CN105670514B - The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic - Google Patents
The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic Download PDFInfo
- Publication number
- CN105670514B CN105670514B CN201610115893.3A CN201610115893A CN105670514B CN 105670514 B CN105670514 B CN 105670514B CN 201610115893 A CN201610115893 A CN 201610115893A CN 105670514 B CN105670514 B CN 105670514B
- Authority
- CN
- China
- Prior art keywords
- nano
- cellulose
- water
- coating
- borne wood
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, it is related to a kind of method of modifying of water-borne wood coating.The purpose of the present invention will solve existing inorganic nano-particle bad dispersibility in water-borne wood coating, organic nanofibers element rhabdolith draw ratio is low, caused modified water-soluble woodenware coating poor mechanical property, and weatherability even sterilizing and purifying air function improve the problem of not good enough.Method：First, the preparation of nano-cellulose aqueous：2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle；3rd, nano material and resin aqueous emulsion are compound, produce the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic.The present invention is carrier using the 1-dimention nano cellulose with high-specific surface area and superior water dispersibility, doped and compounded zero dimension inorganic nanoparticles in situ, improve the combination property of water-borne wood coating by the compound method collaboration of two-phase in-situ hybridization, to widen the application of water-borne wood coating.
Description
Technical field
The present invention relates to a kind of method of modifying of water-borne wood coating.
Background technology
Timber have hygroscopic dilatancy, be subject to bacterium worm it is rotten, easily by ultraviolet lighting aging, be readily burned degraded etc. day
Right defect, therefore often woodwork coating is covered with paint, lacquer, colour wash, etc. in wood surface to improve drawbacks described above.So with the reinforcement of people's environmental consciousness, have
The organic oil soluble paint application of high VOC releases is increasingly restricted, and the environment-friendly aqueous coating of low VOC releases is got over
Favored to get over, turn into the main trend of woodwork coating development.But the scratch-resistant of water-borne wood coating, wear-resisting, hardness, anti-impact
The mechanical performances such as hitting property, anti-ultraviolet ageing performance must carry out improved properties typically not as good as the oil paint of technology maturation to it.
In recent years, the patent being modified using nano material to water-borne wood coating is seen in report.Such as Application No.
201210480069.X patent of invention described in utilize nano-TiO2、Al2O3、SiO2, Ag composite waterborne resin emulsions make it is water-based
Woodwork coating has anti-microbial property, but nano particle directly adulterates in the presence of easily reunion, causes phase with matrix resin interface compatibility difference
The problems such as separation, therefore can not effectively strengthen the mechanical strength of water paint, while Ag importing can have water-borne wood coating
Obvious aberration, reduce the light transmittance and glossiness of coating.The patent of invention of Application No. 201380049182.5 reports water
Property coating in add the preparation method of nano-cellulose and surfactant, but only added by nano-cellulose to the resistance to of coating
Scrape, wearability and anti-ultraviolet ageing performance improve without positive role.The patent of invention report of Application No. 201310588309.2
Road improves the mechanical properties such as the hardness of water-borne wood coating, wearability using nano-cellulose rhabdolith, and solves and receive
The dispersed problem in situ of rice cellulose, but anti-ultraviolet ageing performance can not be improved, and due to the low cause scratch resistance of draw ratio
Improvement and unobvious with toughness.The patent of invention of Application No. 201510647618.1 reports nano-cellulose crystalline substance
Body and TiO2In-situ reaction, pass through stearic acid modified its dispersiveness in polydimethylsiloxane and to each other of improving
The coating production of interface binding power, make coating that there is superhydrophobic characteristic, but nano-cellulose used is rhabdolith, it is long
Than small, the improvement to coating mechanical property such as impact resistance, scratch resistance etc. is limited in footpath, and prepare for oil-soluble coating, have
Machine VOC releases are big, non-modern coatings development trend.The patent of invention of Application No. 201410006256.3, which reports, utilizes nanometer
The method that cellulose and nano silicon dioxide sol prepare super-hydrophobic woodwork coating with water-dispersion type resin compounded, but nanofiber
Element load nano silicon first carries out modifying super hydrophobicity so that it is huge with the polarity difference of water-dispersion type resin, two blind dates
With property is poor, interface compatibility is poor, the nano material of modifying super hydrophobicity is easily reunited, and is caused every mechanical property of coating to improve and is owed
Good or even decline.
In a word, nanoparticle be present during the inorganic nano particle modified water-borne wood coating that above-mentioned published patent is stated
Molecular dispersivity difference causes coating mechanical property, light transmittance to improve the problem of not good enough；And organic nanofibers element is mostly bar-shaped nanometer
Cellulose crystals, draw ratio is low, and toughness, scratch resistance, the wearability improvement to coating are limited, and can not improve painting
The weatherability of layer；Even if nano-cellulose and SiO2、TiO2Compound, used method is affine with polymeric matrix there is also it
Property it is poor, in polymeric matrix bad dispersibility cause coating mechanical property improve it is not good enough the problem of.
The content of the invention
The purpose of the present invention will solve existing inorganic nano-particle bad dispersibility in water-borne wood coating, and organic nano is fine
It is low to tie up plain rhabdolith draw ratio, caused modified water-soluble woodenware coating poor mechanical property, and weatherability even bactericidal purifying are empty
Airway dysfunction improves the problem of not good enough, and the method for providing the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic.
The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, is specifically realized by the following steps
's：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and gone
Hemicellulose processing, obtains purifying cellulose, carries out Biological Pretreatment or Chemical Pretreatment to purifying cellulose, obtains Nanowire
Tie up plain aqueous；
Described Biological Pretreatment refers to cellulase pretreatment, and concrete operations are as follows：Purifying cellulose is added 250mL's
In beaker, it is 0.1%~0.3% to add deionized water to the mass fraction of purifying cellulose, cellulase is added, in 50 DEG C of bars
2h is pre-processed under part, then after 90 DEG C handle 2h, after being filtered by vacuum and washing, be made into again mass concentration for 0.1%~
0.3% cellulose aqueous, then the high-pressure homogeneous machinery processing 30min through 600bar, produce nano-cellulose aqueous；
Purifying cellulose is fitted into 250mL beaker, it is 0.1%~0.3% to add the mass fraction of deionized water extremely,
Sequentially add sodium bromide, TEMPO reagents, under magnetic agitation, using 2.5mL/min addition speed add 5mL mass concentrations as
12% liquor natrii hypochloritis, it is 10~10.5 to recycle the sodium hydroxide regulation pH value that concentration is 0.5mol/L, sustained response
Do not changed to pH value, terminate reaction, add 15mL absolute ethyl alcohol, it is fine after filtering, washing, then by obtained oxidation
Dimension element is placed in 250mL conical flasks, adds 70mL deionized waters and 0.6g sodium chlorites, and pH value is adjusted to 4~5 with glacial acetic acid,
Then in 70 DEG C of magnetic agitation 1h, filter, washing, obtain carboxylated cellulose element, be then made into 0.1%~0.3% carboxylic again
Base cellulose aqueous, then the high-pressure homogeneous machinery processing 5 of homogenizer mechanical dispersion 4min, 600bar through 15000rpm
It is secondary, the ultrasonic 30min of strength under 320W power, nano-cellulose aqueous is made；
Cellulosic material described in step 1 is that granularity is that more than 60 mesh wood powder, granularity is more than 60 mesh agriculture
Crop material powder or waste and old paper；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：In the nano-cellulose aqueous obtained to step 1
Zero dimension inorganic nano-particle is added, ultrasonic wave strength is ultrasonically treated 30min~240min in the case where power is 300W~1000W, obtains
The hybridization compounding liquid dispersed to inorganic nano-particle and nano-cellulose；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in,
In the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains just mixed thing；2., first mixed thing is entered
Row revolving, untill revolving surplus solution is originally mixed object product 1/5~1/2, revolving surplus solution is added to aqueous wooden ware
In coating, in the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains compo；③、
With homogenizer under 15000rpm speed high-speed stirred compo 30min, produce nano-cellulose hybrid inorganic and receive
Rice corpuscles modified water-soluble woodwork coating.
Advantage of the present invention：The present invention proposes a kind of 1-dimention nano utilized with high-specific surface area and superior water dispersibility
Cellulose is carrier, doped compound nano SiO in situ2、Al2O3、TiO2、ZnO、CeO2Etc. zero dimension inorganic nanoparticles, pass through two
The compound method collaboration of phase in-situ hybridization improves the mechanical performances such as the scratch resistance damage of water-borne wood coating, wear-resisting, hardness, impact resistance
And anti-ultraviolet ageing performance, or even its sterilization, the function of purification air are assigned, significantly improve water-borne wood coating uses the longevity
Life, increases the function of water-borne wood coating, to widen the application of water-borne wood coating, improves the added value of Wood products.
The advantages of stating in conjunction with the embodiments, provide advantage of the present invention.
Brief description of the drawings
Fig. 1 is that nano-cellulose TEM schemes in the nano-cellulose aqueous that the step 1 of embodiment 1 obtains；
Fig. 2 is the nanometer particle-modified water-borne wood coating SEM figures of nano-cellulose hybrid inorganic that embodiment 1 obtains；
Fig. 3 is that nano-cellulose TEM schemes in the nano-cellulose aqueous that the step 1 of embodiment 2 obtains；
Fig. 4 is the nanometer particle-modified water-borne wood coating SEM figures of nano-cellulose hybrid inorganic that embodiment 2 obtains.
Embodiment
Embodiment one：Present embodiment is the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic
Method, be specifically realized by the following steps：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and gone
Hemicellulose processing, obtains purifying cellulose, carries out Biological Pretreatment or Chemical Pretreatment to purifying cellulose, obtains Nanowire
Tie up plain aqueous；
Described Biological Pretreatment refers to cellulase pretreatment, and concrete operations are as follows：Purifying cellulose is added 250mL's
In beaker, it is 0.1%~0.3% to add deionized water to the mass fraction of purifying cellulose, cellulase is added, in 50 DEG C of bars
2h is pre-processed under part, then after 90 DEG C handle 2h, after being filtered by vacuum and washing, be made into again mass concentration for 0.1%~
0.3% cellulose aqueous, then the high-pressure homogeneous machinery processing 30min through 600bar, produce nano-cellulose aqueous；
Purifying cellulose is fitted into 250mL beaker, it is 0.1%~0.3% to add the mass fraction of deionized water extremely,
Sequentially add sodium bromide, TEMPO reagents, under magnetic agitation, using 2.5mL/min addition speed add 5mL mass concentrations as
12% liquor natrii hypochloritis, it is 10~10.5 to recycle the sodium hydroxide regulation pH value that concentration is 0.5mol/L, sustained response
Do not changed to pH value, terminate reaction, add 15mL absolute ethyl alcohol, it is fine after filtering, washing, then by obtained oxidation
Dimension element is placed in 250mL conical flasks, adds 70mL deionized waters and 0.6g sodium chlorites, and pH value is adjusted to 4~5 with glacial acetic acid,
Then in 70 DEG C of magnetic agitation 1h, filter, washing, obtain carboxylated cellulose element, be then made into 0.1%~0.3% carboxylic again
Base cellulose aqueous, then the high-pressure homogeneous machinery processing 5 of homogenizer mechanical dispersion 4min, 600bar through 15000rpm
It is secondary, the ultrasonic 30min of strength under 320W power, nano-cellulose aqueous is made；
Cellulosic material described in step 1 is that granularity is that more than 60 mesh wood powder, granularity is more than 60 mesh agriculture
Crop material powder or waste and old paper；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：In the nano-cellulose aqueous obtained to step 1
Zero dimension inorganic nano-particle is added, ultrasonic wave strength is ultrasonically treated 30min~240min in the case where power is 300W~1000W, obtains
The hybridization compounding liquid dispersed to inorganic nano-particle and nano-cellulose；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in,
In the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains just mixed thing；2., first mixed thing is entered
Row revolving, untill revolving surplus solution is originally mixed object product 1/5~1/2, revolving surplus solution is added to aqueous wooden ware
In coating, in the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains compo；③、
With homogenizer under 15000rpm speed high-speed stirred compo 30min, produce nano-cellulose hybrid inorganic and receive
Rice corpuscles modified water-soluble woodwork coating.
Extracting processing described in present embodiment step 1：250mL ropes are put into after cellulosic material is wrapped with filter paper
In family name's extractor, 240mL toluene-ethanos mixed solution is then added as extraction solvent, is extracted in water-bath at 90 DEG C
10h, extracting composition is removed, obtain removing the wood powder of extracting composition；Toluene and ethanol in described toluene-ethano mixed solution
Volume ratio is 2:1.
Delignification processing described in present embodiment step 1：1., by above-mentioned gained remove extracting composition wood powder
It is put into 500mL wide mouthed Erlenmeyer bottles, adds the mixed solution of glacial acetic acid, sodium chlorite and deionized water, 300mL, is used in combination altogether
Preservative film seals；Wherein, glacial acetic acid 0.2mL, sodium chlorite 1g, remaining liquid are water；Then, above-mentioned mixing will be housed
The conical flask of solution is placed at magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control, obtains mixed solution；2., to the mixed solution of gained
According to first add 0.2mL glacial acetic acid and 1g sodium chlorites, the magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control；3., again
2. multiple step operates 4 times, be filtered by vacuum with glass filter or Buchner funnel under 0.08MPa, and is constantly washed directly with distilled water
To filtered fluid in neutrality, finally untill being filtered out without aqueous, delignification process is completed, obtains holocellulose；
Hemicellulose is gone to handle described in present embodiment step 1：Above-mentioned gained holocellulose is loaded 500mL's
In the wide mouthed Erlenmeyer bottle after potassium hydroxide solution rinse for being 5% with mass concentration, 300mL mass concentrations are poured into as 5%
Potassium hydroxide solution, seal rim of a cup with preservative film, stand 12h at room temperature, so that the abundant swollen fiber of alkali lye；It is then placed in 90
Heating stirring 2h in DEG C thermostat water bath；After reaction terminates, vacuum is carried out under 0.08MPa with Buchner funnel or glass filter and is taken out
Filter, and it is in neutrality to be washed repeatedly to filtered fluid with distilled water, finally untill being filtered out without aqueous, hemicellulose process is gone in completion,
Obtain purifying cellulose.
Embodiment two：The difference of present embodiment and embodiment one is：Life described in step 1
The addition quality of thing preprocessing process cellulase is 2 with nano-cellulose mass ratio in nano-cellulose aqueous:1.Other
It is identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Institute in step 1
Sodium bromide during the Chemical Pretreatment stated：TEMPO reagents：The mass ratio of nano-cellulose is 100 in nano-cellulose aqueous:
16:1000.Other are identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Institute in step 2
The zero dimension inorganic nano-particle stated is SiO2、Al2O3、TiO2, ZnO and CeO2In any one or a few composition.Other with
Embodiment one to three is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Walk in step 2
The particle diameter of described zero dimension inorganic nano-particle is 10nm~30nm.Other are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Institute in step 2
The mass ratio of nano-cellulose is (1~5) in the nano-cellulose aqueous that the zero dimension inorganic nano-particle stated obtains with step 1:
10.Other are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Institute in step 3
The cationic surfactant stated is cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, cetyl front three
Any one or a few combination in ammonium chloride or OTAC.Other with embodiment one to
Six is identical.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Institute in step 3
The water-borne wood coating stated is water-soluble polyurethane acrylic resin coating or water-based acrylic resin coating.Other and specific implementation
Mode one to seven is identical.
Watersoluble polyurethane acrylic acid woodwork coating or water soluble acrylic acid woodwork coating described in present embodiment, are purchased from praising
Bao Li Chemical Groups limited company.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：Institute in step 3
The water-soluble polyurethane acrylic resin coating stated is made up of water-soluble polyurethane acrylic resin, deionized water and curing agent, described
The solid content of watersoluble polyurethane acrylic acid woodwork coating is 30%, curing agent in described watersoluble polyurethane acrylic acid woodwork coating
Solid content 0.5%~1%, described curing agent is amino resins class low-temperature self-crosslinking curing agent or acyl group phosphorus oxidation species
Ultraviolet curable agent；Or described water soluble acrylic acid woodwork coating is made up of water-based acrylic resin, deionized water and curing agent,
The solid content of the water soluble acrylic acid woodwork coating is 30%, and consolidating for curing agent contains in described water soluble acrylic acid woodwork coating
The 0.5%~1% of amount, described curing agent is amino resins class low-temperature self-crosslinking curing agent or acyl group phosphorus oxidation species ultraviolet light
Curing agent.Other are identical with embodiment one to eight.
Embodiment ten：Present embodiment is with one of embodiment one to nine difference：Step 3 1. in
The mass ratio of described cationic surfactant and nano-cellulose in hybridization compounding liquid is (0.5~1):100；Step 3 is 2.
Described in water-borne wood coating the mass ratio of solid masses and nano-cellulose in revolving surplus solution be 100:(0.2~
0.8).Other are identical with embodiment one to nine.
Using following verification experimental verifications effect of the present invention
Embodiment 1：The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, specifically by following
What step was completed：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and gone
Hemicellulose processing, obtains purifying cellulose, carries out Biological Pretreatment to purifying cellulose, obtains nano-cellulose aqueous；
Extracting processing described in step 1：250mL Soxhlet extractors are put into after 3g cellulosic materials are wrapped with filter paper
In, 240mL toluene-ethanos mixed solution is then added as extraction solvent, extracts 10h at 90 DEG C in water-bath, removal is taken out
Deduction point, obtain removing the wood powder of extracting composition；The volume ratio of toluene and ethanol is 2 in described toluene-ethano mixed solution:
1；
Cellulosic material described in step 1 is the wood powder that granularity is 120 mesh；
Delignification processing described in step 1：1., above-mentioned gained is removed to the wood powder of extracting composition, and to be put into 500mL wide
In mouth conical flask, the mixed solution of glacial acetic acid, sodium chlorite and deionized water, altogether 300mL, and being sealed with preservative film are added；
Wherein, glacial acetic acid 0.2mL, sodium chlorite 1g, remaining liquid are water；Then, by the taper equipped with above-mentioned mixed solution
Bottle is placed at magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control, obtains mixed solution；2., into the mixed solution of gained according to first plus
Enter 0.2mL glacial acetic acid and 1g sodium chlorites, the magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control；3., 2. repeat step grasps
Make 4 times, be filtered by vacuum with glass filter or Buchner funnel under 0.08MPa, and constantly washed with distilled water until filtered fluid is in
Neutrality, finally untill being filtered out without aqueous, delignification process is completed, obtains holocellulose；
Hemicellulose is gone to handle described in step 1：Above-mentioned gained holocellulose loading 500mL quality has been used into
Concentration is in the wide mouthed Erlenmeyer bottle after 5% potassium hydroxide solution rinse, pours into the potassium hydroxide that 300mL mass concentrations are 5%
Solution, rim of a cup is sealed with preservative film, stands 12h at room temperature, so that the abundant swollen fiber of alkali lye；It is then placed in 90 DEG C of waters bath with thermostatic control
Heating stirring 2h in pot；Reaction terminate after, be filtered by vacuum with Buchner funnel or glass filter under 0.08MPa, and with steaming
Distilled water is washed to filtered fluid in neutrality repeatedly, and finally untill being filtered out without aqueous, hemicellulose process is gone in completion, obtains pure chemical fiber
Dimension element；
Biological Pretreatment described in step 1 refers to cellulase pretreatment, and concrete operations are as follows：By purifying cellulose plus
In the beaker for entering 250mL, it is 0.1% to add deionized water to the mass fraction of purifying cellulose, cellulase is added, in 50 DEG C
Under the conditions of pre-process 2h, then after 90 DEG C handle 2h, after being filtered by vacuum and washing, it is 0.1% to be again made into mass concentration
Cellulose aqueous, then the high-pressure homogeneous machinery processing 30min through 600bar, produce nano-cellulose aqueous；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：Take the Nanowire for 0.1% concentration that step 1 obtains
Plain aqueous 200mL is tieed up, is charged with the Nano-meter SiO_2 that 0.05g particle diameters are 30nm2With the nano-ZnO grain that 0.05g particle diameters are 10nm
Son, in the case where power is 800W, ultrasonic wave strength is ultrasonically treated 30min, obtains hybridization compounding liquid；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in,
In the case where power is 300W, ultrasonic wave strength is ultrasonically treated 30min, obtains just mixed thing；2., first mixed thing is rotated, it is surplus to rotating
Remaining solution is added in 134mL water-borne wood coating untill originally mixing object product 1/5, will to rotate surplus solution, in power
30min is ultrasonically treated for ultrasonic wave strength under 300W, obtains compo；3., with homogenizer 15000rpm speed
Lower high-speed stirred compo 30min, produces the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic.Wherein,
Step 3 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be 1:100；Step
Three 1. described in cationic surfactant be cetyl trimethylammonium bromide；Step 3 2. described in water-borne wood coating
The mass ratio of middle solid masses and nano-cellulose in revolving surplus solution is 100:0.5；Step 3 2. described in Waterborne wood
Device coating is water-soluble polyurethane acrylic resin coating, wherein described water-soluble polyurethane acrylic resin coating is by water-based poly- ammonia
Ester acrylic resin, deionized water and curing agent composition, the solid content of the watersoluble polyurethane acrylic acid woodwork coating is 30%,
And in described watersoluble polyurethane acrylic acid woodwork coating the solid content of curing agent 1%, described curing agent is amino resins
Class low-temperature self-crosslinking curing agent.
Fig. 1 is that nano-cellulose TEM schemes in the nano-cellulose aqueous that the step 1 of embodiment 1 obtains, and is shown by Fig. 1 real
The fibre diameter for applying nano-cellulose in the nano-cellulose aqueous that the step 1 of example 1 obtains is 30nm~50nm scopes, and length is
Tens microns, draw ratio is more than 1000, shows nano-cellulose structure in the nano-cellulose aqueous that the step 1 of embodiment 1 obtains
Fine homogeneous, draw ratio are big.
Fig. 2 is the nanometer particle-modified water-borne wood coating SEM figures of nano-cellulose hybrid inorganic that embodiment 1 obtains, and is led to
The nano-particle crossed in the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic that Fig. 2 displays embodiment 1 obtains
It is dispersed on cellulose membrane, shows that nano-cellulose efficiently solves the scattering problem of inorganic nano-particle as carrier.
The nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic and unmodified wood that embodiment 1 is obtained
Device coating is with 120g/m2Quantity for spray maple surface is applied separately to by spraying method, at 35 DEG C dry 72h after, obtain
The nanometer particle-modified water-borne wood coating paint film of nano-cellulose hybrid inorganic and unmodified woodwork coating that embodiment 1 obtains
Paint film, test mechanical property, glossiness, anti-ultraviolet ageing performance and the bactericidal property of two kinds of paint films, the results showed that, embodiment 1
The more unmodified woodwork coating of hardness of the obtained nanometer particle-modified water-borne wood coating paint film of nano-cellulose hybrid inorganic
Paint film improves 28.7%, and wearability improves 36.2%, and scratch resistance improves 10%, and toughness improves
27.4%, glossiness reduced by only 15.6%, and ultraviolet resistance ageing time improves nearly 1 times, the mould load factor of coating surface
More than 80% is reduced, shows that the method can be effectively improved the combination property of water-borne wood coating, and assign sterilizing function.
Embodiment 2：The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, specifically by following
What step was completed：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and gone
Hemicellulose processing, obtains purifying cellulose, carries out Chemical Pretreatment to purifying cellulose, obtains nano-cellulose aqueous；
Extracting processing described in step 1：250mL Soxhlet extractors are put into after 3g cellulosic materials are wrapped with filter paper
In, 240mL toluene-ethanos mixed solution is then added as extraction solvent, extracts 10h at 90 DEG C in water-bath, removal is taken out
Deduction point, obtain removing the wood powder of extracting composition；The volume ratio of toluene and ethanol is 2 in described toluene-ethano mixed solution:
1；
Cellulosic material described in step 1 is the wood powder that granularity is 120 mesh；
Delignification processing described in step 1：1., above-mentioned gained is removed to the wood powder of extracting composition, and to be put into 500mL wide
In mouth conical flask, the mixed solution of glacial acetic acid, sodium chlorite and deionized water, altogether 300mL, and being sealed with preservative film are added；
Wherein, glacial acetic acid 0.2mL, sodium chlorite 1g, remaining liquid are water；Then, by the taper equipped with above-mentioned mixed solution
Bottle is placed at magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control, obtains mixed solution；2., into the mixed solution of gained according to first plus
Enter 0.2mL glacial acetic acid and 1g sodium chlorites, the magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control；3., 2. repeat step grasps
Make 4 times, be filtered by vacuum with glass filter or Buchner funnel under 0.08MPa, and constantly washed with distilled water until filtered fluid is in
Neutrality, finally untill being filtered out without aqueous, delignification process is completed, obtains holocellulose；
Hemicellulose is gone to handle described in step 1：Above-mentioned gained holocellulose loading 500mL quality has been used into
Concentration is in the wide mouthed Erlenmeyer bottle after 5% potassium hydroxide solution rinse, pours into the potassium hydroxide that 300mL mass concentrations are 5%
Solution, rim of a cup is sealed with preservative film, stands 12h at room temperature, so that the abundant swollen fiber of alkali lye；It is then placed in 90 DEG C of waters bath with thermostatic control
Heating stirring 2h in pot；Reaction terminate after, be filtered by vacuum with Buchner funnel or glass filter under 0.08MPa, and with steaming
Distilled water is washed to filtered fluid in neutrality repeatedly, and finally untill being filtered out without aqueous, hemicellulose process is gone in completion, obtains pure chemical fiber
Dimension element；
Chemical Pretreatment described in step 1 refers to TEMPO oxidation processes, and concrete operations are as follows：Purifying cellulose is loaded
In 250mL beaker, it is 0.25% to add deionized water mass fraction extremely, sequentially add 0.25g sodium bromides and
0.025gTEMPO (2,2,6,6- tetramethyl piperidine oxides), under magnetic agitation, 5mL is added with 2.5mL/min addition speed
Mass concentration is 12% liquor natrii hypochloritis, recycle the sodium hydroxide regulation pH value that concentration is 0.5mol/L be 10~
10.5, sustained response to pH value does not change, and terminates reaction, adds 15mL absolute ethyl alcohol, after filtering, washing, then
Obtained oxycellulose is placed in 250mL conical flasks, 70mL deionized waters and 0.6g sodium chlorites is added, is adjusted with glacial acetic acid
PH value is saved to 4~5, then in 70 DEG C of magnetic agitation 1h, is filtered, washing, is obtained carboxylated cellulose element, be then made into again
0.25% carboxylated cellulose element aqueous, then the high pressure of homogenizer mechanical dispersion 4min, 600bar through 15000rpm are equal
Matter mechanical treatment 5 times, the ultrasonic 30min of strength under 320W power, is made nano-cellulose aqueous；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：Take the nanometer for 0.25% concentration that step 1 obtains
Cellulose aqueous 100mL, it is charged with the nanometer Al that 0.05g particle diameters are 10nm2O3With the nanometer that 0.05g particle diameters are 10nm
TiO2Particle, in the case where power is 800W, ultrasonic wave strength is ultrasonically treated 30min, obtains hybridization compounding liquid；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in,
In the case where power is 300W, ultrasonic wave strength is ultrasonically treated 30min, obtains just mixed thing；2., first mixed thing is rotated, it is surplus to rotating
Remaining solution is added in 167mL water-borne wood coating untill originally mixing object product 1/5, will to rotate surplus solution, in power
30min is ultrasonically treated for ultrasonic wave strength under 300W, obtains compo；3., with homogenizer 15000rpm speed
Lower high-speed stirred compo 30min, produces the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic.Wherein,
Step 3 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be 1:100；Step
Three 1. described in cationic surfactant be OTAC；Step 3 2. described in water-borne wood coating
The mass ratio of middle solid masses and nano-cellulose in revolving surplus solution is 100:0.5；
Step 3 2. described in water-borne wood coating be water-soluble polyurethane acrylic resin coating, wherein described is water-based
Polyurethane acrylic resin coating is made up of water-soluble polyurethane acrylic resin, deionized water and curing agent, the water-based poly- ammonia
The solid content of ester acrylic acid woodwork coating is 30%, and consolidating for curing agent contains in described watersoluble polyurethane acrylic acid woodwork coating
The 1% of amount, described curing agent is acyl group phosphorus oxidation species ultraviolet curable agent.
Fig. 3 is that nano-cellulose TEM schemes in the nano-cellulose aqueous that the step 1 of embodiment 2 obtains, and is shown by Fig. 3 real
The fibre diameter for applying nano-cellulose in the nano-cellulose aqueous that the step 1 of example 2 obtains is 10nm-20nm scopes, and length is number
Micron, draw ratio are more than 100, show nano-cellulose fine structure in the nano-cellulose aqueous that the step 1 of embodiment 2 obtains
Uniformly, major diameter is bigger.
Fig. 4 is the nanometer particle-modified water-borne wood coating SEM figures of nano-cellulose hybrid inorganic that embodiment 2 obtains, and is led to
Cross the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic that Fig. 4 understands that embodiment 2 obtains and nano-particle is presented
It is dispersed on cellulose membrane, shows that nano-cellulose efficiently solves the scattering problem of inorganic nano-particle as carrier.
The nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic and unmodified wood that embodiment 2 is obtained
Device coating is with 120g/m2Quantity for spray maple surface is applied separately to by spraying method, under 600W/cm ultraviolet ray intensity
72h is placed in room temperature again after solidifying 5s, obtains the nanometer particle-modified Waterborne wood of nano-cellulose hybrid inorganic that embodiment 2 obtains
Device coating paint film and unmodified woodwork coating paint film, test the mechanical property, glossiness, anti-ultraviolet ageing performance of two kinds of paint films
And bactericidal property, the results showed that, the nanometer particle-modified water-borne wood coating paint of nano-cellulose hybrid inorganic that embodiment 2 obtains
The more unmodified woodwork coating paint film of hardness of film improves 22.3%, and wearability improves 49.7%, and scratch resistance improves
25.1%, toughness improves 19.5%, and glossiness reduced by only 10.3%, and ultraviolet resistance ageing time improves nearly 1
Times, the mould load factor of coating surface reduces more than 85%, shows that the method can be effectively improved the comprehensive of water-borne wood coating
Can, and assign sterilizing function.
Claims (10)
1. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, it is characterised in that it is by following step
Suddenly complete：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and removes half fibre
Dimension element processing, obtains purifying cellulose, carries out Biological Pretreatment to purifying cellulose, obtains nano-cellulose aqueous；
Described Biological Pretreatment refers to cellulase pretreatment, and concrete operations are as follows：Purifying cellulose is added to 250mL beaker
In, it is 0.1%~0.3% to add deionized water to the mass fraction of purifying cellulose, cellulase is added, under the conditions of 50 DEG C
2h is pre-processed, then after 90 DEG C handle 2h, after being filtered by vacuum and washing, it is 0.1%~0.3% to be made into mass concentration again
Cellulose aqueous, then the high-pressure homogeneous machinery processing 30min through 600bar, produce nano-cellulose aqueous；
Cellulosic material described in step 1 is that granularity is that more than 60 mesh wood powder, granularity is more than 60 mesh crops
Stalk powder or waste and old paper；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：Added in the nano-cellulose aqueous obtained to step 1
Zero dimension inorganic nano-particle, in the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains nothing
Machine nano-particle and the dispersed hybridization compounding liquid of nano-cellulose；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in, in work(
Rate is that ultrasonic wave strength is ultrasonically treated 30min~240min under 300W~1000W, obtains just mixed thing；2., first mixed thing is revolved
Steam, untill revolving surplus solution is originally mixed object product 1/5~1/2, revolving surplus solution is added to water-borne wood coating
In, in the case where power is 300W~1000W, ultrasonic wave strength is ultrasonically treated 30min~240min, obtains compo；3., with height
Fast mixer high-speed stirred compo 30min under 15000rpm speed, produce nano-cellulose hybrid inorganic nanoparticle
Sub- modified water-soluble woodwork coating.
2. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
The quality for the Biological Pretreatment process cellulase being characterised by described in step 1 and Nanowire in nano-cellulose aqueous
Plain mass ratio is tieed up as 2:1.
3. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
It is SiO to be characterised by the zero dimension inorganic nano-particle described in step 22、Al2O3、TiO2, ZnO and CeO2In any one or it is several
The composition of kind.
4. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
The particle diameter for the zero dimension inorganic nano-particle being characterised by described in step 2 is 10nm~30nm.
5. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
It is characterised by nanofiber in the nano-cellulose aqueous that the zero dimension inorganic nano-particle described in step 2 obtains with step 1
The mass ratio of element is (1~5):10.
6. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
It is cetyl trimethylammonium bromide, octadecyl trimethyl bromine to be characterised by the cationic surfactant described in step 3
Change any one or a few the combination in ammonium, hexadecyltrimethylammonium chloride or OTAC.
7. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
It is water-soluble polyurethane acrylic resin coating or water-based acrylic resin to be characterised by the water-borne wood coating described in step 3
Coating.
8. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 7, its
Water-soluble polyurethane acrylic resin coating described in being characterised by is by water-soluble polyurethane acrylic resin, deionized water and curing agent
Composition, the solid content of the watersoluble polyurethane acrylic acid woodwork coating is 30%, and described watersoluble polyurethane acrylic acid woodenware applies
The 0.5%~1% of the solid content of curing agent in material, described curing agent are amino resins class low-temperature self-crosslinking curing agent or acyl group
Phosphorus oxidation species ultraviolet curable agent；Or described water soluble acrylic acid woodwork coating by water-based acrylic resin, deionized water and
Curing agent forms, and the solid content of the water soluble acrylic acid woodwork coating is 30%, and in described water soluble acrylic acid woodwork coating
The 0.5%~1% of the solid content of curing agent, described curing agent are amino resins class low-temperature self-crosslinking curing agent or acyl group phosphorus oxygen
Compound class ultraviolet curable agent.
9. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, its
The mass ratio of cationic surfactant and nano-cellulose in hybridization compounding liquid described in being characterised by step 3 1. is
(0.5~1):100；Step 3 2. described in solid masses and nano-cellulose in revolving surplus solution in water-borne wood coating
Mass ratio is 100:(0.2~0.8).
10. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, it is characterised in that it is by following
What step was completed：
First, the preparation of nano-cellulose aqueous：Cellulosic material is stripped to processing, delignification processing successively and removes half fibre
Dimension element processing, obtains purifying cellulose, carries out Chemical Pretreatment to purifying cellulose, obtains nano-cellulose aqueous；
Extracting processing described in step 1：It is put into after 3g cellulosic materials are wrapped with filter paper in 250mL Soxhlet extractors, so
Add 240mL toluene-ethanos mixed solution afterwards and be used as extraction solvent, extract 10h at 90 DEG C in water-bath, remove extract into
Point, obtain removing the wood powder for extracting composition；The volume ratio of toluene and ethanol is 2 in described toluene-ethano mixed solution:1；
Cellulosic material described in step 1 is the wood powder that granularity is 120 mesh；
Delignification processing described in step 1：1., by above-mentioned gained remove extracting composition wood powder be put into 500mL wide-mouths cone
In shape bottle, the mixed solution of glacial acetic acid, sodium chlorite and deionized water, altogether 300mL, and being sealed with preservative film are added；Wherein,
Glacial acetic acid is 0.2mL, and sodium chlorite 1g, remaining liquid is water；Then, the conical flask equipped with above-mentioned mixed solution is put
In the magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control, mixed solution is obtained；2., into the mixed solution of gained according to first adding
0.2mL glacial acetic acid and 1g sodium chlorites, the magnetic force heating stirring 1h in 75 DEG C of waters bath with thermostatic control；3., repeat step 2. operate 4
It is secondary, it is filtered by vacuum with glass filter or Buchner funnel under 0.08MPa, and constantly washed with distilled water in filtered fluid is in
Property, finally untill being filtered out without aqueous, delignification process is completed, obtains holocellulose；
Hemicellulose is gone to handle described in step 1：Above-mentioned gained holocellulose loading 500mL mass concentration has been used into
In the wide mouthed Erlenmeyer bottle after 5% potassium hydroxide solution rinse, to pour into the potassium hydroxide solution that 300mL mass concentrations are 5%,
Rim of a cup is sealed with preservative film, stands 12h at room temperature, so that the abundant swollen fiber of alkali lye；It is then placed in 90 DEG C of thermostat water baths
Heating stirring 2h；After reaction terminates, it is filtered by vacuum with Buchner funnel or glass filter under 0.08MPa, and use distilled water
Wash repeatedly to filtered fluid in neutrality, finally untill being filtered out without aqueous, hemicellulose process is gone in completion, obtains cleaning cellulose
Element；
Chemical Pretreatment described in step 1 refers to TEMPO oxidation processes, and concrete operations are as follows：Purifying cellulose is loaded
In 250mL beaker, it is 0.25% to add the mass fraction of deionized water extremely, sequentially adds 0.25g sodium bromides and 0.025g
TEMPO, under magnetic agitation, 5mL mass concentrations are added as 12% liquor natrii hypochloritis using 2.5mL/min addition speed, then
The sodium hydroxide for being 0.5mol/L using concentration regulation pH value is 10~10.5, and sustained response to pH value does not change, and terminates
Reaction, adds 15mL absolute ethyl alcohol, 250mL conical flasks is placed in after filtering, washing, then by obtained oxycellulose
In, 70mL deionized waters and 0.6g sodium chlorites are added, pH value is adjusted to 4~5 with glacial acetic acid, then in 70 DEG C of magnetic agitations
1h, filter, washing, obtain carboxylated cellulose element, be then made into 0.25% carboxylated cellulose element aqueous again, then pass through
The high-pressure homogeneous machinery of 15000rpm homogenizer mechanical dispersion 4min, 600bar is handled 5 times, is strongly surpassed under 320W power
Sound 30min, nano-cellulose aqueous is made；
2nd, the hybridization compounding of nano-cellulose and inorganic nano-particle：Take the nanofiber for 0.25% concentration that step 1 obtains
Plain aqueous 100mL, it is charged with the nanometer Al that 0.05g particle diameters are 10nm2O3With the nano-TiO that 0.05g particle diameters are 10nm2Grain
Son, in the case where power is 800W, ultrasonic wave strength is ultrasonically treated 30min, obtains hybridization compounding liquid；
3rd, nano material and resin aqueous emulsion are compound：1., by cationic surfactant add hybridization compounding liquid in, in work(
Rate is that ultrasonic wave strength is ultrasonically treated 30min under 300W, obtains just mixed thing；2., first mixed thing is rotated, it is remaining molten to rotating
Liquid is added in 167mL water-borne wood coating untill originally mixing object product 1/5, will to rotate surplus solution, is in power
Ultrasonic wave strength is ultrasonically treated 30min under 300W, obtains compo；3., with homogenizer under 15000rpm speed
High-speed stirred compo 30min, produce the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic；Wherein, walk
Rapid three 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be 1:100；Step 3
1. cationic surfactant described in is OTAC；Step 3 2. described in water-borne wood coating
The mass ratio of solid masses and nano-cellulose in revolving surplus solution is 100:0.5；
Step 3 2. described in water-borne wood coating be water-soluble polyurethane acrylic resin coating, wherein described water-based poly- ammonia
Ester acrylic resin paint is made up of water-soluble polyurethane acrylic resin, deionized water and curing agent, the aqueous polyurethane third
The solid content of olefin(e) acid woodwork coating is 30%, and the solid content of curing agent in described watersoluble polyurethane acrylic acid woodwork coating
1%, described curing agent is acyl group phosphorus oxidation species ultraviolet curable agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610115893.3A CN105670514B (en) | 2016-03-01 | 2016-03-01 | The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610115893.3A CN105670514B (en) | 2016-03-01 | 2016-03-01 | The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105670514A CN105670514A (en) | 2016-06-15 |
| CN105670514B true CN105670514B (en) | 2017-11-14 |
Family
ID=56306381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610115893.3A Active CN105670514B (en) | 2016-03-01 | 2016-03-01 | The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670514B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955363B (en) * | 2017-12-06 | 2020-10-16 | 陕西科技大学 | Method for modifying bio-based aqueous polyurethane emulsion by ZnO/NCC nano composite particles and product thereof |
| CN108047811A (en) * | 2017-12-27 | 2018-05-18 | 成都新柯力化工科技有限公司 | It is a kind of to improve Nano silver grain method dispersed in aqueous, environmental protective ink |
| CN109575696B (en) * | 2018-06-27 | 2021-06-08 | 宜华生活科技股份有限公司 | Preparation method of nano-cellulose-polyurethane iridescent structural color coating for wood products |
| CN109054584B (en) * | 2018-07-24 | 2020-12-08 | 清远粤绿新材料技术有限公司 | Nano-scale cellulose functional doped modified coating and preparation method thereof |
| CN109251648B (en) * | 2018-08-13 | 2020-07-03 | 山东农业大学 | Method for chemically modifying nano-cellulose aqueous wood lacquer containing hemicellulose |
| CN109897714A (en) * | 2019-02-20 | 2019-06-18 | 常州市宝平不锈钢制品有限公司 | A kind of preparation method of metal rust preventing lotion |
| CN110028702B (en) * | 2019-04-29 | 2022-03-08 | 济南圣泉集团股份有限公司 | Nano-silica-doped nano-cellulose material and preparation method and application thereof |
| CN110067149B (en) * | 2019-05-15 | 2021-08-24 | 陕西科技大学 | Method for preparing high-strength, high-haze and transparency nano paper by using holocellulose |
| CN111019193A (en) * | 2019-11-19 | 2020-04-17 | 南开大学 | Preparation method of modified nanofiber silk aqueous solution |
| CN114181606B (en) * | 2021-11-30 | 2022-07-19 | 安徽扬子地板股份有限公司 | High-moisture-resistance environment-friendly multi-element composite floor and production process thereof |
| CN116061279B (en) * | 2022-12-30 | 2024-05-14 | 山东农业大学 | Modification treatment agent for in-situ reinforcing and toughening of wood and modification method thereof |
| CN116079849B (en) * | 2022-12-30 | 2024-04-02 | 山东农业大学 | Preparation method of high-strength and high-toughness wood based on combination of surface micro-nano reinforcement and densification |
| CN116120797A (en) * | 2023-04-18 | 2023-05-16 | 华南理工大学 | Biomass-based superfine water-based wood paint and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7595372B2 (en) * | 2005-04-07 | 2009-09-29 | Momentive Performance Materials Inc. | Epoxy silane oligomer and coating composition containing same |
| US7732552B2 (en) * | 2006-01-27 | 2010-06-08 | Momentive Performance Materials Inc. | Low VOC epoxy silane oligomer and compositions containing same |
| CN102773892B (en) * | 2012-08-13 | 2014-03-26 | 山东农业大学 | Preparation method of wood-organic-inorganic hybridized nano composite material based on doped nano POSS (Polyhedral Oligomeric Silsesquioxane) |
| CN102775621B (en) * | 2012-08-13 | 2014-03-26 | 山东农业大学 | Method for preparing nanometer SiO2 doped wood-organic-inorganic hybrid nanometer composite material |
| CN102775717B (en) * | 2012-08-13 | 2013-10-30 | 山东农业大学 | Preparation method of wood-organic-inorganic hybridization nano composite material based on nanolayer-shaped clay doping |
-
2016
- 2016-03-01 CN CN201610115893.3A patent/CN105670514B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105670514A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105670514B (en) | The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic | |
| CN105754470B (en) | The method of the cellulose modified water-borne wood coating of two dimensional oxidation graphene hydridization 1-dimention nano | |
| CN1276147C (en) | Preparation method of acrylonitrile fiber containing deacetyl chitin | |
| CN103061174B (en) | The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment | |
| CN104387671B (en) | A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material | |
| JP6794374B2 (en) | Water treatment | |
| CN107456879B (en) | Nano silica/nanofiber water-oil separating composite membrane and preparation method thereof | |
| CN109251648B (en) | Method for chemically modifying nano-cellulose aqueous wood lacquer containing hemicellulose | |
| CN102926016B (en) | Method for preparing modified konjac glucomannan fiber by electrostatic spinning | |
| CN109695182A (en) | A kind of method depickling enhancing treatment fluid and aging paper is handled | |
| CN105461953A (en) | Preparation method of nanometer antibacterial composite membrane based on self-assembling technology | |
| CN107474343A (en) | The method that one kettle way prepares ascidian nano micro crystal cellulose/rubber nano composite material | |
| Hahn et al. | Chitosan application in textile processing and fabric coating | |
| CN106674238A (en) | Tetra-(4-pyridyl) zinc porphyrin self-assembly nanocrystallization method | |
| Kumar et al. | Effects of abaca fiber reinforcement on the dynamic mechanical behavior of vinyl ester composites | |
| CN106757464A (en) | Food oxydating resistance cellulose acetate nanofiber preservative film | |
| CN106554528B (en) | Butadiene-styrene rubber/white carbon black/lignocellulosic/montmorillonite rubber composite material and preparation method thereof | |
| CN105200561A (en) | Method for preparing polyvinyl alcohol nanofibers by taking polyglutamic acid hydrogel as bridge | |
| CN105330561B (en) | Calcium carbonate surface modifier as well as composition of calcium carbonate and modifier and preparation method thereof | |
| CN102493014A (en) | Epsilon-polylysine and polyvinyl alcohol composite biological antibacterial fiber and preparation method thereof | |
| CN103774344B (en) | A kind of low VOC nanometers of flaxen fiber composite material and preparation method | |
| TW201437449A (en) | Manufacturing method of a bamboo pulp cellulose non-woven fabric with odor-removing function | |
| CN105839226A (en) | Efficient antibacterial chitosan fiber and preparation method thereof | |
| CN110042666A (en) | A kind of graft-modification method of hydrophobic garment material fiber | |
| CN110042665A (en) | A kind of surface modified ultra-high molecular weight polyethylene fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |