CN105670514A - Method for modifying waterborne wood coating by nano-crystalline cellulose hybridizing inorganic nanoparticles - Google Patents
Method for modifying waterborne wood coating by nano-crystalline cellulose hybridizing inorganic nanoparticles Download PDFInfo
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Abstract
The invention provides a method for modifying waterborne wood coating by nano-crystalline cellulose hybridizing inorganic nanoparticles, and relates to a modification method of waterborne wood coating. The invention aims to solve the problems of poor mechanical property of the modified waterborne wood coating and poor improvement of weather resistance and sterilization and air purification function caused by poor dispersity of the existing inorganic nanoparticles in the waterborne wood coating, and low length-to-diameter ratio of a rod-like crystal of organic nano-cellulose. The method comprises the steps that 1, nano-cellulose water-humor is prepared; 2, the nano-cellulose and inorganic nanoparticles are hybridized and compounded; 3, nano materials and a waterborne resin emulsion are compounded, and the nano-crystalline cellulose hybridizing inorganic nanoparticle modified waterborne wood coating is obtained. According to the method provided by the invention, one dimensional nano cellulose with high specific surface area and good water dispersibility is adopted as a carrier, zero dimensional inorganic nanoparticles are doped in-situ and compounded, and the application range of the waterborne wood coating is widened through a two-phase in-situ hybridization and compounding method and improvement of overall performance of the waterborne wood coating.
Description
Technical field
The present invention relates to the method for modifying of a kind of water-borne wood coating.
Background technology
Timber has hygroscopic dilatancy, subject to that bacterium worm is rotten, it is aging to be subject to ultraviolet lighting, be readily burned the natural defects such as degraded, therefore wood surface of being everlasting covers with paint, lacquer, colour wash, etc. woodwork coating to improve drawbacks described above. So along with the reinforcement of people's environmental consciousness, the organic oil soluble paint application with high VOC release is increasingly restricted, and the environment-friendly aqueous coating of low VOC release is increasingly favored, and becomes the main trend of woodwork coating development. But mechanical performance, the anti-ultraviolet ageing performance such as the scratch-resistant of water-borne wood coating, wear-resisting, hardness, impact resistance are generally not as good as the oil paint of technology maturation, therefore it must be carried out improved properties.
In recent years, utilize nano material that the patent that water-borne wood coating is modified is seen in report. Nano-TiO is utilized as described in patent of invention that application number is 201210480069.X2、Al2O3、SiO2, Ag composite waterborne resin emulsion make water-borne wood coating have anti-microbial property, but nano-particle directly adulterates, existence easily reunion and matrix resin interface compatibility difference cause problems such as being separated, therefore cannot effectively strengthen the mechanical strength of water paint, the importing of Ag simultaneously can make water-borne wood coating have obvious aberration, reduces light transmittance and the glossiness of coating. Application number be 201380049182.5 patent of invention report the preparation method adding nano-cellulose and surfactant in water paint, but only added by nano-cellulose and the scratch-resistant of coating, wearability and anti-ultraviolet ageing performance improved without positive role. Application number be 201310588309.2 patent of invention report and utilize nano-cellulose rhabdolith to improve the mechanical properties such as the hardness of water-borne wood coating, wearability, and the dispersed problem of original position solving nano-cellulose, but anti-ultraviolet ageing performance can not be improved, and cause the improvement of scratch resistance and toughness owing to draw ratio is low and inconspicuous. Application number be 201510647618.1 patent of invention report nano cellulose crystal and TiO2In-situ reaction, coating production by its dispersibility in polydimethylsiloxane of stearic acid modified raising and interface binding power to each other, coating is made to have superhydrophobic characteristic, but nano-cellulose used is rhabdolith, draw ratio is little, and the improvement of coating mechanical property such as impact resistance, scratch resistance etc. is limited, and preparation be oil-soluble coating, organic VOC release is big, non-modern coatings development trend.Application number be 201410006256.3 patent of invention report the method utilizing nano-cellulose and nano silicon dioxide sol and water-dispersion type resin compounded to prepare super-hydrophobic woodwork coating, but nano-cellulose load nano silicon first carries out modifying super hydrophobicity, make it huge with the polarity difference of water-dispersion type resin, biphase affinity is poor, interface compatibility is poor, the nano material of modifying super hydrophobicity is very easily reunited, and causes every mechanical property of coating to be improved and not good enough even declines.
In a word, there is the problem that nanoparticle bad dispersibility causes coating mechanical property, light transmittance improvement is not good enough during the inorganic nano particle modified water-borne wood coating that above-mentioned published patent is stated; And organic nanofibers element mostly is bar-shaped nano cellulose crystal, draw ratio is low, and the toughness of coating, scratch resistance, wearability are improved all limited, and cannot be improved the weatherability of coating; Even if nano-cellulose and SiO2、TiO2Compound, the method adopted there is also the problem that it is poor with polymeric matrix affinity, bad dispersibility causes coating in polymeric matrix mechanical property improvement is not good enough.
Summary of the invention
The purpose of the present invention to solve existing inorganic nano-particle bad dispersibility in water-borne wood coating, organic nanofibers element rhabdolith draw ratio is low, the modified water-soluble woodenware coating poor mechanical property caused, and the problem that the improvement of weatherability even sterilizing and purifying air function is not good enough, and the method that the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is provided.
The method of the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, is specifically realized by the following steps:
One, the preparation of nano-cellulose water liquid: cellulosic material is sequentially carried out extracting process, delignification processes and goes hemicellulose to process, and obtains purifying cellulose, purifying cellulose carries out Biological Pretreatment or Chemical Pretreatment, obtain nano-cellulose water liquid;
Described Biological Pretreatment refers to cellulase pretreatment, concrete operations are as follows: added by purifying cellulose in the beaker of 250mL, addition deionized water is 0.1%～0.3% to the mass fraction of purifying cellulose, adding cellulase, pretreatment 2h under 50 DEG C of conditions, after then processing 2h at 90 DEG C, after vacuum filtration washing, again being made into the cellulose water liquid that mass concentration is 0.1%～0.3%, the high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid;
Purifying cellulose is loaded in the beaker of 250mL, adding deionized water mass fraction extremely is 0.1%～0.3%, it is sequentially added into sodium bromide, TEMPO reagent, under magnetic agitation, the liquor natrii hypochloritis that 5mL mass concentration is 12% is added with the addition speed of 2.5mL/min, the sodium hydroxide adjustment pH value that recycling concentration is 0.5mol/L is 10～10.5, sustained response does not change to pH value, terminate reaction, add the dehydrated alcohol of 15mL, through sucking filtration, after washing, again the oxidized cellulose obtained is placed in 250mL conical flask, add 70mL deionized water and 0.6g sodium chlorite, pH value is regulated to 4～5 with glacial acetic acid, then at 70 DEG C of magnetic agitation 1h, sucking filtration, washing, obtain carboxylated cellulose element, then the carboxylated cellulose element water liquid of 0.1%～0.3% again it is made into, homogenizer mechanical dispersion 4min then through 15000rpm, the high pressure homogenize machinery of 600bar processes 5 times, powerful ultrasonic 30min under 320W power, prepare nano-cellulose water liquid,
Cellulosic material described in step one is granularity be the timber powder of more than 60 orders, granularity is the agricultural crop straw powder of more than 60 orders or waste and old paper;
Two, the hybridization compounding of nano-cellulose and inorganic nano-particle: add zero dimension inorganic nano-particle in the nano-cellulose water liquid that step one obtains, it is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains inorganic nano-particle and the homodisperse hybridization compounding liquid of nano-cellulose;
Three, nano material and resin aqueous emulsion compound: 1., by cationic surfactant add in hybridization compounding liquid, is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains just mixed thing; 2., just mixed thing is carried out rotation to steam, steaming surplus solution to rotation be originally mixed object amasss 1/5～1/2, surplus solution is steamed in rotation and joins in water-borne wood coating, be ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtain compo; 3., with homogenizer high-speed stirred compo 30min under the speed of 15000rpm, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is obtained.
The invention have the advantages that and the present invention propose a kind of utilization to have the 1-dimention nano cellulose of high-specific surface area and superior water dispersibility be carrier, original position doped compound nano SiO2、Al2O3、TiO2、ZnO、CeO2Etc. zero dimension inorganic nanoparticles, mechanical performance and the anti-ultraviolet ageing performance such as the scratch resistance damage improving water-borne wood coating, wear-resisting, hardness, impact resistance is worked in coordination with by the method for biphase in-situ hybridization compound, even give its sterilization, purify the function of air, significantly improve the service life of water-borne wood coating, increase the function of water-borne wood coating, to widen the range of application of water-borne wood coating, improve the added value of Wood products. The advantage in conjunction with the embodiments stated, provides advantage of the present invention.
Accompanying drawing explanation
Fig. 1 is nano-cellulose TEM figure in the nano-cellulose water liquid that embodiment 1 step one obtains;
Fig. 2 is the nanometer particle-modified water-borne wood coating SEM figure of nano-cellulose hybrid inorganic that embodiment 1 obtains;
Fig. 3 is nano-cellulose TEM figure in the nano-cellulose water liquid that embodiment 2 step one obtains;
Fig. 4 is the nanometer particle-modified water-borne wood coating SEM figure of nano-cellulose hybrid inorganic that embodiment 2 obtains.
Detailed description of the invention
Detailed description of the invention one: present embodiment is the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, is specifically realized by the following steps:
One, the preparation of nano-cellulose water liquid: cellulosic material is sequentially carried out extracting process, delignification processes and goes hemicellulose to process, and obtains purifying cellulose, purifying cellulose carries out Biological Pretreatment or Chemical Pretreatment, obtain nano-cellulose water liquid;
Described Biological Pretreatment refers to cellulase pretreatment, concrete operations are as follows: added by purifying cellulose in the beaker of 250mL, addition deionized water is 0.1%～0.3% to the mass fraction of purifying cellulose, adding cellulase, pretreatment 2h under 50 DEG C of conditions, after then processing 2h at 90 DEG C, after vacuum filtration washing, again being made into the cellulose water liquid that mass concentration is 0.1%～0.3%, the high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid;
Purifying cellulose is loaded in the beaker of 250mL, adding deionized water mass fraction extremely is 0.1%～0.3%, it is sequentially added into sodium bromide, TEMPO reagent, under magnetic agitation, the liquor natrii hypochloritis that 5mL mass concentration is 12% is added with the addition speed of 2.5mL/min, the sodium hydroxide adjustment pH value that recycling concentration is 0.5mol/L is 10～10.5, sustained response does not change to pH value, terminate reaction, add the dehydrated alcohol of 15mL, through sucking filtration, after washing, again the oxidized cellulose obtained is placed in 250mL conical flask, add 70mL deionized water and 0.6g sodium chlorite, pH value is regulated to 4～5 with glacial acetic acid, then at 70 DEG C of magnetic agitation 1h, sucking filtration, washing, obtain carboxylated cellulose element, then the carboxylated cellulose element water liquid of 0.1%～0.3% again it is made into, homogenizer mechanical dispersion 4min then through 15000rpm, the high pressure homogenize machinery of 600bar processes 5 times, powerful ultrasonic 30min under 320W power, prepare nano-cellulose water liquid,
Cellulosic material described in step one is granularity be the timber powder of more than 60 orders, granularity is the agricultural crop straw powder of more than 60 orders or waste and old paper;
Two, the hybridization compounding of nano-cellulose and inorganic nano-particle: add zero dimension inorganic nano-particle in the nano-cellulose water liquid that step one obtains, it is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains inorganic nano-particle and the homodisperse hybridization compounding liquid of nano-cellulose;
Three, nano material and resin aqueous emulsion compound: 1., by cationic surfactant add in hybridization compounding liquid, is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains just mixed thing; 2., just mixed thing is carried out rotation to steam, steaming surplus solution to rotation be originally mixed object amasss 1/5～1/2, surplus solution is steamed in rotation and joins in water-borne wood coating, be ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtain compo; 3., with homogenizer high-speed stirred compo 30min under the speed of 15000rpm, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is obtained.
Extracting described in present embodiment step one processes: put in 250mL Soxhlet extractor after being wrapped by cellulosic material filter paper, it is subsequently adding 240mL toluene-ethano mixed solution as extraction solvent, extracting 10h at 90 DEG C in water-bath, remove extracting composition, obtain removing the wood powder of extracting composition; In described toluene-ethano mixed solution, toluene is 2:1 with the volume ratio of ethanol.
Delignification described in present embodiment step one processes: the wood powder 1., by above-mentioned gained removing extracting composition is put in 500mL wide mouthed Erlenmeyer bottle, adds the mixed solution of glacial acetic acid, sodium chlorite and deionized water, amounts to 300mL, and seals with preservative film; Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water; Then, will be equipped with the conical flask of above-mentioned mixed solution and be placed at magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control, obtain mixed solution; 2., according to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2mL, magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control in the mixed solution of gained; 3., repeat step and 2. operate 4 times, the vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash with distilled water until filtrate is in neutrality, finally leaching to anhydrous liquid, complete delignification process, obtain holocellulose;
The hemicellulose that goes described in present embodiment step one processes: by above-mentioned gained holocellulose load 500mL with in the wide mouthed Erlenmeyer bottle after the potassium hydroxide solution rinse that mass concentration is 5%, pour the potassium hydroxide solution that 300mL mass concentration is 5% into, rim of a cup is sealed with preservative film, left at room temperature 12h, so that the abundant swollen fiber of alkali liquor; It is then placed in heated and stirred 2h in 90 DEG C of thermostat water baths; After reaction terminates, under 0.08MPa, carry out vacuum filtration with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete hemicellulose process, obtain purifying cellulose.
Detailed description of the invention two: the present embodiment difference from detailed description of the invention one is: the addition quality of the Biological Pretreatment process cellulase described in step one is 2:1 with nano-cellulose mass ratio in nano-cellulose water liquid.Other are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment with one of detailed description of the invention one or two difference is: sodium bromide in the Chemical Pretreatment process described in step one: TEMPO reagent: in nano-cellulose water liquid, the mass ratio of nano-cellulose is 100:16:1000. Other are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment with one of detailed description of the invention one to three difference is: the zero dimension inorganic nano-particle described in step 2 is SiO2、Al2O3、TiO2, ZnO and CeO2In any one or a few compositions. Other are identical with detailed description of the invention one to three.
Detailed description of the invention five: present embodiment with one of detailed description of the invention one to four difference is: the particle diameter of step zero dimension inorganic nano-particle described in step 2 is 10nm～30nm. Other are identical with detailed description of the invention one to four.
Detailed description of the invention six: present embodiment with one of detailed description of the invention one to five difference is: in the nano-cellulose water liquid that the zero dimension inorganic nano-particle described in step 2 and step one obtain, the mass ratio of nano-cellulose is (1～5): 10. Other are identical with detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment with one of detailed description of the invention one to six difference is: the cationic surfactant described in step 3 is any one or a few the combination in cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or octadecyl trimethyl ammonium chloride. Other are identical with detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment with one of detailed description of the invention one to seven difference is: the water-borne wood coating described in step 3 is water-soluble polyurethane acrylic resin coating or water-borne acrylic resin coating. Other are identical with detailed description of the invention one to seven.
Watersoluble polyurethane acrylic acid woodwork coating described in present embodiment or water soluble acrylic acid woodwork coating, be purchased from Carpoly Chemical Group Co., Ltd..
Detailed description of the invention nine: present embodiment with one of detailed description of the invention one to eight difference is: the water-soluble polyurethane acrylic resin coating described in step 3 is made up of water-soluble polyurethane acrylic resin, deionized water and firming agent, the solid content of described watersoluble polyurethane acrylic acid woodwork coating is 30%, in described watersoluble polyurethane acrylic acid woodwork coating the 0.5%～1% of the solid content of firming agent, described firming agent is amino resins class low-temperature self-crosslinking firming agent or acyl group phosphorous oxides class ultraviolet curable agent; Or described water soluble acrylic acid woodwork coating is made up of water-borne acrylic resin, deionized water and firming agent; the solid content of described 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 firming agent, described firming agent is amino resins class low-temperature self-crosslinking firming agent or acyl group phosphorous oxides class ultraviolet curable agent. Other are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine difference is: step 3 1. described in cationic surfactant be (0.5～1) with the mass ratio of nano-cellulose in hybridization compounding liquid: 100; Step 3 2. described in the mass ratio of nano-cellulose in surplus solution is steamed in solid masses and rotation in water-borne wood coating is 100:(0.2～0.8).Other are identical with detailed description of the invention one to nine.
Adopt following verification experimental verification effect of the present invention
Embodiment 1: the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, is specifically realized by the following steps:
One, the preparation of nano-cellulose water liquid: cellulosic material is sequentially carried out extracting process, delignification processes and goes hemicellulose to process, and obtains purifying cellulose, purifying cellulose is carried out Biological Pretreatment, obtain nano-cellulose water liquid;
Extracting described in step one processes: put into after being wrapped by 3g cellulosic material filter paper in 250mL Soxhlet extractor, it is subsequently adding 240mL toluene-ethano mixed solution as extraction solvent, extracting 10h at 90 DEG C in water-bath, removes extracting composition, obtains removing the wood powder of extracting composition; In described toluene-ethano mixed solution, toluene is 2:1 with the volume ratio of ethanol;
Cellulosic material described in step one is granularity is the timber powder of 120 orders;
Delignification described in step one processes: the wood powder 1., by above-mentioned gained removing extracting composition is put in 500mL wide mouthed Erlenmeyer bottle, adds the mixed solution of glacial acetic acid, sodium chlorite and deionized water, amounts to 300mL, and seals with preservative film; Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water; Then, will be equipped with the conical flask of above-mentioned mixed solution and be placed at magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control, obtain mixed solution; 2., according to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2mL, magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control in the mixed solution of gained; 3., repeat step and 2. operate 4 times, the vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash with distilled water until filtrate is in neutrality, finally leaching to anhydrous liquid, complete delignification process, obtain holocellulose;
The hemicellulose that goes described in step one processes: by above-mentioned gained holocellulose load 500mL with in the wide mouthed Erlenmeyer bottle after the potassium hydroxide solution rinse that mass concentration is 5%, pour the potassium hydroxide solution that 300mL mass concentration is 5% into, rim of a cup is sealed with preservative film, left at room temperature 12h, so that the abundant swollen fiber of alkali liquor; It is then placed in heated and stirred 2h in 90 DEG C of thermostat water baths; After reaction terminates, under 0.08MPa, carry out vacuum filtration with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete hemicellulose process, obtain purifying cellulose;
Biological Pretreatment described in step one refers to cellulase pretreatment, concrete operations are as follows: added by purifying cellulose in the beaker of 250mL, addition deionized water is 0.1% to the mass fraction of purifying cellulose, adding cellulase, pretreatment 2h under 50 DEG C of conditions, after then processing 2h at 90 DEG C, after vacuum filtration washing, again being made into the cellulose water liquid that mass concentration is 0.1%, the high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid;
Two, the hybridization compounding of nano-cellulose and inorganic nano-particle: take the nano-cellulose water liquid 200mL of 0.1% concentration that step one obtains, be charged with the Nano-meter SiO_2 that 0.05g particle diameter is 30nm2It is the ZnO Nanoparticles of 10nm with 0.05g particle diameter, is ultrasound wave brute force supersound process 30min under 800W at power, obtains hybridization compounding liquid;
Three, nano material and resin aqueous emulsion compound: 1., by cationic surfactant add in hybridization compounding liquid, is ultrasound wave brute force supersound process 30min under 300W at power, obtains just mixed thing;2., just mixed thing is carried out rotation steaming, steaming surplus solution to rotation be originally mixed object long-pending 1/5, by the water-borne wood coating revolving steaming surplus solution and joining 134mL, is ultrasound wave brute force supersound process 30min under 300W at power, obtains compo; 3., with homogenizer high-speed stirred compo 30min under the speed of 15000rpm, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is obtained. Wherein, step 3 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be 1:100; Step 3 1. described in cationic surfactant be cetyl trimethylammonium bromide; Step 3 2. described in the mass ratio of nano-cellulose in surplus solution is steamed in solid masses and rotation in water-borne wood coating is 100:0.5; Step 3 2. described in water-borne wood coating be water-soluble polyurethane acrylic resin coating, wherein said water-soluble polyurethane acrylic resin coating is made up of water-soluble polyurethane acrylic resin, deionized water and firming agent, the solid content of described watersoluble polyurethane acrylic acid woodwork coating is 30%, and in described watersoluble polyurethane acrylic acid woodwork coating the 1% of the solid content of firming agent, described firming agent is amino resins class low-temperature self-crosslinking firming agent.
Fig. 1 is nano-cellulose TEM figure in the nano-cellulose water liquid that embodiment 1 step one obtains, show that in the nano-cellulose water liquid that embodiment 1 step one obtains, the fibre diameter of nano-cellulose is 30nm～50nm scope by Fig. 1, length is tens microns, draw ratio is more than 1000, showing that in the nano-cellulose water liquid that embodiment 1 step one obtains, nano-cellulose fine structure is uniform, draw ratio is big.
Fig. 2 is the nanometer particle-modified water-borne wood coating SEM figure of nano-cellulose hybrid inorganic that embodiment 1 obtains, it is dispersed on cellulose membrane by Fig. 2 nanoparticle shown in the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic that embodiment 1 obtains, it was shown 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 embodiment 1 obtained and unmodified woodwork coating are with 120g/m2Quantity for spray be applied separately to maple surface by spraying method, at 35 DEG C after dry 72h, obtain nano-cellulose hybrid inorganic nanometer particle-modified water-borne wood coating paint film and unmodified woodwork coating paint film that embodiment 1 obtains, the mechanical property of two kinds of paint films of test, glossiness, anti-ultraviolet ageing performance and bactericidal property, result shows, the more unmodified woodwork coating paint film of hardness of the nano-cellulose hybrid inorganic nanometer particle-modified water-borne wood coating paint film that embodiment 1 obtains improves 28.7%, wearability improves 36.2%, scratch resistance improves 10%, toughness improves 27.4%, glossiness reduced by only 15.6%, ultraviolet resistance ageing time improves nearly 1 times, the mycete load factor of coating surface reduces more than 80%, show that this method can be effectively improved the combination property of water-borne wood coating, and give sterilizing function.
Embodiment 2: the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic, is specifically realized by the following steps:
One, the preparation of nano-cellulose water liquid: cellulosic material is sequentially carried out extracting process, delignification processes and goes hemicellulose to process, and obtains purifying cellulose, purifying cellulose is carried out Chemical Pretreatment, obtain nano-cellulose water liquid;
Extracting described in step one processes: put into after being wrapped by 3g cellulosic material filter paper in 250mL Soxhlet extractor, it is subsequently adding 240mL toluene-ethano mixed solution as extraction solvent, extracting 10h at 90 DEG C in water-bath, removes extracting composition, obtains removing the wood powder of extracting composition; In described toluene-ethano mixed solution, toluene is 2:1 with the volume ratio of ethanol;
Cellulosic material described in step one is granularity is the timber powder of 120 orders;
Delignification described in step one processes: the wood powder 1., by above-mentioned gained removing extracting composition is put in 500mL wide mouthed Erlenmeyer bottle, adds the mixed solution of glacial acetic acid, sodium chlorite and deionized water, amounts to 300mL, and seals with preservative film; Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water; Then, will be equipped with the conical flask of above-mentioned mixed solution and be placed at magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control, obtain mixed solution; 2., according to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2mL, magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control in the mixed solution of gained; 3., repeat step and 2. operate 4 times, the vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash with distilled water until filtrate is in neutrality, finally leaching to anhydrous liquid, complete delignification process, obtain holocellulose;
The hemicellulose that goes described in step one processes: by above-mentioned gained holocellulose load 500mL with in the wide mouthed Erlenmeyer bottle after the potassium hydroxide solution rinse that mass concentration is 5%, pour the potassium hydroxide solution that 300mL mass concentration is 5% into, rim of a cup is sealed with preservative film, left at room temperature 12h, so that the abundant swollen fiber of alkali liquor; It is then placed in heated and stirred 2h in 90 DEG C of thermostat water baths; After reaction terminates, under 0.08MPa, carry out vacuum filtration with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete hemicellulose process, obtain purifying cellulose;
Chemical Pretreatment described in step one refers to TEMPO oxidation processes, concrete operations are as follows: loaded by purifying cellulose in the beaker of 250mL, adding deionized water mass fraction extremely is 0.25%, it is sequentially added into 0.25g sodium bromide and 0.025gTEMPO (2, 2, 6, 6-tetramethyl piperidine oxide), under magnetic agitation, the liquor natrii hypochloritis that 5mL mass concentration is 12% is added with the addition speed of 2.5mL/min, the sodium hydroxide adjustment pH value that recycling concentration is 0.5mol/L is 10～10.5, sustained response does not change to pH value, terminate reaction, add the dehydrated alcohol of 15mL, through sucking filtration, after washing, again the oxidized cellulose obtained is placed in 250mL conical flask, add 70mL deionized water and 0.6g sodium chlorite, pH value is regulated to 4～5 with glacial acetic acid, then at 70 DEG C of magnetic agitation 1h, sucking filtration, washing, obtain carboxylated cellulose element, then the carboxylated cellulose element water liquid of 0.25% again it is made into, homogenizer mechanical dispersion 4min then through 15000rpm, the high pressure homogenize machinery of 600bar processes 5 times, powerful ultrasonic 30min under 320W power, prepare nano-cellulose water liquid,
Two, the hybridization compounding of nano-cellulose and inorganic nano-particle: take the nano-cellulose water liquid 100mL of 0.25% concentration that step one obtains, be charged with nanometer Al that 0.05g particle diameter is 10nm2O3It is the nano-TiO of 10nm with 0.05g particle diameter2Particle, is ultrasound wave brute force supersound process 30min under 800W at power, obtains hybridization compounding liquid;
Three, nano material and resin aqueous emulsion compound: 1., by cationic surfactant add in hybridization compounding liquid, is ultrasound wave brute force supersound process 30min under 300W at power, obtains just mixed thing; 2., just mixed thing is carried out rotation steaming, steaming surplus solution to rotation be originally mixed object long-pending 1/5, by the water-borne wood coating revolving steaming surplus solution and joining 167mL, is ultrasound wave brute force supersound process 30min under 300W at power, obtains compo; 3., with homogenizer high-speed stirred compo 30min under the speed of 15000rpm, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is obtained. Wherein, step 3 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be 1:100; Step 3 1. described in cationic surfactant be octadecyl trimethyl ammonium chloride; Step 3 2. described in the mass ratio of nano-cellulose in surplus solution is steamed in solid masses and rotation in water-borne wood coating is 100:0.5;
Step 3 2. described in water-borne wood coating be water-soluble polyurethane acrylic resin coating; wherein said water-soluble polyurethane acrylic resin coating is made up of water-soluble polyurethane acrylic resin, deionized water and firming agent; the solid content of described watersoluble polyurethane acrylic acid woodwork coating is 30%; and in described watersoluble polyurethane acrylic acid woodwork coating the 1% of the solid content of firming agent, described firming agent is acyl group phosphorous oxides class ultraviolet curable agent.
Fig. 3 is nano-cellulose TEM figure in the nano-cellulose water liquid that embodiment 2 step one obtains, show that in the nano-cellulose water liquid that embodiment 2 step one obtains, the fibre diameter of nano-cellulose is 10nm-20nm scope by Fig. 3, length is a few micrometers, draw ratio is more than 100, showing that in the nano-cellulose water liquid that embodiment 2 step one obtains, nano-cellulose fine structure is uniform, major diameter is relatively larger.
Fig. 4 is the nanometer particle-modified water-borne wood coating SEM figure of nano-cellulose hybrid inorganic that embodiment 2 obtains, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic that embodiment 2 obtains as shown in Figure 4 presents nanoparticle and is dispersed on cellulose membrane, it was shown 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 embodiment 2 obtained and unmodified woodwork coating are with 120g/m2Quantity for spray be applied separately to maple surface by spraying method, 72h is placed in room temperature again after solidifying 5s under the ultraviolet ray intensity of 600W/cm, obtain nano-cellulose hybrid inorganic nanometer particle-modified water-borne wood coating paint film and unmodified woodwork coating paint film that embodiment 2 obtains, the mechanical property of two kinds of paint films of test, glossiness, anti-ultraviolet ageing performance and bactericidal property, result shows, the more unmodified woodwork coating paint film of hardness of the nano-cellulose hybrid inorganic nanometer particle-modified water-borne wood coating paint film that embodiment 2 obtains improves 22.3%, wearability improves 49.7%, scratch resistance improves 25.1%, toughness improves 19.5%, glossiness reduced by only 10.3%, ultraviolet resistance ageing time improves nearly 1 times, the mycete load factor of coating surface reduces more than 85%, show that this method can be effectively improved the combination property of water-borne wood coating, and give 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 completes according to the following steps:
One, the preparation of nano-cellulose water liquid: cellulosic material is sequentially carried out extracting process, delignification processes and goes hemicellulose to process, and obtains purifying cellulose, purifying cellulose carries out Biological Pretreatment or Chemical Pretreatment, obtain nano-cellulose water liquid;
Described Biological Pretreatment refers to cellulase pretreatment, concrete operations are as follows: added by purifying cellulose in the beaker of 250mL, addition deionized water is 0.1%～0.3% to the mass fraction of purifying cellulose, adding cellulase, pretreatment 2h under 50 DEG C of conditions, after then processing 2h at 90 DEG C, after vacuum filtration washing, again being made into the cellulose water liquid that mass concentration is 0.1%～0.3%, the high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid;
Described Chemical Pretreatment refers to TEMPO oxidation processes, concrete operations are as follows: loaded by purifying cellulose in the beaker of 250mL, adding deionized water mass fraction extremely is 0.1%～0.3%, it is sequentially added into sodium bromide, TEMPO reagent, under magnetic agitation, the liquor natrii hypochloritis that 5mL mass concentration is 12% is added with the addition speed of 2.5mL/min, the sodium hydroxide adjustment pH value that recycling concentration is 0.5mol/L is 10～10.5, sustained response does not change to pH value, terminate reaction, add the dehydrated alcohol of 15mL, through sucking filtration, after washing, again the oxidized cellulose obtained is placed in 250mL conical flask, add 70mL deionized water and 0.6g sodium chlorite, pH value is regulated to 4～5 with glacial acetic acid, then at 70 DEG C of magnetic agitation 1h, sucking filtration, washing, obtain carboxylated cellulose element, then the carboxylated cellulose element water liquid of 0.1%～0.3% again it is made into, homogenizer mechanical dispersion 4min then through 15000rpm, the high pressure homogenize machinery of 600bar processes 5 times, powerful ultrasonic 30min under 320W power, prepare nano-cellulose water liquid,
Cellulosic material described in step one is granularity be the timber powder of more than 60 orders, granularity is the agricultural crop straw powder of more than 60 orders or waste and old paper;
Two, the hybridization compounding of nano-cellulose and inorganic nano-particle: add zero dimension inorganic nano-particle in the nano-cellulose water liquid that step one obtains, it is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains inorganic nano-particle and the homodisperse hybridization compounding liquid of nano-cellulose;
Three, nano material and resin aqueous emulsion compound: 1., by cationic surfactant add in hybridization compounding liquid, is ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtains just mixed thing; 2., just mixed thing is carried out rotation to steam, steaming surplus solution to rotation be originally mixed object amasss 1/5～1/2, surplus solution is steamed in rotation and joins in water-borne wood coating, be ultrasound wave brute force supersound process 30min～240min under 300W～1000W at power, obtain compo; 3., with homogenizer high-speed stirred compo 30min under the speed of 15000rpm, the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic is obtained.
2. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that the quality of the Biological Pretreatment process cellulase described in step one is 2:1 with nano-cellulose mass ratio in nano-cellulose water liquid.
3. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that sodium bromide in the Chemical Pretreatment process described in step one: TEMPO reagent: in nano-cellulose water liquid, the mass ratio of nano-cellulose is 100:16:1000.
4. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that the zero dimension inorganic nano-particle described in step 2 is SiO2、Al2O3、TiO2, ZnO and CeO2In any one or a few compositions.
5. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that the particle diameter of the zero dimension inorganic nano-particle described in step 2 is 10nm～30nm.
6. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that in the nano-cellulose water liquid that the zero dimension inorganic nano-particle described in step 2 and step one obtain, the mass ratio of nano-cellulose is (1～5): 10.
7. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that the cationic surfactant described in step 3 is any one or a few the combination in cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or octadecyl trimethyl ammonium chloride.
8. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that the water-borne wood coating described in step 3 is water-soluble polyurethane acrylic resin coating or water-borne acrylic resin coating.
9. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterized in that described water-soluble polyurethane acrylic resin coating is made up of water-soluble polyurethane acrylic resin, deionized water and firming agent, the solid content of described watersoluble polyurethane acrylic acid woodwork coating is 30%, in described watersoluble polyurethane acrylic acid woodwork coating the 0.5%～1% of the solid content of firming agent, described firming agent is amino resins class low-temperature self-crosslinking firming agent or acyl group phosphorous oxides class ultraviolet curable agent; Or described water soluble acrylic acid woodwork coating is made up of water-borne acrylic resin, deionized water and firming agent; the solid content of described 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 firming agent, described firming agent is amino resins class low-temperature self-crosslinking firming agent or acyl group phosphorous oxides class ultraviolet curable agent.
10. the method for the nanometer particle-modified water-borne wood coating of nano-cellulose hybrid inorganic according to claim 1, it is characterised in that step 3 1. described in cationic surfactant and hybridization compounding liquid in the mass ratio of nano-cellulose be (0.5～1): 100; Step 3 2. described in the mass ratio of nano-cellulose in surplus solution is steamed in solid masses and rotation in water-borne wood coating is 100:(0.2～0.8).
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