AU2020227121A1 - Preparation method and application of modified starch graft lactic acid oligomer thermoplastic composite - Google Patents
Preparation method and application of modified starch graft lactic acid oligomer thermoplastic composite Download PDFInfo
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- AU2020227121A1 AU2020227121A1 AU2020227121A AU2020227121A AU2020227121A1 AU 2020227121 A1 AU2020227121 A1 AU 2020227121A1 AU 2020227121 A AU2020227121 A AU 2020227121A AU 2020227121 A AU2020227121 A AU 2020227121A AU 2020227121 A1 AU2020227121 A1 AU 2020227121A1
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- lactic acid
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- acid oligomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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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
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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
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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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention discloses a preparation method of a modified starch graft lactic
acid oligomer thermoplastic composite, including: (1) adding 100 parts of modified
starch, 50-100 parts of lactic acid oligomer reactant, 8-15 parts of glycidyl methacrylate,
1-3 parts of citric acid and 0.5-5 parts of initiator into water and stirring evenly;
performing ultrasonic dispersion to form an emulsion, then heating to 70-90°C, and
further stirring for reacting for 5-12 h; and (2) demulsifying the emulsion of the step (1)
and drying to obtain the modified starch graft lactic acid oligomer thermoplastic
composite. The modified starch graft lactic acid oligomer thermoplastic composite, after
being processed into a film, has the advantages of high transparency and ductility,
strong processability, easy degradation in natural conditions and low cost, and can be
widely applied to packaging materials.
Description
[0001] Technical Field
[0002] The present invention relates to a preparation method and application of a modified starch graft lactic acid oligomer thermoplastic composite, belonging to the field of degradable plastics.
[0003] Related Art
[0004] Conventional plastic products, including polyethylene (PE), polypropylene (PP) and polystyrene, have very stable properties and can exist stably in the nature for a long time. These products, referred to as white trash, are hard to degrade and have caused serious environmental pollution. As an attempt to relieve environmental pressure, the focus of research and development has now been put on biodegradable plastics.
[0005] The biodegradable plastics refer to polymer materials that can be degraded into carbon dioxide and water within fairly short time in regular environmental conditions. Common biodegradable plastics available now include: biodegradable homopolyester such as PHA, PLA, PHB, PCL and PHBV, biodegradable copolyester such as PBS and PBSA, and natural products with a polysaccharide structure such as thermoplastic starch resin (TPS) and cellulose acetate. TPS is prepared by modifying starch through esterifying, grafting and other processes. The thermoplastic starch has the advantages of low cost and complete degradation and is a preferred material for the biodegradable plastics. However, a biodegradable film made from common thermoplastic starch is used under restrictions due to the shortcomings of relatively poor mechanical properties, strong water absorbing capacity, etc.
[0006] The present invention aims to provide a preparation method of a modified starch graft lactic acid oligomer thermoplastic composite. The prepared material has perfect mechanical and waterproof performance.
[0007] The aim of the present invention is achieved by the following technical solution.
[0008] A preparation method of a modified starch graft lactic acid oligomer thermoplastic composite includes: (1) adding 100 parts of modified starch, 50-100 parts of lactic acid oligomer reactant, 8-15 parts of glycidyl methacrylate, 1-3 parts of citric acid and 0.5-5 parts of initiator into water and stirring evenly; performing ultrasonic dispersion to form an emulsion, then heating to 70-90°C, and further stirring for reacting for 5-12 h; (2) demulsifying the emulsion of the step (1) and drying to obtain the modified starch graft lactic acid oligomer thermoplastic composite.
[0009] Preferably, a preparation method of the modified starch includes: adding dimethylformamide and pyrrole into plant starch, and stirring for 2 h or more at -60°C; dropwise adding acryloyl chloride while stirring and further stirring for 2 h or more; adding absolute ethyl alcohol for washing, performing suction filtration, and drying to obtain the modified starch.
[0010] Preferably, 30-60 parts of dimethylformamide, 10-15 parts of pyrrole and 0.5-2 parts of acryloyl chloride are added into every 100 parts of plant starch, during preparation of the modified starch.
[0011] Preferably, a preparation method of the lactic acid oligomer reactant includes: stirring 100 parts of lactic acid oligomer, 0.5-1.2 parts of zinc oxide and 0.5-1.5 parts of polyethylene glycol in a mixer for 1-2.5 h at a high speed of 800-1,200 rpm and a temperature of 90-120°C to obtain the lactic acid oligomer reactant.
[0012] Preferably, the initiator is potassium persulfate or ammonium persulfate.
[0013] Preferably, the plant starch is corn starch, sweet potato starch, pea starch, mung bean starch or potato starch.
[0014] The present invention further discloses application of the modified starch graft lactic acid oligomer thermoplastic composite in preparation of a biodegradable film.
[0015] In the invention, the starch is modified and then grafted and crosslinked with the glycidyl methacrylate and the lactic acid oligomer reactant, the modified starch forms a framework of a topological structure with the lactic acid oligomer reactant while the glycidyl methacrylate becomes a graft branch chain. In this way, the modified starch is organically combined with the lactic acid oligomer to give play to the strengths of the starch and the lactic acid oligomer. Furthermore, the crosslinking degree of the material is effectively increased, hydroxyl groups of a side chain are reduced, and the mechanical and waterproof performance of the material are enhanced. The modified starch graft lactic acid oligomer thermoplastic composite, after being processed into a film, has the advantages of high transparency and ductility, strong processability, easy degradation in natural conditions and low cost, and can be widely applied to packaging materials.
[0016] Embodiment 1
[0017] In the preparation method of a modified starch graft lactic acid oligomer thermoplastic composite, a preliminary process includes the following procedures.
[0018] Preparation of modified starch: adding 50 parts of dimethylformamide and 12 parts of pyrrole into 100 parts of plant starch, and stirring for 6 h at 50°C; dropwise adding 1.2 parts of acryloyl chloride while stirring; further stirring for 4 h; adding absolute ethyl alcohol for washing, performing suction filtration, and drying to obtain the modified starch. The plant starch may be common starch available in the market.
[0019] Preparation of lactic acid oligomer reactant: stirring 100 parts of lactic acid oligomer, 0.8 part of zinc oxide and 1.0 part of polyethylene glycol for 2 h in a mixer at a high speed of 1,000 rpm and a temperature of100°C to obtain the lactic acid oligomer reactant. (1) 100 parts of the modified starch, 80 parts of the lactic acid oligomer reactant, 12 parts of glycidyl methacrylate, 2 parts of citric acid and 3 parts of initiator, sulfate persulfate or ammonium persulfate, were added into water and stirred evenly; ultrasonic dispersion is performed to obtain an emulsion; and the emulsion is heated to 80°C and further stirred for reacting for 7 h. (2) a little ethanol was added into the emulsion of the step (1), and then demulsifying and drying were performed to obtain the modified starch graft lactic acid oligomer thermoplastic composite.
[0020] The modified starch graft lactic acid oligomer thermoplastic composite was blow-molded into a 0.03 mm thick film with tensile strength of 32 MPa and elongation at break of 350%.
[0021] Embodiment2
[0022] In the preparation method of a modified starch graft lactic acid oligomer thermoplastic composite, a preliminary process includes the following procedures.
[0023] Preparation of modified starch: adding 30 parts of dimethylformamide and 10 parts of pyrrole into 100 parts of plant starch, and stirring for 2 h or more at 40°C; dropwise adding 0.5 part of acryloyl chloride while stirring; further stirring for 2 h; adding absolute ethyl alcohol for washing, performing suction filtration, and drying to obtain the modified starch. The plant starch may be common starch available in the market.
[0024] Preparation of lactic acid oligomer reactant: stirring 100 parts of lactic acid oligomer, 0.5 part of zinc oxide and 0.5 part of polyethylene glycol for 1 h in a mixer at a high speed of 800 rpm and a temperature of 90°C to obtain the lactic acid oligomer reactant. (1) 100 parts of the modified starch, 50 parts of the lactic acid oligomer reactant, 8 parts of glycidyl methacrylate, 1 part of citric acid and 0.5 part of initiator, sulfate persulfate or ammonium persulfate, were added into water and stirred evenly; ultrasonic dispersion was performed to obtain an emulsion; the emulsion was heated to 70°C and further stirred for reacting for 5 h; and (2) a little ethanol was added into the emulsion of the step (1), and then demulsifying and drying were performed to obtain the modified starch graft lactic acid oligomer thermoplastic composite.
[0025] The modified starch graft lactic acid oligomer thermoplastic composite was blow-molded into a 0.03 mm thick film with tensile strength of 27 MPa and elongation at break of 320%.
[0026] Embodiment 3
[0027] In the preparation method of a modified starch graft lactic acid oligomer thermoplastic composite, a preliminary process includes the following procedures.
[0028] Preparation of modified starch: adding 60 parts of dimethylformamide and 15 parts of pyrrole into 100 parts of plant starch, and stirring for 5 h at 60°C; dropwise adding 2 parts of acryloyl chloride while stirring; further stirring for 5 h; adding absolute ethyl alcohol for washing, performing suction filtration, and drying to obtain the modified starch. The plant starch may be common starch available in the market.
[0029] Preparation of lactic acid oligomer reactant: stirring 100 parts of lactic acid oligomer, 1.2 parts of zinc oxide and 1.5 parts of polyethylene glycol for 2.5 h in a mixer at a high speed of 1,200 rpm and a temperature of 120°C to obtain the lactic acid oligomer reactant. (1) 100 parts of the modified starch, 100 parts of the lactic acid oligomer reactant, parts of glycidyl methacrylate, 3 parts of citric acid and 5 parts of initiator, sulfate persulfate or ammonium persulfate, were added into water and stirred evenly; ultrasonic dispersion was performed to obtain an emulsion; the emulsion was heated to 90°C and further stirred for reacting for 12 h; (2) a little ethanol was added into the emulsion of the step (1), and then demulsifying and drying were performed to obtain the modified starch graft lactic acid oligomer thermoplastic composite.
[0030] The modified starch graft lactic acid oligomer thermoplastic composite was blow-molded into a 0.03 mm thick film with tensile strength of 35 MPa and elongation at break of 390%
Claims (7)
1. A preparation method of a modified starch graft lactic acid oligomer thermoplastic composite, comprising: (1) adding 100 parts of modified starch, 50-100 parts of lactic acid oligomer reactant, 8-15 parts of glycidyl methacrylate, 1-3 parts of citric acid and 0.5-5 parts of initiator into water and stirring evenly; performing ultrasonic dispersion to form an emulsion, then heating to 70-90°C, and further stirring for reacting for 5-12 h; and (2) demulsifying the emulsion of the step (1) and drying to obtain the modified starch graft lactic acid oligomer thermoplastic composite.
2. The preparation method of a modified starch graft lactic acid oligomer thermoplastic composite according to claim 1, wherein: a preparation method of the modified starch comprises: adding dimethylformamide and pyrrole into plant starch, and stirring for 2 h or more at 40-60°C; dropwise adding acryloyl chloride while stirring; further stirring for 2 h or more; adding absolute ethyl alcohol for washing, performing suction filtration, and drying to obtain the modified starch.
3. The preparation method of a modified starch graft lactic acid oligomer thermoplastic composite according to claim 2, wherein: 30-60 parts of dimethylformamide, 10-15 parts of pyrrole and 0.5-2 parts of acryloyl chloride are added into every 100 parts of plant starch, during preparation of the modified starch.
4. The preparation method of a modified starch graft lactic acid oligomer thermoplastic composite according to claim 2, wherein: a preparation method of the lactic acid oligomer reactant comprises: stirring 100 parts of lactic acid oligomer, 0.5 1.2 parts of zinc oxide and 0.5-1.5 parts of polyethylene glycol for 1-2.5 h in a mixer at a high speed of 800-1,200 rpm and a temperature of 90-120°C to obtain the lactic acid oligomer reactant.
5. The preparation method of a modified starch graft lactic acid oligomer thermoplastic composite according to any one of claims 1 to 4, wherein: the initiator is potassium persulfate or ammonium persulfate.
6. The preparation method of a modified starch graft lactic acid oligomer thermoplastic composite according to claim 5, wherein: the plant starch is corn starch, sweet potato starch, pea starch, mung bean starch or potato starch.
7. Application of the modified starch graft lactic acid oligomer thermoplastic composite according to any one of claims 1 to 6 in preparation of a biodegradable film.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2020/108626 WO2022032514A1 (en) | 2020-08-12 | 2020-08-12 | Preparation method of modified starch-grafted polylactic acid oligomer thermoplastic composite material and use thereof |
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| Publication Number | Publication Date |
|---|---|
| AU2020227121A1 true AU2020227121A1 (en) | 2022-03-03 |
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| AU2020227121A Pending AU2020227121A1 (en) | 2020-08-12 | 2020-08-12 | Preparation method and application of modified starch graft lactic acid oligomer thermoplastic composite |
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| AU (1) | AU2020227121A1 (en) |
| WO (1) | WO2022032514A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116082811A (en) * | 2023-01-31 | 2023-05-09 | 安徽华驰环保科技有限公司 | Processing method of degradable packaging bag |
| CN117050241A (en) * | 2023-09-25 | 2023-11-14 | 广东鑫球新材料科技有限公司 | Degradable thermosetting powder, preparation method and application thereof in preparation of filter element |
| CN117089210B (en) * | 2023-10-18 | 2024-02-09 | 广州市瑞合新材料科技有限公司 | Silicon rubber for medical protection and preparation method thereof |
| CN118562103B (en) * | 2024-08-01 | 2024-09-24 | 潍坊市华贝纸塑包装有限公司 | Preparation method of polylactic acid for high-transparency food packaging |
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| CN101353420B (en) * | 2008-09-11 | 2011-05-04 | 上海交通大学 | Solvent-thermal synthesis preparation of polylactic acid-polyethyleneglycol copolymer |
| KR101022786B1 (en) * | 2009-03-30 | 2011-03-17 | 대상 주식회사 | Polylactic acid-containing biodegradable resin composition |
| GB0908928D0 (en) * | 2009-05-26 | 2009-07-01 | Hyflux Ltd | A biodegradable starch film |
| CN103881338B (en) * | 2012-12-19 | 2018-10-09 | 上海载和实业投资有限公司 | A kind of antistatic biodegradation material of novel flame-retardant and preparation method thereof |
| CN108948690B (en) * | 2017-05-18 | 2021-03-09 | 济宁明升新材料有限公司 | Polylactic acid-lignin-starch composite material and preparation method thereof |
| CN108676201A (en) * | 2018-06-07 | 2018-10-19 | 苏州汉丰新材料股份有限公司 | Biology base environment-friendlydegradable degradable material, by the preparation method of its film and its film obtained |
| CN110437392B (en) * | 2019-07-04 | 2020-07-03 | 江南大学 | Three-layer functionalized core-shell particle based on bio-based and preparation method thereof |
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- 2020-08-12 WO PCT/CN2020/108626 patent/WO2022032514A1/en active Application Filing
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