlet, and C is charge door；
Fig. 3 is influence of the blending temperature to ABS/ wood flour composite material tensile strengths；
Fig. 4 is influence of the blending temperature to ABS/ wood flour composite material bending strengths；
Fig. 5 is influence of the blending temperature to ABS/ wood flour composite material notch impact strengths；
Fig. 6 is influence of the blending temperature to ABS/ wood flour composite material unnotched impact strengths；
Fig. 7 is the infrared spectrogram of ABS/ wood flour composite material acetone extraction things：1-pure wood powder；2-embodiment 1, blending
180 DEG C of subcritical water extrusions of thing；3-embodiment 1,200 DEG C of subcritical water extrusions of blend；4-embodiment 2,200 DEG C of blend
Subcritical water extrusion (contains MABS)；
Fig. 8 is ABS/ wood plastic composite sample section SEM photographs：A- comparative examples 1；B- embodiments 1；C- comparative examples 2；d-
Comparative example 6；E- embodiments 2；2 blend of f- embodiments, 200 DEG C of extrusions.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to be pointed out that embodiment is served only for this hair
It is bright to be further detailed, it is impossible to be interpreted as limiting the scope of the invention.The person skilled in the art of this area can be with
Some nonessential modifications and adaptations are carried out according to foregoing invention content.
Embodiment 1 (subcritical water extrusion)：80 mesh Eucalyptus wood powders, are produced by Shanghai Jia Feng wood powders Co., Ltd, will be above-mentioned
Wood powder 200g and ABS (Zhenjiang Qi Mei Chemical Co., Ltd.s) 300g is mixed；Mixture adds a diameter of 20mm draw ratios in the lump
For in 32 co-rotating twin screw extruder (Long-Ke Ya plant equipment Co., Ltd of Nanjing section times), control screw speed exists
100r/min, extrusion temperature is 180 DEG C, carries out melting extrusion blending reaction；Water is injected in metering at screw-rod structure figure B simultaneously,
Pressure in extruder is controlled by measuring pump and reaction temperature, is 1.00MPa at 180 DEG C；Water ring is opened while extrusion reaction
Formula vavuum pump, the escaping gas that vacuum removal is produced when reacting；Extrusion product is cooled down through air, granulated, ABS sills are made
Plastic composite materials.
The product that above-mentioned extrusion is blended into granulation is put into 180 DEG C of mixings in mill, kneads 5min or so rear slice.Gained
Sheet material place 24 hours after, with 180 DEG C of vulcanizing press tabletting, the time is 300 seconds, and then cold press cold pressing sizing, is obtained
To ABS base wood-plastic composite materials, the test of mechanical property is carried out after placing 24 hours.
Embodiment 2 (subcritical water extrusion)：By above-mentioned wood powder 200g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.s) 275g and
Maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement Co., Ltd) 25g is mixed, and mixture is added to above-mentioned pair of spiral shell in the lump
In bar extruder, its screw speed, temperature, waterflood injection rate and pressure condition are same as Example 1.
Embodiment 3 (subcritical water extrusion)：By above-mentioned wood powder 150g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.s) 325g and
Maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement Co., Ltd) 25g is mixed, and mixture is added to above-mentioned pair of spiral shell in the lump
In bar extruder, its screw speed, temperature, waterflood injection rate and pressure condition are same as Example 1.
Embodiment 4 (subcritical water extrusion)：By above-mentioned wood powder 250g, ABS (Zhenjiang Qi Mei Chemical Co., Ltd.s) 225g and
Maleic anhydride grafted ABS (MABS, Nanjing is tough plastic cement Co., Ltd) 25g is mixed, and mixture is added to above-mentioned pair of spiral shell in the lump
In bar extruder, its screw speed, temperature, waterflood injection rate and pressure condition are same as Example 1.
Comparative example 1 (dry state extrusion)：Not water filling in extrusion, other are same as Example 1.
Comparative example 2 (dry state extrusion)：Not water filling in extrusion, other are same as Example 2.
Comparative example 3 (dry state extrusion)：25g maleic anhydrides are added in reactant mixture, not water filling in extrusion, other with
Embodiment 1 is identical.
Comparative example 4 (dry state extrusion)：25g maleic anhydrides are added in reactant mixture, not water filling in extrusion, other with
Embodiment 2 is identical.
Comparative example 5 (hygrometric state extrusion)：15g water is added in reactant mixture, not water filling in extrusion, other and embodiment
1 is identical.
Comparative example 6 (hygrometric state extrusion)：15g water is added in reactant mixture, not water filling in extrusion, other and embodiment
2 is identical.
Embodiment 5 (subcritical water extrusion)：40 mesh poplar wood powders, are produced by Shanghai Jia Feng wood powders Co., Ltd, will be above-mentioned
Wood powder 200g, HDPE (Iranian petrochemical industry Co., Ltd) 300g is mixed, and mixture is added to the twin-screw that temperature is 160 DEG C in the lump
In extruder, its screw speed, waterflood injection rate and pressure condition are same as Example 1.
Embodiment 6 (subcritical water extrusion)：By above-mentioned wood powder 200g, HDPE (Iranian petrochemical industry Co., Ltd) 275g and Malaysia
Acid anhydrides graft PP (MAPP, Nanjing is tough plastic cement Co., Ltd) 25g is mixed, and it is 160 DEG C that mixture is added to temperature in the lump
In double screw extruder, its screw speed, waterflood injection rate and pressure condition are same as Example 1.
Comparative example 7 (dry state extrusion)：Without any auxiliary agent in reactant mixture, on 160 DEG C of double screw extruder
Extrusion, during not water filling, other conditions are same as Example 1.
Comparative example 8 (dry state extrusion)：5%MAPP is added in reactant mixture, is squeezed on 160 DEG C of double screw extruder
Go out, during not water filling, other conditions are same as Example 1.
Embodiment 1 to embodiment 6 and comparative example 1 to the experimental formula of comparative example 8 and mechanical property result is seen below respectively
Tables 1 and 2.
In the data of table 1 show, dry state extrusion blending condition under, comparative example 1,2,3,4 relatively, the component of comparative example 2
After middle addition MABS, the tensile strength and unnotched impact strength of material are highest.MABS is at the interface of composite for this explanation
Place has given play to the effect of obvious interfacial compatibilizer, therefore causes significantly increasing for material mechanical performance.The material of comparative example 3,4
Expect component in contain maleic anhydride (MAH) monomer, although the mechanical property of material is significantly improved compared with comparative example 1, but than
Obvious positive effect has not been given play to compared with MAH in example 4, and this phenomenon have impact on the MAH monomers that dissociate in blending material component
The combination of MABS and wood powder fiber is relevant, therefore comparative example 4 is not best formula composition.
Under hygrometric state extrusion condition, with comparative example 1,2 relatively, the mechanical property of material has substantially comparative example 5,6
Raising, wherein the raising of particularly tensile strength and unnotched impact strength is the most obvious.Under this explanation hygrometric state extrusion condition,
The swelling effect of a small amount of water may promote interface wood-fibred and ABS or the reaction with MABS, cause interface bond strength
Increase, therefore cause significantly increasing for composite materials property.
Under the extrusion condition of subcritical water, embodiment 1,2 and comparative example 5,6 relatively, the tensile strength of material and
Bending strength obtains obvious raising again, and this explanation is under the extrusion condition of subcritical water, due to there is the abundant contact of water under high pressure,
Cause the abundant swelling of interface wood-fibred and its abundant reaction with ABS or with MABS, further plus improve wood moulding answer
The interface bond strength of condensation material, therefore cause the further increase of composite tensile strength and bending strength.But due to boundary
The further reinforcement of face adhesion, reduces buffer capacity of the material to impulsive force, therefore embodiment 1, the jagged and nothing of 2 materials
Notch impact strength is counter to occur in that a small amount of decline.
The material prescription of table 1 and ABS/ wood flour composite material mechanical properties
The material prescription of table 2 and HDPE/ wood flour composite material mechanical properties
Shown in the data of table 2, under dry state extrusion blending condition, comparative example 7,8 compares, the stretching of comparative example 8 and curved
Qu Qiangdu obtains obvious raising, and this explanation MAPP can significantly improve the compatibility between wood moulding, improve mechanical strength.
Under the extrusion condition of subcritical water, embodiment 5 is compared with comparative example 7, and the tensile strength of material and impact are strong
Degree all increases, and illustrates that subcritical water has certain effect to improving interface compatibility.Embodiment 6 compared with comparative example 8,
Tensile strength, the bending strength of material are all improved, and illustrate that subcritical water has synergy with MAPP, can be in original base
The mechanical strength of wood plastic composite is further improved on plinth.
Change comparative example 1, the extrusion blending temperature of embodiment 1 and embodiment 2, other conditions then respectively with comparative example 1, real
Apply example 1 identical with the situation of embodiment 2, obtained composite materials property is respectively referring to the song in Fig. 3, Fig. 4, Fig. 5 and Fig. 6
Line 1, curve 2 and curve 3.
Curve 1,2,3 in Fig. 3,4,5,6 is shown, under identical extruder screw speed conditions, with extrusion blending temperature
The increase of degree, the tensile strengths of ABS/ wood flour composite materials, bending strength, notch impact strength and unnotched impact strength are bright
Aobvious increase, wherein curve 1 (dry state extrusion) reach maximum in 180 DEG C or 190 DEG C, and curve 2 (subcritical water extrusion), song
Line 3 (subcritical water is extruded and contains MABS) then reaches maximum near 200 DEG C, hereafter then declines.This change is said
Bright, with the increase of extrusion blending temperature, subcritical water strengthens the swelling action of wood-fibred, and ABS melt viscosity declines, and this draws
The reinforcement of abundant contacts and interface cohesion reaction of the ABS with wood-fibred in wood powder has been played, therefore has caused composite materials property
Generally increase.But after composite materials property reaches maximum, it is multiple with the further increase of extrusion blending temperature
Condensation material mechanical property then declines, and this causes the pyrogenetic reaction of wood powder with too high extrusion blending temperature, causes wood powder
Coking is gone bad relevant.Wherein curve 2,3 is compared with curve 1, and temperature drift during maximum occurs in curve 2,3, this with Asia
Blend is less with oxygen touch opportunity in air under critical extrusion condition, causes wood powder pyrogenetic reaction to die down relevant.
Curve 1,2,3 in Fig. 3,4,5,6 relatively also shows that under the conditions of identical extrusion blending temperature, Asia is faced
The mechanical property of products therefrom will be substantially better than dry state extrusion condition (curve 1) under boundary's water extrusion condition (curve 2)；Intermingling material
In when containing MABS components, the mechanical property of products therefrom is optimal under its subcritical water extrusion condition (curve 3).This phenomenon
Further illustrate, under subcritical water extrusion condition, due to there is the abundant contact of water under high pressure, cause the abundant of interface wood-fibred
Swelling and its abundant reaction with ABS or with MABS, further add and improve interface bond strength, therefore cause composite power
Learn the further increase of performance.
Curve 3 in Fig. 3,4,5,6 is also shown, under 200 DEG C of subcritical water extrusion condition, ABS/ wood flour composite materials
Tensile strength, bending strength, notch impact strength and unnotched impact strength respectively reach 45.3MPa, 72.4MPa,
1.5kJ/m2, 6.5kJ/m2。
The infrared spectrogram of ABS/ wood flour composite material acetone extraction things is as shown in fig. 7, wherein：1-pure wood powder；2-real
Apply example 1,180 DEG C of subcritical water extrusions of blend；3-embodiment 1,200 DEG C of subcritical water extrusions of blend；4-embodiment 2,
200 DEG C of subcritical water extrusions (containing MABS) of blend；Characteristic peak in the infrared spectrum of ABS/ wood flour composite material acetone extraction things/
Reference peak area ratio is as shown in table 3：
Characteristic peak/reference peak area ratio in the infrared spectrum of the ABS/ wood flour composite material acetone extraction things of table 3
The data display in curve combination table 3 in Fig. 7, with affiliated wood powder in 1240cm-1(C-O-C) absworption peak at place
Under conditions of reference peak, the acetone extraction thing of ABS/ wood flour composite materials is in 1384cm-1(>C=CH-), 1506cm-1(phenyl ring
Skeletal vibration peak) and 1640cm-1(>C=CH2) place characteristic absorption peak intensity with extrusion blending temperature increase or with blend
The addition of middle MABS compositions and significantly increase, this explanation under subcritical water extrusion condition, with the increase of extrusion temperature, or with altogether
MABS addition in mixed thing, causes the reaction between ABS and wood powder interface and the reinforcement of interface binding power, therefore belonging to causing
Butadiene-styrene rubber composition in ABS is bonded to wood powder fiber surface and can not fallen by extracting.
ABS/ wood plastic composite sample section SEM photographs are as shown in figure 8, wherein：A- comparative examples 1；B- embodiments 1；c-
Comparative example 2；D- comparative examples 6；E- embodiments 2；2 blend of f- embodiments, 200 DEG C of extrusions.Photo a, photo c be relatively in Fig. 8
Wood-fibred is pulled out in display, photo a, leaves obvious hole, and matrix is tightly combined with wood-fibred in photo c, though
Right wood-fibred has also been pulled out, but the surface texture of fiber is still high-visible, is illustrated that interface cohesion is close, is shown material group
The influence of MABS compatibilization in point.Photo b, e are relatively shown in Fig. 8, although extrude bar in same subcritical water
Under part, in photo b containing obvious wood-fibred be pulled out formed by wood-fibred in hole, but photo e then combined with matrix
Closely, the material impact of MABS in material composition has been also showed that.Photo d, e, f are relatively shown in Fig. 8, material composition
Although in all contain and remain to see have with reference to more close interface gaps under MABS, hygrometric state extrusion condition in photo d；But in Asia
Under critical extrusion condition or under conditions of subcritical water is extruded and raises blending temperature, photo e, f show wood-fibred and material
Material matrix is tightly combined, and sees there is more deal resin-coating on wood-fibred.
Claims (4)
1. a kind of method that subcritical water extrusion prepares wood plastic composite, it is concretely comprised the following steps：
A. by account for reactant gross mass percentage composition be 40%~80% thermoplastic macromolecule material, account for reactant gross mass hundred
Wood powder and account for the interfacial reaction reagent phase that reactant gross mass percentage composition is 0%~10% that point content is 15%~60%
Mixing；
B., said mixture is added to melting extrusion in the parallel dual-screw extruding machine of certain rotating speed in the lump, while double in the same direction
Screw extruder frit reaction section injection water, by controlling the temperature and pressure of frit reaction section, was blended its melting extrusion
Journey is in the state of subcritical water；Wherein the reaction temperature of melting extrusion be 150~260 DEG C, certain rotating speed it is in the same direction
The screw speed of double screw extruder is 50~200r/min, the temperature of melting extrusion Blending Processes Subcritical water for 150~
260℃；
C. reaction product is cooled down, granulates, dried through vacuum removal volatile matter, then through mill mill, tabletting, is made corresponding
Wood plastic composite.
2. according to the method described in claim 1, it is characterised in that described thermoplastic macromolecule material is ABS, PS, AS, PE
Or any one in PP.
3. according to the method described in claim 1, it is characterised in that described wood powder is one in Eucalyptus wood powder or poplar wood powder
Kind.
4. according to the method described in claim 1, it is characterised in that interfacial reaction reagent is：Silane coupling agent, maleic acid
Acid anhydride, stearic acid, maleic anhydride grafted ABS, maleic anhydride grafting PS, maleic anhydride grafting AS, maleic anhydride graft PP or Malaysia
Acid anhydrides is grafted any one in PE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410697662.9A CN104497471B (en) | 2014-11-26 | 2014-11-26 | A kind of method that subcritical water extrusion prepares wood plastic composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410697662.9A CN104497471B (en) | 2014-11-26 | 2014-11-26 | A kind of method that subcritical water extrusion prepares wood plastic composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104497471A CN104497471A (en) | 2015-04-08 |
| CN104497471B true CN104497471B (en) | 2017-10-24 |
Family
ID=52938934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410697662.9A Expired - Fee Related CN104497471B (en) | 2014-11-26 | 2014-11-26 | A kind of method that subcritical water extrusion prepares wood plastic composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104497471B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778547B (en) * | 2016-03-17 | 2018-07-17 | 南京工业大学 | A kind of method that subcritical alcohol extrusion prepares wood plastic composite |
| CN106674967B (en) * | 2016-12-28 | 2018-11-09 | 上海锦湖日丽塑料有限公司 | A kind of bloom exempts from the environmental-protection flame-retardant makrolon material and preparation method thereof of spraying |
| FI127576B (en) | 2017-03-02 | 2018-09-14 | Sulapac Oy | Novel materials for packaging |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174270A (en) * | 2011-03-17 | 2011-09-07 | 华东理工大学 | Plasticized and toughened wood flour/polypropylene composite and method for preparing same |
| CN103073741A (en) * | 2012-12-26 | 2013-05-01 | 南京工业大学 | Method for inducing desulfurization reaction of vulcanized rubber powder through stress of subcritical water extrusion method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792609B (en) * | 2009-09-08 | 2012-04-18 | 德州三惠木塑科技有限公司 | Formula and preparation method of polyethylene based wood-plastic composite material |
| CN101845523A (en) * | 2010-05-25 | 2010-09-29 | 清华大学 | Subcritical hydrolysis method for preparing hexose with soluble fiber oligosaccharide |
| CN103627081A (en) * | 2012-08-22 | 2014-03-12 | 上海杰事杰新材料(集团)股份有限公司 | Wood plastic material and preparation method thereof |
| CN103102589B (en) * | 2012-12-19 | 2015-06-10 | 上海秋橙新材料科技有限公司 | Polypropylene wood-plastic composite material and preparation method thereof |
| CN103834058A (en) * | 2013-12-31 | 2014-06-04 | 南京工业大学 | Method for subcritical alcohol extrusion stress induced devulcanization of vulcanized rubber powder |
-
2014
- 2014-11-26 CN CN201410697662.9A patent/CN104497471B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174270A (en) * | 2011-03-17 | 2011-09-07 | 华东理工大学 | Plasticized and toughened wood flour/polypropylene composite and method for preparing same |
| CN103073741A (en) * | 2012-12-26 | 2013-05-01 | 南京工业大学 | Method for inducing desulfurization reaction of vulcanized rubber powder through stress of subcritical water extrusion method |
Non-Patent Citations (1)
| Title |
|---|
| 赵蒙蒙."亚临界水中木质素的降解条件与机理探索".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2014,(第11期),B014-100. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104497471A (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Comparison on properties of lignocellulosic flour/polymer composites by using wood, cellulose, and lignin flours as fillers | |
| Chattopadhyay et al. | Bamboo fiber reinforced polypropylene composites and their mechanical, thermal, and morphological properties | |
| Huang et al. | Effect of mechanical activation pretreatment on the properties of sugarcane bagasse/poly (vinyl chloride) composites | |
| CN102942797B (en) | Plant fiber wood-plastic composite material and preparation method thereof | |
| Araujo et al. | Biomicrofibrilar composites of high density polyethylene reinforced with curauá fibers: Mechanical, interfacial and morphological properties | |
| CN107298868A (en) | A kind of enhanced Wood-plastic material of lignin and preparation method thereof | |
| CN102352116B (en) | Wood-plastic composite material and preparation method thereof | |
| CN102690525A (en) | Wood-plastic composite material using sweet sorghum slag as enhanced phase and preparation method for wood-plastic composite material | |
| CN101029178B (en) | Production of polymer/pulp fibre composite material | |
| Hong et al. | Significant improvement in performance of recycled polyethylene/wood flour composites by synergistic compatibilization at multi-scale interfaces | |
| CN101613503A (en) | Water-resistant wood-plastic composite material and preparation method thereof | |
| CN104497471B (en) | A kind of method that subcritical water extrusion prepares wood plastic composite | |
| CN102585358A (en) | Natural fiber reinforced polypropylene composite material and preparation method thereof | |
| CN109081900B (en) | Modified polyol and preparation method thereof, modified polyurethane material and preparation method and application thereof | |
| He et al. | Structure and performance of Poly (vinyl alcohol)/wood powder composite prepared by thermal processing and solid state shear milling technology | |
| Ma et al. | Effect of alkali treatment on structure and mechanical properties of acrylonitrile–butadiene–styrene/bamboo fiber composites | |
| Shoja et al. | Plasticized starch-based biocomposites containing modified rice straw fillers with thermoplastic, thermoset-like and thermoset chemical structures | |
| US20210171764A1 (en) | Polyactic Acid and Lignin Composite Thermoplastic for 3D Printing | |
| Narkchamnan et al. | Thermo-molded biocomposite from cassava starch, natural fibers and lignin associated by laccase-mediator system | |
| CN106188842B (en) | Polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method | |
| EP3571232A1 (en) | Melt-processed material with high cellulose fiber content | |
| WO2016199923A1 (en) | Thermoplastic resin composition and method for producing thermoplastic resin composition | |
| CN102260386B (en) | Ecological composite material and preparation method thereof | |
| CN110467908B (en) | Controllable hydrolysis composite material composition for oil field and preparation method thereof | |
| Shen et al. | Enhanced mechanical properties of polyvinyl chloride-based wood–plastic composites with pretreated corn stalk |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171024 Termination date: 20191126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |