CN109337315B - Green biodegradable plastic master batch and processing technology thereof - Google Patents
Green biodegradable plastic master batch and processing technology thereof Download PDFInfo
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- CN109337315B CN109337315B CN201811109379.4A CN201811109379A CN109337315B CN 109337315 B CN109337315 B CN 109337315B CN 201811109379 A CN201811109379 A CN 201811109379A CN 109337315 B CN109337315 B CN 109337315B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/14—Modified phenol-aldehyde condensates
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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Abstract
The invention discloses a green biodegradable plastic master batch which is prepared by processing the following raw materials in parts by weight: 40-48 parts of polylactic acid, 10-12 parts of modified phenolic resin, 15-19 parts of polyester elastomer, 6-10 parts of bamboo charcoal particles, 3-5 parts of polyethylene glycol, 3-5 parts of chitosan and 0.5-1 part of anti-hydrolysis stabilizer; the invention also discloses a processing technology of the green biodegradable plastic master batch, and the step S1 is to dry the raw materials for later use; step S2, preparing a premix; step S3, mixing an anti-hydrolysis stabilizer and polyethylene glycol; and step S4, mixing and extruding for molding. According to the invention, polylactic acid is used as a plastic master batch matrix, and modified phenolic resin, polyester elastomer, bamboo charcoal particles, polyethylene glycol and chitosan in a scientific ratio are used as auxiliary materials, so that the plastic master batch is biodegradable, green and environment-friendly, and the raw materials are cooperatively matched, so that the obtained plastic master batch is not only green and biodegradable, but also has good mechanical properties.
Description
Technical Field
The invention belongs to the technical field of plastic master batches, and particularly relates to a green biodegradable plastic master batch and a processing technology thereof.
Background
Plastics, as a new material, have been developed vigorously from the middle of the 20 th century and show a continuous growth situation year by year. Plastic products are now in various industries of human activity; the plastic product has wide application in various fields, and the plastic product is more and more difficult to leave in daily life. While the plastic industry has developed, plastic materials have met with two challenges: (1) the resources are limited. High molecular compounds such as plastics are mainly derived from petroleum, which is a non-renewable resource and has gradually depleted on the earth; (2) pollution to the ecological environment. At present, the yield of plastics in the world reaches two hundred million tons, and the yield of plastics in China is about 2000 ten thousand tons every year. More and more plastic products, after a period of use, become waste plastic products. Since the plastic product is hard to be decomposed, the amount of the plastic product to be secondarily recycled is less than 50% of the amount of the plastic product to be produced. Therefore, the waste plastic products form a large amount of garbage, cause serious environmental pollution problems, and threaten the living environment of human beings.
Plastic films and disposable plastic products account for a large proportion of plastic waste. The waste plastic film has small density, large surface area, difficult degradation and difficult recycling, floats in the living environment of people, causes great damage to the ecological environment and forms extremely obvious visual pollution.
Disclosure of Invention
The invention aims to provide a green biodegradable plastic master batch and a processing technology thereof, polylactic acid is used as a plastic master batch matrix, and modified phenolic resin, polyester elastomer, bamboo charcoal particles, polyethylene glycol and chitosan with scientific proportion are used as auxiliary materials, all the raw materials are biodegradable and environment-friendly, and are cooperatively matched, so that the obtained plastic master batch is green and biodegradable, has good mechanical properties, and can be used for processing various film products, blow molding products and injection molding products with different addition amounts.
The purpose of the invention can be realized by the following technical scheme:
a green biodegradable plastic master batch is prepared by processing the following raw materials in parts by weight: 40-48 parts of polylactic acid, 10-12 parts of modified phenolic resin, 15-19 parts of polyester elastomer, 6-10 parts of bamboo charcoal particles, 3-5 parts of polyethylene glycol, 3-5 parts of chitosan and 0.5-1 part of anti-hydrolysis stabilizer;
the green biodegradable plastic master batch is prepared by the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at the temperature of 106 ℃ and 110 ℃ at the rotating speed of 500r/min and 700r/min for 3-5min to obtain a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5-8min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 20-22min at 180 ℃, wherein the rotating speed is 50r/min, and crushing the melted and mixed sample into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
Further, the particle size of the bamboo charcoal particles is 25-75 um.
Further, the anti-hydrolysis stabilizer is SAG-005 or INV-7000.
Further, the modified phenolic resin is prepared by the following method:
(1) putting 89mL of ethanol into a three-neck flask, sequentially adding 9.4g of phenol, 0.1g of azodiisobutyronitrile and 4mg of phosphomolybdic acid, heating to 95 ℃, and stirring until the ethanol is completely dissolved;
(2) adding 1.3g of wheat straw alkali lignin into the solution, heating to 86 ℃, reacting at the constant temperature of 400-;
(3) cooling the reaction liquid to 70 ℃, slowly adding 3.7g of acetaldehyde while stirring, heating the reaction liquid to 95-98 ℃ after the addition, and reacting for 3-4 hours at constant temperature;
(4) and carrying out reduced pressure distillation on the reaction liquid to obtain the modified phenolic resin.
Further, the polyester elastomer is prepared by the following method:
(1) adding sodium dodecyl benzene sulfonate and alkyl glycoside 0810 into deionized water, wherein the ratio of the sodium dodecyl benzene sulfonate to the alkyl glycoside 0810 to the deionized water is 7 g: 4 g: 100mL, stirring until the solid is completely dissolved to obtain a mixed solution;
(2) adding unsaturated polyester resin into the mixed solution by magnetic stirring under the condition of constant-temperature water bath at 37 ℃, wherein the volume ratio of the unsaturated polyester resin to the mixed solution is 1: 24-30; stirring for 48-55min after the addition, and then processing by a homogenizer to prepare unsaturated polyester emulsion;
(3) adding trimethyl allyl isocyanate with the mass of 2wt% of polyester into the unsaturated polyester emulsion, stirring and dispersing for 60-70min at the speed of 800-1000r/min, irradiating the polyester emulsion by adopting electron beams with the radiation dose of 50kGy, and performing spray drying on the crosslinked polyester emulsion to obtain the polyester elastomer.
A processing technology of green biodegradable plastic master batch comprises the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at the temperature of 106 ℃ and 110 ℃ at the rotating speed of 500r/min and 700r/min for 3-5min to obtain a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5-8min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 20-22min at 180 ℃, wherein the rotating speed is 50r/min, and crushing the melted and mixed sample into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
The invention has the beneficial effects that:
(1) according to the invention, the polyester elastomer is added into the raw material of the plastic master batch, when the plastic master batch is stressed, the polyester elastomer dispersed in the polylactic acid matrix can deform under the action of external force to form a stress concentration body, so that the surrounding matrix is promoted to be subjected to brittle-tough transition, a large amount of silver lines and shear yield bands are generated on the surface of the polylactic acid material and in the material, the matrix is facilitated to absorb energy, the silver lines can be further prevented from developing into large cracks, the material is subjected to plastic deformation, and the toughness of the polylactic acid is improved; meanwhile, the polyester elastomer can cause a large amount of silver stripes to be generated under the action of external force, so that the material can absorb more impact energy, and the impact strength of the master batch is improved;
(2) according to the invention, the modified phenolic resin is added into the raw material of the plastic master batch, the phenolic resin is modified by wheat straw alkali lignin, the wheat straw alkali lignin molecule is a natural aromatic polycyclic structure compound taking a phenylpropane structural unit as a main body, and the space structure of the modified phenolic resin introduced with the wheat straw alkali lignin molecule is more complex, so that the rigidity of the resin is increased, the rigidity of the resin and the complexity of the space structure are increased, when the same external load is applied, the shock resistance and the bending capability of the plastic master batch are improved, and meanwhile, the biodegradability of the modified phenolic resin is greatly improved due to the introduction of natural organic polymers;
(3) according to the invention, polyethylene glycol is added into the raw material of the plastic master batch, and the terminal hydroxyl of the polyethylene glycol (PEG) can react with the carboxyl in polylactic acid (PLA), so that the interaction of hydrogen bonds and the like in and among polylactic acid molecules is destroyed, which is equivalent to shielding the groups of the polylactic acid, so that the physical cross-linking points of the polylactic acid are reduced, on the other hand, the molecular weight of the polyethylene glycol is much smaller than that of the polylactic acid, the low molecular weight polyethylene glycol is easier to move, and the space required by the movement of the polylactic acid chain segment can be provided, therefore, the polyethylene glycol can generate plasticizing effect on the polylactic acid;
(4) according to the invention, polylactic acid is used as a plastic master batch matrix, and modified phenolic resin, polyester elastomer, bamboo charcoal particles, polyethylene glycol and chitosan in a scientific ratio are used as auxiliary materials, the raw materials are biodegradable and environment-friendly, and are cooperatively matched, so that the obtained plastic master batch is not only green and biodegradable, but also has good mechanical properties, and can be used for processing various film products, blow molding products and injection molding products in different addition amounts.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
A green biodegradable plastic master batch is prepared by processing the following raw materials in parts by weight: 40-48 parts of polylactic acid, 10-12 parts of modified phenolic resin, 15-19 parts of polyester elastomer, 6-10 parts of bamboo charcoal particles, 3-5 parts of polyethylene glycol, 3-5 parts of chitosan and 0.5-1 part of anti-hydrolysis stabilizer;
the particle size of the bamboo charcoal particles is 25-75 um; the bamboo charcoal particles have small particle size and large specific surface area, so that interface gaps between polylactic acid and polyester elastomers can be filled, the stress transfer from a matrix to a filler is increased, and the elongation at break of the plastic master batch is further improved;
the hydrolysis resistant stabilizer is SAG-005 or INV-7000;
the terminal hydroxyl of the polyethylene glycol (PEG) can react with carboxyl in the polylactic acid (PLA), the interaction of hydrogen bonds and the like in and among polylactic acid molecules is damaged, which is equivalent to shielding the groups of the polylactic acid, so that the physical crosslinking points of the polylactic acid are reduced, on the other hand, the molecular weight of the polyethylene glycol is much smaller than that of the polylactic acid, the activity of the polyethylene glycol with low molecular weight is easier, and the space required by the chain motion of the polylactic acid can be provided, so that the polyethylene glycol can generate plasticizing effect on the polylactic acid;
the modified phenolic resin is prepared by the following method:
(1) putting 89mL of ethanol into a three-neck flask, sequentially adding 9.4g of phenol, 0.1g of azodiisobutyronitrile and 4mg of phosphomolybdic acid, heating to 95 ℃, and stirring until the ethanol is completely dissolved;
(2) adding 1.3g of wheat straw alkali lignin into the solution, heating to 86 ℃, reacting at the constant temperature of 400-;
(3) cooling the reaction liquid to 70 ℃, slowly adding 3.7g of acetaldehyde while stirring, heating the reaction liquid to 95-98 ℃ after the addition, and reacting for 3-4 hours at constant temperature;
(4) carrying out reduced pressure distillation on the reaction liquid to prepare modified phenolic resin;
the wheat straw alkali lignin molecule is a natural aromatic polycyclic structure compound taking a phenylpropane structural unit as a main body, the space structure of the modified phenolic resin introduced with the wheat straw alkali lignin molecule is more complex, so that the rigidity of the resin is increased, the rigidity of the resin and the complexity of the space structure are increased, the impact resistance and the bending capability of the plastic master batch are improved when the same external load is applied, and meanwhile, the biodegradability of the modified phenolic resin is improved to a great extent due to the introduction of natural organic high molecules;
the polyester elastomer is prepared by the following method:
(1) adding sodium dodecyl benzene sulfonate and alkyl glycoside 0810 into deionized water, wherein the ratio of the sodium dodecyl benzene sulfonate to the alkyl glycoside 0810 to the deionized water is 7 g: 4 g: 100mL, stirring until the solid is completely dissolved to obtain a mixed solution;
(2) adding unsaturated polyester resin into the mixed solution by magnetic stirring under the condition of constant-temperature water bath at 37 ℃, wherein the volume ratio of the unsaturated polyester resin to the mixed solution is 1: 24-30; stirring for 48-55min after the addition, and then processing by a homogenizer to prepare unsaturated polyester emulsion;
(3) adding trimethyl allyl isocyanate (a radiation sensitizer) accounting for 2wt% of the polyester into the unsaturated polyester emulsion, stirring and dispersing for 60-70min at the speed of 800-1000r/min, irradiating the polyester emulsion by adopting an electron beam with the radiation dose of 50kGy to crosslink unsaturated bonds of the polyester emulsion, and performing spray drying on the crosslinked polyester emulsion to obtain a polyester elastomer;
the high molecular polymer containing unsaturated bonds generates free radicals when being radiated, and the free radicals are mutually combined to form cross-linking bonds, so that a three-dimensional network structure is formed, the interaction among molecular chains is enhanced, and the elasticity, creep resistance and the like of the polyester elastomer are improved; when the polylactic acid material is stressed, the polyester elastomer dispersed in the polylactic acid matrix can deform under the action of external force to form a stress concentration body, so that the surrounding matrix is promoted to be subjected to brittle-tough transformation, a large number of silver lines and shear yield bands are generated on the surface of the polylactic acid material and in the polylactic acid material, the matrix is facilitated to absorb energy, the silver lines can be further prevented from developing into large cracks, the material is subjected to plastic deformation, and the toughness of the polylactic acid is improved; meanwhile, the polyester elastomer can cause a large amount of silver stripes to be generated under the action of external force, so that the material can absorb more impact energy, and the impact strength of the master batch is improved;
the processing technology of the green biodegradable plastic master batch comprises the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at the temperature of 106 ℃ and 110 ℃ at the rotating speed of 500r/min and 700r/min for 3-5min to obtain a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5-8min, and uniformly mixing;
step S4, putting the uniformly mixed mixture into a closed mixing roll, melting and mixing for 20-22min at 180 ℃, wherein the rotating speed is 50r/min, and crushing the melted and mixed sample into small particles with the diameter of 1.4-1.6mm in a crusher to prepare green biodegradable plastic master batches;
example 1
A green biodegradable plastic master batch is prepared by processing the following raw materials in parts by weight: 40 parts of polylactic acid, 10 parts of modified phenolic resin, 15 parts of polyester elastomer, 6 parts of bamboo charcoal particles, 3 parts of polyethylene glycol, 3 parts of chitosan and 0.5 part of hydrolysis-resistant stabilizer;
the green biodegradable plastic master batch is prepared by processing the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at 106 ℃ at the rotating speed of 500r/min for 3min to prepare a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 20min at 180 ℃, wherein the rotating speed is 50r/min, and the melted and mixed sample is crushed into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
Example 2
A green biodegradable plastic master batch is prepared by processing the following raw materials in parts by weight: 44 parts of polylactic acid, 11 parts of modified phenolic resin, 17 parts of polyester elastomer, 8 parts of bamboo charcoal particles, 4 parts of polyethylene glycol, 4 parts of chitosan and 0.8 part of hydrolysis-resistant stabilizer;
the green biodegradable plastic master batch is prepared by processing the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at 108 ℃ at the rotating speed of 600r/min for 4min to prepare a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 6min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 21min at 180 ℃, wherein the rotating speed is 50r/min, and the melted and mixed sample is crushed into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
Example 3
A green biodegradable plastic master batch is prepared by processing the following raw materials in parts by weight: 48 parts of polylactic acid, 12 parts of modified phenolic resin, 19 parts of polyester elastomer, 10 parts of bamboo charcoal particles, 5 parts of polyethylene glycol, 5 parts of chitosan and 1 part of hydrolysis-resistant stabilizer;
the green biodegradable plastic master batch is prepared by processing the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at 110 ℃ at the rotating speed of 700r/min for 5min to prepare a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 8min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 22min at 180 ℃, wherein the rotating speed is 50r/min, and the melted and mixed sample is crushed into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
The plastic master batches prepared in examples 1 to 3 were subjected to the following specific measurement procedures:
(1) directly adding the plastic master batches prepared in the examples 1-3 and pure polylactic acid particles into a charging barrel of an injection molding machine for injection molding (adding small particles into a charging barrel of a micro injection molding machine for preheating for 5min, the temperature of the charging barrel is 180 ℃, the temperature of a mold is 50 ℃, the injection pressure is 5MPa, the pressure holding time is 10s, and a sample is injected into the mold for molding) to obtain various sample strips, wherein the tensile property test sample strip is a dumbbell type with the width of 10 multiplied by 4mm, the gauge length is 60mm, the bending property test sample strip is 80 multiplied by 10 multiplied by 4mm, the impact property test sample strip is 80 multiplied by 10 multiplied by 4mm, and the gap is 2 mm; the tensile and bending properties were measured according to GB/T1040-2006 and GB/T9341-2008, respectively, and the impact strength was measured according to GB/T1843-2008, 4 replicates were tested, averaged, and the test results are given in the following table:
example 1 example 2 example 3 pure PLA
Tensile strength/MPa 68.567.968.832.6
Flexural Strength/MPa 76.477.178.240.7
Impact Strength/(KJ. m2) 18.519.119.314.8
It can be known that the tensile strength of the plastic master batch prepared in the examples 1 to 3 is higher than 67.9MPa and much higher than that of pure PLA; the bending strength of the plastic master batch prepared in the embodiment 1-3 is higher than 76.4MPa and far higher than that of pure PLA; the impact strength of the plastic master batch prepared in the embodiments 1-3 is higher than 18.5KJ/m2 and is higher than that of pure PLA, which shows that the plastic master batch prepared by the invention has excellent mechanical properties;
(2) the buried degradation performance of soil in natural environment is tested, according to the test (1), the plastic master batches of examples 1-3 and pure PLA granules are made into a 1.2cm × 1.2cm × 1mm sample, the sample is dried to constant weight in a vacuum oven at 40 ℃, the initial mass m0 of the sample is weighed and recorded, the sample is wrapped by a single layer gauze, the sample is marked with a serial number, the sample is buried in the soil with the depth of about 20cm in the natural environment, the sample is taken out after three months, the surface of the sample is washed by tap water, 75% (volume fraction) of ethanol and distilled water in sequence, then the sample is dried to constant weight in the vacuum oven at 40 ℃, the mass m of the degraded sample is recorded, the degradation mass loss rate of the sample is = [ (m0-m)/m0] × 100%, and the degradation mass loss rate of each sample is shown in the following table:
example 1 example 2 example 3 pure PLA
Degradation mass loss rate/% 89928521
It can be known that the mass loss of the plastic master batch prepared in the examples 1 to 3 in natural soil after three months is higher than 85%, most of the plastic master batch is naturally degraded under the action of the microorganisms in the soil, and only 21% of pure PLA is degraded, which shows that the plastic master batch prepared by the invention has strong degradation capability.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. The green biodegradable plastic master batch is characterized by being prepared from the following raw materials in parts by weight: 40-48 parts of polylactic acid, 10-12 parts of modified phenolic resin, 15-19 parts of polyester elastomer, 6-10 parts of bamboo charcoal particles, 3-5 parts of polyethylene glycol, 3-5 parts of chitosan and 0.5-1 part of anti-hydrolysis stabilizer;
the modified phenolic resin is prepared by the following method:
(1) putting 89mL of ethanol into a three-neck flask, sequentially adding 9.4g of phenol, 0.1g of azodiisobutyronitrile and 4mg of phosphomolybdic acid, heating to 95 ℃, and stirring until the ethanol is completely dissolved;
(2) adding 1.3g of wheat straw alkali lignin into the solution, heating to 86 ℃, reacting at the constant temperature of 400-;
(3) cooling the reaction liquid to 70 ℃, slowly adding 3.7g of acetaldehyde while stirring, heating the reaction liquid to 95-98 ℃ after the addition, and reacting for 3-4 hours at constant temperature;
(4) carrying out reduced pressure distillation on the reaction liquid to prepare modified phenolic resin;
the polyester elastomer is prepared by the following method:
(1) adding sodium dodecyl benzene sulfonate and alkyl glycoside 0810 into deionized water, wherein the ratio of the sodium dodecyl benzene sulfonate to the alkyl glycoside 0810 to the deionized water is 7 g: 4 g: 100mL, stirring until the solid is completely dissolved to obtain a mixed solution;
(2) adding unsaturated polyester resin into the mixed solution by magnetic stirring under the condition of constant-temperature water bath at 37 ℃, wherein the volume ratio of the unsaturated polyester resin to the mixed solution is 1: 24-30; stirring for 48-55min after the addition, and then processing by a homogenizer to prepare unsaturated polyester emulsion;
(3) adding trimethyl allyl isocyanate with the mass of 2wt% of polyester into the unsaturated polyester emulsion, stirring and dispersing for 60-70min at the speed of 800-;
the green biodegradable plastic master batch is prepared by the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at the temperature of 106 ℃ and 110 ℃ at the rotating speed of 500r/min and 700r/min for 3-5min to obtain a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5-8min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 20-22min at 180 ℃, wherein the rotating speed is 50r/min, and crushing the melted and mixed sample into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
2. The green biodegradable plastic masterbatch according to claim 1, wherein the particle size of the bamboo charcoal particles is 25-75 um.
3. The green biodegradable plastic masterbatch according to claim 1, wherein said stabilizer against hydrolysis is SAG-005 or INV-7000.
4. The processing technology of the green biodegradable plastic master batch according to claim 1, characterized by comprising the following steps:
step S1, continuously vacuum-drying the polylactic acid and the modified phenolic resin at the temperature of 60 ℃ for 15h, cooling to room temperature, and placing in a drying dish for later use; continuously drying the bamboo charcoal particles and the polyester elastomer at 105 ℃ for 16h, cooling to room temperature, and placing in a drying dish for later use;
step S2, stirring and mixing the dried polylactic acid, the modified phenolic resin, the bamboo charcoal particles and the polyester elastomer at the temperature of 106 ℃ and 110 ℃ at the rotating speed of 500r/min and 700r/min for 3-5min to obtain a premix;
step S3, slowly adding the hydrolysis-resistant stabilizer and the polyethylene glycol into the premix under the condition of keeping the rotating speed unchanged, continuously stirring for 5-8min, and uniformly mixing;
and step S4, putting the uniformly mixed mixture into an internal mixing mill, melting and mixing for 20-22min at 180 ℃, wherein the rotating speed is 50r/min, and crushing the melted and mixed sample into small particles with the diameter of 1.4-1.6mm in a crusher to prepare the green biodegradable plastic master batch.
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| CN112372928A (en) * | 2020-09-29 | 2021-02-19 | 淄博中南医药包装材料股份有限公司 | Preparation method of biodegradable needleless closed infusion joint |
| CN116444966B (en) * | 2023-04-27 | 2024-03-26 | 江阴锦昊昕新型面料科技有限公司 | Biodegradable reinforced fiber material and preparation method thereof |
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