CN112574577B - Nano-material wood veneer - Google Patents
Nano-material wood veneer Download PDFInfo
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- CN112574577B CN112574577B CN202011465638.4A CN202011465638A CN112574577B CN 112574577 B CN112574577 B CN 112574577B CN 202011465638 A CN202011465638 A CN 202011465638A CN 112574577 B CN112574577 B CN 112574577B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention provides a nano-material wood-glue board, which is prepared from delignification recoverable wood-fiber filler, polymethyl methacrylate, polylactic acid, polyamide polyamine epichlorohydrin, soybean protein powder, nano calcium carbonate, graphene and aluminum silicate fiber. According to the preparation method, one part of the prepared graphene-doped polymethyl methacrylate-polylactic acid graft copolymer is used for preparing a surface modified aluminum silicate fiber film with certain wettability and is used as a bonding layer, the other part of the prepared graphene-doped polymethyl methacrylate-polylactic acid graft copolymer is used for forming a particle colloidal solution with good adhesiveness with soybean protein powder and polyamide polyamine epoxy chloropropane, delignification recyclable wood fiber filler and nano calcium carbonate are added to prepare a single-layer plate, and then the bonding layer and the single-layer plate are sequentially superposed and then a cold-pressing post-thermosetting method is adopted to prepare the nano wood veneer which has the functions of preventing the growth of mildew, preventing the delamination under the humid environment or ultraviolet irradiation and having fire and fire resistance.
Description
Technical Field
The invention belongs to the technical field of wood plywood, and particularly relates to a nano-material wood plywood.
Background
At present, China is a large export country of plywood and is also the first large world production country of plywood. However, the plywood products in China are frequently extruded by foreign trade barriers on one hand, and are impacted by international advanced productivity on the other hand, so that huge external challenges and threats are faced, the industrial structure of the plywood is required to be adjusted and upgraded, the production technology is improved, the production process is well controlled, high-quality plywood products are produced practically, continuously and stably, the core competitiveness is improved, and the stable market can be provided.
Most of the wood veneers in the prior art are made of the existing bamboo curtains and solid wood, such as 201310420834.3; or as the technical scheme disclosed in chinese patent 201611171601.4, in order to manufacture a formaldehyde-free wood veneer, an adhesive obtained from modified unsaturated polyester is coated on a solid wood veneer for bonding, the veneer is aged and delaminated under long-term exposure to ultraviolet light, pores between the veneer and the adhesive become too large, the veneer is brittle and cracked due to water shortage in long-term exposure, so that the surface of the veneer is not beautiful, or the veneer is placed in a humid environment, the veneer is swelled and cracked due to the water absorption of the unsaturated polyester resin of the adhesive, and the surface of the veneer is easy to be adhered by microorganisms, so that mold growth is caused, the service life is shortened, and the adopted solid wood material is difficult to obtain or the production cost of the product is high.
Disclosure of Invention
Aiming at the defects, the invention provides the nanometer material wood-glue board which can prevent the growth of mould, is not easy to delaminate under the humid environment or ultraviolet irradiation and has fire-resistant and fireproof performances.
The invention provides the following technical scheme: a preparation material of a nano-material wood veneer comprises the following components in parts by weight:
70-80 parts of delignification recyclable wood fiber filler;
55-65 parts of polymethyl methacrylate;
75-85 parts of polylactic acid;
15-20 parts of polyamide polyamine epoxy chloropropane;
30-40 parts of soybean protein powder;
0.05 to 0.1 portion of sodium ethylene diamine tetracetate;
20-25 parts of sodium dodecyl sulfate;
15-20 parts of sodium persulfate;
7-15 parts of nano calcium carbonate;
10-20 parts of graphene;
20-30 parts of aluminum silicate fiber;
20-30 parts of epoxy resin;
the preparation method of the nano-material wood veneer comprises the following steps:
s1: dissolving the polymethyl methacrylate of the weight component, the polylactic acid of the weight component and the sodium persulfate of the weight component in distilled water, and stirring at 30-40 ℃ for 20-30 min to obtain a precursor solution of the polymethyl methacrylate-polylactic acid graft copolymer;
s2: adding the graphene with the weight components into the mixed solution obtained in the step S1, and oscillating and mixing the graphene with the mixed solution under the ultrasonic wave with the frequency of 30 Hz-50 Hz;
s3: dissolving the sodium dodecyl sulfate in the weight components in distilled water to form a sodium dodecyl sulfate solution with the concentration of 2-2.5M, continuously stirring the mixed solution obtained in the step S2 at the rotating speed of 120-150 rpm for 15min, dropwise adding the sodium dodecyl sulfate solution in the stirring process, centrifuging the obtained mixed solution for 3-4 times, and drying the obtained precipitate at the temperature of 45-60 ℃ for 30-60 min to obtain the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer;
s4: dissolving the soybean protein powder with the weight components in 250-300 ml of distilled water at 28-32 ℃ and 100-200 rpm to form a soybean protein solution, and dissolving one half of the weight components of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the soybean protein solution at the same temperature and rotation speed to form a soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s5: immersing the aluminum silicate fibers of the weight components in the soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution, ultrasonically dissolving and dissolving the mixture at the temperature of 40-50 ℃ and the frequency of 40-60 Hz for 30-45 min, and then airing the mixture for 30-60 min under nitrogen airflow to obtain a wet polymer surface modified aluminum silicate fiber film;
s6: dissolving the polyamide polyamine epichlorohydrin with the weight components in an ethanol solution to form a polyamide polyamine epichlorohydrin ethanol solution, dissolving the remaining half of the weight components of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the polyamide polyamine epichlorohydrin ethanol solution, and stirring at 25-27 ℃ and 200-300 rpm for 1-1.5 h to obtain a polyamide polyamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution, wherein the core is the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, and the shell is polyamide polyamine epichlorohydrin;
s7: uniformly mixing the nanoparticle colloidal solution obtained in the step S6 with the epoxy resin containing the weight components to obtain a nanoparticle adhesive mixture; immersing the delignified recyclable wood fiber filler with the weight components in the nano-particle adhesive mixing agent, stirring at the rotating speed of 800-1000 rpm, continuously adding the nano calcium carbonate with the weight components and the sodium ethylene diamine tetracetate with the weight components during stirring, and finally obtaining the delignified recyclable wood fiber filler loaded with the nano calcium carbonate, wherein the delignified recyclable wood fiber filler is immersed in the prepared nano-particle adhesive mixing agent, and then the sodium ethylene diamine tetracetate and the nano calcium carbonate with chelation are added, so that the delignified recyclable wood fiber filler has certain adhesiveness, the adhesion polymerization degree of the delignified recyclable wood fiber filler and the wet polymer surface modified aluminum silicate fiber film obtained in the step S5 is further enhanced, the tight combination degree of the delignified recyclable wood fiber filler is improved, the finally prepared nano material is not easy to layer, and the polymer surface modified aluminum silicate fiber film cannot generate water absorption expansion due to high humidity of the used environment and then is combined with the delignified recyclable wood fiber filler loaded with the nano calcium carbonate The recyclable wood fiber packing layer is separated and cracked, so that the service life is shortened, and the product quality is reduced;
s8: pressurizing the delignified recyclable wood fiber filler loaded with the nano calcium carbonate obtained in the step S7 for 1 to 1.5 hours under the vacuum degree of 4.5 to 5.5 bars to obtain a delignified recyclable wood fiber filler loaded with the nano calcium carbonate as a veneer layer;
s9: and (3) overlapping the single-layer board obtained in the step (S8) and the wet polymer surface modified aluminum silicate fiber film obtained in the step (S5) in a mold in a crossed manner according to a required quantity, performing cold press molding at the temperature of-15 to-5 ℃ and the pressure of 25 to 40MPa, and performing thermocuring at the temperature of 90 to 140 ℃ for 0.8 to 1.25 hours to obtain the nano-material wood veneer.
Furthermore, the adopted graphene is nano double-layer graphene, and the aperture of the graphene is 5 nm-8 nm.
Further, the preparation method of the delignified recyclable wood fiber filler comprises the following steps:
1) dissolving 30-40 parts of sodium chlorite in an acetic acid solution to form a sodium chlorite acetic acid solution;
2) crushing the recyclable wood fiber filler to 45-75 meshes, heating the sodium chlorite-acetic acid solution obtained in the step 1) to 75-85 ℃, and immersing 70-90 parts of the crushed recyclable wood fiber filler in the heated sodium chlorite-acetic acid solution for 20-30 min at the temperature;
3) and when the recoverable wood fiber filler turns white, cleaning the recoverable wood fiber filler for 3-5 times by using distilled water, then immersing the recoverable wood fiber filler in 3-5 parts of ethanol and 5-8 parts of acetone for dehydration for 15-30 min, taking out and air-drying to obtain the delignified recoverable wood fiber filler.
Further, the pH value of the acetic acid solution in the step 1) is 4-5, and the concentration of the sodium chlorite-acetic acid solution is 1% by mass fraction.
Further, the recyclable wood fiber filler comprises one or more of waste timber, waste paper boxes, bamboo craft processing waste leftover materials, soybean shells, peanut shells, straws or straws.
Furthermore, the particle size of the soybean protein powder is 120-150 meshes.
Furthermore, the particle size of the nano calcium carbonate is 20 nm-35 nm.
Further, the centrifugation condition of the step S3 is to adopt a rotation speed of 5000rpm to 5500 rpm.
Further, the polymer surface modified aluminum silicate fiber film obtained in the step S5 has a wettability of 40% to 60%.
Further, the mass fraction of the polyamide polyamine epichlorohydrin in the polyamide polyamine epichlorohydrin ethanol solution formed in the step S6 is 25% -35%.
The invention has the beneficial effects that:
1. the preparation material of the nano-material wood veneer provided by the application is characterized in that the polymethyl methacrylate-polylactic acid graft copolymer doped with graphene prepared in the preparation process has a cross-linked adhesive network, so that the material has good adhesion and curing performance, and therefore, one part of the material is combined with soybean protein powder to form a precursor solution of the polymethyl methacrylate-polylactic acid graft copolymer doped with graphene by polymerization and further continuously attached to the surface of aluminum silicate fiber to form a polymer surface modified aluminum silicate fiber film with certain wettability and adhesive property, the aluminum silicate fiber has the advantages of high temperature resistance, good thermal stability, low thermal conductivity, small thermal capacity, good mechanical vibration resistance, small thermal expansion, good heat insulation performance and the like, after the surface of the precursor of the polymethyl methacrylate-polylactic acid graft copolymer doped with graphene is modified, due to the effect of doping graphene, the heat preservation and insulation performance and the fire resistance of the aluminum silicate fiber are further enhanced, and meanwhile, the raw materials of graphene, polymethyl methacrylate and polylactic acid in the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer are all environment-friendly and nontoxic raw materials, and toxic and harmful carcinogens such as formaldehyde and the like cannot be released along with the rise of temperature.
2. The polyamide polyamine epichlorohydrin added in the preparation process has a plurality of primary and secondary amino groups, and is easy to form an epoxy ring reaction with the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, so that the polyamide polyamine epichlorohydrin is quickly fused into a cross-linked adhesive network of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, and then the delignified recyclable wood fiber filler is soaked in the crosslinked adhesive network, so that on one hand, the solidification performance of the granular delignified recyclable wood fiber filler is enhanced, the bonding degree of the delignified recyclable wood fiber filler layer which is finally formed and is used as a veneer layer and is loaded with nano calcium carbonate and a polymer surface modified aluminum silicate fiber film is also enhanced, and the delamination phenomenon is prevented.
3. The polyamide polyamine epichlorohydrin adopted by the application has higher reaction activity, can react with hydroxyl in the aluminum silicate fiber and carry out cross-linking polymerization, so that the finally formed surface modified aluminum silicate fiber film generates wet strength and has the effect of enhancing the dryness of the wood veneer.
4. According to the preparation method, epoxy resin is further added in the process of preparing the veneer layer, so that the flowability of the formed polyamide polyamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution can be well adjusted, the veneer layer and the polymer surface modified aluminum silicate fiber thin film layer are better combined, and the added nano calcium carbonate can improve the porosity of the veneer layer and simultaneously enhance the fireproof and fireproof performance of the finally prepared veneer.
5. The polymethyl methacrylate in the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer prepared by the method can improve the dimensional stability of a formed veneer layer, has unique pungent smell, can enable corrosion-resistant mould of the prepared wood veneer to grow, is resistant to ultraviolet irradiation, and further prevents the wood veneer from being applied to a humid environment, microorganisms in the environment are gathered on the surface of a wood building, and aging layering caused by long-term ultraviolet irradiation is prevented, so that the appearance of the wood veneer is not influenced, and health problems of residents are not brought.
6. The wood veneer provided by the invention is formed by cold pressing a plurality of layers of veneers and a plurality of layers of surface modified aluminosilicate fiber films at a low temperature, the compactness between the veneers and the adhesive film can be enhanced at a low temperature and a high pressure, and air in gaps is released, so that the surface modified aluminosilicate fiber films can be rapidly combined with the veneers at the upper side and the lower side in the gradual melting process when being heated at a high temperature, the bonding combination is tighter, and the phenomenon that the wood veneer is gradually layered and aged in humid air is also reduced.
7. The recyclable wood fiber filler in the single-layer board material is subjected to delignification to remove lignin serving as a main light absorption component in the wood, and then the polymer (the radial mesoporous silica-loaded polyhydric alcohol or ether-glycol phase change heat storage material grafted polymethyl methacrylate copolymer) component matched with the refractive index of the wood permeates the pore space to reduce light scattering, so that the absorption efficiency of heat energy brought by the light energy is further enhanced, more heat energy can be released when the ambient temperature is reduced, and the heat preservation effect is further enhanced.
Detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation material of the nano-material wood veneer provided by the embodiment comprises the following components in parts by weight:
70 parts of waste carton fiber filler can be recovered by delignification;
55 parts of polymethyl methacrylate;
75 parts of polylactic acid;
15 parts of polyamide polyamine epichlorohydrin;
30 parts of soybean protein powder with the particle size of 120 meshes;
0.05 part of sodium ethylene diamine tetracetate;
20 parts of sodium dodecyl sulfate;
15 parts of sodium persulfate;
7 parts of nano calcium carbonate with the particle size of 20 nm;
10 parts of graphene with the pore diameter of 5 nm;
20 parts of aluminum silicate fiber;
and 20 parts of epoxy resin.
The preparation method of the delignification recyclable waste carton fiber filler comprises the following steps:
1) dissolving 30 parts of sodium chlorite in an acetic acid solution with the pH value of 4 to form a sodium chlorite acetic acid solution with the mass fraction of 1 percent;
2) crushing recyclable waste carton fiber fillers to 45 meshes, heating the sodium chlorite-acetic acid solution obtained in the step 1) to 75 ℃, and immersing 70 parts of the crushed recyclable waste carton fiber fillers in the heated sodium chlorite-acetic acid solution for 20 min;
3) when the recyclable waste carton fiber filler turns white, the recyclable waste carton fiber filler is washed by distilled water for 3 times, then is immersed in 3 parts of ethanol and 5 parts of acetone for dehydration for 15min, and is taken out and air-dried to obtain the lignin-removed recyclable waste carton fiber filler.
The embodiment also provides a preparation method of the nano-material wood veneer, which comprises the following steps:
s1: dissolving 55 parts of polymethyl methacrylate, 75 parts of polylactic acid and 15 parts of sodium persulfate in distilled water, and stirring at 30 ℃ for 20min to obtain a polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s2: adding 10 parts of graphene with the pore diameter of 5nm into the mixed solution obtained in the step S1, and oscillating and mixing the graphene and the mixed solution under the ultrasonic wave with the frequency of 30 Hz;
s3: dissolving 20 parts of sodium dodecyl sulfate in distilled water to form a sodium dodecyl sulfate solution with the concentration of 2M, mixing the mixed solution obtained in the step S2 at the rotating speed of 120rpm, continuously stirring for 15min, dropwise adding the sodium dodecyl sulfate solution in the stirring process, centrifuging the obtained mixed solution for 3 times at the rotating speed of 5000rpm, and drying the obtained precipitate at 45 ℃ for 30min to obtain the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer;
s4: dissolving soy protein powder with weight components in 250ml of distilled water at 28 ℃ and 100rpm to form a soy protein solution, and dissolving one half of the weight components of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the soy protein solution at the same temperature and rotation speed to form a soy protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s5: immersing 20 parts of aluminum silicate fiber into a precursor solution of the soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, ultrasonically mixing and dissolving the aluminum silicate fiber in the precursor solution at 40 ℃ and 40Hz for 30min, and then drying the aluminum silicate fiber in air under nitrogen flow for 30min to obtain a polymer surface modified aluminum silicate fiber film with the wettability of 40%;
s6: dissolving 55 parts of polyamidoamine epichlorohydrin in an ethanol solution to form a polyamidoamine epichlorohydrin ethanol solution with the mass fraction of the polyamidoamine epichlorohydrin of 25%, dissolving the remaining half weight of the components of the polymethyl methacrylate-polylactic acid graft copolymer doped with graphene obtained in the step S3 in the polyamidoamine epichlorohydrin ethanol solution, stirring for 1h at 25 ℃ and 200rpm to obtain a polyamidoamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution, wherein the core is the polymethyl methacrylate-polylactic acid graft copolymer doped with graphene, and the shell is polyamidoamine epichlorohydrin;
s7: uniformly mixing the nanoparticle colloidal solution obtained in the step S6 with 20 parts of epoxy resin to obtain a nanoparticle adhesive mixture; immersing 70 parts of delignified recyclable waste carton fiber filler in the nanoparticle adhesive mixing agent, stirring at the rotating speed of 800rpm, and continuously adding 7 parts of nano calcium carbonate with the particle size of 20nm and 0.05 part of sodium ethylene diamine tetracetate during stirring to finally obtain the delignified recyclable waste carton fiber filler loaded with the nano calcium carbonate;
s8: pressurizing the delignified recyclable waste carton fiber filler loaded with the nano calcium carbonate obtained in the step S7 for 1h under the vacuum degree of 4.5bar to obtain a delignified recyclable wood fiber filler layer loaded with the nano calcium carbonate, wherein the delignified recyclable wood fiber filler layer is used as a veneer layer;
s9: and (4) overlapping the single-layer board obtained in the step S8 and the wet polymer surface modified aluminum silicate fiber film obtained in the step S5 in a mold in a crossed manner according to a required quantity, performing cold press molding at-15 ℃ and 25MPa, and performing heat curing at 90 ℃ for 0.8h to obtain the nano-material wood veneer provided by the embodiment.
Example 2
The preparation material of the nano-material wood veneer provided by the embodiment comprises the following components in parts by weight:
80 parts of soybean hull and straw fiber filler can be recovered by delignification;
65 parts of polymethyl methacrylate;
85 parts of polylactic acid;
20 parts of polyamide polyamine epichlorohydrin;
40 parts of soybean protein powder with the particle size of 150 meshes;
0.1 part of sodium ethylene diamine tetracetate;
25 parts of sodium dodecyl sulfate;
20 parts of sodium persulfate;
15 parts of nano calcium carbonate with the particle size of 35 nm;
20 parts of graphene with the aperture of 8 cm;
30 parts of aluminum silicate fiber;
and 30 parts of epoxy resin.
The preparation method of the delignification recoverable soybean hull and straw fiber filler comprises the following steps:
1) dissolving 40 parts of sodium chlorite in an acetic acid solution with pH of 5 to form a sodium chlorite acetic acid solution with the mass fraction of 1%;
2) crushing the recyclable soybean shells and the straw fiber filler to 75 meshes, heating the sodium chlorite-acetic acid solution obtained in the step 1) to 85 ℃, and immersing 90 parts of the crushed recyclable soybean shells and the straw fiber filler in the heated sodium chlorite-acetic acid solution for 30min at the temperature;
3) when the recoverable soybean hull and the straw fiber filler turn white, the recoverable soybean hull and the straw fiber filler are washed by distilled water for 5 times, then immersed in 5 parts of ethanol and 8 parts of acetone for dehydration for 30min, taken out and air-dried to obtain the delignified recoverable soybean hull and the straw fiber filler.
The embodiment also provides a preparation method of the nano-material wood veneer, which comprises the following steps:
s1: dissolving 65 parts of polymethyl methacrylate, 85 parts of polylactic acid and 20 parts of sodium persulfate in distilled water, and stirring at 40 ℃ for 30min to obtain a precursor solution of the polymethyl methacrylate-polylactic acid graft copolymer;
s2: adding 20 parts of graphene with the pore diameter of 8nm into the mixed solution obtained in the step S1, and oscillating and mixing under the ultrasonic wave with the frequency of 50 Hz;
s3: dissolving 25 parts of sodium dodecyl sulfate in distilled water to form a sodium dodecyl sulfate solution with the concentration of 2.5M, continuously stirring the mixed solution obtained in the step S2 at the rotating speed of 150rpm for 15min, dropwise adding the sodium dodecyl sulfate solution in the stirring process, centrifuging the obtained mixed solution at the rotating speed of 5500rpm for 4 times, and drying the obtained precipitate at 60 ℃ for 60min to obtain the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer;
s4: dissolving 40 parts of soybean protein powder with the particle size of 150 meshes in 300ml of distilled water at the temperature of 32 ℃ and the rotating speed of 200rpm to form a soybean protein solution, and dissolving one half of the weight of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the soybean protein solution at the same temperature and rotating speed to form a soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s5: immersing 30 parts of aluminum silicate fiber in a soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution, ultrasonically mixing and dissolving the aluminum silicate fiber in the solution at 50 ℃ and 60Hz for 45min, and then drying the aluminum silicate fiber in a nitrogen airflow for 60min to obtain a polymer surface modified aluminum silicate fiber film with the humidity of 60%;
s6: dissolving 20 parts of polyamidoamine epichlorohydrin in an ethanol solution to form a polyamidoamine epichlorohydrin ethanol solution with the mass fraction of the polyamidoamine epichlorohydrin of 35%, dissolving the remaining half weight of the components of the polyamidoamine epichlorohydrin ethanol solution in which the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 is dissolved, stirring the solution at the temperature of 27 ℃ and the rpm of 300 for 1.5 hours to obtain a polyamidoamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution, wherein the core is the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, and the shell is polyamidoamine epichlorohydrin;
s7: uniformly mixing the nanoparticle colloidal solution obtained in the step S6 with 30 parts of epoxy resin to obtain a nanoparticle adhesive mixture; immersing 80 parts of delignified recoverable soybean hull and straw fiber filler in the nanoparticle adhesive mixing agent, stirring at the rotating speed of 1000rpm, and continuously adding 15 parts of nano calcium carbonate with the particle size of 35nm and 0.1 part of sodium ethylene diamine tetracetate during stirring to finally obtain the delignified recoverable soybean hull and straw fiber filler loaded with the nano calcium carbonate;
s8: pressurizing the delignified recoverable soybean hulls loaded with the nano calcium carbonate and the straw fiber filler obtained in the step S7 for 1.5 hours under the vacuum degree of 5.5bar to obtain delignified recoverable soybean hulls loaded with the nano calcium carbonate and a straw fiber filler layer which are used as veneer layers;
s9: and (4) overlapping the single-layer board obtained in the step S8 and the wet polymer surface modified aluminum silicate fiber film obtained in the step S5 in a mold in a crossed manner according to a required quantity, cold-pressing and molding at-5 ℃ and 40MPa, and then thermally curing at 140 ℃ for 1.25 hours to obtain the nano-material wood veneer of the embodiment.
Example 3
The preparation material of the nano-material wood veneer provided by the embodiment comprises the following components in parts by weight:
delignification can be carried out to recover 75 parts of waste leftover material fiber filler in bamboo artware processing;
60 parts of polymethyl methacrylate;
80 parts of polylactic acid;
17.5 parts of polyamide polyamine epichlorohydrin;
35 parts of soybean protein powder with the particle size of 130 meshes;
0.75 part of sodium ethylene diamine tetracetate;
22.5 parts of sodium dodecyl sulfate;
17.5 parts of sodium persulfate;
11 parts of nano calcium carbonate with the particle size of 27.5 nm;
15 parts of graphene with the pore diameter of 6.5 nm;
25 parts of aluminum silicate fiber;
and 25 parts of epoxy resin.
The preparation method of the delignification recyclable waste leftover fiber filler for bamboo artware processing comprises the following steps:
1) dissolving 35 parts of sodium chlorite in an acetic acid solution with the pH value of 4.5 to form a sodium chlorite acetic acid solution with the mass fraction of 1 percent;
2) crushing the recyclable bamboo artware processing waste leftover fiber filler to 60 meshes, heating the sodium chlorite-acetic acid solution obtained in the step 1) to 80 ℃, and immersing 80 parts of the crushed recyclable bamboo artware processing waste leftover fiber filler in the heated sodium chlorite-acetic acid solution for 25 min;
3) when the recyclable bamboo artware processing waste leftover material fiber filler turns white, the recyclable bamboo artware processing waste leftover material fiber filler is washed by distilled water for 4 times, then is immersed in 4 parts of ethanol and 6.5 parts of acetone for dehydration for 20min, and is taken out and air-dried to obtain the delignified recyclable bamboo artware processing waste leftover material fiber filler.
The embodiment also provides a preparation method of the nano-material wood veneer, which comprises the following steps:
s1: dissolving 60 parts of polymethyl methacrylate, 80 parts of polylactic acid and 17.5 parts of sodium persulfate in distilled water, and stirring at 35 ℃ for 25min to obtain a polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s2: adding 15 parts of graphene with the pore diameter of 6.5nm into the mixed solution obtained in the step S1, and oscillating and mixing under the ultrasonic wave with the frequency of 40 Hz;
s3: dissolving 22.5 parts of sodium dodecyl sulfate in distilled water to form a sodium dodecyl sulfate solution with the concentration of 2.25M, continuously stirring the mixed solution obtained in the step S2 at the rotating speed of 135rpm for 15min, dropwise adding the sodium dodecyl sulfate solution in the stirring process, centrifuging the obtained mixed solution at the rotating speed of 5250rpm for 3 times, and drying the obtained precipitate at 55 ℃ for 45min to obtain the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer;
s4: dissolving 35 parts of soybean protein powder with the particle size of 130 meshes in 280ml of distilled water at the temperature of 30 ℃ and the rotating speed of 150rpm to form a soybean protein solution, and dissolving one half of the weight of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the soybean protein solution at the same temperature and rotating speed to form a soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s5: immersing 25 parts of aluminum silicate fiber in a precursor solution of the soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, ultrasonically mixing and dissolving the aluminum silicate fiber at the temperature of 45 ℃ and the frequency of 50Hz for 37min, and then drying the aluminum silicate fiber in air under nitrogen flow for 45min to obtain a polymer surface modified aluminum silicate fiber film with the wettability of 50%;
s6: dissolving 17.5 parts of polyamide polyamine epichlorohydrin in an ethanol solution to form a polyamide polyamine epichlorohydrin ethanol solution with the polyamide polyamine epichlorohydrin mass fraction of 30%, dissolving the remaining half weight of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the polyamide polyamine epichlorohydrin ethanol solution, stirring at 26 ℃ and 250rpm for 1.25h to obtain a polyamide polyamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution, wherein the core is the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, and the shell is polyamide polyamine epichlorohydrin;
s7: uniformly mixing the nano-particle colloidal solution obtained in the step S6 with epoxy resin in weight components to obtain a nano-particle adhesive mixing agent; immersing 75 parts of delignified recyclable bamboo artware processing waste leftover fiber filler in a nanoparticle adhesive mixing agent, stirring at the rotating speed of 900rpm, and continuously adding 11 parts of nano calcium carbonate with the particle size of 27.5nm and 0.75 part of sodium ethylene diamine tetracetate during stirring to finally obtain the delignified recyclable bamboo artware processing waste leftover fiber filler loaded with the nano calcium carbonate;
s8: pressurizing the delignified recyclable bamboo artware processing waste leftover fiber filler loaded with the nano calcium carbonate obtained in the step S7 for 1.25 hours under the vacuum degree of 5bar to obtain a delignified recyclable wood fiber filler layer loaded with the nano calcium carbonate, wherein the delignified recyclable wood fiber filler layer is used as a veneer layer;
s9: and (4) overlapping the single-layer board obtained in the step S8 and the wet polymer surface modified aluminum silicate fiber film obtained in the step S5 in a mold in a crossed manner according to a required quantity, performing cold press molding at-10 ℃ and 32.5MPa, and performing heat curing at 115 ℃ for 1.0h to obtain the nano-material wood veneer of the embodiment.
Comparative example
The wood veneers made of the nano-materials obtained in the embodiments 1-3 and the wood veneers prepared by the binder component in the embodiment one and the method in the embodiment five in Chinese patent 201611171601.4 are cut into wood blocks with the length of 2cm multiplied by 3cm, and then the wood blocks are placed in a closed space with the length of 10cm multiplied by 10cm, heated at a high temperature of 30-40 ℃ and measured for formaldehyde emission by a dryer method; and testing the environmental temperature change rate after the temperature in each closed space is gradually reduced to 0 ℃ at 35 ℃; and after the ultraviolet light with the wavelength of 300 nm-350 nm is adopted for irradiation for 12 hours, the static bending strength MOR and the bending elastic modulus of the material are testedAn amount MOE; placing the wood veneer sheets for 4 weeks under the humidity of 75-85%, and coating the surfaces of the wood veneer sheets of the examples and the comparative examples with 0.05X 103Per cm2The mold density with medium was measured and the number of mold on the surface of the wood veneer after 4 weeks, and the results are shown in table 1.
TABLE 1
As can be seen from the table above, the nano-material wood veneer provided by the application is not easy to delaminate under strong ultraviolet irradiation and a humid environment, has excellent adhesion tightness and good thermal insulation performance, and does not release harmful gases such as formaldehyde.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The nano-material wood veneer is characterized in that the preparation material of the wood veneer comprises the following components in parts by weight:
70-80 parts of delignification recyclable wood fiber filler;
55-65 parts of polymethyl methacrylate;
75-85 parts of polylactic acid;
15-20 parts of polyamide polyamine epoxy chloropropane;
30-40 parts of soybean protein powder;
0.05 to 0.1 portion of sodium ethylene diamine tetracetate;
20-25 parts of sodium dodecyl sulfate;
15-20 parts of sodium persulfate;
7-15 parts of nano calcium carbonate;
10-20 parts of graphene;
20-30 parts of aluminum silicate fiber;
20-30 parts of epoxy resin;
the preparation method of the nano-material wood veneer comprises the following steps:
s1: dissolving the polymethyl methacrylate of the weight component, the polylactic acid of the weight component and the sodium persulfate of the weight component in distilled water, and stirring at 30-40 ℃ for 20-30 min to obtain a precursor solution of the polymethyl methacrylate-polylactic acid graft copolymer;
s2: adding the graphene with the weight components into the mixed solution obtained in the step S1, and oscillating and mixing the graphene with the mixed solution under the ultrasonic wave with the frequency of 30 Hz-50 Hz;
s3: dissolving the sodium dodecyl sulfate in the weight components in distilled water to form a sodium dodecyl sulfate solution with the concentration of 2-2.5M, continuously stirring the mixed solution obtained in the step S2 at the rotating speed of 120-150 rpm for 15min, dropwise adding the sodium dodecyl sulfate solution in the stirring process, centrifuging the obtained mixed solution for 3-4 times, and drying the obtained precipitate at the temperature of 45-60 ℃ for 30-60 min to obtain the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer;
s4: dissolving the soybean protein powder with the weight components in 250-300 ml of distilled water at 28-32 ℃ and 100-200 rpm to form a soybean protein solution, and dissolving one half of the weight components of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the soybean protein solution at the same temperature and rotation speed to form a soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution;
s5: immersing the aluminum silicate fibers of the weight components into the soybean protein polymerization graphene-doped polymethyl methacrylate-polylactic acid graft copolymer precursor solution, ultrasonically mixing and dissolving the mixture for 30-45 min at the temperature of 40-50 ℃ and the frequency of 40-60 Hz, and then airing the mixture for 30-60 min under nitrogen airflow to obtain a wet polymer surface modified aluminum silicate fiber film;
s6: dissolving the polyamide polyamine epichlorohydrin with the weight components in an ethanol solution to form a polyamide polyamine epichlorohydrin ethanol solution, dissolving the remaining half of the weight components of the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer obtained in the step S3 in the polyamide polyamine epichlorohydrin ethanol solution, and stirring at 25-27 ℃ and 200-300 rpm for 1-1.5 h to obtain a polyamide polyamine epichlorohydrin/graphene-doped polymethyl methacrylate-polylactic acid graft copolymer core-shell nanoparticle colloidal solution, wherein the core is the graphene-doped polymethyl methacrylate-polylactic acid graft copolymer, and the shell is polyamide polyamine epichlorohydrin;
s7: uniformly mixing the nanoparticle colloidal solution obtained in the step S6 with the epoxy resin in the weight component to obtain a nanoparticle adhesive mixture; immersing the delignified recyclable wood fiber filler with the weight components in the nanoparticle adhesive mixing agent, stirring at the rotating speed of 800-1000 rpm, and continuously adding the nano calcium carbonate with the weight components and the sodium ethylene diamine tetracetate with the weight components during stirring to finally obtain the delignified recyclable wood fiber filler loaded with the nano calcium carbonate;
s8: pressurizing the delignified recyclable wood fiber filler loaded with the nano calcium carbonate obtained in the step S7 for 1 to 1.5 hours under the vacuum degree of 4.5 to 5.5 bars to obtain a delignified recyclable wood fiber filler loaded with the nano calcium carbonate as a veneer layer;
s9: and (3) overlapping the veneer layer obtained in the step (S8) and the wet polymer surface modified aluminum silicate fiber film obtained in the step (S5) in a mold in a crossed manner according to a required quantity, performing cold press molding at a temperature of between 15 ℃ below zero and 5 ℃ below zero and under a pressure of between 25MPa and 40MPa, and performing thermocuring at a temperature of between 90 ℃ and 140 ℃ for 0.8 to 1.25 hours to obtain the nano-material wood veneer.
2. The nano-material wood-veneer according to claim 1, wherein the method for preparing the delignified recoverable wood fibre filler comprises the following steps:
1) dissolving 30-40 parts of sodium chlorite in an acetic acid solution to form a sodium chlorite acetic acid solution;
2) crushing the recyclable wood fiber filler to 45-75 meshes, heating the sodium chlorite-acetic acid solution obtained in the step 1) to 75-85 ℃, and immersing 70-90 parts of crushed recyclable wood fiber filler in the heated sodium chlorite-acetic acid solution for 20-30 min under the temperature;
3) and when the recoverable wood fiber filler turns white, cleaning the recoverable wood fiber filler for 3-5 times by using distilled water, then immersing the recoverable wood fiber filler in 3-5 parts of ethanol and 5-8 parts of acetone for dehydration for 15-30 min, taking out and air-drying to obtain the delignified recoverable wood fiber filler.
3. The nano-material wood veneer according to claim 2, wherein the pH of the acetic acid solution in the step 1) is 4 to 5, and the concentration of the sodium chlorite acetic acid solution is 1% by mass fraction.
4. The nano-material wood-glue board according to claim 3, wherein the recyclable wood fiber filler comprises one or more of waste timber, waste cardboard boxes, bamboo craft waste scraps, soybean hulls, peanut hulls, straw or stalks.
5. The nano-material wood veneer board according to claim 1, wherein the particle size of the soybean protein powder is 120-150 meshes.
6. The nano-material wood veneer according to claim 1, wherein the nano calcium carbonate has a particle size of 20nm to 35 nm.
7. The nano-material wood veneer according to claim 1, wherein the centrifugation condition of the step S3 is to use a rotation speed of 5000-5500 rpm.
8. The nano-material wood-glue board according to claim 1, wherein the polymer surface-modified aluminum silicate fiber film obtained in the step S5 has a wettability of 40% to 60%.
9. The nano-material wood veneer according to claim 1, wherein the mass fraction of the polyamide polyamine epichlorohydrin in the polyamide polyamine epichlorohydrin ethanol solution formed in the step S6 is 25% to 35%.
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| CN108329889A (en) * | 2018-04-13 | 2018-07-27 | 杨奠基 | A kind of Formaldehyde Free Wood-based Panel adhesive and preparation method thereof |
| CN109370133A (en) * | 2018-10-10 | 2019-02-22 | 南京林业大学 | A kind of method of cellulose enhancing polymethyl methacrylate |
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| CN108329889A (en) * | 2018-04-13 | 2018-07-27 | 杨奠基 | A kind of Formaldehyde Free Wood-based Panel adhesive and preparation method thereof |
| CN109370133A (en) * | 2018-10-10 | 2019-02-22 | 南京林业大学 | A kind of method of cellulose enhancing polymethyl methacrylate |
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