WO2020228317A1 - 表面纳米晶化的含纤维素生物质材料及其制备方法和用途 - Google Patents

表面纳米晶化的含纤维素生物质材料及其制备方法和用途 Download PDF

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WO2020228317A1
WO2020228317A1 PCT/CN2019/125209 CN2019125209W WO2020228317A1 WO 2020228317 A1 WO2020228317 A1 WO 2020228317A1 CN 2019125209 W CN2019125209 W CN 2019125209W WO 2020228317 A1 WO2020228317 A1 WO 2020228317A1
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cellulose
biomass material
containing biomass
nanocrystallized
treatment
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French (fr)
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俞书宏
管庆方
韩子盟
杨怀斌
凌张弛
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/02—Cellulose; Modified cellulose
    • C09D101/04—Oxycellulose; Hydrocellulose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present disclosure relates to the field of nanotechnology, and in particular to a cellulose-containing biomass material with surface nanocrystallization and a preparation method and application thereof.
  • Micro-nano structure control has become an important means in the field of material research and development. Through micro-nano structure control, the performance of a series of traditional materials is improved. For example, by regulating the bionic lamellar structure of ceramic materials, its toughness is improved; by regulating the nano-twin structure of metal materials, a huge improvement in fatigue resistance and other properties have been achieved.
  • biomass As the most abundant renewable resource on the earth, biomass has a wide range of applications. my country is a large agricultural country. It produces a total of one trillion kilograms of biomass each year, which consists of 700 billion kilograms of agricultural straw and 300 billion kilograms of wood waste. The treatment methods for these wastes are either discarded or burned. The former It causes environmental pollution and wastes a lot of land accumulation, and the latter is even more serious. After such a huge amount is burned, it has a huge impact on the earth's climate. In biomass processing technology, the most important processing method starts with biomass materials for further processing. However, a current problem is that the biomass material obtained by direct pulverization has problems such as poor reactivity and small specific surface area, which restricts the processing and application of biomass materials.
  • the purpose of the present disclosure is to provide a cellulose-containing biomass material with high specific surface area, high surface activity and high crystallinity, which provides a very good raw material for further processing of biomass materials.
  • another objective of the present disclosure is to improve a method for nanocrystallization of the surface of a cellulose-containing biomass material.
  • a cellulose-containing biomass material with surface nanocrystals the cellulose-containing biomass material is derived from one or more of the biomass materials containing cellulose components in natural plants or animals, so The surface of the nanocrystallized cellulose-containing biomass material has exposed areas on the surface, and the cellulose in the exposed areas is nano-scale cellulose, and part of the hydroxyl groups in the nano-scale cellulose has been converted into A carboxyl group, so that the cellulose-containing biomass material whose surface is nanocrystallized has at least one of the following properties:
  • the specific surface area of the cellulose-containing biomass material whose surface is nanocrystallized is at least 1.5 m 2 /g, preferably at least 10 m 2 /g, and more preferably at least 30 m 2 /g;
  • the diameter of the nanocrystallized cellulose exposed on the surface of the surface nanocrystallized cellulose-containing biomass material is at least 1 micrometer or less, preferably at least 500 nanometers or less, more preferably at least 100 nanometers or less.
  • the crystallinity of cellulose is at least 65%, preferably 70%, more preferably 75%;
  • the molar ratio of carboxyl groups to the total amount of carboxyl groups is at least 5%, preferably at least 10%, more preferably at least 30%;
  • the viscosity of the surface nanocrystallized cellulose-containing biomass material in water is greater than 40 mPa ⁇ s, preferably 60 mPa ⁇ s, measured by a rotational viscometer method at about 25° C. when the mass fraction of the solution is 6%. Preferably 80mPa ⁇ s;
  • the sedimentation time of the aqueous solution of the surface nanocrystallized cellulose-containing biomass material is at least greater than 200 minutes, preferably at least greater than 500 minutes, and more preferably at least greater than 800 minutes.
  • a method for preparing a cellulose-containing biomass material with surface nanocrystals comprising the following steps:
  • the cellulose-containing biomass material is subjected to surface etching treatment in an etching solution, and the cellulose-containing biomass material is selected from one or more of the biomass materials containing cellulose components in natural plants and animals ;
  • the mechanically processed cellulose-containing biomass material is made into a dispersion or dry powder for storage.
  • the surface etching solution includes at least one selected from the group consisting of: sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium sulfite aqueous solution, sulfur dioxide aqueous solution, Sulfurous acid aqueous solution and a solvent that can dissolve biological macromolecules.
  • ⁇ 8> The preparation method according to ⁇ 6>, wherein the cellulose-containing biomass material described in step A) is in the form of particles, and the particle size is 0.1 ⁇ m to 5 mm.
  • the surface of the prime biomass material is exposed to oxidation of cellulose.
  • the preparation method according to ⁇ 6>, wherein the surface oxidation treatment method described in step B) is oxidation under the catalysis of 2,2,6,6-tetramethylpiperidine-nitrogen-oxide The reagent oxidizes the surface cellulose of the cellulose-containing biomass material, and the oxidizing reagent includes at least one water-soluble oxidant selected from the group consisting of sodium chlorite, sodium hypochlorite, sodium bromate and sodium hypobromite.
  • ⁇ 12> The preparation method according to ⁇ 6>, wherein the mechanical treatment is one or more of stirring, grinding, high-pressure homogenization or high-pressure jet treatment.
  • Figure 1 is a digital photo of the surface nanocrystalline biomass material dispersion prepared in Example 1 of the disclosure
  • Fig. 2 is a comparison of scanning electron micrographs of the surface of wood pellets that have not been treated by the present disclosure ( Figure 2A) and the cellulose-containing biomass particles (saw pellets) after surface nanocrystallization treatment by this method ( Figure 2B). It can be seen that in Figure 2A, the surface of the untreated wood chips is relatively smooth and does not have a large amount of fiber structure; the surface of the wood chips treated by this method has a large number of nano-scale fibers, one end is extended, and the other end is inserted in the particle;
  • Figure 3 shows the carbon NMR spectrum (Bruck Avance III 400WB) characterization of biomass particles after untreated, alkaline treatment and surface nanocrystallization, and shows that after surface nanocrystallization, cellulose-containing biomass particles appear obvious The carboxyl peak of, which proves the generation of carboxyl during the oxidation process;
  • Figure 4 shows the specific surface changes of cellulose-containing biomass particles (sawdust) after untreated, alkali-treated, and surface nano-crystallization, and shows that the specific surface area increases after the surface is nano-crystallized, according to Kantar Instruments Inc. iQ 2 , using multi-point BET method for test calculation;
  • Figure 5 shows the viscosity change of cellulose-containing biomass particles (sawdust) after surface nanocrystallization. This figure shows that the viscosity of the cellulose-containing biomass material after surface nanocrystallization is relatively untreated and alkali treatment technology. Improve; Shanghai Xingliang Optical Instrument Co., Ltd. rotational viscometer NDJ-1 is used. When the cylinder rotates, the polymer liquid in the slit flows due to shearing action;
  • Figure 6 shows the crystallinity changes of cellulose-containing biomass particles (sawdust) after surface nanocrystallization, where A) X-ray diffraction curves of untreated, alkali-treated, surface nanocrystalline cellulose-containing biomass particles , B) The relative crystallinity histogram calculated by the X-ray diffraction curve. After the surface is nanocrystallized, the relative crystallinity increases.
  • a PANalytical X'pert PRO MRD X-ray diffractometer is used to evenly place the sample on the silicon wafer. Put them into the X-ray diffractometer together to get the data;
  • Fig. 7 is a digital photo of the paint obtained according to Application Example 1 of the present disclosure applied to the surface of wood. In the scratch test with a load of 1.45 kg, only minor scratches appeared, but no scratches were found;
  • Figure 8 is a comparison of Figure 7, according to Example 4 of the present disclosure, the same wood chip sample slurry that has not been processed by this method is applied to the same substrate. After drying, no coating is formed, and it is still in powder form. The powder comes off.
  • Figure 9 is a digital photo of the water slurry formed from the surface nanocrystallized cellulose-containing biomass material prepared in Example 1 of the present invention coated on a cement board substrate one month later, it can be seen that its apparent performance remains stable , Does not fall off, peel and wrinkle due to normal temperature and humidity changes in the surrounding environment.
  • Figure 10 is the scratch test of the water slurry formed by the surface nano-crystallized cellulose-containing biomass material prepared in Example 1 of the present invention coated on the cement board substrate, and the scratches appear only when the load reaches 1.50kg , Good scratch resistance.
  • Figure 11 is a digital photo of a comparative slurry coating applied to the cement board substrate one month later. It can be seen that the surface has a very obvious graininess, and the overall is relatively loose, unable to form a strong paint film.
  • Figure 12 is a comparison of the scratch test of the slurry coating applied on the cement board substrate. When the load is 0kg, scratches appear, indicating that its scratch resistance is poor.
  • the first aspect of the present disclosure is to provide a cellulose-containing biomass material with surface nanocrystallization, which has high specific surface, high surface activity and high crystallinity, and provides a very good method for further processing of biomass materials. raw material.
  • cellulose-containing biomass material refers to one or more of the biomass materials containing cellulose components derived from natural plants or animals, including but not limited to natural plant wood, sawdust, leaves, straw, At least one of hay, hemp, bamboo, bagasse, rice husk, and sea husk of natural animals.
  • the cellulose-containing biomass material may be in various shapes, but in view of the ease of processing reaction, a particle form is preferred, especially a particle form with a particle size of 0.1 to 500 microns.
  • the cellulose content of the cellulose-containing biomass material may be 10% to 90%, preferably 20% to 70%, preferably 30% to 50%.
  • surface nanocrystallization means that the surface of the cellulose-containing biomass material has a nanocrystallized microstructure, specifically, it means that the surface of the cellulose-containing biomass material has nano-scale cellulose, and the cellulose Some of the hydroxyl groups in the structure have been converted to carboxyl groups.
  • nano-scale cellulose refers to cellulose with a nano-scale diameter.
  • the surface of the product obtained after the surface nanocrystallization process obtained in Example 1 has fibers with a diameter between 10 and 100 nanometers.
  • the molar ratio of the carboxyl group to the hydroxyl group is at least 0.5%, more preferably in the range of at least 3%, and still more preferably at least 30%.
  • the diameter of the nanocrystallized cellulose exposed on the surface of the surface nanocrystallized cellulose-containing biomass material is at least 1 micron or less, preferably at least 500 nanometers or less, more preferably at least 100 nanometers or less, for example, between 7 and 1000 nm Within the range, in the range of 100-800nm.
  • the fiber length of the surface exposed cellulose after the surface nanocrystallization is in the range of 0.1-5 microns, for example, may be in the range of 0.5-4 microns, or 2-3 microns.
  • the nano-scale fibers are dispersed with one end embedded in the biomass material, and the other end extends from the surface of the biomass material and is well dispersed.
  • the morphology and processing performance of the cellulose-containing biomass material with the surface nanocrystallized surface of the present disclosure are significantly different from the untreated and surface-etched cellulose-containing biomass materials in many aspects.
  • B After the surface is nanocrystallized, the specific surface increases.
  • the surface nanocrystalline material is 3 times that of the untreated sample;
  • the time for the former to fully settle is less than 10 minutes, while the latter does not completely settle after 600 minutes;
  • E) Inventor It is found that due to the increase in specific surface area and surface reactivity, the surface nanocrystalline biomass material slurry is directly dried to directly obtain a film or sheet with a certain strength and bonded together, while the untreated material solution slurry and After the surface etching treatment slurry is dried, only powder can be obtained;
  • the surface of the cellulose-containing biomass material with nanocrystallized surface has exposed areas, and the cellulose in the exposed areas is nano-scale cellulose, and part of the hydroxyl groups in the nano-scale cellulose has been Converted into carboxyl groups so that the surface nanocrystallized cellulose-containing biomass material has at least one of the following properties, preferably at least 2, more preferably at least 3, more preferably at least 4, and more preferably at least 5 items, most preferably have the following properties at the same time:
  • the specific surface area of the cellulose-containing biomass material whose surface is nanocrystallized is at least 1.5 m 2 /g, preferably at least 10 m 2 /g, and more preferably at least 30 m 2 /g;
  • the diameter of the nanocrystallized cellulose exposed on the surface of the surface nanocrystallized cellulose-containing biomass material is at least 1 micrometer or less, preferably at least 500 nanometers or less, more preferably at least 100 nanometers or less.
  • the crystallinity of cellulose is at least 65%, preferably 70%, more preferably 75%;
  • the molar ratio of carboxyl groups to the total amount of carboxyl groups is at least 5%, preferably at least 10%, more preferably at least 30%;
  • the viscosity of the surface nanocrystallized cellulose-containing biomass material in an aqueous solution is measured by a rotational viscometer method at about 25°C to reach 40 mPa ⁇ s, preferably 60 mPa ⁇ s when the mass fraction of the solution is 6%, More preferably 80mPa ⁇ s;
  • the sedimentation time of the aqueous solution of the surface nanocrystallized cellulose-containing biomass material is at least greater than 200 minutes, preferably at least greater than 500 minutes, and more preferably at least greater than 800 minutes.
  • the term "exposed area” refers to the surface area formed by etching treatment on the surface of the cellulose-containing biomass material during alkali treatment. Relative to the surface before alkali treatment, the exposed area may be greater than 0 to 100%, for example, may be at least 5%, at least 10%, at least 20%, at least 50%, at least 80%, at least 90%, preferably at least 100%.
  • the second aspect of the present disclosure provides a method for preparing the surface nanocrystallization of a cellulose-containing biomass material, including the following steps:
  • the biomass material is subjected to surface etching treatment in an etching solution; the biomass material is selected from one or more of the biomass materials containing cellulose components in natural plants and animals;
  • the biomass material includes but is not limited to at least one of natural plant wood, sawdust, leaves, straw, hay, hemp, bamboo, bagasse, rice husk, and sea shell of natural animals.
  • the etching solution is a solution that can dissolve lignin and hemicellulose and a solvent that can dissolve biological macromolecules, and its function is to form a cellulose-exposed area on the surface of the cellulose-containing biomass material.
  • the etching solution is selected from one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide-sodium sulfite aqueous solution, sodium sulfite aqueous solution, sulfurous acid aqueous solution, sulfur dioxide aqueous solution, or selected from acetone and toluene , Ethanol and other solvents that can dissolve biological macromolecules.
  • the mass concentration of the etching solution is 0.1%-50%.
  • the biomass material is first etched and cleaned on the surface in an etching solution, and then the etched surface Surface oxidation treatment of material materials, after mechanical treatment, biomass materials with high specific surface, high surface activity and high crystallinity provide a very good raw material for the further processing of biomass materials.
  • the cellulose-containing biomass material is subjected to surface etching treatment in an etching solution to remove non-cellulose components and expose cellulose. Then, by oxidizing the cellulose, the hydroxyl groups on the surface of the cellulose are converted into carboxyl groups. Further through mechanical treatment, the cellulose swells and is exfoliated into nanocellulose. This process greatly increases the surface area of the biomass material, greatly improves the activity of the biomass material, and makes it easier to further process.
  • the surface oxidation treatment solution refers to an aqueous solution that can selectively oxidize the surface of cellulose nanofibers in a biomass material without destroying the internal structure of the nanofibers.
  • the surface oxidation treatment solution is selected from neutral 2,2,6,6-tetramethylpiperidine-nitrogen-oxide-sodium chlorite solution, 2,2,6,6-tetramethylpiperidine One or more of pyridine-nitrogen-oxide-sodium hypobromite solution, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide-sodium hypochlorite solution, of which 2, 2, 6, 6 -Tetramethylpiperidine-nitrogen-oxide plays a catalytic role, and the amount used is the amount of the catalyst.
  • the mass concentration of the surface oxidation treatment solution is usually 0.1 to 10%, preferably 0.15 to 8%, more preferably 1 to 5%.
  • the mechanical treatment is used to swell and exfoliate the cellulose-containing biomass material cellulose after surface oxidation into nano-cellulose, which can be selected from stirring, grinding, ball milling, and high-pressure homogenization. One or more of.
  • the mixing time ie, etching time
  • the temperature of the mixing is 10-120°C, preferably 30-120°C, more preferably 50-100°C.
  • the oxidation reaction time is 6-240h, preferably 15-150h, more preferably 20-60h.
  • the temperature of the reaction is 10 to 150°C, preferably 20 to 100°C, more preferably 40 to 90°C.
  • the raw materials for nano-crystallization of the surface of the cellulose-containing biomass material the cellulose-containing biomass material, the etching solution, and the oxidation solution.
  • the biomass material in the present disclosure is selected from one or more of the biomass materials containing cellulose components in natural plants and animals.
  • the biomass material is preferably wood chips and straw.
  • the above surface etching solution is used to etch the non-cellulose components on the surface of the cellulose-containing biomass material.
  • the surface etching solution can be a solution that is corrosive to biomass, such as sodium hydroxide, potassium hydroxide, sodium sulfite, sulfur dioxide, sulfurous acid, etc.
  • the surface etching solution includes aqueous solutions of sodium hydroxide, potassium hydroxide, sodium sulfite, sulfur dioxide, sulfurous acid, etc., and other solutions that can dissolve lignin and hemicellulose, as well as acetone, toluene, and ethanol. Solvents that can dissolve biological macromolecules.
  • the mass concentration of the etching solution is 0.1-50%.
  • the etching solution is selected from sodium hydroxide solution with a mass concentration of 10%.
  • the above-mentioned surface oxidation treatment method includes 2,2,6,6-tetramethylpiperidine-nitrogen-oxide catalyzed oxidation method of cellulose, and the surface oxidation treatment method is 2,2,6,6- Under the catalysis of tetramethylpiperidine-nitrogen-oxide, the oxidizing reagent oxidizes the surface cellulose of the particles.
  • the oxidizing reagent includes sodium chlorite, sodium hypochlorite, sodium bromite, sodium hypobromite and other water-soluble oxidants with a concentration of 0.1 ⁇ 10%, the temperature is 10 ⁇ 90°C.
  • the concentration of the 2,2,6,6-tetramethylpiperidine-nitrogen-oxide is 0.05-10 mg/mL.
  • sodium hydroxide and sodium sulfite are preferred as the surface etching solution.
  • the mechanical treatment is conventional treatment methods such as stirring, grinding, high-pressure homogenization, and high-pressure jetting.
  • the mechanical treatment is preferably grinding and high-pressure homogenization treatment.
  • the surface of the cellulose-containing biomass material is nanocrystallized, and the biomass material is subjected to surface etching treatment in an etching solution to achieve surface etching , Exposing cellulose; in this process, the etching solution dissolves part of the non-cellulose components in the cellulose-containing biomass material to expose the cellulose on the surface; the etching temperature is 10-200 °C, the etching time is 1 to 72 hours; in a specific embodiment, the etching temperature is 80 °C, and the time is 24 hours.
  • the surface of the biomass material after the etching treatment is then oxidized.
  • a mild oxidation process catalyzed by 2,2,6,6-tetramethylpiperidine-nitrogen-oxide can be selected
  • the surface of the cellulose nanofibers in the biomass material is oxidized sexually without destroying the internal structure of the nanofibers.
  • the hydroxyl groups on the surface of the cellulose nanofibers are converted into carboxyl groups, the crystallinity of the cellulose is improved, and a large amount of nanocellulose is produced on the surface of the particles.
  • the mechanical treatment is conventional treatment methods such as stirring, grinding, high-pressure homogenization, high-pressure jetting, etc., and mechanical grinding methods are preferably used.
  • the carboxylated surface absorbs water and swells water molecules into the nanofibers during further stirring or other mechanical treatments, so that the cellulose nanofibers that originally aggregated on the surface of the biomass material are dispersed into one end embedded in the biomass material, and the other end Well-dispersed nanofibers.
  • the nanofibers protruding from the surface of these biomass materials are etched, oxidized, and mechanically processed to obtain a cellulose-containing biomass material with a nanocrystallized surface.
  • the hydroxyl portion of the surface of the cellulose nanofiber is converted into The carboxyl group improves the crystallinity of the cellulose and produces a large amount of nanocellulose on the surface of the particles.
  • the biomass material processed by the method has broad application prospects.
  • the temperature of the oxidation reaction is 10 to 90° C. and the time is 12 to 240 h; in a specific embodiment, the temperature of the reaction is 60° C. and the time is 24 h.
  • the present disclosure finally disperses the obtained product in a solution to make a dispersion, or dry to obtain a dry powder; the drying method is atmospheric drying, freeze drying or supercritical CO 2 drying.
  • the surface of the biomass material is first etched and cleaned in an etching solution, and then the surface of the etched biomass material After oxidation treatment and mechanical treatment, biomass materials with high specific surface and high surface activity provide a very good raw material for the further processing of biomass materials.
  • the cellulose-containing biomass material is subjected to surface etching treatment in an etching solution to remove non-cellulose components and expose cellulose. Then, by oxidizing the cellulose, the hydroxyl groups on the surface of the cellulose are converted into carboxyl groups.
  • the surface nano-crystallized biomass material obtained by the present disclosure has many properties.
  • the hydroxyl groups on the surface of the cellulose nanofibers are partially converted into carboxyl groups, the crystallinity of cellulose is improved, and a large amount of nanocellulose is produced on the surface of the particles.
  • One end of the cellulose sticks out and the other end is inserted in the granule. Macroscopically, the specific surface of the particles increases, the slurry viscosity increases, and the slurry sedimentation speed increases. It provides a very good raw material for the further processing of biomass.
  • the surface nanocrystallized cellulose-containing biomass material obtained by the method of the present disclosure has at least one of the following properties, preferably at least two, and more preferably at least 3 items, more preferably have the following properties at the same time:
  • the specific surface of the cellulose-containing biomass material with nanocrystallized surface is increased to about at least 1.5 times, preferably at least 2 times, and more preferably at least 3 times of that before nanocrystallized treatment;
  • the viscosity of the slurry of the surface nanocrystallized cellulose-containing biomass material is increased by about at least 1.5 times, preferably at least 2 times, and more preferably at least 2.5 times of that before the uncrystallization treatment;
  • the sedimentation rate of the slurry of the surface nanocrystallized cellulose-containing biomass material is small, and the sedimentation time is at least greater than 200 minutes, preferably at least greater than 600 minutes, and more preferably at least greater than 700 minutes;
  • the crystallinity of cellulose is increased by at least 10%, preferably 20%, and more preferably 35% compared to before the nanocrystallization treatment.
  • the measurement of the specific surface area is measured by the following process: the measurement is performed using the BET adsorption test method.
  • the measurement of the viscosity is obtained by a rotational viscometer method at about 25°C.
  • the rotary viscometer probe connected to the No. 1 rotor is immersed in a solution with a certain mass fraction, set to 60 revolutions per minute, turn on the rotating motor, and rotate stably for 20 seconds before reading.
  • the settling time is measured as follows: the slurry with a mass fraction of 0.1% is thoroughly stirred with a magnetic stirrer, and immediately poured into a 100 mL graduated cylinder, left to stand and start timing. When the solid matter in the slurry completely settles at the bottom of the measuring cylinder and the upper layer is a clear and transparent liquid, record the time as the settling time.
  • the degree of crystallinity is calculated from the data in the powder X-ray diffraction pattern (XRD).
  • the molar ratio of the carboxyl groups to the total amount of carboxyl groups is measured by the following process: adding dry sample powder to a nuclear magnetic tube, performing a solid nuclear magnetic resonance carbon spectrum test, and calculating it by using the measured carbon spectrum data.
  • the cellulose diameter is obtained through scanning electron microscope observation. For details, see Example 1 below.
  • the surface nano-crystallized cellulose-containing biomass material provided by the present invention is expected to have potential industrial applications in terms of fire prevention, heat insulation, heat preservation, energy saving, anti-corrosion, noise prevention, anti-ultraviolet, antibacterial, abrasion resistance, corrosion resistance, etc. Application prospects.
  • the surface nanocrystallized cellulose-containing biomass material of the present disclosure has a wide range of application prospects, examples of which may include but are not limited to: a) processing raw materials of wood-based panels and wood plastics; b) as a base for preparing composite functional nanomaterials Functionalized and intelligent panels; c) Used as water-based paints, including water-based interior wall paints, water-based protective coatings, etc.; d) Used as a substrate, composite functional nano-coatings, to prepare multifunctional or intelligent coatings, including conductive coatings, antibacterial and anticorrosive coatings , Photocatalyst coatings, sensor coatings, heat insulation and fireproof coatings, etc.; e) Used to prepare biomass sponges; f) As a base, composite functional nano coatings to prepare multifunctional biomass sponges, including heat insulation fireproof sponges, sound insulation sponges, and conductive Sponge, etc.; g) Preparation of high-performance carbon materials after high-temperature carbon decomposition.
  • the applicant found that the surface nanocrystallized cellulose-containing biomass material provided by the present disclosure is directly uniformly dispersed in water to form an aqueous coating (ie, a uniformly dispersed water slurry), because It does not contain any organic solvents and has the environmental protection characteristics, and the special surface structure existing on the surface of the cellulose-containing biomass material with nano-crystallized surface, and has good applications in interior decoration materials.
  • an aqueous coating ie, a uniformly dispersed water slurry
  • the present disclosure provides a cellulose-containing biomass material with surface nanocrystallization and a preparation method thereof.
  • the cellulose-containing biomass material For example, the surface of the particles
  • the cellulose exposed on the surface is oxidized.
  • a biomass material with high specific surface, high surface activity and crystallinity is obtained, which is the further processing of biomass materials. Provides a very good raw material.
  • A) 500g of pine sawdust with a particle size of 200 mesh was soaked in 5L of 10% sodium hydroxide solution at 80°C for 24h; B) The treated sawdust was washed with lye on the surface and soaked in 2, 2 containing 0.1mg/mL , 6,6-tetramethylpiperidine-nitrogen-oxide (chemical formula is C 9 H 18 NO, English name 2,2,6,6-tetramethylpiperidine-1-oxyl) and 1% sodium chlorite pH Oxidize in 6.8 oxidation solution at 60°C for 24h;
  • FIG. 3 shows that the carboxyl peak appears after the above treatment.
  • 3.4% of the hydroxyl groups were converted into carboxyl groups during the treatment.
  • the specific calculation method is: the carboxyl content is equal to one-third of the ratio of the integrated area of the peak of 175 ppm in the carbon NMR spectrum and the integrated area of the double peak between 60-70 ppm; in this example, the carbon NMR spectrum of the sample is displayed at 174 ppm.
  • the peak area is 7424
  • the 60-70 ppm integrated area is 72244, and the calculated molar ratio of carboxyl groups is 3.4%.
  • the specific surface of the obtained product increases, as shown in Figure 4.
  • the specific surface area of the wood pellets after surface crystallization is increased by 2.7 times.
  • the viscosity of the obtained product increases, as shown in Figure 5.
  • the surface crystallization of wood chips particles in an aqueous solution with a mass fraction of 6% increases the viscosity by 2.5 times, and the viscosity is measured by a rotational viscometer method at about 25°C.
  • the aqueous solution of the cellulose-containing biomass material with nano-crystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, so the settling time is more than one month.
  • the crystallinity of the obtained product increases, as shown in Figure 6.
  • the obtained dry powder can be uniformly dispersed in the water phase without sedimentation, and the birch chips without surface nano-crystallization processing will directly sediment.
  • a large number of nano-cellulose structures are produced on the surface of the product after nano-crystallization treatment, and the fiber diameter is between 10-100 nanometers and the length is between 0.5-5 micrometers.
  • the birch chips that are not processed by the method of the invention have a smooth surface and no nano-cellulose structure.
  • the specific surface of the product obtained increases.
  • the specific surface area of the birch wood particles after surface crystallization is increased by 2.4 times, specifically 43.2 m 2 /g.
  • the viscosity of the obtained product increases.
  • the viscosity increases by 2.1 times, specifically, 42 mPa ⁇ s measured at about 25° C.
  • the viscosity is measured by a rotational viscometer. Method is measured at about 25°C.
  • the crystallinity of the obtained product increased to 67%.
  • the aqueous solution of the cellulose-containing biomass material with nanocrystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, and the settling time is more than one month.
  • the obtained dry powder can be uniformly dispersed in the water phase without sedimentation, while the rape straw powder without surface nano-crystallization processing will directly sediment.
  • a large number of nano-cellulose structures are produced on the surface of the product after nano-crystallization treatment, and the fiber diameter is between 10-100 nanometers and the length is between 0.5-5 micrometers.
  • the rape straw powder that is not processed by the method of the invention has a smooth surface and no nano-cellulose structure.
  • the specific surface of the product obtained increases.
  • the surface crystallization of rape straw powder has a specific surface area increased by 2.5 times, specifically 42.5 m 2 /g.
  • the viscosity of the obtained product increases.
  • the viscosity increases by 2.5 times. Specifically, it is 52.5 mPa ⁇ s measured at about 25° C.
  • the viscosity is determined by the rotational viscosity. The meter is measured at about 25°C.
  • the crystallinity of the obtained product increased to 73.6%.
  • the aqueous solution of the cellulose-containing biomass material with nano-crystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, so the settling time is more than one month.
  • the obtained product can be uniformly dispersed in the water phase without sedimentation, while the rice straw powder without surface nano-crystallization treatment will directly sediment.
  • a large number of nano-cellulose structures are produced on the surface of the product after nano-crystallization treatment, and the fiber diameter is between 10-100 nanometers and the length is between 0.5-5 micrometers.
  • the rice straw powder not processed by the method of the invention has a smooth surface and no nano-cellulose structure.
  • the specific surface of the product obtained increases.
  • the specific surface area of the rice straw powder after surface crystallization is increased by 2.3 times, specifically 48.3 m 2 /g.
  • the viscosity of the obtained product increases.
  • the viscosity increases by 2.2 times. Specifically, it is 41.8 mPa ⁇ s measured at about 25° C.
  • the viscosity is determined by the rotational viscosity. The meter is measured at about 25°C.
  • the aqueous solution of the cellulose-containing biomass material with nano-crystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, so the settling time is more than one month.
  • the platanus leaves are pulverized into powder by a milling machine, and after passing through a 200-mesh sieve, 500g is taken in 5L of 10% sodium hydroxide solution and soaked at 80°C for 24h;
  • the obtained product can be uniformly dispersed in the water phase without sedimentation, while the platanus leaf powder without surface nano-crystallization treatment will directly sediment.
  • the fiber diameter is between 10-100 nanometers and the length is between 0.5-5 microns.
  • the platanus leaf powder that is not processed by the method of the invention has a smooth surface and no nano-cellulose structure.
  • the specific surface of the product obtained increases.
  • the specific surface area of the platanus leaf powder after surface crystallization is increased by 2.6 times, specifically 41.6 m 2 /g.
  • the viscosity of the obtained product increases.
  • the surface crystallization of the platanus leaf powder if dispersed in a 6% by mass aqueous solution, will increase the viscosity by 2.4 times. Specifically, it is 55.2 mPa ⁇ s measured at about 25° C. The viscosity is measured by rotating The viscometer method is measured at about 25°C.
  • the aqueous solution of the cellulose-containing biomass material with nano-crystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, so the settling time is more than one month.
  • maple leaves are ground into a powder through a milling machine, and after passing through a 200-mesh sieve, take 500g and soak in 5L of 10% sodium hydroxide solution at 80°C for 24h;
  • the obtained product can be uniformly dispersed in the water phase without sedimentation, while the maple tree leaf powder without surface nano-crystallization treatment will directly sediment.
  • a large number of nano-cellulose structures are produced on the surface of the product after nano-crystallization treatment, and the fiber diameter is between 10-100 nanometers and the length is between 0.5-5 micrometers.
  • the maple leaf powder that is not processed by the method of the invention has a smooth surface and no nano-cellulose structure.
  • the specific surface of the product obtained increases.
  • the specific surface area of the maple leaf powder after surface crystallization is increased by 2.8 times, specifically 44.8 m 2 /g.
  • the viscosity of the obtained product increases.
  • the maple tree leaf powder that has undergone surface crystallization is dispersed in an aqueous solution with a mass fraction of 6%, the viscosity increases by 2.7 times. Specifically, it is 56.7 mPa ⁇ s measured at about 25°C.
  • the viscometer method is measured at about 25°C.
  • the crystallinity of the obtained product increased to 71.2%.
  • the aqueous solution of the cellulose-containing biomass material with nano-crystallized surface maintains a uniformly dispersed state for a long time. After being placed for one month, there is no agglomeration precipitation or flocculation, so the settling time is more than one month.
  • Example 1 Disperse the surface nanocrystalline biomass particles obtained in Example 1 in water to obtain a slurry with a concentration of 20%, which is an aqueous coating;
  • the surface nanocrystalline cellulose-containing biomass material prepared in Example 1 was directly dispersed in water to obtain a slurry with a solid content of 60% by mass, and the slurry was applied to building interior decoration materials. .
  • the slurry was painted on a 10*10 cm cement board substrate, placed vertically, and dried naturally in an indoor environment with a humidity of 53% and a temperature of 25°C.
  • Figure 9 is a digital photo of the water slurry formed from the surface nanocrystallized cellulose-containing biomass material prepared in Example 1 of the present invention coated on a cement board substrate one month later, it can be seen that its apparent performance remains stable , Does not fall off, peel and wrinkle due to normal temperature and humidity changes in the surrounding environment.
  • Figure 10 is a scratch test of a cement board substrate coated with an aqueous slurry formed from a surface nanocrystalline cellulose-containing biomass material prepared in Example 1 of the present invention, which only appears when the load reaches 1.50kg Good scratch and scratch resistance.
  • the cellulose-containing biomass material that has not undergone surface nanocrystallization is directly dispersed in water to obtain a slurry with a solid content of 60% by mass, which is called a comparative slurry.
  • the comparative slurry was applied to the interior decoration materials of the building, and it was painted on a 10*10cm cement board substrate. If it is placed vertically, the paint will slide down. Therefore, place it horizontally and place it in the humidity. 53%, the temperature is naturally dried in an indoor environment of 25°C.
  • Figure 11 is a digital photo of a comparative slurry coating applied to the cement board substrate one month later. It can be seen that the surface has a very obvious graininess, and the overall is relatively loose, unable to form a strong paint film.
  • Figure 12 is a comparison of the scratch test of the slurry coating applied on the cement board substrate. When the load is 0kg, scratches appear, indicating that its scratch resistance is poor.

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Abstract

本公开提供一种表面纳米晶化的含纤维素生物质材料及其制备方法和应用，所述含纤维素生物质材料来源于天然植物或动物中含有纤维素成分的生物质材料中的一种或多种，所述表面纳米晶化的含纤维素生物质材料的表面存在纳米尺度的纤维素，并且所述纤维素结构中的部分羟基已经转化为羧基，以使得所述表面纳米晶化的含纤维素生物质材料具有高比表面、高表面活性和高结晶度，为生物质材料的进一步加工，提供了一种非常好的原料。

Description

表面纳米晶化的含纤维素生物质材料及其制备方法和用途 技术领域
本公开涉及纳米技术领域，具体地涉及一种表面纳米晶化的含纤维素生物质材料及其制备的方法和用途。
背景技术
微纳结构调控已成为材料研究、开发领域的重要手段。通过微纳结构调控，改善了一系列传统材料的性能。例如，通过对陶瓷材料进行仿生片层结构调控，改善了其韧性；通过对金属材料的纳米孪晶结构进行调控，实现了抗疲劳等性能的巨大提升。
生物质作为地球上最丰富的可再生资源，有着广泛的应用。我国是农业大国，每年产生共计一万亿千克的生物质，其中由有七千亿千克的农业秸秆和3千亿千克的林木废材组成，这些废弃物的处理方法不是被废弃就是燃烧，前者造成环境污染，浪费大量土地堆积无用，而后者则更严重，如此庞大的数量经过燃烧后对于地球的气候造成了巨大的影响。生物质加工技术中，最主要的加工方式从生物质材料开始做进一步加工。然而，目前存在的一个问题是，直接粉碎得到的生物质材料存在反应活性差、比表面积小等问题，限制了生物质材料的加工和应用。
因此，发展简单高效的方法，实现对生物质材料表面反应活性及表面积提高，对生物质材料的加工具有重要意义。
发明内容
本公开的目的在于提供一种具有高比表面、高表面活性、高结晶度的含纤维素生物质材料，为生物质材料的进一步加工提供了一种非常好的原料。同时，本公开的另一目的在于提高一种含纤维素生物质材料表面纳米晶化的方法。
为此，本公开提供如下的技术方案。
<1>.一种表面纳米晶化的含纤维素生物质材料，所述含纤维素生物质材料来源于天然植物或动物中含有纤维素成分的生物质材料中的一种或多种，所述表面纳米晶化的含纤维素生物质材料的表面存在暴露区域，并且在所述暴露区域中的纤维素为纳 米尺度的纤维素，并且所述纳米尺度的纤维素中的部分羟基已经转化为羧基，以使得所述表面纳米晶化的含纤维素生物质材料具有以下各项性能中的至少一项：
i)所述表面纳米晶化的含纤维素生物质材料的比表面积至少为1.5m 2/g，优选至少为10m 2/g，更优选至少30m 2/g；
ii)所述表面纳米晶化的含纤维素生物质材料的表面暴露的纳米晶化后的纤维素直径至少为1微米以下，优选至少500纳米以下，更优选至少100纳米以下。
iii).所述表面纳米晶化的含纤维素生物质材料中，纤维素的结晶度至少为65％，优选70％，更优选75％；
iv).所述表面纳米晶化的含纤维素生物质材料中，羧基占羟基与羧基总量的摩尔比至少为5％，优选地至少10％，更优选至少30％；
v)所述表面纳米晶化的含纤维素生物质材料在水中的粘度在溶液质量分数为6％情况下通过旋转粘度计法在约25℃测量为大于40mPa·s，优选60mPa·s，更优选80mPa·s；
vi)所述表面纳米晶化的含纤维素生物质材料的水溶液的沉降时间至少大于200分钟，优选至少大于500分钟，更优选至少大于800分钟。
<2>.根据<1>所述的表面纳米晶化的含纤维素生物质材料，其中所述表面纳米晶化后的表面暴露的纤维素的纤维长度在0.1-5微米的范围内。
<3>.根据<1>所述的表面纳米晶化的含纤维素生物质材料，其中所述含纤维素生物质材料的纤维素含量为10～90％，优选为20～70％，优选为30～50％。
<4>.根据<1>所述的表面纳米晶化的含纤维素生物质材料，其中所述天然植物或动物是选自天然植物的木材、锯末、树叶、秸秆、干草、麻、竹子、甘蔗渣、稻壳以及天然动物的海壳中的至少一种。
<5>.根据<1>所述的表面纳米晶化的含纤维素生物质材料，其中所述含纤维素生物质材料为颗粒形式。
<6>.一种表面纳米晶化的含纤维素生物质材料的制备方法，包括以下步骤：
A)将含纤维素生物质材料在刻蚀溶液中做表面刻蚀处理，所述含纤维素生物质材料选自天然植物、动物中含有纤维素成分的生物质材料中的一种或多种；
B)将刻蚀处理后的含纤维素生物质材料表面氧化处理；
C)将表面氧化后的含纤维素生物质材料机械处理；
D)将机械处理后的含纤维素生物质材料制成分散液或干粉保存。
<7>、根据<6>所述的制备方法，其中，所述表面刻蚀溶液包括选自以下各项中的至少一种：氢氧化钠水溶液，氢氧化钾水溶液，亚硫酸钠水溶液，二氧化硫水溶液、亚硫酸水溶液、以及能溶解生物大分子的溶剂。
<8>、根据<6>所述的制备方法，其中步骤A)中所述的含纤维素生物质材料为颗粒形式，并且粒度为0.1微米到5毫米。
<9>、根据<6>所述的制备方法，其中，所述表面氧化处理方法包括在2，2，6，6-四甲基哌啶-氮-氧化物催化作用下对所述含纤维素生物质材料的表面暴露纤维素的氧化。
<10>、根据<6>所述的制备方法，其中步骤A)所述刻蚀溶液的质量浓度为0.1～50％。
<11>、根据<6>所述的制备方法，其中步骤B)所述的表面氧化处理方法为在2，2，6，6-四甲基哌啶-氮-氧化物的催化下，氧化试剂氧化所述含纤维素生物质材料的表面纤维素，所述氧化试剂包括选自亚氯酸钠、次氯酸钠、亚溴酸钠和次溴酸钠中的至少一种的水溶性氧化剂。
<12>、根据<6>所述的制备方法，其中所述机械处理为搅拌、研磨、高压匀浆或高压喷射处理中的一种或几种。
<13>、根据<6>所述的制备方法，其中在步骤A)中，所述刻蚀温度为10-200℃，时间为1～72h。
<14>、根据<6>所述的制备方法，其中在步骤B)中，所述氧化处理反应的时间为6～240h，所述氧化处理反应的温度为10～150℃。
<15>、制备根据<1>-<5>中任一项所述的表面纳米晶化的含纤维素生物质材料和根据权利要求<6>-<14>中任一项所述的制备方法获得的表面纳米晶化的含纤维素生物质材料在制备薄膜、板材、水性涂料、复合功能纳米材料、生物质海绵、高性能碳材料或气凝胶材料中的用途。
<16>、根据权利要求<15>所述的用途，其中将所述表面纳米晶化的含纤维素生物质材料的浆料直接干燥后，直接得到具有一定强度的、粘结在一起的薄膜或者板材。
<17>、根据权利要求<15>所述的用途，其中将所述表面纳米晶化的含纤维素生物质材料的浆料冷冻干燥后，得到有一定强度和弹性的气凝胶材料。
<14>.根据权利要求<15>所述的用途，其中所述用途包括在室内装饰材料中的用途。
附图说明
图1为本公开实施例1制备的表面纳米晶化生物质材料分散液的数码照片；
图2是未经本公开处理的木屑颗粒表面(图2A)与经过本方法表面纳米晶化处理后(图2B)的含纤维素生物质颗粒(木屑颗粒)的扫描电子显微镜照片对比。可以看到，图2A中，未经处理的木屑表面相对光滑，没有大量的纤维结构；经过本方法处理的木屑颗粒表面具有大量的纳米尺度纤维，一端伸出，另一端插在颗粒中；
图3示出了未处理、碱处理以及表面纳米晶化后，生物质颗粒的核磁共振碳谱(布鲁克Avance III 400WB)表征，并且表明了表面纳米晶化后，含纤维素生物质颗粒出现明显的羧基峰，证明氧化过程中，羧基的产生；
图4示出了未处理、碱处理、表面纳米晶化后，含纤维素生物质颗粒(木屑)的比表面变化，并且表明了表面纳米晶化后，比表面积增加，通过美国康塔仪器公司iQ 2，采用多点BET法进行测试计算；
图5示出了表面纳米晶化后，含纤维素生物质颗粒(木屑)的粘度变化，该图显示相对未处理、以及碱处理技术，表面纳米晶化后的含纤维素生物质材料粘度明显提高；使用的是上海星量光学仪器有限公司旋转粘度计NDJ-1，当圆筒旋转时，狭缝中的聚合物液体因受到剪切作用而发生流动；
图6示出了表面纳米晶化后，含纤维素生物质颗粒(木屑)的结晶度变化，其中A)未处理、碱处理，表面纳米晶化的含纤维素生物质颗粒的X射线衍射曲线，B)通过X衍射曲线计算出的相对结晶度柱状图，表面纳米晶化后，相对结晶度增加，使用了PANalytical X’pert PRO MRD X射线衍射仪，将样品均匀放在硅片上，并一起放进X射线衍射仪中得到数据；
图7是根据本公开的应用实施例1获得的涂料涂刷于木材表面的数码照片。载荷为1.45公斤的划痕测试中，只出现轻微划痕，没有划穿；
图8是作为图7的对比，其根据本公开实施实例4，未经本方法处理的同种木屑样品浆料，涂至相同基底，干燥后未形成涂层，依然为粉末状，倾斜后，粉末脱落。
图9为本发明实施例1制备的表面纳米晶化的含纤维素生物质材料所形成的水浆料涂覆在水泥板基底上一个月后的数码照片，可以看出其表观性能保持稳定，并不因周围环境的正常温度湿度变化而脱落、起皮和褶皱。
图10为本发明实施例1制备的表面纳米晶化的含纤维素生物质材料所形成的水 浆料涂覆在水泥板基底上的划痕测试，其在载荷达到1.50kg时才出现划痕，耐刮擦性能良好。
图11为比较浆料涂料涂覆在水泥板基底上一个月后的数码照片，可以看出其表观既有很明显的颗粒感，整体较为松散，无法形成一个强韧的涂料漆膜。
图12为比较浆料涂料涂覆在水泥板基底上的划痕测试，在载荷为0kg时出现划痕，表明其耐刮擦性能较差。
具体实施方式
本公开的第一方面是提供一种表面纳米晶化的含纤维素生物质材料，其具有高比表面、高表面活性和高结晶性，为生物质材料的进一步加工提供了一种非常好的原料。
术语“含纤维素生物质材料”是指来源于天然植物或动物中含有纤维素成分的生物质材料中的一种或多种，其包括但不限于天然植物的木材、锯末、树叶、秸秆、干草、麻、竹子、甘蔗渣、稻壳以及天然动物的海壳中的至少一种。所述含纤维素生物质材料可以处于各种形状，但是从处理反应的容易性考虑，优选颗粒形式，尤其是粒径为0.1～500微米的颗粒形式。所述含纤维素生物质材料的纤维素含量可以为10～90％，优选为20～70％，优选为30～50％。
术语“表面纳米晶化”是指含纤维素生物质材料的表面具有纳米晶化的微观结构，具体地，是指含纤维素生物质材料的表面存在纳米尺度的纤维素，并且所述纤维素结构中的部分羟基已经转化为羧基。术语“纳米尺度的纤维素”是指直径为纳米尺度的纤维素，例如实施例1中获得的表面纳米晶化处理后获得的产物表面具有直径在10～100纳米之间的纤维。优选地，所述羧基相对于所述羟基的摩尔比为至少0.5％，更优选为至少3％范围，还更优选为至少30％。所述表面纳米晶化的含纤维素生物质材料的表面暴露的纳米晶化后的纤维素直径至少为1微米以下，优选至少500纳米以下，更优选至少100纳米以下，例如，在7-1000nm范围内，在100-800nm范围内。所述表面纳米晶化后的表面暴露的纤维素的纤维长度在0.1-5微米的范围内，例如，可以在0.5-4微米、或2-3微米的范围内。在本公开的表面纳米晶化的含纤维素生物质材料中，所述纳米尺度的纤维分散为一端嵌入在生物质材料内部，另一端从生物质材料表面伸出且分散良好。
本公开的表面纳米晶化的含纤维素生物质材料的相貌和加工性能相对于未处理的、以及表面刻蚀处理的含纤维素生物质材料存在多方面明显的差别。例如，A)微 观形貌上，原始生物质材料表面较光滑，表面刻蚀处理后的颗粒表面暴露出微米尺度纤维素，而表面纳米晶化后的材料表面产生大量的纳米尺度纤维素；B)表面纳米晶化后，比表面增加。例如，表面纳米晶化材料比表面为未处理样品的3倍；C)表面纳米晶化材料，由于表面存在的大量纳米尺度纤维素形成长程的氢键作用，以及相互交缠，粘度明显增加。例如，相对于未处理材料溶液浆料以及表面刻蚀处理浆料，相同浓度的表面纳米晶化生物质材料浆料的粘度增加为2.5倍；D)相对于未处理材料溶液浆料以及表面刻蚀处理浆料，相同浓度的表面纳米晶化生物质材料浆料的沉降速率大大降低，例如，前者充分沉降的时间小于10分钟，而后者在600分钟后，依然没有完全沉降；E)发明人发现，由于比表面积增大及表面反应活性增加，表面纳米晶化生物质材料浆料直接干燥后，直接得到具有一定强度的、粘结在一起的薄膜或者板材，而未处理材料溶液浆料以及表面刻蚀处理浆料干燥后，只能得到粉末；F)发明人还发现，由于比表面积增大及表面反应活性增加，表面纳米晶化生物质材料浆冷冻干燥后，得到有一定强度和弹性的气凝胶材料，而未处理材料溶液浆料以及表面刻蚀处理浆料通过冷冻干燥后，只能得到粉末。
因此，所述表面纳米晶化的含纤维素生物质材料的表面存在暴露区域，并且在所述暴露区域中的纤维素为纳米尺度的纤维素，并且所述纳米尺度纤维素中的部分羟基已经转化为羧基，以使得所述表面纳米晶化的含纤维素生物质材料具有以下各项性能中的至少一项，优选至少2项，更优选至少3项，更优选至少4项，更优选至少5项，最优选同时具备以下的各项性能：
i)所述表面纳米晶化的含纤维素生物质材料的比表面积至少为1.5m 2/g，优选至少为10m 2/g，更优选至少30m 2/g；
ii)所述表面纳米晶化的含纤维素生物质材料的表面暴露的纳米晶化后的纤维素直径至少为1微米以下，优选至少500纳米以下，更优选至少100纳米以下。
iii).所述表面纳米晶化的含纤维素生物质材料中，纤维素的结晶度至少为65％，优选70％，更优选75％；
iv).所述表面纳米晶化的含纤维素生物质材料中，羧基占羟基与羧基总量的摩尔比至少为5％，优选地至少10％，更优选至少30％；
v)所述表面纳米晶化的含纤维素生物质材料在水溶液中的粘度在溶液质量分数为6％情况下通过旋转粘度计法在约25℃测量为达到40mPa·s，优选60mPa·s，更优选80mPa·s；
vi)所述表面纳米晶化的含纤维素生物质材料的水溶液沉降时间至少大于200分钟，优选至少大于500分钟，更优选至少大于800分钟。
在本公开中，术语“暴露区域”是指含纤维素生物质材料表面在碱处理时被刻蚀处理形成的表面区域。相对于碱处理之前的表面，所述暴露区域可以为大于0至100％，例如，可以为至少5％，至少10％，至少20％，至少50％，至少80％，至少90％，优选至少100％。
本公开的第二方面提供了一种含纤维素生物质材料表面纳米晶化的制备方法，包括以下步骤：
A)将生物质材料在刻蚀溶液中做表面刻蚀处理；所述生物质材料选自天然植物、动物中含有纤维素成分的生物质材料中的一种或多种；
B)将刻蚀处理后的生物质材料表面氧化处理；
C)将表面氧化后生物质材料机械处理。
D)将所述机械处理后生物质材料制成分散液或干粉保存。
优选地，所述生物质材料包括但不限于天然植物的木材、锯末、树叶、秸秆、干草、麻、竹子、甘蔗渣、稻壳以及天然动物的海壳中的至少一种。
在本公开中，所述刻蚀溶液为能溶解木质素及半纤维素的溶液以及能溶解生物大分子的溶剂，其作用在于在含纤维素生物质材料表面形成暴露出纤维素的区域。优选地，所述刻蚀溶液选自氢氧化钠水溶液，氢氧化钾水溶液，氢氧化钠-亚硫酸钠水溶液，亚硫酸钠水溶液，亚硫酸水溶液，二氧化硫水溶液中的一种或多种，或者选自丙酮，甲苯，乙醇等能溶解生物大分子的溶剂。优选地，所述刻蚀溶液的质量浓度为0.1％～50％。
在本公开所提供的这种含纤维素生物质材料表面纳米晶化的方法中，其首先将生物质材料在刻蚀溶液中做表面刻蚀处理并洗净，然后将刻蚀处理后的生物质材料表面氧化处理，机械处理后，具有高比表面、高表面活性和高结晶性的生物质材料，为生物质材料的进一步加工，提供了一种非常好的原料。本公开通过将含纤维素生物质材料在刻蚀溶液中做表面刻蚀处理，去除非纤维素成分，暴露出纤维素。然后通过对纤维素进行氧化处理，使纤维素表面的羟基转化为羧基。进一步通过机械处理，纤维素发生溶胀并被剥离成纳米纤维素。该过程极大地增加了生物质材料的表面积，极大地提升了生物质材料的活性，使其更容易进一步加工。
因此，在本公开中，所述表面氧化处理溶液是指可以选择性地氧化生物质材料中 纤维素纳米纤维的表面，而不会破坏纳米纤维的内部结构的水溶液。优选地，所述表面氧化处理溶液选自中性2，2，6，6-四甲基哌啶-氮-氧化物-亚氯酸钠溶液，2，2，6，6-四甲基哌啶-氮-氧化物-次溴酸钠溶液，2，2，6，6-四甲基哌啶-氮-氧化物-次氯酸钠溶液中的一种或多种，其中2，2，6，6-四甲基哌啶-氮-氧化物起到催化作用，用量为催化剂用量。所述表面氧化处理溶液的质量浓度通常为0.1～10％，优选0.15～8％，更优选1～5％。
在本公开中，所述机械处理是起到使表面氧化后的含纤维素生物质材料纤维素发生溶胀并被剥离成纳米纤维素的作用，可以选自搅拌，研磨，球磨，高压均浆中的一种或多种。
优选地，步骤A)中，所述混合的时间(即，刻蚀时间)为1～120小时(h)，优选3-80h，更优选20-40h。所述混合的温度(即，刻蚀温度)为10-120℃，优选30-120℃，更优选50～100℃。
优选地，步骤B)中，所述氧化反应的时间为6～240h，优选15-150h，更优选20-60h。所述反应的温度为10～150℃，优选20～100℃，更优选40～90℃。
按照本公开，首先含纤维素生物质材料表面纳米晶化的原料：含纤维素生物质材料，刻蚀溶液，氧化溶液。本公开中所述生物质材料选自天然植物、动物中含有纤维素成分的生物质材料中的一种或多种。在一个具体实施实例中，所述生物质材料优选为木屑和秸秆。
上述表面刻蚀溶液用于刻蚀含纤维素生物质材料表面的非纤维素成分。表面刻蚀溶液可选择对生物质具有腐蚀反应性的溶液，例如氢氧化钠，氢氧化钾，亚硫酸钠，二氧化硫，亚硫酸等。在一个具体实施实例中，所述表面刻蚀溶液包括氢氧化钠，氢氧化钾，亚硫酸钠，二氧化硫，亚硫酸等的水溶液以及其他能溶解木质素及半纤维素的溶液，以及丙酮，甲苯，乙醇等能溶解生物大分子的溶剂。所述刻蚀溶液质量浓度为0.1～50％。在一个具体实施方式中，所述刻蚀溶液选自质量浓度10％的氢氧化钠溶液。
上述表面氧化处理方法包括2，2，6，6-四甲基哌啶-氮-氧化物催化的对纤维素的氧化方法中，所述表面氧化处理方法为在2，2，6，6-四甲基哌啶-氮-氧化物的催化下，氧化试剂氧化颗粒表面纤维素，所述氧化试剂包括亚氯酸钠，次氯酸钠，亚溴酸钠，次溴酸钠等水溶性氧化剂，浓度为0.1～10％，温度为10～90℃。在一个具体实施方式中，，所述2，2，6，6-四甲基哌啶-氮-氧化物浓度为0.05-10mg/mL。在一个具体实施实例中，优选氢氧化钠，亚硫酸钠作为表面刻蚀溶液。
在一个具体实施实例中，所述机械处理为搅拌、研磨、高压匀浆、高压喷射等常规处理手段。在一个具体实施方式中，所述机械处理优选为研磨和高压匀浆处理。
根据本公开，在准备好作为原料的含纤维素生物质材料之后，则进行含纤维素生物质材料表面纳米晶化，将生物质材料在刻蚀溶液中做表面刻蚀处理，实现表面刻蚀，暴露出纤维素；在此过程中，所述刻蚀溶液将含纤维素生物质材料中的部分非纤维素成分溶解，使表面的纤维素暴露出来；所述刻蚀的温度为10-200℃，所述刻蚀的时间为1～72h；在一个具体实施方式中，所述刻蚀的温度为80℃，时间为24h。
按照上述发明，然后将上述刻蚀处理后的生物质材料表面氧化处理，在此过程中，2，2，6，6-四甲基哌啶-氮-氧化物催化的温和的氧化过程可以选择性地氧化生物质材料中纤维素纳米纤维的表面，而不会破坏纳米纤维的内部结构。氧化完成后，纤维素纳米纤维表面的羟基部分转化为羧基，纤维素的结晶度提高，颗粒表面产生大量的纳米纤维素，所述表面产生的纳米纤维素一端伸出，另一端插在颗粒中。所述机械处理为搅拌、研磨、高压匀浆、高压喷射等常规处理手段，优选采用机械研磨方法处理。
羧基化的表面在进一步的搅拌或其他机械处理过程中吸水溶胀水分子进去纳米纤维间，使生物质材料表面的原本聚集成束的纤维素纳米纤维分散为一端嵌入在生物质材料内部，另一端分散良好的纳米纤维。这些生物质材料表面伸出的纳米纤维，经过上述刻蚀，氧化，机械处理后，得到表面纳米晶化的含纤维素生物质材料，所述材料中，纤维素纳米纤维表面的羟基部分转化为羧基，纤维素的结晶度提高，颗粒表面产生大量的纳米纤维素，所述表面产生的纳米纤维素一端伸出，另一端插在颗粒中。宏观上，所述颗粒比表面增加，浆料粘度增加，浆料沉降速度下降。使经过该方法处理的生物质材料具有广泛的应用前景。所述氧化反应的温度为10～90℃，时间为12～240h；在一个具体实施方式中，所述反应的温度为60℃，时间为24h。
本公开最后将得到的产品分散于溶液制成分散液，或干燥得到干粉；所述干燥的方式为常压烘干、冷冻干燥或超临界CO 2干燥。
综上，本公开提供的含纤维素生物质材料表面纳米晶化方法中，首先将生物质材料在刻蚀溶液中做表面刻蚀处理并洗净，然后将刻蚀处理后的生物质材料表面氧化处理，机械处理后，具有高比表面、高表面活性的生物质材料，为生物质材料的进一步加工，提供了一种非常好的原料。本公开通过将含纤维素生物质材料在刻蚀溶液中做表面刻蚀处理，去除非纤维素成分，暴露出纤维素。然后通过对纤维素进行氧化处理，使纤维素表面的羟基转化为羧基。进一步通过机械处理，纤维素发生溶胀并被剥离成 纳米纤维素，得到高比表面积，高反应活性的表面纳米晶化生物质材料。本公开所得到的表面纳米晶化生物质材料具有很多性能，纤维素纳米纤维表面的羟基部分转化为羧基，纤维素的结晶度提高，颗粒表面产生大量的纳米纤维素，所述表面产生的纳米纤维素一端伸出，另一端插在颗粒中。宏观上，所述颗粒比表面增加，浆料粘度增加，浆料沉降速度增加。为生物质的进一步加工提供了非常好的原料。
相对于处理之前的原料纤含纤维素生物质材料，本公开的方法所获得所述表面纳米晶化的含纤维素生物质材料具有以下性能中的至少一项，优选至少2项，更优选至少3项，更优选同时具备以下性能：
i)所述表面纳米晶化的含纤维素生物质材料的比表面增加至未纳米晶化处理之前的约至少1.5倍，优选至少2倍，更优选至少3倍；
ii)所述表面纳米晶化的含纤维素生物质材料的浆料粘度增加为未晶化处理之前的约至少1.5倍，优选至少2倍，更优选至少2.5倍；
iii)所述表面纳米晶化的含纤维素生物质材料的浆料的沉降速率小，沉降时间至少大于200分钟，优选至少大于600分钟，更优选至少大于700分钟；以及
iv).所述表面纳米晶化的含纤维素生物质材料中，纤维素的结晶度相对于未纳米晶化处理之前增加至少10％，优选20％，更优选35％。
在本公开中，所述比表面的测量通过如下过程测量：利用BET吸附测试法进行测定。
在本公开中，所述粘度的测量是通过旋转粘度计法在约25℃测量获得的。具体地，将连接了一号转子的旋转粘度计探头浸入一定质量分数的溶液中，设定60转/分钟，开启转动电机，稳定旋转20秒后，进行读数。
在本公开中，所述沉降时间是通过如下测量的：将质量分数为0.1％的浆料使用磁力搅拌器充分搅匀，立刻倒入100mL量筒内，静置并开始计时。当浆料中固体物质完全沉降在量筒底部，上层为澄清透明液体时，记录此时时间为沉降时间。
在本公开中，所述结晶度通过粉末X衍射图谱(XRD)中的数据计算获得。
在本公开中，所述羧基占羟基与羧基总量的摩尔比通过如下过程测量：将干燥的样品粉末加入核磁管中，进行固体核磁共振碳谱测试，利用测得碳谱数据计算获得。
在本公开中，所述纤维素直径通过扫描电子显微镜观察获得，具体可以参见下面的实施例1中所示。
本发明所提供的表面纳米晶化的含纤维素生物质材料预期，将在防火、隔热、保 温、节能、防腐、防噪音、抗紫外、抗菌、耐磨、耐腐蚀等方面具有潜在的工业应用前景。本公开的表面纳米晶化的含纤维素生物质材料具有广泛的应用前景，其实例可能包括但不限于：a)人造板、木塑的加工原料；b)作为基地，复合功能纳米材料，制备功能化、智能化板材；c)用作水性涂料，包含水性内墙涂料、水性保护涂层等；d)作为基底，复合功能纳米涂料，制备多功能或智能涂料，包括导电涂料、抗菌防腐涂料、光触媒涂料、传感涂料、隔热防火涂料等；e)用于制备生物质海绵；f)作为基地，复合功能纳米涂料，制备多功能生物质海绵，包含隔热防火海绵、隔音海绵、导电海绵等；g)高温碳解后制备高性能碳材料。
作为一个更具体的实例，申请人发现，将本公开所提供的表面纳米晶化的含纤维素生物质材料直接均匀分散在水中所形成的水性涂料(即，分散均匀的水浆料)，由于其不含任何有机溶剂的环保特性，以及所述表面纳米晶化的含纤维素生物质材料表面上存在的特殊表面结构，而在室内装饰材料方面具有良好的应用，具体可以参见申请人在下面提供的一个应用实施例。
综上所述，针对现有含纤维素生物质加工技术中的挑战，本公开提供了一种表面纳米晶化的含纤维素生物质材料及其制备方法，通过对含纤维素生物质材料(比如颗粒)的表面刻蚀处理，再对暴露在表面的纤维素氧化，机械处理后，得到一种具有高比表面、高表面活性和结晶性的生物质材料，为生物质材料的进一步加工，提供了一种非常好的原料。
为了进一步理解本公开，下面结合实施例对本公开提供的含纤维素生物质材料表面纳米晶化方法进行详细说明，本公开的保护范围限于以下的实施例。
实施例
实施例1
A)将粒径200目的松木屑500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；B)将处理后的木屑洗净表面碱液，浸泡于含有0.1mg/mL的2，2，6，6-四甲基哌啶-氮-氧化物(化学式为C 9H 18NO，英文名2，2，6，6-tetramethylpiperidine-1-oxyl)和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械搅拌处理，具体为德国IKA RW20搅拌器，转速每分钟500转，搅拌时间为2小时；
D)将所述机械处理后生物质颗粒分散于水溶液保存。如图1所示，所得产品为分散均匀的浆料，不发生沉降，而未经表面纳米晶化处理的木屑，直接发生沉降。
纳米晶化处理后，所得产品表面产生大量纳米纤维素，如图2所示。未经本公开方法处理的木屑，表面光滑，没有纳米纤维素结构(图2A)；而经过本公开方法处理的木屑，表面产生大量纳米纤维结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间(图2B)。
纳米晶化处理后，纤维素上部分羟基转化为羧基，如图3所示。图3核磁共振碳谱显示，经过上述处理后，出现了羧基峰。通过计算，处理过程中3.4％的羟基转化成为了羧基。具体计算方式为：所述羧基含量等于核磁碳谱在175ppm的峰积分面积与60-70ppm间双峰积分面积之比的三分之一；在该实例中，样品核磁共振碳谱在174ppm处出峰面积为7424，60-70ppm积分面积为72244，计算得出羧基摩尔比为3.4％。
纳米晶化处理后，所得产品比表面增加，如图4所示。本实施例中，经过表面晶化的木屑颗粒，比表面积增加了2.7倍。
纳米晶化处理后，所得产品粘度增加，如图5所示。本实施例中，经过表面晶化的木屑颗粒，质量分数6％的水溶液中，粘度增加2.5倍，所述粘度通过旋转粘度计法在约25℃测量。所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态，放置一月后，无结块沉淀和絮凝，因此沉降时间大于一个月。
纳米晶化处理后，所得产品结晶度增加，如图6所示。结晶度由XRD图谱中2θ＝22.7处衬度减去2θ＝18处衬度的差，除以2θ＝22.7处衬度计算得出。
实施例2
A)将油菜秸秆粉500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的木屑洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械球磨处理，球磨条件为在250毫升球磨罐中，装入木屑含量15％的水溶液，放入行星式球磨机，速度设置值为27，球磨时间为8小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
实施例3
A)将松木锯末500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的木屑洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械搅拌处理，具体为德国IKA RW20搅拌器，转速每分钟400转，搅拌时间为3小时；
D)将所述机械处理后生物质颗粒分散于水溶液保存。
实施例4
A)将桦木锯末用磨粉机磨成粉末，过100目筛子后取500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的木屑洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械球磨处理，球磨条件为在250毫升球磨罐中，装入木屑含量15％的水溶液，放入行星式球磨机，速度设置值为27，球磨时间为8小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
纳米晶化处理后，所得干粉均匀可分散于水相中，不发生沉降，而未经表面纳米晶化处理的桦木屑，直接发生沉降。同时，纳米晶化处理后的产品表面产生大量纳米纤维素结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间。未经本发明方法处理的桦木屑，表面光滑，没有纳米纤维素结构。
纳米晶化处理后，纤维素上部分羟基转化为羧基。通过计算核磁共振碳谱显示出现的羧基峰，可知处理过程中2.9％的羟基转化成为了羧基。
纳米晶化处理后，所得产品比表面增加。本实施例中，经过表面晶化的桦木屑颗粒，比表面积增加了2.4倍，具体为43.2m 2/g。
纳米晶化处理后，所得产品粘度增加。本实施例中，经过表面晶化的桦木屑颗粒，若分散于质量分数6％的水溶液中，粘度增加2.1倍，具体地，在约25℃测量为42mPa·s，所述粘度通过旋转粘度计法在约25℃测量。
纳米晶化处理后，所得产品结晶度增加到67％。
所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态， 放置一月后，无结块沉淀和絮凝，沉降时间大于一个月。
实施例5
A)将油菜秸秆通过磨粉机磨成粉末，过200目筛后取500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的油菜秸秆粉末洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械搅拌处理，具体为德国IKA RW20搅拌器，转速每分钟400转，搅拌时间为3小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
纳米晶化处理后，所得干粉可均匀分散于水相中，不发生沉降，而未经表面纳米晶化处理的油菜秸秆粉末，直接发生沉降。同时，纳米晶化处理后的产品表面产生大量纳米纤维素结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间。未经本发明方法处理的油菜秸秆粉末，表面光滑，没有纳米纤维素结构。
纳米晶化处理后，纤维素上部分羟基转化为羧基。通过计算核磁共振碳谱显示出现的羧基峰，可知处理过程中33％的羟基转化成为了羧基。
纳米晶化处理后，所得产品比表面增加。本实施例中，经过表面晶化的油菜秸秆粉末，比表面积增加了2.5倍，具体为42.5m 2/g。
纳米晶化处理后，所得产品粘度增加。本实施例中，经过表面晶化的油菜秸秆粉末，若分散于质量分数6％的水溶液中，粘度增加2.5倍，具体地，在约25℃测量为52.5mPa·s，所述粘度通过旋转粘度计法在约25℃测量。
纳米晶化处理后，所得产品结晶度增加到73.6％。
所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态，放置一月后，无结块沉淀和絮凝，因此沉降时间大于一个月。
实施例6
在此提供150目的表面纳米晶化水稻秸秆颗粒的制备过程
A)将水稻秸秆通过磨粉机磨成粉末，过150目筛后取500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的油菜秸秆粉末洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲 基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械球磨处理，球磨条件为在250毫升球磨罐中，装入木屑含量15％的水溶液，放入行星式球磨机，速度设置值为27，球磨时间为8小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
纳米晶化处理后，所得产品可均匀分散于水相中，不发生沉降，而未经表面纳米晶化处理的水稻秸秆粉末，直接发生沉降。同时，纳米晶化处理后的产品表面产生大量纳米纤维素结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间。未经本发明方法处理的水稻秸秆粉末，表面光滑，没有纳米纤维素结构。
纳米晶化处理后，纤维素上部分羟基转化为羧基。通过计算核磁共振碳谱显示出现的羧基峰，可知处理过程中3.2％的羟基转化成为了羧基。
纳米晶化处理后，所得产品比表面增加。本实施例中，经过表面晶化的水稻秸秆粉末，比表面积增加了2.3倍，具体为48.3m 2/g。
纳米晶化处理后，所得产品粘度增加。本实施例中，经过表面晶化的水稻秸秆粉末，若分散于质量分数6％的水溶液中，粘度增加2.2倍，具体地，在约25℃测量为41.8mPa·s，所述粘度通过旋转粘度计法在约25℃测量。
所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态，放置一月后，无结块沉淀和絮凝，因此沉降时间大于一个月。
实施例7
在此提供尺寸为200目的表面纳米晶化法国梧桐树叶颗粒的制备过程
A)将法国梧桐树叶通过磨粉机磨成粉末，过200目筛后取500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的法国梧桐树叶粉末洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械搅拌处理，具体为德国IKA RW20搅拌器，转速每分钟400转，搅拌时间为3小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
纳米晶化处理后，所得产品可均匀分散于水相中，不发生沉降，而未经表面纳米晶化处理的法国梧桐树叶粉末，直接发生沉降。同时，纳米晶化处理后的产品表面产 生大量纳米纤维素结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间。未经本发明方法处理的法国梧桐树叶粉末，表面光滑，没有纳米纤维素结构。
纳米晶化处理后，纤维素上部分羟基转化为羧基。通过计算核磁共振碳谱显示出现的羧基峰，可知处理过程中3.3％的羟基转化成为了羧基。
纳米晶化处理后，所得产品比表面增加。本实施例中，经过表面晶化的法国梧桐树叶粉末，比表面积增加了2.6倍，具体为41.6m 2/g。
纳米晶化处理后，所得产品粘度增加。本实施例中，经过表面晶化的法国梧桐树叶粉末，若分散于质量分数6％的水溶液中，粘度增加2.4倍，具体地，在约25℃测量为55.2mPa·s，所述粘度通过旋转粘度计法在约25℃测量。
纳米晶化处理后，所得产品结晶度增加到68％。
所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态，放置一月后，无结块沉淀和絮凝，因此沉降时间大于一个月。
实施例8
尺寸为200目的表面纳米晶化枫树树叶颗粒的制备过程
A)将枫树树叶通过磨粉机磨成粉末，过200目筛后取500g在10％的氢氧化钠溶液5L中，80℃浸泡24h；
B)将处理后的枫树树叶粉末洗净表面碱液，浸泡于含有0.1mg/mL 2，2，6，6-四甲基哌啶-氮-氧化物和1％亚氯酸钠的pH＝6.8的氧化溶液中，在60℃下，氧化24h；
C)将表面氧化后生物质颗粒机械球磨处理，球磨条件为在250毫升球磨罐中，装入木屑含量15％的水溶液，放入行星式球磨机，速度设置值为27，球磨时间为8小时；
D)将所述机械处理后生物质颗粒冷冻干燥成干粉保存。
纳米晶化处理后，所得产品可均匀分散于水相中，不发生沉降，而未经表面纳米晶化处理的枫树树叶粉末，直接发生沉降。同时，纳米晶化处理后的产品表面产生大量纳米纤维素结构，纤维直径在10～100纳米之间，长度为0.5～5微米之间。未经本发明方法处理的枫树树叶粉末，表面光滑，没有纳米纤维素结构。
纳米晶化处理后，纤维素上部分羟基转化为羧基。通过计算核磁共振碳谱显示出现的羧基峰，可知处理过程中3.5％的羟基转化成为了羧基。
纳米晶化处理后，所得产品比表面增加。本实施例中，经过表面晶化的枫树树叶 粉末，比表面积增加了2.8倍，具体为44.8m 2/g。
纳米晶化处理后，所得产品粘度增加。本实施例中，经过表面晶化的枫树树叶粉末，若分散于质量分数6％的水溶液中，粘度增加2.7倍，具体地，在约25℃测量为56.7mPa·s，所述粘度通过旋转粘度计法在约25℃测量。
纳米晶化处理后，所得产品结晶度增加到71.2％。
所述表面纳米晶化的含纤维素生物质材料的水溶液长时间维持均匀分散的状态，放置一月后，无结块沉淀和絮凝，因此沉降时间大于一个月。
应用实施例1
A)将实施例1得到的表面纳米晶化的生物质颗粒，分散于水中，得到浓度为20％的浆料，为水性涂料；
B)将所述水性涂料涂刷于木板表面，自然干燥，得到均匀涂层。
涂料涂刷于木材表面后拍摄的数码照片参见图7所示。从图7可以看出所得的涂层是均匀的。并且，载荷为1.45公斤的划痕测试中，只出现轻微划痕，没有划穿。作为对比，如图8所示，未经本方法处理的同种木屑样品浆料，涂至相同基底，干燥后未形成涂层，依然为粉末状，倾斜后，粉末脱落。
应用实施例2
用作墙膜等建筑内装饰材料。
将实施例1中制得的表面纳米晶化的含纤维素生物质材料直接分散在水中，得到制成固含量60质量％的浆料，并且将该浆料在建筑内装饰材料上进行应用试验。将该浆料涂刷在10*10cm的水泥板基底上，将其垂直竖立放置，于湿度在53％、温度在25℃的室内环境中自然干燥。
图9为本发明实施例1制备的表面纳米晶化的含纤维素生物质材料所形成的水浆料涂覆在水泥板基底上一个月后的数码照片，可以看出其表观性能保持稳定，并不因周围环境的正常温度湿度变化而脱落、起皮和褶皱。
图10为本发明实施例1制备的制备的表面纳米晶化的含纤维素生物质材料所形成的水浆料涂覆在水泥板基底上的划痕测试，其在载荷达到1.50kg时才出现划痕，耐刮擦性能良好。
应用比较例1
将未进行表面纳米晶化的含纤维素生物质材料直接分散在水中，得到制成固含量60质量％的浆料，并称为比较浆料。
将比较浆料在建筑内装饰材料上进行应用试验，将其涂刷在10*10cm的水泥板基底上，将其垂直竖立放置会发生涂料下滑的现象，因此将其水平放置，置于湿度在53％、温度在25℃的室内环境中自然干燥。
图11为比较浆料涂料涂覆在水泥板基底上一个月后的数码照片，可以看出其表观既有很明显的颗粒感，整体较为松散，无法形成一个强韧的涂料漆膜。
图12为比较浆料涂料涂覆在水泥板基底上的划痕测试，在载荷为0kg时出现划痕，表明其耐刮擦性能较差。
以上具体实施方式和实施例的说明只是用于帮助理解本公开的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理和精神的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。

Claims (14)

  1. 一种表面纳米晶化的含纤维素生物质材料，所述含纤维素生物质材料来源于天然植物或动物中含有纤维素成分的生物质材料中的一种或多种，所述表面纳米晶化的含纤维素生物质材料的表面存在暴露区域，并且在所述暴露区域中的纤维素为纳米尺度的纤维素，并且所述纳米尺度纤维素中的部分羟基已经转化为羧基，以使得所述表面纳米晶化的含纤维素生物质材料具有以下各项性能中的至少一项：
    i)所述表面纳米晶化的含纤维素生物质材料的比表面积至少为1.5m 2/g；
    ii)所述表面纳米晶化的含纤维素生物质材料的表面暴露的纳米晶化后的纤维素直径至少为1微米以下；
    iii).所述表面纳米晶化的含纤维素生物质材料中，纤维素的结晶度至少为65％；
    iv).所述表面纳米晶化的含纤维素生物质材料中，羧基占羟基与羧基总量的摩尔比至少为5％；
    v).所述表面纳米晶化的含纤维素生物质材料在水中溶液粘度在溶液质量分数为6％情况下通过旋转粘度计法在约25℃测量为至少40mPa·s；以及
    vi).所述表面纳米晶化的含纤维素生物质材料的水溶液沉降时间至少大于200分钟。
  2. 根据权利要求1所述的表面纳米晶化的含纤维素生物质材料，其中所述表面纳米晶化后的表面暴露的纤维素的纤维长度在0.1-5微米的范围内。
  3. 根据权利要求1所述的表面纳米晶化的含纤维素生物质材料，其中所述含纤维素生物质材料的纤维素含量为10～90％。
  4. 根据权利要求1所述的表面纳米晶化的含纤维素生物质材料，其中所述天然植物或动物是选自天然植物的木材、锯末、树叶、秸秆、干草、麻、竹子、甘蔗渣、稻壳以及天然动物的海壳中的至少一种。
  5. 一种表面纳米晶化的含纤维素生物质材料的制备方法，包括以下步骤：
    A)将含纤维素生物质材料在刻蚀溶液中做表面刻蚀处理，所述含纤维素生物质材料选自天然植物、动物中含有纤维素成分的生物质材料中的一种或多种；
    B)将刻蚀处理后的含纤维素生物质材料表面氧化处理；
    C)将表面氧化后的含纤维素生物质材料机械处理；
    D)将机械处理后的含纤维素生物质材料制成分散液或干粉保存。
  6. 根据权利要求5所述的制备方法，其中，所述表面刻蚀溶液包括选自以下各项中的至少一种：氢氧化钠水溶液，氢氧化钾水溶液，亚硫酸钠水溶液，二氧化硫水溶液、亚硫酸水溶液、以及能溶解生物大分子的溶剂。
  7. 根据权利要求5所述的制备方法，其中，所述表面氧化处理方法包括在2，2，6，6-四甲基哌啶-氮-氧化物催化作用下对所述含纤维素生物质材料的表面暴露纤维素的氧化。
  8. 根据权利要求5所述的制备方法，其中在步骤A)中，所述刻蚀温度为10-200℃，时间为1～72h。
  9. 根据权利要求5所述的制备方法，其中在步骤B)中，所述氧化处理的时间为6～240h，所述氧化处理的温度为10～150℃。
  10. 根据权利要求5所述的制备方法，其中步骤B)所述的表面氧化处理方法为在2，2，6，6-四甲基哌啶-氮-氧化物的催化下，氧化试剂氧化所述含纤维素生物质材料的表面纤维素，所述氧化试剂包括选自亚氯酸钠、次氯酸钠、亚溴酸钠和次溴酸钠中的至少一种的水溶性氧化剂。
  11. 根据权利要求5所述的制备方法，其中所述机械处理为搅拌、研磨、高压匀浆或高压喷射处理中的一种或几种。
  12. 根据权利要求1-4中任一项所述的表面纳米晶化的含纤维素生物质材料和根据权利要求5-9中任一项所述的制备方法获得的表面纳米晶化的含纤维素生物质材料在制备薄膜、板材、水性涂料、复合功能纳米材料、生物质海绵、高性能碳材料或气凝胶材料中的用途。
  13. 根据权利要求12所述的用途，其中所述用途包括将所述表面纳米晶化的含纤维素生物质材料的浆料直接加工成薄膜、板材、水性涂料、复合功能纳米材料、生物质海绵、高性能碳材料或气凝胶材料的用途。
  14. 根据权利要求12所述的用途，其中所述用途包括在室内装饰材料中的用途。
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