CN111019308A - 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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- CN111019308A CN111019308A CN201911270971.7A CN201911270971A CN111019308A CN 111019308 A CN111019308 A CN 111019308A CN 201911270971 A CN201911270971 A CN 201911270971A CN 111019308 A CN111019308 A CN 111019308A
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 45
- 239000004033 plastic Substances 0.000 title claims abstract description 45
- 238000009413 insulation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 75
- 239000004626 polylactic acid Substances 0.000 claims abstract description 75
- 239000004005 microsphere Substances 0.000 claims abstract description 70
- 239000004964 aerogel Substances 0.000 claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 54
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 50
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 50
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 50
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 50
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000071 blow moulding Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 10
- 238000007603 infrared drying Methods 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 241000196324 Embryophyta Species 0.000 claims description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 9
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- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229920000136 polysorbate Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011240 wet gel Substances 0.000 claims description 9
- 239000007957 coemulsifier Substances 0.000 claims description 8
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 7
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 7
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 7
- 239000011425 bamboo Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
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- 239000011487 hemp Substances 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 239000004965 Silica aerogel Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 241001330002 Bambuseae Species 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
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- 229920000642 polymer Polymers 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 and generally Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
The invention discloses a heat insulationThe PLA composite plastic bottle comprises the following components in parts by weight: 45-65 parts of polylactic acid powder and SiO25-15 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/cm3The 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 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 SiO25-15 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: taking alkaline silica sol as a silicon source, and adding 4% by mass of nitric acid aqueous solution 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 SiO2An 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel microspheres.
The SiO2The aerogel microspheres have the particle size of 4-20 μm and the pore diameter of 10-40 nm.
SiO2The 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. At the same time, the method preparesSiO2The 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 an organosilicon compound containing two groups with different chemical properties in the molecule, wherein one part of the groups can react with the chemical groups on the surface of an inorganic substance to form firm chemical bonds, and the other part of the groups have the property of being organophilic and can react with or physically wind organic molecules, so that two materials with different properties are firmly combined. 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/SiO2In the process of aerogel microspheres, on one hand, the amino group of KH550 and SiO2The silicon hydroxyl on the surface of the aerogel microsphere generates coupling effect and is attached to SiO2Aerogel microsphere surface; on the other hand, the siloxane groups and the polylactic acid matrix are subjected to covalent bond interaction, so that the polylactic acid matrix and SiO are improved2The direct interface compatibility of the aerogel microspheres enables the composite PLA/SiO2Aerogel 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 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 selected dispersant can regulate 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 SiO2Heating 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 SiO2Aerogel microspheres;
the SiO25-15 parts of aerogel microspheres and 1.5 parts of 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)2Adding 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 at the temperature of 160-180 ℃ for 1-3h 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) alkaline silica sol is used as a silicon source, 4 percent by mass of nitric acid aqueous solution and ethanol are added, wherein the volumes of the silica sol, the ethanol and the nitric acidThe ratio is 1: 1.6: 0.4 to obtain SiO2An 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel 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)2Heating 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 SiO2Aerogel 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)2Adding 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 SiO2An alcoholic solution. 20 parts of n-heptane as an oil phase, 5 parts of span 80 and 1 part of Tween 85 as an emulsifier, and 1 part of n-butanol as an auxiliary emulsifierThe 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel 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)2Heating 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 SiO2Aerogel 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 SiO2Adding 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 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 SiO2An 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, adding the alcohol sol prepared above into oil phase under stirring to disperseAnd (4) uniformity. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel microspheres.
(2) Mixing absolute ethyl alcohol and distilled water according to the volume ratio of 9: 1, adding 0.8 part of silane coupling agent and 11 parts of SiO obtained in the step (1)2Heating 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 SiO2Aerogel 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)2Adding 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 SiO2An 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 SiO2An alcogel microsphere. Finally washing the wet gel microspheres,Aging, solvent displacement and drying to obtain SiO2Aerogel 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)2Heating 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 SiO2Aerogel 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)2Adding 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 at 180 ℃ for 2h to obtain the heat-insulating 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 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 SiO2An 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel 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 SiO obtained in step (1)2Adding 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 3
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 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 SiO2An 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 for mixing, adding the alcohol sol into oil phase under stirring,so that the dispersion is uniform. Then 2mol/L ammonia water is dripped into the mixed solution to be neutral, and the mixture is continuously stirred for 30min to obtain SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel 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 20 parts of SiO obtained in step (1)2Adding 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 SiO2An 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel 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)2Heating aerogel microsphere in water bath at 30 deg.C for prehydrolysis and magnetic forceStirring for 2 h. Then drying for 6h at 85 ℃ to obtain modified SiO2Aerogel 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)2Adding 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.
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 added2When the aerogel microspheres are used, the mechanical performance of the composite material is slightly improved mainly due to SiO2The 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 added2When 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 is2When 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 reduced, which indicates that the added fiber enhances the strength and toughness of the material, improves the regularity of molecular chains, thereby improving the crystallinity and stabilizing the crystalline state.
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 SiO25-15 parts of aerogel microspheres, 0.5-1.5 parts of silane coupling agent (KH550), 1-5 parts of natural plant fibers, 0.01-0.05 part of plasticizer and 0.8-2 parts of dispersing agent.
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 SiO2The preparation method of the aerogel microspheres comprises the following steps: 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 SiO2An 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 SiO2An alcogel microsphere. Finally, washing, aging, solvent replacement and drying the wet gel microspheres to obtain SiO2Aerogel microspheres. The SiO2The 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 according to 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 SiO2Heating 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 SiO2Aerogel 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)2Adding 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;
(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 at the temperature of 160-180 ℃ for 1-3h to obtain the heat-insulation type PLA composite plastic bottle.
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