CN115819913A - Biodegradable PBS-based modified film for garbage bags - Google Patents
Biodegradable PBS-based modified film for garbage bags Download PDFInfo
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- CN115819913A CN115819913A CN202211689039.XA CN202211689039A CN115819913A CN 115819913 A CN115819913 A CN 115819913A CN 202211689039 A CN202211689039 A CN 202211689039A CN 115819913 A CN115819913 A CN 115819913A
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- luteolin
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- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 62
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims abstract description 29
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000009498 luteolin Nutrition 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010096 film blowing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920001896 polybutyrate Polymers 0.000 claims abstract 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000012982 microporous membrane Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000002137 ultrasound extraction Methods 0.000 claims description 4
- 241000628997 Flos Species 0.000 claims description 2
- 241000205585 Aquilegia canadensis Species 0.000 claims 2
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000011246 composite particle Substances 0.000 abstract description 6
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 241001570521 Lonicera periclymenum Species 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- -1 poly succinic acid butylene glycol ester Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 244000167230 Lonicera japonica Species 0.000 description 1
- 235000017617 Lonicera japonica Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006467 substitution reaction 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a biodegradable PBS (poly (butylene succinate)) based modified film for garbage bags, which belongs to the technical field of degradable films and comprises the following raw materials in parts by mass: 80-120 parts of modified PBS particles, 7.2-10.8 parts of luteolin and 26.16-39.24 parts of PBAT particles, and the preparation method comprises the following steps: step A1, melting the modified PBS particles, and adding luteolin to obtain PBS composite particles; a2, blending the PBS composite material particles and the PBAT particles; and A3, drying the blend, and then obtaining the PBS-based modified film by using a film blowing machine, wherein the modified PBS particles prepared by maleic anhydride are used as main raw materials, the compatibility of the system can be improved, the toughness of the composite material can be improved by adding PBAT, and the addition of luteolin with wide source and low price is used for reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of degradable films, and particularly relates to a biodegradable PBS (poly (butylene succinate)) based modified film for garbage bags.
Background
The plastic garbage bag is indispensable in people's life, because it has no pungent smell, it is convenient and fast to use, offer convenience for daily life, but the traditional garbage bag is difficult to degrade and the use amount is very big, cause very serious environmental pollution and greenhouse effect problem, therefore popularizing and applying the biodegradable garbage bag is imperative, it is one of the effective ways of the green development of the present material too, but the biodegradable material has better performance in the use, the macromolecule material that can degrade naturally after using, this material can lighten environmental pollution apparently, in various degradable macromolecule polymer materials, poly succinic acid butylene glycol ester (PBS) is a degradable material with good combination property, but because PBS crystallinity is 40-60%, the structure is comparatively regular, have fragility, and the production cost is higher, therefore has limited its popularization and application.
Disclosure of Invention
The invention aims to provide a biodegradable PBS (poly (butylene succinate)) based modified film for garbage bags, which aims to solve the problems of high brittleness and high production cost of PBS in the background technology.
The purpose of the invention can be realized by the following technical scheme:
a biodegradable PBS-based modified film for garbage bags comprises the following raw materials in parts by mass: 96.95-108.05 parts of modified PBS particles, 7.2-10.8 parts of luteolin and 26.16-39.24 parts of PBAT particles;
the preparation process comprises the following steps:
step A1, heating the modified PBS particles to 150-160 ℃, adding luteolin after the modified PBS particles are completely melted, uniformly mixing, performing melt extrusion by a double-screw extruder, and granulating to obtain PBS composite particles;
step A2, drying the PBS composite material particles and the PBAT particles in a drying oven at 70-90 ℃ for 18-20 hours to achieve constant weight, adding the dried PBS composite material particles and the dried PBAT particles into a torque rheometer for melt blending, and taking the modified PBS particles as a compatilizer to effectively improve the interfacial compatibility of the polymer, so that the mechanical property of the material is improved;
and A3, extruding the blend, cooling and granulating to obtain the required blend particles, and putting the blend particles into a film blowing machine to blow and form a film so as to obtain the PBS-based modified film.
Further, the preparation of the modified PBS particles comprises the following steps:
mixing maleic anhydride, dicumyl peroxide and PBS, then performing melt extrusion at 155-165 ℃ by using a double-screw extruder, and granulating to obtain modified PBS particles, wherein the dicumyl peroxide can be used as an initiator to initiate the polymerization reaction of the maleic anhydride grafted PBS.
Further, the mass ratio of the maleic anhydride to the dicumyl peroxide to the PBS is 1.5-2.5:0.45-0.55:95-105.
Furthermore, the luteolin is an extract of honeysuckle leaves, the honeysuckle is selected because the honeysuckle leaves are large in quantity, easy to collect and obtain, and the luteolin content in the honeysuckle leaves is high, but the luteolin is wasted as a byproduct of the honeysuckle.
Further, the extraction of the luteolin comprises the following steps:
soaking dried and pulverized flos Lonicerae leaves in mixed solution of methanol and sodium hydroxide for 10-12h, then performing ultrasonic extraction at 50-65 deg.C for 30-40min, filtering, concentrating, and filtering with microporous membrane to obtain luteolin.
Further, the dosage ratio of the honeysuckle leaves, the methanol and the sodium hydroxide solution is 0.5-1g:10-25mL, wherein the mass fraction of the sodium hydroxide solution is 20-30%.
The invention has the beneficial effects that:
the lonicera japonica leaf extract luteolin is introduced into the modified PBS particles to prepare the PBS composite particles, the luteolin is wide in source and low in cost as a natural antioxidant, the luteolin added into the composite material can be used as a heterogeneous component to induce the PBS, heterogeneous nucleation points are formed at the contact surface of the composite material to play a role of a nucleating agent, the efficient nucleating agent can effectively change the crystal size of the PBS, the crystallization speed is increased, the structure is refined, and the smoothness and the transparency of the appearance of a product are improved;
the polybutylene terephthalate adipate (PBAT) adopted by the invention has flexibility of a long methylene chain and rigidity of an aromatic ring, the rigid aromatic component can improve the melting point of PBS, the mechanical property of the PBS can be improved, the biodegradation property of the PBS can not be influenced, and the flexible aliphatic component can improve the brittleness and the degradation property of the PBS;
the modified PBS particles are used as a main raw material, the maleic anhydride grafted PBS particles can increase the interfacial compatibility of the polymer, so that the melting temperature, the tensile strength and the elongation at break of the composite material are improved, and the garbage bag prepared from the composite material has the advantages of environmental protection and biodegradability, so that no burden is caused on the environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of modified PBS particles comprises the following steps:
1.5 parts of maleic anhydride, 0.45 part of dicumyl peroxide and 95 parts of PBS were mixed, and then melt-extruded at 155 ℃ by a twin-screw extruder and granulated to obtain modified PBS particles.
Example 2
A preparation method of modified PBS particles comprises the following steps:
2 parts of maleic anhydride, 0.5 part of dicumyl peroxide and 100 parts of PBS were mixed, and then melt-extruded at 160 ℃ by a twin-screw extruder and granulated to obtain modified PBS particles.
Example 3
A preparation method of modified PBS particles comprises the following steps:
2.5 parts of maleic anhydride, 0.55 part of dicumyl peroxide and 105 parts of PBS were mixed, and then melt-extruded at 165 ℃ by a twin-screw extruder and granulated to obtain modified PBS particles.
Example 4
Luteolin is prepared by the following steps:
soaking 0.5g dried and pulverized folium Lonicerae in 10mL mixed solution of methanol and 1mL 20% sodium hydroxide for 10h, performing ultrasonic extraction at 50 deg.C for 30min, filtering, concentrating, and filtering with 0.45 μm microporous membrane to obtain luteolin.
Example 5
Luteolin is prepared by the following steps:
soaking 0.75g dried and pulverized folium Lonicerae in 17.5mL mixed solution of methanol and 3mL 25% sodium hydroxide for 11h, ultrasonic extracting at 57.5 deg.C for 35min, filtering with 0.45 μm microporous membrane to obtain luteolin.
Example 6
Luteolin is prepared by the following steps:
soaking 1g dried and pulverized folium Lonicerae in 25mL mixed solution of methanol and 5mL sodium hydroxide with mass fraction of 30% for 12h, performing ultrasonic extraction at 65 deg.C for 40min, filtering, concentrating, and filtering with 0.45 μm microporous membrane to obtain luteolin.
Example 7
A biodegradable PBS-based modified film for garbage bags is prepared by the following steps:
step A1, heating 96.95 parts of modified PBS particles to 150 ℃, adding 7.2 parts of luteolin after complete melting, uniformly mixing, performing melt extrusion by a double-screw extruder, and granulating to obtain modified PBS composite particles;
step A2, drying 87.2 parts of PBS composite material particles and 26.16 parts of PBAT particles in a 70 ℃ oven for 20 hours to reach constant weight, and adding the dried PBS composite material particles and PBAT particles into a torque rheometer for melt blending;
and A3, extruding the blend, cooling and granulating to obtain the required blend particles, and putting the blend particles into a film blowing machine to blow and form a film so as to obtain the PBS-based modified film.
Example 8
A biodegradable PBS-based modified film for garbage bags is prepared by the following steps:
step A1, heating 102.5 parts of modified PBS particles to 155 ℃, completely melting, adding 9 parts of luteolin, uniformly mixing, performing melt extrusion by using a double-screw extruder, and granulating to obtain PBS composite particles;
step A2, drying 109 parts of PBS composite material particles and 27.7 parts of PBAT particles in an oven at 80 ℃ for 21 hours to reach constant weight, and adding the dried PBS composite material particles and PBAT particles into a torque rheometer for melt blending;
and A3, extruding the blend, cooling and granulating to obtain the required blend particles, and putting the blend particles into a film blowing machine to blow and form a film so as to obtain the PBS-based modified film.
Example 9
A biodegradable PBS-based modified film for garbage bags is prepared by the following steps:
step A1, heating 108.05 parts of modified PBS particles to 160 ℃, adding 10.8 parts of luteolin after complete melting, uniformly mixing, performing melt extrusion by a double-screw extruder, and granulating to obtain PBS composite particles;
step A2, drying 109 parts of PBS composite material particles and 39.24 parts of PBAT particles in a 90 ℃ oven for 22 hours to reach constant weight, and adding the dried PBS composite material particles and PBAT particles into a torque rheometer for melt blending;
and A3, extruding the blend, cooling and granulating to obtain the required blend particles, and putting the blend particles into a film blowing machine to blow and form a film so as to obtain the PBS-based modified film.
Comparative example 1
Compared with example 7, PBAT is not added in the preparation process of the biodegradable PBS-based modified film for garbage bags, the rest steps and parameters are the same, repeated description is omitted in the comparative example, and the biodegradable PBS-based modified film for garbage bags is finally obtained.
Comparative example 2
Compared with example 8, luteolin is not added in the preparation process of the biodegradable PBS-based modified film for garbage bags in the comparative example, the rest steps and parameters are the same, the comparative example is not repeated, and the biodegradable PBS-based modified film for garbage bags is finally obtained.
The DSC test is carried out on the sample, and the samples of example 7 to example 9 and comparative example 1 to comparative example 2 are weighed and pressed into sample pieces in a sample tray and tested under the protection of high-purity nitrogen. Setting the heating rate to be 10 ℃/min, heating from room temperature 23 ℃ to 200 ℃, similarly setting the cooling rate to be 10 ℃/min, cooling from 200 ℃ to-50 ℃, and finally heating to 200 ℃ again at the heating rate of 10 ℃/min;
the samples were subjected to mechanical property tests, and the samples prepared in examples 7 to 9 and comparative examples 1 to 2 were cut into a dumbbell shape with reference to the GB/TI3022-91 standard, and were subjected to a test at a tensile rate of I0mm/min, and the elongation at break of the modified PBS sample was measured and calculated. The results are shown in table 1:
TABLE 1
| Item | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Elongation at break/% | 394.6 | 414.6 | 434.6 | 77.7 | 380.7 |
| Tm/℃ | 115.71 | 117.2 | 116.62 | 116.7 | 105.3 |
As can be seen from table 1, compared with comparative example 1 and comparative example 2, the biodegradable PBS-based modified films for trash bags prepared in examples 7 to 9 have higher elongation at break and higher melting point, because PBAT and luteolin are added in the preparation process of examples 7 to 9 to modify PBS, luteolin added in the composite material can be used as a heterogeneous component to induce PBS, a heterogeneous nucleation point is formed at the contact surface of the composite material to act as a nucleating agent, so that the PBS polymer is crystallized due to steric hindrance, the degradability of the composite material is ensured, and the composite material has improved comprehensive properties, while PBAT has flexibility of long methylene chain and rigidity of aromatic ring, better ductility and higher flexibility, and has higher melt flow rate, and the PBS is modified by PBAT, so that the toughness of PBS can be significantly improved.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The biodegradable PBS-based modified film for the garbage bags is characterized by comprising the following raw materials in parts by mass: 96.95-108.05 parts of modified PBS particles, 7.2-10.8 parts of luteolin and 26.16-39.24 parts of PBAT particles;
the PBS-based modified film is prepared by the following steps:
step A1, heating modified PBS particles to be completely melted, adding luteolin, uniformly mixing, performing melt extrusion by using a double-screw extruder, and granulating to obtain PBS composite material particles;
step A2, drying the PBS composite material particles and the PBAT particles in an oven at 70-90 ℃ to constant weight, adding the dried modified PBS particles and the dried PBAT particles into a torque rheometer to perform melt blending to obtain a blend;
and A3, extruding the blend, cooling and granulating to obtain the required blend particles, and putting the blend particles into a film blowing machine to blow and form a film so as to obtain the PBS-based modified film.
2. The biodegradable PBS-based modified film for garbage bags according to claim 1, wherein: the preparation of the modified PBS particles comprises the following steps:
the modified PBS particles are prepared by mixing maleic anhydride, dicumyl peroxide and PBS, then using a double-screw extruder to melt and extrude at 155-165 ℃ and pelleting.
3. The biodegradable PBS-based modified film for garbage bags according to claim 2, wherein: the mass ratio of the maleic anhydride to the dicumyl peroxide to the PBS is 1.5-2.5:0.45-0.55:95-105.
4. The biodegradable PBS-based modified film for garbage bags according to claim 1, wherein: the luteolin is a honeysuckle leaf extract and is prepared by the following steps:
soaking dried and pulverized flos Lonicerae leaves in mixed solution of methanol and sodium hydroxide for 10-12h, performing ultrasonic extraction at 50-65 deg.C for 30-40min, vacuum filtering, concentrating, and filtering with microporous membrane to obtain luteolin.
5. The biodegradable PBS-based modified film for garbage bags according to claim 4, wherein: the mass ratio of the honeysuckle leaves to the methanol to the sodium hydroxide solution is 0.5-1:10-25, and the mass fraction of the sodium hydroxide solution is 20-30%.
6. The biodegradable PBS-based modified film for garbage bags according to claim 1, wherein: in step A1, the modified PBS particles were heated to 150-160 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211689039.XA CN115819913B (en) | 2022-12-27 | 2022-12-27 | Biodegradable PBS-based modified film for garbage bags |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211689039.XA CN115819913B (en) | 2022-12-27 | 2022-12-27 | Biodegradable PBS-based modified film for garbage bags |
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| CN115819913B CN115819913B (en) | 2024-11-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337660A (en) * | 2017-07-24 | 2017-11-10 | 仲恺农业工程学院 | Method for extracting luteolin from honeysuckle |
| WO2019155398A1 (en) * | 2018-02-07 | 2019-08-15 | Csir | Biodegradable plastic |
| CN110835457A (en) * | 2019-11-15 | 2020-02-25 | 上海海洋大学 | Full-biomass porous material slow-release antibacterial active preservative film and preparation method thereof |
| CN113278265A (en) * | 2021-06-25 | 2021-08-20 | 华东理工大学 | Degradable lignin-based composite agricultural mulching film and preparation method thereof |
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2022
- 2022-12-27 CN CN202211689039.XA patent/CN115819913B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107337660A (en) * | 2017-07-24 | 2017-11-10 | 仲恺农业工程学院 | Method for extracting luteolin from honeysuckle |
| WO2019155398A1 (en) * | 2018-02-07 | 2019-08-15 | Csir | Biodegradable plastic |
| CN110835457A (en) * | 2019-11-15 | 2020-02-25 | 上海海洋大学 | Full-biomass porous material slow-release antibacterial active preservative film and preparation method thereof |
| CN113278265A (en) * | 2021-06-25 | 2021-08-20 | 华东理工大学 | Degradable lignin-based composite agricultural mulching film and preparation method thereof |
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