CN115386160A - Degradable modified polyethylene material and preparation method thereof - Google Patents
Degradable modified polyethylene material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 119
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 117
- -1 polyethylene Polymers 0.000 title claims abstract description 117
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 112
- 229920002472 Starch Polymers 0.000 claims abstract description 26
- 239000008107 starch Substances 0.000 claims abstract description 26
- 235000019698 starch Nutrition 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 22
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 22
- 229920001661 Chitosan Polymers 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 50
- 241000196324 Embryophyta Species 0.000 claims description 33
- 241000209094 Oryza Species 0.000 claims description 29
- 235000007164 Oryza sativa Nutrition 0.000 claims description 29
- 235000009566 rice Nutrition 0.000 claims description 29
- 241000609240 Ambelania acida Species 0.000 claims description 26
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 26
- 239000010905 bagasse Substances 0.000 claims description 26
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 25
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 25
- 241001330002 Bambuseae Species 0.000 claims description 25
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 25
- 239000011425 bamboo Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 240000006240 Linum usitatissimum Species 0.000 claims 2
- 239000010903 husk Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 241000208202 Linaceae Species 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 9
- 240000003183 Manihot esculenta Species 0.000 description 8
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- 229920002488 Hemicellulose Polymers 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000010635 coffee oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
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- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 238000003889 chemical engineering Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 238000009863 impact test Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 230000009965 odorless effect Effects 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The application relates to the field of high polymer materials, and particularly discloses a degradable modified polyethylene material and a preparation method thereof. The degradable polyethylene material comprises 100-150 parts by weight of linear low-density polyethylene, 6-10 parts by weight of starch, 5-8 parts by weight of chitosan, 8-14 parts by weight of plant fiber, 4-8 parts by weight of shell powder and 1.2-1.6 parts by weight of silane coupling agent; the preparation method comprises the following steps: firstly, all the raw materials are mixed and stirred for 3-5min at the rotating speed of 1800-2000r/min to obtain a mixed material, and then the mixed material is melted, blended, extruded and granulated at the temperature of 150-180 ℃ to obtain the degradable modified polyethylene material. The degradable polyethylene material is green and environment-friendly in raw materials, can be degraded and recycled, and has strong mechanical properties.
Description
Technical Field
The application relates to the field of high polymer materials, in particular to a degradable modified polyethylene material and a preparation method thereof.
Background
Polyethylene is a thermoplastic resin obtained by polymerizing ethylene monomer or ethylene monomer and a small amount of alpha-olefin, has excellent chemical stability, electrical insulation and low-temperature resistance, is nontoxic and odorless, has small water absorption, and is widely applied to the production and manufacture of films, containers, packaging materials, wires and cables and daily necessities.
Although the polyethylene products greatly facilitate our daily life, the waste polyethylene products have great harm to the environment due to the very slow natural degradation of polyethylene, which seriously hinders the development of polyethylene products. Therefore, it is common to add fully degradable polymers, such as starch, collagen and protein, to polyethylene materials to accelerate the degradation of polyethylene. The biodegradable polyethylene material has the advantages of no toxicity, light pollution in the production process, good biocompatibility and the like, but has the defects of poor mechanical property and the like compared with the common polyethylene material. Therefore, the inventor considers that the research on the biodegradable polyethylene material with stronger mechanical property has very important significance.
Disclosure of Invention
In order to solve the technical problems, the application provides a degradable modified polyethylene material and a preparation method thereof.
In a first aspect, the degradable modified polyethylene material provided by the application adopts the following technical scheme:
a degradable modified polyethylene material comprises the following raw materials:
100-150 parts by weight of linear low density polyethylene;
6-10 parts of starch;
5-8 parts of chitosan;
8-14 parts of plant fiber;
4-8 parts of shell powder; and the number of the first and second groups,
1.2-1.6 parts by weight of silane coupling agent.
By adopting the technical scheme, the biodegradable polyethylene material is prepared by mixing starch, chitosan and linear low-density polyethylene, and compared with a common polyethylene material, the degradation speed is obviously accelerated. Meanwhile, the plant fiber and the shell powder are added into the polyethylene material, and the plant fiber and the shell powder are mixed and matched for use by utilizing the characteristics of low density and high specific strength of the plant fiber, so that a cross-linked space network structure is formed among polymer chains of the polyethylene material, a good mechanical supporting effect is jointly played, and the mechanical property of the polyethylene material can be obviously improved. And the silane coupling agent is added into the polyethylene material, so that the starch, the chitosan, the plant fiber and the shell powder can be fully dispersed in a blending system, the compatibility of the starch, the chitosan, the plant fiber and the shell powder with the linear low-density polyethylene is improved, and the mechanical property of the polyethylene material is further improved.
Preferably, the raw materials used comprise the following components:
130 parts by weight of linear low density polyethylene;
8 parts of starch;
6.5 parts of chitosan;
11 parts of plant fiber;
6 parts of shell powder; and the number of the first and second groups,
1.4 parts by weight of a silane coupling agent.
By adopting the technical scheme, the application further controls the usage amount of the linear low-density polyethylene, the starch, the chitosan, the plant fiber, the shell powder and the silane coupling agent, can further exert the reinforcing effect of the plant fiber and the shell powder on the polyethylene material, and simultaneously further improves the compatibility of the starch, the chitosan, the plant fiber, the shell powder and the linear low-density polyethylene, thereby further improving the mechanical property of the polyethylene material.
Preferably, the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber in a weight ratio of (0.4-0.8) to (0.6-1.0) to (0.5-0.9).
Through adopting above-mentioned technical scheme, this application adopts bagasse fibre, bamboo fibre and flax fiber to mix collocation and use, and full play synergism each other utilizes the higher tensile strength of three, specific strength and degradability, forms cross-linking space network structure between the polymer chain of polyethylene material, has fully played the effect of mechanical support, under the prerequisite that does not influence the degradation speed of degradable polyethylene material, has improved the mechanical properties of polyethylene material.
Preferably, the weight ratio of the bagasse fiber, the bamboo fiber and the flax fiber is 0.5.
By adopting the technical scheme, the weight ratio of the bagasse fiber, the bamboo fiber and the flax fiber is further controlled, and the synergistic effect among the bagasse fiber, the bamboo fiber and the flax fiber can be further exerted, so that the mechanical property of the degradable polyethylene material is further improved.
Preferably, the raw material further comprises 8-12 parts by weight of coffee grounds and 7-10 parts by weight of rice hull ash.
By adopting the technical scheme, the main components of the coffee grounds are hemicellulose, cellulose and lignin, the main component of the rice hull ash is silicon dioxide, and the hemicellulose, the cellulose and the lignin are biomass waste materials generated in the food processing process. The polyethylene material and the shell powder can be added into the polyethylene material, and can be used as a reinforcing filler of the polyethylene material together with the shell powder and the plant fibers, so that the mechanical property of the polyethylene material is improved together. Meanwhile, the interface adhesion degree of the filler and the linear low-density polyethylene is improved by utilizing two pore structures with different sizes on the surface of the rice hull ash, so that the mechanical property of the polyethylene material is further improved.
Preferably, the coffee grounds are heat-treated by the following method:
firstly, drying the coffee grounds for 1-2h at the temperature of 105-110 ℃, then increasing the temperature to 225-250 ℃ at the heating rate of 5-7 ℃/min, keeping the temperature for 2-2.5h at constant temperature, and then cooling to obtain the coffee grounds after heat treatment.
By adopting the technical scheme, before the coffee grounds are added into the polyethylene material, the coffee grounds are subjected to a heat treatment process, so that the content of hydrophilic groups in the coffee grounds can be reduced, the hydrophilicity of the coffee grounds is reduced, the interface compatibility of the coffee grounds and the linear low-density polyethylene is improved, and meanwhile, the particle size of the coffee grounds is reduced, so that the coffee grounds can be fully dispersed in a blending system, the reinforcing effect of the coffee grounds on the polyethylene material is improved, and the mechanical property of the polyethylene material is further improved. And the heat treatment can also separate out the coffee oil in the coffee grounds, thereby reducing the negative influence of the coffee oil on the polyethylene material.
Preferably, the rice hull ash is modified by the following method:
uniformly mixing the coupling agent, ethanol and water in the weight ratio of 1 (10-12) to (8-10), then adding acetic acid to adjust the pH value to 4-5 to obtain a mixed solution, and then mixing and stirring the rice hull ash and the mixed solution in the weight ratio of 1 (100-110) for 20-30min at the rotating speed of 1200-1300r/min to obtain the modified rice hull ash.
By adopting the technical scheme, the rice hull ash is modified by the coupling agent, the compatibility of the rice hull ash and the linear low density polyethylene is improved, and the interface bonding force of the rice hull ash and the linear low density polyethylene is enhanced, so that the reinforcing effect of the rice hull ash on the polyethylene material is improved, and the mechanical property of the polyethylene material is further improved.
Preferably, the raw material also comprises 0.2-0.5 weight part of nano SiO 2 。
By adopting the technical scheme, the nano SiO 2 Nano SiO adopting hydrophobic treatment 2 . Nano SiO treated by hydrophobic treatment 2 Adding into polyethylene material to obtain nanometer SiO 2 Can be more uniformly dispersed in a blending system, can fully play a role in reinforcing the polyethylene material, improves the tensile strength and the elongation at break of the polyethylene material, and ensures that the polyethylene material has stronger mechanical property.
Preferably, the nano SiO 2 The weight ratio to starch is 1.
By adopting the technical scheme, the application further limits the nano SiO 2 The dosage ratio of the nano SiO to the starch can be further exerted 2 The heterogeneous nucleation effect of the polyethylene material increases the retrogradation degree of starch, so that the polyethylene material is more regular and compact, and the tensile strength of the polyethylene material is further improved.
In a second aspect, the application provides a preparation method of a degradable modified polyethylene material, which comprises the following steps: firstly, all the raw materials are mixed and stirred for 3-5min at the rotating speed of 1800-2000r/min to obtain a mixed material, and then the mixed material is melted, blended, extruded and granulated at the temperature of 150-180 ℃ to obtain the degradable modified polyethylene material.
By adopting the technical scheme, all the raw materials are premixed at a high rotating speed, so that all the components can be fully dispersed, and then the components are melted and blended, so that the prepared polyethylene material has high mechanical property. The preparation method is simple in steps, easy to operate and suitable for large-scale industrial production.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the degradable polyethylene material disclosed by the application utilizes plant fibers and food processing waste as reinforcing materials, so that the mechanical property of the degradable polyethylene material is greatly improved on the premise of not influencing the degradation speed of the polyethylene material;
2. the degradable polyethylene material has the advantages of low cost of raw materials, environmental protection, degradable recovery and accordance with a sustainable development route;
3. the preparation method of the degradable polyethylene material is simple in steps, easy to operate and suitable for large-scale industrial production.
Detailed Description
<Sources of materials>
The linear low density polyethylene of the present application is purchased from Shanghai bridge micro-chemical engineering technologies, inc. model LL0230AT;
the starch is edible cassava starch, and is purchased from Jinan Sancheng chemical Co., ltd;
the chitosan is purchased from Jiangsu Caoshu Biotechnology Limited, model CW20201125;
the shell powder is purchased from Wanduo mineral processing Limited company in Lingshou county, and has the specification of 800 meshes;
the silane coupling agent is purchased from Shandong Hengyuxin materials Co., ltd, specification KH550;
the bagasse fiber of the application is purchased from Guangxi Nanning sugar industry, inc., standard chemical pulp;
the coffee grounds are purchased from Guangdong Li Mei New Material science and technology Limited company and have the mesh number of 100;
the rice hull ash is purchased from Jiangsu Yuneng energy company, and the content of silicon dioxide is 93 percent;
the coupling agent of the present application is available from Shanghai Michelin Biochemical technology Ltd, model KH560;
nano SiO of the present application 2 Purchased from Nanjing Baokite New materials, inc., surface properties: hydrophobic in nature.
<Examples>
Example 1
A preparation method of a degradable modified polyethylene material comprises the following steps:
firstly, 100kg of linear low-density polyethylene, 10kg of cassava starch, 5kg of chitosan, 14kg of plant fiber, 4kg of shell powder and 1.6kg of silane coupling agent KH550 are mixed and stirred for 3min at the rotating speed of 1800r/min to obtain a mixture, and then the mixture is melted, blended, extruded and granulated at the temperature of 150 ℃ to obtain the degradable modified polyethylene material;
wherein, the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber with the weight ratio of 0.4; specifically, 3.7kg of bagasse fibers, 5.6kg of bamboo fibers and 4.7kg of flax fibers.
Example 2
A preparation method of a degradable modified polyethylene material comprises the following steps:
firstly, 150kg of linear low-density polyethylene, 6kg of cassava starch, 8kg of chitosan, 8kg of plant fiber, 8kg of shell powder and 1.2kg of silane coupling agent KH550 are mixed and stirred for 5min at the rotating speed of 2000r/min to obtain a mixture, and then the mixture is melted, blended, extruded and granulated at the temperature of 180 ℃ to obtain the degradable modified polyethylene material;
wherein, the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber with the weight ratio of 0.8; specifically, the bagasse fiber is 2.37kg, the bamboo fiber is 2.96kg, and the flax fiber is 2.67kg.
Example 3
A preparation method of a degradable modified polyethylene material comprises the following steps:
firstly, 130kg of linear low-density polyethylene, 8kg of cassava starch, 6.5kg of chitosan, 11kg of plant fiber, 6kg of shell powder and 1.4kg of silane coupling agent KH550 are mixed and stirred for 5min at the rotating speed of 2000r/min to obtain a mixture, and then the mixture is melted, blended, extruded and granulated at the temperature of 180 ℃ to obtain the degradable modified polyethylene material;
wherein, the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber with the weight ratio of 0.8; specifically, 3.26kg of bagasse fibers, 4.07kg of bamboo fibers and 3.67kg of flax fibers.
Example 4
A preparation method of a degradable modified polyethylene material comprises the following steps:
firstly, 150kg of linear low-density polyethylene, 6kg of cassava starch, 8kg of chitosan, 8kg of plant fiber, 8kg of shell powder and 1.2kg of silane coupling agent KH550 are mixed and stirred for 5min at the rotating speed of 2000r/min to obtain a mixture, and then the mixture is melted, blended, extruded and granulated at the temperature of 180 ℃ to obtain the degradable modified polyethylene material;
wherein the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber in a weight ratio of 0.5; specifically, 2kg of bagasse fibers, 3.2kg of bamboo fibers and 2.8kg of flax fibers.
Example 5
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 8kg of coffee grounds and 10kg of rice hull ash were also added to the mix.
Example 6
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 12kg of coffee grounds and 7kg of rice hull ash were also added to the mix.
Example 7
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 5kg of coffee grounds and 12kg of rice hull ash were also added to the mix.
Example 8
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 15kg of coffee grounds and 5kg of rice hull ash were also added to the mix.
Example 9
A method for preparing a degradable modified polyethylene material, which is different from the method in example 6 in that: the coffee grounds are subjected to heat treatment by adopting the following method:
firstly, drying 12kg of coffee grounds for 1h at the temperature of 105 ℃, then raising the temperature to 225 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2h at constant temperature, and then cooling to obtain the heat-treated coffee grounds.
Example 10
A method for preparing a degradable modified polyethylene material, which is different from the method in example 6 in that: the coffee grounds are subjected to heat treatment by adopting the following method:
firstly, drying 12kg of coffee grounds for 2h at the temperature of 110 ℃, then raising the temperature to 250 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 2.5h at constant temperature, and then cooling to obtain the heat-treated coffee grounds.
Example 11
A method for preparing a degradable modified polyethylene material, which is different from the method in example 6 in that: the rice hull ash is modified by the following method:
uniformly mixing 80kg of coupling agent KH560, 800kg of ethanol and 640kg of water, then adding acetic acid to adjust the pH value to 4 to obtain a mixed solution, and then mixing and stirring 7kg of rice hull ash and 700kg of mixed solution at the rotating speed of 1200r/min for 20min to obtain the modified rice hull ash.
Example 12
A method for preparing a degradable modified polyethylene material, which is different from the method in example 6 in that: the rice hull ash is modified by the following method:
uniformly mixing 80kg of coupling agent KH560, 960kg of ethanol and 800kg of water, then adding acetic acid to adjust the pH value to 5 to obtain a mixed solution, and then mixing and stirring 7kg of rice hull ash and 770kg of mixed solution at the rotating speed of 1300r/min for 30min to obtain the modified rice hull ash.
Example 13
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 0.2kg of nano SiO is also added into the mixture 2 。
Example 14
Degradable modified polyethyleneThe preparation method of the alkene material is different from the preparation method of the example 2 in that: 0.5kg of nano SiO is also added into the mixture 2 。
Example 15
A method for preparing a degradable modified polyethylene material, which is different from the method in example 14 in that: nano SiO 2 The weight ratio of the nano SiO to the starch is 1 2 It was 0.3kg.
Example 16
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 0.05kg of nano SiO is also added into the mixture 2 。
Example 17
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: 1.8kg of nano SiO is also added into the mixture 2 。
Example 18
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: the weight ratio of the bagasse fibers to the bamboo fibers to the flax fibers is 0.2.
Example 19
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: the weight ratio of the bagasse fibers to the bamboo fibers to the flax fibers is 1.5.
Example 20
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: bagasse fibers were not added to the plant fibers, 4.21kg of bamboo fibers and 3.79kg of flax fibers.
Example 21
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: bamboo fibers are not added into the plant fibers, 3.76kg of bagasse fibers and 4.24kg of flax fibers.
Example 22
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: flax fibers are not added into the plant fibers, the bagasse fibers account for 3.56kg, and the bamboo fibers account for 4.44kg.
Example 23
A method for preparing a degradable modified polyethylene material, which is different from the method in example 2 in that: the flax fiber is replaced by the ramie fiber, and the rest is the same.
<Comparative example>
Comparative example 1
The difference from example 2 is that: no plant fiber is added into the mixture, and the rest is the same.
Comparative example 2
The difference from example 2 is that: no shell powder was added to the mixture, and the rest was the same.
Comparative example 3
The difference from example 2 is that: 50kg of linear low-density polyethylene, 15kg of cassava starch, 3kg of chitosan, 27kg of plant fiber (8 kg of bagasse fiber, 10kg of bamboo fiber and 9kg of flax fiber), 2kg of shell powder and 2kg of silane coupling agent KH550 are contained in the mixture.
Comparative example 4
The difference from example 2 is that: 200kg of linear low-density polyethylene, 5kg of cassava starch, 10kg of chitosan, 2.7kg of plant fiber (0.8 kg of bagasse fiber, 1kg of bamboo fiber and 0.9kg of flax fiber), 10kg of shell powder and 0.8kg of silane coupling agent KH550 in the mixture.
<Performance detection>
1. The polyethylene materials prepared in examples 1-23 and comparative examples 1-4 were tested for tensile strength and elongation at break with reference to GB 1040-92 method for testing tensile properties of plastics, the tensile speed was 50mm/min, and the test results are shown in Table 1;
2. the polyethylene materials obtained in examples 1 to 23 and comparative examples 1 to 4 were subjected to notched impact strength test with reference to "GB 1043-93 rigid plastic simply-supported beam impact test method", and the test results are shown in Table 1.
Table 1 table of performance test results
As can be seen from Table 1, the polyethylene materials obtained in examples 1-2 of the present application had tensile strengths of 15.6MPa or more, elongations at break of 116.8% or more, and notched impact strengths of 4.5KJ/m 2 The degradable polyethylene material prepared by the method has high tensile strength, elongation at break, notch impact strength and strong mechanical property.
The tensile strength, the elongation at break and the notch impact strength of the example 3 are all higher than those of the examples 1-2, which shows that the application can further control the use amount of the linear low-density polyethylene, the tapioca starch, the chitosan, the plant fiber, the shell powder and the silane coupling agent KH550, and can further improve the mechanical properties of the degradable polyethylene material.
The tensile strength, the elongation at break and the notch impact strength of the embodiment 4 are all larger than those of the embodiments 1-2, which shows that the weight ratio of bagasse fibers, bamboo fibers and flax fibers in plant fibers is further controlled, and the mechanical property of the degradable polyethylene material can be further improved.
The tensile strength, elongation at break and notched impact strength of examples 5-6 are all significantly greater than those of example 2, which shows that the mechanical properties of the degradable polyethylene material can be significantly improved by adding coffee grounds and rice hull ash into the polyethylene material.
The tensile strength, elongation at break and notched impact strength of examples 7-8 are all greater than those of example 2, but the tensile strength, elongation at break and notched impact strength of examples 7-8 are all less than those of examples 5-6, which shows that the mechanical properties of the degradable polyethylene material can be further improved by further controlling the addition amount of the coffee grounds and the rice hull ash.
The tensile strength, the elongation at break and the notch impact strength of the embodiments 9-10 are all higher than those of the embodiment 6, which shows that the application can obviously enhance the reinforcing effect of the coffee grounds on the polyethylene material by performing the heat treatment process on the coffee grounds in advance, thereby improving the mechanical property of the degradable polyethylene material.
The tensile strength, the elongation at break and the notch impact strength of the examples 11 to 12 are all higher than those of the example 6, which shows that the application of modifying the rice hull ash can obviously improve the dispersion degree of the rice hull ash in the blending system, thereby improving the mechanical property of the degradable polyethylene material.
Examples 13-14 all had greater tensile strength, elongation at break, and notched impact strength than example 2, indicating that the present application also added nano-SiO to the polyethylene material 2 Can improve the mechanical property of the degradable polyethylene material.
Example 15, in which tensile strength, elongation at break and notched impact strength were all greater than example 14, demonstrates that the present application further controls nano-SiO 2 And the weight ratio of the degradable polyethylene material to the starch can further improve the mechanical property of the degradable polyethylene material.
The tensile strength, elongation at break and notched impact strength of examples 16-17 are all greater than those of example 2, but the tensile strength, elongation at break and notched impact strength of examples 16-17 are all less than those of examples 13-14, indicating that the present application further controls the nano SiO 2 The addition amount of (b) can further improve the mechanical properties of the degradable polyethylene material.
The tensile strength, the elongation at break and the notch impact strength of the examples 18 to 19 are all lower than those of the example 2, which shows that the mechanical property of the degradable polyethylene material can be improved by controlling the weight ratio of the bagasse fiber, the bamboo fiber and the flax fiber.
The tensile strength, the elongation at break and the notch impact strength of the examples 20-23 are all smaller than those of the example 2, which shows that the cooperation of the bagasse fibers, the bamboo fibers and the flax fibers can be fully exerted, so that the mechanical properties of the polyethylene material are improved.
The tensile strength, elongation at break and notched impact strength of the comparative examples 1-2 are all obviously lower than those of the example 2, which shows that the mechanical properties of the degradable polyethylene material are improved by adopting the mutual matching of the plant fiber and the shell powder.
Comparative examples 3 to 4, in which tensile strength, elongation at break and notched impact strength were all lower than those of example 2, demonstrate that controlling the amount of components such as linear low density polyethylene used in the present application can improve the mechanical properties of degradable polyethylene materials.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. The degradable modified polyethylene material is characterized by comprising the following raw materials:
100-150 parts by weight of linear low density polyethylene;
6-10 parts of starch;
5-8 parts of chitosan;
8-14 parts of plant fiber;
4-8 parts of shell powder; and the number of the first and second groups,
1.2-1.6 parts by weight of silane coupling agent.
2. The degradable modified polyethylene material of claim 1, wherein the raw materials comprise the following components:
130 parts by weight of linear low density polyethylene;
8 parts of starch;
6.5 parts of chitosan;
11 parts of plant fiber;
6 parts of shell powder; and the number of the first and second groups,
1.4 parts by weight of a silane coupling agent.
3. A degradable modified polyethylene material according to claim 1 or 2, wherein the plant fiber comprises bagasse fiber, bamboo fiber and flax fiber in a weight ratio of (0.4-0.8) to (0.6-1.0) to (0.5-0.9).
4. The degradable modified polyethylene material according to claim 3, wherein the weight ratio of the bagasse fiber, the bamboo fiber and the flax fiber is 0.5.
5. The degradable modified polyethylene material of claim 1, wherein the raw material further comprises 8-12 parts by weight of coffee grounds and 7-10 parts by weight of rice hull ash.
6. The degradable modified polyethylene material of claim 5, wherein the coffee grounds are heat-treated by the following method:
firstly, drying the coffee grounds for 1-2h at the temperature of 105-110 ℃, then increasing the temperature to 225-250 ℃ at the heating rate of 5-7 ℃/min, keeping the temperature for 2-2.5h at constant temperature, and then cooling to obtain the coffee grounds after heat treatment.
7. The degradable modified polyethylene material according to claim 5, wherein the rice husk ash is modified by the following method:
uniformly mixing the coupling agent, ethanol and water in a weight ratio of 1 (10-12) to 8-10, adding acetic acid to adjust the pH value to 4-5 to obtain a mixed solution, and then mixing and stirring the rice hull ash and the mixed solution in a weight ratio of 1 (100-110) at a rotating speed of 1200-1300r/min for 20-30min to obtain the modified rice hull ash.
8. The degradable modified polyethylene material of claim 1, wherein the raw material further comprises 0.2-0.5 weight parts of nano SiO 2 。
9. The degradable modified polyethylene material of claim 8, wherein the nano SiO is 2 The weight ratio to starch is 1.
10. A method for preparing the degradable modified polyethylene material of any one of claims 1 to 9, comprising the steps of:
firstly, mixing and stirring all the raw materials at the rotating speed of 1800-2000r/min for 3-5min to obtain a mixture, then melting, blending, extruding and granulating the mixture at the temperature of 150-180 ℃ to obtain the degradable modified polyethylene material.
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