CN114672055B - Preparation of degradable hydrophobic film with terminal cationic starch as base material - Google Patents
Preparation of degradable hydrophobic film with terminal cationic starch as base material Download PDFInfo
- Publication number
- CN114672055B CN114672055B CN202210442928.XA CN202210442928A CN114672055B CN 114672055 B CN114672055 B CN 114672055B CN 202210442928 A CN202210442928 A CN 202210442928A CN 114672055 B CN114672055 B CN 114672055B
- Authority
- CN
- China
- Prior art keywords
- starch
- film
- terminal
- silicone oil
- degradable hydrophobic
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
-
- 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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/08—Ethers
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/08—Ethers
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
Abstract
The invention discloses a preparation method of a degradable hydrophobic film taking terminal cationic starch as a base material, belonging to the technical field of high polymer materials. The invention flows the terminal cationic starch into a film under the action of an external electric field under certain conditions, and then the surface of the starch film is modified by hydrophobization by using the hydroxyl silicone oil, so that the interfacial tension of the surface of the starch film is reduced, the hydrophobicity of the starch is improved, and finally the starch composite film with better mechanical property and hydrophobicity is obtained. The mechanical property of the degradable hydrophobic film is greatly improved, the breaking strength of the degradable hydrophobic film is improved by 85 percent compared with that of a starch film without an electric field, and the degradable hydrophobic film has anisotropy of mechanical property; the contact angle is improved by 83.3 percent after the hydroxyl silicone oil is treated.
Description
Technical Field
The invention relates to a preparation method of a degradable hydrophobic film taking terminal cationic starch as a base material, belonging to the technical field of high polymer materials.
Background
Starch is one of the most abundant organic high molecular compounds in nature and is produced by plant growth and metabolism in nature. Starch is widely applied in the fields of textile, light industry, chemical industry, national defense, petroleum, medicine, energy, biotechnology and the like.
Because starch molecules are of a polyhydroxy structure and have strong hydrophilicity and hygroscopicity, the formed film has low moisture barrier property and high moisture sensitivity, and the mechanical property of the film is greatly changed when the environmental humidity is changed, so that the application of the starch film is severely limited.
The hydroxyl silicone oil is widely applied to improving the hydrophobic property of materials such as fiber fabrics, films and the like due to lower interfacial tension and good film forming property.
Disclosure of Invention
In order to solve the problems, the invention improves the hydrophobicity of the starch film by a surface coating technology. The method comprises the following main processes of firstly modifying starch, introducing alkynyl to the reducing tail end of the starch through a reductive amination method, then carrying out click chemical reaction on alpha-azide-Boc reagent to obtain starch with a Boc group at the tail end, and finally carrying out Boc deprotection reaction to obtain terminal cationic starch; secondly, the starch film is formed by casting under the action of an external electric field; and finally, carrying out hydrophobic modification treatment on the surface of the starch film by using hydroxyl silicone oil.
A first object of the present invention is to provide a method for preparing a degradable hydrophobic film, the method comprising:
dispersing terminal cationic starch, hydroxypropyl starch and sorbitol in water, uniformly mixing, and heating for gelatinization to obtain a membrane solution; then the film liquid is casted into a film under the action of an external electric field; then spraying the hydroxyl silicone oil solution on the film, and curing to obtain the degradable hydrophobic film;
the terminal cationic starch is prepared by the following method:
(1) Modifying starch with propylene oxide to obtain hydroxypropyl starch (HPHACS);
(2) Carrying out condensation reaction on the obtained hydroxypropyl starch and propargylamine serving as substrates to obtain terminal alkyne starch;
(3) Dispersing the obtained terminal alkyne starch and N-Boc-3-azido-propylamine in N, N-dimethylformamide, and adding a catalyst for reaction; then adding a mixed solution of trifluoroacetic acid and dichloromethane for continuous reaction; after the reaction is finished, the reaction product is concentrated, extracted and washed to obtain Terminal Cationic Starch (TCS).
In one embodiment of the invention, the mass ratio of terminal cationic starch to hydroxypropyl starch is 5.
In one embodiment of the present invention, sorbitol is added in an amount of 10wt% with respect to the total mass of the terminal cationic starch and hydroxypropyl starch.
In one embodiment of the invention, the temperature for heating and pasting is 90-100 ℃; the time is 1h.
In one embodiment of the present invention, the condition of the applied electric field is 10 to 20V/mm.
In one embodiment of the invention, the mass fraction of the hydroxyl silicone oil relative to the total mass of the terminal cationic starch and the hydroxypropyl starch is 2-6%. Preferably 4%.
In one embodiment of the present invention, the mass ratio of the hydroxy silicone oil to the curing agent thereof in the hydroxy silicone oil solution is 10. The hydroxyl silicone oil solution and the curing agent are fixedly matched and can be purchased from Jinan Xingfeng Huanlong chemical company, inc.
In one embodiment of the invention, the medium of the hydroxy silicone oil solution is ethyl acetate.
In one embodiment of the invention, the hydroxyl silicone oil solution is sprayed by a spray gun, and the moving speed of the spray gun is 2-4cm/s; preferably 3cm/s.
In one embodiment of the invention, the spray distance between the spray gun and the starch film is 10-20cm.
In one embodiment of the invention, the degradable hydrophobic film is obtained after curing in an oven at 105 ℃ for 5 minutes.
In one embodiment of the present invention, the starch in step (1) may be selected from high amylose corn starch, with amylose content of 70-80%.
In one embodiment of the present invention, in step (1), the hydroxypropyl starch is prepared by the following steps: dispersing starch in water to obtain 35wt% starch milk, heating and stirring at 50-60 deg.C for 15-30 hr; then adding 30wt% of propylene oxide, naOH and Na in the dry weight of the starch into the mixture in two times 2 SO 4 Mixing, reacting at 30-40 deg.C to obtain hydroxypropyl starch (HPHACS).
In one embodiment of the invention, naOH is used in an amount of 1.5wt% based on the dry weight of the starch.
In one embodiment of the invention, na 2 SO 4 The amount of the water is 20 percent of the mass of the water.
In one embodiment of the invention, the reaction time is 20 to 30 hours.
In one embodiment of the present invention, in step (2), the hydroxypropyl starch and propargylamine are used in an amount of 10g (1-2) mL.
In one embodiment of the present invention, in step (2), the condensation reaction includes adding a catalyst, sodium cyanoborohydride, to catalyze the condensation, specifically: dispersing hydroxypropyl starch and propargylamine in an acetic acid-sodium acetate buffer solution, and then adding sodium cyanoborohydride every 24 hours for 4 times to obtain a mixture; the mixture is subjected to condensation reaction at 40-60 ℃.
In one embodiment of the invention, the catalyst is added in an amount of 2 to 5wt% per time relative to the hydroxypropyl starch. Specifically, the content of the compound (B) can be 2.84wt%.
In one embodiment of the invention, the amount of acetic acid-sodium acetate buffer relative to hydroxypropyl starch is 35mL/g.
In one embodiment of the invention, the pH of the acetic acid-sodium acetate buffer =5.
In one embodiment of the present invention, in the step (3), the mass fraction of N-Boc-3-azido-propylamine relative to the terminal alkyne starch is 3 to 5wt%; specifically 3.2wt% can be selected.
In one embodiment of the present invention, in step (3), N, N-dimethylformamide is used in an amount of 4mL/g relative to hydroxypropyl starch.
In one embodiment of the present invention, in step (3), the catalyst is sodium ascorbate and CuSO 4 ·5H 2 O, the mass ratio of the two is (2-4): 1; specifically, 2.5.
In one embodiment of the invention, in step (3), the catalyst is added in an amount of 1 to 2wt% relative to the terminal alkyne starch.
In one embodiment of the present invention, in the step (3), the volume ratio of the mixed solution of trifluoroacetic acid and dichloromethane to N, N-dimethylformamide is 1:1.
in one embodiment of the present invention, in the step (3), in the mixed solution of trifluoroacetic acid and dichloromethane, the volume ratio of trifluoroacetic acid to dichloromethane is 1:1.
in one embodiment of the invention, in the step (3), the obtained terminal alkyne starch and N-Boc-3-azido-propylamine are dispersed in N, N-dimethylformamide, and a catalyst is added to react for 10 to 15 hours at 70 to 90 ℃; then adding a mixed solution of trifluoroacetic acid and dichloromethane, and continuing the heat preservation reaction for 4-6h.
The second purpose of the invention is to provide a degradable hydrophobic film based on the preparation method.
The third purpose of the invention is to provide the application of the degradable hydrophobic film in the aspect of packaging materials.
The invention has the beneficial effects that:
the mechanical property of the terminal cationic starch composite membrane is greatly improved under the action of the electric field, and the breaking strength of the terminal cationic starch composite membrane is improved by 85 percent compared with that of a starch membrane without the electric field. The contact angle is improved by 83.3 percent after the hydroxyl silicone oil is treated. In addition, the breaking strength of the starch composite membrane obtained under the induction of the electric field is improved by 72.6 percent in the direction parallel to the electric field than in the direction vertical to the magnetic field, and the starch composite membrane has anisotropy of mechanical properties.
Drawings
FIG. 1 shows the effect of different amounts of the hydroxy silicone oil on the hydrophobicity of the starch film in example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
Hydrophobicity test: the starch film was cut into elongated specimens and glued to a glass slide with both sides, and the slide was placed on the stage of a contact angle measuring instrument with the droplet size set to 5 μ L.
Example 1: preparation of degradable hydrophobic film with terminal cationic starch as base material
(1) Preparing hydroxypropyl starch:
dispersing high amylose corn starch (with amylose content of 79% and water content of 13.34% and purchased from Shanghai-Haiwang Biotechnology Co., ltd.) in water to obtain high amylose corn starch milk with concentration of 35wt% and pH of 6.5, and heating and stirring at 55 deg.C for 20h; then adding 30wt% of propylene oxide based on the dry weight of starch in two times, and then addingNaOH with the weight of 1.5 percent of the dry weight of the starch and Na with the weight of 20 percent of the water 2 SO 4 Mixing, and reacting at 35 deg.C for 24 hr. After the reaction, neutralization, filtration, washing with water, and drying, hydroxypropyl starch (HPHACS) was obtained.
(2) Preparing terminal alkyne starch:
preparing 350mL of acetic acid-sodium acetate buffer (pH = 5), dissolving 10g of hydroxypropyl starch in 350mL of acetic acid-sodium acetate buffer at 50 ℃, adding 1.239mL of propargylamine under stirring, adding 0.284g of sodium cyanoborohydride every 24h, and adding 4 times to obtain a mixture; the mixture was stirred at 50 ℃ for 96h, then dialyzed, concentrated, and freeze-dried to give the terminal alkyne starch.
(3) Preparing terminal cationic starch:
10g of terminal alkyne starch and 320mg of N-Boc-3-azido-propylamine were uniformly dispersed into 40mL of N, N-dimethylformamide, and then 87.4mg of sodium ascorbate and 35.5mg of CuSO were added in this order 4 ·5H 2 O, stirring the solution in an oil bath at the temperature of 80 ℃ for 12 hours; then adding 40mL of a mixed solution of trifluoroacetic acid and dichloromethane (the volume ratio of the trifluoroacetic acid to the dichloromethane is 1), and continuously stirring and reacting for 6h under the protection of nitrogen; after the reaction is stopped, the product is concentrated, extracted and washed to obtain the Terminal Cationic Starch (TCS).
(4) Preparing a degradable hydrophobic film:
dispersing TCS and HPHACS in water according to the mass ratio of 5, then adding 10% sorbitol (based on the dry weight of TCS + HPHACS starch), uniformly mixing, stirring for 1 hour at 95 ℃, gelatinizing the starch, and obtaining a membrane solution; then the film liquid is casted into a film under the action of an external electric field of 15V/mm; then, 2%, 4%, 6% of hydroxy silicone oil (based on dry weight of TCS + HPHACS starch) was dissolved in 50mL of ethyl acetate, and a hydroxy silicone-based curing agent (a hydroxy silicone oil was obtained from jinan xing fei chemical company, ltd, with a curing agent) was added at a mass ratio of 10; and spraying the hydroxyl silicone oil solution onto the film at a moving speed of 3cm/s by using a spray gun, controlling the distance between the spray gun and the starch film to be 20cm, and curing in an oven at 105 ℃ for 5 minutes to obtain the degradable hydrophobic film.
The hydrophobic effect of the obtained degradable hydrophobic film was measured, and the results are shown in fig. 1 and table 1.
TABLE 1
Comparative example 1:
omitting the catalyst in steps (2) and (3) (i.e. no sodium cyanoborohydride is added in step (2), and no sodium ascorbate and CuSO are added in step (3) 4 ·5H 2 O), controlling the addition amount of the hydroxyl silicone oil to be 4 percent, and keeping other parameters unchanged.
Comparative example 2:
changing the mass ratio of TCS to HS in the step (4) to be 3: and 7, controlling the addition amount of the hydroxyl silicone oil to be 4%, and keeping other parameters unchanged.
Comparative example 3:
and (5) omitting an electric field in the film laying process in the step (4), controlling the addition amount of the hydroxyl silicone oil to be 4%, and keeping other parameters unchanged.
Comparative example 4:
the hydroxyl silicone oil in the step (4) is omitted, and other parameters are kept unchanged.
Comparative example 5:
and (4) changing the spraying speed in the step (4) to be 6cm/s, controlling the addition of the hydroxyl silicone oil to be 4%, and keeping other parameters unchanged.
Comparative example 6:
and (4) changing the spraying distance in the step (4) to be 40cm, controlling the addition of the hydroxyl silicone oil to be 4%, and keeping other parameters unchanged.
TABLE 2
TABLE 3
As shown in tables 2-3, the use of the catalyst directly affects the experimental results, and part of the terminal cationic starch cannot be synthesized, so that the terminal cationic starch cannot be oriented under the action of an electric field, and the mechanical properties of the terminal cationic starch are affected. Comparative example 4 has a smaller contact angle due to the presence of more hydrophilic groups, while comparative examples 5 and 6 have an effect on the hydrophobic property due to uneven spraying or less spraying.
Comparing the hydrophobicity of each starch film, the use of the hydroxyl silicone oil reduces the interfacial tension of the starch film surface, improves the hydrophobicity of the starch, and improves the contact angle by 83.3 percent.
Comparative example 7: comparison of different terminal cationic starches
Referring to example 1, the amount of propylene oxide was changed to replace 30wt% of starch with 10% and 40%, respectively, the amount of the hydroxyl silicone oil was controlled to be 4%, and the others were unchanged to obtain the corresponding terminal cationic starch; and preparing the corresponding composite film.
The resulting films were tested for properties and the results are shown in table 4 below:
TABLE 4
| The amount of propylene oxide relative to starch | Contact angle | Tensile Strength (MPa) | Elongation at Break (%) |
| 10％ | 105.2 | 23.5 | 14.4 |
| 30% (example 1) | 103.9 | 38.2 | 13.5 |
| 40％ | 103.2 | 37.4 | 8.9 |
Comparative example 8:
and (5) replacing the terminal cationic starch used in the step (4) with quaternary ammonium cationic starch, and controlling the addition amount of the hydroxyl silicone oil to be 4% to obtain a corresponding film product. The corresponding performance results are shown in table 5. The quaternary ammonium cationic starch is prepared according to the prior document ' performance research of quaternary ammonium cationic starch/PVA (polyvinyl alcohol) blend membrane ' Liu Li super ', applied chemical engineering ' 2017, no. 02 '.
TABLE 5
| Starch | Contact angle | Tensile Strength (MPa) | Elongation at Break (%) |
| Quaternary ammonium salt cationic starch | 105.2 | 27.3 | 18.2 |
Claims (10)
1. A method of making a degradable hydrophobic film, the method comprising:
dispersing terminal cationic starch, hydroxypropyl starch and sorbitol in water, uniformly mixing, and heating for gelatinization to obtain a membrane solution; then the film liquid is casted into a film under the action of an applied electric field; spraying the hydroxyl silicone oil solution on the membrane, and curing to obtain the degradable hydrophobic membrane;
the terminal cationic starch is prepared by the following method:
(1) Modifying starch with propylene oxide to obtain hydroxypropyl starch;
(2) Carrying out condensation reaction on the obtained hydroxypropyl starch and propargylamine serving as substrates to obtain terminal alkyne starch;
(3) Dispersing the obtained terminal alkyne starch and N-Boc-3-azido-propylamine in N, N-dimethylformamide, and adding a catalyst for reaction; then adding a mixed solution of trifluoroacetic acid and dichloromethane for continuous reaction; after the reaction is finished, concentrating, extracting and washing to obtain terminal cationic starch;
in the step (2), the condensation reaction comprises adding a catalyst of sodium cyanoborohydride for catalytic condensation;
in the step (3), the catalyst is sodium ascorbate and CuSO 4 ·5H 2 O。
2. The method according to claim 1, wherein the mass ratio of terminal cationic starch to hydroxypropyl starch is 5.
3. The method according to claim 1, wherein sorbitol is added in an amount of 10wt% based on the total mass of the terminal cationic starch and the hydroxypropyl starch.
4. The method according to claim 1, wherein the mass fraction of the hydroxyl silicone oil relative to the total mass of the terminal cationic starch and the hydroxypropyl starch is 2-6%.
5. The method according to claim 1, wherein the hydroxy silicone oil solution is sprayed by a spray gun, the moving speed of the spray gun being 2-4cm/s.
6. The method of claim 1, wherein the spray distance between the spray gun and the starch film is 10-20cm.
7. The method according to claim 1, wherein in the step (1), the hydroxypropyl starch is prepared by: dispersing starch in water to obtain 35wt% starch milk, heating and stirring at 50-60 deg.C for 15-30 hr; then adding 30wt% of propylene oxide, naOH and Na in starch dry weight into the mixture in two times 2 SO 4 Mixing, reacting at 30-40 deg.C to obtain hydroxypropyl starch.
8. The process of claim 1, wherein in step (3), the mass fraction of N-Boc-3-azido-propylamine relative to the terminal alkyne starch is 3 to 5wt%.
9. A degradable hydrophobic film prepared by the method of any one of claims 1 to 8.
10. Use of the degradable hydrophobic film of claim 9 in packaging materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210442928.XA CN114672055B (en) | 2022-04-25 | 2022-04-25 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210442928.XA CN114672055B (en) | 2022-04-25 | 2022-04-25 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672055A CN114672055A (en) | 2022-06-28 |
| CN114672055B true CN114672055B (en) | 2023-01-03 |
Family
ID=82079908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210442928.XA Active CN114672055B (en) | 2022-04-25 | 2022-04-25 | Preparation of degradable hydrophobic film with terminal cationic starch as base material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672055B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05278738A (en) * | 1992-04-06 | 1993-10-26 | Nishikawa Rubber Co Ltd | Biologically decomposing vessel |
| CN102226001B (en) * | 2011-04-26 | 2012-08-22 | 东北师范大学 | Fully biodegradable nano-starch graft polylactic acid |
| CN106582314B (en) * | 2017-02-26 | 2019-01-25 | 浙江理工大学 | A kind of small-bore hydrophobic composite membrane preparation method for membrane distillation |
| CN107459583B (en) * | 2017-08-08 | 2020-04-28 | 中山大学 | Highly hyperbranched cationic polysaccharide derivative containing dendritic polyamide-amine group and preparation method thereof |
| CN107375237A (en) * | 2017-09-08 | 2017-11-24 | 吉林大学 | Starch capsules with reduction response a kind of of modified with folic acid and preparation method thereof |
| CN112225829B (en) * | 2020-10-29 | 2021-08-24 | 江南大学 | Polysaccharide with charged tail end and preparation method thereof |
| CN113005771A (en) * | 2021-02-08 | 2021-06-22 | 武汉轻工大学 | Preparation method of hydrophobic starch food packaging film |
| CN114231172A (en) * | 2021-12-29 | 2022-03-25 | 苏州东杏表面技术有限公司 | UV-resistant hydrophobic membrane material and preparation method and application thereof |
-
2022
- 2022-04-25 CN CN202210442928.XA patent/CN114672055B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114672055A (en) | 2022-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Cellulose-chitosan beads crosslinked by dialdehyde cellulose | |
| CN106106522B (en) | A kind of nano zine oxide-load silver chitosan compound anti-bacteria agent and preparation method thereof | |
| JP5761736B2 (en) | Sericin nanofiber and production method thereof, metal ion adsorbent, dyeing function enhancement material, chemical resistance enhancement material, sericin / fibroin composite nanofiber and production method thereof | |
| CN105524909B (en) | Chitosan magnetic micro-sphere, preparation method and application for enzyme immobilization | |
| Yu et al. | Durable antibacterial finishing of cotton fabric based on thiol–epoxy click chemistry | |
| CN107383405A (en) | A kind of compound proton exchange membrane and preparation method thereof | |
| CN109608554B (en) | Preparation method of antibacterial cationic nano-fibrillated cellulose | |
| CN111234047A (en) | Exopolysaccharide rich in fucose and preparation method and application thereof | |
| CN107938343B (en) | Application of O-chlorotriazine type chitosan quaternary ammonium salt in antibacterial finishing of natural fabric | |
| CN104514158B (en) | A kind of application of chitosan quaternary ammonium salt in reactive dye salt-free dyeing | |
| Hao et al. | Utilizing cellulase as a hydrogen peroxide stabilizer to combine the biopolishing and bleaching procedures of cotton cellulose in one bath | |
| CN114672055B (en) | Preparation of degradable hydrophobic film with terminal cationic starch as base material | |
| CN113583545B (en) | Amination GO/cyclodextrin modified waterborne epoxy resin anticorrosive paint | |
| Zhang et al. | Preparation of antimicrobial PVDF and EVOH membranes by grafting quaternary ammonium compounds | |
| JP3924612B2 (en) | Complex of silk protein and chitosan and method for producing the same | |
| Yin et al. | Synthesis of 2-hydroxypropyl trimethylammonium chloride chitosan and its application in bamboo fiber paper | |
| CN111138662B (en) | Preparation method and application of active hydrophilic formaldehyde-free color fixing agent | |
| CN104860551A (en) | Preparation method of chitosan modified starch impregnating compound | |
| CN109438742A (en) | A kind of preparation method of cross-linking modified alginate films | |
| CN102517897A (en) | Polycarboxylic acid anti-crease finishing technology for low-strength damaged cotton fabric | |
| CN101880963B (en) | Preparation method of cellulose based nano composite fabric containing silsesquioxane particles | |
| CN114182524B (en) | Antibacterial polyester shuttle woven grey cloth and production process thereof | |
| CN110606956B (en) | Chitosan-cellulose composite material and dressing thereof | |
| CN112538185A (en) | Preparation method of polylactic acid gas barrier composite membrane | |
| Jiang et al. | Preparation and physical properties of chitosan-coated calcium sulphate whiskers |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221214 Address after: 234000 No.69 Suhuai South Road, Suzhou economic development zone, Anhui Province Applicant after: ANHUI ZIJIN NEW MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. Address before: 518000 708, Huiyi building, No. 9, Zhongxin Road, Taoyuan community, Dalang street, Longhua District, Shenzhen, Guangdong Applicant before: Shenzhen Hongyue Information Technology Co.,Ltd. Effective date of registration: 20221214 Address after: 518000 708, Huiyi building, No. 9, Zhongxin Road, Taoyuan community, Dalang street, Longhua District, Shenzhen, Guangdong Applicant after: Shenzhen Hongyue Information Technology Co.,Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Applicant before: Jiangnan University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation of a degradable hydrophobic film based on terminal cationic starch Effective date of registration: 20230925 Granted publication date: 20230103 Pledgee: Anhui Suzhou Rural Commercial Bank Co.,Ltd. Pledgor: ANHUI ZIJIN NEW MATERIAL SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2023980058470 |