CN117757231A - Special material for potato covered cultivation full-biodegradable mulching film and preparation method thereof - Google Patents
Special material for potato covered cultivation full-biodegradable mulching film and preparation method thereof Download PDFInfo
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- CN117757231A CN117757231A CN202311357107.7A CN202311357107A CN117757231A CN 117757231 A CN117757231 A CN 117757231A CN 202311357107 A CN202311357107 A CN 202311357107A CN 117757231 A CN117757231 A CN 117757231A
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- 239000000463 material Substances 0.000 title claims abstract description 75
- 235000002595 Solanum tuberosum Nutrition 0.000 title claims abstract description 49
- 244000061456 Solanum tuberosum Species 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 polyethylene Polymers 0.000 claims abstract description 33
- 239000002362 mulch Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 4
- 229920000704 biodegradable plastic Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000004633 polyglycolic acid Substances 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000000057 synthetic resin Substances 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 abstract description 15
- 229920000573 polyethylene Polymers 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 239000002689 soil Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 8
- 235000012015 potatoes Nutrition 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- 238000010096 film blowing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Protection Of Plants (AREA)
Abstract
The invention discloses a special material for a full-biodegradable mulching film for potato cover cultivation and a preparation method thereof. The material is developed according to the cultivation growth period and characteristics of the potatoes and is specially used for the production of the potato covered cultivation mulch. Popularization and application prove that the mulching film produced by the material is used for potato cultivation and natural embrittlement and rupture for 90 days. Through soil burying test, the biological degradation is completed within one year. Through a comparison test, each performance of the material reaches or exceeds the performance of the polyethylene mulching film material, and the material can be used for producing potato mulching films instead of polyethylene.
Description
Technical Field
The invention belongs to the technical field of novel fully biodegradable polymer materials, and particularly relates to a special material for a fully biodegradable mulching film for potato cover cultivation and a preparation method thereof.
Background
Although the field of biodegradable mulching films has been developed in a breakthrough manner, the industrialization and popularization of the biodegradable mulching films have been slow due to various reasons. The technical reasons are mainly two: firstly, the mechanical strength is generally insufficient, and the large-scale operation is difficult, which is one of the main reasons for limiting the wide application of the full-biodegradable mulch film. The physical and chemical properties of the biodegradable mulch film material determine that the tensile strength is poor, so that the mechanized mulch film coating operation cannot be performed in agricultural areas mainly comprising mechanical operation. Therefore, the tensile strength of the mulching film is improved by perfecting and improving the formula of the mulching film, and the operation requirement of agricultural machinery is met, so that conditions can be created for large-scale application of the biodegradable mulching film. Secondly, the biodegradable mulching film has poor rupture time and degradation controllability, and is difficult to meet different climatic conditions and the growth needs of crops. The existing biodegradable mulching film products are broken and degraded too early, the covering time is far lower than the crop mulching film covering safety period, and the main functions of heating, preserving soil moisture, inhibiting weeds and the like are difficult to ensure, so that the popularization of the mulching film is hindered.
Disclosure of Invention
For the problems in the background technology, special full-biodegradable mulch film materials are required to be developed aiming at different climatic conditions and growth periods of crops.
In the north (the Ningxia Hui autonomous region, ji county), the potato needs about 135-150 days from planting to harvesting, and not only the mulching film material is required to have good tensile strength, but also the degradation speed is required not to be too high.
The technical scheme provided by the invention is as follows:
a potato cover cultivation full-biodegradable plastic film special material which is characterized in that: the material comprises the following components in parts by mass:
the preparation method of the opening master batch comprises the following steps: the raw materials comprise, by mass, polybutylene terephthalate-adipate: and (3) an opening agent: and (3) a compatilizer: dispersant = 23-70:20-50:5-12:5-15; firstly weighing an opening agent (superfine silicon dioxide) and a dispersing agent, adding the superfine silicon dioxide into a kneading pot, starting stirring, then uniformly adding the dispersing agent, and continuing stirring for 40-45 minutes for later use; then weighing polybutylene terephthalate-adipic acid butanediol ester and compatilizer, sequentially adding the kneaded superfine silicon dioxide, polybutylene terephthalate-adipic acid butanediol ester and compatilizer into a high-speed stirrer, and stirring for 5-15 minutes for later use; and finally, feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 90-170 ℃, cooling, mixing and packaging to obtain the opening master batch.
As a further preferred embodiment of the above invention, polybutylene terephthalate-adipate is KHB21AP11B, commercially available from Yingkou Kapsinization Co., ltd. The polyglycolic acid is film blowing resin of Pande (Shanghai) International trade company, and has molecular weight of about 60 ten thousand and melt flow rate of 1-5/10min.
As a further preferred aspect of the invention, the light stabilizer is selected from the high pigment carbon black XP5650B produced by Kabot corporation.
As a further preferred aspect of the invention, the lubricant is selected from silicone masterbatch, KJ-A01, manufactured by Kjeldahl plastic toughening materials Co., ltd.
As a further preferable aspect of the above invention, the stirring rate of the open master batch is 80 to 1000 rpm.
As a further preferred aspect of the invention, the opening agent is selected from ultrafine silica produced by Weifang scintillation nanomaterial Co., ltd. And having a fineness of 3000-5000 mesh.
As a further preferred aspect of the invention, the compatibilizer is selected from the group consisting of Ning wave energy photo-new materials technology Co., ltd. Maleic anhydride graft modified polylactic acid, grade GPM805.
As a further preferred embodiment of the above invention, the dispersant is TR044W manufactured by STRUKTOL Co., U.S.A.
The preparation method of the special material for the full-biodegradable mulching film for potato coverage cultivation comprises the following steps:
step one, preparation of an open master batch
(1) According to the formula of the opening master batch, the superfine silicon dioxide and the dispersing agent are weighed, firstly, the superfine silicon dioxide is added into a kneading pot, stirring is started, then the dispersing agent is uniformly added, and stirring is continued for 40-45 minutes for standby;
(2) Weighing polybutylene terephthalate-adipic acid and a compatilizer according to an opening master batch formula, sequentially adding the kneaded ultrafine silicon dioxide, polybutylene terephthalate-adipic acid and the compatilizer into a high-speed stirrer, and stirring for 5-15 minutes for later use;
(3) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 90-170 ℃, cooling, mixing and packaging to obtain the opening master batch.
Step two, preparation of special material for potato cover cultivation full-biodegradable mulch film
(1) According to the formula, all the components are sequentially added into a high-speed stirrer and stirred for 5-10 minutes for standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
The invention also provides application of the special material for the full-biodegradable mulching film for potato coverage cultivation in potato planting.
Compared with the prior art, the invention better solves the problems of controlling the tensile strength and the degradation speed of the potato full-biodegradable mulch film material, and has the beneficial effects that:
1) The preferred polybutylene terephthalate-adipate has properties similar to those of polyethylene, excellent extensibility and film forming properties, but low tensile strength and very excellent strength of polyglycolic acid, and the combination of the two can complement the properties.
2) The high pigment carbon black is preferably a light stabilizer, which can absorb ultraviolet light, control the aging speed of the mulching film and has the weeding function.
3) Preferably superfine silicon dioxide, compatilizer maleic anhydride grafted modified polylactic acid and dispersant TR044W, wherein polybutylene terephthalate-adipic acid butanediol ester is used as a carrier to prepare master batch, and a proper amount of the master batch is added to increase the opening performance of the material and improve the compatibility of the formula components.
4) The popularization and application prove that the mulching film produced by the material is used for cultivating potatoes (green potato No. 9), the mechanical mulching operation is normal, and natural embrittlement and rupture are carried out for 90 days. Through soil burying test, the biological degradation is completed within one year.
5) Compared with natural-color full-biodegradable plastic mulching film for cultivating potatoes, the plastic mulching film has obvious weeding function.
6) The mulching film special for potato mulching cultivation production and the common polyethylene mulching film are adopted to simultaneously perform potato mulching cultivation, the polyethylene mulching film still maintains good toughness for 90 days, the degradation speed is very slow, and the soil is buried for one year. The mulching film of the material of the invention is naturally embrittled and ruptured after 90 days, and is completely biodegraded after being buried in soil for one year. From the mechanical property, the properties of the material of the invention reach or exceed the properties of the polyethylene mulch film material. From the viewpoint of potato yield, the polyethylene film mulching cultivation is about 3500 jin/mu, and the special material film mulching cultivation can reach more than 4000 jin/mu. Therefore, the material can be used for producing potato mulching cultivation mulching films instead of polyethylene. Compared with natural-color full-biodegradable plastic mulching film for cultivating potatoes, the plastic mulching film has obvious weeding function.
Drawings
The invention is further described below with reference to the drawings and examples.
FIG. 1 is a photograph of a potato cultivation test base and a mulch film covered embrittlement rupture site.
FIG. 2 is a photograph of a field of a polyethylene film covered cultivated potato.
Detailed Description
Materials:
the polybutylene terephthalate-adipate is selected from Kapsinized Co., ltd., brand KHB21AP11B,
the polyglycolic acid is film blowing resin of Pande (Shanghai) International trade company, has molecular weight of about 60 ten thousand, melt flow rate of 1-5/10min,
the light stabilizer is high pigment carbon black of Kabot corporation of America, with the trade name XP5650B,
the lubricant is silicone master batch of KJ-A01 of Kjeldahl plastic toughening material Co-Ltd,
the opening agent is selected from superfine silica of Weifang, scintillant nano material limited company with fineness of 3000-5000 mesh,
the compatilizer is selected from maleic anhydride grafted modified polylactic acid of Ning wave energy photo new material technology Co., ltd, with the brand of GPM805,
the dispersant is STRUKTOL Co., USA, brand TR044W.
Preparation of open master batch
1) Formulation of
2) Preparation of open master batch
(1) According to the above formulation, the ultrafine silica and the dispersant are weighed, and the ultrafine silica is added to the kneading
Stirring in a pot at 100 rpm; then evenly adding the dispersing agent, and continuously stirring for 40 minutes, 100 revolutions per minute for standby.
(2) According to the formula, the polybutylene terephthalate-adipate and the compatilizer are weighed, and the kneaded ultrafine silicon dioxide, polybutylene terephthalate-adipate and the compatilizer are sequentially added into a high-speed stirrer for 1000 revolutions per minute, stirred for 10 minutes for standby.
(3) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 90-170 ℃, cooling, mixing and packaging to obtain the opening master batch.
Example 1
1) Formulation of
2) Process for producing a solid-state image sensor
(1) According to the formula, all the components of the material are sequentially added into a high-speed stirrer and stirred for 10 minutes for standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
Example 2
1) Formulation of
2) Process for producing a solid-state image sensor
(1) According to the formula, all the components of the materials are sequentially added into a high-speed stirrer and stirred for 10 minutes,
standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
Example 3
1) Formulation of
2) Process for producing a solid-state image sensor
(1) According to the formula, all the components of the material are sequentially added into a high-speed stirrer and stirred for 10 minutes for standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
Example 4
1) Formulation of
2) Process for producing a solid-state image sensor
(1) According to the formula, all the components of the materials are sequentially added into a high-speed stirrer and stirred for 10 minutes,
standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
Example 5
1) Formulation of
2) Process for producing a solid-state image sensor
(1) According to the formula, all the components of the material are sequentially added into a high-speed stirrer and stirred for 5-10 minutes for standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
Comparative example 1, polybutylene terephthalate-adipate, commercial Co., ltd. KappaWin, KHB21AP11B,
comparative example 2, linear polyethylene 7042 resin, manufactured by lanzhou petrochemical production.
The samples obtained in examples 1 to 5 and comparative example 1 were subjected to performance test, and the results were as follows:
the samples obtained in examples 1 to 5 and comparative example 2 were subjected to performance test, and the results were as follows:
the tensile strength is tested according to GB/T1040.2-2006.
The test standard of the fracture growth rate is GB/T1040.2-2006.
The flow rate is tested in GB/T3682-2000B
By comparing the results of the product performance tests of examples 1-5 with the results of the test of comparative example 1, it can be seen that the formulation of example 4 has the best overall performance.
By comparing the results of the product performance tests of examples 1-5 with the results of the test of comparative example 2, it can be seen that the formulation of example 4 has the best overall performance and can replace polyethylene 7042. The polyethylene degradation speed is slow, and the special material for the potato mulching film has better biodegradability.
As shown in fig. 1, the mulch film of example 4 was used for an experiment (13 mu planting) of potato (green potato No. 9), the experiment starting time was 2023 years and 4 months, and the experiment site was the experimental base of potato seed in the western ji county of the autonomous district of Ningxia. The mulching film produced by the material is used for potato cultivation, the mechanical mulching operation is normal, and natural embrittlement and rupture can be realized within 90 days. As shown in fig. 2, the polyethylene mulch film of comparative example 2 maintained good toughness after 90 days without brittle fracture.
In addition, through soil burying test, the biological degradation is completed within one year. The soil burying test method comprises the following steps: respectively taking a full-biodegradable mulching film and a polyethylene mulching film, burying the full-biodegradable mulching film and the polyethylene mulching film in natural soil at the same time, and watering once per month, wherein the depth of the full-biodegradable mulching film is 10 cm. Digging out for 6 months (180 days), and observing degradation. And (5) continuously burying the soil for 12 months (360 days), and digging out again to observe degradation.
The foregoing description of the preferred embodiments of the invention should not be construed as limiting the scope of the invention, but rather as covering all changes and modifications that fall within the metes and bounds of the claims.
Claims (10)
1. A potato cover cultivation full-biodegradable plastic film special material which is characterized in that: the material comprises the following components in parts by mass:
the preparation method of the opening master batch comprises the following steps: the raw materials comprise, by mass, polybutylene terephthalate-adipate: and (3) an opening agent: and (3) a compatilizer: dispersant = 23-70:20-50:5-12:5-15; firstly weighing ultrafine silica serving as an opening agent and a dispersing agent, adding the ultrafine silica into a kneading pot, starting stirring, uniformly adding the dispersing agent, and continuously stirring for 40-45 minutes for later use; then weighing polybutylene terephthalate-adipic acid butanediol ester and compatilizer, sequentially adding the kneaded superfine silicon dioxide, polybutylene terephthalate-adipic acid butanediol ester and compatilizer into a high-speed stirrer, and stirring for 5-15 minutes for later use; and finally, feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 90-170 ℃, cooling, mixing and packaging to obtain the opening master batch.
2. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the polybutylene terephthalate-adipic acid and the polyglycolic acid are all synthetic resins of blown film grade.
3. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the light stabilizer is high pigment carbon black.
4. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the lubricant is a silicone master batch.
5. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: when the open master batch is prepared, the stirring speed is 80-1000 rpm.
6. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the fineness of the superfine silicon dioxide is 3000-5000 meshes.
7. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the compatilizer is maleic anhydride grafted modified polylactic acid.
8. The material special for the full-biodegradable mulching film for potato cultivation covered by the material is characterized in that: the dispersant is TR044W manufactured by STRUKTOL Inc. of America.
9. The method for preparing the special material for the potato cover cultivation full-biodegradable mulch film according to any one of claims 1 to 8, wherein the method comprises the following steps: the method comprises the following steps:
step one, preparation of an open master batch
(1) According to the formula of the opening master batch, the superfine silicon dioxide and the dispersing agent are weighed, firstly, the superfine silicon dioxide is added into a kneading pot, stirring is started, then the dispersing agent is uniformly added, and stirring is continued for 40-45 minutes for standby;
(2) Weighing polybutylene terephthalate-adipic acid and a compatilizer according to an opening master batch formula, sequentially adding the kneaded ultrafine silicon dioxide, polybutylene terephthalate-adipic acid and the compatilizer into a high-speed stirrer, and stirring for 5-15 minutes for later use;
(3) Feeding the materials stirred at high speed into a double screw extruder for extrusion granulation, controlling the temperature to be 90-170 ℃, cooling, mixing and packaging to obtain an open master batch;
step two, preparation of special material for potato cover cultivation full-biodegradable mulch film
(1) According to the formula, all the components are sequentially added into a high-speed stirrer and stirred for 5-10 minutes for standby;
(2) And (3) feeding the materials stirred at high speed into a double-screw extruder for extrusion granulation, controlling the temperature to be 160-220 ℃, cooling, mixing, detecting and packaging to obtain the special material for the potato covered cultivation full-biodegradable mulch film.
10. Use of a material dedicated to potato cultivation with full-biodegradable mulch film according to any one of claims 1 to 8 in potato cultivation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311357107.7A CN117757231A (en) | 2023-10-19 | 2023-10-19 | Special material for potato covered cultivation full-biodegradable mulching film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311357107.7A CN117757231A (en) | 2023-10-19 | 2023-10-19 | Special material for potato covered cultivation full-biodegradable mulching film and preparation method thereof |
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| CN117757231A true CN117757231A (en) | 2024-03-26 |
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ID=90320587
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|---|---|---|---|
| CN202311357107.7A Pending CN117757231A (en) | 2023-10-19 | 2023-10-19 | Special material for potato covered cultivation full-biodegradable mulching film and preparation method thereof |
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| Country | Link |
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| CN (1) | CN117757231A (en) |
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- 2023-10-19 CN CN202311357107.7A patent/CN117757231A/en active Pending
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