CN111019308B - Heat-insulation type PLA composite plastic bottle and preparation method thereof - Google Patents
Heat-insulation type PLA composite plastic bottle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-insulation type PLA composite plastic bottle and a preparation method thereof, wherein the heat-insulation type PLA composite plastic bottle comprises the following components in parts by weight: 45-65 parts of polylactic acid powder and SiO 2 5-15 parts of aerogel microspheres, 1-1.5 parts of silane coupling agent KH5500.5, 1-5 parts of natural plant fibers, 0.01-0.05 part of plasticizer and 0.8-2 parts of dispersing agent. The plastic bottle prepared by the invention is environment-friendly and biodegradable, the silicon dioxide aerogel is a light porous structure material and has good heat insulation performance, and the prepared plastic bottle has certain heat insulation and preservation functions under the condition of meeting the requirement of good mechanical performance of a composite material by compounding the silicon dioxide aerogel and polylactic acid.
Description
Technical Field
The invention relates to the technical field of plastic product production, in particular to a heat-insulation type PLA composite plastic bottle and a preparation method thereof.
Background
Polylactic acid is a novel environment-friendly biodegradable material developed in recent years, the raw material of the polylactic acid is renewable natural resource, and the polylactic acid has low energy consumption, good environment friendliness, biocompatibility, mechanical property and processability, is an ideal petroleum substitute product and has wide application prospect. People widely use disposable plastic bottles for drinking water, and generally, plastic bottles provide only one chamber for storing liquid, but cannot insulate heat.
The silicon dioxide aerogel is a light porous inorganic non-metallic material, is constructed by silicon dioxide particles, has a three-dimensional nano network structure, has the porosity of 80-99.8 percent and the pore size of 10-100 nm, belongs to a mesoporous structure, and has the lowest density of 0.003g/cm 3 The thermal conductivity coefficient of a common thermal insulation material can be as low as 0.045W/m.k, while the thermal conductivity coefficient of the silica aerogel microspheres can be as high as 0.01W/m.k, but the loose net-shaped framework structure of the aerogel causes the matrix to have poor mechanical property and cannot bear large internal effect, so that the application of the aerogel is greatly limited. Therefore, the aerogel and the polylactic acid material are compounded, so that the heat insulation function required by the polylactic acid material is met, and meanwhile, the polylactic acid material also plays a skeleton supporting role for the aerogel, so that the mechanical property of the aerogel is improved.
Chinese patent CN107298445A discloses a polylactic acid enhanced silica aerogel and a preparation method thereof, and the polylactic acid enhanced silica aerogel prepared by the preparation method provided by the invention has good skeleton stability. In addition, the method does not need to be subjected to tedious solvent replacement, and has the advantages of short production process flow, low cost and simple operation. However, the prepared composite material has unstable mechanical properties, and the silica aerogel is not uniformly dispersed in a polylactic acid system and is not applied to the aspects of heat insulation and heat preservation.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a heat insulation type PLA composite plastic bottle and a preparation method thereof. The composite material prepared by the method has higher economic benefit and social value.
The heat-insulation type PLA composite plastic bottle comprises the following raw materials in parts by weight:
45-65 parts of polylactic acid powder and SiO 2 5-15 parts of aerogel microspheres, 1-1.5 parts of silane coupling agent KH5500.5, 1-5 parts of natural plant fibers, 0.01-0.05 part of plasticizer and 0.8-2 parts of dispersing agent.
The length of the polylactic acid powder is 30-40 mm.
The polylactic acid powder with the grain diameter of 30-40mm is selected, so that the uniformity and the dispersibility of the mixed material in the stirring process are improved, the surface contact area of the polylactic acid powder and other substances is increased, the interfacial reaction activity with other substances is increased, and the reaction rate is improved.
The preparation method of the heat insulation type PLA composite plastic bottle comprises the following preparation steps: adding 4% by mass of nitric acid aqueous solution and ethanol into alkaline silica sol serving as a silicon source, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
The SiO 2 The aerogel microspheres have the particle size of 4-20 μm and the pore diameter of 10-40 nm.
SiO 2 The aerogel microspheres have small particle size and good dispersibility in a mixture system, and can contact and combine with the polylactic acid surface in the largest area under the action of a silane coupling agent, so that the compatibility of the two substances is improved. Meanwhile, the method prepares SiO 2 The aerogel microspheres have the advantages of high specific surface area, small mesoporous particle size and small pore volume, and reduce the convection degree of air in the aerogel, thereby reducing the thermal conductivity of the composite material and improving the overall thermal insulation performance of the composite material.
The silane coupling agent KH550 is a kind of silane coupling agent containing two different chemical properties in its moleculePart of the organic silicon compound of the matter group can react with the chemical group on the surface of the inorganic matter to form a firm chemical bond, and the other part of the organic silicon compound of the matter group has the property of being organophilic and can react with organic matter molecules or be physically wound, thereby firmly combining two materials with different properties. KH550 contains two relatively reactive groups in the molecule: amino and siloxane groups, as coupling agents between the inorganic gel and the organic polymer groups, increase the adhesion of the two phases. In the KH550 modified compound PLA/SiO 2 In the process of aerogel microspheres, on one hand, the amino group of KH550 and SiO 2 The silicon hydroxyl on the surface of the aerogel microsphere generates coupling effect and is attached to SiO 2 Aerogel microsphere surface; on the other hand, the siloxane groups and the polylactic acid matrix generate covalent bond interaction, thereby improving the polylactic acid matrix and the SiO 2 The direct interface compatibility of the aerogel microspheres enables the composite PLA/SiO 2 Aerogel microballon becomes a whole, and the key of thermal-insulated PLA bottle is the introduction thermal insulation material, secondly to the evenly distributed of thermal insulation material, guarantees that it does not take place the coagulation phenomenon at raw materials mixing in-process, and then reaches the less silica aerogel quantity of control, plays better thermal-insulated effect.
For the heat insulation effect, the effects of high porosity and low density in the aerogel are mainly utilized, a large number of fine gaps exist in the aerogel, and when the aerogel is prepared into a plastic bottle, the aerogel has good heat insulation performance in the air part in the plastic bottle due to low heat transfer coefficient. In order to achieve good thermal insulation properties, it is desirable that the aerogel be uniformly dispersed and that the integrity of the voids therein be maintained.
Because plastic bottles can also be used to contain liquids, and therefore, the liquids are required not to leak, the aerogel used in the present invention must ensure that the pore size of the aerogel is small, so that the liquids do not leak.
The natural plant fiber is one or two of cotton fiber, sisal fiber, hemp fiber and bamboo fiber.
The natural plant fiber 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 and durability of the product.
The natural plant fiber is a nanofiber, and the length of the fabric fiber is 10-40 μm.
The plasticizer is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
Although the plasticizer is added in a small amount in the invention, the secondary valence bonds among polymer molecules are weakened, so that the mobility of polymer molecular chains is increased, the plasticity of the polymer is increased, the brittleness of the polymer is reduced, and the elongation, the flexibility and the flexibility are improved.
The dispersing agent is one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate.
The dispersant selected by the invention can adjust the mobility of each particle in the whole composite system, improve the dispersibility of the particles and prevent the particles from agglomerating.
The preparation method of the heat insulation type PLA composite plastic bottle comprises the following steps:
(1) mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding a certain amount of silane coupling agent and SiO 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours. Then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres;
the SiO 2 5-15 parts of aerogel microspheres and 1.5 parts of a silane coupling agent KH 5500.5;
(2) weighing polylactic acid powder, natural plant fiber, plasticizer and dispersant according to the weight parts, and adding the modified SiO obtained in the step (1) 2 Adding aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 160-180 ℃ by using a double-screw extruder, and vacuum drying at 60-80 ℃ for 12-24 h;
45-65 parts of polylactic acid powder, 1-5 parts of natural plant fiber, 0.01-0.05 part of plasticizer and 0.8-2 parts of dispersant.
(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 and isothermal maintenance at 120-180 ℃ 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 for 1-3h at the temperature of 160-180 ℃ to obtain the heat insulation type PLA composite plastic bottle.
The heat insulation type PLA composite plastic bottle prepared by adopting the technical scheme has the following advantages:
1. the prepared micron-sized silica aerogel is compounded with polylactic acid, so that the compatibility of a reaction interface with the polylactic acid is improved, the prepared plastic bottle has a smooth surface and no crack, and meanwhile, the silica aerogel has an ultrahigh specific surface area and a small pore volume, prevents the convection of internal air, reduces the thermal conductivity and improves the heat insulation and preservation performance of the material.
2. The polylactic acid biodegradable material is added into the raw materials, the production process is simple, three wastes are not generated, the requirements of environmental protection are met, and the polylactic acid biodegradable material has great economic benefit and social value.
Drawings
FIG. 1: example 1 glass bottle-like bottle prepared
Detailed Description
The following examples are further illustrative of the present invention.
Example 1
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) adding 4% nitric acid aqueous solution and ethanol by mass percent, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix well, and adding the alcohol sol into oil phase under stirring to disperse well. Then mixing and dissolvingDripping 2mol/L ammonia water into the solution to be neutral, and continuously stirring for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding 0.5 part of silane coupling agent and 5 parts of SiO obtained in the step (1) 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours. Then dried for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres.
(3) Weighing 45 parts of polylactic acid powder, 1 part of cotton fiber, 0.01 part of epoxidized soybean oil and 0.8 part of barium stearate, and adding the materials into the mixture to obtain modified SiO in the step (2) 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 160 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(4) And (3) injecting the master batch obtained in the step (3) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(5) And (4) carrying out heat treatment on the sample obtained in the step (4) by adopting an infrared drying tunnel, and annealing at 160 ℃ for 1h to obtain the heat-insulating PLA composite plastic bottle.
Example 2
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) adding 4% nitric acid aqueous solution and ethanol by mass percent, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally washing, aging and solvent replacing the wet gel microspheresAnd after drying, SiO is obtained 2 Aerogel microspheres.
(2) Mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding 0.7 part of silane coupling agent and 8 parts of SiO obtained in the step (1) 2 Heating the aerogel microspheres in a water bath at 30 ℃ to prehydrolyze and magnetically stirring for 2 hours. Then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres.
(3) Weighing 50 parts of polylactic acid powder, 2 parts of sisal fiber, 0.02 part of glycerol and 0.9 part of barium stearate, and adding the obtained mixture into the mixture obtained in the step (2) to obtain modified SiO 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 170 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(4) And (3) injecting the master batch obtained in the step (3) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(5) And (4) carrying out heat treatment on the sample obtained in the step (4) by adopting an infrared drying tunnel, and annealing at 170 ℃ for 2h to obtain the heat-insulating PLA composite plastic bottle.
Example 3
A heat insulation type PLA composite plastic bottle comprises the following steps:
(1) adding 4% nitric acid aqueous solution and ethanol by mass percent, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Mixing absolute ethanol and distilled water at a volume ratio of 9: 1, adding0.8 part of a silane coupling agent and 11 parts of SiO obtained in step (1) 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours. Then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres.
(3) Weighing 55 parts of polylactic acid powder, 3 parts of bamboo fiber, 0.02 part of glycerol and 0.9 part of barium stearate, and adding the materials into the mixture to obtain modified SiO in the step (2) 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 180 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(4) And (3) injecting the master batch obtained in the step (3) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(5) And (4) carrying out heat treatment on the sample obtained in the step (4) by adopting an infrared drying tunnel, and annealing at 180 ℃ for 2h to obtain the heat-insulating PLA composite plastic bottle.
Example 4
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) adding 4% nitric acid aqueous solution and ethanol by mass percent, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding 1.2 parts of silane coupling agent and 12 parts of SiO obtained in the step (1) 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours. Then drying at 85 deg.C for 6h to obtain the final productSiO2 2 Aerogel microspheres.
(3) Weighing 60 parts of polylactic acid powder, 4 parts of bamboo fiber, 0.04 part of polyethylene glycol and 0.9 part of barium stearate, and adding the modified SiO obtained in the step (2) 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 180 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(4) And (3) injecting the master batch obtained in the step (3) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(5) And (4) carrying out heat treatment on the sample obtained in the step (4) by adopting an infrared drying tunnel, and annealing at 180 ℃ for 2h to obtain the heat-insulating PLA composite plastic bottle.
Comparative example 1
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) weighing 55 parts of polylactic acid powder, 3 parts of bamboo fiber, 0.02 part of glycerol and 0.9 part of barium stearate, adding into a high-speed mixer, uniformly mixing, extruding and granulating by using a double-screw extruder at 180 ℃, and vacuum drying for 12 hours at 80 ℃.
(2) And (2) injecting the master batch obtained in the step (1) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(3) And (3) carrying out heat treatment on the sample obtained in the step (2) by adopting an infrared drying tunnel, and annealing for 2 hours at 180 ℃ to obtain the heat-insulation PLA composite plastic bottle.
Comparative example 2
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) taking alkaline silica sol as a silicon source, and adding nitric acid aqueous solution (4% by mass) and ethanol, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12g/L. Stirring at 40 deg.C for 30min to mix well, and adding the alcohol sol into oil phase under stirring to disperse well. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Weighing 55 parts of polylactic acid powder, 3 parts of bamboo fiber, 0.02 part of glycerol and 0.9 part of barium stearate, and adding 11 parts of the mixture obtained in the step (1) to obtain SiO 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 180 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(3) And (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 120 ℃ by using a hot air blow molding method and maintaining the temperature isothermally.
(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 2h to obtain the heat-insulating PLA composite plastic bottle.
Comparative example 3
A heat insulation type PLA composite plastic bottle comprises the following steps:
(1) taking alkaline silica sol as a silicon source, and adding a nitric acid aqueous solution (4% by mass) and ethanol, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally washing, aging, solvent replacing and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Weighing 55 parts of polylactic acid powder, 3 parts of bamboo fiber and 0.02 part of glycerol0.9 part of barium stearate, to which 20 parts of SiO obtained in step (1) was added 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 180 ℃ by using a double-screw extruder, and vacuum-drying at 80 ℃ for 12 hours.
(3) And (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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(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 2h to obtain the heat-insulating PLA composite plastic bottle.
Comparative example 4
A heat insulation type PLA composite plastic bottle is prepared by the following steps:
(1) adding 4% nitric acid aqueous solution and ethanol by mass percent, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcoholic solution. 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of Tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L. Stirring at 40 deg.C for 30min to mix, and adding the alcohol sol into oil phase under stirring to disperse. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO 2 Aerogel microspheres.
(2) Mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding 1.2 parts of silane coupling agent and 12 parts of SiO obtained in the step (1) 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours. Then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres.
(3) Weighing 60 parts of polylactic acid powder, 0.04 part of polyethylene glycol and 0.9 part of barium stearate, and adding the modified SiO obtained in the step (2) 2 Adding aerogel microspheres into a high-speed mixer, uniformly mixing, and then adopting a double-screw extruder at 180 DEG CExtruded to granulate and dried in vacuum at 80 ℃ for 12 h.
(4) And (3) injecting the master batch obtained in the step (3) 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 120 ℃ by using a hot air blow molding method and maintaining the temperature of the master batch isothermally.
(5) And (4) carrying out heat treatment on the sample obtained in the step (4) by adopting an infrared drying tunnel, and annealing at 180 ℃ for 2h to obtain the heat-insulating PLA composite plastic bottle.
The tensile strength, elongation at break, impact strength and thermal conductivity were measured according to GB/T1040-1992, GB/T1040.1-2006, GB/T1043-1993 and GB/T3399-1982, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the heat-insulating PLA composite plastic bottles prepared in examples 1 to 4 have good mechanical properties and low thermal conductivity, the lowest thermal conductivity can reach 0.09W/m.K, the heat conduction effect is low, and the heat-insulating PLA composite plastic bottles have good heat-insulating and heat-preserving effects. Meanwhile, in comparative example 1, it can be seen that SiO was not added 2 When the aerogel microspheres are used, the mechanical performance of the composite material is slightly improved mainly due to SiO 2 The aerogel microsphere particles have weak acting force, so the aerogel microsphere particles have the defects of low strength, poor toughness and the like. Comparative examples 2 to 3 show that when SiO which has not been modified is added 2 When the aerogel microspheres are used, the mechanical property and the heat-insulating property of the composite material are relatively poor, which shows that the SiO is 2 When the aerogel microspheres are not modified, the interface compatibility between the particles and polylactic acid molecules is poor, the dispersibility of the aerogel microspheres in the composite material is difficult to ensure, the mechanical property is poor, and the heat conductivity coefficient is high. Comparative example 4 shows that when no fiber is added, the mechanical properties of the prepared composite material are all reduced, which indicates that the strength and toughness of the material are enhanced by adding the fiber, and the regularity of molecular chains is improved, so that the crystallinity is improved, and the crystallization state is stabilized.
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.
Claims (7)
1. The utility model provides a compound plastic bottle of thermal-insulated type PLA which characterized in that:
the composition is characterized by comprising the following raw materials in parts by weight: 45-65 parts of polylactic acid powder and SiO 2 5-15 parts of aerogel microspheres, 1-1.5 parts of silane coupling agent KH5500.5, 1-5 parts of natural plant fibers, 0.01-0.05 part of plasticizer and 0.8-2 parts of dispersing agent;
the preparation method of the composite plastic bottle comprises the following steps:
(1) mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding a certain amount of silane coupling agent and SiO 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours; then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres;
(2) weighing polylactic acid powder, natural plant fiber, plasticizer and dispersant according to the weight parts, and adding the modified SiO obtained in the step (1) 2 Adding the aerogel microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 160-180 ℃ by using a double-screw extruder, and drying in vacuum for 12-24h at 60-80 ℃.
2. An insulating PLA composite plastic bottle according to claim 1, wherein:
the length of the polylactic acid powder is 30-40 mm.
3. An insulating PLA composite plastic bottle according to claim 1, wherein:
the SiO 2 The preparation method of the aerogel microspheres comprises the following steps: adding 4% by mass of nitric acid aqueous solution and ethanol into alkaline silica sol serving as a silicon source, wherein the volume ratio of the silica sol to the ethanol to the nitric acid is 1: 1.6: 0.4 to obtain SiO 2 An alcohol solution; 20 parts of n-heptane is used as an oil phase, 5 parts of span 80 and 1 part of tween 85 are used as emulsifiers, 1 part of n-butanol is used as a co-emulsifier, and the concentration of the emulsifier is 0.12 g/L; stirring at 40 deg.C for 30minUniformly mixing, and then adding the prepared alcohol sol into an oil phase under the stirring condition to uniformly disperse the alcohol sol; then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO 2 (ii) alcogel microspheres; finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2 aerogel microspheres; the SiO 2 The aerogel microspheres have the particle size of 4-20 μm and the pore diameter of 10-40 nm.
4. An insulating PLA composite 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.
5. An insulating PLA composite plastic bottle according to claim 1, wherein:
the plasticizer is one of epoxidized soybean oil, triethyl citrate, glycerol and polyethylene glycol.
6. An insulating PLA composite plastic bottle according to claim 1, wherein:
the dispersing agent is one or more of barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate and copper stearate.
7. A method of making an insulated PLA composite plastic bottle as claimed in any one of claims 1 to 6 wherein:
the method comprises the following steps:
(1) mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding a certain amount of silane coupling agent and SiO 2 Heating the aerogel microspheres in a water bath at 30 ℃ for prehydrolysis and magnetically stirring for 2 hours; then drying for 6h at 85 ℃ to obtain modified SiO 2 Aerogel microspheres;
(2) weighing polylactic acid powder, natural plant fiber, plasticizer and dispersant according to the weight parts, and adding the modified SiO obtained in the step (1) 2 AerogelAdding the microspheres into a high-speed mixer, uniformly mixing, extruding and granulating at 160-180 ℃ by using a double-screw extruder, and drying in vacuum for 12-24h at 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 for 1-3h at the temperature of 160-180 ℃ to obtain the heat insulation type PLA composite plastic bottle.
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| CN114196181A (en) * | 2022-01-11 | 2022-03-18 | 惠通北工生物科技(北京)有限公司 | Polylactic acid and silicon dioxide aerogel composite master batch and preparation method thereof |
| CN114410090B (en) * | 2022-01-25 | 2023-08-15 | 佛山市顺德区建德包装实业有限公司 | Preparation method of packaging film |
| CN114750488A (en) * | 2022-04-13 | 2022-07-15 | 安徽国风新材料股份有限公司 | BOPLA gas-barrier heat-insulation film for food packaging and preparation method thereof |
| CN115627058B (en) * | 2022-10-24 | 2023-07-18 | 湖北中烟工业有限责任公司 | High-void-ratio fiber composite material for flavoring pipe and preparation method thereof |
| CN116589773A (en) * | 2023-05-26 | 2023-08-15 | 广州耀威塑胶有限公司 | Thermal insulation type plastic bottle and preparation process thereof |
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