CN105778547B - A kind of method that subcritical alcohol extrusion prepares wood plastic composite - Google Patents
A kind of method that subcritical alcohol extrusion prepares wood plastic composite Download PDFInfo
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Abstract
The present invention relates to a kind of methods that subcritical alcohol extrusion prepares wood plastic composite, belong to high molecular material reaction technology research field.Thermoplastic macromolecule material that reactant gross mass percentage composition is 20%~80% will be accounted for, wood powder that reactant gross mass percentage composition is 20%~80% is accounted for and is mixed with the interfacial reaction auxiliary agent for accounting for reactant gross mass percentage composition 0% 20%, mixture carries out melting extrusion blending reaction in the double screw extruder with subcritical alcohol extrusion reaction condition and suitable screw speed.Squeeze out product through cooling, at item, be granulated, then through mill mixing, vulcanizing press tabletting, that is, obtain wood plastic composite.Present invention enhancement thermoplastic macromolecule material is reacted with wood-fibred surface.Extrusion reaction process is easily controllable, it is nontoxic, yield is high, low energy consumption, be easy to enlargement, scale, environmental pollution is small, can get excellent in mechanical performance wood plastic composite.
Description
Technical field：
The present invention relates to a kind of methods that subcritical alcohol extrusion prepares wood plastic composite, belong to extrusion reaction engineering and height
Molecular material force-chemical reaction research field.
Technical background：
It is nineteen eighty-three, produced in USA first wood plastic composite (Wood Plastic Composites, WPCs).Closely
Nian Lai, as area of woods reduction and the resource based on oil are increasingly reduced, social environment consciousness day by day enhances, and wood moulding is multiple
As one kind, using plant fiber or powder and thermoplastic polymer as primary raw material, auxiliary agent appropriate is added in condensation material, extruded,
Injection molding or compression moulding and with the environmentally protective composite material similar to the high-performance of wood characteristics, high added value, permitted
Multinational family is included in energy-saving and environment friendly product, receives and vigorously supports.
Currently, the demand of wood plastic composite is being continuously increased in the world, global yield is more than 1,500,000 tons.
WPCs can make full use of waste plastic and waste and old wood, the advantages of playing each component, overcome because strength of wood is low, variability is big and
Limitation is used caused by the low grade of organic material elasticity modulus, is reduced environmental pollution.
It is relatively nervous for the comprehensive utilization of agriculture and forestry organic waste material and waste plastic, alleviation natural timber to research and develop WPCs
Pressure have great importance.It is embedded in plant fiber in the polymer matrix and limits moisture absorption, therefore it is true to avoid timber
The growth of bacterium and the timber of biological degradability.Compared with inorganic filler, plant fiber have biological degradability, extensively using property,
Density is low, the advantages such as at low cost.The thermoplastic for being used to prepare WPCs mainly has polyethylene (PE), polypropylene (PP) and polychlorostyrene
Ethylene (PVC) etc., the factor for influencing wood-plastic composite performance include that plant fiber disperses uneven, melting mixing mistake in the base
Degradable and between plastics poor compatibility etc. in journey, wherein most outstanding is exactly that interface compatibility is poor and wood plastics composite
Material key problem urgently to be resolved hurrily.
The method for improving plant fiber and polymer compatibility at present has heat treatment, alkali process, directly fluorination, steam quick-fried
Broken, corona, radiation and addition coupling agent etc..
Heat treating process is a kind of benign method of modifying, just growing into it is a kind of improve lignocellulosic filler hygroscopicity,
The process of dimensional stability, antibiont degradability.Heat treatment process also has the defect of its own, including mechanical properties decrease, face
Color is undesirable and odor profiles etc..Traditional baking oven heat treatment mode is gradually replaced by microwave heating, and microwave heating is one
Efficient context friendly processing method is planted, in the reactive mixture high dielectric loss and highly polar substance preferential absorption energy.
Alkali metal soln facture is a kind of traditional treatment method being widely used in cotton fiber processing, equally be used to plant
The surface treatment of fibres achievees the purpose that improve cellulose intensity, and improves the water imbibition of fiber, enhances it and gathers
Close the binding ability at object interface.
Directly fluorination is usually used in the surface treatment of polymer, improves polymer oil resistivity and chemical solvent resistance, makes polymerization
Object hydrophobicity enhances.Also it is used for wood-fibred processing, in order to reduce wood-fibred hydrophily and reinforce the adhesive property with polymer.
Low Temperature Plasma Treating technology can be carried out at the fiber surface of seriation according to gases used difference
Reason, makes fiber surface generate free radicals a kind of charging method with functional group.
The surface that corona treatment techniques are usually used in material is modified, and under the conditions of not influencing material self performance, improves material
Surface nature has many advantages, such as that easy-regulating, pollution-free, processing speed is fast, can be continuously produced.Furthermore, it is possible to which largely activation is fine
The aldehyde radical in dimension table face changes the surface energy of cellulose fibre.
1822, Cagniard did the report of substance critical phenomena for the first time.1879, Hanny and Hogarth had found admittedly
Body dissolves in supercritical fluid, and experimental basis is provided for supercritical fluid application.1985, U.S. Modell etc. was reported for the first time
Using sawdust as raw material supercritical water gasification hydrogen production.
Super/subcritical fluids have unique physical and chemical performance：It is excellent solvability, lower viscosity, higher
Diffusion coefficient and heat transfer coefficient.Small pressure change can cause the big variation of physical property, especially become in Near The Critical Point
Change extremely notable.Super/subcritical fluids have been used for answering for natural material, micro mist, chemical reaction, aeroge and aeroge synthesis
Condensation material extraction process.And super/subcritical fluids extrusion molding is to surpass/undercritical conditions using extruding machine with two screw rods engaging in the same direction
Under prepare wood plastic composite, it can continuous production, yield it is high, shear action is generated in extrusion, promotes mixing point
It dissipates, to achieve the purpose that improve wood plastic composite comprehensive performance.
Super/subcritical fluids in addition to water, further comprise alcohol compound (methanol, ethyl alcohol, propyl alcohol), CO2Deng these
Super/subcritical state of substance is reported for handling organic wastewater, solid refuse, waste old etc..Nanjing work in 2014
Sparetime university learns (ZL20141126) such as a tinkling of pieces of jade and proposes a kind of method that subcritical water extrusion prepares wood plastic composite, and subcritical
Water has strong oxidizing property, all has oxidative degradation to wood powder and resin matrix, reduces the interface knot of wood plastic composite
With joint efforts.
Invention content：
The purpose of the present invention proposes that a kind of subcritical alcohol extrusion prepares wood and plastic composite to improve the deficiencies in the prior art
The method of material melts wood powder and thermoplastic as under solvent and reaction-ability medium existence condition in subcritical alcohol
Melt extrusion blending reaction so that component portion degrades, dissolves or liquefies in wood powder, plays swelling to wherein microfibre in addition and divides
From effect, is conducive to increase wood powder and resin matrix and compatilizer interaction, improves the interface of thermoplastic and wood powder
Reaction, the mechanical property for improving interface binding power, improving wood plastic composite, can also make melting extrusion reaction more mild
It is carried out under the conditions of temperature, pressure and shear stress field.
The concrete scheme taken of the present invention is：A kind of method that subcritical alcohol extrusion prepares wood plastic composite, tool
Body step is：
A. by account for reactant gross mass percentage composition be 20%~80% thermoplastic macromolecule material, account for the total matter of reactant
Amount percentage composition is 20%~80% wood powder, to account for reactant gross mass percentage composition be that 0%~20% auxiliary agent mixes；
B. above-mentioned reaction mixture is added to together in the parallel dual-screw extruding machine of certain rotating speed and carries out melting extrusion,
Alcohol is injected at the middle part of double screw extruder machine barrel simultaneously, its blending reaction is made to be in the subcritical state of alcohol；
C. reaction product cools down, at item, granulation, through vacuum removal volatile matter then through mill mixing, vulcanizing press
Tabletting obtains wood plastic composite.
It is preferred that above-mentioned thermoplastic macromolecule material is polyvinyl chloride, polypropylene, polyethylene, the fine copolymerization of styrene-propene
At least one of object, acrylonitrile-butadiene-phenylethylene copolymer or polystyrene.
It is preferred that above-mentioned wood powder is one kind in Eucalyptus wood powder or poplar wood powder；The size of wood powder is 40 mesh~120
Between mesh.
It is preferred that above-mentioned alcohol is any one in methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol or amylalcohol
Kind.
Melting extrusion reaction temperature is 150 DEG C~260 DEG C in preferred steps B；Pressure is 0.4MPa~5.2MPa；Twin-screw
The screw speed of extruder is 50rpm~200rpm.
It is preferred that above-mentioned auxiliary agent is：Silane coupling agent, maleic anhydride, maleic anhydride graft PP, maleic anhydride are grafted HDPE/
PE, maleic anhydride grafting AS, maleic anhydride grafted ABS, maleic anhydride grafting PS, stearic acid (Stearic Acid, SA), poly- second
One or more of alkene wax (Polyethylene Wax, PW), solid or atoleine (Paraffin).
Melting extrusion reaction prepares the technological process of wood plastic composite and extruder screw rod structure figure is shown in attached drawing 1 and attached drawing
2.This experiment screw extruder used is co-rotating twin screw extruder group of the second order to quadravalence, by conveying screwing element,
Mediate screwing element, compression screwing element and left-hand thread element mixing composition, when subcritical alcohol extrusion reaction operates, B injections
Mouth is connected with microprocessor pump drive and pressure gauge.The control of extruder reaction temperature is at 150 DEG C~260 DEG C, extruder screw rotating speed
Control is in 50rpm~200rpm；The mixture of wood powder and thermoplastic is added by C charge doors, while being measured and being noted in B inlets
Enter alcohol, the speed and reaction temperature that inlet pressure is injected by alcohol control；Reaction product is through cooling, granulation, then through open mill
It is kneaded, vulcanizing press tabletting, wood plastic composite sample is made.
Advantageous effect：
1. being prepared compared with wood plastic composite using double screw extruder with simple, due to there is subcritical alcohol as solvent
With the presence of reaction medium, the viscosity of reaction system is reduced, increases H ions and hemicellulose and lignin in wood powder in alcohol
The possibility to react, while also promoting microfibre swelling and occurring with interfacial reaction reagent or plastics continuous phase anti-
It answers, enhances the interface binding power of wood plastic composite, and then improve the mechanical property of wood plastic composite.
2. due to there is subcritical alcohol as solvent, improve the mobility of reaction system, thus can improve wood powder content into
Row melting extrusion is reacted, hence it is evident that reduces the cost of wood plastic composite.
3. melting extrusion reaction process is easily controllable, the extent of reaction and subcritical alcohol condition can be according to screw speed, spiral shells
Bar draw ratio, screw-rod structure combining form and reaction temperature are adjusted.
4. melting extrusion process can realize serialization, automated production, operator's working strength is substantially reduced, was reacted
Journey serialization is easy to automate, and operator's labor intensity is small, contact stain is few.
5. compared with steam gas explosion method, due to being carried out in double screw extruder, blending will be squeezed out and enhancement interface is anti-
Answer it is integrated, reaction process is efficient, low energy consumption, it can be achieved that enlargement, large-scale production.
Description of the drawings：
Fig. 1 is the process flow chart of the present invention；
The extruding machine with two screw rods engaging screw rod in the same direction that Fig. 2 is a diameter of 35mm of capital equipment of the present invention, draw ratio is 44
Constitutional diagram；Wherein A is gas discharge outlet, and B is alcohol inlet, and C is charge door；
Fig. 3 is influence of the extrusion blending temperature of embodiment 1 and comparative example 1 to PP/ wood flour composite material tensile strengths,
Middle 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Fig. 4 is influence of the extrusion blending temperature of embodiment 1 and comparative example 1 to PP/ wood flour composite material bending strengths,
Middle 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Fig. 5 is influence of the extrusion blending temperature of embodiment 1 and comparative example 1 to PP/ wood flour composite material bending moduluses,
Middle 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Fig. 6 is the extrusion blending temperature of embodiment 1 and comparative example 1 to PP/ wood flour composite material unnotched impact strengths
It influences, wherein 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Fig. 7 is the infrared spectrogram of the PP/ wood flour composite material dimethylbenzene extracts of embodiment 1 and comparative example 1：1- is without stream
Body (190 DEG C, 120rpm)；2- subcritical waters (190 DEG C, 1.3MPa, 120rpm)；The subcritical normal propyl alcohols of 3- (190 DEG C, 1.6MPa,
120rpm)；The subcritical ethyl alcohol of 4- (190 DEG C, 2.4MPa, 120rpm)；
Fig. 8 is the SEM photograph of the PP/ wood flour composite material sample sections of embodiment 1 and comparative example 1：A- is without fluid (190
DEG C, 120rpm)；B- subcritical waters (190 DEG C, 1.3MPa, 120rpm)；The subcritical normal propyl alcohols of c- (190 DEG C, 1.6MPa,
120rpm)；The subcritical ethyl alcohol of d- (190 DEG C, 2.4MPa, 120rpm)；
Fig. 9 is shadow of the compatilizer type and content to PP/ wood flour composite material tensile strengths of embodiment 4 and comparative example 4
It rings, wherein 1-MAPP-50；2-MAPP-90；3-MAPOE；
Figure 10 is shadow of the compatilizer type and content to PP/ wood flour composite material bending strengths of embodiment 4 and comparative example 4
It rings, wherein 1-MAPP-50；2-MAPP-90；3-MAPOE；
Figure 11 is shadow of the compatilizer type and content to PP/ wood flour composite material bending moduluses of embodiment 4 and comparative example 4
It rings, wherein 1-MAPP-50；2-MAPP-90；3-MAPOE；
Figure 12 impacts by force PP/ wood flour composite material non-notch for embodiment 4 and the compatilizer type and content of comparative example 4
The influence of degree, wherein 1-MAPP-50；2-MAPP-90；3-MAPOE；
Figure 13 is shadow of the compatilizer type and content to PP/ wood flour composite material notch strengths of embodiment 4 and comparative example 4
It rings, wherein 1-MAPP-50；2-MAPP-90；3-MAPOE；
Figure 14 is the shadow for squeezing out blending temperature to HDPE/ wood flour composite material tensile strengths of embodiment 6 and comparative example 6
It rings, wherein 1- is without fluid (170 DEG C, 150rpm)；2- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of 3-
(170 DEG C, 1.0MPa, 150rpm)；The subcritical ethyl alcohol of 4- (170 DEG C, 1.6MPa, 150rpm)；
Figure 15 is the shadow for squeezing out blending temperature to HDPE/ wood flour composite material bending strengths of embodiment 6 and comparative example 6
It rings, wherein 1- is without fluid (170 DEG C, 150rpm)；2- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of 3-
(170 DEG C, 1.0MPa, 150rpm)；The subcritical ethyl alcohol of 4- (170 DEG C, 1.6MPa, 150rpm)；
Figure 16 is the shadow for squeezing out blending temperature to HDPE/ wood flour composite material bending moduluses of embodiment 6 and comparative example 6
It rings, wherein 1- is without fluid (170 DEG C, 150rpm)；2- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of 3-
(170 DEG C, 1.0MPa, 150rpm)；The subcritical ethyl alcohol of 4- (170 DEG C, 1.6MPa, 150rpm)；
Figure 17 is the shadow for squeezing out blending temperature to HDPE/ wood flour composite material notch strengths of embodiment 6 and comparative example 6
It rings, wherein 1- is without fluid (170 DEG C, 150rpm)；2- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of 3-
(170 DEG C, 1.0MPa, 150rpm)；The subcritical ethyl alcohol of 4- (170 DEG C, 1.6MPa, 150rpm)；
Figure 18 is the infrared spectrogram of the HDPE/ wood flour composite material dimethylbenzene extracts of embodiment 6 and comparative example 6：1-
Pure wood powder；2- is without fluid (170 DEG C, 150rpm)；3- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of 4-
(170 DEG C, 1.0MPa, 150rpm)；The subcritical ethyl alcohol of 5- (170 DEG C, 1.6MPa, 150rpm)；
Figure 19 is the SEM photograph of the HDPE/ wood flour composite material sample sections of embodiment 6 and comparative example 6：A- is without fluid
(170 DEG C, 150rpm)；B- subcritical waters (170 DEG C, 0.8MPa, 150rpm)；The subcritical normal propyl alcohols of c- (170 DEG C, 1.0MPa,
150rpm)；The subcritical ethyl alcohol of d- (170 DEG C, 1.6MPa, 150rpm)；
Figure 20 is influence of the extrusion blending temperature of embodiment 7 and comparative example 7 to ABS/ wood flour composite material tensile strengths,
Wherein 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Figure 21 is influence of the extrusion blending temperature of embodiment 7 and comparative example 7 to ABS/ wood flour composite material bending strengths,
Wherein 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Figure 22 is influence of the extrusion blending temperature of embodiment 7 and comparative example 7 to ABS/ wood flour composite material bending moduluses,
Wherein 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Figure 23 is the extrusion blending temperature of embodiment 7 and comparative example 7 to ABS/ wood flour composite material notch impact strengths
It influences, wherein 1- is without fluid；2- subcritical waters；The subcritical normal propyl alcohols of 3-；The subcritical ethyl alcohol of 4-；
Figure 24 is the infrared spectrogram of the ABS/ wood flour composite material dimethylbenzene extracts of embodiment 7 and comparative example 7：1- is sub-
Critical (200 DEG C, 1.6MPa, 100rpm)；The subcritical ethyl alcohol of 2- (200 DEG C, 3.0MPa, 100rpm)；The subcritical normal propyl alcohols of 3-
(200 DEG C, 1.9MPa, 100rpm)；
Figure 25 is the SEM photograph of the ABS/ wood flour composite material sample sections of embodiment 7 and comparative example 7：A- is without fluid
(180 DEG C, 100rpm)；B- subcritical waters (200 DEG C, 1.6MPa, 100rpm)；The subcritical normal propyl alcohols of c- (200 DEG C, 1.9MPa,
100rpm)；The subcritical ethyl alcohol of d- (200 DEG C, 3.0MPa, 100rpm).
Specific implementation mode：
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 should not be understood as limiting the scope of the invention.The person skilled in the art of this field can be with
Some nonessential modifications and adaptations are carried out according to foregoing invention content.
Embodiment one：80 mesh Eucalyptus wood powders (Shanghai Yun Can woodworks Co., Ltd) 560g and PP-T30S is chosen (to prolong in Shaanxi
Long (group) Yan'an petrochemical plant) 200g, MAPP-50 (Nanjing is tough plastic cement Co., Ltd) 40g, atoleine (insults in Shanghai
Peak chemical reagent Co., Ltd, chemistry are pure) 16g, polyethylene wax (Shanghai Jinshan star plastics Co., Ltd) 8g, stearic acid 1801
(Malaysian natural oil Chemical Co., Ltd.) 8g, they are mutually mixed.A diameter of 35mm, major diameter is added in mixture together
Than for 44 three rank co-rotating twin screw extruders (Long-Ke Ya mechanical equipments Co., Ltd of Nanjing section times, expressing technique and squeeze
Go out device screw combinations figure and see attached drawing 1, attached drawing 2), control screw speed 120rpm, extrusion temperature be respectively 170 DEG C (water,
0.80MPa；Normal propyl alcohol, 1.0MPa；Ethyl alcohol, 1.60MPa), 180 DEG C of (water, 1.00MPa；Normal propyl alcohol, 1.2MPa；Ethyl alcohol,
2.0MPa), 190 DEG C of (water, 1.3MPa；Normal propyl alcohol, 1.6MPa；Ethyl alcohol, 2.4MPa), 200 DEG C of (water, 1.9MPa；Normal propyl alcohol,
1.6MPa；Ethyl alcohol, 3.0MPa), 210 DEG C of (water, 1.9MPa；Normal propyl alcohol, 2.4MPa；Ethyl alcohol, 3.6MPa), it is total to carry out melting extrusion
Mixed reaction；Simultaneously corresponding fluid (water, normal propyl alcohol, ethyl alcohol), the pressure in extruder are injected in the B Metrology Divisions of screw-rod structure figure
It is controlled by metering pump and reaction temperature, extrusion reaction while opens water-ring vacuum pump, and what vacuum removal generated when reacting waves
Hair property gas；Product is squeezed out through natural cooling, granulation, obtains PP base wood-plastic composite material pellets.
The product that the blending of above-mentioned extrusion is granulated is put into open mill and is kneaded for 160 DEG C or so, after being kneaded 5min or so
Slice, after the sheet material of gained is placed 24 hours, using 115mm × 115mm × 4mm mold 170 DEG C vulcanizing press into
Row tabletting, time 300s, then cold press cold pressing 10min sizings, obtain PP/ wood flour composite materials, are pressed after placing 24 hours
The quasi- sample preparation of sighting target, carrying out the test of mechanical property, (tensile strength is carried out according to GB/T1040.2-2006, and sample is double spade-type, is surveyed
Examination speed is 50mm/min；Bending property is carried out according to GB/T9341-2008, sample thickness 4mm, span 64mm, test
Speed is 2mm/min；Impact strength is carried out according to GB/T1043-2006, and batten notch type is A types).
Infrared spectrum (FT-IR) measures：The PP/ wood powder compound particles of preparation are placed in dimethylbenzene extract it is about 12 small
When, the wood powder after extracting is dried in vacuo 12 hours, and KBr tablettings carry out infrared measurement after tabletting, and the wavelength measured is
500~4000cm-1, resolution ratio 2cm-1。
Scanning electron microscope (SEM) is analyzed：The sample after tension test is taken, with liquid nitrogen brittle failure, Vacuum Deposition then is carried out to section
Gold observes the variation of its cross-section morphology to enhance its electric conductivity.
Comparative example one：At relevant temperature (170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C), screw speed is 120rpm items
Under part, unimplanted fluid during blending extrusion, other are identical as embodiment one.
The mechanical property of comparative example one and the PP/ wood flour composite materials of embodiment one is shown in Fig. 3.
Curve 1,2,3 and 4 is shown in Fig. 3,4,5 and 6, under identical screw speed, with the liter of extrusion reaction temperature
The trend for first increasing and reducing afterwards is presented in height, the mechanical property of PP/ wood flour composite materials.This illustrates the liter of extrusion reaction temperature
Height may make PP melt viscosities decline, and promote PP to be come into full contact with wood powder, strengthen interfacial reaction, therefore cause composite material power
Learn the increase of performance.However, wood powder is temperature-sensitive material, continuing raising temperature easily makes wood powder coking rotten, and temperature is excessively high, object
Expect that the too low head pressure that easily leads to of viscosity is too small, interfacial reaction is insufficient, while PP molecular motions are violent in matrix, intermolecular work
Firmly reduce, crystalline region is converted to amorphous region, can lead to the reduction of PP/ wood powder wood plastic composite mechanical properties instead.
Curve 1,2,3 and 4, which compares, in Fig. 3,4,5 and 6 also found, under identical extrusion reaction temperature condition, sub-critical flow
Better than no fluid condition, this illustrates that subcritical fluids are more advantageous to the reaction at interface, can promote wood-fibred body extrusion reaction condition
Swelling is conducive to PP or MAPP and wood powder and interacts, while since the presence of subcritical fluids can be in extrusion
Completely cut off air to a certain extent, alleviates the phenomenon that wood powder is degraded because of high temperature, to improve the mechanics of PP/ wood flour composite materials
Performance.Correlation curve 2,3 and 4 shows that the mechanical property of the PP/ wood flour composite materials prepared under sub-critical water extraction is relatively low, can
It can be that the oxidisability of subcritical water is better than subcritical alcohol, have certain oxidative degradation to wood powder or resin matrix, lead to it
Mechanical property is poor.And the oxidisability of subcritical alcohol is relatively low, it is compound to improve compared with the interface cohesion that can promote composite material
The mechanical property of material.
Choose the sample that embodiment one and temperature in comparative example one are 190 DEG C carry out infrared spectrogram (FT-IR) measurement (see
Fig. 7).
Curve in Fig. 7,1506cm-1(phenyl ring skeletal vibration peak) is the characteristic peak of lignin in affiliated wood powder, is made with this
For reference peak.2923cm-1And 2855cm-1It is the absorption peak of methyl stretching vibration respectively, curve 1,2,3 and 4 is shown, is faced in Asia
Under the conditions of boundary's liquid extruding, the intensity of absorption peak is more than the intensity under no fluid condition.1460cm-1And 1380cm-1The feature at place
The stretching vibration for being attributed to C-H in methyl is absorbed, under the action of subcritical alcohol, the intensity of absorption peak obviously increases, and in Asia
Under the action of critical, 1380cm-1The characteristic absorption peak at place dies down, illustrate the strong oxidizing property of subcritical water weaken wood powder with
The interface cohesion of matrix.1630cm-1And 1060cm-1The absorption peak at place is attributed to the stretching vibration of carbonyl and ehter bond, this demonstrate
Esterification has occurred in the hydroxyl in anhydride group and wood powder in maleic anhydride.As it can be seen that under the conditions of subcritical fluids, absorb
The intensity at peak is higher than the intensity under no fluid condition, and subcritical alcohol is more conducive to the generation of esterification than subcritical water, improves
The interface binding power of composite material, to further increasing its mechanical property.
It chooses the sample that embodiment one is 190 DEG C with temperature in comparative example one and sem analysis (see Fig. 8) is carried out to section.
It in Fig. 8, can be seen that from photo a, wood-fibred is combined less close with polypropylene, and wood-fibred is pulled out in section, is stayed
Descend many holes, the surface of wood-fibred smooth；From photo b as it can be seen that although wood-fibred is pulled out, cavity, hole are left
Rough surface illustrates that wood-fibred and resin matrix have certain binding force；Photo c and d show that matrix is combined tightly with wood-fibred
Close, the former the latter by tight, this illustrates that two alternate combinations are improved, and fiber has centainly in resin matrix
Dispersion effect, it is seen then that subcritical alcohol be better than subcritical water, it can more preferably promote the interface cohesion of composite material.
Embodiment two：Choose the 80 mesh Eucalyptus wood powders (Shanghai Yun Can woodworks Co., Ltd) of 480g, the PP- of 240g
They are mutually mixed, mixture are added together above-mentioned by the MAPP-50 of T30S, 80g, polyethylene wax 8g, stearic acid 8g
In double screw extruder, screw speed 120rpm, temperature are 190 DEG C, while injecting second in the B Metrology Divisions of screw-rod structure figure
Alcohol (2.4MPa), other conditions are identical as embodiment one.
Comparative example two：It is 190 DEG C in temperature, under the conditions of rotating speed is 120rpm, unimplanted fluid during blending extrusion,
His condition is identical as embodiment two.
Table 1 squeezes out influence of the blending condition to PP/ wood flour composite material mechanical properties
Embodiment three：Choose the 80 mesh Eucalyptus wood powders (Shanghai Yun Can woodworks Co., Ltd) of 560g, the PP- of 160g
They are mutually mixed, mixture are added together above-mentioned by the MAPP-50 of T30S, 80g, polyethylene wax 8g, stearic acid 8g
In double screw extruder, screw speed 120rpm, temperature are 190 DEG C, while injecting second in the B Metrology Divisions of screw-rod structure figure
Alcohol (2.4MPa), other conditions are identical as embodiment one.
Comparative example three：It is 190 DEG C in temperature, under the conditions of rotating speed is 120rpm, unimplanted fluid during blending extrusion,
His condition is identical as embodiment three.
Table 2 squeezes out influence of the blending condition to PP/ wood flour composite material mechanical properties
Tables 1 and 2 shows that the PP/ wood flour composite materials prepared under no fluid condition, mechanical property is with wood powder content
Increase and declines, especially when wood powder content reaches 70%, wood powder occupies most of space, reduces the mobility of system,
There are more gaps in composite material, may counteract a part of rigidity so that the mechanical property of composite material is remarkably decreased.And
The composite material prepared under the conditions of subcritical alcohol is smaller with the increase of wood powder content its mechanical property variation, it is seen then that subcritical
The mechanical property of the lower composite material of alcohol effect is best.
Example IV：The 80 mesh Eucalyptus wood powders (Shanghai Yun Can woodworks Co., Ltd) for choosing 560g, are added compatible respectively
Agent MAPP-50, MAPP-90 and MAPOE, the content for changing compatilizer are respectively Eucalyptus powder, PP-T30S and compatilizer total content
2.5%, 5%, 7.5%, 10%, the 12.5% of 800g, polyethylene wax 8g, stearic acid 8g, be mixed object be added together it is above-mentioned
In double screw extruder, screw speed 120rpm, temperature are 190 DEG C, while injecting second in the B Metrology Divisions of screw-rod structure figure
Alcohol (2.4MPa), other conditions are identical as embodiment one.
Comparative example four：It is 190 DEG C, rotating speed 120rpm in temperature, while ethyl alcohol is injected in the B Metrology Divisions of screw-rod structure figure
(2.4MPa) is not added with compatilizer in mixture, other are identical as example IV.
The mechanical property for the PP/ wood flour composite materials that example IV and comparative example four obtain is shown in Fig. 9,10,11,12,13.
Curve 1 shows that it is anti-with the polar group in wood powder when MAPP-50 contents are less in Fig. 9,10,11,12,13
Answer insufficient, remaining a large amount of hydroxyl group causes wood powder also to have stronger polarity, this makes the boundary of PP/ wood flour composite materials
Face binding force is poor.And when MAPP-50 contents are excessive, it is intermolecular to react to each other, polymolecular layer is formed, is reduced
Its probability to react with active, the nonactive group in wood powder and polypropylene, the interface binding power between three-phase will become
It is weak.When composite material is by outer force effect, can be destroyed at the weaker place of interface binding power, macro manifestations are exactly composite material
Mechanical properties decrease.Therefore, there are an optimum values for the content of MAPP-50, can make the synthesis mechanics of PP/ wood flour composite materials
Performance reaches maximum.
Its mechanical property can be with when MAPP-90 contents are 5% for curve 1,2 as it can be seen that PP/ wood flour composite materials in comparison diagram
Reach level when MAPP-50 contents are 10%, this is because the former grafting rate is higher than the latter, content has been reached at 5%
Reaction efficiency when to the latter 10%.And PP/ wood flour composite materials MAPP-50 contents be 10% when, in subcritical ethyl alcohol item
The amplitude that erosion-resisting characteristics improves under part is maximum, illustrate that under the effect of subcritical ethyl alcohol, MAPP-50 can be good at and wood fibre
Esterification occurs for the hydroxyl on element, reduces the polarity and hydrophily of wood powder, effectively improves interface phase of the wood powder with PP
Capacitive causes the erosion-resisting characteristics of PP/ wood flour composite materials to significantly improve.Curve 3 shows that composite material is 5% in MAPOE contents
When comprehensive performance it is best, wherein with MAPOE contents increase, the unnotched impact strength and notch impact strength of composite material are in
Linearly increasing, this illustrates that MAPOE can greatly improve the erosion-resisting characteristics of PP/ wood flour composite materials.
Embodiment five：Choose the 80 mesh Eucalyptus wood powders (Shanghai Yun Can woodworks Co., Ltd) of 560g, the PP T30S of 160g
The MAPP-50 (Nanjing is tough plastic cement Co., Ltd) of (Shaanxi extend (group) Yan'an petrochemical plant), 80g, embodiment 5 (a)
Middle addition 8gSA；8gSA, 8gPW are added in embodiment 5 (b)；8gPW is added in embodiment 5 (c)；Titanium is added in embodiment 5 (d)
Acid esters, wherein titanate esters/ethyl alcohol (wt/wt)=1/99 are injected with subcritical fluids；Silane coupling agent is added in embodiment 5 (e)
KH550, wherein KH550/ ethyl alcohol (wt/wt)=2/98 are injected in the form of subcritical fluids.Mixture is added together above-mentioned double
In screw extruder, screw speed 120rpm, 190 DEG C of temperature, pressure 2.4MPa note ethyl alcohol speed and pressure condition and implementation
Example one is identical.
Comparative example five：It is 190 DEG C, rotating speed 120rpm in temperature, while ethyl alcohol is injected in the B Metrology Divisions of screw-rod structure figure
(2.4MPa) is not added with any auxiliary agent in mixture, and other conditions are identical as embodiment five.
Influence of the 3 auxiliary agent content of table to PP/ wood flour composite material mechanical properties
Table 3 shows that PP/ wood flour composite materials show preferable mechanical property in individually addition PW, illustrate subcritical
Ethyl alcohol may interact with PW, promote wood powder preferably to disperse, cause the mechanical property of its composite material higher.And in ethyl alcohol
In with KH550 or titanate esters, the mechanical property of composite material can be made to further enhance, illustrate subcritical ethyl alcohol act under,
There is higher mass-transfer efficiency when KH550 or titanate esters are as solute, substantially promote it between wood powder, PP and MAPP-50
Reaction, enhances interface binding power, to improve the mechanical property of PP/ wood flour composite materials.
Embodiment six：80 mesh poplar wood powder 480g (Shanghai Jia Feng wood powders Co., Ltd) are chosen, (Iranian petrochemical industry is limited by HDPE
Company) 248g, MAHDPE (Nanjing is tough plastic cement Co., Ltd) 72g, atoleine (Shanghai Ling Feng chemical reagent Co., Ltd,
Chemistry is pure) 14.4g mixed, mixture is added together in above-mentioned double screw extruder, control screw speed in 150rpm,
Extrusion temperature is respectively 160 DEG C of (water, 0.6MPa；Normal propyl alcohol, 0.7MPa；Ethyl alcohol, 1.2MPa), 170 DEG C of (water, 0.80MPa；Just
Propyl alcohol, 1.0MPa；Ethyl alcohol, 1.60MPa), 180 DEG C of (water, 1.00MPa；Normal propyl alcohol, 1.2MPa；Ethyl alcohol, 2.0MPa), 190 DEG C
(water, 1.3MPa；Normal propyl alcohol, 1.6MPa；Ethyl alcohol, 2.4MPa), 200 DEG C of (water, 1.9MPa；Normal propyl alcohol, 1.6MPa；Ethyl alcohol,
3.0MPa), melting extrusion blending reaction is carried out；Simultaneously corresponding fluid (water, positive third are injected in the B Metrology Divisions of screw-rod structure figure
Alcohol, ethyl alcohol), other conditions are identical as embodiment one.
Comparative example six：At relevant temperature (160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C), rotating speed is 150rpm conditions
Under, unimplanted fluid in Blending Processes is squeezed out, other conditions are identical as embodiment five.
Curve 1,2,3 and 4 is found in Figure 14,15,16 and 17, and HDPE/ wood powders prepared by subcritical fluids extrusion molding are compound
Material, mechanical property are better than fluid free composite material, illustrate that sub-critical flow physical efficiency promotes dispersion of the wood powder in resin,
Diffusivity is strong, and mass-transfer efficiency is high, is conducive to reacting to each other between maleic anhydride and wood powder and resin, enhances interface knot
It closes, improves the mechanical property of composite material.At 170 DEG C, the mechanical property of HDPE/ wood flour composite materials reaches maximum.
When temperature is higher than 170 DEG C, the mechanical property of HDPE/ wood flour composite materials starts to be decreased obviously, and may be due to wood powder
The raising of temperature-sensitive material, temperature easily makes wood powder coking, resin that can also occur centainly to degrade, these can all make the mechanical property of material
It can decline.Experiment show subcritical alcohol extrusion molding better than subcritical water squeeze out because the oxidisability of subcritical alcohol be weaker than it is subcritical
Water will not have wood powder or matrix strong oxidative degradation, and can improve wood powder and disperse in the base, promote composite material
Interface cohesion, to improve the mechanical property of composite material.
Choose the sample that embodiment six and temperature in comparative example six are 170 DEG C carry out infrared spectrogram (FT-IR) measurement (see
Figure 18).
In figure 18, curve 1,2,3,4 and 5 is relatively it is found that in reference peak intensity 1238cm-1(the C- in wood-fibred
O-C) under the conditions of similar, curve 2,3,4 and 5 is in 2918,2845cm-1There is characteristic peak, they are all C-H in methylene
Stretching vibration.Illustrate that anhydride group occurs with wood-fibred surface at MAHDPE or MAHDPE and subcritical fluids concurrent conditions
Chemical action, so that the polymer on its surface is not easy to be extracted.1464cm-1For the bending vibration of C-H in methylene,
1382cm-1For the bending vibration of C-H in methyl, curve 2,3,4 and 5 is in 718cm-1There is the peak of long-chain methylene in place, and bent
Line 1 does not occur, this more illustrates that chemical action has occurred with wood-fibred surface in anhydride group so that exists in extract
Long-chain methylene.1727、1628cm-1For the carbonylic stretching vibration peak formed after wood-fibred and wood-fibred and acid anhydrides effect, carbonyl
Stretching vibration peak is more and more stronger, illustrates the generation for being conducive to esterification under the conditions of subcritical fluids, wherein in subcritical alcohol
Under the conditions of peak intensity higher than peak under sub-critical water extraction intensity.
Embodiment six and the SEM of the HDPE/ wood flour composite material sections of comparative example six are shown in Figure 19.
A, b, c and d are relatively as it can be seen that still have certain gap and fiber table in Figure 19 at fluid free sample interface
Face is relatively smooth, illustrates that fracture herein is occurred in the form of part interface unsticking and base fracture.Wood-fibred and interlaminar resin in b
Gap becomes smaller, and material interface is tightly combined in c, d, and all there are fine in a part of matrix resin, especially d for fiber surface
Dimension top end surface still has resin, say that the fracture mode of face herein is mainly broken with matrix resin based on, also further illustrate
Subcritical alcohol is more advantageous to the interface cohesion of composite material.
Embodiment seven：Choose 40 mesh Eucalyptus wood powders (Shanghai Jia Feng wood powders Co., Ltd) 200g, (Zhenjiang ABS PA-757K
Qi Mei Chemical Co., Ltd.s) 275g, maleic anhydride grafted ABS (MABS) (Nanjing Qiangren Plastics Material Co., Ltd.) 25g progress
Mixing.Mixture is added together in above-mentioned double screw extruder, control screw speed is respectively in 100rpm, extrusion temperature
170 DEG C of (water, 0.80MPa；Normal propyl alcohol, 1.0MPa；Ethyl alcohol, 1.60MPa), 180 DEG C of (water, 1.00MPa；Normal propyl alcohol, 1.2MPa；
Ethyl alcohol, 2.0MPa), 190 DEG C of (water, 1.3MPa；Normal propyl alcohol, 1.6MPa；Ethyl alcohol, 2.4MPa), 200 DEG C of (water, 1.9MPa；Positive third
Alcohol, 1.6MPa；Ethyl alcohol, 3.0MPa), 210 DEG C of (water, 1.9MPa；Normal propyl alcohol, 2.4MPa；Ethyl alcohol, 3.6MPa), it carries out melting and squeezes
Go out blending reaction, while corresponding fluid (water, normal propyl alcohol, ethyl alcohol), mid-infrared light are injected in the B Metrology Divisions of screw-rod structure figure
Composing in the sample preparation of (FT-IR) uses acetone extraction, other conditions identical as embodiment one.
Comparative example seven：At corresponding temperature (170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C), rotating speed is 100rpm conditions
Under, unimplanted fluid in Blending Processes is squeezed out, other conditions are identical as embodiment seven.
The mechanical property of the obtained ABS/ wood flour composite materials of embodiment seven and comparative example seven is shown in Figure 20,21,22 respectively
With 23.
By curve in Figure 20,21,22 and 23 1,2,3 and 4 as it can be seen that the mechanical property of ABS/ wood flour composite materials is with crowded
The raising for going out temperature significantly improves, and wherein curve 1 reaches maximum at 180 DEG C or so, and curve 2,3,4 is reached at 200 DEG C or so
To maximum.This variation explanation, with the increase for squeezing out blending temperature, the melt viscosity of ABS constantly declines, and which results in ABS
With the reinforcement of wood powder come into full contact with and interface cohesion reacts, therefore cause the generally increase of composite materials property.But
After composite materials property reaches maximum, with further increasing for blending temperature is squeezed out, composite materials property is then
Occur declining, this causes the pyrogenetic reaction of wood powder with excessively high extrusion blending temperature, causes wood powder coking to be gone bad related.Its
For middle curve 2,3,4 compared with curve 1, there is temperature drift when maximum in curve 2,3,4, this squeezes out item with subcritical fluids
Blend and the oxygen touch opportunity in air are less under part, cause wood powder pyrogenetic reaction to die down related.
The mechanical property that subcritical fluids squeeze out the ABS/ wood flour composite materials prepared is apparently higher than answering for no fluid preparation
The mechanical property of condensation material, this may have certain pressure due to subcritical fluids, cause the abundant molten of interface wood-fibred
It is swollen and its fully reacted with ABS or with MABS, the combination between composite material interface is enhanced, so that the power of composite material
Performance is learned to be promoted.And the mechanical property of composite material prepared by subcritical alcohol is better than subcritical water, since subcritical water has
There is stronger oxidisability, has oxidative degradation to wood powder and resin matrix, the polarity of followed by water is too strong, and ABS is weak pole
Property, the difference of compatibility affects the combination between free radical and resin, to affect ABS/ wood flour composite materials
Mechanical property.The oxidisability of subcritical alcohol is weaker than subcritical water, and the polarity of alcohol is less than the polarity of water, compound so as to enhance
Combination between material interface so that the mechanical property of composite material is promoted.
It chooses the sample that temperature is 200 DEG C in embodiment seven and carries out infrared spectrogram (FT-IR) measurement (see Figure 24).
Figure 24 shows, with affiliated wood powder in 1240cm-1(C-O-C) absorption peak at is ABS/ wood under the conditions of reference peak
The acetone extraction object of powder composite material is in 1384cm-1(>C=CH-), 1506cm-1(phenyl ring skeletal vibration peak) and 1640cm-1(>C
=CH2) at characteristic absorption peak intensity it is minimum under conditions of subcritical water, illustrate the strong oxidizing property of subcritical water to wood powder or
Resin matrix produces oxidative degradation, to affect the interface cohesion of wood powder and resin matrix in composite material, and
Absorption peak strength is remarkably reinforced under conditions of subcritical alcohol, illustrates in the case where subcritical alcohol acts on, between ABS or MABS and wood powder interface
Reaction and its interface binding power be improved significantly so that in composite material>C=CH- cannot be fallen by all extractings, largely
The surface for remaining in wood powder, to improve the mechanical property of composite material.
It chooses the sample that embodiment seven is 200 DEG C with temperature in comparative example seven and sem analysis (see Figure 25) has been carried out to section.
Photo a, b, c and d compare display in Figure 25, be pulled out containing apparent wood-fibred in photo a and the hole that is formed,
Although fiber is not extracted directly in photo b, and shows that the combination of wood-fibred and polymeric matrix is more close in figure,
It still can be with there is interfacial gaps between high-visible wood-fibred and matrix.The median surfaces photo c, d gap very unobvious, almost
It is sightless, illustrates to be better than subcritical water in subcritical alcohol, can make combination between wood-fibred and polymeric matrix more
Add securely, can effectively improve the interface cohesion of ABS/ wood flour composite materials.
Claims (5)
1. a kind of method that subcritical alcohol extrusion prepares wood plastic composite, the specific steps are：
A. by account for reactant gross mass percentage composition be 20% ~ 80% thermoplastic macromolecule material, account for reactant gross mass percentage
It is 0% ~ 20% that content, which is 20% ~ 80% wood powder, accounts for reactant gross mass percentage composition, and percentage composition is not that 0% auxiliary agent mixes,
And the gross mass of reactant is 100%；
B. above-mentioned reaction mixture is added to together in the parallel dual-screw extruding machine of certain rotating speed and carries out melting extrusion, simultaneously
Alcohol is injected at the middle part of double screw extruder machine barrel, its blending reaction is made to be in the subcritical state of alcohol；Wherein melting extrusion is anti-
It is 150 DEG C ~ 260 DEG C to answer temperature；Pressure is 0.4MPa ~ 5.2MPa；The screw speed of double screw extruder is 50rpm ~ 200rpm；
C. reaction product cools down, at item, granulation, through vacuum removal volatile matter then through mill mixing, vulcanizing press pressure
Piece obtains wood plastic composite.
2. according to the method described in claim 1, it is characterized in that the thermoplastic macromolecule material is polyvinyl chloride, poly- third
At least one in alkene, polyethylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer or polystyrene
Kind.
3. according to the method described in claim 1, it is characterized in that the wood powder is one in Eucalyptus wood powder or poplar wood powder
Kind；The size of wood powder is between the mesh of 40 mesh ~ 120.
4. according to the method described in claim 1, it is characterized in that the alcohol is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, just
Any one in butanol, sec-butyl alcohol or amylalcohol.
5. according to the method described in claim 1, it is characterized in that the auxiliary agent is：Silane coupling agent, maleic anhydride, Malaysia
Acid anhydrides graft PP, maleic anhydride are grafted HDPE/PE, maleic anhydride is grafted AS, maleic anhydride grafted ABS, maleic anhydride are grafted PS,
One or more of stearic acid, polyethylene wax, solid or atoleine.
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| JP2005296906A (en) * | 2004-04-16 | 2005-10-27 | Shiro Saka | Biomass treating method for treating biomass under supercritical or subcritical condition of alcohol using mixture solvent obtained by adding water to various aliphatic alcohol |
| 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 |
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