CN110982151A - Lignocellulose-based degradable plastic material preparation process - Google Patents
Lignocellulose-based degradable plastic material preparation process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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Abstract
The invention discloses a lignocellulose-based degradable plastic material preparation process, which comprises the steps of S1 carrying out nitridation reaction treatment on lignocellulose to obtain nitrided lignocellulose; s2, mixing starch, a high molecular resin polymer, a chain transfer agent and a cross-linking agent, adding into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 150-; s3, ageing the banburying product in an ageing chamber to obtain an aged product; s4, mixing the aged product, the nitrogenated lignocellulose and the dispersing agent, adding into an extruder, extruding, cooling and granulating to obtain the wood-plastic composite material; the lignocellulose-based degradable plastic material preparation process provided by the invention can greatly improve the mechanical property of the traditional starch plastic material and improve the application range of the traditional starch plastic material.
Description
Technical Field
The invention belongs to the technical field of energy conservation and environmental protection, and particularly relates to a preparation process of a lignocellulose-based degradable plastic material.
Background
Along with rapid development of economy and science and technology, the rhythm of human life is faster and faster, fast food becomes the main working meal for people to work, the use of disposable tableware is increased, disposable plastic tableware on the market is generally made of high molecular compounds such as polystyrene, polypropylene, polyvinyl chloride and the like, the disposable plastic tableware brings convenience to people, and simultaneously can generate various side effects to form direct pollution to human bodies and pollution to the environment, the high molecular compounds such as polystyrene, polypropylene, polyvinyl chloride and the like are difficult to biodegrade, the degradation period is extremely long, and the degradation period can reach about 200 years under the common environment, so that a large amount of white garbage is caused to the natural environment, and the environment is polluted; meanwhile, a lot of chemical agents added into the existing degradable disposable tableware can be decomposed when being heated and are inhaled by food, so that trace pollution is caused to human bodies, and the health is damaged due to long-term deposition.
Starch plastic is one of the main materials of the existing degradable tableware, and because starch molecular chains contain a large amount of hydrophilic hydroxyl groups and polyolefin has very small polarity, the structure and polarity of the starch plastic are greatly different, so that the compatibility during the preparation of the starch plastic is poor, and meanwhile, the prepared starch plastic has low mechanical strength, so that the application of the starch plastic is greatly limited.
Disclosure of Invention
The invention is realized by the following technical scheme.
A lignocellulose-based degradable plastic material preparation process comprises
S1, carrying out nitridation reaction treatment on the lignocellulose to obtain nitrided lignocellulose;
s2, mixing starch, a high molecular resin polymer, a chain transfer agent and a cross-linking agent, adding into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 150-;
s3, ageing the banburying product in an ageing chamber to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the dispersing agent, adding into an extruder, extruding, cooling and granulating to obtain the wood-plastic composite material.
The nitridation reaction is as follows:
adding lignocellulose into 5-6% ethanol solution, and stirring at 500r/min for 30min to obtain lignocellulose dispersion;
adding urea into the lignocellulose dispersion liquid, heating to 70-75 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product.
The mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300-350 mL.
The weight portion ratio of the urea to the lignocellulose is 1: 5-7; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%.
The mixing weight ratio of the starch to the high molecular resin polymer to the chain transfer agent to the cross-linking agent is 2-3: 10: 0.1: 0.3.
the starch is soybean starch, and the high molecular resin polymer is polyethylene resin.
The chain transfer agent is mercaptan, and the crosslinking agent is vinyl triethoxysilane.
The aging treatment is carried out by placing for more than 10 hours under the environment that the temperature is 80 ℃ and the relative humidity of air is 60 percent.
The aging product, the nitrogenated lignocellulose and the dispersing agent are mixed according to the weight ratio of 10: 1-1.5: 0.5.
the dispersing agent is glycerol.
According to the technical scheme, the beneficial effects of the invention are as follows:
the lignocellulose-based degradable plastic material preparation process can greatly improve the mechanical property of the traditional starch plastic material and improve the application range of the traditional starch plastic material, can greatly improve the structural characteristics of lignocellulose by carrying out nitridation reaction treatment on the lignocellulose, can damage a cellulose surface crystallization area to a certain extent by nitridation reaction treatment, reduces the crystallinity of the surface of the lignocellulose, greatly improves the compatibility between the prepared nitrided lignocellulose and a high-molecular resin polymer, can increase the rigidity of a composite material by an internal crystallization structure at the same time, improves the strength to a certain extent, can be combined with a starch macromolecular chain to a certain extent by taking the nitrided lignocellulose as a bridge action, and can greatly improve the problem of poor compatibility of the starch in the high-molecular resin polymer system, the starch and the high molecular resin polymer are subjected to banburying treatment by taking the chain transfer agent and the cross-linking agent as auxiliaries, so that the bonding characteristic between the starch and the high molecular resin polymer can be improved to a certain extent, and a certain amount of starch molecular chains and high molecular resin polymer molecular chains can be promoted to be crosslinked through the bonding effect of the chain transfer agent and the cross-linking agent, so that the starch molecular chains and the high molecular resin polymer molecular chains are promoted to be bonded together, and the defect of high brittleness of the composite material caused by poor compatibility of the starch molecular chains and the high molecular resin polymer is avoided.
Detailed Description
The invention provides a lignocellulose-based degradable plastic material preparation process, and a person skilled in the art can use the contents to reference the process and appropriately improve the process parameters to realize the process. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
A lignocellulose-based degradable plastic material preparation process comprises
S1 the nitridation reaction treatment of lignocellulose to obtain nitrided lignocellulose can greatly improve the structural characteristics of lignocellulose, through the nitridation reaction treatment, the cellulose surface crystallization area can be damaged to a certain extent, the crystallinity of the lignocellulose surface is reduced, so that the compatibility between the prepared nitrogenated lignocellulose and the high molecular resin polymer is greatly improved, meanwhile, the rigidity of the composite material can be increased through the internal crystal structure, so that the strength is improved to a certain extent, and can be combined with starch macromolecular chains in a certain degree by using the nitrogenated lignocellulose as a bridge, therefore, the problem of poor compatibility of starch in a high molecular resin polymer system can be greatly improved, and the mechanical property of the composite material is further remarkably improved;
s2, mixing starch, a high molecular resin polymer, a chain transfer agent and a cross-linking agent, adding the mixture into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 150-;
s3, ageing the banburying product in an ageing chamber to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the dispersing agent, adding into an extruder, extruding, cooling and granulating to obtain the finished product, wherein the extruder is a double-screw extruder, the temperature of each zone is controlled at 105 ℃, 110 ℃, 115 ℃ and 115 ℃, the head temperature is 112 ℃, and the rotating speed is 150 r/min.
The nitridation reaction is as follows:
adding lignocellulose into 5-6% ethanol solution, and stirring at 500r/min for 30min to obtain lignocellulose dispersion;
adding urea into the lignocellulose dispersion liquid, heating to 70-75 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product.
The mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300-350 mL.
The weight portion ratio of the urea to the lignocellulose is 1: 5-7; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%.
The mixing weight ratio of the starch to the high molecular resin polymer to the chain transfer agent to the cross-linking agent is 2-3: 10: 0.1: 0.3.
the starch is soybean starch, and the high molecular resin polymer is polyethylene resin.
The chain transfer agent is mercaptan, and the crosslinking agent is vinyl triethoxysilane.
The aging treatment is carried out by placing for more than 10 hours under the environment that the temperature is 80 ℃ and the relative humidity of air is 60 percent.
The aging product, the nitrogenated lignocellulose and the dispersing agent are mixed according to the weight ratio of 10: 1-1.5: 0.5.
the dispersing agent is glycerol.
For further understanding of the present application, the following description specifically describes a lignocellulose-based degradable plastic material preparation process provided by the present application with reference to the following examples:
example 1
The preparation process of the lignocellulose-based degradable plastic material comprises
S1, performing nitridation reaction treatment on the lignocellulose to obtain nitrided lignocellulose, wherein the nitridation reaction is as follows: adding lignocellulose into an ethanol solution with the mass fraction of 5%, stirring at the rotating speed of 500r/min for 30min to obtain lignocellulose dispersion liquid, wherein the mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300mL, wherein the weight part ratio of urea to lignocellulose is 1: 5; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%; adding urea into the lignocellulose dispersion liquid, heating to 70 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product;
s2, mixing soybean starch, polyethylene resin, mercaptan and vinyl triethoxysilane in a weight ratio of 2: 10: 0.1: 0.3, adding the mixture into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 150 ℃, and the internal mixing time is 20min to obtain an internal mixing product;
s3, aging the banburying product in an aging chamber, wherein the aging treatment is to place the banburying product for more than 10 hours at the temperature of 80 ℃ and the relative air humidity of 60 percent to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the glycerol according to the weight ratio of 10: 1: 0.5, mixing and adding into an extruder, extruding, cooling and granulating to obtain the product, wherein the extruder is a double-screw extruder, the temperature of each zone is controlled at 105 ℃, 110 ℃, 115 ℃ and 115 ℃, the head temperature is 112 ℃, and the rotating speed is 150 r/min.
Example 2
The preparation process of the lignocellulose-based degradable plastic material comprises
S1, performing nitridation reaction treatment on the lignocellulose to obtain nitrided lignocellulose, wherein the nitridation reaction is as follows: adding lignocellulose into an ethanol solution with the mass fraction of 6%, stirring at the rotating speed of 500r/min for 30min to obtain lignocellulose dispersion liquid, wherein the mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300-350mL, wherein the weight ratio of urea to lignocellulose is 1: 7; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%; adding urea into the lignocellulose dispersion liquid, heating to 75 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product;
s2, mixing soybean starch, polyethylene resin, mercaptan and vinyl triethoxysilane according to the weight ratio of 3:10: 0.1: 0.3, adding the mixture into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 160 ℃, and the internal mixing time is 25min to obtain an internal mixing product;
s3, aging the banburying product in an aging chamber, wherein the aging treatment is to place the banburying product for more than 10 hours at the temperature of 80 ℃ and the relative air humidity of 60 percent to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the glycerol according to the weight ratio of 10: 1.5: 0.5, mixing and adding into an extruder, extruding, cooling and granulating to obtain the product, wherein the extruder is a double-screw extruder, the temperature of each zone is controlled at 105 ℃, 110 ℃, 115 ℃ and 115 ℃, the head temperature is 112 ℃, and the rotating speed is 150 r/min.
Example 3
The preparation process of the lignocellulose-based degradable plastic material comprises
S1, performing nitridation reaction treatment on the lignocellulose to obtain nitrided lignocellulose, wherein the nitridation reaction is as follows: adding lignocellulose into an ethanol solution with the mass fraction of 5.5%, stirring at the rotating speed of 500r/min for 30min to obtain lignocellulose dispersion liquid, wherein the mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300-350mL, wherein the weight ratio of urea to lignocellulose is 1: 6; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%; adding urea into the lignocellulose dispersion liquid, heating to 72 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product;
s2, mixing soybean starch, polyethylene resin, mercaptan and vinyl triethoxysilane in a weight ratio of 2.5: 10: 0.1: 0.3, adding the mixture into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 156 ℃, and the internal mixing time is 20-25min to obtain an internal mixing product;
s3, aging the banburying product in an aging chamber, wherein the aging treatment is to place the banburying product for more than 10 hours at the temperature of 80 ℃ and the relative air humidity of 60 percent to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the glycerol according to the weight ratio of 10: 1.2: 0.5, mixing and adding into an extruder, extruding, cooling and granulating to obtain the product, wherein the extruder is a double-screw extruder, the temperature of each zone is controlled at 105 ℃, 110 ℃, 115 ℃ and 115 ℃, the head temperature is 112 ℃, and the rotating speed is 150 r/min.
Mechanical properties
The materials of the embodiment are injected into plastic sample strips (30 cm multiplied by 10cm multiplied by 1 mm) with the same specification by an injection molding machine (the same injection molding process), a universal tester is adopted to detect the tensile strength and the elongation at break according to GB 1040-79, each group of samples is measured for 10 times, the average value is taken, and the tensile rate is 20 mm/min:
TABLE 1
| Tensile strength MPa | Elongation at break% | |
| Example 1 | 3.82 | 169 |
| Example 2 | 3.57 | 162 |
| Example 3 | 3.24 | 155 |
| Control group | 1.82 | 95 |
Control group: mixing soybean starch, polyethylene resin and glycerol according to a weight ratio of 3:10:0.5, adding into an extruder, extruding, cooling and granulating to obtain a material, wherein the extruder is a double-screw extruder, the temperature of each zone is controlled at 105 ℃, 110 ℃, 115 ℃ and 115 ℃, the head temperature is 112 ℃, and the rotating speed is 150 r/min;
as can be seen from Table 1, the process of the present invention can greatly improve the mechanical properties of the conventional starch plastic material and increase the application range thereof.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions and substitutions within the spirit and scope of the present invention.
Claims (10)
1. A lignocellulose-based degradable plastic material preparation process is characterized by comprising the following steps:
s1, carrying out nitridation reaction treatment on the lignocellulose to obtain nitrided lignocellulose;
s2, mixing starch, a high molecular resin polymer, a chain transfer agent and a cross-linking agent, adding into an internal mixer for internal mixing treatment, wherein the internal mixing temperature is 150-;
s3, ageing the banburying product in an ageing chamber to obtain an aged product;
s4, mixing the aged product, the nitrogenated lignocellulose and the dispersing agent, adding into an extruder, extruding, cooling and granulating to obtain the wood-plastic composite material.
2. The lignocellulose-based degradable plastic material preparation process of claim 1, wherein the nitridation reaction is as follows:
adding lignocellulose into 5-6% ethanol solution, and stirring at 500r/min for 30min to obtain lignocellulose dispersion;
adding urea into the lignocellulose dispersion liquid, heating to 70-75 ℃, stirring at the rotating speed of 500r/min for 10min, adding hydrogen peroxide, continuously stirring for reaction for 2 hours, filtering, washing, and drying to constant weight to obtain the product.
3. The lignocellulose-based degradable plastic material preparation process according to claim 2, wherein the mixing mass ratio of the lignocellulose to the ethanol solution is 100 g: 300-350 mL.
4. The lignocellulose-based degradable plastic material preparation process according to claim 2, wherein the weight part ratio of urea to lignocellulose is 1: 5-7; the mixing mass ratio of the hydrogen peroxide to the lignocellulose dispersion liquid is 1:12, and the mass fraction of the hydrogen peroxide is 8%.
5. The lignocellulose-based degradable plastic material preparation process according to claim 1, wherein the mixing weight ratio of the starch, the high molecular resin polymer, the chain transfer agent and the cross-linking agent is 2-3: 10: 0.1: 0.3.
6. the process according to claim 1 or 5, wherein the starch is soybean starch, and the high molecular resin polymer is polyethylene resin.
7. The process for preparing a lignocellulose-based degradable plastic material as recited in claim 1 or 5, wherein the chain transfer agent is mercaptan, and the cross-linking agent is vinyltriethoxysilane.
8. The process for preparing a lignocellulose-based degradable plastic material as recited in claim 1, wherein the aging treatment is carried out by standing for more than 10 hours at 80 ℃ and 60% relative air humidity.
9. The lignocellulose-based degradable plastic material preparation process according to claim 1, wherein the mixing weight ratio of the aged product, the nitrogenated lignocellulose and the dispersant is 10: 1-1.5: 0.5.
10. the process for preparing a lignocellulose-based degradable plastic material as recited in claim 1, wherein the dispersant is glycerol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848998A (en) * | 2020-08-17 | 2020-10-30 | 杭州励郝新材料有限公司 | Environment-friendly degradable cotton cellulose plastic film and preparation method and application thereof |
| TWI798154B (en) * | 2022-02-11 | 2023-04-01 | 元隆國際科技股份有限公司 | Preparation method of cellulose-based bio-based material and high-barrier fully biodegradable packaging bottle containing the material |
| CN116925514A (en) * | 2023-09-15 | 2023-10-24 | 广州市奥鑫美塑胶有限公司 | Novel organic degradable material sheet and manufacturing method thereof |
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2019
- 2019-12-20 CN CN201911323732.3A patent/CN110982151A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848998A (en) * | 2020-08-17 | 2020-10-30 | 杭州励郝新材料有限公司 | Environment-friendly degradable cotton cellulose plastic film and preparation method and application thereof |
| TWI798154B (en) * | 2022-02-11 | 2023-04-01 | 元隆國際科技股份有限公司 | Preparation method of cellulose-based bio-based material and high-barrier fully biodegradable packaging bottle containing the material |
| CN116925514A (en) * | 2023-09-15 | 2023-10-24 | 广州市奥鑫美塑胶有限公司 | Novel organic degradable material sheet and manufacturing method thereof |
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