CN109111710B - Heat-resistant PLA-based degradable plastic bottle and preparation method thereof - Google Patents
Heat-resistant PLA-based degradable plastic bottle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a heat-resistant PLA-based degradable plastic bottle, which comprises the following components in parts by weight: 40-60 parts of polylactic acid, 20-50 parts of polycarbonate, 0.1-0.5 part of ZnO hollow spheres, 0.01-0.05 part of amino silane coupling agent, 0.01-0.05 part of antioxidant, 1-5 parts of natural plant fibers and 0.01-0.05 part of plasticizer. The process is environment-friendly, and the prepared plastic bottle has excellent heat resistance, high transparency, tensile resistance, degradability, antibacterial property and other comprehensive properties. The polycarbonate is prepared from plant-derived dihydric alcohol by a phosgene method, the consumption of petroleum resources is reduced, the polycarbonate is compounded with PLA to improve the heat resistance of the polycarbonate, and the ZnO hollow sphere has the characteristics of improving the transparency of the material, resisting bacteria, inhibiting bacteria and the like due to the unique hollow structure.
Description
Technical Field
The invention relates to the technical field of plastic product production, in particular to a heat-resistant PLA-based degradable plastic bottle and a preparation method thereof.
Background
With the popularization of plastic packaging bottles, the problems brought by the plastic packaging bottles are more and more obvious, and due to the good corrosion resistance of the plastic packaging bottles, some waste plastic packaging bottles which cannot be reused are difficult to decompose and return to nature, so that the waste plastic is accumulated, and the phenomenon is commonly called 'white pollution'. The main components of the white pollution are polypropylene, polyvinyl chloride and polyethylene, and the white pollution can not be degraded in the field for decades, so a series of soil problems are caused, and the negative effects of environmental protection caused by the degradation cause serious concerns and worries of various social circles, so that the development of degradable plastics becomes urgent.
Polylactic acid (PLA), also known as polylactide, is an aliphatic polyester produced by dehydration polymerization of lactic acid produced by microbial fermentation as a monomer. The renewable biomass materials such as corn, sugarcane, cassava and the like are used as raw materials, and the renewable biomass materials are wide in source and can be regenerated. The production process of the polylactic acid is low-carbon and environment-friendly, has less pollution, and the product can be composted and degraded after being used, thereby realizing the circulation in the nature. In addition, the biodegradable plastic has wide application and lower cost than other common degradable plastics such as PBAT, PBS and PHA, so the biodegradable plastic becomes a biodegradable material which is most actively developed and developed in the most rapid way in recent years.
However, the main factors restricting the application of PLA are the heat resistance and toughness, and in order to improve the heat resistance of PLA, blending other resins and modifying PLA are a great way to improve the performance of PLA. Polycarbonate is colorless and transparent, heat-resistant, impact-resistant and flame-retardant at BI level, has good mechanical properties at a common use temperature, is an excellent engineering plastic, and quickly enters the sight of people due to good compatibility with PLA.
Chinese patent 201410733882.2 discloses a preparation method of a high-toughness polycarbonate/polylactic acid-based alloy, the blending system of the two solves the problems of serious insufficient brittleness, poor heat resistance and the like of PLA, but the introduction of polycarbonate reduces the advantage that PLA can be completely degraded, only partial degradation can be achieved, and the polycarbonate raw material source also causes certain consumption on petroleum resources and is not environment-friendly.
The zinc oxide has larger energy band gap and exciton constraint energy and high transparency, is a common chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint coating, ointment, adhesive, food, batteries, flame retardant and the like. The nano ZnO hollow sphere has a special hollow structure and fine crystal grains, so that the surface electronic structure and the crystal structure of the nano ZnO hollow sphere are changed, special properties which are not possessed by common zinc oxide powder are generated, the diffuse reflectance to light is low, and the transparency is high; due to the high specific surface area activity, the cross-linking density of the ZnO hollow spheres and the PLA is improved, the tensile strength of the material is increased, and meanwhile, the ZnO hollow spheres play a role in supporting a framework in the composite material due to the rigidity of the ZnO hollow spheres, so that the crystallization of the PLA is promoted, and the heat resistance of the PLA material is improved; has high biological activity, high absorption rate and strong oxidation resistance, can finish the degradation of organic matters (or containing chlorine), and can achieve a series of unique performances of resisting and inhibiting bacteria, removing odor, preventing mildew and the like when being used as a packaging material.
Chinese patent 201510868361.2 discloses a polylactic acid-zinc oxide pillared organic soapstone nano-composite material and a preparation method and a product thereof, wherein the raw material comprises lactic acid or L-lactide or D, L-lactide or meso-lactide and zinc oxide pillared organic soapstone. Compared with the existing polylactic acid base material, the polylactic acid-zinc oxide pillared organic soapstone nano composite material has the advantages of improved tensile strength, heat resistance and antibacterial effect. However, the mechanical properties of the material obtained by compounding the zinc oxide and the PLA are improved to some extent, but the improvement range is small, and the required product performance grade of the product cannot be achieved.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a heat-resistant PLA-based degradable plastic bottle and a preparation method thereof.
The heat-resistant PLA-based degradable plastic bottle disclosed by the invention is composed of the following raw materials in parts by weight:
40-60 parts of polylactic acid, 20-50 parts of polycarbonate, 0.1-0.5 part of ZnO hollow spheres, 0.01-0.05 part of amino silane coupling agent, 0.01-0.05 part of antioxidant, 1-5 parts of natural plant fibers and 0.01-0.05 part of plasticizer.
The preparation method of the heat-resistant PLA-based degradable plastic bottle comprises the following preparation steps: the polycarbonate is prepared from plant-derived raw materials, comprises sugar ether glycol as a raw material and is prepared by adopting a phosgene direct method, and specifically can be prepared by firstly preparing an aqueous solution with NaOH as a water phase, taking dichloromethane as another phase and taking amines as a catalyst to react for 1-3h at 50 ℃.
The dihydric alcohol synthesized polycarbonate is sugar ether glycol from plants, so that the consumption of petroleum resources can be reduced, the biodegradation advantage of PLA is reduced by adopting a composite material prepared from other dihydric alcohols, only partial degradation can be achieved, and the biodegradation performance can be improved by using the sugar ether glycol from plants.
The preparation method of the heat-resistant PLA-based degradable plastic bottle comprises the following preparation steps: the particle size of the prepared ZnO hollow sphere is about 500-800 nm. The preparation steps of the ZnO hollow sphere are as follows: (1) taking a certain amount of glucose, adding deionized water, stirring until the glucose is completely dissolved, then transferring the glucose into a polytetrafluoroethylene lining, then putting the glucose into a reaction kettle, and reacting for 12 hours at 180 ℃; (2) after the reaction is finished, cooling, and then centrifugally drying to obtain black brown powdered carbon spheres; (3) and (3) adding zinc nitrate and urea into the carbon spheres obtained in the step (2), carrying out ultrasonic treatment for 10min, reacting at 80 ℃ for 3h, cooling after the reaction is finished, carrying out centrifugal drying, and calcining to obtain the ZnO hollow spheres.
The selected nano ZnO hollow sphere has a special property which is not possessed by common zinc oxide powder due to the change of a surface electronic structure and a crystal structure of the nano ZnO hollow sphere due to the unique hollow structure and the miniaturization of crystal grains, and has low diffuse reflectance to light and high transparency; due to the high specific surface area activity, the cross-linking density of the ZnO hollow spheres and the PLA is improved, the tensile strength of the material is increased, and meanwhile, the ZnO hollow spheres play a role in supporting a framework in the composite material due to the rigidity of the ZnO hollow spheres, so that the crystallization of the PLA is promoted, and the heat resistance of the PLA material is improved; meanwhile, the antibacterial and bacteriostatic fabric has antibacterial and bacteriostatic effects.
The heat-resistant PLA-based degradable plastic bottle is further preferably prepared from the following raw materials in parts by weight: 50 parts of polylactic acid, 30 parts of polycarbonate, 0.3 part of ZnO hollow spheres, 0.05 part of aminosilane coupling agent, 0.03 part of antioxidant, 5 parts of natural plant fibers and 0.02 part of plasticizer.
The amino silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane and N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
After the selected aminosilane coupling agent is combined with the surface of the ZnO hollow sphere, the ZnO hollow sphere can be uniformly dispersed in the PLA base material, and the obtained modification effect is better.
The antioxidant is one of phenols 1010, sulfur DSTP and phosphorus 168.
The natural plant fiber is one or two of cotton fiber, sisal fiber, hemp fiber and bamboo fiber.
The natural plant fiber selected by the invention has wide sources, is green and environment-friendly, has high strength and toughness because of being rich in fiber, and improves the regularity of a molecular chain when being compounded with PLA, thereby improving the crystallinity, stabilizing the crystallization state and improving the heat resistance of the product.
The plasticizer is one of epoxidized soybean oil, triethyl citrate, nonyl citrate and polyethylene glycol.
The preparation method of the heat-resistant PLA-based degradable plastic bottle comprises the following specific steps:
(1) weighing the ZnO hollow spheres according to the weight parts, adding an aminosilane coupling agent solution into the ZnO hollow spheres, mixing and stirring uniformly, drying the obtained ZnO hollow spheres with the surfaces soaked with the coupling agent, and cooling to normal temperature to obtain modified ZnO hollow spheres;
(2) weighing polylactic acid, polycarbonate, an antioxidant, natural plant fiber and a plasticizer according to the parts by weight, adding the modified ZnO hollow spheres obtained in the step (1) into a high-speed mixer, uniformly mixing, extruding and granulating at the temperature of 160-80 ℃ by using a double-screw extruder, and drying in vacuum for 12-24 hours at the temperature of 60-80 ℃;
(3) injecting the master batch obtained in the step (2) into a prepared cavity of a mold through an injection molding machine in a temperature and pressure combined mode, and then performing blow molding at the temperature of 170-190 ℃ by adopting a hot air blow molding method;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at the temperature of 160-.
The heat-resistant PLA-based degradable plastic bottle prepared by adopting the technical scheme has the following advantages:
1. the polycarbonate is prepared from the plant-derived dihydric alcohol, is environment-friendly, meets the full biodegradability of materials, ensures the transparency of the materials, reduces the consumption of petroleum resources, and accords with the modern sustainable development theme.
2. The polycarbonate has good impact resistance, high refractive index, good processing performance, high transparency and heat resistance, has good mechanical properties at common use temperature, is compounded with PLA and has good compatibility, the heat resistance and the mechanical properties of the PLA are improved, the transparency of a plastic bottle is ensured, the using amount of the PLA with relatively high price is reduced, and the cost is reduced.
3. The ZnO hollow sphere has an ultra-high specific surface area due to the hollow structure inside, and compared with ZnO powder, electrons and crystal structures on the surface of the ZnO hollow sphere are correspondingly changed, so that the cross-linking density of the ZnO hollow sphere and PLA is improved, the regularity of molecular chains is also correspondingly improved, the heat resistance and tensile resistance of the material are improved, and the material has the functions of eliminating peculiar smell, resisting bacteria and inhibiting bacteria.
4. The heat-resistant PLA-based degradable plastic bottle has simple production process and no three wastes, meets the requirement of environmental protection, and has great social benefit and economic benefit.
Detailed Description
The following examples are further illustrative of the present invention.
Example 1
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 0.2 part of ZnO hollow spheres according to the weight parts, adding 0.01 part of gamma-aminopropyl triethoxysilane solution into the ZnO hollow spheres, mixing and stirring uniformly, drying the obtained ZnO hollow spheres with the surfaces soaked with the gamma-aminopropyl triethoxysilane, and cooling to normal temperature to obtain modified ZnO hollow spheres;
(2) weighing 40 parts of polylactic acid, 20 parts of polycarbonate, 0.02 part of phenols 1010, 1 part of cotton fiber and 0.01 part of epoxidized soybean oil according to parts by weight, adding the obtained modified ZnO hollow spheres into the high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 160 ℃, and vacuum drying for 24 hours at 80 ℃;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 170 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 160 ℃ for 2h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the preparation steps of the polycarbonate are as follows:
10 parts of isosorbide and 10 parts of mannitol which are plant-derived materials are adopted as raw materials to prepare an aqueous solution with 1 part of NaOH as a water phase by a phosgene direct method, dichloromethane is used as another phase, amines are used as catalysts, and the polycarbonate is obtained by reacting for 3 hours at 50 ℃.
The preparation method of the ZnO hollow sphere comprises the following steps:
(1) taking 5 parts of glucose, adding 100 parts of deionized water, stirring until the glucose is completely dissolved, transferring the glucose into a polytetrafluoroethylene lining, then putting the glucose into a reaction kettle, and reacting for 12 hours at 180 ℃; (2) after the reaction is finished, cooling, and then centrifugally drying to obtain black brown powdered carbon spheres; (3) and (3) adding 1 part of zinc nitrate and 3 parts of urea into the carbon spheres obtained in the step (2), carrying out ultrasonic treatment for 10min, reacting at 80 ℃ for 3h, cooling after the reaction is finished, carrying out centrifugal drying, and calcining to obtain the ZnO hollow spheres.
Example 2
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 0.3 part of ZnO hollow sphere according to the weight part, adding 0.02 part of gamma-aminopropyl trimethoxy silane solution into the ZnO hollow sphere, mixing and stirring uniformly, drying the obtained ZnO hollow sphere with the surface soaked with the gamma-aminopropyl trimethoxy silane, and cooling to normal temperature to obtain a modified ZnO hollow sphere;
(2) weighing 45 parts of polylactic acid, 25 parts of polycarbonate, 0.03 part of sulfur DSTP, 2 parts of sisal fiber and 0.02 part of triethyl citrate according to parts by weight, adding the mixture into the modified ZnO hollow sphere obtained in the step (1), adding the mixture into a high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 170 ℃, and carrying out vacuum drying for 24 hours at 80 ℃;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 150 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 170 ℃ for 2h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the preparation steps of the polycarbonate are as follows:
10 parts of isosorbide and 10 parts of dulcitol which are plant-derived materials are adopted as raw materials to prepare an aqueous solution with 1 part of NaOH as a water phase by adopting a phosgene direct method, dichloromethane is used as another phase, amines are used as catalysts, and the polycarbonate is obtained by reacting for 3 hours at 50 ℃.
Wherein the ZnO hollow sphere is the ZnO hollow sphere prepared in example 1.
Example 3
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 0.4 part of ZnO hollow sphere according to the weight part, adding 0.03 part of N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane solution into the ZnO hollow sphere, mixing and stirring uniformly, drying the obtained ZnO hollow sphere with the surface soaked with the N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, and cooling to normal temperature to obtain a modified ZnO hollow sphere;
(2) weighing 50 parts of polylactic acid, 30 parts of polycarbonate, 0.04 part of phosphorus 168, 3 parts of hemp fiber and 0.03 part of nonyl citrate according to parts by weight, adding the mixture into the modified ZnO hollow sphere obtained in the step (1), adding the mixture into a high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 180 ℃, and carrying out vacuum drying at 80 ℃ for 24 hours;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 160 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 180 ℃ for 3h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the preparation steps of the polycarbonate are as follows:
10 parts of mannitol and 10 parts of dulcitol which are plant-derived materials are adopted as raw materials, and are prepared into an aqueous solution with 1 part of NaOH to serve as a water phase by a phosgene direct method, dichloromethane serves as another phase, amines serve as catalysts, and the polycarbonate is obtained after reaction for 3 hours at 50 ℃.
Wherein the ZnO hollow sphere is the ZnO hollow sphere prepared in example 1. Example 4
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 0.5 part of ZnO hollow sphere according to the weight part, adding 0.04 part of N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane solution into the ZnO hollow sphere, mixing and stirring the mixture uniformly, drying the obtained ZnO hollow sphere with the surface soaked with the N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, and cooling the dried ZnO hollow sphere to the normal temperature to obtain a modified ZnO hollow sphere;
(2) weighing 60 parts of polylactic acid, 40 parts of polycarbonate, 0.05 part of phenols 1010, 5 parts of bamboo fiber and 0.04 part of polyethylene glycol according to parts by weight, adding the mixture into the modified ZnO hollow sphere obtained in the step (1), adding the mixture into a high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 190 ℃, and carrying out vacuum drying at 80 ℃ for 24 hours;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 170 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 190 ℃ for 3h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the preparation steps of the polycarbonate are as follows:
20 parts of mannitol from plants is used as a raw material to prepare an aqueous solution with 1 part of NaOH as a water phase by adopting a phosgene direct method, dichloromethane is used as another phase, amines are used as catalysts, and the polycarbonate is obtained by reacting for 3 hours at 50 ℃.
Wherein the ZnO hollow sphere is the ZnO hollow sphere prepared in example 1. Comparative example 1
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 0.3 part of ZnO hollow sphere according to the weight part, adding 0.02 part of gamma-aminopropyl trimethoxy silane solution into the ZnO hollow sphere, mixing and stirring uniformly, drying the obtained ZnO hollow sphere with the surface soaked with the gamma-aminopropyl trimethoxy silane, and cooling to normal temperature to obtain a modified ZnO hollow sphere;
(2) weighing 45 parts by weight of polylactic acid, 0.03 part by weight of sulfur DSTP, 2 parts by weight of sisal fiber and 0.02 part by weight of triethyl citrate, adding the mixture into the modified ZnO hollow sphere obtained in the step (1), adding the mixture into a high-speed mixer, uniformly mixing, extruding and granulating the mixture at 170 ℃ by using a double-screw extruder, and carrying out vacuum drying at 80 ℃ for 24 hours;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 150 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 170 ℃ for 2h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the ZnO hollow sphere is the ZnO hollow sphere prepared in example 1. Comparative example 2
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 45 parts of polylactic acid, 25 parts of polycarbonate, 0.03 part of sulfur DSTP, 2 parts of sisal fiber and 0.02 part of triethyl citrate according to parts by weight, adding the materials into a high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 170 ℃, and carrying out vacuum drying for 24 hours at 80 ℃;
(2) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 150 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(3) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 170 ℃ for 2h to obtain the heat-resistant PLA-based degradable plastic bottle.
Wherein the preparation steps of the polycarbonate are as follows:
10 parts of mannitol and 10 parts of dulcitol which are plant-derived materials are adopted as raw materials, and are prepared into an aqueous solution with 1 part of NaOH to serve as a water phase by a phosgene direct method, dichloromethane serves as another phase, amines serve as catalysts, and the polycarbonate is obtained after reaction for 3 hours at 50 ℃.
Comparative example 3
A heat-resistant PLA-based degradable plastic bottle is prepared by the following steps:
(1) weighing 45 parts by weight of polylactic acid, 0.03 part by weight of sulfur DSTP, 2 parts by weight of sisal fiber and 0.02 part by weight of triethyl citrate, adding the components into a high-speed mixer, uniformly mixing, extruding and granulating at 170 ℃ by using a double-screw extruder, and carrying out vacuum drying at 80 ℃ for 24 hours;
(2) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 150 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(3) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at 170 ℃ for 2h to obtain the heat-resistant PLA-based degradable plastic bottle.
The bending performance and the impact performance of the test sample are tested by adopting standards IS0178 and IS0179, experiments are carried out according to GB/T1633-2000, the Vicat softening point temperature of the test sample IS tested, and the antibacterial performance of the test sample IS tested by adopting a JC/T897-2014 improvement method.
The samples of the examples and comparative examples were tested and the results are shown in Table 1
TABLE 1
As can be seen from table one, the heat-resistant PLA-based degradable plastic bottles prepared in embodiments 1 to 4 of the present invention have good toughness, good mechanical properties, can effectively resist external force impact, and have a high softening temperature, good heat resistance, and good antibacterial properties; according to comparative examples 1-3, the polycarbonate and ZnO hollow spheres can improve the mechanical property and heat resistance of the material, other conditions are unchanged, the heat-resistant PLA-based degradable plastic bottle prepared without adding the polycarbonate and ZnO hollow spheres has poor mechanical property and heat resistance, and a sample has no antibacterial property when the ZnO hollow spheres are not added.
Claims (7)
1. A heat-resistant type PLA base degradable plastic bottle which characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 40-60 parts of polylactic acid, 20-50 parts of polycarbonate, 0.1-0.5 part of ZnO hollow spheres, 0.01-0.05 part of amino silane coupling agent, 0.01-0.05 part of antioxidant, 1-5 parts of natural plant fiber and 0.01-0.05 part of plasticizer;
the polycarbonate is prepared by taking plant-derived sugar ether glycol as a raw material, preparing an aqueous solution with NaOH as a water phase by adopting a phosgene direct method, taking dichloromethane as another phase, taking amines as a catalyst, and reacting at 30-70 ℃ for 1-3 hours;
the particle size of the ZnO hollow sphere is 500-800nm, and the preparation steps of the ZnO hollow sphere are as follows: (1) taking a certain amount of glucose, adding deionized water, stirring until the glucose is completely dissolved, then transferring the glucose into a polytetrafluoroethylene lining, then putting the glucose into a reaction kettle, and reacting for 12 hours at 180 ℃; (2) after the reaction is finished, cooling, and then centrifugally drying to obtain black brown powdered carbon spheres; (3) and (3) adding zinc nitrate and urea into the carbon spheres obtained in the step (2), carrying out ultrasonic treatment for 10min, reacting at 80 ℃ for 3h, cooling after the reaction is finished, carrying out centrifugal drying, and calcining to obtain the ZnO hollow spheres.
2. A heat resistant PLA-based degradable plastic bottle according to claim 1, wherein: the sugar ether glycol is one or two of isosorbide, mannitol and dulcitol.
3. A heat resistant PLA-based degradable plastic bottle according to claim 1, wherein: the amino silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane and N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
4. A heat resistant PLA-based degradable plastic bottle according to claim 1, wherein: the antioxidant is one or more of phenols 1010, sulfur DSTP and phosphorus 168.
5. A heat resistant PLA-based degradable plastic bottle according to claim 1, wherein: the natural plant fiber is one or two of cotton fiber, sisal fiber, hemp fiber and bamboo fiber.
6. A heat resistant PLA-based degradable plastic bottle according to claim 1, wherein: the plasticizer is one of epoxidized soybean oil, triethyl citrate, nonyl citrate and polyethylene glycol.
7. A method of making a heat resistant PLA-based degradable plastic bottle according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) weighing the ZnO hollow spheres according to the weight parts, adding an aminosilane coupling agent solution into the ZnO hollow spheres, mixing and stirring uniformly, drying the obtained ZnO hollow spheres with the surfaces soaked with the coupling agent, and cooling to normal temperature to obtain modified ZnO hollow spheres;
(2) weighing polylactic acid, polycarbonate, an antioxidant, natural plant fiber and a plasticizer according to the parts by weight, adding the modified ZnO hollow spheres obtained in the step (1) into a high-speed mixer, uniformly mixing, extruding and granulating at the temperature of 160-80 ℃ by using a double-screw extruder, and drying in vacuum for 12-24 hours at the temperature of 60-80 ℃;
(3) injecting the master batch obtained in the step (2) into a prepared die cavity in a temperature and pressure combined mode through an injection molding machine, and then performing blow molding at 120-180 ℃ by adopting a hot air blow molding method and maintaining the temperature;
(4) and (4) carrying out heat treatment on the sample obtained in the step (3) by adopting an infrared drying tunnel, and annealing at the temperature of 160-.
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| CN110655717A (en) * | 2019-10-24 | 2020-01-07 | 安徽省环瞰塑业有限公司 | Environment-friendly plastic bottle and preparation method thereof |
| CN112406071B (en) * | 2020-11-23 | 2022-07-12 | 中国科学院宁波材料技术与工程研究所 | Physical aging-resistant polylactic acid blow molding product, and preparation method and application thereof |
| CN112745647A (en) * | 2020-12-30 | 2021-05-04 | 重庆和泰润佳股份有限公司 | Non-breathable biodegradable resin and preparation method thereof |
| CN114716745A (en) * | 2021-01-05 | 2022-07-08 | 玉溪玉象包装材料有限公司 | Preparation method of easily degradable three-waste-free liquid daily chemical product packaging bottle |
| CN113212921B (en) * | 2021-05-08 | 2023-06-02 | 漳州市圣铭工贸股份有限公司 | Degradable plastic bottle and preparation method thereof |
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