CN114369202A - Preparation method of nano-cellulose hollow microspheres and coating material thereof - Google Patents
Preparation method of nano-cellulose hollow microspheres and coating material thereof Download PDFInfo
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- CN114369202A CN114369202A CN202110601960.3A CN202110601960A CN114369202A CN 114369202 A CN114369202 A CN 114369202A CN 202110601960 A CN202110601960 A CN 202110601960A CN 114369202 A CN114369202 A CN 114369202A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
Abstract
The invention discloses a nano-cellulose hollow microsphere composite material and a nano-cellulose hollow microsphere coating material, and the preparation method comprises the following steps: firstly, carrying out esterification modification on nano-cellulose to obtain a modified nano-cellulose Pickering emulsifier; then dispersing the modified nanocellulose Pickering emulsifier into deionized water to obtain a modified nanocellulose aqueous solution; the modified nano-cellulose aqueous solution is used as water, the mixed solution of dichloromethane and acrylate monomers is used as an oil phase, and the nano-cellulose hollow microsphere composite material is obtained by a Pickering emulsion polymerization method. Compared with the solid modified nanocellulose emulsion, the nanocellulose hollow microsphere composite material improves the dispersibility of nanocellulose in a solvent and reduces agglomeration, and the hollow structure can shorten a gas molecule passing path, improve the diffusion rate of gas and realize the permeability of the coating while enhancing and toughening, so that the substrate is endowed with good permeability, and the application of the substrate in the fields of fabrics, leather and the like is improved.
Description
Technical Field
The invention relates to a preparation method of a nano-cellulose hollow microsphere composite material and a coating material thereof, belonging to the technical field of nano-cellulose composite materials.
Background
The nano-cellulose is a new green nano-polymer material, not only has the excellent characteristics of natural cellulose such as biodegradability and good biocompatibility, but also has the advantages of large specific surface area, high length-diameter ratio, high strength, high rigidity, high Young modulus and the like, and the excellent properties open up a new way for the development and application of the nano-cellulose in the fields of composite materials, energy sources, electronics, medicines, papermaking, foods, textiles and the like. In recent years, nanocellulose has been used to reinforce high molecular weight polymers (such as polyvinyl alcohol, aqueous polyurethane, polylactic acid, polycaprolactone, etc.), and nanocellulose composite coating materials having light weight, transparency, and high strength have been developed. The aim of enhancing the mechanical property of the nano-cellulose composite coating is achieved by increasing the contact area, improving the interface compatibility and the hydrogen bond binding force, forming a three-dimensional network structure with a matrix and the like, but the mechanical property of the composite coating is improved, the flow of gas molecules is blocked, the further application of the nano-cellulose composite material in the coating fields of textile, leather and the like is limited, and the research of the nano-cellulose composite material with enhanced toughness and high air permeability is rarely reported in the open at present.
The polymer hollow microspheres have been widely noticed by researchers, and compared with solid polymer microspheres, the polymer hollow microspheres have the advantages of excellent air permeability, ultraviolet shielding property and the like due to the fact that the interior of the polymer hollow microspheres is of a cavity structure, so that the polymer hollow microspheres are widely applied as coating additives in the industrial fields of leather, papermaking, building coatings and the like. However, at present, no published reports on the research on the nano-cellulose hollow microsphere composite material at home and abroad are found.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-cellulose hollow microsphere composite material, and the composite material prepared by the method can endow a base material with good air permeability and mechanical properties, so that the application field of the nano-cellulose composite material is further expanded.
The invention also aims to provide a nano-cellulose hollow microsphere coating material with enhanced toughness and high air permeability.
The first technical scheme is as follows:
the preparation method of the nano-cellulose hollow microsphere composite material comprises the following steps: step 1, carrying out esterification surface modification on nano-cellulose to obtain a modified nano-cellulose Pickering emulsifier; step 2, dispersing the modified nanocellulose Pickering emulsifier into deionized water to obtain a modified nanocellulose aqueous solution; and 3, taking the modified nano-cellulose aqueous solution as a water phase and a mixed solution of dichloromethane and acrylic ester monomers as an oil phase, and obtaining the nano-cellulose hollow microsphere composite material by a Pickering emulsion polymerization method.
The invention is characterized by the following and further improvements:
preferably, step 1 comprises: and (3) carrying out ultrasonic treatment on 70-90 parts of nano cellulose anhydrous pyridine solution for 10-30 min, then adding 10-30 parts of modifier, stirring at room temperature for 6-14 h, and after the reaction is finished, preparing the esterified modified nano cellulose Pickering emulsifier.
More preferably, the modifier is any one of succinic anhydride, acetic anhydride, maleic anhydride, methacrylic acid and acrylic acid.
More preferably, the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1 g/mL.
Preferably, in the step 2, the mass concentration of the modified nano-cellulose aqueous solution is 0.1 g/mL.
Preferably, step 3 comprises: mixing the modified nano-cellulose aqueous solution with the mixed solution of dichloromethane and acrylic ester monomers, and emulsifying for 3-15 min to obtain a Pickering emulsion; and then heating the Pickering emulsion to 72-80 ℃, dropwise adding 3-15 parts of ammonium persulfate aqueous solution and 1-5 parts of cross-linking agent, keeping the temperature and stirring for 90-130 min after dropwise adding, stopping heating, naturally cooling to 10-30 ℃, and volatilizing the solvent to obtain the nano-cellulose hollow microsphere composite material.
Preferably, in the step 3, the mass ratio of the modified nano-cellulose aqueous solution to the mixed solution of dichloromethane and acrylate monomers is 2: 8-8: 2.
Preferably, in the step 3, the mixed solution of dichloromethane and acrylic ester monomers comprises dichloromethane and acrylic ester monomers, and the mass ratio of dichloromethane to acrylic ester is 30: 1-10: 1.
Preferably, in step 3, the cross-linking agent is glutaraldehyde, ethylene glycol dimethacrylate or epoxy silane XR-500.
Preferably, in the step 3, the mass concentration of the ammonium persulfate aqueous solution is 0.2 g/mL.
The second technical scheme is as follows:
a nano-cellulose hollow microsphere coating material comprises the nano-cellulose hollow microsphere composite material prepared according to any one of the embodiments and a film layer attached to a substrate.
Preferably, the substrate comprises leather, fabric, ceramic, glass, building.
The invention has the beneficial effects that: according to the preparation method of the nano-cellulose hollow microsphere composite material, firstly, the surface modified nano-cellulose is esterified to obtain the modified nano-cellulose Pickering emulsifier, and on one hand, the modified nano-cellulose Pickering emulsifier is stable in structure and has emulsifying performance, so that the dispersibility of the nano-cellulose in a solvent can be improved, and the agglomeration is reduced; on the other hand, the modified nanocellulose Pickering emulsifier can provide a polymerization place for a later-stage monomer to ensure the stability of the emulsion, and can be polymerized with an acrylate monomer to improve the flexibility of a nanocellulose composite film; the strength of the shell layer can be enhanced through the action of the cross-linking agent, so that the structure of the nano-cellulose hollow microsphere composite material is regular.
The nano-cellulose hollow microsphere composite material prepared by the preparation method of the nano-cellulose hollow microsphere composite material is suitable for continuous coating materials, when water vapor and gas pass through a coating film formed by the water vapor and the gas, the hollow structure of the nano-cellulose hollow microsphere composite material can shorten the passing path of gas molecules, improve the diffusion rate of the gas, effectively endow the coating with good air permeability and mechanical properties, show good application prospects in the fields of leather, textile, coating and the like, and can greatly improve the added value of products.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a hollow microsphere composite material of nano-cellulose prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The embodiment of the invention provides a preparation method of a nano-cellulose hollow microsphere, which comprises the following steps:
step 2, dispersing the modified nanocellulose Pickering emulsifier into deionized water to obtain a modified nanocellulose aqueous solution;
and 3, taking the modified nano-cellulose aqueous solution as a water phase and a mixed solution of dichloromethane and acrylic ester monomers as an oil phase, and obtaining the nano-cellulose hollow microsphere composite material by a Pickering emulsion polymerization method.
The embodiment of the invention also provides a reinforced and toughened high-permeability nano-cellulose hollow microsphere coating material, which comprises the nano-cellulose hollow microsphere coating material and a film layer attached to a base material. The substrate can be leather, fabric, ceramic, glass, building, etc.
Compared with the solid modified nano-cellulose emulsion, the nano-cellulose hollow microsphere composite material provided by the embodiment of the invention has the advantages that the dispersibility in a solvent is improved and the agglomeration is reduced; on the other hand, the coating material formed on the base material can enhance and toughen the base material and simultaneously endow the base material with good air permeability, thereby improving the use comfort of the base material in the fields of fabrics, leather and the like.
The hollow nano-cellulose microspheres prepared by the method are subjected to film forming on a base material or self film forming to obtain a coating material, and when water vapor and gas pass through the coating film, the hollow structure can shorten the gas molecule passing path, improve the gas diffusion rate and improve the gas permeability of the coating.
Example 1
1) Preparing a modified nanocellulose Pickering emulsifier: preparing 70 parts of nano-cellulose anhydrous pyridine solution, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1g/mL, carrying out ultrasonic treatment for 10min, then adding the nano-cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 30 parts of succinic anhydride, stirring at room temperature for 6h, precipitating the modified nano-cellulose after the reaction is finished, then repeatedly washing and centrifuging the nano-cellulose with absolute ethyl alcohol, and then placing the nano-cellulose anhydrous pyridine solution in a vacuum drying oven to constant weight to obtain white solid powder, thus obtaining the modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano-cellulose aqueous solution: weighing 1 part of the modified nano-cellulose prepared in the step 1, and dissolving the modified nano-cellulose in deionized water to obtain a modified nano-cellulose aqueous solution; wherein the mass concentration of the modified nano-cellulose solution is 0.1 g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: mixing the modified nano-cellulose aqueous solution obtained in the step 2 with 19.2 parts of dichloromethane and acrylate monomer mixed solution (wherein the ratio of dichloromethane to acrylate monomer is 10:1), wherein the mass ratio of an oil phase to a water phase is 2: 8; emulsifying for 3min under the action of a high-shear disperser to obtain Pickering emulsion; and then adding the mixture into a 250mL three-neck flask, heating to 72 ℃, dropwise adding 3 parts of ammonium persulfate aqueous solution with the mass concentration of 0.2g/mL and 1 part of glutaraldehyde, keeping the temperature and stirring for 90min after the dropwise adding is finished, stopping heating, naturally cooling to 10 ℃, opening, stirring and volatilizing for 1h to obtain the nano-cellulose hollow microsphere composite material.
Example 2
1) Preparing a modified nanocellulose Pickering emulsifier: preparing 75 parts of nano-cellulose anhydrous pyridine solution, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1g/mL, performing ultrasonic treatment for 15min, adding the nano-cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 25 parts of acetic anhydride, stirring at room temperature for 8h, precipitating the esterified and modified nano-cellulose after the reaction is finished, repeatedly washing and centrifuging the nano-cellulose by using absolute ethyl alcohol, and then placing the nano-cellulose in a vacuum drying oven to constant weight to obtain white solid powder, thus preparing the esterified and modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano-cellulose aqueous solution: weighing 1 part of the modified nano-cellulose prepared in the step 1, and dissolving the modified nano-cellulose in deionized water to obtain a modified nano-cellulose aqueous solution; wherein the mass concentration of the modified nano-cellulose solution is 0.1 g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: emulsifying the modified nano-cellulose aqueous solution obtained in the step 2 with 38.4 parts of mixed solution of dichloromethane and acrylate monomers (the ratio of the dichloromethane to the acrylate monomers is 15:1) for 6min under the action of a high-shear disperser, wherein the mass ratio of an oil phase to a water phase is 4:6, and thus obtaining Pickering emulsion; and then adding the mixture into a 250mL three-neck flask, heating to 74 ℃, dropwise adding 6 parts of ammonium persulfate aqueous solution with the mass concentration of 0.2g/mL and 2 parts of glutaraldehyde, keeping the temperature and stirring for 100min after dropwise adding, stopping heating, naturally cooling to 15 ℃, opening, stirring and volatilizing for 2h to obtain the nano-cellulose hollow microsphere composite material.
Example 3
1) Preparing a modified nanocellulose Pickering emulsifier: preparing 80 parts of nano-cellulose anhydrous pyridine solution, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1g/mL, carrying out ultrasonic treatment for 20min, then adding the nano-cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 20 parts of maleic anhydride, stirring at room temperature for 10h, after the reaction is finished, precipitating the esterified and modified nano-cellulose, then repeatedly washing and centrifuging by using absolute ethyl alcohol, then placing the obtained product in a vacuum drying oven to constant weight to obtain white solid powder, and thus obtaining the esterified and modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano-cellulose aqueous solution: weighing 3 parts of the modified nanocellulose prepared in the step 1, and dissolving the modified nanocellulose into deionized water to obtain a modified nanocellulose aqueous solution; wherein the mass concentration of the modified nano-cellulose solution is 0.1 g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: emulsifying the modified nano-cellulose aqueous solution obtained in the step 2 with 48 parts of mixed solution of dichloromethane and acrylate monomers (the ratio of the dichloromethane to the acrylate monomers is 20:1) for 9min under the action of a high-shear disperser, wherein the mass ratio of an oil phase to a water phase is 5:5, so as to obtain Pickering emulsion; and then adding the mixture into a 250mL three-neck flask, heating to 76 ℃, dropwise adding 9 parts of ammonium persulfate aqueous solution with the mass concentration of 0.2g/mL and 3 parts of epoxy silane XR-500, keeping the temperature and stirring for 110min after the dropwise adding is finished, stopping heating, naturally cooling to 20 ℃, opening, stirring and volatilizing for 3h to obtain the nano-cellulose hollow microsphere composite material.
Fig. 1 is a scanning electron micrograph of the hollow nanocellulose microspheres prepared in example 3, and it can be seen from fig. 1 that: the nano-cellulose hollow microspheres show a spherical structure, the size of the nano-cellulose hollow microspheres is about 500nm, the nano-cellulose hollow microspheres are mutually extruded and deformed to form a continuous coating, part of the nano-cellulose hollow microspheres are extruded into a convex spherical structure, the interior of the coating is of a porous hollow structure, and the coating structure endows the base material with good air permeability.
Example 4
1) Preparing a modified nanocellulose Pickering emulsifier: preparing 85 parts of nano-cellulose anhydrous pyridine solution, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1g/mL, carrying out ultrasonic treatment for 25min, then adding the nano-cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 15 parts of methacrylic acid, stirring at room temperature for 12h, after the reaction is finished, precipitating the esterified and modified nano-cellulose, then repeatedly washing and centrifuging by using absolute ethyl alcohol, then placing the obtained product in a vacuum drying oven to constant weight to obtain white solid powder, and thus obtaining the esterified and modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano-cellulose aqueous solution: weighing 4 parts of the modified nanocellulose prepared in the step 1, and dissolving the modified nanocellulose into deionized water to obtain a modified nanocellulose aqueous solution; wherein the mass concentration of the modified nano-cellulose solution is 0.1 g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: emulsifying the modified nano-cellulose aqueous solution obtained in the step 2 with 57.6 parts of mixed solution of dichloromethane and acrylate monomers (the ratio of the dichloromethane to the acrylate monomers is 25:1) for 12min under the action of a high-shear disperser, wherein the mass ratio of an oil phase to a water phase is 6:4, so as to obtain Pickering emulsion; and then adding the mixture into a 250mL three-neck flask, heating to 78 ℃, dropwise adding 12 parts of ammonium persulfate aqueous solution with the mass concentration of 0.2g/mL and 4 parts of epoxy silane XR-500, keeping the temperature and stirring for 120min after dropwise adding, stopping heating, naturally cooling to 25 ℃, opening, stirring and volatilizing for 4h to obtain the nano-cellulose hollow microsphere composite material.
Example 5
1) Preparing a modified nanocellulose Pickering emulsifier: preparing 90 parts of nano-cellulose anhydrous pyridine solution, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1g/mL, carrying out ultrasonic treatment for 30min, then adding the nano-cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 10 parts of acrylic acid, stirring for 14h at room temperature, after the reaction is finished, precipitating the modified nano-cellulose, then repeatedly washing and centrifuging the nano-cellulose with absolute ethyl alcohol, and then placing the nano-cellulose anhydrous pyridine solution in a vacuum drying oven to constant weight to obtain white solid powder, thus preparing the esterified modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano-cellulose aqueous solution: weighing 5 parts of the modified nano-cellulose prepared in the step 1, and dissolving the modified nano-cellulose in deionized water to obtain a modified nano-cellulose aqueous solution; wherein the mass concentration of the modified nano-cellulose solution is 0.1 g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: emulsifying the modified nano-cellulose aqueous solution obtained in the step 2 with 76.8 parts of mixed solution of dichloromethane and acrylate monomers (the ratio of the dichloromethane to the acrylate monomers is 30:1) for 15min under the action of a high-shear disperser, wherein the mass ratio of an oil phase to a water phase is 8:2, so as to obtain Pickering emulsion; and then adding the mixture into a 250mL three-neck flask, heating to 80 ℃, dropwise adding 15 parts of ammonium persulfate aqueous solution with the mass concentration of 0.2g/mL and 5 parts of ethylene glycol dimethacrylate, keeping the temperature and stirring for 130min after dropwise adding, stopping heating, naturally cooling to 30 ℃, opening, stirring and volatilizing for 5h to obtain the nano-cellulose hollow microsphere composite material.
Respectively forming films on the nano-cellulose hollow microspheres prepared in the embodiment and the modified nano-cellulose aqueous solution obtained in the step 1 on a base material to respectively obtain a nano-cellulose hollow microsphere coating material and a modified nano-cellulose coating material, and performing fabric finishing and water vapor permeability testing on the nano-cellulose hollow microsphere coating material and the modified nano-cellulose coating material. Specifically, the hollow nano-cellulose microspheres and the modified nano-cellulose are diluted to the same solid content, and are finished on the fabric in a double-dipping and double-rolling mode to form a coating film on the surface of the fabric, and the mass of the coating film is recorded as m0A fabric sample is placed in a moisture permeable cup containing a certain amount of deionized water, and the mass of the fabric sample is weighed as m1Then placing the moisture permeable cup in a concentrated sulfuric acid dryer, and recording the mass of the moisture permeable cup to be m after 24 hours2The amount of water vapor passing through the same fabric area in 24h is w ═ m1-m2The results are shown in Table I. As can be seen, the nanocellulose hollow microsphere coating has obvious water vapor permeability after 24 hours.
TABLE-test results of water vapor permeability of fabrics
Claims (10)
1. The preparation method of the nano-cellulose hollow microsphere composite material is characterized by comprising the following steps:
step 1, carrying out esterification surface modification on nano-cellulose to obtain a modified nano-cellulose Pickering emulsifier;
step 2, dispersing the modified nanocellulose Pickering emulsifier into deionized water to obtain a modified nanocellulose aqueous solution;
and 3, taking the modified nano-cellulose aqueous solution as a water phase and a mixed solution of dichloromethane and acrylic ester monomers as an oil phase, and obtaining the nano-cellulose hollow microsphere composite material by a Pickering emulsion polymerization method.
2. The method of preparing a hollow microsphere composite of nanocellulose according to claim 1,
the step 1 comprises the following steps: and (3) carrying out ultrasonic treatment on 70-90 parts of nano cellulose anhydrous pyridine solution for 10-30 min, then adding 10-30 parts of modifier, stirring at room temperature for 6-14 h, and after the reaction is finished, preparing the esterified modified nano cellulose Pickering emulsifier.
3. The method for preparing the hollow microsphere composite material of claim 2, wherein the modifier is any one of succinic anhydride, acetic anhydride, maleic anhydride, methacrylic acid and acrylic acid.
4. The method for preparing the nano-cellulose hollow microsphere composite material as claimed in claim 2, wherein the mass concentration of the nano-cellulose anhydrous pyridine solution is 0.1 g/mL.
5. The method for preparing the nano-cellulose hollow microsphere composite material as claimed in claim 1, wherein in the step 2, the mass concentration of the modified nano-cellulose aqueous solution is 0.1 g/mL.
6. The method of preparing a hollow microsphere composite of nanocellulose according to claim 1,
the step 3 comprises the following steps: mixing the modified nano-cellulose aqueous solution with the mixed solution of dichloromethane and acrylic ester monomers, and emulsifying for 3-15 min to obtain a Pickering emulsion; and then heating the Pickering emulsion to 72-80 ℃, dropwise adding 3-15 parts of ammonium persulfate aqueous solution and 1-5 parts of cross-linking agent, keeping the temperature and stirring for 90-130 min after dropwise adding, stopping heating, naturally cooling to 10-30 ℃, and volatilizing the solvent to obtain the nano-cellulose hollow microsphere composite material.
7. The preparation method of the hollow nano-cellulose microsphere composite material as claimed in claim 1 or 6, wherein in the step 3, the mass ratio of the modified nano-cellulose aqueous solution to the mixed solution of dichloromethane and acrylic ester monomers is 2: 8-8: 2.
8. The preparation method of the hollow nano-cellulose microsphere composite material of claim 1 or 6, wherein in the step 3, the mixed solution of dichloromethane and acrylic ester monomers comprises dichloromethane and acrylic ester monomers, and the mass ratio of dichloromethane to acrylic ester is 30: 1-10: 1.
9. The method for preparing the hollow microsphere composite material of claim 6, wherein in the step 3, the cross-linking agent is glutaraldehyde, ethylene glycol dimethacrylate or epoxy silane XR-500.
10. A nanocellulose hollow microsphere coating material, comprising: the hollow microsphere composite material of nano cellulose prepared by the method of claim 1 and a film layer attached on a substrate.
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| CN115612120B (en) * | 2022-10-10 | 2024-04-19 | 四川大学 | Method for preparing novel aqueous polyurethane based on Pickering emulsion method |
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