CN102775621A - Method for preparing nanometer SiO2 doped wood-organic-inorganic hybrid nanometer composite material - Google Patents
Method for preparing nanometer SiO2 doped wood-organic-inorganic hybrid nanometer composite material Download PDFInfo
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- CN102775621A CN102775621A CN201210287499XA CN201210287499A CN102775621A CN 102775621 A CN102775621 A CN 102775621A CN 201210287499X A CN201210287499X A CN 201210287499XA CN 201210287499 A CN201210287499 A CN 201210287499A CN 102775621 A CN102775621 A CN 102775621A
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Abstract
The invention discloses a method for preparing a nanometer SiO2 doped wood-organic-inorganic hybrid nanometer composite material, and relates to a method for preparing a wood composite material. The method is invented for solving the technical problems that the wood-organic polymer composite material is poor in thermal stability, low in impact toughness and poor in the mechanical property of the wood-inorganic (nanometer) composite material. The method comprises the following steps of: firstly, ultrasonically dispersing nanometer SiO2 (unsaturated double bonds on the surface) into a monomer solution; compounding an initiator and a crosslinking agent to form an impregnation liquid; putting wood into the impregnation liquid and placing the impregnated wood into a reaction kettle; after the reaction kettle is hermetic, vacuumizing the reaction kettle; releasing the vacuumization, and then pressurizing by air; reducing the pressure to the constant pressure; taking out the wood; covering the impregnated wood by an aluminum-foil paper; heating the impregnated wood covered by the aluminum-foil paper; removing the aluminum-foil paper; and further heating the wood to prepare the composite material. The polymer in the wood-organic-inorganic hybrid nanometer composite material is well compatible to a wood substrate interface, so that the prepared composite material is high in mechanical strength, heat stability, size stability and anti-corrosion performance.
Description
Technical field
The present invention relates to the preparation method of composite wooden material.
Background technology
Impregnate the timber-organic polymer composite material for preparing with polymerization method based on monomer and have good mechanical performance and weather resistance (antiseptic property and dimensional stability) more; And the ecological environment material nd characteristic that has kept timber; Decoration material field in indoor and outdoor building structural materials, special place has the market requirement, and the efficient utilization of timber especially low-quality timber is had crucial meaning; But the many poor heat resistance because of polymkeric substance of this type material have lower thermostability (as being measurement index with maximum pyrolysis temperature); Even be lower than timber itself; And many fragility characteristics because of polymkeric substance cause the impelling strength of said material significantly to reduce, and then have limited the application of widening of said material.
Inorganic body is preferable to the improvement of timber single performance (like thermotolerance); Can make timber-inorganic composite materials be applied in the field that some weather resistance is had higher requirements; Especially the part specific function of the timber that nano-meter characteristic is given of nano inorganic body is expected to the timber applications expanding to value segment; But inorganic body is less to the general contribution of improvement of timber (especially low-quality timber) mechanical property, has limited the widespread use of this material.
And the inorganic-organic hybridization nano matrix material is because of having the weather resistance of organic high-strength mechanical property and inorganic body concurrently; And down collaborative compound some specific function of giving of both nanoscales; All present tempting application prospect in fields such as mechanics, calorifics, optics, electromagnetism and biology, become one of hot research direction of present material scientific domain.Wherein, nanometer SiO
2Particle is with its cheap price, good thermostability, and the asepsis environment-protecting characteristic becomes hybrid inorganic-organic materials and prepares the most frequently used nano inorganic body.
Summary of the invention
The present invention for solve timber-organic polymer composite material poor heat stability, impelling strength is low and the technical problem of timber-inorganic (nanometer) composite materials property difference, provides a kind of based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material.
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material carries out according to the following steps:
One, take by weighing 1 mass parts functional monomer and toughness agent and mix, the quality of toughness agent is 1%～150% of a functional monomer quality, obtains monomer solution;
Two, take by weighing the nanometer SiO of the monomer solution quality 0.1%～1% that step 1 obtains
2(surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa is with dried nanometer SiO
2Joining in the monomer solution, is that 15 ℃～30 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing linking agent, initiator and acetone; Wherein the quality of initiator accounts for 0.5%～1% of monomer solution quality that step 1 obtains; The quality of linking agent accounts for 1%～10% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of linking agent quality;
Four, the linking agent that step 3 is taken by weighing is dissolved in the acetone, obtains cross-linking agent solution, and the initiator that again step 3 is taken by weighing joins nanometer SiO with cross-linking agent solution
2In the homodisperse monomer solution, stir, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Then timber and steeping fluid are inserted in the retort; Be evacuated to after airtight in the retort vacuum tightness for-0.08MPa～-0.095MPa, keep vacuum tightness be-0.08MPa～-condition 15min～25min of 0.095MPa;
Six, removes vacuum, return to normal pressure, and then the pressure in air pressurized to the retort is 0.8MPa～1MPa that keep-uping pressure is condition 20min～30min of 0.8MPa～1MPa;
Seven, the pressure in the retort is reduced to normal pressure; Take out timber; Timber parcel after will flooding with aluminium-foil paper, to be heated to temperature then be 75 ℃～85 ℃ and keep this temperature 8h～10h, removes aluminium-foil paper; To continue to be heated to temperature again be 105 ℃～115 ℃ and keep this temperature 8h～10h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material;
Functional monomer described in the step 1 is one or both the combination in SY-Monomer G (GMA) and the glycidyl allyl ether (AGE);
Toughness agent described in the step 1 is a kind of or wherein several kinds the combination in ethylene glycol dimethacrylate (EGDMA), polyoxyethylene glycol-200-dimethacrylate (PEG200DMA) and the polyoxyethylene glycol-400-dimethacrylate (PEG400DMA);
Initiator described in the step 3 is Diisopropyl azodicarboxylate (AIBN) or Lucidol (BPO);
Linking agent described in the step 3 is response type linking agent or catalytic type linking agent; Said response type linking agent be maleic anhydride (MALEIC ANHYDRIDE) (MAN), a kind of or wherein combination of several kinds of arbitrary proportions in Succinic anhydried and the Tetra hydro Phthalic anhydride, said catalytic type linking agent is a triethylamine.
Method of the present invention is based on the natural vesicular structure of timber, utilizes the hybrid inorganic-organic technology, organic monomer and inorganic nano-particle is mixed and ultra-sonic dispersion, and impregnate in the timber pore through the mixed solution of vacuum-pressure treatment with organism and inorganic body; And then under heating condition, make organism and inorganic body original position hybrid polymer in timber pore, obtain the doped organic and inorganic wood nano composite material of hybridized polymer and wood composite.Functional monomer SY-Monomer G of the present invention (GMA) and glycidyl allyl ether (AGE); All have can with the epoxide group of hydroxyl generation chemically bonded on the wood substrates and can with the functional functional groups such as the two keys of C=C of the monomer generation radical polymerization that contains unsaturated double-bond, can improve the interface compatibility between polymkeric substance and wood substrates; Simultaneously, these functional monomers and toughness agent reaction can make polymer formation bodily form crosslinking structure, give higher mechanical property of polymkeric substance and thermostability; Ether chain structure in the toughness agent can give polymkeric substance certain snappiness, thereby improves the big shortcoming of bodily form cross-linked polymer fragility.The present invention is except that utilizing heater means to promote epoxide group and the hydroxyl generation bonding; Also utilize organic acid anhydride or trimethylamine as response type/catalytic type linking agent; Make functional monomer under the heating condition of gentleness; Effectively open epoxide group,, realize both bindings with the hydroxyl generation nucleophilic substitution reaction on the wood cell wall.Modified Nano SiO of the present invention
2Particle surface can be participated in the copolymerization of functional monomer and toughness agent because of containing the C=C unsaturated double-bond, thereby the hybridized nanometer of realizing organism and inorganic body is compound; Relend the chemical bond-linking that helps functional monomer and wood components, realize timber, organism and inorganic nano SiO
2Three's in-situ hybridization, and then form the organic and inorganic wood nano composite material.Contact closely between the polymkeric substance in the organic and inorganic wood nano composite material of the present invention and wood cell wall, do not have obvious slit, good interface compatibility; Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 90%～110%, 100%～150%, 50%～130%, 140%～170% than the timber material respectively; Initial pyrolysis temperature and maximum pyrolysis temperature improve 5～15 ℃ and 12～21 ℃ than the timber material respectively; Dimensional stability behind the progressive flooding 200h (is measurement index with the anti-rate that expands) improves 50%～60% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 95%～98% than the timber material; So have excellent mechanical strength, thermostability, dimensional stability and antiseptic property; Can be used as indoor furniture and outdoor architecture structured material, be applied to wood materials is had the field of increased durability and mechanical property requirements.
Description of drawings
Fig. 1 is that experiment one is the square section stereoscan photograph of the timber-polymer composites of monomer preparation with the TEB 3K;
Fig. 2 is that experiment one is the impact profile scanning electromicroscopic photograph of the timber-polymer composites of monomer preparation with the TEB 3K;
Fig. 3 is that experiment two is the square section stereoscan photograph of the timber-polymer composites of monomer preparation with SY-Monomer G (GMA);
Fig. 4 is that experiment two is the impact profile scanning electromicroscopic photograph of the timber-polymer composites of monomer preparation with SY-Monomer G (GMA);
Fig. 5 is the square section stereoscan photograph of the timber-polymer composites of experiment three preparations;
Fig. 6 is the impact profile scanning electromicroscopic photograph of the timber-polymer composites of experiment three preparations;
Fig. 7 is the square section stereoscan photograph of the timber-polymer composites of experiment four preparations;
Fig. 8 is the impact profile scanning electromicroscopic photograph of the timber-polymer composites of experiment four preparations;
Fig. 9 be the experiment five the preparation based on nanometer SiO
2The square section stereoscan photograph of adulterated organic and inorganic wood nano composite material;
Figure 10 be the experiment five the preparation based on nanometer SiO
2The impact profile scanning electromicroscopic photograph of adulterated organic and inorganic wood nano composite material;
Figure 11 is the pairing X-ray energy spectrum of a Fig. 9 scintigram;
Figure 12 is nanometer SiO in the experiment five
2The AFM AFM of nano-dispersed figure in organic polymer;
Figure 13 be the poplar material, the experiment four the preparation timber-polymer composites and test five the preparation based on nanometer SiO
2The TG curve of adulterated organic and inorganic wood nano composite material, a representes the TG curve of poplar material among the figure, b representes to test the TG curve of the timber-polymer composites of four preparations, c represent to test five preparations based on nanometer SiO
2The TG curve of adulterated organic and inorganic wood nano composite material;
Figure 14 be the poplar material, the experiment four the preparation timber-polymer composites and test five the preparation based on nanometer SiO
2The DTG curve of adulterated organic and inorganic wood nano composite material, a representes the DTG curve of poplar material among the figure, b representes to test the DTG curve of the timber-polymer composites of four preparations, c represent to test five preparations based on nanometer SiO
2The DTG curve of adulterated organic and inorganic wood nano composite material.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment is based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material carries out according to the following steps:
One, take by weighing 1 mass parts functional monomer and toughness agent and mix, the quality of toughness agent is 1%～150% of a functional monomer quality, obtains monomer solution;
Two, take by weighing the nanometer SiO of the monomer solution quality 0.1%～1% that step 1 obtains
2(surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 15 ℃～30 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing linking agent, initiator and acetone; Wherein the quality of initiator accounts for 0.5%～1% of monomer solution quality that step 1 obtains; The quality of linking agent accounts for 1%～10% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of linking agent quality;
Four, the linking agent that step 3 is taken by weighing is dissolved in the acetone, obtains cross-linking agent solution, and the initiator that again step 3 is taken by weighing joins nanometer SiO with cross-linking agent solution
2In the homodisperse monomer solution, stir, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Then timber and steeping fluid are inserted in the retort; Be evacuated to after airtight in the retort vacuum tightness for-0.08MPa～-0.095MPa, keep vacuum tightness be-0.08MPa～-condition 15min～25min of 0.095MPa;
Six, removes vacuum, return to normal pressure, and then the pressure in air pressurized to the retort is 0.8MPa～1MPa that keep-uping pressure is condition 20min～30min of 0.8MPa～1MPa;
Seven, the pressure in the retort is reduced to normal pressure; Take out timber; Timber parcel after will flooding with aluminium-foil paper, to be heated to temperature then be 75 ℃～85 ℃ and keep this temperature 8h～10h, removes aluminium-foil paper; To continue to be heated to temperature again be 105 ℃～115 ℃ and keep this temperature 8h～10h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material;
Functional monomer described in the step 1 is one or both the combination in SY-Monomer G (GMA) and the glycidyl allyl ether (AGE);
Toughness agent described in the step 1 is a kind of or wherein several kinds the combination in ethylene glycol dimethacrylate (EGDMA), polyoxyethylene glycol-200-dimethacrylate (PEG200DMA) and the polyoxyethylene glycol-400-dimethacrylate (PEG400DMA);
Initiator described in the step 3 is Diisopropyl azodicarboxylate (AIBN) or Lucidol (BPO);
Linking agent described in the step 3 is response type linking agent or catalytic type linking agent; Said response type linking agent is a kind of or wherein combination of several kinds of arbitrary proportions in maleic anhydride (MAN), Succinic anhydried and the Tetra hydro Phthalic anhydride, and said catalytic type linking agent is a triethylamine.
When the functional monomer described in the present embodiment step 1 is composition, between each composition be arbitrarily than.
When the toughness agent described in this embodiment step 1 is compsn, between each composition be arbitrarily than.
Nanometer SiO described in this embodiment step 2
2(surface band unsaturated double-bond) is available from the great bright material Science and Technology Co., Ltd. in Zhejiang.
Embodiment two: this embodiment and embodiment one are different is that the quality of toughness agent in the step 1 is 50% of a functional monomer quality.Other is identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is to take by weighing the nanometer SiO that accounts for the monomer solution quality 0.5% that step 1 obtains in the step 2
2(surface band unsaturated double-bond).Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is with nanometer SiO in the step 2
2Joining in the monomer solution back is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature.
Embodiment five: this embodiment and embodiment one are different be that the quality of initiator accounts for monomer solution quality that step 1 obtains in the step 3 0.8%.Other is identical with embodiment one.
Embodiment six: this embodiment and embodiment one are different be that the quality of linking agent accounts for monomer solution quality that step 1 obtains in the step 3 5%.Other is identical with embodiment one.
Embodiment seven: this embodiment and embodiment one are different is that the vacuum tightness that is evacuated to after airtight in the step 5 in the retort is-0.09MPa, and keeps vacuum tightness to be-the condition 20min of 0.09MPa.Other is identical with embodiment one.
Embodiment eight: what this embodiment and embodiment one were different is that the pressure that the step 6 air is forced in the retort is 0.9MPa, and keep-ups pressure and be the condition 25min of 0.9MPa.Other is identical with embodiment one.
Embodiment nine: this embodiment and embodiment one are different is that to be heated to temperature in the step 7 be 80 ℃ and keeps this temperature 9h.Other is identical with embodiment one.
Embodiment ten: this embodiment and embodiment one are different is that to continue to be heated to temperature in the step 7 again be 110 ℃ and keeps this temperature 9h.Other is identical with embodiment one.
Adopt following experimental verification effect of the present invention:
Experiment one:
The preparation method of timber-polymer composites who with the TEB 3K is the monomer preparation is following:
One, takes by weighing the TEB 3K of 1 mass parts, obtain monomer solution;
Two, take by weighing account for the monomer solution quality 1% that step 1 obtains Diisopropyl azodicarboxylate (AIBN) as initiator;
Three, will join through the Diisopropyl azodicarboxylate (AIBN) that step 2 takes by weighing in the monomer solution that step 1 obtains, mix, obtain steeping fluid;
Four, timber is put into the steeping fluid that step 3 obtains, then timber and steeping fluid are inserted in the retort in the lump, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Five, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Six, the pressure of retort is reduced to normal pressure; Take out timber then; Timber after will flooding with aluminium-foil paper wraps up, and to be heated to temperature then be 80 ℃ and keep 8h, removes aluminium-foil paper; Continue under 80 ℃ of conditions again and heat 8h, promptly being able to TEB 3K is the timber-polymer composites of monomer preparation.
Experiment two:
The preparation method of timber-polymer composites who with SY-Monomer G (GMA) is monomer preparation is following:
One, takes by weighing 1 mass parts GMA, be made into monomer solution;
Two, take by weighing respectively account for the monomer solution quality 1% that obtains through step 1 Diisopropyl azodicarboxylate (AIBN) as initiator;
Three, will join in the monomer solution that step 1 obtains through the Diisopropyl azodicarboxylate (AIBN) that step 2 takes by weighing respectively, mix, obtain steeping fluid;
Four, respectively timber is put into the steeping fluid that step 3 obtains, then timber and steeping fluid are inserted in the retort in the lump, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Five, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Six, the pressure of retort is reduced to normal pressure; Take out timber then; Timber after will flooding with aluminium-foil paper wraps up, and to be heated to temperature then be 80 ℃ and keep 8h, removes aluminium-foil paper; Continue at again under 110 ℃ of conditions and heat 8h, promptly be able to the timber-polymer composites of SY-Monomer G (GMA) for the monomer preparation.
Experiment three:
The preparation method of timber-polymer composites is following:
One, takes by weighing the polyoxyethylene glycol-200-dimethacrylate (PEG200DMA) of 1 mass parts SY-Monomer G (GMA) and SY-Monomer G quality 5% and mixing, obtain monomer solution;
Two, take by weighing account for the monomer solution quality 1% that obtains through step 1 Diisopropyl azodicarboxylate (AIBN) as initiator;
Three, will join in the monomer solution that step 1 obtains through the Diisopropyl azodicarboxylate (AIBN) that step 2 takes by weighing, mix, obtain steeping fluid;
Four, respectively timber is put into the steeping fluid that step 3 obtains, insert in the lump then in the retort, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Five, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Six, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper, continue at again under 110 ℃ of conditions and heat 8h, promptly get timber-polymer composites.
Experiment four:
The preparation method of timber-polymer composites is following:
One, take by weighing 1 mass parts SY-Monomer G (GMA), SY-Monomer G quality 5% polyoxyethylene glycol-200-dimethacrylate (PEG200DMA) and SY-Monomer G quality 6% maleic anhydride (MAN) and mix, be made into monomer solution;
Two, take by weighing account for the monomer solution quality 1% that obtains through step 1 Diisopropyl azodicarboxylate (AIBN) as initiator;
Three, will join in the monomer solution that step 1 obtains through the Diisopropyl azodicarboxylate (AIBN) that step 2 takes by weighing, mix, obtain steeping fluid;
Four, timber is put into the steeping fluid that step 3 obtains, then timber and steeping fluid are inserted in the retort in the lump, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Five, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Six, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper, continue at again under 110 ℃ of conditions and heat 8h, promptly get timber-polymer composites.
Experiment five:
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material carries out according to the following steps:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and functional monomer GMA quality 5%, and mix, obtain monomer solution;
Two, take by weighing the nanometer SiO that accounts for the monomer solution quality 0.5% that step 1 obtains
2(surface band unsaturated double-bond), and with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa is again with dried nanometer SiO
2Joining in the monomer solution, is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing initiator A IBN, response type linking agent maleic anhydride (MAN) and acetone solvent; Wherein the quality of initiator A IBN accounts for 1% of monomer solution quality that step 1 obtains; The quality of response type linking agent maleic anhydride (MAN) accounts for 6% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of response type linking agent maleic anhydride (MAN);
Four, the response type linking agent that step 3 is taken by weighing is dissolved in the acetone that step 3 takes by weighing, and obtains the response type cross-linking agent solution, and the initiator that again response type cross-linking agent solution and step 3 is taken by weighing joins that step 2 obtains contains nanometer SiO
2In the homodisperse monomer mixture solution, mix, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains, then timber and steeping fluid are inserted in the retort in the lump, be evacuated to vacuum tightness in the retort after airtight to reach-0.08MPa and keep 20min;
Six, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa and keep 20min;
Seven, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper afterwards, to continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material.
This experiment make based on nanometer SiO
2Contact closely between the polymkeric substance in the adulterated organic and inorganic wood nano composite material and wood cell wall, do not have obvious slit, good interface compatibility (Fig. 9, Figure 10); Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 107%, 143%, 123% and 167% (table 1) than the timber material respectively; Figure 12 shows nanometer SiO
2The size that with the diameter is 30nm is dispersed in the polymeric matrix, has reflected this preparation technology's reasonableness; Figure 13-TG/DTG curve shown in Figure 14 shows; Timber-the polymer composites of the initial pyrolysis temperature of organic and inorganic wood nano composite material and corresponding experiment four preparations between 280 ℃～300 ℃, be a height than the initial pyrolysis temperature of the extension of timber material (275 ℃) all; And the maximum pyrolysis temperature of organic and inorganic wood nano composite material reaches 386 ℃, and the corresponding peak temperature than the timber and the timber-polymer composites of experiment four preparations improves 21 ℃ and 6 ℃ respectively, shows to a certain extent through nanometer SiO
2The thermostability of the composite wooden material of hydridization is the highest, is high far beyond the timber material, and the thermostability that has reached expection is improved purpose; In addition; Dimensional stability behind the progressive flooding 200h (is measurement index with the anti-rate that expands) improves 53% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 95% (brown rot), 97% (white rot) (table 2) than the timber material, so the wooden hybridized nano composite material under this embodiment has excellent mechanical strength, thermostability, dimensional stability and antiseptic property.
Can find out from Fig. 1-Fig. 2; The polymkeric substance that forms behind the methyl methacrylate polymerization is filled in the wood cell chamber isolatedly; There is tangible interface gaps (shown in Fig. 1 dotted line circle) between polymer phase and wood cell wall matrix; And the lumen interpolymer is neat typical brittle polymer surface of fracture, shows that the interface compatibility of this timber-polymer composites is poor, and belongs to hard brittle material; Polymkeric substance was through epoxide group and the timber hydroxyl reaction of GMA during Fig. 3-square section SEM shown in Figure 8 schemed; Cause it to combine with wood substrates closely; The good interface compatibility that shows polymkeric substance and wood substrates indirectly; But the transverse section of timber-polymer composites of Fig. 3-shown in Figure 4 is the neat surface of fracture that typical brittle polymer appears; And the transverse section of timber-polymer composites of Fig. 5-shown in Figure 8 is ' constriction ' surface of fracture that typical obdurability polymkeric substance is appeared, and the timber-polymer composites that shows Fig. 3-Fig. 4 is a hard brittle material, and timber-polymer composites of Fig. 5-Fig. 8 is a toughness material.Fig. 9-shown in Figure 10 through nanometer SiO
2Adulterated organic and inorganic wood nano composite material presents the good hybridized polymer and the interface compatibility of wood substrates; And typical obdurability material section, embody this wooden hybridized nano composite material indirectly and realized hybridized polymer and the wood cell wall chamical binding of expection, toughness height, the target that fragility is low; The EDX spectrogram of Figure 11 and the AFM of Figure 12 figure have then shown nanometer SiO
2Existence, and the nano-dispersed state in organic polymer: nanometer SiO
2Be that size about 30nm is dispersed in the polymkeric substance with the diameter, indirect proof the preparation technology's under this embodiment reasonableness.
Figure 13, Figure 14 show; The timber material temperature at maximum heat degradation rate peak occurs near 365 ℃; And the timber-polymer composites of testing three preparations is 345 ℃; Experiment two be that timber-polymer composites that monomer prepares is 350 ℃ with SY-Monomer G (GMA), and timber-polymer composites Wood-P (MAN-GMA) CompoSite that makes with MAN and GMA composite (GMA: MAN=100: 6, mass ratio) is 365 ℃; Timber-the polymer composites of experiment four is 380 ℃, and experiment five is based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material then reaches 386 ℃; Show that timber-organic polymer composite material under the contrast experiment of this embodiment is because of catalytic crosslinking and the polymerization of GMA, PEG200DMA and MAN; Change through polymer architecture; Given modified wood higher thermostability, the organic and inorganic wood nano composite material of this experiment then except the change of polymkeric substance self structure, is also passed through nanometer SiO
2In-situ doped with polymkeric substance; Further change the structure of hybridized polymer; And then combine the advantage of organic polymer and inorganic nano body, and cause it to possess higher thermostability than timber material and timber-organic polymer composite material, reached expection modification purpose.
Can know by data shown in the table 1 (contrasting), compare with the timber material, based on functional monomer (system) modified wood with based on nanometer SiO based on the composite wooden material of functional monomer and optimization system thereof and the mechanical property of poplar material
2The bending strength of adulterated organic and inorganic wood nano composite material, ultimate compression strength and hardness all are improved significantly, and show that (hydridization) polymkeric substance has a positive effect as strengthening the improvement of body to the timber mechanics performance.Wherein, The whole modified wood based on GMA, MMA of three mechanical properties based on the timber-polymer composites of optimizational function property monomer system of experiment four preparations is high; Show the adding of PEG200DMA, the structure of the polymkeric substance that forms under the optimization system is played enhancement as the toughness agent; In addition, the adding of MAN is also influential to three mechanical properties of matrix material, has shown that MAN has all played certain function as the response type linking agent to the improvement of interface and polymer architecture.And in several kinds of innovation wood composite materials, three mechanical properties with the organic and inorganic wood nano composite material are the highest especially.For impelling strength, the negative fragility that increases timber of GMA system, and the functional monomer system of optimizing has significantly been improved the impelling strength of timber, has improved 1.12 times than the timber material; Based on nanometer SiO
2The impelling strength of adulterated organic and inorganic wood nano composite material is the highest, has improved 123% than the timber material, shows based on nanometer SiO
2Doping way can further improve the impelling strength of timber and timber-polymer composites.Simultaneously, SEM-EDX observe (Fig. 9-Figure 11) its transverse section also shows, hybridized polymer shows tangible ' strength contracts ' splitting traces under shock stress, this also indirect verification the good impelling strength of this wooden hybridized nano composite material.Therefore, based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material has excellent mechanical property, reaches even partly surpassed the mechanical property of the most of high-quality tree lumber in northeast.
Anticorrosion rate of weight loss result by shown in the table 2 (timber material and based on the antiseptic property of the composite wooden material of optimizational function property monomer system) can know; Compare with the timber material; Two kinds of functional monomer system modified woods (timber-polymer composites of experiment three preparations and the timber-polymer composites of experiment four preparations) improve 95.12% and 96.15% respectively to the antiseptic property of brown rot fungus, and the antiseptic property of whiterot fungi is improved 96.78% and 97.57% respectively; With inorganic boron class sanitas (boric acid: borax=5: 1; Mass ratio) handling timber with organic IPBC sanitas (3-iodo-2-propynyl butyl carbamate) compares; The functional monomer system modified wood of optimizing (timber-polymer composites of experiment four preparations) is higher to the antiseptic property of brown rot fungus and whiterot fungi, shows that such system modified wood has good antiseptic property; And based on nanometer SiO
2The organic and inorganic wood nano composite material of doping way has reduced by 95.85% to the rate of weight loss of brown rot fungus than the timber material; Rate of weight loss to whiterot fungi reduces by 97.43% than the timber material; Roughly suitable with timber-polymer composites, shown that such composite wooden material has good antiseptic property.Rate of weight loss difference between the timber-polymer composites of this wooden hybridized nano composite material and experiment four preparations so can think that both antiseptic properties are suitable basically, does not have notable difference less than 5%.
Table 1
Annotate: polymer quality accounts for 80～90% of timber material quality in the various composite wooden materials; Testing data is 5 parallel test results' a average; Hardness numerical value is the force value of pressure head when being pressed into wood surface 2.81mm, and (tangential) hardness uses sample dimensions to be: and 50 * 50 * 20 (mm) (L * R * T)
Table 2
Annotate: it is the raising ratio of the rate of weight loss of composite wooden material with respect to the rate of weight loss of its corresponding timber material that * improves multiple
Experiment six:
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and functional monomer GMA quality 10%, and mix, obtain monomer solution;
Two, take by weighing the nanometer SiO that accounts for the monomer solution quality 0.5% that step 1 obtains
2(surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing initiator A IBN, response type linking agent maleic anhydride (MAN) and acetone solvent; Wherein the quality of initiator A IBN accounts for 1% of the monomer solution quality that obtains through step 1; The quality of response type linking agent maleic anhydride (MAN) accounts for 6% of the monomer solution quality that obtains through step 1, and the quality of acetone is 2.5 times of response type linking agent;
Four, will be dissolved in the acetone that step 3 takes by weighing through the response type linking agent that step 3 takes by weighing, obtain the response type cross-linking agent solution, join through what step 2 obtained with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again and contain nanometer SiO
2In the homodisperse monomer mixture solution, mix, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains, insert in the lump then in the retort, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Six, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Seven, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper afterwards, to continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material.
Contact closely between the polymkeric substance in the organic and inorganic wood nano composite material that this experiment makes and wood cell wall, do not have obvious slit, good interface compatibility; Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 101%, 137%, 118% and 155% than the timber material respectively; Initial pyrolysis temperature of extension and maximum pyrolysis temperature improve 11 ℃ and 18 ℃ than the timber material is corresponding respectively; In addition; Dimensional stability behind its progressive flooding 200h (is measurement index with the anti-rate that expands) improves 51% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 95.7% (brown rot), 96.1% (white rot) than the timber material, so the wooden hybridized nano composite material under this embodiment has excellent mechanical strength, thermostability, dimensional stability and antiseptic property.
Experiment seven:
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and functional monomer GMA quality 5%, and mix, obtain monomer solution;
Two, take by weighing 1.0% the nanometer SiO that accounts for monomer solution quality that step 1 obtains
2(surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing initiator A IBN, response type linking agent maleic anhydride (MAN) and acetone solvent; Wherein the quality of initiator A IBN accounts for 1% of the monomer solution quality that obtains through step 1; The quality of response type linking agent MAN accounts for 6% of the monomer solution quality that obtains through step 1, and the quality of acetone is 2.5 times of response type linking agent;
Four, will be dissolved in the acetone that step 3 takes by weighing through the response type linking agent that step 3 takes by weighing, obtain the response type cross-linking agent solution, join through what step 2 obtained with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again and contain nanometer SiO
2In the homodisperse monomer mixture solution, mix, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains, insert in the lump then in the retort, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Six, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Seven, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper afterwards, to continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material.
Contact closely between the polymkeric substance in the organic and inorganic wood nano composite material that this experiment makes and wood cell wall, do not have obvious slit, good interface compatibility; Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 103%, 140%, 120% and 159% than the timber material respectively; Initial pyrolysis temperature of extension and maximum pyrolysis temperature improve 13 ℃ and 19 ℃ than the timber material is corresponding respectively; In addition; Dimensional stability behind its progressive flooding 200h (is measurement index with the anti-rate that expands) improves 50% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 95.2% (brown rot), 96.5% (white rot) than the timber material, so the wooden hybridized nano composite material under this embodiment has excellent mechanical strength, thermostability, dimensional stability and antiseptic property.
Experiment eight:
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material:
One, takes by weighing the toughness agent polyoxyethylene glycol-400-dimethacrylate of 1 mass parts functional monomer GMA and 5%, and mix, obtain monomer solution;
Two, by massfraction than taking by weighing 0.5% the modified Nano SiO that accounts for monomer solution that step 1 obtains
2Particle (surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing initiator A IBN, response type linking agent maleic anhydride (MAN) and acetone solvent; Wherein the quality of initiator A IBN accounts for 1% of monomer solution quality that step 1 obtains; The quality of response type linking agent maleic anhydride (MAN) accounts for 6% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of response type linking agent;
Four, will be dissolved in the acetone that step 3 takes by weighing through the response type linking agent that step 3 takes by weighing, obtain the response type cross-linking agent solution, join through what step 2 obtained with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again and contain nanometer SiO
2In the homodisperse monomer mixture solution, mix, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains, insert in the lump then in the retort, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Six, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Seven, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper afterwards, to continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material.
Contact closely between the polymkeric substance in the organic and inorganic wood nano composite material that this experiment makes and wood cell wall, do not have obvious slit, good interface compatibility; Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 97%, 128%, 130% and 146% than the timber material respectively; Initial pyrolysis temperature of extension and maximum pyrolysis temperature improve 8 ℃ and 11 ℃ than the timber material is corresponding respectively; In addition; Dimensional stability behind its progressive flooding 200h (is measurement index with the anti-rate that expands) improves 57% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 95.6% (brown rot), 96.0% (white rot) than the timber material, so the wooden hybridized nano composite material under this embodiment has excellent mechanical strength, thermostability, dimensional stability and antiseptic property.
Experiment nine:
Based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and 5%, and mix, obtain monomer solution;
Two, by massfraction than taking by weighing 0.5% the modified Nano SiO that accounts for monomer solution that step 1 obtains
2Particle (surface band unsaturated double-bond) is then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing initiator A IBN, catalytic type linking agent triethylamine and acetone solvent; Wherein the quality of initiator A IBN accounts for 1% of the monomer solution quality that obtains through step 1; The quality of catalytic type linking agent triethylamine accounts for 5% of the monomer solution quality that obtains through step 1, and the quality of acetone is 2.5 times of linking agent;
Four, will be dissolved in through the catalytic type linking agent that step 3 takes by weighing in the acetone that step 3 takes by weighing, and join through what step 2 obtained with it with through the initiator that step 3 takes by weighing again and contain nanometer SiO
2In the homodisperse monomer mixture solution, mix, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains, insert in the lump then in the retort, the vacuum tightness that is evacuated in the retort after airtight reaches-0.08MPa, and keeps 20min;
Six, remove vacuum, return to normal pressure, and then air pressurized makes the pressure in the retort reach 0.8MPa, and keep 20min;
Seven, the pressure of retort is reduced to normal pressure, take out timber then, the timber after will flooding with aluminium-foil paper wraps up; To be heated to temperature then be 80 ℃ and keep 8h; Remove aluminium-foil paper afterwards, to continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material.
Contact closely between the polymkeric substance in the organic and inorganic wood nano composite material that this experiment makes and wood cell wall, do not have obvious slit, good interface compatibility; Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 110%, 139%, 101% and 165% than the timber material respectively; Initial pyrolysis temperature of extension and maximum pyrolysis temperature improve 12 ℃ and 17 ℃ than the timber material is corresponding respectively; In addition; Dimensional stability behind its progressive flooding 200h (is measurement index with the anti-rate that expands) improves 54% than the timber material; Anti-fungi sleeping and eating ability (being antiseptic property) improves 96.1% (brown rot), 96.5% (white rot) than the timber material; So the wooden hybridized nano composite material under this embodiment has excellent mechanical strength, thermostability, dimensional stability and antiseptic property; Can be used as indoor furniture and outdoor structure material, be applied to wood materials is had the field of increased durability and mechanical property requirements.
Claims (10)
1. based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that based on nanometer SiO
2The preparation method of adulterated organic and inorganic wood nano composite material carries out according to the following steps:
One, take by weighing the functional monomer and the toughness agent of 1 mass parts and mixing, the quality of toughness agent is 1%～150% of a functional monomer quality, obtains monomer solution;
Two, take by weighing the nanometer SiO that accounts for the monomer solution quality 0.1%～1% that step 1 obtains
2, then with nanometer SiO
2Drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa, and with dried nanometer SiO
2Joining in the monomer solution, is that 15 ℃～30 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature then, obtains containing nanometer SiO
2Homodisperse monomer mixture solution;
Three, take by weighing linking agent, initiator and acetone; Wherein the quality of initiator accounts for 0.5%～1% of monomer solution quality that step 1 obtains; The quality of linking agent accounts for 1%～10% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of linking agent quality;
Four, the linking agent that step 3 is taken by weighing is dissolved in the acetone, obtains cross-linking agent solution, and the initiator that again step 3 is taken by weighing joins with cross-linking agent solution and contains nanometer SiO
2In the homodisperse monomer solution, stir, obtain steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Then timber and steeping fluid are inserted in the retort; Be evacuated to after airtight in the retort vacuum tightness for-0.08MPa～-0.095MPa, and keep vacuum tightness be-0.08MPa～-condition 15min～25min of 0.095MPa;
Six, removes vacuum, return to normal pressure, and then the pressure in air pressurized to the retort is 0.8MPa～1MPa that keep-uping pressure is condition 20min～30min of 0.8MPa～1MPa;
Seven, the pressure in the retort is reduced to normal pressure; Take out timber; Timber parcel after will flooding with aluminium-foil paper, to be heated to temperature then be 75 ℃～85 ℃ and keep this temperature 8h～10h, removes aluminium-foil paper; To continue to be heated to temperature again be 105 ℃～115 ℃ and keep this temperature 8h～10h, promptly gets based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material;
Functional monomer described in the step 1 is one or both the combination in SY-Monomer G and the glycidyl allyl ether;
Toughness agent described in the step 1 is a kind of or wherein several kinds the combination in ethylene glycol dimethacrylate, polyoxyethylene glycol-200-dimethacrylate and the polyoxyethylene glycol-400-dimethacrylate;
Initiator described in the step 3 is Diisopropyl azodicarboxylate or Lucidol;
Linking agent described in the step 3 is response type linking agent or catalytic type linking agent, and said response type linking agent is a kind of or wherein combination of several kinds of arbitrary proportions in maleic anhydride, Succinic anhydried and the Tetra hydro Phthalic anhydride, and said catalytic type linking agent is a triethylamine.
2. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material, the quality that it is characterized in that toughness agent in the step 1 is 50% of a functional monomer quality.
3. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that taking by weighing in the step 2 nanometer SiO that accounts for the monomer solution quality 0.5% that step 1 obtains
2
4. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that in the step 2 nanometer SiO
2Joining in the monomer solution back is that 20 ℃, frequency are supersound process 40min under the condition of 300Hz in temperature.
5. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that the quality of initiator in the step 3 accounts for 0.8% of monomer solution quality that step 1 obtains.
6. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that the quality of linking agent in the step 3 accounts for 5% of monomer solution quality that step 1 obtains.
7. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material, the vacuum tightness that it is characterized in that being evacuated to after airtight in the step 5 in the retort is-0.09MPa, and keeps vacuum tightness to be-the condition 20min of 0.09MPa.
8. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that the pressure that the step 6 air is forced in the retort is 0.9MPa, and keep-ups pressure and be the condition 25min of 0.9MPa.
9. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material, to it is characterized in that being heated in the step 7 temperature be 80 ℃ and keep this temperature 9h.
10. said based on nanometer SiO according to claim 1
2The preparation method of adulterated organic and inorganic wood nano composite material is characterized in that continuing to be heated to temperature in the step 7 again and is 110 ℃ and keeps this temperature 9h.
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| CN101100079A (en) * | 2007-07-13 | 2008-01-09 | 北京工业大学 | Core-shell type multifunctional composite wood precursor solution and its preparation method |
| CN101905471A (en) * | 2010-08-18 | 2010-12-08 | 东北林业大学 | Preparation method of organic and inorganic wood composite material |
| CN102190936A (en) * | 2011-04-08 | 2011-09-21 | 华南理工大学 | Swelling-preventing polyacrylate dispersion/SiO2 hybrid aqueous wood coating |
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| US5151238A (en) * | 1988-06-07 | 1992-09-29 | National Research Development Corporation | Process for producing composite materials |
| CN101100079A (en) * | 2007-07-13 | 2008-01-09 | 北京工业大学 | Core-shell type multifunctional composite wood precursor solution and its preparation method |
| CN101905471A (en) * | 2010-08-18 | 2010-12-08 | 东北林业大学 | Preparation method of organic and inorganic wood composite material |
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