CN111621073A - Preparation method of bio-based degradable environment-friendly bag - Google Patents
Preparation method of bio-based degradable environment-friendly bag Download PDFInfo
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- CN111621073A CN111621073A CN202010318559.4A CN202010318559A CN111621073A CN 111621073 A CN111621073 A CN 111621073A CN 202010318559 A CN202010318559 A CN 202010318559A CN 111621073 A CN111621073 A CN 111621073A
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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
- C08L23/06—Polyethene
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
Abstract
The invention discloses a bio-based degradable environment-friendly material which is prepared by taking polyethylene and starch as raw materials, adding thermoplastic polyurethane into a reaction system, and then granulating by using a double-welding-rod extruder to obtain a master batch, and drying and maintaining the master batch. The bio-based degradable environment-friendly material is simple in preparation and synthesis scientific process, relatively few reactors are used in the experimental process, the whole experimental process is carried out under normal pressure, and toxic gas and waste water cannot be released from raw materials. The risk is small in comprehensive consideration. Meanwhile, the main raw materials are starch, polylactic acid and polyethylene, the price is low, the raw materials are easily purchased, and the product has excellent water resistance, oil resistance and other properties; has suitable shelf life and is not easy to deteriorate; the waste is easy to degrade; gas and other substances are not released in the using process, and the environment-friendly product prepared from the material can enable the content of the bio-based reduced biochar to reach more than 25%.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a bio-based degradable environment-friendly material which can replace PE.
Background
The plastic industry is a product industry and an emerging material industry. In recent years, the plastic industry has developed rapidly with the rapid development of the civil economy, particularly the petrochemical industry. The apparent consumption of synthetic resin in 1998 was about 14940 ten thousand tons and that of plastic articles was 1427.6 ten thousand tons. As an important industrial material and a consumption material, the plastic material and the product are widely applied to the fields of industry, agriculture, packaging industry, high technology and various aspects of people's life, and are juxtaposed with steel, wood and cement to form four main supporting column materials. Plays an increasingly important role in promoting the technical progress of national economic reserve departments and meeting the needs of people in life. In recent years, about 400 million tons of plastic for packaging in China, about 120 million tons of plastic packaging waste generated each year when about 30% of disposable plastic packages which are difficult to recycle account for, and about 40 million tons of plastic mulching films are thin (less than 8 μm), so that the plastic mulching films are broken in farmlands after use and contain a large amount of sandy soil, are difficult to recycle, and about 40 million tons of disposable daily sundries and medical supplies which are difficult to recycle. The comprehensive utilization of the various secondary plastic wastes reaches about 200 ten thousand tons. According to the investigation of cities such as Beijing, Shanghai and Tianjin, the mass fraction of the plastic waste in an urban solid waste treatment system (ASW) is about 3-7%, and the volume fraction accounts for 10-20%. The environmental problems caused by the method are increasingly serious, and great attention and strong reverberation are brought to the whole society. For this reason, the government of China has paid great attention to, and countermeasures and measures are being actively studied. The widespread use of plastic products in industry and daily life generates large quantities of plastic waste that is difficult to dispose of, creating a serious environmental hazard. The reduction and solution of the environmental pollution problem of waste plastics have attracted much attention from countries in the world, and the use and development of biodegradable plastics have become one of the important means for solving the problem of "white pollution" in countries.
Starch is fast to regenerate, can be completely biodegraded, and has high environmental friendliness, so that the research on the application of the starch as biodegradable plastic is more and more emphasized. The starch molecules contain more hydrogen bonds and larger intermolecular force, generally contain 15-45% of crystalline components, the glass transition temperature of an amorphous region is very close to the decomposition temperature, and the melting point of a crystalline region is far higher than the decomposition temperature, so that the natural starch does not have plasticity. If some small molecular plasticizers with hydrogen bonds are added into the starch, the plasticizer can partially form hydrogen bonds with the starch, and the density of the hydrogen bonds among the starch molecules is reduced through mechanical isolation, so that the intermolecular force of the starch is reduced, the glass transition temperature and the melting point of the starch molecules are reduced, and the thermoplastic starch can be prepared. Small molecule plasticizers are typically polyols, with glycerol being the most widely used. However, the thermoplastic starch prepared in this way may have a "retrogradation" phenomenon during use, i.e., the starch is recrystallized due to the failure of the plasticizer, and the crystallized starch becomes brittle and loses the use performance, which is an important factor limiting the use performance of the starch. Chemical modification of starch is an important alternative method, and because starch contains a large number of hydroxyl groups in the molecule, reaction with hydroxyl groups such as esterification and the like is one of the common methods for starch modification. In the modified esterified starch, partial hydroxyl is converted into ester groups, the density of the hydroxyl is reduced, the hydrogen bonding effect between chains is weakened, the melting point of a crystal region is reduced, when the melting point is lower than the decomposition temperature, the melting of microcrystals can be realized before decomposition, the starch has real thermoplasticity, and the esterification modification is the effect of chemical bonds, so that the prepared starch plastic does not have the phenomenon of 'regeneration'. In addition, the mechanical property and the water resistance of the starch plastic are poor, so that the application of the starch plastic is limited.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a bio-based degradable environment-friendly material which is simple to prepare, biodegradable and excellent in mechanical property.
In order to achieve the purpose, the invention provides the following technical scheme: a bio-based degradable environment-friendly material is characterized in that: the method specifically comprises the following steps:
s1, mixing 30-40 parts of starch, 10-20 parts of polylactic acid and 15-20 parts of thermoplastic polyurethane at high speed for 2 hours, adding 1-2 parts of auxiliary agent into the mixture, and continuously mixing for 1 hour to obtain modified starch;
s2, heating the modified starch to 110 ℃, adding 5-8 parts of coupling agent into the modified starch, stirring and mixing for 2h, drying, mixing for 1h in a double-roller open mill, and performing crosslinking plasticization between the modified starch and the coupling agent to generate a modified starch primary compound;
s3, adding 18-25 parts of glycerol into the modified starch primary compound obtained in the step S2, mixing and stirring for 2 hours, fully dispersing and lubricating the mixture, and effectively adjusting the viscosity of the mixture;
and S4, adding 50-60 parts of polyethylene and 1-2 parts of hydrolysis resisting agent into the mixture, uniformly mixing, and feeding into a double-welding-rod extruder for granulating to obtain the finished product.
In the above-mentioned bio-based degradable environment-friendly material, the coupling agent in the step S2 is an aluminate coupling agent.
In the above biodegradable environment-friendly material, the additives in the step S4 are: ethylene-vinyl acetate copolymer (EVA), Polycaprolactone (PCL) and polyhydroxyalkanoate.
In the above-mentioned bio-based degradable environment-friendly material, the assistant in the step S1 is light calcium powder or nano silica particles.
In the above-mentioned bio-based degradable environment-friendly material, the drying temperature in the step S2 is 70 to 90 ℃.
Compared with the prior art, the invention has the advantages that: the bio-based degradable environment-friendly material has the advantages that the formula science synthetic route is simple in process, reactors used in the experimental process are relatively few, and the whole experimental process is carried out under normal pressure; the preparation method takes polyethylene and starch as raw materials, and can effectively improve the flexibility and the wear resistance of the polyethylene/starch bio-based environment-friendly bag by adding thermoplastic polyurethane into a reaction system; on the other hand, the mechanical property of the polyethylene/starch bio-based environment-friendly material can be effectively improved by adding the hydrolysis-preventing agent into the reaction system, and the water resistance of the environment-friendly material is improved; in the bio-based degradable environment-friendly material, polyethylene and cheap and easily-obtained starch are mainly used as raw materials, a coupling agent, an auxiliary agent, a plasticizer and the like are added into a reaction system, so that the biochar content of the bio-based degradable environment-friendly material can be increased, the biochar content of the bio-based degradable environment-friendly material in the current market is generally below 18 percent, the biochar content of the bio-based degradable environment-friendly bag can reach above 25 percent by adopting the preparation method, and compared with the traditional bio-based degradable environment-friendly material, the biochar content in the bio-based degradable environment-friendly material is greatly increased and greatly improved.
The bio-based degradable environment-friendly material has the following advantages;
1. the paint has excellent water resistance, oil resistance and other properties;
2. has suitable shelf life and is not easy to deteriorate;
3. the waste is easy to degrade, and no harmful substances and gas are released after combustion;
4. gas and other substances are not released in the using process;
5. the content of the biochar reaches more than 25 percent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, although the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The invention will be explained in more detail below with reference to specific examples:
the first embodiment is as follows:
s1, mixing 30 parts of starch, 10 parts of polylactic acid and 15 parts of thermoplastic polyurethane at a high speed for 2 hours, adding 1 part of light calcium powder into the mixture, and continuously mixing for 1 hour to obtain modified starch;
s2, heating the modified starch to 110 ℃, adding 5 parts of aluminate coupling agent into the modified starch mixture, stirring and mixing for 2h, drying at 80 ℃, mixing for 1h in a double-drum open mill, and performing crosslinking plasticization between the modified starch and the aluminate coupling agent to obtain a modified starch primary compound;
s3, adding 18 parts of glycerol into the modified starch primary compound obtained in the step S2, mixing and stirring for 2 hours to fully disperse and lubricate the mixture and effectively adjust the viscosity of the mixture;
and S4, adding 50 parts of polyethylene and 1 part of hydrolysis resisting agent into the mixture, uniformly mixing, feeding into an extrusion welding rod machine for granulation, and drying to obtain the finished product.
The biological-based degradable environment-friendly material has the weight loss rate of 10 percent after the quality guarantee period is 30 days under the condition of a compost test, the weight loss rate of 40 percent under the condition of a soil burying test is 60 days, the biological carbon content is about 20 percent and can be biodegraded within 180 days.
The second embodiment is as follows:
s1, mixing 40 parts of starch, 20 parts of polylactic acid and 20 parts of thermoplastic polyurethane for 2 hours, adding 2 parts of nano silicon dioxide particles into the mixture, and continuously mixing for 1 hour to obtain a modified starch mixture;
s2, heating the modified starch mixture to 110 ℃, adding 8 parts of aluminate coupling agent into the modified starch mixture, stirring and mixing for 2 hours, drying at 80 ℃, mixing for 1 hour in a double-drum open mill, and performing crosslinking and plasticizing between the modified starch mixture and the aluminate coupling agent to obtain a modified starch primary compound;
s3, adding 25 parts of glycerol into the modified starch primary compound obtained in the step S2, mixing and stirring for 2 hours to fully disperse and lubricate the mixture, and effectively adjusting the viscosity of the mixture;
and S4, adding 60 parts of polyethylene and 2 parts of hydrolysis resistant agent into the mixture, uniformly mixing, feeding into an extruder for granulation, and drying to obtain the finished product.
The biological-based degradable environment-friendly material has the weight loss rate of 15 percent under the condition of composting test for 30 days after the quality preservation period, the weight loss rate of 30 percent under the condition of soil burying test for 60 days, the biological degradation rate of 75 percent within 180 days, and the biological carbon content of about 25 percent.
The third concrete embodiment:
s1, mixing 30 parts of starch, 10 parts of polylactic acid and 20 parts of thermoplastic polyurethane for 2 hours, adding 1 part of nano silicon dioxide particles into the mixture, and continuously mixing for 1 hour to obtain a modified starch mixture;
s2, heating the modified starch mixture to 110 ℃, adding 5 parts of aluminate coupling agent into the modified starch mixture, stirring and mixing for 2 hours, drying at 90 ℃, mixing for 1 hour in a double-drum open mill, and performing crosslinking and plasticizing between the modified starch mixture and the aluminate coupling agent to obtain a modified starch primary compound;
s3, adding 18 parts of glycerol into the modified starch primary compound obtained in the step S2, mixing and stirring for 2 hours to fully disperse and lubricate the mixture and effectively adjust the viscosity of the mixture;
and S4, adding 60 parts of polyethylene and 1 part of hydrolysis resistant agent into the mixture, uniformly mixing, feeding into an extruder for granulation, drying and curing to obtain the polyethylene-polyethylene composite material.
After the quality guarantee period of the bio-based degradable environment-friendly material, the weight loss rate can reach 15% under the condition of a compost test for 30 days, the weight loss rate can reach 29% under the condition of a soil burying test for 60 days, the bio-based degradable environment-friendly material can be biodegraded within 180 days, and the content of biological carbon is about 22%.
By combining the first embodiment, the second embodiment and the third embodiment, the bio-based degradable environment-friendly material has the following advantages;
1. 1, the paint has excellent water resistance, oil resistance and other properties;
2. has suitable shelf life and is not easy to deteriorate;
3. the waste is easy to degrade;
4. gas and other substances are not released in the using process;
5. the content of the biochar reaches more than 20-25 percent.
In the bio-based degradable environment-friendly material, polyethylene and cheap and easily-obtained starch are mainly used as raw materials, a coupling agent, an auxiliary agent, a plasticizer and the like are added into a reaction system, so that the biochar content of the bio-based degradable environment-friendly material can be increased, the biochar content of the bio-based degradable environment-friendly material in the current market is generally 18% -20%, after the bio-based degradable environment-friendly material is adopted, the biochar content of the bio-based degradable environment-friendly material can reach about 25%, and compared with the traditional bio-based degradable environment-friendly material, the biochar content of the material is greatly increased.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A bio-based degradable environment-friendly material is characterized in that: the method specifically comprises the following steps:
s1, mixing 50-60 parts of starch, 10-20 parts of polylactic acid and 15-20 parts of thermoplastic polyurethane for 2 hours, adding 1-2 parts of auxiliary agent into the mixture, and continuously mixing for 1 hour to obtain a modified starch mixture;
s2, heating the modified starch mixture to 110 ℃, adding 5-8 parts of coupling agent into the modified starch mixture, stirring and mixing for 2h, drying, mixing for 1h in a double-roller open mill, and performing crosslinking plasticization between the modified starch mixture and the coupling agent to obtain a modified starch primary compound;
s3, adding 18-25 parts of glycerol into the modified starch primary compound obtained in the step S2, mixing and stirring for 2 hours, fully dispersing and lubricating the mixture, and effectively adjusting the viscosity of the mixture;
and S4, adding 30-40 parts of polyethylene and 1-2 parts of hydrolysis resistant agent into the mixture, uniformly mixing, feeding into a double-welding-rod extruder for granulation, and drying to obtain the polyethylene-polyethylene composite material.
2. The bio-based degradable environment-friendly material as claimed in claim 1, wherein: the coupling agent in the step S2 is an aluminate coupling agent.
3. The bio-based degradable environment-friendly material as claimed in claim 1, wherein: the additives in the step S4 are as follows: ethylene-vinyl acetate copolymer (EVA), Polycaprolactone (PCL) and polyhydroxyalkanoate.
4. The bio-based degradable environment-friendly material as claimed in claim 1, wherein: and the auxiliary agent in the step S1 is light powder or nano silicon dioxide particles.
5. The bio-based degradable environment-friendly material as claimed in claim 1, wherein: and the drying temperature in the step S2 is 60-80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010318559.4A CN111621073A (en) | 2020-04-21 | 2020-04-21 | Preparation method of bio-based degradable environment-friendly bag |
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| CN202010318559.4A CN111621073A (en) | 2020-04-21 | 2020-04-21 | Preparation method of bio-based degradable environment-friendly bag |
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| CN111621073A true CN111621073A (en) | 2020-09-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105726A (en) * | 2021-04-06 | 2021-07-13 | 贵州省材料产业技术研究院 | Preparation method of biodegradable biochar repair membrane material |
| CN116178831A (en) * | 2023-02-23 | 2023-05-30 | 江苏锐巴新材料科技有限公司 | Degradable rubber industrial feeding bag and preparation method thereof |
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| CN103980684A (en) * | 2014-05-15 | 2014-08-13 | 华东理工大学 | Toughening and waterproof starch plastic and preparation method thereof |
| CN105713273A (en) * | 2015-09-18 | 2016-06-29 | 安徽柒柒塑业有限公司 | Polyethylene starch biodegradable plastic film |
-
2020
- 2020-04-21 CN CN202010318559.4A patent/CN111621073A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980684A (en) * | 2014-05-15 | 2014-08-13 | 华东理工大学 | Toughening and waterproof starch plastic and preparation method thereof |
| CN105713273A (en) * | 2015-09-18 | 2016-06-29 | 安徽柒柒塑业有限公司 | Polyethylene starch biodegradable plastic film |
Non-Patent Citations (1)
| Title |
|---|
| 王文广: "聚合物改性原理", 华中科技大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105726A (en) * | 2021-04-06 | 2021-07-13 | 贵州省材料产业技术研究院 | Preparation method of biodegradable biochar repair membrane material |
| CN116178831A (en) * | 2023-02-23 | 2023-05-30 | 江苏锐巴新材料科技有限公司 | Degradable rubber industrial feeding bag and preparation method thereof |
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