CN111500037B - High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof - Google Patents
High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof Download PDFInfo
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- CN111500037B CN111500037B CN202010495302.6A CN202010495302A CN111500037B CN 111500037 B CN111500037 B CN 111500037B CN 202010495302 A CN202010495302 A CN 202010495302A CN 111500037 B CN111500037 B CN 111500037B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention provides a high-density bamboo powder modified polylactic acid biodegradable plastic and a preparation method thereof. The high-density bamboo powder modified polylactic acid biodegradable plastic provided by the invention comprises the following components in parts by mass: 35-60 parts of polylactic acid, 25-40 parts of modified bamboo powder, 10-15 parts of starch, 1.5-2.5 parts of silicate, 3-5 parts of glycerol and 0.5-2 parts of coupling agent. According to the technical scheme, bamboo powder cellulose is subjected to graft modification treatment, the N, N-dimethyl amide/aluminum chloride mixed system is an initiator for graft copolymerization reaction of the bamboo powder cellulose and caprolactone, the hydrophilic chain segment and the lipophilic chain segment which are incompatible with each other are bonded together by adopting a graft copolymerization method, and the modified bamboo powder is easily crosslinked with polylactic acid to form a copolymer under the action of a coupling agent, so that the mechanical property of the bamboo-plastic composite material is improved, the consumption of the polylactic acid is further reduced along with the increase of the addition amount of the bamboo powder, and the cost is saved.
Description
Technical Field
The invention relates to the technical field of food packaging, in particular to high-density bamboo powder modified polylactic acid biodegradable plastic and a preparation method thereof.
Background
With the improvement of public environmental awareness, the increase of environmental concern and the increasing shortage of petroleum resources, the research and development of biodegradable plastics have attracted extensive attention and attention in recent years. Among them, polylactic acid (PLA) is a renewable resource-based polymer, is a completely biodegradable aliphatic polyester, and is one of the most commercially available biodegradable polymers at present. Polylactic acid has high strength, but is brittle and poor in heat resistance, and application is limited to some extent. In order to improve the mechanical property of polylactic acid, the bamboo fiber and the plastic are organically combined to prepare the bamboo-plastic composite material, the bamboo-plastic composite material has the characteristics of the plastic and the bamboo, is moisture-proof, corrosion-resistant, moth-proof, non-cracking, non-warping, non-toxic and tasteless, has good secondary processability, has a very wide application prospect, but has poor interface compatibility of the fiber and the polylactic acid, and the mechanical property of the composite material is reduced due to the excessively high addition amount of the bamboo powder, so that the further application of the bamboo-plastic composite material is limited.
Disclosure of Invention
The invention mainly aims to provide a high-density bamboo powder modified polylactic acid biodegradable plastic and a preparation method thereof, and aims to solve the problems that the interface compatibility of fibers and polylactic acid is poor, and the mechanical property of a composite material is reduced due to the excessively high addition amount of bamboo powder.
In order to achieve the purpose, the invention provides a high-density bamboo powder modified polylactic acid biodegradable plastic which comprises the following components in parts by weight:
35-60 parts of polylactic acid, 25-40 parts of modified bamboo powder, 10-15 parts of starch, 1.5-2.5 parts of silicate, 3-5 parts of glycerol and 0.5-2 parts of coupling agent.
Preferably, the composition comprises the following components:
45-55 parts of polylactic acid, 30-40 parts of modified bamboo powder, 12-15 parts of starch, 1.5-2.5 parts of silicate, 3-5 parts of glycerol and 0.5-2 parts of coupling agent.
Preferably, the preparation method of the modified bamboo powder comprises the following steps:
(1) preparing aluminum chloride and N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution according to the mass ratio of 1: 15-20;
(2) soaking the bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying;
(3) soaking the bamboo powder subjected to freeze drying in the step (2) in a dimethylacetamide solution for 3-8 h, filtering, and freeze drying;
dimethylacetamide
(4) Uniformly mixing the bamboo powder subjected to freeze drying in the step (3) with the N, N-dimethyl amide/aluminum chloride mixed solution obtained in the step (1) according to the mass ratio of 1: 3-6, and heating the mixed system to 150 ℃ in a nitrogen atmosphere;
(5) and (4) adding caprolactone into the mixed system obtained in the step (4), continuously stirring and reacting for 12 hours, centrifugally separating after the reaction is finished, washing and drying to obtain the modified bamboo powder.
Preferably, the amount of caprolactone added in step (5) is 10-15% by mass of the mixed system.
Preferably, the washing solvent in the step (5) is dimethyl sulfoxide, and the washing times are 2-4 times.
Preferably, the starch is at least one of modified corn starch and modified wheat starch.
Preferably, the silicate is a layered silicate comprising: any one or more of aluminum silicate, calcium silicate, magnesium silicate, sodium silicate and potassium silicate.
Preferably, the coupling agent is one of a silane coupling agent and a titanate coupling agent.
In order to achieve the purpose, the invention also provides a preparation method of the high-density bamboo powder modified polylactic acid biodegradable plastic, which comprises the following steps:
(1) proportionally placing polylactic acid, modified bamboo powder, starch, silicate, glycerol and a coupling agent into a high-speed mixer to be mixed to obtain a mixed material;
(2) adding the mixed raw materials in the step (1) from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation;
(3) and (3) extruding and molding the sample obtained by extruding and granulating in the step (2) by a single-screw extruder, controlling the extrusion temperature to be 125-160 ℃, extruding and granulating.
According to the technical scheme, bamboo powder cellulose is subjected to graft modification treatment, the N, N-dimethyl amide/aluminum chloride mixed system is an initiator for graft copolymerization reaction of the bamboo powder cellulose and caprolactone, the hydrophilic chain segment and the lipophilic chain segment which are incompatible with each other are bonded together by adopting a graft copolymerization method, and the modified bamboo powder is easily crosslinked with polylactic acid to form a copolymer under the action of a coupling agent, so that the mechanical property of the bamboo-plastic composite material is improved, the consumption of the polylactic acid is further reduced along with the increase of the addition amount of the bamboo powder, and the cost is saved. In the implementation process of the scheme, the polylactic acid, the bamboo powder and the starch can be dispersed more uniformly by adding the phyllosilicate, so that the particles are prevented from agglomerating, the grafting rate in the melting process of the polylactic acid, the bamboo powder and the starch is improved, and the mechanical property and the stability of the bamboo-plastic composite material are further improved.
Detailed Description
The technical solutions in the embodiments of the present invention are described clearly and completely below, and it is obvious that 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.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 15kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.5kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 2
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 17kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.7kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 3
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 20kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 3.1kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 4
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 22kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 3.3kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Comparative example 1
The preparation method of the bamboo powder/polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 2.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Mechanical Property test
The tensile property and the bending property of the bamboo powder modified polylactic acid biodegradable plastic are tested by adopting a CMT-5504 type universal mechanical testing machine. The tensile properties and the bending properties were tested according to the national standards GB/T1040-92 and GB/T9341-2000, respectively. The test results are shown in Table 1.
TABLE 1 mechanical Properties of polylactic acid biodegradable plastics in examples 1 to 4 and comparative example 1
As can be seen from table 1, compared to comparative example 1 in which the bamboo powder is not modified, the addition amount of the bamboo powder in comparative example 1 is significantly lower than that of the bamboo powder in examples 1 to 4, and even when the addition amount of the bamboo powder is reduced, the mechanical properties of the bamboo powder/polylactic acid composite plastic prepared in comparative example 1 are significantly lower than those of the bamboo powder modified polylactic acid biodegradable plastic prepared in examples 1 to 4. The method shows that the compatibility of the bamboo powder and a polylactic acid two-phase system can be improved by treating the bamboo powder with the N, N-dimethyl amide/aluminum chloride mixed solution, so that the addition of the bamboo powder is further improved and the cost of the material is reduced under the condition of ensuring the mechanical property of the composite plastic.
Water absorption measurement
The bamboo powder has good hydrophilicity, and the cellulose, hemicellulose, lignin and other components contained in the bamboo powder contain a large amount of hydroxyl groups, so that when the composite material is contacted with water, the hydroxyl groups are quickly combined with the water to form hydrogen bonds to absorb water, and the size stability of the final product of the composite material is reduced. Therefore, the bamboo powder is modified, a large amount of hydrophilic hydroxyl groups are prevented from being exposed outside and contacting with water molecules, and the bamboo powder modified polylactic acid biodegradable plastic prepared by compounding the bamboo powder modified polylactic acid biodegradable plastic with polylactic acid has important significance for reducing the water absorption of the composite material.
According to the requirements of GB1034-98 test method for water absorption of plastics, a sample with the size of 10mm multiplied by 2mm is dried in vacuum at 50 ℃ for 48h, weighed (recorded as m1), the sample is soaked in distilled water at room temperature (25 ℃) for 24h, then the sample is taken out and wiped on the surface by using filter paper, and weighed again (recorded as m2), and the water absorption is calculated according to the following formula. The test results are shown in Table 2.
TABLE 2 Water absorption test results of polylactic acid biodegradable plastics in examples 1 to 4 and comparative example 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | |
| Water absorption (%) | 2.8 | 2.7 | 2.9 | 3.1 | 6.8 |
As can be seen from table 2, the bamboo powder modified polylactic acid biodegradable plastics prepared in examples 1 to 4 all showed lower water absorption compared to comparative example 1, which indicates that the water absorption of the bamboo powder/polylactic acid composite plastic can be significantly reduced after the bamboo powder is modified in the N, N-dimethylamide/aluminum chloride mixed solution.
Example 5
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 15kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and adding 1.5kg of caprolactone into the mixed system, continuously stirring and reacting for 12h, centrifugally separating after the reaction is finished, washing and drying to obtain the modified bamboo powder.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 6
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 15kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.1kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 7
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 15kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 3.1kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 8
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 15kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and adding 3.5kg of caprolactone into the mixed system, continuously stirring and reacting for 12h, centrifugally separating after the reaction is finished, washing and drying to obtain the modified bamboo powder.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 3.0kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Mechanical Property test
The tensile property and the bending property of the bamboo powder modified polylactic acid biodegradable plastic are tested by adopting a CMT-5504 type universal mechanical testing machine. The tensile properties and the bending properties were tested according to the national standards GB/T1040-92 and GB/T9341-2000, respectively. The test results are shown in Table 3.
Table 3, examples 5 to 8 test results of mechanical properties of the bamboo powder modified polylactic acid biodegradable plastic
As can be seen from table 3, the addition amount of caprolactone has an important effect on the mechanical properties of the bamboo powder modified polylactic acid biodegradable plastic, and when the addition amount of caprolactone is too high or too low, the tensile properties and bending properties of the modified polylactic acid biodegradable plastic are reduced to some extent. Caprolactone is a monomer of polycaprolactone, and after the caprolactone is mixed with bamboo powder, graft polymerization is carried out under the catalytic action of an N, N-dimethyl amide/aluminum chloride mixed system, so that the arrangement structure of bamboo powder molecular chains is changed, the compatibility of the bamboo powder and polylactic acid is improved, and the addition proportion of the bamboo powder in a material is increased.
Water absorption measurement
According to the requirements of GB1034-98 test method for water absorption of plastics, a sample with the size of 10mm multiplied by 2mm is dried in vacuum at 50 ℃ for 48h, weighed (recorded as m1), the sample is soaked in distilled water at room temperature (25 ℃) for 24h, then the sample is taken out and wiped on the surface by using filter paper, and weighed again (recorded as m2), and the water absorption is calculated according to the following formula. The test results are shown in Table 4.
Table 4, Water absorption test results of the bamboo powder modified polylactic acid biodegradable plastic of examples 5 to 8
| Example 5 | Example 6 | Example 7 | Example 8 | |
| Water absorption (%) | 2.9 | 2.7 | 2.6 | 4.7 |
As can be seen from table 2, when the amount of caprolactone added was too high, the water absorption of the modified polylactic acid biodegradable plastic was significantly increased, and when the amount of caprolactone added was less than the predetermined amount, the water absorption of the modified polylactic acid biodegradable plastic was hardly affected. Therefore, it is presumed that although caprolactone can change the hydrophilicity of the bamboo powder molecular chain segment through the grafting reaction and improve the compatibility of the bamboo powder and the polylactic acid, too much caprolactone can preferentially generate the polymerization reaction with the polylactic acid, that is, caprolactone participates in the polymerization of the polylactic acid to form a competition reaction, so that the bamboo powder reaction is incomplete, and the exposed hydrophilic group is exposed to improve the hydrophilicity of the material.
Example 9
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 17kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.7kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 2kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 10
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 17kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.7kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 2.5kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 11
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 17kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.7kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 4kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
Example 12
The preparation method of the modified bamboo powder comprises the following steps:
preparing 1kg of aluminum chloride and 17kg of N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution; soaking 5kg of bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying; soaking the freeze-dried bamboo powder in a dimethylacetamide solution for 3-8 h, filtering, and freeze-drying; uniformly mixing the freeze-dried bamboo powder with an N, N-dimethyl amide/aluminum chloride mixed solution, and heating the mixed system to 150 ℃ in a nitrogen atmosphere; and 2.7kg of caprolactone is added into the mixed system, the mixture is continuously stirred and reacts for 12 hours, centrifugal separation is carried out after the reaction is finished, and the modified bamboo powder is obtained by washing and drying.
The preparation method of the bamboo powder modified polylactic acid biodegradable plastic comprises the following steps:
putting 4.0kg of polylactic acid, 4.5kg of modified bamboo powder, 1.2kg of starch, 0.15kg of silicate, 0.35kg of glycerol and 0.1kg of coupling agent into a high-speed mixer, and mixing to obtain a mixed material; adding the mixed raw materials from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 ℃ for extrusion granulation; and extruding and molding the sample obtained by extrusion granulation by a single screw extruder, controlling the extrusion temperature to be 125-160 ℃, and extruding and granulating.
The tensile property and the bending property of the bamboo powder modified polylactic acid biodegradable plastic are tested by adopting a CMT-5504 type universal mechanical testing machine. The tensile properties and the bending properties were tested according to the national standards GB/T1040-92 and GB/T9341-2000, respectively. The test results are shown in Table 5.
TABLE 5 mechanical property test results of the biodegradable plastics modified with bamboo powder in examples 9 to 12
As can be seen from table 5, the additive amount of the bamboo powder in the bamboo powder modified polylactic acid biodegradable plastic prepared by the present application can be close to the amount of the polylactic acid, that is, the amount of the polylactic acid can be reduced under the condition that the mechanical properties of the bamboo powder modified polylactic acid biodegradable plastic are not significantly changed, so that the preparation cost of the material can be further reduced. However, when the mass ratio of the bamboo powder addition amount to the polylactic acid is 1:1, the tensile property and the bending property of the prepared bamboo powder modified polylactic acid biodegradable plastic begin to be remarkably reduced, namely the dosage ratio of the bamboo powder to the polylactic acid is required to be controlled not to exceed 1.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention as they come within the spirit of the present invention, and their direct and indirect use in other related fields are intended to be included within the scope of the present invention.
Claims (7)
1. The high-density bamboo powder modified polylactic acid biodegradable plastic is characterized by comprising the following components in parts by weight:
35-60 parts of polylactic acid, 25-40 parts of modified bamboo powder, 10-15 parts of starch, 1.5-2.5 parts of silicate, 3-5 parts of glycerol and 0.5-2 parts of coupling agent;
the preparation method of the modified bamboo powder comprises the following steps:
(1) preparing aluminum chloride and N, N-dimethyl amide into an N, N-dimethyl amide/aluminum chloride mixed solution according to the mass ratio of 1: 15-20;
(2) soaking the bamboo powder in an acetone solution for 15-24 h, filtering, and freeze-drying;
(3) soaking the bamboo powder subjected to freeze drying in the step (2) in a dimethylacetamide solution for 3-8 h, filtering, and freeze drying;
(4) uniformly mixing the bamboo powder subjected to freeze drying in the step (3) with the N, N-dimethyl amide/aluminum chloride mixed solution obtained in the step (1) according to the mass ratio of 1: 3-6, and heating the mixed system to 150 ℃ in a nitrogen atmosphereoC；
(5) Adding caprolactone into the mixed system obtained in the step (4), continuously stirring and reacting for 12 hours, centrifugally separating after the reaction is finished, washing and drying to obtain the modified bamboo powder;
in the step (5), the addition amount of the caprolactone accounts for 10-15% of the mixed system.
2. The high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in claim 1, which comprises the following components:
45-55 parts of polylactic acid, 30-40 parts of modified bamboo powder, 12-15 parts of starch, 1.5-2.5 parts of silicate, 3-5 parts of glycerol and 0.5-2 parts of coupling agent.
3. The high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in claim 1, wherein the washing solvent in the step (5) is dimethyl sulfoxide, and the number of washing times is 2-4.
4. The high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in claim 1, wherein the starch is at least one of modified corn starch and modified wheat starch.
5. The high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in claim 1, wherein the silicate is a layered silicate comprising: any one or more of aluminum silicate, calcium silicate, magnesium silicate, sodium silicate and potassium silicate.
6. The high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in claim 1, wherein the coupling agent is one of a silane coupling agent and a titanate coupling agent.
7. A preparation method of high-density bamboo powder modified polylactic acid biodegradable plastic, which comprises the components of the high-density bamboo powder modified polylactic acid biodegradable plastic as claimed in any one of claims 1 to 6, and is characterized by comprising the following steps:
(1) proportionally placing polylactic acid, modified bamboo powder, starch, silicate, glycerol and a coupling agent into a high-speed mixer to be mixed to obtain a mixed material;
(2) adding the mixed raw materials in the step (1) from a feeding port of a double-screw extruder, and controlling the extrusion temperature to be 125-150 DEG CoC, extruding and granulating;
(3) extruding and molding the sample obtained by extruding and granulating in the step (2) by a single-screw extruder, and controlling the extrusion temperature to be 125-160 DEGoAnd C, extruding and pelletizing.
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| CN107828195A (en) * | 2017-10-27 | 2018-03-23 | 浙江新力新材料股份有限公司 | A kind of PLA/bamboo powder/starch biological base alloy material and preparation method thereof entirely |
| CN109054104A (en) * | 2018-07-04 | 2018-12-21 | 安徽省舒城华竹实业有限公司 | A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing |
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| CN107828195A (en) * | 2017-10-27 | 2018-03-23 | 浙江新力新材料股份有限公司 | A kind of PLA/bamboo powder/starch biological base alloy material and preparation method thereof entirely |
| CN109054104A (en) * | 2018-07-04 | 2018-12-21 | 安徽省舒城华竹实业有限公司 | A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing |
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