CN102775717A - Wood-organic-inorganic hybridization nano composite material based on nanolayer-shaped clay doping and preparation method of material - Google Patents
Wood-organic-inorganic hybridization nano composite material based on nanolayer-shaped clay doping and preparation method of material Download PDFInfo
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- CN102775717A CN102775717A CN2012102873681A CN201210287368A CN102775717A CN 102775717 A CN102775717 A CN 102775717A CN 2012102873681 A CN2012102873681 A CN 2012102873681A CN 201210287368 A CN201210287368 A CN 201210287368A CN 102775717 A CN102775717 A CN 102775717A
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Abstract
The invention discloses a wood-organic-inorganic hybridization nano composite material based on nanolayer-shaped clay doping and a preparation method of the wood-organic-inorganic hybridization nano composite material, relating to a preparation method of wooden composite materials and aiming at solving the technical problems that a wood-organic polymer composite material is poor in thermal stability and low in impact toughness and that a wood-inorganic composite material is poor in dynamics property. The method comprises the followings steps of: ultrasonically dispersing organic ammonium modified smectite organic clay into monomer solution, compounding an initiator and a cross-linking agent so as to form a steeping liquor, further putting the wood into the steeping liquor and putting into a reaction tank, sealing and vacuumizing, further devacuumizing, pressurizing by air, decreasing the pressure to a normal pressure, taking out the wood, wrapping the steeped wood by using aluminum-foil paper, heating, detaching the aluminum-foil paper and continuing heating so as to obtain the material. The wood-organic-inorganic hybridization nano composite material provided by the invention is good in compatibility of the polymer and the wood substrate boundary, and has excellent mechanical strength, heat stability, dimensional stability and anti-corrosion property.
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.
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, and a kind of preparation method based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay is provided.
Preparing method based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay carries out according to the following steps:
One, takes by weighing the toughness agent of 1 mass parts functional monomer and functional monomer quality 1%～150%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay of monomer solution quality 0.01%～0.3%; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Again dried organic ammonium modification smectite organic clay is scattered in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 0.1%～10%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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, cross-linking agent solution and initiator is joined in the homodisperse monomer mixture solution of organic clay that step 2 obtains again, and mixes, and obtains steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Timber and steeping fluid are inserted in the retort in the lump then; Be evacuated to vacuum tightness in the retort after airtight to reach-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 the adulterated organic and inorganic wood nano composite material of nano lamellar clay;
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.
Method of the present invention is based on the natural vesicular structure of timber, utilizes the hybrid inorganic-organic technology, organic monomer and nano inorganic body 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.The sheet surfaces of modified Nano laminated clay of the present invention is because of containing the organic amine positively charged ion; Can produce the intensive interaction with the epoxide group of functional monomer and the cyclic anhydride group of response type linking agent; Help organism to insert even peel off inorganic sheet, 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 nano inorganic laminated clay Clay three'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 100%～120%, 120%～160%, 90%～130%, 160%～200% than the timber material respectively; Initial pyrolysis temperature and maximum pyrolysis temperature improve 5～15 ℃ and 15～30 ℃ 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 is the square section stereoscan photograph based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay of experiment five preparations;
Figure 10 is the impact profile scanning electromicroscopic photographs of experiment five preparations based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay;
Figure 11 is the pairing X-ray energy spectrum of a Fig. 9 scintigram;
Figure 12 is experiment five: based on the AFM AFM figure of organic ammonium modification smectite organic clay nano-dispersed in pure organic polymer in the adulterated organic and inorganic wood nano composite material experiment of nano lamellar clay;
Figure 13 is the TEM shape appearance figure of organic ammonium modification smectite organic clay dispersion state in based on the organic polymer of the adulterated organic and inorganic wood nano composite material of nano lamellar clay of experiment five preparations;
Figure 14 is the enlarged view of Figure 13;
Figure 15 is the timber-polymer composites of poplar material, experiment four preparations and the TG curve based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay of testing five preparations; A representes the TG curve of poplar material among the figure; B representes to test the TG curve of four timber-polymer composites, and c representes to test the five TG curves based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay;
Figure 16 is the timber-polymer composites of poplar material, experiment four preparations and the DTG curve based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay of testing five preparations; A representes the DTG curve of poplar material among the figure; B representes to test the DTG curve of four timber-polymer composites, and c representes to test the five DTG curves based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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 carries out based on the preparation method of the adulterated organic and inorganic wood nano composite material of nano lamellar clay according to the following steps:
One, takes by weighing the toughness agent of 1 mass parts functional monomer and functional monomer quality 1%～150%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay of monomer solution quality 0.01%～0.3%; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Again dried organic ammonium modification smectite organic clay is scattered in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 0.1%～10%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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, cross-linking agent solution and initiator is joined in the homodisperse monomer mixture solution of organic clay that step 2 obtains again, and mixes, and obtains steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Timber and steeping fluid are inserted in the retort in the lump then; Be evacuated to vacuum tightness in the retort after airtight to reach-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 the adulterated organic and inorganic wood nano composite material of nano lamellar clay;
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.
When the functional monomer described in this embodiment step 1 is compsn, between each composition be arbitrarily than.
When the toughness agent described in this embodiment step 1 is compsn, between each composition be arbitrarily than.
The smectite of organic ammonium modification described in this embodiment step 2 organic clay is available from the nanosecond science and technology tomorrow ltd in Zhoushan, Zhejiang.
Embodiment two: what this embodiment and embodiment one were different is that organic ammonium modification smectite organic clay is dissolved in the ethanol in the step 2, obtains organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%.Other is identical with embodiment one.
Embodiment three: this embodiment and embodiment one are different is that organic ammonium modification smectite organic clay mass concentration be 0.1%～10% mixed solution in temperature is that 20 ℃, frequency are supersound process 20min under the condition of 300Hz in the step 2.Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is that the mixed solution through supersound process joins in the monomer solution in the step 2, forms mass concentration and be 0.1% the monomer mixture solution that contains organic clay.Other is identical with embodiment one.
Embodiment five: this embodiment and embodiment one are different is to be that 20 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature in the step 2, forms the homodisperse monomer mixture solution of organic clay.Other is identical with embodiment one.
Embodiment six: this embodiment and embodiment one are different is that the quality of toughness agent in the step 1 is 5% of a functional monomer.Other is identical with embodiment one.
Embodiment seven: this embodiment and embodiment one are different is that the quality of organic ammonium modification smectite organic clay in the step 2 is 0.2% of a monomer solution quality.Other is identical with embodiment one.
Embodiment eight: 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 nine: 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 ten: this embodiment and embodiment one are different is that to be heated to temperature in the step 7 earlier be 80 ℃ and keeps this temperature 9h, removes that to continue to be heated to temperature again behind the aluminium-foil paper be 110 ℃ and keep 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:
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 organic ammonium modification smectite organic clay that accounts for the monomer solution quality 0.1% that step 1 obtains; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Dried organic ammonium modification smectite organic clay is dissolved in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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 through the response type linking agent that step 3 takes by weighing in the acetone that step 3 takes by weighing; Obtain the response type cross-linking agent solution; Join in the homodisperse monomer mixture solution of the organic clay that step 2 obtains with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again; 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; 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 afterwards; To continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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, and good interface compatibility (Fig. 9-Figure 10); Bending strength, crushing strength parallel to the grain, impelling strength and hardness improve 116%, 144%, 118% and 181% (table 1) than the timber material respectively; Figure 12-AFM figure and TEM figure shown in Figure 14 shows that fully Clay is dispersed in the hybridized polymer matrix with the intercalation form under this preparation technology; Figure 15-TG/DTG curve shown in Figure 16 shows; The initial pyrolysis temperature of organic and inorganic wood nano composite material and corresponding timber-polymer composites is all between 280 ℃～300 ℃; All than the initial pyrolysis temperature of the extension of timber material (275 ℃) height, and both rate of weight loss before 400 ℃ are all low than the timber material; Simultaneously; The maximum pyrolysis temperature of organic and inorganic wood nano composite material reaches 390 ℃; Corresponding peak temperature than the timber-polymer composites of timber, experiment four preparations improves 25 ℃ and 10 ℃ respectively; Show through the thermostability of the adulterated organic and inorganic wood nano composite material of organic ammonium modification smectite organic clay the highest, high far beyond the timber material, even be higher than based on nanometer SiO
2The thermostability (maximum pyrolysis temperature is 386 ℃) of the organic and inorganic wood nano composite material of doping (0.5wt%), 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 95.95% (brown rot), 97.61% (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 the 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 combined with wood substrates closely during Fig. 3-square section SEM shown in Figure 8 schemed; Show that indirectly polymkeric substance passes through epoxide group and the timber hydroxyl reaction of GMA; Cause the good interface compatibility of itself and wood substrates; 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 presents the good hybridized polymer and the interface compatibility of wood substrates through the adulterated organic and inorganic wood nano composite material of nano lamellar clay; 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 clear nano lamellar clay Clay of the TEM chart of the EDX spectrogram of Figure 11, AFM figure, Figure 13 and Figure 14 of Figure 12 is present in the polymeric matrix with the intercalation form.
Figure 15-Figure 16 shows; The timber material temperature at maximum heat degradation rate peak occurs near 365 ℃; Timber-the polymer composites of experiment four preparations is 380 ℃, and that tests five preparations then reaches 390 ℃ based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay, shows that timber-organic polymer composite material under the contrast experiment 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 testing five preparations is then except the change of organic polymer self structure, through the in-situ inserted hydridization of organic polymer and nano lamellar clay; Combine the advantage of organic polymer and inorganic nano organic ammonium modification smectite organic clay; And further improved the structure of hybridized polymer, and then make it possess higher thermostability than timber material and timber-organic polymer composite material, even be superior to nanometer SiO
2Adulterated organic and inorganic wood nano composite material (maximum pyrolysis temperature is 386 ℃) has reached expection modification purpose.
Can know by data shown in the table 1; Compare with the timber material; All be improved significantly based on functional monomer (system) modified wood (experiment three, four preparation timber-polymer composites) with based on bending strength, ultimate compression strength and the hardness of the organic and inorganic wood nano composite material of the clay intercalated hydridization of nano lamellar, 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 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 compare with several kinds of timber-polymer composites, the highest based on three mechanical properties of the adulterated organic and inorganic wood nano composite material of nano lamellar clay.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; Impelling strength based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay is higher; Improved 118% than the timber material, shown the impelling strength that further to improve timber and timber-polymer composites based on nano lamellar clay doping way.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, have excellent mechanical property, reach even partly surpassed the mechanical property of the most high-quality tree lumber in northeast based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
Anticorrosion rate of weight loss result by shown in the table 2 can know; Compare with the timber material; Two kinds of functional monomers (system) modified wood (timber-polymer composites of experiment three preparations and the timber-polymer composites of experiment four preparations) improves 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 the rate of weight loss of brown rot fungus has been reduced by 95.95% than the timber material based on the organic and inorganic wood nano composite material of nano lamellar clay doping way; Rate of weight loss to whiterot fungi reduces by 97.61% than the timber material, with timber-polymer composites with based on nanometer SiO
2Adulterated organic and inorganic wood nano composite material is roughly suitable, has shown that such composite wooden material has good antiseptic property.This wooden hybridized nano composite material is with the timber-polymer composites of experiment four preparations, based on nanometer SiO
2Rate of weight loss difference between adulterated organic and inorganic wood nano composite material so can think that both antiseptic properties are suitable basically, does not have notable difference all less than 5%.
Table 1 is based on the mechanical property contrast of the composite wooden material and the poplar material of functional monomer and optimization system thereof
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 timber material and based on the antiseptic property of the composite wooden material of optimizational function property monomer system
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:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and 10%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay that accounts for the monomer solution quality 0.1% that step 1 obtains; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Dried organic ammonium modification smectite organic clay is dissolved in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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 through the response type linking agent that step 3 takes by weighing in the acetone that step 3 takes by weighing; Obtain the response type cross-linking agent solution; Join in the homodisperse monomer mixture solution of the organic clay that step 2 obtains with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again; 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; 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 afterwards; To continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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%, 137%, 127% and 177% than the timber material respectively; First pyrolysis temperature of its extension and maximum pyrolysis temperature have improved 11 ℃ and 21 ℃ than the corresponding peak temperature of timber 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 95.22% (brown rot), 97.05% (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:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and 5%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay that accounts for the monomer solution quality 0.3% that step 1 obtains; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Dried organic ammonium modification smectite organic clay is dissolved in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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 through the response type linking agent that step 3 takes by weighing in the acetone that step 3 takes by weighing; Obtain the response type cross-linking agent solution; Join in the homodisperse monomer mixture solution of the organic clay that step 2 obtains with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again; 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; 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 afterwards; To continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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 104%, 132%, 119% and 187% than the timber material respectively; Initial pyrolysis temperature of its extension and maximum pyrolysis temperature have improved 15 ℃ and 23 ℃ than the corresponding peak temperature of timber 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 95.79% (brown rot), 97.33% (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:
One, takes by weighing the toughness agent ethylene glycol dimethacrylate EGDMA of 1 mass parts functional monomer GMA and 5%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay that accounts for the monomer solution quality 0.1% that step 1 obtains; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Dried organic ammonium modification smectite organic clay is dissolved in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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 through the response type linking agent that step 3 takes by weighing in the acetone that step 3 takes by weighing; Obtain the response type cross-linking agent solution; Join in the homodisperse monomer mixture solution of the organic clay that step 2 obtains with the response type cross-linking agent solution with through the initiator that step 3 takes by weighing again; 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; 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 afterwards; To continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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%, 115% and 185% than the timber material respectively; Initial pyrolysis temperature of its extension and maximum pyrolysis temperature have improved 9 ℃ and 19 ℃ than the corresponding peak temperature of timber 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 95.90% (brown rot), 97.84% (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:
One, takes by weighing the toughness agent PEG200DMA of 1 mass parts functional monomer GMA and 5%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay that accounts for the monomer solution quality 0.1% that step 1 obtains; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Dried organic ammonium modification smectite organic clay is dissolved in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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 monomer solution quality that step 1 obtains; The quality of catalytic type linking agent triethylamine accounts for 5% of monomer solution quality that step 1 obtains, and the quality of acetone is 2.5 times of linking agent;
Four, will be dissolved in the acetone that step 3 takes by weighing through the catalytic type linking agent triethylamine that step 3 takes by weighing; Join in the homodisperse monomer mixture solution of the organic clay that step 2 obtains with it with through the initiator that step 3 takes by weighing again; 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; 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 afterwards; To continue to be heated to temperature again be 110 ℃ and keep 8h, promptly gets based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
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 120%, 155%, 103% and 190% than the timber material respectively; The initial pyrolysis temperature of its extension has improved 15 ℃ and 27 ℃ than the corresponding peak temperature of timber respectively with its maximum pyrolysis temperature; 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 95.12% (brown rot), 97.50% (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 the preparation method of the adulterated organic and inorganic wood nano composite material of nano lamellar clay, it is characterized in that carrying out according to the following steps based on the preparation method of the adulterated organic and inorganic wood nano composite material of nano lamellar clay:
One, takes by weighing the toughness agent of 1 mass parts functional monomer and functional monomer quality 1%～150%, and mix, obtain monomer solution;
Two, take by weighing the organic ammonium modification smectite organic clay of monomer solution quality 0.01%～0.3%; Then with organic ammonium modification smectite organic clay drying treatment 24h under 105 ℃, the vacuum-drying condition of 0.01MPa; Again dried organic ammonium modification smectite organic clay is scattered in the ethanol; Obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 0.1%～10%; Be that 15 ℃～30 ℃, frequency are supersound process 20min under the condition of 300Hz in temperature then; And then the mixed solution that will pass through supersound process joins in the monomer solution, and is that 15 ℃～30 ℃, frequency are further supersound process 20min under the condition of 300Hz in temperature, obtains the homodisperse monomer mixture solution of organic clay;
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, cross-linking agent solution and initiator is joined in the homodisperse monomer mixture solution of organic clay that step 2 obtains again, and mixes, and obtains steeping fluid;
Five, timber is put into the steeping fluid that step 4 obtains; Timber and steeping fluid are inserted in the retort in the lump then; Be evacuated to vacuum tightness in the retort after airtight to reach-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 the adulterated organic and inorganic wood nano composite material of nano lamellar clay;
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. according to the said preparation method of claim 1 based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay; It is characterized in that organic ammonium modification smectite organic clay is dissolved in the ethanol in the step 2, obtain organic ammonium modification smectite organic clay mass concentration and be clay/alcohol mixeding liquid of 1%.
3. according to the said preparation method of claim 1, it is characterized in that organic ammonium modification smectite organic clay mass concentration in the step 2 be 0.1%～10% mixed solution in temperature is that 20 ℃, frequency are supersound process 20min under the condition of 300Hz based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
4. according to the said preparation method of claim 1 based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay; It is characterized in that the mixed solution through supersound process joins in the monomer solution in the step 2, the formation mass concentration is 0.1% the monomer mixture solution that contains organic clay.
5. according to the said preparation method of claim 1 based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay; It is characterized in that in the step 2 in temperature being that 20 ℃, frequency are further supersound process 20min under the condition of 300Hz, form the homodisperse monomer mixture solution of organic clay.
6. according to the said preparation method based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay of claim 1, the quality that it is characterized in that toughness agent in the step 1 is 5% of a functional monomer.
7. according to the said preparation method of claim 1, it is characterized in that the quality of organic ammonium modification smectite organic clay in the step 2 is 0.2% of a monomer solution quality based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
8. according to the said preparation method of claim 1, it is characterized in that the quality of initiator in the step 3 accounts for 0.8% of monomer solution quality that step 1 obtains based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
9. according to the said preparation method of claim 1, it is characterized in that the quality of linking agent in the step 3 accounts for 5% of monomer solution quality that step 1 obtains based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay.
10. according to the said preparation method of claim 1 based on the adulterated organic and inorganic wood nano composite material of nano lamellar clay; To it is characterized in that being heated to earlier in the step 7 temperature be 80 ℃ and keep this temperature 9h, removes that to continue to be heated to temperature again behind the aluminium-foil paper be 110 ℃ and keep this temperature 9h.
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| CN105670514A (en) * | 2016-03-01 | 2016-06-15 | 山东农业大学 | Method for modifying waterborne wood coating by nano-crystalline cellulose hybridizing inorganic nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664001A (en) * | 2000-09-21 | 2005-09-07 | 罗姆和哈斯公司 | Aqueous nanocomposite dispersions: processes, compositions, and uses thereof |
| CN1878797A (en) * | 2003-11-11 | 2006-12-13 | 亨斯迈先进材料（瑞士）有限公司 | Initiator systems for polymerisable compositions |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1664001A (en) * | 2000-09-21 | 2005-09-07 | 罗姆和哈斯公司 | Aqueous nanocomposite dispersions: processes, compositions, and uses thereof |
| CN1878797A (en) * | 2003-11-11 | 2006-12-13 | 亨斯迈先进材料（瑞士）有限公司 | Initiator systems for polymerisable compositions |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105670514A (en) * | 2016-03-01 | 2016-06-15 | 山东农业大学 | Method for modifying waterborne wood coating by nano-crystalline cellulose hybridizing inorganic nanoparticles |
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