CN114369202B - Preparation method of nanocellulose hollow microsphere and coating material thereof - Google Patents
Preparation method of nanocellulose hollow microsphere and coating material thereof Download PDFInfo
- Publication number
- CN114369202B CN114369202B CN202110601960.3A CN202110601960A CN114369202B CN 114369202 B CN114369202 B CN 114369202B CN 202110601960 A CN202110601960 A CN 202110601960A CN 114369202 B CN114369202 B CN 114369202B
- Authority
- CN
- China
- Prior art keywords
- nanocellulose
- cellulose
- nano
- hollow microsphere
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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, esterifying and modifying 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 acrylic ester monomers is used as an oil phase, and the nano-cellulose hollow microsphere composite material is obtained through a Pickering emulsion polymerization method. According to the invention, the unique properties of the nanocellulose and the hollow structure are combined to prepare the reinforced and toughened high-breathability nanocellulose hollow microsphere coating material, compared with solid modified nanocellulose emulsion, the nanocellulose hollow microsphere composite material improves the dispersibility of the nanocellulose in a solvent on one hand, reduces aggregation, and can shorten a gas molecule passing path, improve the gas diffusion rate and realize the breathability of the coating while reinforcing and toughening on the other hand, so that the substrate is endowed with good breathability, and the application of the nanocellulose hollow microsphere composite material 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 nanocellulose is an emerging green nanocellulose polymer material, has the excellent characteristics of biodegradability, good biocompatibility and the like of natural cellulose, and also has the advantages of large specific surface area, high length-diameter ratio, high strength, high rigidity, high Young's modulus and the like, and the excellent performances open up a new road for the development and application of the nanocellulose in the fields of composite materials, energy sources, electronics, medicine, papermaking, foods, textiles and the like. In recent years, nanocellulose has been used to reinforce high molecular polymers (such as polyvinyl alcohol, aqueous polyurethane, polylactic acid, polycaprolactone, etc.), and nanocellulose composite coating materials with light weight, transparency and high strength have been developed. The purpose of enhancing the mechanical properties of the nano cellulose composite coating film is achieved by increasing the contact area, improving the interface compatibility, improving the hydrogen bonding force, forming a three-dimensional network structure with a matrix and the like, but the flow of gas molecules is blocked while the mechanical properties of the composite coating film are improved, so that the further application of the nano cellulose composite material in the coating fields of spinning, leather and the like is limited, and at present, the research on the reinforced and toughened high-breathability nano cellulose composite material is freshly reported.
Polymer hollow microspheres have been widely paid attention to by researchers, and have advantages such as excellent air permeability and ultraviolet shielding property due to the hollow structure of the interior, compared with solid polymer microspheres, and therefore, they are widely used as coating additives in industrial fields such as leather, paper making, building coating materials, and the like. However, at present, no public report is made on the research of the nano cellulose hollow microsphere composite material at home and abroad.
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 further aims to provide a nano-cellulose hollow microsphere coating material with reinforced, toughened and high air permeability.
The technical scheme is as follows:
the preparation method of the nanocellulose 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 step 3, taking the modified nano-cellulose aqueous solution as a water phase, taking 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 in that:
preferably, step 1 comprises: and (3) carrying out ultrasonic treatment on 70-90 parts of nanocellulose anhydrous pyridine solution for 10-30 min, adding 10-30 parts of modifier into the nanocellulose anhydrous pyridine solution, stirring the mixture for 6-14 h at room temperature, and obtaining the esterified modified nanocellulose Pickering emulsifier after the reaction is finished.
Further preferably, the modifier is any one of succinic anhydride, acetic anhydride, maleic anhydride, methacrylic acid and acrylic acid.
Further preferably, the mass concentration of the nanocellulose anhydrous pyridine solution is 0.1g/mL.
Preferably, in the step 2, the mass concentration of the modified nano cellulose aqueous solution is 0.1g/mL.
Preferably, step 3 includes: 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 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 into the Pickering emulsion, after the dropwise adding is finished, carrying out heat preservation and stirring for 90-130 min, 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 acrylic ester 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 the dichloromethane to the acrylic ester monomers is 30:1-10:1.
Preferably, in the 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 0.2g/mL.
The second technical scheme is as follows:
the nano cellulose hollow microsphere coating material comprises the nano cellulose hollow microsphere composite material prepared in any embodiment and a membrane layer attached to a substrate.
Preferably, the substrate comprises leather, fabric, ceramic, glass, building.
The beneficial effects of the invention are as follows: according to the preparation method of the nano-cellulose hollow microsphere composite material, the surface modified nano-cellulose is esterified firstly to obtain the modified nano-cellulose Pickering emulsifier, on one hand, the modified nano-cellulose Pickering emulsifier is stable in structure and has emulsifying property, so that the dispersibility of the nano-cellulose in a solvent can be improved, and agglomeration is reduced; on the other hand, the modified nanocellulose Pickering emulsifier can provide a polymerization place for a later-stage monomer so as to ensure the stability of emulsion, and can polymerize with an acrylic monomer to improve the softness of the nanocellulose composite film; the strength of the shell layer can be enhanced through the action of the cross-linking agent, so that the nano-cellulose hollow microsphere composite material is regular in structure.
The nano-cellulose hollow microsphere composite material obtained 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 nano-cellulose hollow microsphere composite material, the hollow structure of the nano-cellulose hollow microsphere composite material can shorten the passage path of gas molecules, improve the diffusion rate of the gas, effectively endow the coating with good air permeability and mechanical property, and has good application prospect in the fields of leather, textile, coating and the like, and the added value of products can be greatly improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a nanocellulose hollow microsphere composite material 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 nanocellulose 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 step 3, taking the modified nano-cellulose aqueous solution as a water phase, taking 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-breathability nano-cellulose hollow microsphere coating material, which comprises the nano-cellulose hollow microsphere coating material and a film layer attached to a substrate. Wherein the substrate may be leather, fabric, ceramic, glass, building, etc.
Compared with the continuous coating of the nano-cellulose hollow microsphere composite material and the solid modified nano-cellulose emulsion, the nano-cellulose hollow microsphere composite material provided by the embodiment of the invention improves the dispersibility in a solvent and reduces aggregation; 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, so that the use comfort of the base material in the fields of fabrics, leather and the like is improved.
The nano cellulose hollow microsphere prepared by the method is formed into a film on a substrate or a coating material is obtained by forming the film on the nano cellulose hollow microsphere, when water vapor and gas pass through a coating film, the hollow structure can shorten the gas molecule passing path, improve the gas diffusion rate and improve the air 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 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 until the weight is constant, thus obtaining white solid powder, and obtaining the modified nano-cellulose Pickering emulsifier.
2) Preparing a modified nano cellulose aqueous solution: 1 part of the modified nano cellulose prepared in the step 1 is weighed and dissolved in deionized water to obtain a modified nano cellulose aqueous solution; wherein the mass concentration of the modified nano cellulose solution is 0.1g/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 mixed solution of dichloromethane and acrylic ester monomers (wherein the ratio of the dichloromethane to the acrylic ester monomers is 10:1), and the mass ratio of the oil phase to the water phase is 2:8; emulsifying for 3min under the action of a high shear dispersing machine to obtain Pickering emulsion; 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, preserving heat and stirring for 90min after the dropwise adding is finished, stopping heating, naturally cooling to 10 ℃, and stirring and volatilizing for 1h at an opening 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, carrying out ultrasonic treatment for 15min, then adding the nano cellulose anhydrous pyridine solution into a 100mL three-neck flask, adding 25 parts of acetic anhydride, stirring for 8h at room temperature, precipitating the esterified and 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 until the weight is constant, thus obtaining white solid powder, and obtaining the esterified and modified nano cellulose Pickering emulsifier.
2) Preparing a modified nano cellulose aqueous solution: 1 part of the modified nano cellulose prepared in the step 1 is weighed and dissolved in deionized water to obtain a modified nano cellulose aqueous solution; wherein the mass concentration of the modified nano cellulose solution is 0.1g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: mixing the modified nanocellulose aqueous solution obtained in the step 2 with 38.4 parts of mixed solution of dichloromethane and acrylic ester monomers (the ratio of dichloromethane to acrylic ester monomers is 15:1), wherein the mass ratio of oil phase to water phase is 4:6, and emulsifying for 6min under the action of a high-shear dispersing machine to obtain Pickering emulsion; 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, preserving heat and stirring for 100min after the dropwise adding is finished, stopping heating, naturally cooling to 15 ℃, and stirring and volatilizing for 2h at an opening 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, precipitating the esterified and 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 until the weight is constant, thus obtaining white solid powder, and obtaining the esterified and modified nano cellulose Pickering emulsifier.
2) Preparing a modified nano cellulose aqueous solution: weighing 3 parts of the modified nano cellulose prepared in the step 1, and dissolving the modified nano cellulose into deionized water to obtain a modified nano cellulose aqueous solution; wherein the mass concentration of the modified nano cellulose solution is 0.1g/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 acrylic ester monomers (the ratio of the dichloromethane to the acrylic ester monomers is 20:1) for 9min under the action of a high-shear dispersing machine, wherein the mass ratio of the oil phase to the water phase is 5:5, so as to obtain Pickering emulsion; 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, preserving heat and stirring for 110min after the dropwise adding is finished, stopping heating, naturally cooling to 20 ℃, and stirring and volatilizing for 3h at an opening to obtain the nano-cellulose hollow microsphere composite material.
Fig. 1 is a scanning electron microscope photograph of the nanocellulose hollow microsphere prepared in example 3, and it can be seen from fig. 1: the nano cellulose hollow microspheres show a spherical structure, the size is about 500nm, the nano cellulose hollow microspheres are mutually extruded and deformed to form a continuous coating, part of the hollow microspheres are extruded to form a convex spherical structure, the inside of the coating is a porous hollow structure, and the coating structure endows the substrate 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, precipitating the esterified and 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 until the weight is constant, thus obtaining white solid powder, and obtaining the esterified and modified nano cellulose Pickering emulsifier.
2) Preparing a modified nano cellulose aqueous solution: weighing 4 parts of the modified nano cellulose prepared in the step 1, and dissolving the modified nano cellulose into deionized water to obtain a modified nano cellulose aqueous solution; wherein the mass concentration of the modified nano cellulose solution is 0.1g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: mixing the modified nanocellulose aqueous solution obtained in the step 2 with 57.6 parts of mixed solution of dichloromethane and acrylic ester monomers (the ratio of dichloromethane to acrylic ester monomers is 25:1), wherein the mass ratio of oil phase to water phase is 6:4, and emulsifying for 12min under the action of a high-shear dispersing machine to obtain Pickering emulsion; 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, carrying out heat preservation and stirring for 120min after the dropwise adding is finished, stopping heating, naturally cooling to 25 ℃, and carrying out open 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 at room temperature for 14h, precipitating 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 until the weight is constant, thus obtaining white solid powder, and obtaining 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 into deionized water to obtain a modified nano cellulose aqueous solution; wherein the mass concentration of the modified nano cellulose solution is 0.1g/mL.
3) Preparing a nano-cellulose hollow microsphere composite material: mixing the modified nanocellulose aqueous solution obtained in the step 2 with 76.8 parts of mixed solution of dichloromethane and acrylic ester monomers (the ratio of dichloromethane to acrylic ester monomers is 30:1), and emulsifying the mixture for 15min under the action of a high-shear dispersing machine, wherein the mass ratio of an oil phase to a water phase is 8:2, so as to obtain Pickering emulsion; 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, preserving heat and stirring for 130min after the dropwise adding is finished, stopping heating, naturally cooling to 30 ℃, and stirring and volatilizing for 5h at an opening to obtain the nano-cellulose hollow microsphere composite material.
The nanocellulose hollow microsphere prepared in the embodiment and the modification obtained in the step 1 are subjected toThe nano cellulose aqueous solution is respectively formed into a film on a substrate to respectively obtain a nano cellulose hollow microsphere coating material and a modified nano cellulose coating material, and the nano cellulose hollow microsphere coating material and the modified nano cellulose coating material are subjected to fabric finishing and water vapor permeability testing. Specifically, the nanocellulose hollow microspheres and the modified nanocellulose are diluted to have the same solid content, and are arranged on a fabric in a two-dip two-roll mode, so that a coating film is formed on the surface of the fabric, and the mass of the coating film is recorded as m 0 Placing a fabric sample in a moisture permeable cup containing deionized water, wherein the weight of the fabric sample is m 1 Then the moisture permeable cup is placed in a concentrated sulfuric acid dryer, and the mass of the moisture permeable cup is recorded to be m after 24 hours 2 The water vapor permeability through the same fabric area in 24h is w=m 1 -m 2 The results are shown in Table one. It can be seen that the nano-cellulose hollow microsphere coating film has obvious water vapor permeability after 24 hours.
Table I results of the fabric Water vapor permeability test
Claims (4)
1. The preparation method of the nanocellulose 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;
comprising the following steps: carrying out ultrasonic treatment on 70-90 parts of nanocellulose anhydrous pyridine solution for 10-30 min, then adding 10-30 parts of modifier into the nanocellulose anhydrous pyridine solution, stirring the mixture at room temperature for 6-14 h, and after the reaction is finished, preparing an esterified modified nanocellulose Pickering emulsifier;
the modifier is any one of succinic anhydride, acetic anhydride, maleic anhydride, methacrylic acid and acrylic acid;
step 2, dispersing the modified nanocellulose Pickering emulsifier into deionized water to obtain a modified nanocellulose aqueous solution;
the mass concentration of the modified nano cellulose aqueous solution is 0.1g/mL;
step 3, taking the modified nano-cellulose aqueous solution as a water phase, taking 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;
comprising 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 Pickering emulsion; 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 into the Pickering emulsion, after the dropwise adding is finished, preserving heat and stirring for 90-130 min, stopping heating, naturally cooling to 10-30 ℃, and volatilizing the solvent to obtain the nano-cellulose hollow microsphere composite material;
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;
the mixed solution of the dichloromethane and the acrylic ester monomer comprises the dichloromethane and the acrylic ester monomer, and the mass ratio of the dichloromethane to the acrylic ester monomer is 30:1-10:1.
2. The method for preparing a nanocellulose hollow microsphere composite material according to claim 1, wherein in step 1, the mass concentration of the nanocellulose anhydrous pyridine solution is 0.1g/mL.
3. The method for preparing a nanocellulose hollow microsphere composite material as claimed in claim 1 wherein in step 3, the cross-linking agent is glutaraldehyde, ethylene glycol dimethacrylate or epoxysilane XR-500.
4. A nanocellulose hollow microsphere coating material, comprising: a membrane layer of nanocellulose hollow microsphere composite material attached to a substrate prepared by the method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110601960.3A CN114369202B (en) | 2021-05-31 | 2021-05-31 | Preparation method of nanocellulose hollow microsphere and coating material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110601960.3A CN114369202B (en) | 2021-05-31 | 2021-05-31 | Preparation method of nanocellulose hollow microsphere and coating material thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114369202A CN114369202A (en) | 2022-04-19 |
| CN114369202B true CN114369202B (en) | 2023-07-14 |
Family
ID=81137850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110601960.3A Active CN114369202B (en) | 2021-05-31 | 2021-05-31 | Preparation method of nanocellulose hollow microsphere and coating material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114369202B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612120B (en) * | 2022-10-10 | 2024-04-19 | 四川大学 | Method for preparing novel aqueous polyurethane based on Pickering emulsion method |
| CN116606578B (en) * | 2023-04-14 | 2024-08-09 | 中国皮革制鞋研究院有限公司 | Leather finishing agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650353A (en) * | 2015-03-19 | 2015-05-27 | 桂林理工大学 | Method for preparing conductive polymer microsphere by stabilizing Pickering emulsion through nanocellulose |
| WO2017121369A1 (en) * | 2016-01-14 | 2017-07-20 | 陕西科技大学 | Slow-release mildew-proof casein-based hollow microsphere coating material and preparation method therefor |
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
| FR3060982A1 (en) * | 2016-12-22 | 2018-06-29 | L'oreal | AQUEOUS PHOTOPROTECTIVE COMPOSITION CONTAINING POLYACRYLATE CONCENTRATED PARTICLES AND AT LEAST ONE WATER SOLUBLE ORGANIC UV FILTER |
| WO2020093137A1 (en) * | 2018-11-08 | 2020-05-14 | Fpinnovations | Polymer microspheres of hierarchically structured cellulose nanocrystals and method to produce the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130428B (en) * | 2017-06-15 | 2019-02-01 | 东华大学 | A kind of superhydrophobic fabric and preparation method thereof |
-
2021
- 2021-05-31 CN CN202110601960.3A patent/CN114369202B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650353A (en) * | 2015-03-19 | 2015-05-27 | 桂林理工大学 | Method for preparing conductive polymer microsphere by stabilizing Pickering emulsion through nanocellulose |
| WO2017121369A1 (en) * | 2016-01-14 | 2017-07-20 | 陕西科技大学 | Slow-release mildew-proof casein-based hollow microsphere coating material and preparation method therefor |
| FR3060982A1 (en) * | 2016-12-22 | 2018-06-29 | L'oreal | AQUEOUS PHOTOPROTECTIVE COMPOSITION CONTAINING POLYACRYLATE CONCENTRATED PARTICLES AND AT LEAST ONE WATER SOLUBLE ORGANIC UV FILTER |
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
| WO2020093137A1 (en) * | 2018-11-08 | 2020-05-14 | Fpinnovations | Polymer microspheres of hierarchically structured cellulose nanocrystals and method to produce the same |
Non-Patent Citations (4)
| Title |
|---|
| A Solvent Co-cross-linked Organogel with Fast Self-Healing Capability and Reversible Adhesiveness at Extreme Temperatures;Xing Su等;ACS Applied Materials & Interfaces;第12卷;29757−29766 * |
| NCC/AESO Pickering乳液的制备及其改善纸张水蒸气阻隔性能的研究;刘仁;中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(第2期);B016-776 * |
| Starch-based films enriched with nanocellulose-stabilized Pickering emulsions containing different essential oils for possible applications in food packaging;Alana G. Souza等;Food Packaging and Shelf Life;第27卷;100615（1-11） * |
| 纳米纤维素基无机复合抗菌膜材料的研究进展;刘威等;浙江理工大学学报;第45卷(第2期);273-283 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114369202A (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114369202B (en) | Preparation method of nanocellulose hollow microsphere and coating material thereof | |
| CN103147290B (en) | Functional nano textile and preparation method thereof | |
| CN108329490A (en) | A kind of preparation method of the degradable composite barrier material of polylactic acid/modified nanometer cellulose | |
| CN107938169B (en) | A kind of POSS modified nano fiber film and its preparation method and application | |
| BRPI0919455A2 (en) | aqueous binder, use of an aqueous binder, process for producing molded articles from fibrous and / or granular substrates, and molded articles | |
| CN108795018B (en) | Preparation method of polyurethane/cellulose multifunctional shape memory polymer material | |
| CN101899128A (en) | Hollow nano silica microsphere modified polyacrylate nuclear shell structure composite emulsion and thin film | |
| CN110560016B (en) | Preparation method of patulin molecularly imprinted nanofiber membrane | |
| CN115093684B (en) | Modified degradation material for improving melt strength and preparation method thereof | |
| CN105273216B (en) | 3 D stereo surpasses the preparation method of fold polylactic acid microsphere | |
| CN111286852B (en) | Preparation method of long-acting anti-fouling fabric based on nanogel treatment | |
| CN116333175A (en) | Microcrystalline cellulose modification method, composite packaging film and preparation method | |
| CN115636986A (en) | Nano-cellulose composite filler and preparation method and application thereof | |
| CN114990883A (en) | Preparation and application of Janus film with structural color | |
| CN106995601B (en) | A kind of biodegradable polymers composite material and preparation method | |
| CN109354851A (en) | A kind of preparation method of biology base unsaturated polyester resin flame-retardant composite material | |
| CN105820356A (en) | Preparation method of photocrosslinked polyvinyl alcohol/nanocrystal cellulose (PVA/CNC) composite film | |
| CN106832085A (en) | A kind of high temperature resistant, high rigidity acrylate and vinyl acetate emulsion of color inhibition and preparation method thereof | |
| CN105544193A (en) | Hydrophilic modification method for polyester fibers with bromoethane and PVA | |
| CN110903606A (en) | Plant oil-based composite material and preparation method thereof | |
| CN110437595A (en) | A kind of antistatic biodegradable polymers composite material and preparation method | |
| CN115873170B (en) | Preparation of fluorine-containing porous material and nano microsphere by amphiphilic polyphosphazene stabilized fluorine-containing emulsion | |
| CN114957567A (en) | Method for grafting sodium p-styrenesulfonate monomer on polyether-ether-ketone and application | |
| CN113430673A (en) | Anti-aging nano zinc oxide modified polylactic acid fiber and preparation method thereof | |
| CN112144306B (en) | Water-based pigment printing adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |