CN116355371A - Degradable polylactic acid dropper and preparation method thereof - Google Patents
Degradable polylactic acid dropper and preparation method thereof Download PDFInfo
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- CN116355371A CN116355371A CN202310367957.9A CN202310367957A CN116355371A CN 116355371 A CN116355371 A CN 116355371A CN 202310367957 A CN202310367957 A CN 202310367957A CN 116355371 A CN116355371 A CN 116355371A
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 56
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 32
- -1 polybutylene succinate Polymers 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229920002472 Starch Polymers 0.000 claims abstract description 23
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 23
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 23
- 239000008107 starch Substances 0.000 claims abstract description 23
- 235000019698 starch Nutrition 0.000 claims abstract description 23
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 22
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims abstract description 21
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000071 blow moulding Methods 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 8
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- 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
Abstract
The invention discloses a degradable polylactic acid dropper and a preparation method thereof, relates to the technical field of high polymer materials, and solves the problems of difficult degradation, large brittleness and low elongation at break of the existing dropper, and the degradable polylactic acid dropper comprises the following raw materials in parts by weight: 20-60 parts of polylactic acid, 1-10 parts of nano precipitated calcium carbonate, 1-10 parts of montmorillonite, 5-15 parts of polybutylene succinate, 1-8 parts of amino silicone oil, 2-8 parts of citric acid ester, 3-12 parts of a coupling agent, 4-10 parts of a plasticizer, 3-15 parts of glass fiber, 3-8 parts of a heat-resistant agent, 3-8 parts of a waterproof agent, 2-15 parts of an antioxidant, 4-12 parts of a light stabilizer and 2-8 parts of plant starch; the raw materials have high biocompatibility and stable performance, can protect ecological environment, and have good social benefit; the prepared polylactic acid modified material has good acid resistance, mechanical property, heat resistance and stretching resistance, good aging prevention effect and simple preparation method.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a degradable polylactic acid dropper and a preparation method thereof.
Background
The disposable plastic dropper is an indispensable experimental consumable in the industries of food research, medicine and the like, is mainly used for sucking liquid, and is a disposable product, and the dropper is not miscible, so that the disposable dropper is large in dosage. The material is mainly Low Density Polyethylene (LDPE), the LDPE is the lightest variety in polyethylene, the calendaring molding property is poor, the LDPE is suitable for being processed into tubular films by a blow molding method, the LDPE is used for packaging foods, fiber products, daily chemical products and the like, the LDPE is stable in performance and difficult to degrade, white pollution is caused to ecological environment, the problem of increasingly serious white pollution is faced, people hope to find a plastic substitute which can replace the existing plastic performance and does not cause white pollution, and degradable plastics are generated.
Polylactic acid (PLA) is a thermoplastic aliphatic resin obtained by taking starch in crops (such as beet, sweet potato, corn and the like) as a raw material, fermenting the starch by microorganisms and then carrying out chemical synthesis reaction, and is an environment-friendly renewable green high polymer material. PLA is widely applied to various fields of biomedicine, textile clothing, packaging materials, agricultural materials, automobile electronics and the like by virtue of excellent mechanical properties, processability, degradation performance, biocompatibility and the like, and is a green polymer material with wide application prospect.
Polylactic acid (PLA), however, has a high brittleness and a low elongation at break, limiting its wider application.
Disclosure of Invention
The invention aims to solve the problems of difficult degradation, large brittleness and low elongation at break of the existing dropper, and provides a degradable polylactic acid dropper and a preparation method thereof.
The invention adopts the following technical scheme for realizing the purposes:
the degradable polylactic acid dropper comprises the following raw materials in parts by weight: 20-60 parts of polylactic acid, 1-10 parts of nano precipitated calcium carbonate, 1-10 parts of montmorillonite, 5-15 parts of polybutylene succinate, 1-8 parts of amino silicone oil, 2-8 parts of citric acid ester, 3-12 parts of a coupling agent, 4-10 parts of a plasticizer, 3-15 parts of glass fiber, 3-8 parts of a heat-resistant agent, 3-8 parts of a waterproof agent, 2-15 parts of an antioxidant, 4-12 parts of a light stabilizer and 2-8 parts of plant starch.
Further, the degradable polylactic acid dropper comprises the following raw materials in parts by weight: 50 parts of polylactic acid, 1 part of nano precipitated calcium carbonate, 2 parts of montmorillonite, 10 parts of polybutylene succinate, 2 parts of amino silicone oil, 3 parts of citric acid ester, 8 parts of coupling agent, 6 parts of plasticizer, 8 parts of glass fiber, 5 parts of heat resistant agent, 5 parts of waterproof agent, 4 parts of antioxidant, 6 parts of light stabilizer and 6 parts of plant starch.
Further, the degradable polylactic acid dropper comprises the following raw materials in parts by weight: 50 parts of polylactic acid, 1 part of nano precipitated calcium carbonate, 2 parts of montmorillonite, 15 parts of polybutylene succinate, 2 parts of amino silicone oil, 4 parts of citric acid ester, 6 parts of coupling agent, 8 parts of plasticizer, 6 parts of glass fiber, 5 parts of heat-resistant agent, 8 parts of waterproof agent, 4 parts of antioxidant, 6 parts of light stabilizer and 6 parts of plant starch.
Further, the dosage of the amino silicone oil is 0.5% -4% of the mass of the polylactic acid.
The increase of nano precipitated calcium carbonate and montmorillonite can improve tensile strength, both have good dispersibility, and can form large aggregates along with the increase of particle proportion, because of the microstructure of the nano composite material and the interaction between nano particles and polylactic acid, the nano precipitated calcium carbonate and montmorillonite play a role in synergistic toughening, and because the content of the nano precipitated calcium carbonate and the montmorillonite is lower in the integral raw material composition, the nano precipitated calcium carbonate and the montmorillonite exist in a blending matrix in a certain dispersion state, and because of gaps formed by stress concentration generated by phase separation, more impact energy can be absorbed, so that the elongation at break is increased.
In order to achieve the above purpose, the invention also provides a preparation method of the degradable polylactic acid dropper, which specifically comprises the following steps:
step 1: blending polylactic acid and polybutylene succinate serving as matrixes according to the mass ratio to obtain a blended matrix;
step 2: adding nano precipitated calcium carbonate, montmorillonite, amino silicone oil, citrate, a coupling agent, a plasticizer, glass fiber, a heat resistant agent, a waterproof agent, an antioxidant, a light stabilizer and hydroxy cellulose into a blending matrix according to mass ratio, and uniformly mixing;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the middle blank is prepared by adopting an extrusion method or an injection method.
Further, the polylactic acid and the polybutylene succinate in the step 1 are dried for 24 hours under the vacuum condition of 50 ℃ and then mixed under the temperature condition of 90 ℃.
Further, the screw rotation speed in the step 3 is 75r/min, and the temperature is 150 ℃.
Further, the blow molding machine of step 4 heats the parison to 88-110 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation.
Further, the stretching rod of the blow molding machine in step 4 is moved at a speed of 0.5 to 3.5m/s into the preform and stretches the preform to the bottom of the blow mold, and compressed nitrogen gas having a pressure of 0.2 to 3.0MPa is slowly blown into the preform while the stretching rod is moved toward the preform, so as to prevent contact between the preform and the stretching rod.
Further, when the stretching rod reaches the bottom, the pressure of the compressed air is adjusted to 0.6-4.0MPa to completely fill the device, so that the dropper assumes the shape of a blow mold, and compressed nitrogen is continuously blown into the dropper before the dropper is taken out of the mold, and is kept for 2-20s to cool the dropper.
The beneficial effects of the invention are as follows:
(1) The invention adopts degradable polylactic acid as a main manufacturing raw material, and the polylactic acid is a polyester polymer obtained by taking lactic acid as a main raw material for polymerization, is a novel biodegradable material, and has good thermal stability and solvent resistance;
(2) The raw material composition of the invention has high biocompatibility and stable performance, can replace the traditional LDPE plastic material dropper, can protect ecological environment, and has good social benefit;
(3) The polylactic acid modified material prepared by the invention has good acid resistance, mechanical property, heat resistance and tensile resistance, good aging prevention effect and simple preparation method;
(4) The process conditions and the method can improve the physical and mechanical properties of the plastic, can obviously improve the tensile strength, the impact toughness, the rigidity, the transparency and the luster, and improve the barrier property to oxygen, carbon dioxide and water vapor; the product dropper has excellent transparency, impact strength, hardness, rigidity, surface glossiness and barrier property.
Drawings
FIG. 1 is a photograph of a large agglomerate observed in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
Step 1: drying 42 parts of polylactic acid and 8 parts of polybutylene succinate under a vacuum condition at 50 ℃ for 24 hours, and then taking the dried polybutylene succinate as a matrix for blending at a temperature of 90 ℃ to obtain a blended matrix;
step 2: adding 1 part of nano precipitated calcium carbonate, 2 parts of montmorillonite, 1 part of amino silicone oil, 8 parts of citrate, 12 parts of coupling agent, 10 parts of plasticizer, 15 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 15 parts of antioxidant, 12 parts of light stabilizer and 8 parts of plant starch into a blending matrix according to the mass ratio, and uniformly mixing;
wherein the plant starch is plant cationic starch, preferably tapioca cationic starch and taro cationic starch. Wherein the optimal ratio of the cassava cationic starch and the taro cationic starch is 1:3.
The tertiary aminoalkyl ether or quaternary ammonium starch ether type may be selected from molecular structures.
In the formula, because the polylactic acid polymer chain contains an oxygen atom negative charge center, electrostatic adsorption is generated between positive charge groups in the cationic starch and polylactic acid negative charge oxygen atoms, good adhesive force is generated, and the adhesive force is stronger because the adhesive force also has the effect of eliminating static electricity on polylactic acid molecular chains.
Step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 88 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preform at a speed of 0.5m/s and stretches the preform to the bottom of the blow mold, and when the stretching rod moves towards the preform, compressed nitrogen with a pressure of 0.2MPa is slowly blown into the preform to prevent contact between the preform and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 0.6MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 2s to cool the dropper before the dropper was taken out of the mold.
Example 2
Step 1: drying 50 parts of polylactic acid and 10 parts of polybutylene succinate under the vacuum condition of 50 ℃ for 24 hours, and then taking the dried polylactic acid and 10 parts of polybutylene succinate as a matrix for blending under the temperature condition of 90 ℃ to obtain a blended matrix;
step 2: 2 parts of nano precipitated calcium carbonate, 4 parts of montmorillonite, 2 parts of amino silicone oil, 5 parts of citrate, 10 parts of coupling agent, 8 parts of plasticizer, 13 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 11 parts of antioxidant, 12 parts of light stabilizer and 8 parts of plant starch are added into a blending matrix according to the mass ratio, and uniformly mixed;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 90 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preform at a speed of 1.0m/s and stretches the preform to the bottom of the blow mold, and when the stretching rod moves towards the preform, compressed nitrogen with a pressure of 0.5MPa is slowly blown into the preform to prevent contact between the preform and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 1.5MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 5s to cool the dropper before the dropper was taken out of the mold.
Example 3
Step 1: drying 50 parts of polylactic acid and 15 parts of polybutylene succinate under a vacuum condition at 50 ℃ for 24 hours, and then taking the dried polylactic acid and 15 parts of polybutylene succinate as a matrix for blending at a temperature of 90 ℃ to obtain a blended matrix;
step 2: 3 parts of nano precipitated calcium carbonate, 6 parts of montmorillonite, 2 parts of amino silicone oil, 5 parts of citrate, 10 parts of coupling agent, 8 parts of plasticizer, 13 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 9 parts of antioxidant, 6 parts of light stabilizer and 4 parts of plant starch are added into a blending matrix according to the mass ratio, and uniformly mixed;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 95 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preform at a speed of 1.5m/s and stretches the preform to the bottom of the blow mold, and when the stretching rod moves towards the preform, compressed nitrogen with a pressure of 1.0MPa is slowly blown into the preform to prevent contact between the preform and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 1.5MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 8s to cool the dropper before the dropper was taken out of the mold.
Example 4
Step 1: drying 55 parts of polylactic acid and 10 parts of polybutylene succinate under a vacuum condition at 50 ℃ for 24 hours, and then taking the dried polylactic acid and 10 parts of polybutylene succinate as a matrix for blending at a temperature of 90 ℃ to obtain a blended matrix;
step 2: adding 4 parts of nano precipitated calcium carbonate, 8 parts of montmorillonite, 2 parts of amino silicone oil, 5 parts of citrate, 10 parts of coupling agent, 8 parts of plasticizer, 13 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 9 parts of antioxidant, 6 parts of light stabilizer and 4 parts of plant starch into a blending matrix according to the mass ratio, and uniformly mixing;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 100 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preformed unit at a speed of 0.5-3.5m/s, stretches the preformed unit to the bottom of the blow molding die, and when the stretching rod moves towards the preformed unit, compressed nitrogen with a pressure of 2.0MPa is slowly blown into the preformed unit so as to prevent contact between the preformed unit and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 2.0MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 10s to cool the dropper before the dropper was taken out of the mold.
Example 5
Step 1: drying 60 parts of polylactic acid and 10 parts of polybutylene succinate under a vacuum condition at 50 ℃ for 24 hours, and then taking the dried polylactic acid and 10 parts of polybutylene succinate as a matrix for blending at a temperature of 90 ℃ to obtain a blended matrix;
step 2: adding 5 parts of nano precipitated calcium carbonate, 10 parts of montmorillonite, 2 parts of amino silicone oil, 5 parts of citrate, 7 parts of coupling agent, 6 parts of plasticizer, 10 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 9 parts of antioxidant, 6 parts of light stabilizer and 4 parts of plant starch into a blending matrix according to the mass ratio, and uniformly mixing;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 100 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preform at a speed of 3.0m/s and stretches the preform to the bottom of the blow mold, and when the stretching rod moves toward the preform, compressed nitrogen with a pressure of 2.5MPa is slowly blown into the preform to prevent contact between the preform and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 3.0MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 15s to cool the dropper before the dropper was taken out of the mold.
Example 6
Step 1: drying 40 parts of polylactic acid and 10 parts of polybutylene succinate under a vacuum condition at 50 ℃ for 24 hours, and then taking the dried polylactic acid and 10 parts of polybutylene succinate as a matrix for blending at a temperature of 90 ℃ to obtain a blended matrix;
step 2: adding 5 parts of nano precipitated calcium carbonate, 10 parts of montmorillonite, 2 parts of amino silicone oil, 5 parts of citrate, 6 parts of coupling agent, 4 parts of plasticizer, 8 parts of glass fiber, 8 parts of heat resistant agent, 8 parts of waterproof agent, 9 parts of antioxidant, 6 parts of light stabilizer and 4 parts of plant starch into a blending matrix according to the mass ratio, and uniformly mixing;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material; wherein the rotating speed of the screw is 75r/min and the temperature is 150 ℃;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the blow molding machine heats the parison to 110 ℃ by an infrared heater and performs circumferential blow molding while stretching in the axial direction to achieve biaxial orientation; the stretching rod of the blow molding machine moves into the preform at a speed of 3.5m/s and stretches the preform to the bottom of the blow mold, and when the stretching rod moves toward the preform, compressed nitrogen with a pressure of 3.0MPa is slowly blown into the preform to prevent contact between the preform and the stretching rod; when the stretching rod reached the bottom, the pressure of the compressed air was adjusted to 4.0MPa to completely fill the device, so that the dropper assumed the shape of a blow mold, and compressed nitrogen was continuously blown into the dropper and held for 20s to cool the dropper before the dropper was taken out of the mold.
The tensile strength of the degradable polylactic acid droppers prepared by the preparation methods of examples 1 to 6 was measured, and the measurement data are shown in the following table.
According to the above detection results, the addition of the nano inorganic filler can improve the tensile strength, and when the filling amount of the two nano particles is about 5-10%, the two nano particles have good dispersibility, and as the proportion of the particles increases, large agglomerates can be observed due to the microstructure of the nano composite material and the interaction between the nano particles and the polylactic acid. When the ratio of nano calcium carbonate to montmorillonite is 1:2, the adsorption capacity during blending is good, and the dispersion performance can be improved, and the impact resistance, fatigue resistance, dimensional stability, gas barrier property and the like can be improved. The nano precipitated calcium carbonate and montmorillonite have synergistic toughening effect, and are filled in a blending matrix in a certain dispersed way when the content is low, and the voids formed by concentrated stress generated by phase separation can absorb more impact energy to increase the elongation at break, but when the addition proportion is further increased, the elongation at break shows a trend of decreasing, and when the addition proportion is increased, rapid development of cracks is extremely easy to induce, macroscopic stress cracking is formed to cause the decrease of the toughness of the material, so that the optimal addition proportion of the precipitated calcium carbonate and the montmorillonite is 1:2, and the optimal total addition amount is 6%.
Claims (10)
1. The degradable polylactic acid dropper is characterized by comprising the following raw materials in parts by weight: 20-60 parts of polylactic acid, 1-10 parts of nano precipitated calcium carbonate, 1-10 parts of montmorillonite, 5-15 parts of polybutylene succinate, 1-8 parts of amino silicone oil, 2-8 parts of citric acid ester, 3-12 parts of a coupling agent, 4-10 parts of a plasticizer, 3-15 parts of glass fiber, 3-8 parts of a heat-resistant agent, 3-8 parts of a waterproof agent, 2-15 parts of an antioxidant, 4-12 parts of a light stabilizer and 2-8 parts of plant starch.
2. The degradable polylactic acid dropper as claimed in claim 1, comprising the following raw materials in parts by weight: 50 parts of polylactic acid, 1 part of nano precipitated calcium carbonate, 2 parts of montmorillonite, 10 parts of polybutylene succinate, 2 parts of amino silicone oil, 3 parts of citric acid ester, 8 parts of coupling agent, 6 parts of plasticizer, 8 parts of glass fiber, 5 parts of heat resistant agent, 5 parts of waterproof agent, 4 parts of antioxidant, 6 parts of light stabilizer and 6 parts of plant starch.
3. The degradable polylactic acid dropper as claimed in claim 1, comprising the following raw materials in parts by weight: 50 parts of polylactic acid, 1 part of nano precipitated calcium carbonate, 2 parts of montmorillonite, 15 parts of polybutylene succinate, 2 parts of amino silicone oil, 4 parts of citric acid ester, 6 parts of coupling agent, 8 parts of plasticizer, 6 parts of glass fiber, 5 parts of heat-resistant agent, 8 parts of waterproof agent, 4 parts of antioxidant, 6 parts of light stabilizer and 6 parts of plant starch.
4. The degradable polylactic acid dropper according to claim 1, wherein the amount of the amino silicone oil is 0.5-4% of the mass of the polylactic acid.
5. A method for preparing the degradable polylactic acid dropper according to any one of claims 1 to 4, which is characterized by comprising the following steps:
step 1: blending polylactic acid and polybutylene succinate serving as matrixes according to the mass ratio to obtain a blended matrix;
step 2: adding nano precipitated calcium carbonate, montmorillonite, amino silicone oil, citrate, a coupling agent, a plasticizer, glass fiber, a heat resistant agent, a waterproof agent, an antioxidant, a light stabilizer and hydroxy cellulose into a blending matrix according to mass ratio, and uniformly mixing;
step 3: adding the materials uniformly mixed in the step 2 into a screw base machine, and heating, melting and extruding to obtain a blending base material;
step 4: adding the blended base material into an injection molding machine to mold a preformed piece, and transferring the parison into a blow molding machine to be blow molded; wherein the middle blank is prepared by adopting an extrusion method or an injection method.
6. The method for preparing a degradable polylactic acid dropper according to claim 5, wherein the polylactic acid and the polybutylene succinate in the step 1 are dried under a vacuum condition at 50 ℃ for 24 hours and then mixed under a temperature condition at 90 ℃.
7. The method for preparing the degradable polylactic acid dropper according to claim 5, wherein the screw rotation speed in the step 3 is 75r/min, and the temperature is 150 ℃.
8. The method of producing a degradable polylactic acid dropper according to claim 5, wherein the blow molding machine of step 4 heats the parison to 88 to 110 ℃ by an infrared heater and performs the circumferential blow molding while stretching in the axial direction to achieve biaxial orientation.
9. The method of manufacturing a degradable polylactic acid dropper according to claim 5, wherein the stretching rod of the blow molding machine in step 4 is moved into the preform at a speed of 0.5-3.5m/s and stretches the preform to the bottom of the blow mold, and compressed nitrogen gas having a pressure of 0.2-3.0MPa is slowly blown into the preform while the stretching rod is moved toward the preform to prevent contact between the preform and the stretching rod.
10. The method of manufacturing a degradable polylactic acid dropper according to claim 9, wherein when the stretching rod reaches the bottom, the pressure of the compressed air is adjusted to 0.6-4.0MPa to completely fill the device, so that the dropper takes the shape of a blow mold, and compressed nitrogen is continuously blown into the dropper before the dropper is taken out of the mold, and maintained for 2-20s to cool the dropper.
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