CN108774384B - Polylactic acid-based composite material and preparation method thereof - Google Patents
Polylactic acid-based composite material and preparation method thereof Download PDFInfo
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- CN108774384B CN108774384B CN201810544724.0A CN201810544724A CN108774384B CN 108774384 B CN108774384 B CN 108774384B CN 201810544724 A CN201810544724 A CN 201810544724A CN 108774384 B CN108774384 B CN 108774384B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
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- 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
- C08L2205/24—Crystallisation aids
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a polylactic acid-based composite material and a preparation method thereof, belonging to the field of processing of high-molecular composite materials. The preparation method of the polylactic acid-based composite material comprises the following steps: adding the filler, the reinforcing agent, the toughening agent and part of polylactic acid into a mixer, and premixing to obtain a premix; dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution; adding the premix into the extruder through the main feeding port, adding the remaining polylactic acid into the extruder from the side feeding port, and simultaneously adding SCCO2Adding the solution from the middle area of the extruder, and performing melt extrusion and granulation by the extruder to obtain the polylactic acid-based composite material. The invention prepares the nucleating agent into SCCO2The solution combines part of the feeding mode of the side feeding of the polylactic acid, so that the prepared polylactic acid-based composite material has the characteristics of high toughness and high strength; in addition, the polylactic acid-based composite material prepared by the invention can be biodegraded and recycled.
Description
Technical Field
The invention relates to a polylactic acid-based composite material and a preparation method thereof, belonging to the field of processing of high-molecular composite materials.
Background
In recent years, with the development of polymer industry, polymer materials are more and more favored by consumers due to the advantages of light weight, simplicity, low price and the like, the dosage is continuously increased, and the application field is more and more extensive. However, the degradation of the conventional polymer is difficult, which causes a serious problem of "white pollution".
Polylactic acid (PLA) is a completely biodegradable material and is concerned by scientific research institutions and enterprises in various countries. However, polylactic acid has a low crystallization rate, high brittleness, poor toughness and poor heat resistance, and thus, the application of polylactic acid in structural members and functional members is limited.
Chinese patent publication No. CN201310450893 discloses a 3D printing modified polylactic acid material and a preparation method thereof, wherein polylactic acid is modified by adding a cross-linking agent, a toughening agent and a reinforcing agent, but the modification method adopts low-temperature planetary ball mill grinding, the time consumption is long, the cost is high by adopting nitrogen for cooling, the working procedures are more, and the modification method is not suitable for large-scale industrial mass production. Meanwhile, the cross-linking agent is introduced in the modification method, so that the biodegradation time of the polylactic acid is prolonged.
Chinese patent publication No. CN101168617A discloses a method for toughening and modifying polylactic acid, which modifies polylactic acid by blending polylactic acid and toughening modifier in proportion, melting and extruding, but the modification method has the defects of poor dispersibility of the toughening agent in a polylactic acid matrix and poor modification effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a polylactic acid-based composite material, and the polylactic acid-based composite material prepared by the method has the characteristics of high toughness and high strength.
In addition, the invention also provides the polylactic acid-based composite material prepared by the method.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a polylactic acid-based composite material comprises the following steps:
adding the filler, the reinforcing agent, the toughening agent and part of polylactic acid into a mixer, and premixing to obtain a premix;
dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution;
adding the premix into the extruder through the main feeding port, adding the remaining polylactic acid into the extruder from the side feeding port, and simultaneously adding SCCO2Adding the solution from the middle area of the extruder, and performing melt extrusion and granulation by the extruder to obtain the polylactic acid-based composite material.
In the above preparation method, a part of the polylactic acid and the remaining part of the polylactic acid constitute the entire polylactic acid.
The invention adopts SCCO2Firstly, the nucleating agent is dissolved and then added to the middle part of an extruder to ensure that S isCCO2The solution and the polylactic acid are fully mixed and extruded in a closed high-pressure environment in the screw cylinder of the extruder, so that the contact area of the nucleating agent and the polylactic acid is increased, the dispersion and mixing of the nucleating agent in a polylactic acid matrix are enhanced, more number of fine and uniform crystal nuclei are induced to form, and the impact strength and the heat resistance of the polylactic acid-based composite material are improved. In addition, the polylactic acid is added into the extruder in a side feeding mode, so that the external lubrication effect of the melt at the rear section of the extruder is reduced, the friction resistance at the rear end is increased, the shearing is improved, and the dispersion of the filler in the polylactic acid is enhanced, thereby improving the toughness of the polylactic acid-based composite material.
The invention prepares the nucleating agent into SCCO2The solution is combined with a special feeding mode, so that the prepared polylactic acid-based composite material has the characteristics of high toughness and high strength. In addition, the polylactic acid-based composite material prepared by the invention can be biodegraded and recycled.
As a preferred embodiment of the preparation method of the polylactic acid-based composite material, the weight ratio of the polylactic acid, the filler, the reinforcing agent, the toughening agent and the nucleating agent is polylactic acid: filling agent: reinforcing agent: a toughening agent: a nucleating agent (60-90): (5-20): (1-4): (3-12): (1-4). Wherein the weight ratio of the polylactic acid is calculated according to the total polylactic acid.
As a preferred embodiment of the method for producing a polylactic acid-based composite material according to the present invention, at least one of the following (a) to (e):
(a) the weight average molecular weight of the polylactic acid is 5000-10000 g/mol;
(b) the filler is calcium carbonate, talcum powder, barium sulfate, diatomite or mica powder, and preferably talcum powder; the particle size of the filler is preferably 3-12 μm;
(c) the reinforcing agent is graphene, preferably graphene prepared by adopting an improved Hummers method, namely a reduced graphene oxide method;
(d) the toughening agent is poly adipic acid-1, 4-butanediol ester (PBA) or poly succinic acid-butanediol ester (PBS), and the PBA is more preferable;
(e) the nucleating agent is methylene bis (2, 4-di-tert-butylphenyl) aluminum phosphate or 2, 2' -methylene-bis (4, 6-di-n-butylphenol) sodium phosphate.
As a preferable embodiment of the method for preparing the polylactic acid-based composite material according to the present invention, the portion of the polylactic acid accounts for 70% to 90% by weight of the total polylactic acid.
As a preferred embodiment of the method for preparing the polylactic acid-based composite material according to the present invention, the method for preparing the premix comprises the steps of: (1) adding a part of the filler and a part of the polylactic acid into a mixer for mixing, and performing melt extrusion and granulation on the mixture obtained by mixing through an extruder to obtain master batches; (2) and (2) adding the master batch, the reinforcing agent, the toughening agent and part of the rest of the polylactic acid obtained in the step (1) into a mixer, and premixing to obtain the premix.
When the premix is prepared, a part of polylactic acid and the filler are prepared into master batches, so that the interface bonding capability of the filler and the polylactic acid matrix is enhanced, and the compatibility is greatly improved.
As a more preferred embodiment of the method for preparing the polylactic acid-based composite material according to the present invention, the method for preparing the premix comprises the steps of: (1) adding a part of the filler, the coupling agent and part of the polylactic acid into a mixer for mixing, and performing melt extrusion and granulation on the mixture obtained by mixing through an extruder to obtain master batches; (2) and (2) adding the master batch obtained in the step (1), the reinforcing agent, the toughening agent, the antioxidant, the plasticizer and part of the rest of the polylactic acid into a mixer, and premixing to obtain the premix.
When the premix is prepared, the coupling agent is further added, and the coupling agent plays a role of a bridge and is beneficial to improving the compatibility. Meanwhile, the antioxidant property of the polylactic acid-based composite material is improved by adding the antioxidant.
As a preferred embodiment of the preparation method of the polylactic acid-based composite material of the present invention, the coupling agent is a silane coupling agent, a titanate coupling agent, or a borate coupling agent, more preferably, the coupling agent is a titanate coupling agent; the antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (antioxidant CA), tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1035), and N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098); the plasticizer is ethylene hydroxyl bis stearamide.
As a preferable embodiment of the method for preparing a polylactic acid-based composite material according to the present invention, in the step (1), the polylactic acid added to the mixer accounts for 20% to 40% by weight of the total polylactic acid.
As a preferred embodiment of the method for preparing a polylactic acid-based composite material according to the present invention, the extruder comprises 12 zones, the premix is fed into the extruder through a main feeding port provided in zone 1, the remaining part of the polylactic acid is fed into the extruder through a side feeding port provided in zone five, and SCCO2The solution was added from zone 7 of the extruder. Wherein S isCCO2The solution may be fed to the extruder from a zone after the side-feeding of the polylactic acid, or from a zone before the side-feeding of the polylactic acid, e.g., SCCO2The solution may also be added from zone 3 of the extruder.
As a preferable embodiment of the method for producing a polylactic acid-based composite material according to the present invention, the extruder is a twin-screw extruder.
As a more preferable embodiment of the method for producing a polylactic acid-based composite material according to the present invention, the fourth zone of the extruder is provided with an air vent, the tenth zone is provided with an air vent, and the eleventh zone is provided with a vacuum extraction device.
As a more preferable embodiment of the method for producing a polylactic acid-based composite material according to the present invention, the extruder comprises a screw having a first zone provided with a large-lead single start screw, fourth, fifth and tenth zones provided with a large-lead double start screw, second, seventh and twelfth zones provided with a small-lead double start screw, third, sixth, eighth and ninth zones provided with a shear screw, and an eleventh zone provided with a small-lead double start screw having a large lead with a transition. Wherein the lead length of the large lead thread ranges from 20mm to 50mm, and the lead length of the small lead thread ranges from 10mm to 20 mm.
The invention also provides the polylactic acid-based composite material prepared by the method.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares the nucleating agent into SCCO2The solution combines part of the feeding mode of the side feeding of the polylactic acid, so that the prepared polylactic acid-based composite material has the characteristics of high toughness and high strength. In addition, the polylactic acid-based composite material prepared by the invention can be biodegraded and recycled.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In the following examples, the extruder used was a twin-screw extruder, specifically, the twin-screw extruder had a structure of: comprises 12 equal-length screw barrels (namely divided into 12 zones), a main feeding port is arranged in the first zone and is connected with a metering scale, an exhaust pressure relief port is arranged in the fourth zone, a side feeding port is arranged in the fifth zone and is connected with a side feeding motor, and a gas injection port is arranged in the seventh zone and is connected with SCCO2The solution storage is connected, the tenth area is provided with an air exhaust and pressure relief opening, and the eleventh area is provided with a vacuum extraction device.
The double-screw extruder comprises screws, wherein a first area of the double-screw extruder is provided with large-lead single-head threads, fourth, fifth and tenth areas are provided with large-lead double-head threads, second, seventh and twelfth areas are provided with small-lead double-head threads, third, sixth, eighth and ninth areas are provided with shearing threads, and an eleventh area is provided with small-lead transitional double-head threads with large leads. Wherein the lead length of the large lead thread ranges from 20mm to 50mm, and the lead length of the small lead thread ranges from 10mm to 20 mm.
Of course, the extruder used is not limited to the above twin-screw extruder, and other extruders having a main feeding port, a side feeding port and a liquid injection port may be used for the production of the polylactic acid-based composite material of the present invention.
In the following examples, the preparation raw materials of the polylactic acid-based composite material comprise the following components in parts by weight: 60-90 parts of polylactic acid, 5-20 parts of filler, 1-4 parts of reinforcing agent, 3-12 parts of toughening agent and 1-4 parts of nucleating agent. Wherein the polylactic acid is calculated by the weight part of the total polylactic acid.
In a preferred embodiment, the preparation raw materials of the polylactic acid-based composite material further comprise the following components in parts by weight: 1-5 parts of coupling agent, 0.5-2 parts of antioxidant and 0.5-1 part of plasticizer.
Example 1
In an embodiment of the preparation method of the polylactic acid-based composite material of the present invention, the preparation method of the polylactic acid-based composite material in this embodiment is:
(1) preparing graphene by adopting a Hummer' S method, namely a reduced graphene oxide method, wherein SDS (sodium dodecyl sulfate) is added for assisting dispersion when the graphene oxide is ultrasonically dispersed in water;
(2) adding the filler, the coupling agent and a part of polylactic acid into a high-speed mixer for mixing, wherein the mixing speed is 600RPM-900RPM, performing melt extrusion on the mixture obtained by mixing through a double-screw extruder, granulating, and drying until the moisture content is lower than 0.2% (the drying temperature is 80 ℃) to obtain master batches; wherein the temperature of the double-screw extruder is 190-210 ℃;
(3) adding all the master batches obtained in the step (2), graphene, a toughening agent, an antioxidant, a plasticizer and a part of polylactic acid into a high-speed mixer, wherein the mixing speed is 600RPM-900RPM, and premixing to obtain a premix;
(4) dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution;
(5) adding the premix into the twin-screw extruder through a main feeding port arranged in the 1 st zone, adding the rest part of polylactic acid into the extruder through a side feeding port arranged in the 5 th zone of the twin-screw extruder, and simultaneously adding SCCO2Pumping the solution from a 7 th zone of a double-screw extruder, performing melt extrusion and granulation by the double-screw extruder, and drying the granulated product in a dehumidification dryer at the temperature of 80 ℃ for 2-4 hours to obtain the polylactic acid-based composite material; wherein the rotating speed of the double-screw extruder is 450RPM, and the temperature of each temperature zone in the 1-12 zones of the extruder is respectively set as follows: 170 ℃, 220 ℃, 200 ℃, 220 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 210 ℃ and 220 ℃.
In the present example, specific selection and parts by weight of each raw material are shown in table 1.
Examples 2 to 3
The preparation method of the polylactic acid-based composite material according to examples 2 to 3 is the same as that of example 1, and the specific selection and parts by weight of each raw material in examples 2 to 3 are shown in table 1.
Meanwhile, the polylactic acid-based composite material obtained in examples 1 to 3 was injection molded into a sample bar, and the mechanical properties of the obtained finished product were tested, with the performance results shown in table 1.
Wherein the tensile strength test is in reference to standard GB/T1040-2006; the bending strength test reference standard GB/T9341-2008; the elastic modulus test reference standard GB/T1040-2006; the thermal deformation temperature test is referenced to GB/T1633-2000; the notch impact strength test is referred to standard GB/T1843-2008; the melt index test is referred to the GB/T3682-2000 standard.
TABLE 1
Example 4
The mechanical properties of the polylactic acid-based composite material are mainly determined by five raw materials of polylactic acid, a filling agent, a reinforcing agent, a toughening agent and a nucleating agent and preparation methods thereof, in the embodiment, the experimental group (according to the method of the invention), the first control group, the second control group and the third polylactic acid-based composite material of the control group are prepared by different methods respectively, and the influence of different preparation methods on the mechanical properties of the polylactic acid-based composite material under the same other conditions is investigated.
The preparation method of the experimental group polylactic acid-based composite material comprises the following steps:
(1) adding the filler, the reinforcing agent, the toughening agent and part of polylactic acid into a mixer, and premixing to obtain a premix;
(2) dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution;
(3) adding the premix into the extruder through the main feeding port, adding the remaining polylactic acid into the extruder from the side feeding port, and simultaneously adding SCCO2Adding the solution from the middle area of the extruder, and performing melt extrusion and granulation by the extruder to obtain the polylactic acid-based composite material.
Wherein, the polylactic acid in the step (1) accounts for 70 to 90 percent of the total weight of the polypropylene; in the step (3), the weight ratio of the polylactic acid added from the side feeding port to the total polylactic acid is 10-30%.
The preparation method of the control group polylactic acid-based composite material comprises the following steps: adding all polylactic acid, a filling agent, a reinforcing agent, a toughening agent and a nucleating agent into a high-speed mixer, and premixing to obtain a premix; and adding the premix into an extruder through a main feeding port, and performing melt extrusion and granulation through the extruder to obtain the polylactic acid-based composite material.
The preparation method of the polylactic acid-based composite material of the control group comprises the following steps: adding 70-90% of polylactic acid, filler, reinforcing agent, toughening agent and nucleating agent in the total polylactic acid into a high-speed mixer, and premixing to obtain a premix; and adding the premix into an extruder through a main feeding port, adding the rest polylactic acid into the extruder from a side feeding port, and performing melt extrusion and granulation through the extruder to obtain the polylactic acid-based composite material.
The preparation method of the control group of the polylactic acid-based composite material comprises the following steps: adding all polylactic acid, a filling agent, a reinforcing agent, a toughening agent and a nucleating agent into a high-speed mixer, and premixing to obtain a premix; dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution; adding premix into the extruder from a side feeding port, and simultaneously adding SCCO2Adding the solution from the middle area of the extruder, and performing melt extrusion and granulation by the extruder to obtain the polylactic acid-based composite material.
In the four methods, the weight average molecular weight of the polylactic acid is 5000-10000 g/mol; the reinforcing agent is graphene; the filler is calcium carbonate, talcum powder, barium sulfate, diatomite or mica powder, and the particle size of the filler is 3-12 mu m; the toughening agent is poly adipic acid-1, 4-butanediol ester or poly succinic acid-butanediol ester; the nucleating agent is methylene bis (2, 4-di-tert-butylphenyl) aluminum phosphate or 2, 2' -methylene-bis (4, 6-di-n-butylphenol) sodium phosphate;
drying the polylactic acid-based composite material prepared by the four methods in a dehumidification dryer at the temperature of 80 ℃ for 2-4 hours, carrying out injection molding on the dried finished product to form a sample strip, and testing the mechanical property of the obtained finished product according to the standard. The mechanical property results of the polylactic acid-based composite materials of the experimental group are shown in table 2; the mechanical property results of the control polylactic acid-based composite material are shown in table 3; the mechanical property results of the polylactic acid-based composite material of the control group are shown in table 4; the results of the mechanical properties of the control polylactic acid-based composite material are shown in table 5.
TABLE 2
TABLE 3
TABLE 4
TABLE 5
From the above tables 2 to 5Therefore, the tensile and impact properties, the heat distortion temperature and the like of the material are improved to different degrees by adding the modifiers such as the reinforcing agent, the nucleating agent, the filler, the toughening agent and the like. Simultaneously by side feeding polylactic acid, with SCCO2Compared with the method of adding the nucleating agent only by adopting a main feeding mode, the method has the advantages that the mechanical property, the thermal deformation temperature and the like of the material are obviously improved, and the method has the advantages.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The preparation method of the polylactic acid-based composite material is characterized by comprising the following steps:
1) adding the filler, the reinforcing agent, the toughening agent and part of polylactic acid into a mixer, and premixing to obtain a premix;
2) dissolving a nucleating agent in supercritical CO2In (1) to obtain SCCO2A solution;
3) adding the premix into the extruder through the main feeding port, adding the remaining polylactic acid into the extruder from the side feeding port, and simultaneously adding SCCO2Adding the solution from the middle area of the extruder, and performing melt extrusion and granulation by the extruder to obtain the polylactic acid-based composite material;
the weight ratio of the polylactic acid to the filler to the reinforcing agent to the toughening agent to the nucleating agent is as follows: filling agent: reinforcing agent: a toughening agent: a nucleating agent (60-90): (5-20): (1-4): (3-12): (1-4);
at least one of the following (a) to (e):
(a) the weight average molecular weight of the polylactic acid is 5000-10000 g/mol;
(b) the filler is calcium carbonate, talcum powder, barium sulfate, diatomite or mica powder;
(c) the reinforcing agent is graphene;
(d) the toughening agent is poly adipic acid-1, 4-butanediol ester or poly succinic acid-butanediol ester;
(e) the nucleating agent is methylene bis (2, 4-di-tert-butylphenyl) aluminum phosphate or 2, 2' -methylene-bis (4, 6-di-n-butylphenol) sodium phosphate.
2. The method for preparing a polylactic acid-based composite according to claim 1, wherein the portion of the polylactic acid in step 1) is 70 to 90% by weight of the total polylactic acid.
3. The method for preparing a polylactic acid-based composite material according to claim 1, wherein the method for preparing the premix comprises the steps of: (1) adding a part of the filler and a part of the polylactic acid into a mixer for mixing, and performing melt extrusion and granulation on the mixture obtained by mixing through an extruder to obtain master batches; (2) and (2) adding the master batch, the reinforcing agent, the toughening agent and part of the rest of the polylactic acid obtained in the step (1) into a mixer, and premixing to obtain the premix.
4. The method for preparing a polylactic acid-based composite material according to claim 3, wherein the method for preparing the premix comprises the steps of: (1) adding a part of the filler, the coupling agent and part of the polylactic acid into a mixer for mixing, and performing melt extrusion and granulation on the mixture obtained by mixing through an extruder to obtain master batches; (2) and (2) adding the master batch obtained in the step (1), the reinforcing agent, the toughening agent, the antioxidant, the plasticizer and part of the rest of the polylactic acid into a mixer, and premixing to obtain the premix.
5. The method for producing a polylactic acid-based composite material according to claim 4, wherein said coupling agent is a silane coupling agent, a titanate coupling agent, or a borate coupling agent; the antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tris (2, 4-di-tert-butylphenyl) phosphite, thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; the plasticizer is ethylene hydroxyl bis stearamide.
6. The method for producing a polylactic acid-based composite material according to any one of claims 3 to 5, wherein in the step (1), the polylactic acid added to the mixer accounts for 20 to 40% by weight of the total polylactic acid.
7. The method of preparing a polylactic acid-based composite according to claim 1, wherein the extruder comprises 12 zones, the premix is fed into the extruder through a main feeding port provided in the 1 st zone, the remaining part of the polylactic acid is fed into the extruder through a side feeding port provided in the fifth zone, and SCCO2The solution was added from zone 7 of the extruder.
8. A polylactic acid-based composite material obtained by the method according to any one of claims 1 to 7.
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| CN102352094A (en) * | 2011-09-20 | 2012-02-15 | 奇瑞汽车股份有限公司 | High-toughness and highly heat-resistant polylactic acid (PLA) alloy material and preparation method thereof |
| CN103205013A (en) * | 2013-03-22 | 2013-07-17 | 浙江工业大学 | Polymer supercritical carbon dioxide foaming nucleating agent and preparation method and application thereof |
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| CN102352094A (en) * | 2011-09-20 | 2012-02-15 | 奇瑞汽车股份有限公司 | High-toughness and highly heat-resistant polylactic acid (PLA) alloy material and preparation method thereof |
| CN103205013A (en) * | 2013-03-22 | 2013-07-17 | 浙江工业大学 | Polymer supercritical carbon dioxide foaming nucleating agent and preparation method and application thereof |
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