CN112940389A - Anaerobic degradation material and preparation method thereof - Google Patents
Anaerobic degradation material and preparation method thereof Download PDFInfo
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- CN112940389A CN112940389A CN202110240773.7A CN202110240773A CN112940389A CN 112940389 A CN112940389 A CN 112940389A CN 202110240773 A CN202110240773 A CN 202110240773A CN 112940389 A CN112940389 A CN 112940389A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to an anaerobic degradable material and a preparation method thereof, wherein the anaerobic degradable material comprises polyethylene, probiotic anaerobic degradable plastic master batch, anaerobic enzyme accelerator, EVA, corn starch, compatibilizer, fluoroelastomer, coupling agent and dispersant. The invention mainly solves the defect that the traditional polyethylene material is not degradable, and prevents the problem of white pollution in the environment. Anaerobic biodegradation is a brand-new and subversive cross-boundary innovation technology. The composite material which takes the polymer matrix, the beneficial bacteria material and the anaerobic accelerant as main bodies is taken as a trace additive material. The polyethylene anaerobic degradation material prepared by the invention can keep good integrity, shelf life and strength and excellent anaerobic degradation performance after being prepared into a finished product. And anaerobic biodegradation is initiated only upon entering a landfill or upon meeting certain conditions. The price is low, the environment is friendly, and the requirement of the environmental protection concept is met.
Description
Technical Field
The invention belongs to the technical field of high-molecular degradable materials, and particularly relates to an anaerobic degradable material and a preparation method thereof.
Background
Polyethylene is used as the most important plastic raw material, and products thereof are widely applied to various fields. However, the environmental pollution problem is gradually highlighted. The molecular chain structure of the polyethylene material is difficult to open and break under the action of sunlight and microorganisms, so that the polyethylene material is difficult to degrade, and the waste of the polyethylene material is caused to be white pollution for a long time, and the polyethylene material is based on the environment-friendly concept of sustainable development.
In the prior degradable plastic, a certain amount of additives (such as starch, modified starch or other celluloses, photosensitizers, biodegradable agents and the like) are added to reduce the stability of plastic products, so that the plastic products are easily degraded in the natural environment. For example, a degradable plastic containing a plasticizer ECO as a main component (added in whole or more than 50%) has a degradation effect of a polymer itself. Although the degradable plastics can realize degradation, the overall degradable material is relatively expensive, and shows that the material performance is relatively low in strength and relatively poor in toughness. Meanwhile, the degradation mechanism in the current degradable plastics is based on aerobic degradation. Aerobic degradation is a process of decomposing organic macromolecular compounds in the environment into small molecular substances by aerobic microorganisms under aerobic conditions. It is also based on the mechanism of aerobic degradation that more of the plastic-chewing agent ECO is often required to be added to the degradable plastic.
However, when the aerobic degradation is applied to a plastic product containing polyethylene as a main component, it cannot be achieved. Because the plastic products using polyethylene as main component have high strength, toughness and stability. The purpose of degradation cannot be realized by the current aerobic degradation method.
Disclosure of Invention
The first purpose of the invention is to provide an anaerobic degradation material, which can ensure the stable structure and performance and can degrade in an anaerobic degradation mode.
The technical scheme for realizing the first purpose of the invention is as follows: the anaerobic degradation material comprises the following components in parts by weight: polyethylene: 70-100 parts of beneficial bacterium type anaerobic degradation plastic master batch: 0-5 parts of an anaerobic enzyme promoter: 0-5 parts of EVA: 5-15 parts of corn starch: 1-15 parts of a compatibilizer: 0.1-5 parts of fluoroelastomer: 0.01-0.06 parts of coupling agent: 2-8 parts of a dispersant: 1-5 parts.
The polyethylene comprises 30-50 parts of low density polyethylene and 40-50 parts of linear low density polyethylene. The polyethylene is a mixture of low density polyethylene and linear low density polyethylene, which is used to ensure the strength and toughness of the material. The existing polyethylene material can not achieve good degradation effect on the premise of ensuring the strength and toughness.
The corn starch is superfine starch granules, and the diameter of the corn starch granules is 1250-2500 meshes.
The anaerobic enzyme promoter is inorganic salt.
The probiotic anaerobic plastic degradation master batch is petroleum-based or plant-based anaerobic plastic degradation master batch.
The coupling agent is a silane coupling agent KH570 or an aluminate coupling agent.
The dispersant is two or more of polyethylene wax, stearic acid, zinc stearate, calcium stearate or polyethylene glycol.
The compatibilizer is OPE-4.
Preferably, the inorganic salt is a carbon salt or a nitrogen salt.
As a further optimization, the beneficial bacteria type anaerobic plastic degradation master batch is PLA or plant-based starch or PBS or ECO.
Under the proper specific environmental condition, the specific anaerobic bacteria of the anaerobic degradation material are activated and react with beneficial bacteria materials in the composite material distributed in the plastic to form breakthrough, under the action of the anaerobic accelerant, the specific anaerobic organisms work in an accelerating way to generate a large amount of free radical monomers, the forts of strong and stable plastic molecular structures are opened, and finally CH4, CO2, water and the like are generated.
The second purpose of the invention is to provide a preparation method of the anaerobic degradation material, which can effectively ensure that the prepared anaerobic degradation material has better degradation effect.
The technical scheme for realizing the second purpose of the invention is as follows: the preparation method of the anaerobic degradation material comprises the following steps:
s1, crushing the corn starch into superfine particles, and controlling the diameter of the superfine particles to be 1250-2500 meshes;
s2, drying the corn starch, adding a coupling agent for surface treatment, and then adding a compatibilizer;
s3, mixing the material obtained in the step S2, polyethylene, EVA, anaerobic enzyme accelerator, probiotic anaerobic degradation master batch, dispersant and fluoroelastomer, adding the mixture into a plastic high-speed stirrer for stirring, and fully and uniformly mixing; then mixing in a double-screw extruder, and extruding to obtain the anaerobic degradation material.
And (3) as further optimization, mixing the material obtained in the step (S2), polyethylene, EVA, anaerobic enzyme accelerator and beneficial bacteria type anaerobic degradation master batch, adding the mixture into a plastic high-speed stirrer, and stirring the mixture for 30 minutes at the rotation speed of 600 r/min-800 r/min and the temperature of 15-30 ℃ to fully and uniformly mix the mixture.
As further optimization, the preheating temperature of the screw region of the double-screw extruder is 200-300 ℃, and the rotating speed of the screw is 250-400 r/min.
The invention has the positive effects that: (1) the anaerobic degradable material has the advantages of high strength, low cost, anaerobic degradation and the like, and does not influence the service performance of plastic products. Will retain its good integrity, shelf life and strength. Anaerobic biodegradation is started only when the biological material enters a landfill or meets certain conditions. When the plastic is in a proper specific environment condition, specific anaerobic bacteria are activated and react on beneficial bacteria materials in the combined materials distributed in the plastic to form breakthrough, under the action of an anaerobic accelerant, specific anaerobic organisms accelerate to work to generate a large amount of free radical monomers, forts of strong and stable plastic molecular structures are opened, the final material can be completely and naturally biodegraded within 1-5 years, and products are carbon dioxide, methane, water and the like.
(2) The corn starch is one of aerobic degradable plastic series fillers, but the factors of larger particle diameter, slightly lower compatibility and the like exist in the preparation of the anaerobic degradable material in the prior art, and the ultrafine corn starch particles are added into the anaerobic degradable material, so that the surface activity of the material under the anaerobic condition can be promoted to be increased, the surface adsorption capacity is improved, chemical adsorption can also occur besides physical adsorption, and the material degradation rate can be improved.
(3) The invention effectively solves the degradation problem of polyethylene plastics, and has good application prospect in the field of plastic application.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a graph showing a degradation test of an anaerobically degradable material according to the present invention.
Detailed Description
(example 1)
The anaerobic degradation material comprises, by weight, 40 parts of low-density polyethylene, 50 parts of linear low-density polyethylene, 1 part of anaerobic enzyme accelerator, 2 parts of beneficial bacteria type anaerobic degradation plastic master batch, 5 parts of EVA (ethylene-vinyl acetate copolymer), 5 parts of corn starch, 0.1 part of compatibilizer, 0.01 part of fluoroelastomer, 2 parts of coupling agent and 2 parts of dispersing agent.
The beneficial bacterium type anaerobic plastic degradation master batch is an ECO degradation master batch serving as a plastic gnawing agent, a coupling agent is a silane coupling agent KH570, a dispersing agent is polyethylene wax, zinc stearate and calcium stearate, a compatibilizer is OPE-4, and a solvent is petroleum ether.
The preparation method of the anaerobic degradation material comprises the following steps:
s1, crushing the corn starch into superfine particles, and controlling the diameter of the superfine particles to be 1250-2500 meshes;
s2, drying the corn starch, adding a silane coupling agent for surface treatment, and then adding a compatibilizer;
s3, mixing the material obtained in the step S2, low-density polyethylene, linear low-density polyethylene, EVA (ethylene-vinyl acetate copolymer), an anaerobic enzyme promoter, a probiotic anaerobic degradation master batch, a dispersing agent and a fluoroelastomer, adding the mixture into a plastic high-speed mixer, stirring for 30 minutes at the rotation speed of 600 r/min-800 r/min and the temperature of 20 ℃ to fully mix the mixture uniformly, and then mixing in a double-screw extruder, wherein the preheating temperature of a screw area of the double-screw extruder is 270 ℃, the rotation speed of the screw is 250 r/min-400 r/min, and extruding to obtain the anaerobic degradation material.
Using the composition of this example, the standard sample prepared was 100mm × 10mm × 4mm, and the product performance test results were as follows (according to the national standard GB 1040-79 "Plastic tensile test method"): tensile strength (Mpa): 21.2; elongation at break: 496.
the degradation test record for this example is as follows:
the degradation test graph of this example can be seen in fig. 1.
(example 2)
The anaerobic degradation material comprises, by weight, 40 parts of low-density polyethylene, 50 parts of linear low-density polyethylene, 1.5 parts of anaerobic enzyme accelerant, 4 parts of beneficial bacteria type anaerobic degradation plastic master batch, 10 parts of EVA (ethylene-vinyl acetate copolymer), 10 parts of corn starch, 0.4 part of compatibilizer, 0.02 part of fluoroelastomer, 6 parts of coupling agent and 2 parts of dispersing agent.
The probiotic anaerobic plastic degradation master batch is an ECO degradation master batch serving as a plastic gnawing agent, a coupling agent is a silane coupling agent KH570, a dispersing agent is polyethylene wax, zinc stearate and calcium stearate, and a solubilizing agent is OPE-4.
The procedure for the preparation of the above anaerobically degraded material was as in example 1.
Using the composition of this example, the standard sample prepared was 100mm × 10mm × 4mm, and the product performance test results were as follows (according to the national standard GB 1040-79 "Plastic tensile test method"): tensile strength (Mpa): 23.7; elongation at break: 428.
(example 3)
The anaerobic degradation material comprises, by weight, 40 parts of low-density polyethylene, 50 parts of linear low-density polyethylene, 2 parts of anaerobic enzyme accelerant, 5 parts of beneficial bacteria type anaerobic degradation plastic master batch, 12 parts of EVA (ethylene-vinyl acetate copolymer), 12 parts of corn starch, 0.5 part of compatibilizer, 0.03 part of fluoroelastomer, 5 parts of coupling agent and 2 parts of dispersing agent.
The probiotic anaerobic plastic degradation master batch is an ECO degradation master batch serving as a plastic gnawing agent, a coupling agent is a silane coupling agent KH570, a dispersing agent is polyethylene wax, zinc stearate and calcium stearate, and a solubilizing agent is OPE-4.
The procedure for the preparation of the above anaerobically degraded material was as in example 1.
Using the composition of this example, the standard sample prepared was 100mm × 10mm × 4mm, and the product performance test results were as follows (according to the national standard GB 1040-79 "Plastic tensile test method"): tensile strength (Mpa): 20.6; elongation at break: 547.
the above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. An anaerobic degradable material, which is characterized in that: comprises the following components in parts by weight: polyethylene: 70-100 parts of beneficial bacterium type anaerobic degradation plastic master batch: 0-5 parts of an anaerobic enzyme promoter: 0-5 parts of EVA: 5-15 parts of corn starch: 1-15 parts of a compatibilizer: 0.1-5 parts of fluoroelastomer: 0.01-0.06 parts of coupling agent: 2-8 parts of a dispersant: 1-5 parts.
2. An anaerobically degradable material according to claim 1 wherein: the polyethylene comprises 30-50 parts of low-density polyethylene and 40-50 parts of linear low-density polyethylene.
3. An anaerobically degradable material according to claim 1 wherein: the corn starch is superfine starch granules, and the diameter of the corn starch is 1250-2500 meshes.
4. An anaerobically degradable material according to claim 1 wherein: the anaerobic enzyme promoter is inorganic salt.
5. An anaerobically degradable material according to claim 1 wherein: the probiotic anaerobic plastic degradation master batch is a petroleum-based or plant-based anaerobic plastic degradation master batch.
6. An anaerobically degradable material according to claim 1 wherein: the coupling agent is a silane coupling agent KH570 or an aluminate coupling agent.
7. An anaerobically degradable material according to claim 1 wherein: the dispersing agent is two or more of polyethylene wax, stearic acid, zinc stearate, calcium stearate or polyethylene glycol.
8. An anaerobically degradable material according to claim 1 wherein: the compatibilizer is OPE-4.
9. An anaerobically degradable material according to claim 4 wherein: the inorganic salt is carbon salt or nitrogen salt.
10. An anaerobically degradable material according to claim 5 wherein: the probiotic anaerobic plastic degradation master batch is PLA or plant-based starch or PBS or ECO.
11. A method for preparing the anaerobic degradable material of claim 1, which comprises the steps of:
s1, crushing the corn starch into superfine particles, and controlling the diameter of the superfine particles to be 1250-2500 meshes;
s2, drying the corn starch, adding a coupling agent for surface treatment, and then adding a compatibilizer;
s3, mixing the material obtained in the step S2, polyethylene, EVA, anaerobic enzyme accelerator, probiotic anaerobic degradation master batch, dispersant and fluoroelastomer, adding the mixture into a plastic high-speed stirrer for stirring, and fully and uniformly mixing; then mixing in a double-screw extruder, and extruding to obtain the anaerobic degradation material.
12. The method of claim 11, wherein: and (4) mixing the material obtained in the step (S2), polyethylene, EVA, anaerobic enzyme accelerator and probiotic anaerobic degradation master batch, adding the mixture into a plastic high-speed stirrer, and stirring the mixture for 30 minutes at the rotation speed of 600 r/min-800 r/min and the temperature of 15-30 ℃ to fully and uniformly mix the mixture.
13. The production method according to claim 11 or 12, characterized in that: the preheating temperature of the screw region of the double-screw extruder is 200-300 ℃, and the rotating speed of the screw is 250-400 r/min.
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| CN114085509A (en) * | 2021-11-29 | 2022-02-25 | 洛阳绿之汇塑料降解科技有限公司 | Universal masterbatch for anaerobic digestion degradation and preparation method thereof |
| CN114806014A (en) * | 2022-05-10 | 2022-07-29 | 宁波金富亮塑料科技有限公司 | Polypropylene ecological plastic convenient for biodegradation and preparation method thereof |
| CN116135920A (en) * | 2021-11-18 | 2023-05-19 | 纳米及先进材料研发院有限公司 | Additive for accelerating anaerobic biodegradation of high polymer material and preparation and use methods thereof |
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