CN110194885B - Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane - Google Patents
Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane Download PDFInfo
- Publication number
- CN110194885B CN110194885B CN201910485306.3A CN201910485306A CN110194885B CN 110194885 B CN110194885 B CN 110194885B CN 201910485306 A CN201910485306 A CN 201910485306A CN 110194885 B CN110194885 B CN 110194885B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- polylactic acid
- nano
- stirring
- titanium dioxide
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a preparation method of a modified nano-cellulose reinforced polylactic acid composite membrane, which comprises the following steps: preparing nano-cellulose by a sulfuric acid method, then preparing titanium dioxide modified nano-cellulose, and finally obtaining the polylactic acid composite membrane by a solution pouring method. According to the invention, the titanium dioxide modified nano-cellulose is compounded with polylactic acid, the problem of poor compatibility of the nano-cellulose and polylactic acid matrix is solved by modifying with titanium dioxide, the adhesion effect of an interface is improved, and the polylactic acid is enhanced by modifying the nano-cellulose with titanium dioxide.
Description
Technical Field
The invention belongs to the field of preparation of polylactic acid composite membranes, and particularly relates to a preparation method of a modified nano-cellulose reinforced polylactic acid composite membrane.
Background
The polylactic acid can be processed by renewable plant resources such as corn, sugarcane, beet and the like, and has wide sources and rich industrial resources; polylactic acid is a biodegradable polymer, and the final decomposition products are water and carbon dioxide, so that no toxic gas is discharged. Polylactic acid has many excellent properties such as high rigidity, light weight, and in addition, good molding processability such as low process temperature, good thermoplasticity, heat-sealability, etc. Therefore, polylactic acid is one of the representatives of commercialization in the market as an environment-friendly bio-based plastic, and has strong competitiveness and broad prospects. However, polylactic acid has the disadvantages of low thermal stability, poor toughness, poor impact resistance and the like, and the application potential of the polylactic acid in various fields is limited. Therefore, the toughening modification of the polylactic acid has very important significance.
Cellulose is also widely sourced from various agricultural material resources, and the industrial scale is large. Nanocellulose has many excellent properties, such as high strength, high young's modulus, high hydrophilicity, high crystallinity, etc., while having degradable and biocompatible properties, and is commonly used to reinforce polymers to obtain composite materials with excellent properties. The nano-cellulose has the defects of easy agglomeration and poor dispersibility, and can be improved by modifying organic or inorganic nano-particles. The titanium dioxide modified nano-cellulose has no related research report and has certain novelty. The titanium dioxide modified nano-cellulose reinforced polylactic acid can play a role in reinforcing the nano-cellulose and improve the mechanical property of the polylactic acid, thereby widening the application field of the polylactic acid.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a modified nano-cellulose reinforced polylactic acid composite membrane, overcoming the defects of complicated experimental steps of adding an activating agent, a coupling agent, a catalyst, a dispersing agent and the like and limited physical mixing effect by adopting a mixer in the prior art.
The composite membrane is prepared by directly pouring titanium dioxide modified nanocellulose and polylactic acid through solution.
The preparation method of the polylactic acid composite membrane comprises the following steps:
(1) preparing nano titanium dioxide modified nano cellulose:
dissolving nano-cellulose with water under stirring to obtain a nano-cellulose suspension, adjusting the pH value to be less than or equal to 3, then adding a titanium tetrachloride solution into the nano-cellulose suspension under ice bath and magnetic stirring, standing for 2-4h until the color of the mixed solution turns grey, heating to 55-65 ℃ under stirring, keeping for 1-2h, enabling the mixed solution to become transparent, adjusting the solution to be neutral, aging at room temperature, filtering to separate a white precipitate, washing with distilled water, and drying a filter cake in a vacuum freeze dryer to obtain powdery titanium dioxide modified nano-cellulose; wherein the ratio of the nano-cellulose to the titanium tetrachloride is 1: 0.001-0.01;
(2) preparing a titanium dioxide modified nanocellulose reinforced polylactic acid composite membrane by a solution pouring method:
dissolving polylactic acid in a solvent under magnetic stirring, adding titanium dioxide modified nano-cellulose, dissolving, performing ultrasonic dispersion, vacuum degassing, spreading the mixed solution on a substrate, and drying at room temperature to obtain the modified nano-cellulose reinforced polylactic acid composite membrane.
The preferred mode of the above preparation method is as follows:
in the step (1), the nanocellulose is prepared by adopting a sulfuric acid method: the specific nano-cellulose is prepared by the following method: mixing paper pulp and a sulfuric acid solution, stirring to obtain a suspension, diluting, centrifuging at a high speed, washing, centrifuging again, dialyzing, performing ultrasonic treatment, and drying to obtain nano cellulose; wherein the mass volume ratio of the paper pulp to the sulfuric acid is 1 g: 10-50 mL.
In the preparation method of the nano-cellulose, the stirring time is 0.5-1 h; the dilution is performed by adopting 10 times of deionized water; the high-speed centrifugation is as follows: the centrifugation speed is 9000r/min, and the centrifugation time is 10-30 min; after washing, the centrifugation is as follows: rinsing (washing) the precipitate with distilled water, centrifuging again, and repeating for 4-6 times; the ultrasonic treatment comprises the following steps: the power is 40QW, and the ultrasonic time is 3-5 minutes.
The ratio of the nano-cellulose to the water in the nano-cellulose suspension in the step (1) is 1 g: 100 and 200 mL.
Heating to 55-65 ℃ under the stirring condition in the step (1), specifically adopting a hot plate, and adjusting to 55-65 ℃ under the stirring condition; the adjusting solution is neutral: 35 percent (volume percentage) of ammonia water is added dropwise until the solution is neutral.
The aging time in the step (1) is 12-24 h.
The ratio of the polylactic acid to the solvent in the step (2) is 1 g: 25-100 ml; the mass ratio of the titanium dioxide modified nano-cellulose to the polylactic acid is 0.01-0.05: 1;
the solvent is dichloromethane; the polylactic acid has a number average molecular weight of 120000.
In the step (2), the magnetic stirring temperature is 50-70 ℃ and the time is 2-8 h; the ultrasonic dispersion time is 20-30 min; vacuum degassing for 0.5-1 h; drying at room temperature for 12-24 h.
Further, in the step (2), the magnetic stirring temperature is 70 ℃ and the time is 2 hours; the ultrasonic dispersion time is 30 min; the vacuum degassing time is 0.5 h; the drying time at room temperature was 24 h.
The substrate in the step (2) is a polytetrafluoroethylene plate.
The invention relates to a polylactic acid composite membrane prepared by the method.
The invention provides an application of the polylactic acid composite membrane.
Advantageous effects
According to the invention, the titanium dioxide modified nano-cellulose is compounded with polylactic acid, the experimental steps are simple, experimental auxiliaries such as an activating agent, a coupling agent, a catalyst and a dispersing agent in the prior art are not required to be added, the problem of poor compatibility of the nano-cellulose and the polylactic acid matrix is solved by modifying with the titanium dioxide, the adhesion effect of an interface is improved by adopting a chemical blending method, and the polylactic acid is enhanced by modifying the nano-cellulose with the titanium dioxide.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used are shown in table 1.
Raw materials used in Table 1
Tensile Property test the tensile properties of the plastics were determined according to GB/T1040-.
Example 1
5g of pulp cellulose are mixed with 100ml of a 64% sulfuric acid solution at 50 ℃ for 1 hour with vigorous stirring at 750 r/min. The suspension was diluted with 10 times deionized water. The dilution was then centrifuged at 9000r/min for 30 minutes to precipitate the cellulose and remove excess acid. The precipitate was rinsed with distilled water and centrifuged again, and the process was repeated 4-6 times. Dialyzing with distilled water until the dialysate is neutral. And (3) carrying out ultrasonic treatment on the neutralized suspension in an ultrasonic cell crusher at the ultrasonic power of 40QW for 5 minutes to obtain a suspension of the nano cellulose. And finally drying in a vacuum freeze dryer to obtain powdery nano cellulose.
Weighing 10g of prepared nano-cellulose, using 1500ml of deionized water to magnetically stir and fully dissolve the nano-cellulose to obtain nano-cellulose suspension, dropwise adding sulfuric acid, and adjusting the pH value to be less than or equal to 3. 3.3ml of titanium tetrachloride solution was added to the suspension with magnetic stirring, with the temperature controlled in an ice bath. After 2h when the mixture turns grey, it is transferred to a hot plate and adjusted to 65 ℃ with stirring. After 1h, when the mixed solution becomes transparent, 35% ammonia water is dripped until the mixed solution is neutral. With the addition of ammonia, the mixture turned milky white. And aging the neutralized mixed solution at room temperature for 24 hours, filtering and separating white precipitate, washing with distilled water for 2-3 times, and drying a filter cake in a vacuum freeze dryer to obtain the powdery titanium dioxide modified nano-cellulose.
Weighing 2g of polylactic acid, magnetically stirring for 2 hours at 70 ℃, dissolving in 25ml of dichloromethane, adding 0.02g of prepared titanium dioxide modified nanocellulose, ultrasonically dispersing for 30 minutes after complete dissolution, vacuum degassing for 0.5 hour, paving the mixed solution on a flat polytetrafluoroethylene plate, and drying for 24 hours at room temperature to obtain the modified nanocellulose reinforced polylactic acid composite membrane.
The tensile strength of the film sample prepared by the method is 46.86MPa by using a tensile test of 15 mm multiplied by 100 mm. Compared with the prior art, the required energy consumption and the material cost are greatly reduced.
Example 2
5g of pulp cellulose are mixed with 100ml of 64% sulfuric acid solution at 50 ℃ for 1 hour with vigorous stirring at 750 r/min. The suspension was diluted with 10 times deionized water. The dilution was then centrifuged at 9000r/min for 30 minutes to precipitate the cellulose and remove excess acid. The precipitate was rinsed with distilled water and centrifuged again, and the process was repeated 4-6 times. Dialyzing with distilled water until the dialysate is neutral. And (3) carrying out ultrasonic treatment on the neutralized suspension in an ultrasonic cell crusher at the ultrasonic power of 40QW for 5 minutes to obtain a suspension of the nano cellulose. And finally drying in a vacuum freeze dryer to obtain powdery nano cellulose.
Weighing 10g of prepared nano-cellulose, using 1500ml of deionized water to magnetically stir and fully dissolve the nano-cellulose to obtain nano-cellulose suspension, dropwise adding sulfuric acid, and adjusting the pH value to be less than or equal to 3. 10ml of titanium tetrachloride solution was added to the suspension with magnetic stirring, with the temperature controlled in an ice bath. After 3h when the mixture turns grey, it is transferred to a hot plate and adjusted to 65 ℃ with stirring. After 1.5h, when the mixed solution becomes transparent, 35% ammonia water is added dropwise until the mixed solution is neutral. With the addition of ammonia, the mixture turned milky white. And aging the neutralized mixed solution at room temperature for 24 hours, filtering and separating white precipitate, washing with distilled water for 2-3 times, and drying a filter cake in a vacuum freeze dryer to obtain the powdery titanium dioxide modified nano-cellulose.
Weighing 2g of polylactic acid, magnetically stirring for 2 hours at 70 ℃, dissolving in 25ml of dichloromethane, adding 0.02g of prepared titanium dioxide modified nanocellulose, ultrasonically dispersing for 30 minutes after complete dissolution, vacuum degassing for 0.5 hour, paving the mixed solution on a flat polytetrafluoroethylene plate, and drying for 24 hours at room temperature to obtain the modified nanocellulose reinforced polylactic acid composite membrane.
The tensile strength of the film sample prepared by the method is 52.17MPa when the tensile test is carried out by using 15 mm multiplied by 100mm of the film sample prepared by the method.
Example 3
5g of pulp cellulose are mixed with 100ml of 64% sulfuric acid solution at 50 ℃ for 1 hour with vigorous stirring at 750 r/min. The suspension was diluted with 10 times deionized water. The dilution was then centrifuged at 9000r/min for 30 minutes to precipitate the cellulose and remove excess acid. The precipitate was rinsed with distilled water and centrifuged again, and the process was repeated 4-6 times. Dialyzing with distilled water until the dialysate is neutral. And (3) carrying out ultrasonic treatment on the neutralized suspension in an ultrasonic cell crusher at the ultrasonic power of 40QW for 5 minutes to obtain a suspension of the nano cellulose. And finally drying in a vacuum freeze dryer to obtain powdery nano cellulose.
Weighing 10g of prepared nano-cellulose, using 1500ml of deionized water to magnetically stir and fully dissolve the nano-cellulose to obtain nano-cellulose suspension, dropwise adding sulfuric acid, and adjusting the pH value to be less than or equal to 3. 16.7ml of titanium tetrachloride solution are added to the suspension with magnetic stirring, the temperature being controlled in an ice bath. After 4h when the mixture turns grey, it is transferred to a hot plate and adjusted to 65 ℃ with stirring. After the mixed solution becomes transparent for 2 hours, 35 percent ammonia water is dripped until the mixed solution is neutral. With the addition of ammonia, the mixture turned milky white. And aging the neutralized mixed solution at room temperature for 24 hours, filtering and separating white precipitate, washing with distilled water for 2-3 times, and drying a filter cake in a vacuum freeze dryer to obtain the powdery titanium dioxide modified nano-cellulose.
Weighing 2g of polylactic acid, magnetically stirring for 2 hours at 70 ℃, dissolving in 25ml of dichloromethane, adding 0.02g of prepared titanium dioxide modified nanocellulose, ultrasonically dispersing for 30 minutes after complete dissolution, vacuum degassing for 0.5 hour, paving the mixed solution on a flat polytetrafluoroethylene plate, and drying for 24 hours at room temperature to obtain the modified nanocellulose reinforced polylactic acid composite membrane.
Tensile test was carried out using a self-made film specimen 15X 100mm, and the tensile strength reached 41.53 MPa.
Claims (8)
1. A preparation method of a polylactic acid composite membrane comprises the following steps:
(1) dissolving nano-cellulose in water by stirring to obtain a nano-cellulose suspension, adjusting the pH to be less than or equal to 3, adding a titanium tetrachloride solution into the nano-cellulose suspension under ice bath and magnetic stirring, standing, heating to 55-65 ℃ under the stirring condition, keeping for 1-2h, adjusting the solution to be neutral, aging at room temperature, filtering, washing and drying to obtain titanium dioxide modified nano-cellulose;
(2) dissolving polylactic acid in a solvent under magnetic stirring, adding titanium dioxide modified nano-cellulose, dissolving, performing ultrasonic dispersion, vacuum degassing, spreading the mixed solution on a substrate, and drying at room temperature to obtain the modified nano-cellulose reinforced polylactic acid composite membrane.
2. The method according to claim 1, wherein the nanocellulose in step (1) is prepared by: mixing paper pulp and a sulfuric acid solution, stirring to obtain a suspension, diluting, centrifuging, washing, centrifuging again, dialyzing, performing ultrasonic treatment, and drying to obtain nano cellulose; wherein the mass volume ratio of the paper pulp to the sulfuric acid is 1 g: 10-50 mL.
3. The method according to claim 1, wherein the ratio of the nanocellulose and the water in the nanocellulose suspension in the step (1) is 1 g: 100 and 200 mL.
4. The preparation method according to claim 1, wherein the heating to 55-65 ℃ under stirring in step (1) is carried out by using a hot plate and adjusting to 55-65 ℃ under stirring; the adjusting solution is neutral: and dropwise adding 35% ammonia water until the solution is neutral.
5. The method according to claim 1, wherein the aging time in the step (1) is 12 to 24 hours.
6. The method according to claim 1, wherein the ratio of polylactic acid to the solvent in the step (2) is 1 g: 25-100 ml; the mass ratio of the titanium dioxide modified nano-cellulose to the polylactic acid is 0.01-0.05: 1; the solvent is dichloromethane; the polylactic acid has a number average molecular weight of 120000.
7. The preparation method according to claim 1, wherein the magnetic stirring temperature in the step (2) is 50-70 ℃ and the time is 2-8 h; the ultrasonic dispersion time is 20-30 min; vacuum degassing for 0.5-1 h; drying at room temperature for 12-24 h.
8. A polylactic acid composite membrane prepared by the method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485306.3A CN110194885B (en) | 2019-06-05 | 2019-06-05 | Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485306.3A CN110194885B (en) | 2019-06-05 | 2019-06-05 | Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110194885A CN110194885A (en) | 2019-09-03 |
| CN110194885B true CN110194885B (en) | 2021-09-21 |
Family
ID=67753942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910485306.3A Active CN110194885B (en) | 2019-06-05 | 2019-06-05 | Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110194885B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007034726A1 (en) * | 2007-07-23 | 2009-01-29 | Henkel Ag & Co. Kgaa | Removal of by-products from crosslinkable preparations |
| CN103934036B (en) * | 2014-04-24 | 2016-06-15 | 北京科技大学 | A kind of preparation method of titanium dioxide-cellulose composite material |
| CN104693464B (en) * | 2015-02-10 | 2018-01-02 | 北京林业大学 | A kind of preparation method of lignin nano-cellulose enhancing polymeric lactic acid compound film |
| CN107033562A (en) * | 2016-11-28 | 2017-08-11 | 盐城工学院 | Root of kudzu vine nano-cellulose fiber polylactic acid plastic film and preparation method thereof |
| CN108329490A (en) * | 2018-03-22 | 2018-07-27 | 常德市金润新材料科技有限公司 | A kind of preparation method of the degradable composite barrier material of polylactic acid/modified nanometer cellulose |
-
2019
- 2019-06-05 CN CN201910485306.3A patent/CN110194885B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110194885A (en) | 2019-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105566872B (en) | Poly-dopamine modified lithium halloysite nanotubes/lactic acid composite material and its preparation and application | |
| WO2015037658A1 (en) | Cellulose nanofibers, method for producing same, aqueous dispersion using cellulose nanofibers, and fiber-reinforced composite material | |
| CN111349253B (en) | Modified lignin/PBS (Poly Butylene succinate) bioplastic film and preparation method thereof | |
| CN103044871A (en) | Preparation method of polylactic acid/nano-cellulose composite material | |
| Oksman et al. | Novel bionanocomposites: processing, properties and potential applications | |
| CN111690240A (en) | Polylactic acid/nano cellulose composite material and preparation method thereof | |
| CN106009570B (en) | PLA bamboo nano-cellulose whisker ultra micro bamboo charcoal composite material method for manufacturing thin film | |
| CN105153660A (en) | Full-biodegradation bacterial cellulose/polylactic acid composite material and preparing method thereof | |
| CN109135226B (en) | Polylactic acid/polyaniline/nanocrystalline cellulose composite conductive film and preparation method thereof | |
| CN116970242B (en) | Calcium sulfate whisker reinforced polypropylene and preparation method thereof | |
| CN109232935A (en) | One kind is based on poly (arylene ether nitrile) pen film material and its preparation and application | |
| Gu et al. | Natural lignin nanoparticles: a promising nano-crosslinker for constructing fluorescent photoswitchable supramolecular hydrogels | |
| CN112194884A (en) | Modified cellulose whisker composite high polymer material and preparation method and application thereof | |
| CN110194885B (en) | Preparation method of modified nano-cellulose reinforced polylactic acid composite membrane | |
| CN115433442B (en) | Biodegradable tough composite material and preparation method thereof | |
| CN110903606B (en) | Plant oil-based composite material and preparation method thereof | |
| CN101831001B (en) | Method for preparing konjak glucomannan acetate thermoplastic material | |
| CN110128803A (en) | A kind of preparation method of modified BCW/PHBV composite material | |
| CN116253972A (en) | Preparation method of reinforced PBT composite material | |
| CN102030892B (en) | Preparation method of glutinous rice flour grafted polycaprolactone thermoplastic material | |
| AU2022326295A1 (en) | Type ii unmodified cellulose microfibers, and method for manufacturing type ii unmodified cellulose microfibers and compact of same | |
| CN108395579A (en) | A kind of preparation method of novel high-strength complex fiber material | |
| CN113604019A (en) | High-toughness polylactic acid composite material and preparation method thereof | |
| CN110437503A (en) | The nano-cellulose base aeroge and preparation method thereof of chemical crosslinking enhancing is cooperateed with based on Electrostatic Absorption | |
| CN109265609A (en) | A kind of grafting hollow ball 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 |