CN108530927A - A kind of preparation method of the transparent high strength composite of wood fibre - Google Patents
A kind of preparation method of the transparent high strength composite of wood fibre Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The preparation method of of the invention and a kind of transparent high strength composite of wood fibre, including：The lignin in wood matrix is removed by chemical treatment, then through hydrophobic oleophilic oil modification and drying process, obtains hydrophobic oleophilic oil delignification wood matrix；It will be in high molecular polymer monomer solution hydrophobic oleophilic oil delignification wood matrix as obtained by full-cell process or lowry method injection, then cause high molecular polymer monomer in hydrophobic oleophilic oil delignification wood matrix and polymerisation occurs, obtain the transparent high strength composite of the wood fibre.Composite material prepared by the present invention has very high intensity, and with the transparency well.
Description
Technical field
The present invention relates to a kind of preparation method of organic transparent high strength composite more particularly to the transparent height of wood fibre
The preparation method of strength composite materials.
Background technology
The composite material of the enhanced high molecular polymer of wood fibre is a kind of novel high-performance material.2004
Year, professor Yano of Tokyo Univ Japan has separated the cellulose fento of one-dimensional micron grade with Physical from wood for the first time
Silk cluster ([1] H.Yano. (Applied Physics material science) Appl.Phys.A.78 (2004), 547-552).2010, Japan east
The method of professor Isogai of capital university tetramethyl piperidine compounds chemical stripping, has separated 1-dimention nano grade from wood
Cellulose microfibril, which is dispersed in water in all-transparent, it was demonstrated that cellulose can be used for transparent material ([2]
A.Isogai. (nanoscale) Nanoscale.3 (2011) 71-85).2011, professor Yano of Tokyo Univ Japan was using wood
Matter cellulose fibre is compound with high molecular polymer, is made that first high-strength transparence paper, the visible light-transmissive of the cellophane paper
Rate maintains an equal level with commercial PET film substantially, and elasticity modulus is 4-5 times of commercial PET film, and fracture tensile strength can also reach commercial
2-3 times ([3] H.Yano. (nanoscale) Nanoscale.3 (2011) 71-85) of PET film.2013, Maryland, US was big
Professor Hu applies high-strength transparence paper in area of solar cell, it is found that high-strength transparence paper can be collected preferably
The solar energy of non-normal incidence improves energy utilization rate ([4] L.Hu. (nanometer bulletin) Nano of solar cell
Lett.14(2014)765-773).Since the composite material of the enhanced high molecular polymer of cellulose fibre has and biological can drop
Solution, the transparency is good, intensity is high and the excellent properties such as the coefficient of expansion is smaller, has just been had received widespread attention since self-discovery.
Timber, wood materials and biomass resource, can be so that carbon carry out processing again admittedly after combined processing is processed
Fixed and encapsulation, and CO is reduced in whole process2Discharge, to mitigate " greenhouse effects ", this is to human survival
The contribution of environment.Timber or biomass composite can not only make low quality wood, minor diameter timber, waste and old wood and agricultural surplus
Excess is efficiently utilized, and has ecological effect rarely known by the people.For territory, our forest reserves compare
It is poor, the 60% of afforestation rate deficiency time average level, the 130th of the world is occupied, thus the carbon of forest stores total amount
It is insufficient.Therefore, from the angle of maintaining ecological balance, the composite material of the enhanced high molecular polymer of cellulose fibre, section
That learns is utilized timber, reduces greenhouse effects, maintains ecological safety.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of the transparent high strength composite of wood fibre, including：
The lignin in wood matrix is removed by chemical treatment, then through hydrophobic oleophilic oil modification and drying process, is dredged
Water lipophile delignification wood matrix；
By high molecular polymer monomer solution hydrophobic oleophilic oil delignification wood as obtained by full-cell process or lowry method injection
In head matrix, then causes high molecular polymer monomer in hydrophobic oleophilic oil delignification wood matrix and polymerisation occurs, obtain
To the transparent high strength composite of the wood fibre.
The present invention removes the lignin in wood matrix by chemically treated mode, then through hydrophobic oleophilic oil modification and
Be dried, the pore structure of wood matrix will not be destroyed, while assigning the performance of wood matrix hydrophobic oleophilic oil, make its with it is most
Number high molecular polymer monomer solution all has good wetting property.Then applied by full-cell process or lowry method certain
Ambient pressure makes in the high molecular polymer monomer solution injection gained hydrophobic oleophilic oil delignification wood matrix of low viscosity
The high molecular polymer monomer distribution is obtained in the pore structure of hydrophobic oleophilic oil delignification wood matrix.Finally cause again
High molecular polymer monomer is in the hole of hydrophobic oleophilic oil delignification wood matrix in hydrophobic oleophilic oil delignification wood matrix
Home position polymerization reaction occurs in gap structure, finally obtains the transparent high strength composite of wood fibre.
Preferably, the chemical treatment is small for wood matrix is placed in chemical reagent the reaction 1~10 at 25~100 DEG C
When.
Also, preferably, the chemical reagent is in the mixed solution and perchloric acid of hydrogen peroxide, sodium hypochlorite and sodium hydroxide
At least one.
Preferably, the hydrophobic oleophilic oil modification is to immerse the delignification wood matrix after chemical treatment to contain to change
It is reacted 12~24 hours in the solution of property agent, a concentration of 0.01~0.1mol/ of modifying agent in the solution containing modifying agent
L.When the present invention selects modifying agent, the hydroxyl shape in the delignification wood matrix after should meeting and being chemically treated on cellulose
At chemical bond, and to contain hydrophobic group in the modifying agent so that delignification wood matrix has hydrophobic oleophilic oil
Property.
Also, preferably, the modifying agent is positive stearylmercaptan, n- dodecyl mereaptan or stearic acid.
Preferably, described be dried as freeze-drying, vacuum drying or supercritical drying.It will not shadow after drying process
Ring the porosity and surface chemistry composition of wood.
Preferably, the full-cell process includes：
The hydrophobic oleophilic oil delignification wood matrix is placed in container and is vacuum-treated, high molecular polymer monomer is added
Solution after container until full of vacuum is released；
Then 1~3MPa is forced into until the immersion amount of high molecular polymer monomer solution is saturated, then is restored after vacuum processing
To normal pressure.Also, preferably, the vacuum degree of the vacuum processing be 79~86kPa, the time be 15 minutes~2 hours, preferably 1
~2 hours.Specifically, it is vacuum-treated after hydrophobic oleophilic oil delignification wood matrix being placed in process tank, generally
Vacuum degree is 79~86kPa, keeps 15~60min.Vacuum is initially added into high molecular polymer monomer after reaching a certain level molten
Liquid should keep the vacuum constant at this time, in case the injection of high molecular polymer monomer solution is uneven；Polyphosphazene polymer is full of in process tank
Vacuum is released after monomer adduct solution, and is initially pressurized to maximum pressure (1~3MPa), then keeps maximum pressure until immersing
Until amount saturation.After pressure releases, high molecular polymer monomer solution can by the gas " recoil " that wood interior retains on a small quantity,
After high molecular polymer monomer solution is discharged, process tank will also vacuumize again, by the high molecular polymerization for recycling wood
Object monomer solution fills hole present in wood.It keeps vacuum for a period of time, releases vacuum.
Preferably, the lowry method is：The hydrophobic oleophilic oil delignification wood matrix is placed in and is filled with high score
In the container of sub- polymer monomer solution, be forced into 1~3MPa until high molecular polymer monomer solution immersion amount be saturated, then
Restore to normal pressure after vacuum processing.Also, preferably, the vacuum degree of the vacuum processing is 79~86kPa, the time is 15 minutes
~2 hours, preferably 1~2 hour.Specifically, it is filled after hydrophobic oleophilic oil delignification wood matrix being placed in process tank
Full high molecular polymer monomer solution, and it is initially pressurized to maximum pressure (1~3MPa), then maximum pressure is kept until immersing
Until amount saturation.After pressure releases, high molecular polymer monomer solution can by the gas " recoil " that wood interior retains on a small quantity,
After high molecular polymer monomer solution is discharged, process tank will also vacuumize again, by the high molecular polymerization for recycling wood
Object monomer solution fills hole present in wood.It keeps vacuum for a period of time, releases vacuum.
Preferably, the high molecular polymer monomer solution is methyl methacrylate solution, bis-phenol A glycidyl ether is molten
Liquid or dimethyl siloxane solution.
Preferably, heating by ultraviolet lighting or at 50-80 DEG C and polymerizeing to cause high molecular polymer monomer
Reaction；The power of the ultraviolet lighting is 10~30W, and the time is 1~3h.
On the other hand, the present invention also provides a kind of transparent high-strength composites of wood fibre prepared according to the above method
Material, the transparent high strength composite of wood fibre include that hydrophobic oleophilic oil is modified delignification wood matrix and distribution
High molecular polymer in the pore structure that the hydrophobic oleophilic oil is modified delignification wood matrix.
Preferably, in the transparent high strength composite of wood fibre high molecular polymer mass content be 30~
70wt%.
Preferably, the high molecular polymer is polymethyl methacrylate, epoxy resin or dimethyl silicone polymer.
Optical transmittance of the transparent high strength composite of wood fibre provided by the invention at 550nm be 75~
90%.
The Young's modulus of the transparent high strength composite of wood fibre provided by the invention is 2.51GPa~2.91GPa, is broken
It is 59.8Mpa~76.1Mpa to split tensile strength.
Compared with prior art, it is enhanced that the method that the present invention uses the injection of high molecular polymer monomer obtains wood fibre
The composite material of high molecular polymer, simple production process are low for equipment requirements.The primary raw material wherein used is wood, at
This is low and renewable.Prepared composite material has very high intensity, and with the transparency well.
The present invention has the characteristics that pollution-free, low energy consumption, low cost, the Wood fiber composite material transparency of preparation is good,
Intensity is high, and has the characteristics that light weight, cheap, has good industrial prospect, can be widely applied to photoelectricity, biology is cured
In the fields such as medicine, agricultural, food and environment.
Description of the drawings
Fig. 1 is the SEM image of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 1；
Fig. 2 is the SEM image of the compound poly bisphenol glycidol ether of willow wood fibre in embodiment 2；
Fig. 3 is the SEM image of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 3；
Fig. 4 is the SEM image of the compound polymethyl methacrylate materials of beech wood fibre in embodiment 4；
Fig. 5 is the SEM image of the compound polymethyl methacrylate materials of linden wood fibre in embodiment 5；
Fig. 6 is the optical transmittance curve of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 1；
Fig. 7 is the optical transmittance curve of the compound poly bisphenol glycidol ether of willow wood fibre in embodiment 2；
Fig. 8 is the optical transmittance curve of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 3；
Fig. 9 is the optical transmittance curve of the compound polymethyl methacrylate materials of beech wood fibre in embodiment 4；
Figure 10 is the optical transmittance curve of the compound polymethyl methacrylate materials of linden wood fibre in embodiment 5；
Figure 11 is the stress-strain diagram of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 1；
Figure 12 is the stress-strain diagram of the compound poly bisphenol glycidol ether of willow wood fibre in embodiment 2；
Figure 13 is the stress-strain diagram of the compound polymethyl methacrylate materials of willow wood fibre in embodiment 3；
Figure 14 is the stress-strain diagram of the compound polymethyl methacrylate materials of beech wood fibre in embodiment 4；
Figure 15 is the stress-strain diagram of the compound polymethyl methacrylate materials of linden wood fibre in embodiment 5；
Figure 16 is the optical transmittance curve of the compound polymethyl methacrylate materials of linden wood fibre in comparative example；
Figure 17 is the stress-strain diagram of the compound polymethyl methacrylate materials of linden wood fibre in comparative example.
Specific implementation mode
It is further illustrated the present invention below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the present invention, the transparent high strength composite of wood fibre includes hydrophobic oleophilic oil delignification wood base
Body and the high molecular polymer being distributed in the pore structure of the hydrophobic oleophilic oil modification delignification wood matrix.It is described
The mass content of high molecular polymer is 30~70wt% in the transparent high strength composite of wood fibre, according to wood raw material
Type different content is varied from, but ensures the hole that aperture 50nm or more is not present in wood.The high molecular polymer can
For polymethyl methacrylate, epoxy resin or dimethyl silicone polymer.
The present invention handles the lignin in removal wood by chemical method first.Then delignification wood matrix is used
Special drying means drying.Finally high molecular polymer monomer is gone by special injection method injection hydrophobic oleophilic oil wooden
In plain wood matrix, causes high molecular polymer polymerization, obtain the transparent high strength composite of wood fibre.Following exemplary
Illustrate the preparation method of the transparent high strength composite of wood fibre provided by the invention.
The lignin in wood is removed by chemical treatment.Specifically, wood is removed by the method that chemical reagent impregnates
In lignin, that is, wood matrix is placed in chemical reagent and is reacted 1~10 hour at 25~100 DEG C, A product are obtained.Made
Chemical reagent can be selected from least one of mixed solution or perchloric acid of hydrogen peroxide, sodium hypochlorite and sodium hydroxide.Its
Described in hydrogen peroxide concentration can be 15wt%~30wt%, perchloric acid concentration can be 12wt%~15wt%, sodium hydroxide
In the mixed solution of sodium hypochlorite and sodium hydroxide, sodium hypochlorite concentration can be 3wt%~5wt%, and naoh concentration can be
15wt%~20wt%.
Delignification wood matrix after chemical treatment is immersed in the solution containing modifying agent and is reacted 12~24 hours, institute
State a concentration of 0.01~0.1mol/L of modifying agent in the solution containing modifying agent.It is organic molten in the solution containing modifying agent
Agent can be ethyl alcohol, isopropanol, toluene, ethyl acetate etc..Or before immersing the solution containing modifying agent, first with the organic solvent
(for example, ethyl alcohol, isopropanol, toluene, ethyl acetate etc.) cleans the delignification wood matrix after the chemical treatment, and removal exists
Chemical reagent in delignification wood matrix.As an example, by A product (the delignification wood after chemical treatment
Matrix) it is cleaned with ethyl alcohol, and be immersed in the ethanol solution of modifying agent and react 12~24 hours, the modifying agent is positive 18 sulphur
Alcohol, n- dodecyl mereaptan or stearic acid.Then processing is dried, obtains B product (hydrophobic oleophilic oil delignification wood matrix).Institute
It can be freeze-drying, vacuum drying or supercritical drying to state drying process.Specifically, with freeze-drying, vacuum drying or super
Critical drying will not destroy the pore structure of wood.Wherein, vacuum drying can use vacuum drying chamber, vacuum degree 100Pa
~200Pa, temperature are 80 DEG C~100 DEG C.Supercritical drying can use supercritical carbon dioxide extraction apparatus.Freeze-drying can
It is 6-12 hours dry in the case where subzero 40 DEG C of subzero 20-.
High molecular polymer monomer solution is injected into B product, is C product.The method of the injection can be that full-cell process or half limit
Note method.The high molecular polymer monomer solution is methyl methacrylate solution, bis-phenol A glycidyl ether solution or dimethyl
Siloxane solution, i.e. high molecular polymer monomer can be methyl methacrylate, bis-phenol A glycidyl ether or dimethyl silica
Alkane.Wherein full-cell process includes：The hydrophobic oleophilic oil delignification wood matrix is placed in container (for example, process tank) very
Vacancy is managed, and adds high molecular polymer monomer solution until full of vacuum is released after container.Then be forced into 1~3MPa until
(high molecular polymer monomer solution immerses hydrophobic oleophilic oil delignification wood base to the immersion amount of high molecular polymer monomer solution
The amount of body) saturation, then restore to normal pressure after vacuum processing.As an example, it will be gone after hydrophobic oleophilic oil and drying process
Lignin wood is placed in process tank and vacuumizes, and vacuum degree is 79~86kPa, keeps 15~60min；It then will be in process tank
Full of releasing vacuum after methyl methacrylate solution, and it is initially pressurized to 1~3MPa, keeps 15~60min；Work as pressure releases
Afterwards, it is 79~86kPa that process tank will also vacuumize and keep 1~2h of vacuum, vacuum degree again, finally releases vacuum.Wherein half limits
Note method can be that the hydrophobic oleophilic oil delignification wood matrix is placed in the container for being filled with high molecular polymer monomer solution
In, being forced into 1~3MPa, (high molecular polymer monomer solution immerses hydrophobic up to the immersion amount of high molecular polymer monomer solution
The amount of lipophile delignification wood matrix) (required time is generally dependent on applies stressed size and wood matrix to saturation
Size.Time may generally be 10-60 minutes), then restore to normal pressure after vacuum processing.As an example, by hydrophobic oleophilic oil
And the delignification wood after being dried immerses 1-2h in methyl methacrylate solution, is forced into 1-3Mpa and keeps 15-
Then 60min is evacuated to 79~86kPa and keeps 1~2h and restore to normal pressure.As a detailed example, by methyl-prop
A kind of injection (lowry method) hydrophobic oleophilic oil in e pioic acid methyl ester, bis-phenol A glycidyl ether and dimethyl siloxane removes wood
2h in quality wood matrix is forced into 3Mpa and keeps 15min, is then evacuated to 80kPa and keeps 2h and restore to normal pressure.
Cause the high molecular polymer polymerization in C product, obtain the transparent high strength composite of wood fibre, is finished product.Draw
The method for sending out high molecular polymer monomer polymerization can be heat treatment or ultraviolet processing.Specifically, pass through ultraviolet lighting (irradiation
Power can be 10~30W, and irradiation time can be 1~3h) or 50 DEG C~80 DEG C at heat, cause high molecular polymer polymerization, it is poly-
Close the time be 6~for 24 hours, obtain transparency cellulose fiber-reinforced composites.
In above-mentioned preparation method, the raw material of wood matrix can be selected from one kind in willow, linden, beech.
As an example, wood is immersed in 80 DEG C by (1), 4~5h in the hydrogen peroxide solution of a concentration of 30wt%.(2)
Wood obtained by step (1) is cleaned with ethyl alcohol, and is immersed in the ethanol solution of positive stearylmercaptan and is being dried in vacuo after reaction 12h
Dry in device, the vacuum degree of vacuum drying chamber is 100~200Pa, and drying temperature is 80~100 DEG C, drying time is 20~
24h.(3) wood obtained by step (2) is immersed into 1~2h in methyl methacrylate solution, is forced into 3Mpa and keeps 15min, so
After be evacuated to 200Pa.(3) compound obtained is heating and curing 5h at 60~80 DEG C, finally obtains the transparent height of wood fibre
Strength composite materials.
The optics light transmittance of the transparent high strength composite of wood fibre prepared by the present invention at 550nm can be 75%~
90%.The Young's modulus of the transparent high strength composite of wood fibre can be 2.51GPa~2.91GPa, and fracture tensile strength can
For 59.8Mpa~76.1Mpa.
Embodiment is enumerated further below so that the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.If without specified otherwise, polyphosphazene polymer of the present invention
Monomer adduct solution is made of polymer monomer completely.
Embodiment 1
By 5cm long, the willow of 5cm wide, 0.5cm thickness is immersed in 80 DEG C, in the hydrogen peroxide solution of a concentration of 30wt% (used time 4h).
Obtained delignification wood is cleaned with ethyl alcohol, and be immersed in positive stearylmercaptan ethanol solution (positive stearylmercaptan it is dense
Degree is 0.05mol/L) in react 12h, and dry in vacuum desiccator (vacuum degree of vacuum drying chamber is 200Pa, dry temperature
Degree is 80 DEG C, drying time 20h).By the delignification wood after hydrophobic oleophilic oil and drying process, (hydrophobic oleophilic oil is gone wooden
Plain wood matrix) it is placed in process tank and vacuumizes, vacuum degree 79kPa keeps 30min.Then first will be full of in process tank
Vacuum is released after base methyl acrylate solution, and is initially pressurized to 1MPa, keeps 60min.After pressure releases, process tank is also wanted
Vacuumize and keep vacuum 2h, vacuum degree 79kPa finally to release vacuum again.The compound of acquisition is heating and curing at 60 DEG C
5h, finally obtains the compound polymethyl methacrylate materials of willow wood fibre, poly-methyl methacrylate in the composite material
The content of ester is 59.3wt%.
Embodiment 2
The willow of 5cm long, 5cm wide, 0.5cm thickness are immersed in 90 DEG C, the mixing of 5wt% sodium hypochlorite and 20wt% sodium hydroxides
In solution (used time 5h).Obtained delignification wood is cleaned with ethyl alcohol, and is immersed in the ethanol solution of n- dodecyl mereaptan
18h is reacted in (a concentration of 0.05mol/L of n- dodecyl mereaptan), and supercritical carbon dioxide extraction apparatus is used in combination to dry.It will be hydrophobic
Delignification wood after oleophylic and drying process is placed in process tank and vacuumizes, and vacuum degree 83kPa keeps 45min.So
Vacuum is released after bis-phenol A glycidyl ether solution will be full of in process tank afterwards, and is initially pressurized to 3MPa, keeps 15min.Work as pressure
After power releases, process tank will also vacuumize and keep vacuum 2h, vacuum degree 83kPa finally to release vacuum again.What is obtained is compound
Object cures 2h under the ultra violet lamp of irradiation power 15W, finally obtains the compound poly bisphenol glycidol ether of willow wood fibre
Material, the content of poly bisphenol glycidol ether is 59.5wt% in the composite material.
Embodiment 3
By 5cm long, the willow of 5cm wide, 0.5cm thickness is immersed in 100 DEG C, in the perchloric acid solution of 15wt% (used time 4h).By institute
Obtained delignification wood is cleaned with ethyl alcohol, and is immersed in stearic ethanol solution (stearic a concentration of 0.05mol/
L reaction for 24 hours, is used in combination supercritical carbon dioxide extraction apparatus to dry in).By the delignification wood after hydrophobic oleophilic oil and drying process
Head is placed in process tank and full of 2MPa is pressurized to after dimethyl silicone polymer solution, keeps 20min.After pressure releases, place
Reason tank vacuumizes and keeps vacuum 2h, vacuum degree 83kPa finally to release vacuum.The compound of acquisition cures at 60 DEG C
12h finally obtains the compound polydimethyl siloxane material of willow wood fibre.Dimethyl silicone polymer in the composite material
Content is 60.5wt%.
Embodiment 4
By 5cm long, the beech of 5cm wide, 0.5cm thickness is immersed in 80 DEG C, in the hydrogen peroxide solution of a concentration of 30wt% (used time 4h).
Obtained delignification wood is cleaned with ethyl alcohol, and it is (stearic a concentration of to be immersed in stearic ethanol solution
It is reacted for 24 hours in 0.05mol/L), and (vacuum degree of vacuum drying chamber is 200Pa, and drying temperature is for drying in vacuum desiccator
80 DEG C, drying time 20h).Delignification wood after hydrophobic oleophilic oil and drying process is placed in process tank and is vacuumized,
Vacuum degree is 80kPa, keeps 50min.Then vacuum is released after methyl methacrylate solution being full of in process tank, and is started
It is pressurized to 3MPa, keeps 15min.After pressure releases, process tank will also vacuumize and keep the vacuum 1.5h, vacuum degree to be again
80kPa finally releases vacuum.The compound of acquisition is heating and curing 5h at 60 DEG C, and it is compound poly- to finally obtain beech wood fibre
Methyl methacrylate material.The content of polymethyl methacrylate is 37.3wt% in the composite material.
Embodiment 5
By 5cm long, the linden of 5cm wide, 0.5cm thickness is immersed in 80 DEG C, in the hydrogen peroxide solution of a concentration of 30wt% (used time 4h).
Obtained delignification wood is cleaned with ethyl alcohol, and be immersed in positive stearylmercaptan ethanol solution (positive stearylmercaptan it is dense
Degree is 0.05mol/L) in react 16h, and dry in vacuum desiccator (vacuum degree of vacuum drying chamber is 200Pa, dry temperature
Degree is 80 DEG C, drying time 20h).Delignification wood after hydrophobic oleophilic oil and drying process is placed in process tank and is taken out
Vacuum, vacuum degree 81kPa keep 45min.Then vacuum is released after methyl methacrylate solution being full of in process tank,
And it is initially pressurized to 2MPa, keep 20min.After pressure releases, process tank will also vacuumize and keep vacuum 1h, vacuum degree again
For 81kPa, vacuum is finally released.The compound of acquisition is heating and curing 5h at 60 DEG C, and it is compound to finally obtain linden wood fibre
Polymethyl methacrylate materials.The content of polymethyl methacrylate is 40.1wt% in the composite material.
Wood fibre is transparent high-strength in Fig. 1-5 respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
Spend the SEM image of composite material.From can be seen that high molecular polymer does not fall off significantly in Fig. 2-6, illustrate polyphosphazene polymer
Closing between object and wood fibre has very strong adhesion strength.
The transparent height of wood fibre in Fig. 6-10 respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
The optical transmittance curve of strength composite materials.From in Fig. 2-6 it can be seen that the transparent high strength composite of wood fibre exist
Optics light transmittance at 550nm is 75%~90%, illustrates that the transparent high strength composite transparency of wood fibre is very good.Its
Optical transmittance of the transparent high strength composite of wood fibre at 550nm obtained by middle embodiment 1-5 be respectively 85%,
82%, 75%, 90%, 79%.
The transparent height of wood fibre in Figure 11-15 respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
The stress-strain diagram of strength composite materials.From the poplar that can be seen that the transparent high strength composite of wood fibre in Figure 11-15
Family name's modulus is 2.51GPa~2.91GPa, and fracture tensile strength is 59.8Mpa~76.1Mpa, illustrates that wood fibre is transparent high-strength
It is a kind of composite material of high intensity to spend composite material.The transparent high strength composite of wood fibre obtained by wherein embodiment 1-5
Young's modulus be respectively 2.55GPa, 2.65GPa, 2.77GPa, 2.91GPa, 2.85GPa, fracture tensile strength is respectively
76.1Mpa、59.8Mpa、60.1Mpa、62.9Mpa、63.8Mpa。
Comparative example (method for using Lars)
By 5cm long, the linden of 5cm wide, 0.5cm thickness is immersed in 80 DEG C, (the used time in the sodium chlorite solution of a concentration of 1wt%
12h), obtained delignification wood ethyl alcohol and acetone are respectively washed 3 times.Again by methyl methacrylate solution 75
Prepolymerization 15min at DEG C, by after prepolymerization viscous solution and delignification wood simultaneously be placed in process tank, vacuumize
30min releases vacuum and keeps 30min, recycles 3 times.Finally obtain the compound polymethyl methacrylate materials of linden wood fibre.
The content of polymethyl methacrylate is 35.5wt% in the composite material.
Figure 16-17 is respectively the optics of the compound polymethyl methacrylate materials of linden wood fibre in comparative example through bent
Line and stress-strain diagram.From in Figure 16-17 it can be seen that comparative example in the compound polymethyl methacrylate of linden wood fibre
Optical transmittance of the material at 550nm is 57%, Young's modulus 1.83GPa, fracture tensile strength 39.6Mpa.Explanation
The wood fibre composite resin material optical transmittance and mechanical strength of conventional method production are all relatively low.
Claims (16)
1. a kind of preparation method of the transparent high strength composite of wood fibre, which is characterized in that including：
The lignin in wood matrix is removed by chemical treatment, then through hydrophobic oleophilic oil modification and drying process, is dredged
Water lipophile delignification wood matrix；
By high molecular polymer monomer solution hydrophobic oleophilic oil delignification wood as obtained by full-cell process or lowry method injection
In head matrix, then causes high molecular polymer monomer in hydrophobic oleophilic oil delignification wood matrix and polymerisation occurs, obtain
To the transparent high strength composite of the wood fibre.
2. preparation method according to claim 1, which is characterized in that the chemical treatment is that wood matrix is placed in chemistry
It is reacted 1~10 hour at 25~100 DEG C in reagent.
3. preparation method according to claim 2, which is characterized in that the chemical reagent is selected from hydrogen peroxide, sodium hypochlorite
At least one of with the mixed solution of sodium hydroxide and perchloric acid.
4. preparation method according to any one of claim 1-3, which is characterized in that the hydrophobic oleophilic oil modification is
Delignification wood matrix after chemical treatment is immersed in the solution containing modifying agent and is reacted 12~24 hours, it is described containing changing
A concentration of 0.01~0.1mol/L of modifying agent in the solution of property agent.
5. preparation method according to claim 4, which is characterized in that the modifying agent is positive stearylmercaptan, positive 12 sulphur
Alcohol or stearic acid.
6. preparation method according to any one of claims 1-5, which is characterized in that described be dried is done for freezing
Dry, vacuum drying or supercritical drying.
7. according to the preparation method described in any one of claim 1-6, which is characterized in that the full-cell process includes：
The hydrophobic oleophilic oil delignification wood matrix is placed in container and is vacuum-treated, high molecular polymer monomer is added
Solution after container until full of vacuum is released；
Then 1~3MPa is forced into until the immersion amount of high molecular polymer monomer solution is saturated, then is restored after vacuum processing
To normal pressure.
8. according to the preparation method described in any one of claim 1-6, which is characterized in that the lowry method is：It will be described
Hydrophobic oleophilic oil delignification wood matrix is placed in the container for being filled with high molecular polymer monomer solution, it is forced into 1~
3MPa is until the immersion amount of high molecular polymer monomer solution is saturated, then is restored to normal pressure after vacuum processing.
9. according to the preparation method described in any one of claim 7 or 8, which is characterized in that the vacuum degree of the vacuum processing
For 79~86kPa, the time is 15 minutes~2 hours, preferably 1~2 hour.
10. according to the preparation method described in any one of claim 1-9, which is characterized in that the high molecular polymer monomer
Solution is methyl methacrylate solution, bis-phenol A glycidyl ether solution or dimethyl siloxane solution.
11. according to the preparation method described in any one of claim 1-10, which is characterized in that by ultraviolet lighting or 50~
It heats to cause high molecular polymer monomer generation polymerisation at 80 DEG C；The power of the ultraviolet lighting is 10~30W, when
Between be 1~3 hour.
12. the transparent high-strength composite material of wood fibre prepared by a kind of method according to any one of claim 1-11
Material, which is characterized in that the transparent high strength composite of wood fibre include hydrophobic oleophilic oil delignification wood matrix, with
And it is distributed in the high molecular polymer that the hydrophobic oleophilic oil is modified in the pore structure of delignification wood matrix.
13. according to the transparent high strength composite of wood fibre described in claim 12, which is characterized in that the wood fibre is saturating
The mass content of high molecular polymer is 30~70wt% in bright high strength composite.
14. according to the transparent high strength composite of the wood fibre of claim 12 or 13, which is characterized in that the macromolecule
Polymer is polymethyl methacrylate, epoxy resin or dimethyl silicone polymer.
15. according to the transparent high strength composite of any one of the claim 12-14 wood fibres, which is characterized in that institute
It is 75~90% to state optical transmittance of the transparent high strength composite of wood fibre at 550nm.
16. according to the transparent high strength composite of any one of the claim 12-15 wood fibres, which is characterized in that institute
The Young's modulus for stating the transparent high strength composite of wood fibre is 2.51GPa~2.91GPa, and fracture tensile strength is
59.8Mpa~76.1Mpa.
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