CN110564121A - preparation method of high-toughness heat-resistant fully-degradable straw - Google Patents
preparation method of high-toughness heat-resistant fully-degradable straw Download PDFInfo
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- CN110564121A CN110564121A CN201910880574.5A CN201910880574A CN110564121A CN 110564121 A CN110564121 A CN 110564121A CN 201910880574 A CN201910880574 A CN 201910880574A CN 110564121 A CN110564121 A CN 110564121A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a preparation method of a high-toughness heat-resistant fully-degradable straw, which comprises the following steps of A, weighing 30-50% of polyhydroxyalkanoate powder and 50-70% of polylactic acid powder, drying, and then uniformly mixing to prepare a first mixture; b, weighing hydrotalcite powder with the mass of 0.5-2% of that of the first mixture; step C, weighing a polyester stabilizer accounting for 0.1-2.5% of the mass of the first mixture and a nucleating agent accounting for 0.1-2.5% of the mass of the first mixture; and D, fully mixing the first mixture, the second mixture, the polyester stabilizer and the nucleating agent, performing melt extrusion by a double-screw extruder, performing water-cooling granulation, and drying to prepare master batches. The straw prepared from the master batch has the advantages of high toughness, heat resistance and full biodegradation, the heat-resistant temperature of the straw is higher than 90 ℃, and the problems of low toughness, heat intolerance and incomplete degradation of the existing disposable environment-friendly straw are solved.
Description
Technical Field
the invention relates to the field of straw preparation, in particular to a preparation method of a high-toughness heat-resistant fully-degradable straw.
background
The existing disposable straw is generally made of petrochemical materials such as polypropylene and polyethylene, the material of the straw is stable in property and not easy to degrade, and additives are added in the processing process, so that the straw contains residues of heavy metals or plasticizers, and the straw is not beneficial to environmental protection. In recent years, polylactic acid is also used for manufacturing disposable straws, the polylactic acid is a thermoplastic polyester material and has better mechanical property and processability, and the disposable straws made of the polylactic acid can be naturally and rapidly degraded in various ways after being discarded, thereby meeting the current environmental protection requirements. However, polylactic acid has outstanding defects, poor heat resistance and insufficient toughness, and the application of polylactic acid materials to disposable straws is greatly limited because the heat softening temperature of the polylactic acid is below 70 ℃. At present, degradable disposable straws produced by taking straws, glutinous rice flour, rice starch, tapioca flour and the like as raw materials are produced, but the problems of incomplete degradation, complex processing procedures and the like exist.
disclosure of Invention
The invention aims to provide a preparation method of a high-toughness heat-resistant fully-degradable straw, which solves the problems of low toughness, heat intolerance and incomplete degradation of the existing disposable environment-friendly straw.
in order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-toughness heat-resistant fully-degradable straw comprises the following steps:
step A, weighing 30-50% of polyhydroxyalkanoate powder and 50-70% of polylactic acid powder according to the mass percentage, drying, and then uniformly mixing to prepare a first mixture;
B, weighing hydrotalcite powder with the mass of 0.5-2% of that of the first mixture according to the mass percent, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 0.5-1% of that of the hydrotalcite powder, so as to prepare a second mixture;
Step C, weighing a polyester stabilizer accounting for 0.1-2.5% of the first mixture by mass and a nucleating agent accounting for 0.1-2.5% of the first mixture by mass according to the mass percentage;
step D, fully mixing the first mixture, the second mixture, the polyester stabilizer and the nucleating agent, performing melt extrusion by a double-screw extruder, performing water-cooling granulation, and drying to prepare master batches;
e, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
Step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
And G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
In the preparation method of the high-toughness heat-resistant fully-degradable straw, the main raw materials of the master batch are polyhydroxyalkanoate powder and polylactic acid powder, the polylactic acid is a thermoplastic polyester material and has good mechanical property and processability, and the polylactic acid product can be naturally and rapidly degraded in various ways after being discarded, but the polylactic acid has poor heat resistance and insufficient toughness, the heat softening temperature is below 70 ℃, and the application of the polylactic acid material on the straw is greatly limited; the polyhydroxyalkanoate is a biomass polymer, has high polymerization degree and high crystallinity, can improve the crystallinity of polylactic acid powder, and improves the shock resistance and tear resistance of the polylactic acid powder, so that the prepared master batch has the heat softening temperature of 90-95 ℃, the tensile strength of 25-35 MPa, the elongation at break of 100-200% and the melt index of 4-7 g/10 min; the straw prepared from the master batch has the advantages of high toughness, heat resistance and full biodegradation, and the heat-resistant temperature of the straw is higher than 90 ℃.
The mass percentage of the polyhydroxyalkanoate powder in the first mixture is required to be not more than the mass percentage of the polylactic acid powder, and if the mass percentage of the polyhydroxyalkanoate powder is more than the mass percentage of the polylactic acid powder, the plasticizing effect of the prepared master batch is deteriorated, the toughness and tensile strength are inferior to those of the polylactic acid powder, and the extrusion is difficult when melting in step D. The hydrotalcite powder added in the master batch can improve the heat resistance of the master batch and play a role of a filler. The nucleating agent can improve the crystallization rate of the polyhydroxyalkanoate powder and the polylactic acid powder, and in addition, the hydrotalcite powder also has a certain nucleating effect.
Preferably, in the step D, the melting temperature of the double-screw extruder is 180-190 ℃, and the screw rotating speed is 200-450 r/min. The melting temperature of the double-screw extruder is required to be 180-190 ℃, and if the temperature is lower than 180 ℃, the viscosity of the polyhydroxyalkanoate powder is higher, and the feeding of the screw is difficult; above 190 ℃ the polyhydroxyalkanoate powder is susceptible to degradation.
preferably, in the step A, the molecular weight of the polyhydroxyalkanoate powder is 400000-600000, wherein the molar content of 4HB (4-hydroxybutyric acid) is 8% -12%; the melting point of the polyhydroxyalkanoate powder is 140-160 ℃, and the melt flow index of the polyhydroxyalkanoate powder is 5-7 g/10 min.
Preferably, in the step A, the molecular weight of the polylactic acid powder is 50000-100000, the melting point of the polylactic acid powder is 165-175 ℃, the melt flow index of the polylactic acid powder is 15-30 g/10min, the glass transition temperature of the polylactic acid powder is 55-60 ℃, and the tensile strength of the polylactic acid powder is more than 55 MPa.
The polyhydroxy fatty acid ester powder has large molecular weight, can improve the melting point of the polyhydroxy fatty acid ester powder, and the polyhydroxy fatty acid ester powder is provided with the melt flow index, so that the master batch has better melt index, has good fluidity after melting and is convenient to extrude. The molecular weight of the polylactic acid powder is 50000-100000, the melting point of the polylactic acid powder is close to that of the polyhydroxy fatty acid ester powder, and good melt extrusion effect is ensured during blending and granulating in the step D.
Preferably, the drying method of the polyhydroxyalkanoate powder in the step A is as follows:
putting the polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 8-10 hours, wherein the drying temperature is set to be 70-80 ℃, and the water content of the polyhydroxyalkanoate powder is controlled to be below 30 PPM.
Preferably, the drying method of the polylactic acid powder in the step a is as follows:
putting the polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 6-8 hours, wherein the drying temperature is set to be 70-80 ℃.
And respectively drying the polyhydroxyalkanoate powder and the polylactic acid powder to prevent agglomeration from occurring when the polyhydroxyalkanoate powder and the polylactic acid powder are mixed, so that the quality of the straw is influenced.
Preferably, the particle mesh number of the hydrotalcite powder is 3000-5000 meshes. If the particle mesh number of the hydrotalcite powder is larger than 5000 meshes, the hydrotalcite powder is easy to agglomerate and is not easy to disperse during mixing in the step D, and the quality of the prepared straw is influenced; if the particle size of the hydrotalcite powder is less than 3000 mesh, the hydrotalcite powder cannot sufficiently exert the function as a filler.
preferably, the step D specifically includes:
step D1, placing the first mixture, the second mixture, the polyester stabilizer and the nucleating agent into a high-speed mixer, and stirring for 30-40 min at a stirring speed of 30-40 rpm to prepare a third mixture;
and D2, putting the third mixture into a double-screw extruder for melt extrusion, water-cooling and granulating, and then drying to prepare master batches.
Preferably, the nucleating agent is uracil.
In the preparation method of the high-toughness heat-resistant fully-degradable straw, the prepared master batch has the heat softening temperature of 90-95 ℃, the tensile strength of 25-35 MPa, the breaking elongation of 100-200% and the melt index of 4-7 g/10 min; the straw prepared from the master batch has the advantages of high toughness, heat resistance and full biodegradation, and the heat-resistant temperature of the straw is higher than 90 ℃.
Detailed Description
the technical solution of the present invention is further explained by the following embodiments.
Example 1
the preparation method of the high-toughness heat-resistant fully-degradable straw comprises the following steps:
Step A1, weighing 30% of polyhydroxyalkanoate powder and 70% of polylactic acid powder according to the mass percentage, wherein the molar content of 4HB in the polyhydroxyalkanoate powder is 8%;
step A2, putting the polyhydroxyalkanoate powder into a vacuum drum drying device for drying for 8 hours, setting the drying temperature to be 70 ℃, and controlling the water content of the polyhydroxyalkanoate powder to be below 30 PPM;
step A3, putting polyhydroxyalkanoate powder into vacuum drum drying equipment for drying for 6 hours, wherein the drying temperature is set to 80 ℃;
step A4, uniformly mixing polyhydroxyalkanoate powder and polylactic acid powder to prepare a first mixture;
B, weighing hydrotalcite powder with the mass being 2% of that of the first mixture according to the mass percentage, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 1% of that of the hydrotalcite powder, and the grain number of the hydrotalcite powder is 4500 meshes, so as to prepare a second mixture;
Step C, weighing a polyester stabilizer accounting for 0.2 percent of the mass of the first mixture and uracil accounting for 0.3 percent of the mass of the first mixture according to mass percent;
step D1, placing the first mixture, the second mixture, the polyester stabilizer and the uracil into a high-speed mixer, and stirring for 30min at a stirring speed of 30rpm to obtain a third mixture;
Step D2, putting the third mixture into a double-screw extruder for melt extrusion and water-cooling granulation, wherein the melting temperature of the double-screw extruder is 180-190 ℃, the rotating speed of a screw is 200-450 r/min, and then drying to prepare master batches;
e, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
Step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
and G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
example 2
The preparation method of the high-toughness heat-resistant fully-degradable straw comprises the following steps:
step A1, weighing 40% of polyhydroxyalkanoate powder and 60% of polylactic acid powder according to the mass percentage, wherein the molar content of 4HB in the polyhydroxyalkanoate powder is 10%;
step A2, putting the polyhydroxyalkanoate powder into a vacuum drum drying device for drying for 9 hours, setting the drying temperature to be 80 ℃, and controlling the water content of the polyhydroxyalkanoate powder to be below 30 PPM;
Step A3, putting polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 8 hours, wherein the drying temperature is set to 80 ℃;
step A4, uniformly mixing polyhydroxyalkanoate powder and polylactic acid powder to prepare a first mixture;
B, weighing hydrotalcite powder with the mass being 1.5% of that of the first mixture according to the mass percentage, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 0.5% of that of the hydrotalcite powder, and the grain mesh number of the hydrotalcite powder is 5000 meshes, so as to prepare a second mixture;
Step C, weighing a polyester stabilizer accounting for 2.5 percent of the mass of the first mixture and uracil accounting for 1 percent of the mass of the first mixture according to mass percent;
Step D1, placing the first mixture, the second mixture, the polyester stabilizer and the uracil into a high-speed mixer, and stirring for 40min at the stirring speed of 30rpm to obtain a third mixture;
Step D2, putting the third mixture into a double-screw extruder for melt extrusion and water-cooling granulation, wherein the melting temperature of the double-screw extruder is 180-190 ℃, the rotating speed of a screw is 200-450 r/min, and then drying to prepare master batches;
E, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
and G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
example 3
the preparation method of the high-toughness heat-resistant fully-degradable straw comprises the following steps:
Step A1, weighing 50% of polyhydroxyalkanoate powder and 50% of polylactic acid powder according to the mass percentage, wherein the molar content of 4HB in the polyhydroxyalkanoate powder is 12%;
step A2, putting the polyhydroxyalkanoate powder into a vacuum drum drying device for drying for 10 hours, setting the drying temperature to be 70 ℃, and controlling the water content of the polyhydroxyalkanoate powder to be below 30 PPM;
step A3, putting polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 7 hours, wherein the drying temperature is set to be 70 ℃;
step A4, uniformly mixing polyhydroxyalkanoate powder and polylactic acid powder to prepare a first mixture;
B, weighing hydrotalcite powder with the mass being 0.5% of that of the first mixture according to the mass percent, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 0.8% of that of the hydrotalcite powder, and the grain mesh number of the hydrotalcite powder is 3000 meshes, so as to prepare a second mixture;
step C, weighing 1.5 mass percent of polyester stabilizer and 2.5 mass percent of uracil of the first mixture according to mass percent;
Step D1, placing the first mixture, the second mixture, the polyester stabilizer and the uracil into a high-speed mixer, and stirring for 30min at a stirring speed of 40rpm to obtain a third mixture;
step D2, putting the third mixture into a double-screw extruder for melt extrusion and water-cooling granulation, wherein the melting temperature of the double-screw extruder is 180-190 ℃, the rotating speed of a screw is 200-450 r/min, and then drying to prepare master batches;
E, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
and G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
Example 4
the preparation method of the high-toughness heat-resistant fully-degradable straw comprises the following steps:
Step A1, weighing 45% of polyhydroxyalkanoate powder and 55% of polylactic acid powder according to the mass percentage, wherein the molar content of 4HB in the polyhydroxyalkanoate powder is 11%;
Step A2, putting the polyhydroxyalkanoate powder into a vacuum drum drying device for drying for 10 hours, setting the drying temperature to be 70 ℃, and controlling the water content of the polyhydroxyalkanoate powder to be below 30 PPM;
step A3, putting polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 7 hours, wherein the drying temperature is set to be 70 ℃;
Step A4, uniformly mixing polyhydroxyalkanoate powder and polylactic acid powder to prepare a first mixture;
b, weighing hydrotalcite powder with the mass being 1% of that of the first mixture according to the mass percentage, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 0.6% of that of the hydrotalcite powder, and the grain number of the hydrotalcite powder is 3500 meshes, so as to prepare a second mixture;
Step C, weighing a polyester stabilizer accounting for 2.1 percent of the mass of the first mixture and uracil accounting for 0.9 percent of the mass of the first mixture according to the mass percent;
Step D1, placing the first mixture, the second mixture, the polyester stabilizer and the uracil into a high-speed mixer, and stirring for 30min at a stirring speed of 30rpm to obtain a third mixture;
step D2, putting the third mixture into a double-screw extruder for melt extrusion and water-cooling granulation, wherein the melting temperature of the double-screw extruder is 180-190 ℃, the rotating speed of a screw is 200-450 r/min, and then drying to prepare master batches;
E, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
And G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
example 5
The preparation method of the high-toughness heat-resistant fully-degradable straw comprises the following steps:
step A1, weighing 35% of polyhydroxyalkanoate powder and 65% of polylactic acid powder according to mass percentage, wherein the molar content of 4HB in the polyhydroxyalkanoate powder is 9%;
step A2, putting the polyhydroxyalkanoate powder into a vacuum drum drying device for drying for 10 hours, setting the drying temperature to be 70 ℃, and controlling the water content of the polyhydroxyalkanoate powder to be below 30 PPM;
Step A3, putting polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 7 hours, wherein the drying temperature is set to be 70 ℃;
Step A4, uniformly mixing polyhydroxyalkanoate powder and polylactic acid powder to prepare a first mixture;
B, weighing hydrotalcite powder with the mass being 1.5% of that of the first mixture according to the mass percent, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 1% of that of the hydrotalcite powder, and the grain number of the hydrotalcite powder is 4000 meshes, so as to prepare a second mixture;
Step C, weighing a polyester stabilizer accounting for 0.3 percent of the mass of the first mixture and uracil accounting for 0.3 percent of the mass of the first mixture according to the mass percent;
step D1, placing the first mixture, the second mixture, the polyester stabilizer and the uracil into a high-speed mixer, and stirring for 30min at a stirring speed of 30rpm to obtain a third mixture;
Step D2, putting the third mixture into a double-screw extruder for melt extrusion and water-cooling granulation, wherein the melting temperature of the double-screw extruder is 180-190 ℃, the rotating speed of a screw is 200-450 r/min, and then drying to prepare master batches;
E, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
And G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
in examples 1 to 5, the molecular weight of polyhydroxyalkanoate powder is 400000 to 600000, the melting point of polyhydroxyalkanoate powder is 140 ℃ to 160 ℃, and the melt flow index of polyhydroxyalkanoate powder is 5 to 7g/10 min;
the molecular weight of the polylactic acid powder is 50000-100000, the melting point of the polylactic acid powder is 165-175 ℃, the melt flow index of the polylactic acid powder is 15-30 g/10min, the glass transition temperature of the polylactic acid powder is 55-60 ℃, and the tensile strength of the polylactic acid powder is more than 55MPa
comparative example 1
the first mixture of this comparative example contained only dry polylactic acid powder, and the other raw materials and procedures were the same as those of example 1.
comparative example 2
in this comparative example, the first mixture consisted of 60% polyhydroxyalkanoate powder and 40% polylactic acid powder by mass percent, and the other raw materials and procedures were the same as in example 1.
Comparative example 3
in this comparative example, the preparation of the second mixture was eliminated, and the other raw materials and procedures were the same as those of example 1.
the master batches and straws prepared in examples 1 to 5 and comparative examples 1 to 3 were tested for their properties, and the results are shown in table 1.
TABLE 1
the detection results of the embodiments 1 to 5 and the comparative examples 1 to 3 show that the polyhydroxyalkanoate is a biomass polymer, has high polymerization degree and high crystallinity, can improve the crystallinity of the polylactic acid powder, and improves the impact resistance and the tear resistance of the polylactic acid powder, so that the prepared master batch has the heat softening temperature of 90-95 ℃, the tensile strength of 25-35 MPa, the elongation at break of 100-200% and the melt index of 4-7 g/10 min; the straw prepared from the master batch has the advantages of high toughness, heat resistance and full biodegradation, and the heat-resistant temperature of the straw is higher than 90 ℃.
the mass percentage of the polyhydroxyalkanoate powder in the first mixture is required to be not more than the mass percentage of the polylactic acid powder, and if the mass percentage of the polyhydroxyalkanoate powder is more than the mass percentage of the polylactic acid powder, the plasticizing effect of the prepared master batch is deteriorated, the toughness and tensile strength are inferior to those of the polylactic acid powder, and the extrusion is difficult when melting in step D.
the hydrotalcite powder added in the master batch can improve the heat resistance of the master batch and play a role of a filler.
the technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (9)
1. a preparation method of a high-toughness heat-resistant fully-degradable straw is characterized by comprising the following steps:
step A, weighing 30-50% of polyhydroxyalkanoate powder and 50-70% of polylactic acid powder according to the mass percentage, drying, and then uniformly mixing to prepare a first mixture;
b, weighing hydrotalcite powder with the mass of 0.5-2% of that of the first mixture according to the mass percent, and adding a silane coupling agent into the hydrotalcite powder to perform surface modification treatment on the hydrotalcite powder, wherein the adding amount of the silane coupling agent is 0.5-1% of that of the hydrotalcite powder, so as to prepare a second mixture;
step C, weighing a polyester stabilizer accounting for 0.1-2.5% of the first mixture by mass and a nucleating agent accounting for 0.1-2.5% of the first mixture by mass according to the mass percentage;
step D, fully mixing the first mixture, the second mixture, the polyester stabilizer and the nucleating agent, performing melt extrusion by a double-screw extruder, performing water-cooling granulation, and drying to prepare master batches;
e, placing the master batches into a bin of a straw extruder, heating and stirring, and performing extrusion molding through an extrusion channel with a screw and a circular die head arranged at the end part of the extrusion channel to form a continuous tubular material;
Step F, drawing the extruded continuous tubular material into a cooling tank containing an ice-water mixture by a suction pipe extruder for continuous cooling;
and G, cutting the cooled continuous tubular material into preset lengths by using a straw extruder to obtain the high-toughness heat-resistant fully-degradable straw.
2. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method comprises the following steps: in the step D, the melting temperature of the double-screw extruder is 180-190 ℃, and the rotating speed of the screws is 200-450 r/min.
3. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method comprises the following steps: in the step A, the molecular weight of the polyhydroxy fatty acid ester powder is 400000-600000, wherein the molar content of 4HB is 8% -12%; the melting point of the polyhydroxyalkanoate powder is 140-160 ℃, and the melt flow index of the polyhydroxyalkanoate powder is 5-7 g/10 min.
4. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method comprises the following steps: in the step A, the molecular weight of the polylactic acid powder is 50000-100000, the melting point of the polylactic acid powder is 165-175 ℃, the melt flow index of the polylactic acid powder is 15-30 g/10min, the glass transition temperature of the polylactic acid powder is 55-60 ℃, and the tensile strength of the polylactic acid powder is more than 55 MPa.
5. The method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method for drying the polyhydroxyalkanoate powder in the step A comprises the following steps:
putting the polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 8-10 hours, wherein the drying temperature is set to be 70-80 ℃, and the water content of the polyhydroxyalkanoate powder is controlled to be below 30 PPM.
6. The method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the drying method of the polylactic acid powder in the step A comprises the following steps:
Putting the polyhydroxyalkanoate powder into vacuum drum drying equipment to be dried for 6-8 hours, wherein the drying temperature is set to be 70-80 ℃.
7. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method comprises the following steps: the particle mesh number of the hydrotalcite powder is 3000-5000 meshes.
8. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the step D specifically comprises the following steps of:
step D1, placing the first mixture, the second mixture, the polyester stabilizer and the nucleating agent into a high-speed mixer, and stirring for 30-40 min at a stirring speed of 30-40 rpm to prepare a third mixture;
and D2, putting the third mixture into a double-screw extruder for melt extrusion, water-cooling and granulating, and then drying to prepare master batches.
9. the method for preparing the high-toughness heat-resistant fully-degradable straw according to claim 1, wherein the method comprises the following steps: the nucleating agent is uracil.
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| CN114106534A (en) * | 2021-11-30 | 2022-03-01 | 桂林电器科学研究院有限公司 | PLA/PHA heat-resistant straw and preparation method thereof |
| CN116606538A (en) * | 2023-06-26 | 2023-08-18 | 苏州优矿塑新材料股份有限公司 | Degradable composite material based on reaction compatibilization, environment-friendly straw and preparation method thereof |
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