CN106084272A - A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof - Google Patents
A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof Download PDFInfo
- Publication number
- CN106084272A CN106084272A CN201610470667.7A CN201610470667A CN106084272A CN 106084272 A CN106084272 A CN 106084272A CN 201610470667 A CN201610470667 A CN 201610470667A CN 106084272 A CN106084272 A CN 106084272A
- Authority
- CN
- China
- Prior art keywords
- starch
- parts
- thin film
- caprolactone
- antibacterial
- 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.)
- Pending
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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
A kind of starch degradable thin film of antibacterial caprolactone grafting, it is characterized in that, it is prepared from by the raw material of following weight portion: corn starch 100 parts, wheaten starch 8 10 parts, polyvinyl alcohol 58 parts, 35 parts of fructose, DMF 80 100 parts, acetic anhydride 8 10 parts, pyridine 100 120 parts, diethylene glycol dimethyl ether 120 150 parts, sodium naphthalene solution 15 20 parts, caprolactone 58 parts, petroleum ether 200 300 parts, oxolane 200 300 parts, glycerol 58 parts, polycaprolactone 58 parts, the silver ammino solution of 1 2% is appropriate, the polyethylenimine solution of 0.8 1.0mg/mL is appropriate, water is appropriate.Starch of the present invention can be biodegradable, abundance, cheap, environmentally friendly；The starch degradable thin film of the antibacterial caprolactone grafting that the present invention prepares has good biocompatibility and antibacterial, bactericidal property, and environmentally friendly, can effectively alleviate white pollution problems.
Description
Technical field
The present invention relates to thin film fabrication techniques field, the starch degradable being specifically related to a kind of antibacterial caprolactone grafting is thin
Film and preparation method thereof.
Technical background
Flourish along with plastics industry, the environmental pollution that waste plastic film rubbish brings also is on the rise, white
Pollute and become the environmental problem attracted attention in the whole world.Therefore, people have to go into overdrive to develop biological degredation plastic thin film,
Administer plastic refuse pollution problem brought to environment.
Starch is a kind of abundance, cheap natural macromolecular material, is also a kind of inexhaustible
Renewable resource, it can be biodegradable in a variety of environmental conditions, and final catabolite carbon dioxide and water can pass through
The photosynthesis recirculation of plant, will not cause any pollution to environment.Therefore, to be widely used in degradation plastic thin for starch
The research of film and product development, and have been achieved for great progress.
Author Song little Li, in the preparation and performance study one literary composition of starch-based degradable laminated film, utilizes starch, shell poly-
Sugar, glycerol, Paligorskite are prepared for a kind of starch-based degradable laminated film, and glycerol is starch film plasticizer, and Paligorskite changes
The mechanical property of kind starch film, the starch-based degradable laminated film of preparation has good biodegradability.
Summary of the invention
The technical problem to be solved is to provide that a kind of technique is simple, production cost is low and environment amenable
Antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof.
The technical problem to be solved uses following technical scheme to realize:
The starch degradable thin film of a kind of antibacterial caprolactone grafting, it is characterised in that it is prepared by the raw material of following weight portion
Form: corn starch 100 parts, wheaten starch 8-10 part, polyvinyl alcohol 5-8 part, fructose 3-5 part, DMF 80-100 part, acetic anhydride
8-10 part, pyridine 100-120 part, diethylene glycol dimethyl ether 120-150 part, sodium naphthalene solution 15-20 part, caprolactone 5-8 part, oil
Ether 200-300 part, oxolane 200-300 part, glycerol 5-8 part, polycaprolactone 5-8 part, 1-2% silver ammino solution is appropriate, 0.8-
The polyethylenimine solution of 1.0mg/mL is appropriate, water is appropriate.
The starch degradable thin film of a kind of antibacterial caprolactone grafting, it is characterised in that it is prepared from by following steps:
(1) wheaten starch is the driest, then under conditions of stirring, it is warmed up to 130-140 DEG C with DMF, keep 4-5h, cooling
To 90-100 DEG C, dropping acetic anhydride and pyridine, continue to react 5-6h, cooling at 90-100 DEG C, be poured in cold water after dripping
Precipitation, filters, washs to neutrality, is dried, for white powder material, i.e. starch acetate；
(2) in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen device, diethylene glycol dimethyl ether is added
And starch acetate, it is warmed up to 90-100 DEG C and makes it dissolve fully, be then down to room temperature, add naphthalene sodium under nitrogen protection molten
Liquid, after reacting about 15-20min, adds caprolactone, reacts 10-12h at 110-130 DEG C, and product is carried out with the petroleum ether of 1/3
After precipitation, then with oxolane dissolving, remaining petroleum ether precipitation secondary, product is white solid thing, i.e. caprolactone after drying
The starch of grafting；
(3) corn starch, the starch of caprolactone grafting, polycaprolactone, polyvinyl alcohol addition are equivalent to corn starch weight portion
In the water of 10-12 times, ultrasonic disperse 20-30min；Adding glycerol and fructose, at 70-80 DEG C, gelatinizing 40-60min machinery stir
Mix；It is poured on while hot on the smooth glass plate of preheating, stands 10-20min, at 70-80 DEG C, be dried 20-24h, take off film；
(4) thin film that step (3) obtains is dipped in 30-60min in the polyethylenimine solution that concentration is 0.8-1.0mg/mL, takes
Going out, rinse with water, nitrogen dries up；It is dipped in again in the silver ammino solution of 1-2%, is warming up to 65-75 DEG C, and insulation reaction 5-8h, nitrogen
Dry up, obtain the starch degradable thin film of a kind of antibacterial caprolactone grafting.
The starch degradable thin film of a kind of antibacterial caprolactone grafting, it is characterised in that the preparation of described sodium naphthalene solution
Method is: naphthalene and metallic sodium are placed in oxolane, reacts 10-12h under room temperature and nitrogen are protected, and obtaining concentration is 0.8-
The sodium naphthalene solution of 1mol/L.
The starch degradable thin film of a kind of antibacterial caprolactone grafting, it is characterised in that before described DMF and pyridine use
All need to be dried through anhydrous sodium sulfate.
The invention has the beneficial effects as follows: starch of the present invention can be biodegradable, abundance, price are low
Honest and clean, environmentally friendly；Polycaprolactone as binding agent and plasticizer, and at starch surface grafting caprolactone, can effectively facilitate
Uniformly mixing between polycaprolactone with starch, improve the mechanical property of thin film；The addition of glycerol can improve starch indissoluble, infusibility
Problem, starch is played plasticization；Thin film is dipped in 1 silver ammino solution by the present invention so that starch film Surface coating one
Layer nano silver particles, enhances the anti-microbial property of starch film；Starch film intensity that the present invention prepares is high, low cost and can giving birth to
Thing is degraded, and can effectively alleviate white pollution problems.
Detailed description of the invention
The starch degradable thin film of the antibacterial caprolactone grafting of the present embodiment, it is by the raw material preparation of following weight portion
Become: corn starch 100 parts, wheaten starch 8 parts, polyvinyl alcohol 5 parts, 5 parts of fructose, DMF 100 parts, acetic anhydride 8 parts, pyridine 120
Part, diethylene glycol dimethyl ether 150 parts, sodium naphthalene solution 15 parts, caprolactone 5 parts, petroleum ether 300 parts, oxolane 300 parts, glycerol 5
Part, polycaprolactone 8 parts, 1-2% silver ammino solution polyethylenimine solution appropriate, 0.8-1.0mg/mL appropriate, water is appropriate.
The starch degradable thin film of a kind of antibacterial caprolactone grafting of the present embodiment, it is characterised in that it is by walking as follows
Suddenly it is prepared from:
(1) wheaten starch is the driest, then under conditions of stirring, it is warmed up to 130 DEG C with DMF, keep 4h, cool to 100
DEG C, dropping acetic anhydride and pyridine, continue to react 6h, cooling at 100 DEG C, be poured in cold water precipitation, filter, wash after dripping
To neutral, it is dried, for white powder material, i.e. starch acetate；
(2) in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen device, diethylene glycol dimethyl ether is added
And starch acetate, it is warmed up to 100 DEG C and makes it dissolve fully, be then down to room temperature, add sodium naphthalene solution under nitrogen protection, instead
Caprolactone should be added after about 20min, at 110 DEG C, react 12h, after product precipitates with the petroleum ether of 1/3, then with tetrahydrochysene
Furan dissolves, remaining petroleum ether precipitation secondary, and product is white solid thing after drying, i.e. the starch of caprolactone grafting；
(3) corn starch, the starch of caprolactone grafting, polycaprolactone, polyvinyl alcohol addition are equivalent to corn starch weight portion
In the water of 12 times, ultrasonic disperse 30min；Add glycerol and fructose, gelatinizing 60min mechanical agitation at 80 DEG C；It is poured on pre-while hot
On the smooth glass plate of heat, stand 20min, at 80 DEG C, be dried 20h, take off film；
(4) thin film that step (3) obtains is dipped in 60min in the polyethylenimine solution that concentration is 0.8mg/mL, takes out, use water
Rinsing, nitrogen dries up；Being dipped in the silver ammino solution of 2% again, be warming up to 70 DEG C, and insulation reaction 8h, nitrogen dries up, and obtains one
The starch degradable thin film of antibacterial caprolactone grafting.
After tested, the starch degradable thin film hot strength of the antibacterial caprolactone grafting of the present embodiment is more than 30MPa, disconnected
Splitting percentage elongation and be more than 150%, light transmittance is more than 90%, and thin film both sides temperature difference is more than 5 DEG C.
Claims (4)
1. the starch degradable thin film of an antibacterial caprolactone grafting, it is characterised in that it is by the raw material system of following weight portion
For forming: corn starch 100 parts, wheaten starch 8-10 part, polyvinyl alcohol 5-8 part, fructose 3-5 part, DMF 80-100 part, acetic acid
Acid anhydride 8-10 part, pyridine 100-120 part, diethylene glycol dimethyl ether 120-150 part, sodium naphthalene solution 15-20 part, caprolactone 5-8 part, stone
Oil ether 200-300 part, oxolane 200-300 part, glycerol 5-8 part, polycaprolactone 5-8 part, 1-2% silver ammino solution appropriate,
The polyethylenimine solution of 0.8-1.0mg/mL is appropriate, water is appropriate.
2. the starch degradable thin film of an antibacterial caprolactone grafting, it is characterised in that it is prepared from by following steps:
Wheaten starch is the driest, then under conditions of stirring, it is warmed up to 130-140 DEG C with DMF, keep 4-5h, cool to
90-100 DEG C, dropping acetic anhydride and pyridine, continue to react 5-6h, cooling after dripping at 90-100 DEG C, it is heavy to be poured in cold water
Form sediment, filter, wash to neutrality, be dried, for white powder material, i.e. starch acetate；
In the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen device, add diethylene glycol dimethyl ether and shallow lake
Powder acetas, is warmed up to 90-100 DEG C and makes it dissolve fully, be then down to room temperature, add sodium naphthalene solution under nitrogen protection, instead
Should add caprolactone after about 15-20min, react 10-12h at 110-130 DEG C, product precipitates with the petroleum ether of 1/3
After, then with oxolane dissolving, remaining petroleum ether precipitation secondary, product is white solid thing after drying, i.e. caprolactone grafting
Starch；
Corn starch, the starch of caprolactone grafting, polycaprolactone, polyvinyl alcohol addition are equivalent to corn starch weight portion 10-
In the water of 12 times, ultrasonic disperse 20-30min；Add glycerol and fructose, gelatinizing 40-60min mechanical agitation at 70-80 DEG C；Take advantage of
Heat is poured on the smooth glass plate of preheating, stands 10-20min, is dried 20-24h, takes off film at 70-80 DEG C；
The thin film that step (3) obtains is dipped in 30-60min in the polyethylenimine solution that concentration is 0.8-1.0mg/mL, takes out,
Rinsing with water, nitrogen dries up；Being dipped in the silver ammino solution of 1-2% again, be warming up to 65-75 DEG C, and insulation reaction 5-8h, nitrogen blows
Dry, obtain the starch degradable thin film of a kind of antibacterial caprolactone grafting.
3. the starch degradable thin film of an antibacterial caprolactone grafting, it is characterised in that the preparation side of described sodium naphthalene solution
Method is: naphthalene and metallic sodium are placed in oxolane, reacts 10-12h under room temperature and nitrogen are protected, and obtaining concentration is 0.8-
The sodium naphthalene solution of 1mol/L.
4. the starch degradable thin film of an antibacterial caprolactone grafting, it is characterised in that before described DMF and pyridine use all
Need to be dried through anhydrous sodium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610470667.7A CN106084272A (en) | 2016-06-24 | 2016-06-24 | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610470667.7A CN106084272A (en) | 2016-06-24 | 2016-06-24 | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106084272A true CN106084272A (en) | 2016-11-09 |
Family
ID=57253580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610470667.7A Pending CN106084272A (en) | 2016-06-24 | 2016-06-24 | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106084272A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674836A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | Polyvinyl alcohol fruit/vegetable fresh-keeping film capable of resisting bacteria and preparation method thereof |
| CN106674837A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | Anti-static polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof |
| CN106674835A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | High-light-transmittance polyvinyl alcohol fruit/vegetable preservative film and preparation method thereof |
| CN115340724A (en) * | 2022-07-11 | 2022-11-15 | 金聚合科技(宁波)有限公司 | Starch-based antibacterial material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552963A (en) * | 2011-11-21 | 2012-07-11 | 北京科技大学 | Preparation method of starch/nano-silver antibacterial composite film |
| CN103289131A (en) * | 2013-05-22 | 2013-09-11 | 南京财经大学 | Preparation method for starch-polyvinyl alcohol biologically-cross-linked nano-composite plastic film |
-
2016
- 2016-06-24 CN CN201610470667.7A patent/CN106084272A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552963A (en) * | 2011-11-21 | 2012-07-11 | 北京科技大学 | Preparation method of starch/nano-silver antibacterial composite film |
| CN103289131A (en) * | 2013-05-22 | 2013-09-11 | 南京财经大学 | Preparation method for starch-polyvinyl alcohol biologically-cross-linked nano-composite plastic film |
Non-Patent Citations (2)
| Title |
|---|
| 何立红 等: "淀粉乙酸酯的阴离子接枝己内酯聚合研究", 《高分子学报》 * |
| 秦卫东 等: "《食品添加剂学》", 28 February 2014, 中国纺织出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674836A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | Polyvinyl alcohol fruit/vegetable fresh-keeping film capable of resisting bacteria and preparation method thereof |
| CN106674837A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | Anti-static polyvinyl alcohol fruit and vegetable fresh-keeping film and preparation method thereof |
| CN106674835A (en) * | 2016-12-14 | 2017-05-17 | 陈强 | High-light-transmittance polyvinyl alcohol fruit/vegetable preservative film and preparation method thereof |
| CN115340724A (en) * | 2022-07-11 | 2022-11-15 | 金聚合科技(宁波)有限公司 | Starch-based antibacterial material and preparation method thereof |
| CN115340724B (en) * | 2022-07-11 | 2023-10-24 | 金聚合科技(宁波)有限公司 | Starch-based antibacterial material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105885114A (en) | Silica-enhanced caprolactone-starch degradable thin film and preparation method thereof | |
| CN106084272A (en) | A kind of antibacterial starch degradable thin film of caprolactone grafting and preparation method thereof | |
| CN106065090A (en) | Caprolactone starch degradable thin film that a kind of polyvinyl alcohol strengthens and preparation method thereof | |
| Sawut et al. | Photopolymerisation and characterization of maleylatedcellulose-g-poly (acrylic acid) superabsorbent polymer | |
| Zheng et al. | Facile fabrication of self-healing carboxymethyl cellulose hydrogels | |
| Zdanowicz et al. | Ionic liquids as starch plasticizers or solvents | |
| CN103421215A (en) | Starch composition, starch-based film, and preparation method of starch-based film | |
| Liang et al. | Preparation and characterization of an eco-friendly dust suppression and sand-fixation liquid mulching film | |
| Lu et al. | Improvement of bio-based polyurethane and its optimal application in controlled release fertilizer | |
| CN104448660B (en) | Superabsorbent resin as well as preparation method and applications thereof | |
| CN106366354A (en) | Lignocellulose starch degradable film and preparation method thereof | |
| CN105885116A (en) | Polylactic acid-caprolactone-starch extrusion blown film and preparation method thereof | |
| CN103589197B (en) | Method for preparing flexibilizer by adopting oxidized graphene and application thereof | |
| CN105482140A (en) | Preparation method of polylactic acid/starch surface grafted sulfuric acid aminated chitosan composite thin film | |
| CN106366352A (en) | Caprolactone-starch degradable thin film with enhanced calcium carbonate and preparing method thereof | |
| Ni et al. | Eco-friendly photothermal hydrogel evaporator for efficient solar-driven water purification | |
| CN103755987A (en) | Preparation method for heat-resisting and high-transparence polyimide thin film | |
| Liu et al. | Eco-friendly superabsorbent composites based on calcined semicoke and polydimethylourea phosphate: Synthesis, swelling behavior, degradability and their impact on cabbage growth | |
| CN101642584B (en) | Medical cassava starch composite film and preparation method thereof | |
| CN104262667A (en) | Alginate-based material external controllable ionic crosslinked method | |
| CN106317473A (en) | Temperature-resistant caprolactone-grafted starch degradable film and preparation method thereof | |
| CN104497877A (en) | Quick self-drying modified raw lacquer and preparation method thereof | |
| CN106220901A (en) | Caprolactone starch degradable thin film that a kind of corn straw strengthens and preparation method thereof | |
| CN106243401A (en) | Caprolactone starch degradable thin film that a kind of zein strengthens and preparation method thereof | |
| CN106243403A (en) | A kind of tear-resistant starch degradable thin film of caprolactone grafting and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |