CN106674615A - Preparation method of enhanced type polycaprolactone biodegradable plastics - Google Patents
Preparation method of enhanced type polycaprolactone biodegradable plastics Download PDFInfo
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- CN106674615A CN106674615A CN201611030354.6A CN201611030354A CN106674615A CN 106674615 A CN106674615 A CN 106674615A CN 201611030354 A CN201611030354 A CN 201611030354A CN 106674615 A CN106674615 A CN 106674615A
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- polycaprolactone
- starch
- toluene
- biodegradable plastics
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- 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
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a preparation method of enhanced type polycaprolactone biodegradable plastics, belonging to the technical field of biodegradable plastics. According to the preparation method, after azeotropic water removal is carried out on starch and toluene, hydroxyl groups on the surfaces of starch granules act with stannous octoate to form active centers, the active centers initiate ring-opening polymerization of caprolactone according to a coordination-insertion mechanism to obtain a starch polycaprolactone graft copolymer, the internal membranes of washed egg shells are stripped off, then the egg shells are dried and ground into egg shell powder, and subsequently, a silane coupling agent, the starch polycaprolactone graft copolymer and the egg shell powder are added into a mixing roll to carry out extrusion granulation to obtain the enhanced type polycaprolactone biodegradable plastics. The prepared enhanced type polycaprolactone biodegradable plastics has excellent waterproof property, higher structural strength, good tenacity and excellent overall properties due to reasonable formulation design and preparation process, and can solve the deficiency of the existing biodegradable plastics in aspects of waterproof property and mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of enhancement mode polycaprolactone biodegradable plastic, belongs to biodegradable plastic skill
Art field.
Background technology
Plastics are, with monomer as raw material, by addition polymerization or the macromolecular compound of polycondensation polymerized, to be commonly called as plastics
Or resin, can freely change composition and body styles, by synthetic resin and filler, plasticizer, stabilizer, lubricant, colorant
Deng additive composition.With the fast development of China's economy, plastic is more and more, but the use of substantial amounts of plastic
Also can produce and be not easily decomposed garbage in a large number, cause " white pollution ", the living environment and production to the mankind brings greatly
Harm, in addition the primary raw material source of plastics is the petroleum resources of scarcity of resources, there is certain sense of crisis.For this purpose, research and development one
Planting biodegradable plastic not only can be reduced " white pollution ", can also alleviate the various environmental pollutions of plastic initiation, while
The dependency degree to petroleum resources can be reduced, more preferable application demand is adapted to.
At present, the plastics kind of the fully biodegradable of industry exploitation is a lot, also real mostly with plant amylum as raw material
The high-efficiency comprehensive utilization of resource is showed.But in use mostly there are the following problems for these plastic products：1st, water resistance
Deficiency, there is infiltration phenomenon, and 2, intensity and toughness are not fully up to expectations.Therefore, development and the use of biodegradable plastic is China's plastics
The only way which must be passed of industry development.
The content of the invention
The invention mainly solves the technical problem of：There is water proofing property in use for traditional biological degradative plastics
Can be not enough, there are infiltration phenomenon, the poor defect of intensity and toughness, there is provided a kind of enhancement mode polycaprolactone biodegradable plastic
Preparation method, by after starch and toluene azeotropic water removing, the hydroxyl and stannous octoate of starch particle surface act on forming work the present invention
Property center, the active center is caused the ring-opening polymerisation of caprolactone by coordination insertion mechanism, starch polycaprolactone graft copolymerization is obtained
Thing, takes clean Ovum crusta Gallus domesticuss and peels off after egg membrane, is dried and grinds to form Ovum crusta Gallus domesticuss powder, subsequently will be silane coupled
Agent, starch polycaprolactone graft copolymer, Ovum crusta Gallus domesticuss powder adds extruding pelletization in kneading machine, obtains enhancement mode polycaprolactone biological
Degradative plastics.Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention is designed and preparation technology by rational formula,
So that biodegradable plastic has excellent water resistance, higher structural strength and good toughness, excellent combination property, energy
Enough solve the weak point that existing biodegradable plastic exists in terms of water resistance and mechanical property.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）100~120g corn starchs are weighed, in adding 200~240mL toluene, the azeotropic water removing 2 under 130~140 DEG C of oil baths
After~3h, with 2~3mL/min, 50~60mL of Deca mass fractions as 1% stannous octoate toluene solution, while with 300~400r/
Min stirs 1~2h, and subsequently again with 1~2mL/min Deca 90~100mL caprolactones, keeping temperature continues to react 20~24h, obtains
Copolymer mixture；
（2）By above-mentioned copolymer mixture, in adding 600~800mL toluene, under 20~30 DEG C of waters bath with thermostatic control, with 300~
400r/min stirs 10~15h, subsequently filters, and filtering residue 3~5 times is washed with toluene, then filtering residue is placed in vacuum drying oven,
It is dried to constant weight at 60~70 DEG C, obtains starch polycaprolactone graft copolymer, it is standby；
（3）30~50g Ovum crusta Gallus domesticuss are weighed, after being washed with deionized Ovum crusta Gallus domesticuss surface 2~3 times, then it is immersed in 200~
300mL mass fractions are 20~30min in 5% sodium hydroxide solution, after peeling off egg membrane, are washed with deionized eggshell extremely
Cleaning mixture proceeds to eggshell in drying baker in neutrality, is dried to constant weight at 105~110 DEG C, then continues at and grind in mortar 1
~2h, obtains pretreatment Ovum crusta Gallus domesticuss powder；
（4）0.03~0.05g silane resin acceptor kh-550s are weighed, in adding 100~150mL dehydrated alcohol, with 300~400r/
Min is stirred to silane coupler and is completely dissolved, and adds 60~70g steps（2）The starch polycaprolactone graft copolymer of preparation,
At 75~85 DEG C, continue stirring and be evaporated to dryness, after subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 4~5g kneading machine is added
In, after 15~20min of melt blending at 110~140 DEG C, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
The application process of the present invention：Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention is added to into inflation film manufacturing machine
In, arrange parameter screw diameter be Ф 45mm, screw slenderness ratio 28：1, screw speed is 12~100r/min, and head film mouth is straight
Footpath is Ф 50~Ф 75mm, and diameter of traction-roller is Ф 650mm, and traction linear velocity is 8~50m/min, and thin film folding footpath width is 130
~600mm, a diameter of Ф 450mm of vane, Blown Film, after testing, enhancement mode polycaprolactone prepared by the present invention is biological
Degradative plastics tensile strength reaches 35~38MPa, and elongation at break is 34.5~36.5%, and tearing strength is 38.4-41.8KN/
M, and process route is simple, can be degradable, green pollution-free.
The invention has the beneficial effects as follows：
（1）Enhancement mode polycaprolactone biodegradable plastic good mechanical properties prepared by the present invention, with higher tensile strength
And elongation at break, process route simply, can be degradable, green pollution-free；
（2）Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention has excellent water resistance, higher structure strong
Degree and good toughness, excellent combination property, market application foreground is wide.
Specific embodiment
100~120g corn starchs are weighed, in adding 200~240mL toluene, the azeotropic water removing under 130~140 DEG C of oil baths
After 2~3h, with 2~3mL/min, 50~60mL of Deca mass fractions as 1% stannous octoate toluene solution, while with 300~400r/
Min stirs 1~2h, and subsequently again with 1~2mL/min Deca 90~100mL caprolactones, keeping temperature continues to react 20~24h, obtains
Copolymer mixture；By above-mentioned copolymer mixture, in adding 600~800mL toluene, under 20~30 DEG C of waters bath with thermostatic control, with
300~400r/min stirs 10~15h, subsequently filters, and filtering residue 3~5 times is washed with toluene, then filtering residue is placed in into vacuum drying
In case, at 60~70 DEG C be dried to constant weight, obtain starch polycaprolactone graft copolymer, weigh 30~50g Ovum crusta Gallus domesticuss, spend from
Behind sub- water washing Ovum crusta Gallus domesticuss surface 2~3 times, then 200~300mL mass fractions are immersed in in 5% sodium hydroxide solution 20
~30min, after peeling off egg membrane, is washed with deionized eggshell to cleaning mixture in neutrality, and eggshell is proceeded in drying baker,
It is dried to constant weight at 105~110 DEG C, then continues at 1~2h of grinding in mortar, obtains pretreatment Ovum crusta Gallus domesticuss powder；Weigh 0.03~
0.05g silane resin acceptor kh-550s, in adding 100~150mL dehydrated alcohol, are stirred to silane coupled with 300~400r/min
Agent is completely dissolved, and adds 60~70g starch polycaprolactone graft copolymers, at 75~85 DEG C, continues stirring and is evaporated to dryness,
After subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 4~5g add kneading machine in, at 110~140 DEG C melt blending 15~
After 20min, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
Example 1
100g corn starchs are weighed, in adding 200mL toluene, under 130 DEG C of oil baths after azeotropic water removing 2h, with 2mL/min Deca
50mL mass fractions are 1% stannous octoate toluene solution, while 1h is stirred with 300r/min, subsequently again with 1mL/min Deca 90mL
Caprolactone, keeping temperature continues to react 20h, obtains copolymer mixture；By above-mentioned copolymer mixture, in adding 600mL toluene,
Under 20 DEG C of waters bath with thermostatic control, 10h is stirred with 300r/min, subsequently filtered, and filtering residue 3 times is washed with toluene, then filtering residue is placed in
In vacuum drying oven, at 60 DEG C be dried to constant weight, obtain starch polycaprolactone graft copolymer, weigh 30g Ovum crusta Gallus domesticuss, spend from
Behind sub- water washing Ovum crusta Gallus domesticuss surface 2 times, then 200mL mass fractions are immersed in for 20min in 5% sodium hydroxide solution, peeled off
After egg membrane, eggshell is washed with deionized to cleaning mixture in neutrality, eggshell is proceeded in drying baker, be dried at 105 DEG C
To constant weight, then continue at and grind in mortar 1h, obtain pretreatment Ovum crusta Gallus domesticuss powder；0.03g silane resin acceptor kh-550s are weighed, is added
In 100mL dehydrated alcohol, stirred to silane coupler with 300r/min and be completely dissolved, add the grafting of 60g starch polycaprolactone
Copolymer, at 75 DEG C, continues stirring and is evaporated to dryness, and after subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 4g kneading machine is added
In, after melt blending 15min at 110 DEG C, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention is added in inflation film manufacturing machine, arrange parameter screw rod is straight
Footpath be Ф 45mm, screw slenderness ratio 28：1, screw speed is 12r/min, a diameter of Ф 50mm of head film mouth, and diameter of traction-roller is
Ф 650mm, traction linear velocity is 8m/min, and thin film rolls over footpath width for 130mm, a diameter of Ф 450mm of vane, and Blown Film is
Can, after testing, enhancement mode polycaprolactone biodegradable plastic tensile strength prepared by the present invention reaches 35MPa, elongation at break
For 34.5, tearing strength is 38.4KN/m, and process route is simple, can be degradable, green pollution-free.
Example 2
120g corn starchs are weighed, in adding 240mL toluene, under 140 DEG C of oil baths after azeotropic water removing 3h, with 3mL/min Deca
60mL mass fractions are 1% stannous octoate toluene solution, while 2h is stirred with 400r/min, subsequently again with 2mL/min Deca
100mL caprolactones, keeping temperature continues to react 24h, obtains copolymer mixture；By above-mentioned copolymer mixture, 800mL first is added
In benzene, under 30 DEG C of waters bath with thermostatic control, 15h is stirred with 400r/min, subsequently filtered, and filtering residue 5 times is washed with toluene, then by filtering residue
In being placed in vacuum drying oven, it is dried to constant weight at 70 DEG C, obtains starch polycaprolactone graft copolymer, weigh 50g Ovum crusta Gallus domesticuss, uses
Behind deionized water wash Ovum crusta Gallus domesticuss surface 3 times, then 300mL mass fractions are immersed in for 30min in 5% sodium hydroxide solution,
After peeling off egg membrane, eggshell is washed with deionized to cleaning mixture in neutrality, eggshell is proceeded in drying baker, at 110 DEG C
It is dried to constant weight, then continues at and grind in mortar 2h, obtains pretreatment Ovum crusta Gallus domesticuss powder；0.05g silane resin acceptor kh-550s are weighed,
In adding 150mL dehydrated alcohol, stirred to silane coupler with 400r/min and be completely dissolved, add 70g starch polycaprolactones
Graft copolymer, at 85 DEG C, continues stirring and is evaporated to dryness, and adds after subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 5g mixed
In mill, after melt blending 20min at 140 DEG C, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention is added in inflation film manufacturing machine, arrange parameter screw rod is straight
Footpath be Ф 45mm, screw slenderness ratio 28：1, screw speed is 100r/min, a diameter of Ф 75mm of head film mouth, diameter of traction-roller
For Ф 650mm, traction linear velocity is 50m/min, and thin film rolls over footpath width for 600mm, a diameter of Ф 450mm of vane, Blown Film
, after testing, enhancement mode polycaprolactone biodegradable plastic tensile strength prepared by the present invention reaches 38 MPa, extension at break
Rate is 36.5%, and tearing strength is 41.8KN/m, and process route is simple, can be degradable, green pollution-free.
Example 3
110g corn starchs are weighed, in adding 220mL toluene, under 135 DEG C of oil baths after azeotropic water removing 3h, with 3mL/min Deca
55mL mass fractions are 1% stannous octoate toluene solution, while 2h is stirred with 350r/min, subsequently again with 2mL/min Deca 95mL
Caprolactone, keeping temperature continues to react 22h, obtains copolymer mixture；By above-mentioned copolymer mixture, in adding 700mL toluene,
Under 25 DEG C of waters bath with thermostatic control, 13h is stirred with 350r/min, subsequently filtered, and filtering residue 4 times is washed with toluene, then filtering residue is placed in
In vacuum drying oven, at 65 DEG C be dried to constant weight, obtain starch polycaprolactone graft copolymer, weigh 40g Ovum crusta Gallus domesticuss, spend from
Behind sub- water washing Ovum crusta Gallus domesticuss surface 3 times, then 250mL mass fractions are immersed in for 25min in 5% sodium hydroxide solution, peeled off
After egg membrane, eggshell is washed with deionized to cleaning mixture in neutrality, eggshell is proceeded in drying baker, be dried at 108 DEG C
To constant weight, then continue at and grind in mortar 2h, obtain pretreatment Ovum crusta Gallus domesticuss powder；0.04g silane resin acceptor kh-550s are weighed, is added
In 125mL dehydrated alcohol, stirred to silane coupler with 350r/min and be completely dissolved, add the grafting of 65g starch polycaprolactone
Copolymer, at 80 DEG C, continues stirring and is evaporated to dryness, and after subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 5g kneading machine is added
In, after melt blending 18min at 125 DEG C, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
Enhancement mode polycaprolactone biodegradable plastic prepared by the present invention is added in inflation film manufacturing machine, arrange parameter screw rod is straight
Footpath be Ф 45mm, screw slenderness ratio 28：1, screw speed is 30r/min, a diameter of Ф 65mm of head film mouth, and diameter of traction-roller is
Ф 650mm, traction linear velocity is 32m/min, and thin film rolls over footpath width for 350mm, a diameter of Ф 450mm of vane, and Blown Film is
Can, after testing, enhancement mode polycaprolactone biodegradable plastic tensile strength prepared by the present invention reaches 36MPa, elongation at break
For 35.5%, tearing strength is 39.8KN/m, and process route is simple, can be degradable, green pollution-free.
Claims (1)
1. a kind of preparation method of enhancement mode polycaprolactone biodegradable plastic, it is characterised in that concrete preparation process is：
（1）100~120g corn starchs are weighed, in adding 200~240mL toluene, the azeotropic water removing 2 under 130~140 DEG C of oil baths
After~3h, with 2~3mL/min, 50~60mL of Deca mass fractions as 1% stannous octoate toluene solution, while with 300~400r/
Min stirs 1~2h, and subsequently again with 1~2mL/min Deca 90~100mL caprolactones, keeping temperature continues to react 20~24h, obtains
Copolymer mixture；
（2）By above-mentioned copolymer mixture, in adding 600~800mL toluene, under 20~30 DEG C of waters bath with thermostatic control, with 300~
400r/min stirs 10~15h, subsequently filters, and filtering residue 3~5 times is washed with toluene, then filtering residue is placed in vacuum drying oven,
It is dried to constant weight at 60~70 DEG C, obtains starch polycaprolactone graft copolymer, it is standby；
（3）30~50g Ovum crusta Gallus domesticuss are weighed, after being washed with deionized Ovum crusta Gallus domesticuss surface 2~3 times, then it is immersed in 200~
300mL mass fractions are 20~30min in 5% sodium hydroxide solution, after peeling off egg membrane, are washed with deionized eggshell extremely
Cleaning mixture proceeds to eggshell in drying baker in neutrality, is dried to constant weight at 105~110 DEG C, then continues at and grind in mortar 1
~2h, obtains pretreatment Ovum crusta Gallus domesticuss powder；
（4）0.03~0.05g silane resin acceptor kh-550s are weighed, in adding 100~150mL dehydrated alcohol, with 300~400r/
Min is stirred to silane coupler and is completely dissolved, and adds 60~70g steps（2）The starch polycaprolactone graft copolymer of preparation,
At 75~85 DEG C, continue stirring and be evaporated to dryness, after subsequently mixing with the above-mentioned pretreatment Ovum crusta Gallus domesticuss powder of 4~5g batch mixer is added
In, after 15~20min of melt blending at 110~140 DEG C, extruding pelletization obtains enhancement mode polycaprolactone biodegradable plastic.
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| CN201611030354.6A CN106674615A (en) | 2016-11-22 | 2016-11-22 | Preparation method of enhanced type polycaprolactone biodegradable plastics |
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| CN201611030354.6A CN106674615A (en) | 2016-11-22 | 2016-11-22 | Preparation method of enhanced type polycaprolactone biodegradable plastics |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651965A (en) * | 2021-04-08 | 2021-11-16 | 华中科技大学同济医学院附属协和医院 | High molecular compound, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183937A (en) * | 2013-03-21 | 2013-07-03 | 清华大学深圳研究生院 | Modified polyactic acid composite material and preparation method thereof |
| CN103183938A (en) * | 2013-03-21 | 2013-07-03 | 清华大学深圳研究生院 | Polycaprolactone/poly butylene succinate/eggshell powder composite material and preparation method thereof |
-
2016
- 2016-11-22 CN CN201611030354.6A patent/CN106674615A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183937A (en) * | 2013-03-21 | 2013-07-03 | 清华大学深圳研究生院 | Modified polyactic acid composite material and preparation method thereof |
| CN103183938A (en) * | 2013-03-21 | 2013-07-03 | 清华大学深圳研究生院 | Polycaprolactone/poly butylene succinate/eggshell powder composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI CHEN ET AL: "A novel approach to grafting polymerization of ε-caprolactone onto starch granules", 《CARBOHYDRATE POLYMERS》 * |
| 蔡朝霞等: "《蛋品加工新技术》", 31 January 2013, 中国农业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651965A (en) * | 2021-04-08 | 2021-11-16 | 华中科技大学同济医学院附属协和医院 | High molecular compound, preparation method and application thereof |
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Application publication date: 20170517 |