CN113817299B - PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof - Google Patents

PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof Download PDF

Info

Publication number
CN113817299B
CN113817299B CN202110948334.1A CN202110948334A CN113817299B CN 113817299 B CN113817299 B CN 113817299B CN 202110948334 A CN202110948334 A CN 202110948334A CN 113817299 B CN113817299 B CN 113817299B
Authority
CN
China
Prior art keywords
pla
chain extender
ionic
composite material
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110948334.1A
Other languages
Chinese (zh)
Other versions
CN113817299A (en
Inventor
王平
高尚
杨利
陈鑫亮
宋涛
凌嘉诚
葛倪林
丁运生
冯绍杰
孙晓红
刘超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Jianzhu University
Original Assignee
Anhui Jianzhu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Jianzhu University filed Critical Anhui Jianzhu University
Priority to CN202110948334.1A priority Critical patent/CN113817299B/en
Publication of CN113817299A publication Critical patent/CN113817299A/en
Application granted granted Critical
Publication of CN113817299B publication Critical patent/CN113817299B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/912Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/914Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a PLA-based blending composite material with an ion and chemical double cross-linking structure and a preparation method thereof, belonging to the technical and scientific fields of high polymer materials and being characterized in that the PLA-based blending composite material comprises the following raw materials in percentage by mass: 60% -64% of PLA; 20% -22% of biodegradable polyester elastomer; 2% -5% of a three-arm star-shaped ionic chain extender; 4% -5% of an ionic polymer; 3% -6% of multi-wall carbon nano-tubes; 2 to 4 percent of hydrolysis resistant agent. Firstly, carbon nanotubes with different surface states, PLA and a three-arm star-shaped ionic chain extender are blended to prepare a blending filler master batch, and then the master batch is blended with a biodegradable polyester elastomer, so that the carbon tubes migrate to the biodegradable polyester elastomer with lower melt viscosity under the dual actions of dynamics and thermodynamics, and a concentration gradient of the carbon tubes is formed at the interface of the PLA and the biodegradable polyester elastomer. According to the invention, the three-arm star-shaped ionic chain extender is compounded with the ionomer, so that the compatibility of blending components is improved, and simultaneously, a chemical crosslinking structure and an ionic crosslinking structure are constructed in a matrix of the blending composite material, so that the material has higher mechanical properties and dielectric properties.

Description

PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof
Technical Field
The invention belongs to the technical and scientific fields of high polymer materials, particularly relates to a modified polylactic acid material, and particularly relates to a PLA-based blending composite material which has high dielectric constant, high flexibility and high strength and has an ionic and chemical double crosslinking structure, and a preparation method thereof.
Background
With the rapid development of electronic information technology, conductive polymers and high molecular dielectric materials with excellent dielectric properties gradually attract people's attention and are widely applied in the electronic information industry. However, the abandonment of the traditional polymer dielectric material and devices has great influence on the environment, so how to prepare the environment-friendly polymer dielectric material is a hotspot of industrial development and scientific research at present. Polylactic acid (PLA) is one of the main materials for replacing the traditional non-degradable petroleum-based materials in scientific research and industrial fields due to the characteristics of nature and nature, but the PLA material is brittle and has poor conductivity, so that the PLA cannot meet the application requirements of high-performance electronic devices. At present, the toughness of the PLA material is improved by introducing an elastomer, the electrical property of the PLA material is enhanced by doping substances and non-substances, but the PLA material has poor compatibility and interface interaction, so that the strength of the PLA material is obviously reduced while the toughness is improved, and the PLA material has limited degree of improving the electrical property by doping and poor stability. CN109912949A discloses that poly butylene succinate diol based polyurethane prepolymer is usedMethod for modifying toughened PLA, patent CN104194294A, discloses a method for improving interfacial compatibility between PLA blend components by adding hyperbranched triazine, but the above patent has limited improvement on PLA mechanical properties, wherein the impact strength does not exceed 10kJ/m 2 And does not relate to the electrical properties of the material. CN102943315A discloses PLA conductive fiber prepared from conductive fillers such as carbon black, carbon nanotube, graphene, gas-phase carbon nanofiber, copper sulfide, cuprous sulfide and cuprous iodide, but the material prepared by the patent has the condition of uneven dispersion of the fillers and generally low mechanical strength of the composite material, and the electrical property of the material is mainly determined by the conductive fillers, but the influence of the ion interaction on the electrical property of the material is not involved, and meanwhile, the interaction between the fillers and the matrix and the dispersion state of the fillers in the matrix cannot be controlled.
Therefore, with the increasing environmental problems and the scientific development of polymer materials, a PLA-based blended composite material with high dielectric constant, high flexibility, high strength and an ionic and chemical double cross-linking structure has a wide prospect.
Disclosure of Invention
The invention discloses a PLA-based blending composite material with an ion and chemical double-crosslinking structure and a preparation method thereof, belonging to the technical and scientific fields of high polymer materials and being characterized in that the PLA-based blending composite material comprises the following raw materials in percentage by mass: 60% -64% of PLA; 20% -22% of biodegradable polyester elastomer; 2% -5% of a three-arm star-shaped ionic chain extender; 4% -5% of ionic polymer; 3% -6% of multi-wall carbon nano-tubes; 2 to 4 percent of hydrolysis resistant agent. Firstly, carbon nanotubes with different surface states, PLA and a three-arm star-shaped ionic chain extender are blended to prepare a blending filler master batch, and then the master batch is blended with a biodegradable polyester elastomer, so that the carbon tubes migrate to the biodegradable polyester elastomer with lower melt viscosity under the dual actions of dynamics and thermodynamics, and a concentration gradient of the carbon tubes is formed at the interface of the PLA and the biodegradable polyester elastomer. According to the invention, the three-arm star-shaped ionic chain extender is compounded with the ionomer, so that the compatibility of the blending components is improved, and simultaneously, a chemical crosslinking structure and an ionic crosslinking structure are constructed in the matrix of the blending composite material, so that the material is endowed with higher mechanical property and dielectric property.
The specific scheme is as follows:
a PLA-based blending composite material with an ion and chemical double-crosslinking structure is characterized in that the PLA-based blending composite material comprises the following raw materials in percentage by mass:
PLA 60%-64%;
20% -22% of biodegradable polyester elastomer; the biodegradable polyester elastomer is one or more polymers with high toughness, such as polybutylene terephthalate adipate (PBAT), polycaprolactone (PCL), polypropylene carbonate (PPC) and the like;
2% -5% of a three-arm star-shaped ionic chain extender;
4% -5% of an ionic polymer; the ionic polymer is one or a mixture of ethylene-methacrylate copolymer with cation of sodium, potassium, magnesium or zinc;
3% -6% of multi-wall carbon nano-tubes; the multi-walled carbon nanotube is one or a mixture of more of a carbon nanotube with hydroxyl, amino and carboxyl grafted on the surface and a conventional multi-walled carbon nanotube without surface treatment;
2% -4% of an anti-hydrolysis agent; the main component of the hydrolysis resistant agent is one or more of polycarbodiimide and other imine compounds;
the three-arm star-shaped ionic chain extender is a three-arm star-shaped compound containing a quaternary ammonium ion ring structure and an epoxy group as shown in a formula II;
Figure BDA0003217648760000031
further, the melt mass flow rate of the PLA is 2g/10min-40g/10min under the test conditions that the temperature is 210 ℃ and the load weight is 2.16kg, the flexural modulus is 100-150MPa, the elastic modulus is 3000-4000MPa, the tensile strength is 40-60MPa, the elongation at break is 4-10%, the melting point is 155-180 ℃, and the density is 1.2-1.3g/cm 3
Further, the elastomer has a density of 0.9 to 1.3g/cm 3 The melt mass flow rate is 3g/10min-43g/10min at a temperature of 190 ℃ under the test conditions of a load weight of 2.16 kg. The crystallization temperature is 50-115 ℃, the melting point is 60-130 ℃, the crystallinity is 25-40%, and the Shore hardness (A) is 40-90.
Further, the ionic polymer is one or a mixture of ethylene-methacrylate copolymer with cation of sodium, potassium, magnesium or zinc. The ionomer has a density of 0.92 to 1.22g/cm 3 The melt mass flow rate is 0.5g/10min-10g/10min under the test conditions of the temperature of 190 ℃ and the load weight of 2.16kg, and the melting point is 60-110 ℃.
Furthermore, the multi-walled carbon nanotube is one or a mixture of more of a carbon nanotube with hydroxyl, carboxyl and amino grafted on the surface and a conventional multi-walled carbon nanotube without surface treatment, the diameter is 4-6 nanometers, the purity is more than 98 percent, and the length is 10-20 micrometers.
Furthermore, the main component of the hydrolysis resistant agent is one or more of polycarbodiimide and other imine compounds. The molecular weight is 360-400g/mol, and the density is 1.02-1.05g/cm 3 The melting temperature is 60-100 ℃, and the content of carbodiimide is more than 12%.
Further, a preparation method for preparing the PLA-based blended composite material is characterized by comprising the following steps: firstly, performing vacuum drying on PLA, a biodegradable polyester elastomer and an ionomer at 60 ℃ for 12 hours to remove water, controlling the water content of all materials to be lower than 200ppm, then adding the PLA, a multi-walled carbon nanotube and a three-arm star-shaped ionic chain extender into a high-speed mixer in proportion, blending at the rotating speed of 4000-5000r/min, stopping blending when the surface of the PLA is softened and slightly melted and the carbon nanotube and the three-arm star-shaped ionic chain extender are coated on the surface of the PLA, then adding the mixture into a double-screw extruder at the temperature of 140-210 ℃ for melt blending extrusion, and granulating after air cooling at 40-50 ℃ to obtain the blended filler master batch. And then the master batch, the biodegradable polyester elastomer, the ionomer, the anti-hydrolysis agent and the like are fully mixed in a high-speed mixer at the rotating speed of 2000-4000r/min, then melt extrusion is carried out in a double-screw extruder at the temperature of 130-200 ℃, and air cooling granulation at the temperature of 30-40 ℃ is carried out to obtain the PLA-based blending composite material with the ionic and chemical double cross-linking structure.
Further, the method also comprises a step of preparing the three-arm star-shaped ionic chain extender, and specifically comprises the following steps:
step a, adding an ammonium hydroxide aqueous solution into a flask provided with a thermometer and a stirring device, then dropwise adding propargyl bromide into the aqueous solution, reacting at room temperature for 3 hours, and precipitating ammonium bromide, wherein the solution is yellow in color; then stirring the mixture at room temperature for 24 hours, raising the temperature to 50 ℃, continuing stirring for 48 hours, and finishing the reaction after the propargyl bromide completely reacts; the product is subsequently extracted 3 times with diethyl ether and dried over sodium sulfate, and finally the residue is purified by column chromatography with a diethyl ether/hexane volume ratio of 1:1;
and step b, adding the triperopargylamine prepared in the step a into a flask containing a mixed solvent of N, N, N' -Pentamethyldivinyltriamine (PMDETA) and N, N-Dimethylformamide (DMF), heating to 90 ℃, slowly dropwise adding 3- (azidomethyl) -2, 2-dimethyl-ethylene oxide, and reacting for 48 hours. After the reaction is finished, cooling the reactant to room temperature, pouring the reactant into deionized water, extracting the reactant with DMF for multiple times, extracting the reactant twice with deionized water and saturated NaCl solution respectively, extracting and washing the reactant with anhydrous Na 2 SO 4 Drying overnight, filtering, and evaporating the solvent under reduced pressure to obtain a compound (I);
Figure BDA0003217648760000061
step c, slowly dropwise adding dimethyl sulfate into the compound (I) prepared in the step b, and stirring and reacting at the constant temperature of 60 ℃ for 24 hours; and (3) cooling to room temperature after the reaction is finished, adding deionized water, standing, precipitating a solid, performing suction filtration, washing with deionized water, recrystallizing with methanol-water, and drying. Preparing a compound (II), namely the three-arm star-shaped ionic chain extender;
Figure BDA0003217648760000062
the invention has the following beneficial effects:
1) The three-arm star-shaped ionic chain extender is a three-arm star-shaped compound containing quaternary ammonium ions and epoxy groups at the same time, and the ionic elements in the chain extender can improve the reaction efficiency of the epoxy groups and terminal hydroxyl and terminal carboxyl in PLA and biodegradable polyester in the blending process, so that a chemical crosslinking structure is formed in a matrix, and the compatibility of the PLA and an elastomer is improved. Meanwhile, quaternary ammonium cation and counter ion can interact with cation and counter ion in the ionomer through static electricity, hydrogen bond and the like to form an ionic crosslinking structure in a polymer matrix. The chemical and ionic crosslinking structure endows the material with high toughness and strength.
2) Under the catalytic action of the three-arm star-shaped ionic chain extender, active groups on the surface of the functionalized carbon nano tube can respectively perform physical/chemical actions with PLA, the biodegradable polyester elastomer and the chain extender, so that the dispersion performance of the functionalized carbon nano tube in a matrix is improved, and the electrical property of the material is improved. In addition, the three-arm star-shaped ionic chain extender and an ionic crosslinking network formed by ionic elements in the ionomer and the conjugation of the ionic elements and the carbon tubes can strengthen the interaction between the carbon tubes and the matrix and further improve the electrical property of the PLA-based composite material from the material body.
3) In the aspect of processing technology, firstly, carbon nano tubes with different surface states, PLA and a three-arm star-shaped ionic chain extender are mixed at a high speed, in the high-speed mixing process, the polymer surface is subjected to micro-melting under the action of strong friction force, and the chain extender and the filler are coated on the surface of the micro-melted polymer and subjected to chain extension and coupling reaction. And then, preparing the filler master batch by melt extrusion and temperature-controllable hot air drying processes, wherein the master batch is dried in a hot air environment, the moisture content is extremely low, and the PLA can be pre-crystallized. When the master batch and the biodegradable polyester elastomer are subjected to melt blending and extrusion, the PLA crystal can regulate and control the aggregation structure of the biodegradable polyester, and the carbon tube can migrate to the biodegradable polyester elastomer with lower melt viscosity under the dual actions of dynamics and thermodynamics, so that the concentration gradient of the carbon tube is formed at the interface of the PLA and the biodegradable polyester elastomer, and the controllable dispersion of inorganic fillers such as the carbon tube and the like in a matrix is realized. Finally, the compatibility of the blending components is improved, and simultaneously, a chemical crosslinking structure and an ionic crosslinking structure are constructed in the matrix of the blending composite material, so that the material is endowed with higher mechanical property and dielectric property.
4) The PLA blending composite material has higher toughness and rigidity, and the dielectric property of the material is excellent, so that the PLA blending composite material has wide prospects in the aspects of electrode materials, electromagnetic shielding materials, sensor materials, electrochromic materials and the like.
Drawings
FIG. 1a is a flow chart of a synthetic structure of a three-arm star-shaped ionic chain extender, a structural formula of an intermediate (I) in FIG. 1b, and a structural formula of a product (II) in FIG. 1c
FIG. 2 three-armed star-shaped ionic chain extender 1 H-NMR spectrum
FIG. 3 TEM morphologies of various examples and comparative examples
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
The following examples used the raw materials:
PLA, polylactic acid, wherein the MFR of the polylactic acid is 7g/10min under the test conditions that the temperature is 210 ℃ and the load weight is 2.16kg, the elongation at break is 6 percent, the notch impact strength is 0.3J/m, the melting point is 175 ℃, and the density is 1.22g/cm 3 4032D from Nature Works, USA is selected.
PBAT polybutylene adipate terephthalate with density of 1.2g/cm 3 The MFR of the modified polyolefin is 43g/10min under the test conditions of the temperature of 190 ℃ and the load weight of 2.16kg, and the modified polyolefin is selected from Guangzhou Jinfa science and technology GmbH in China.
PCL: polycaprolactone with a density of 1.146g/cm 3 The MFR is 3g/min at 160 ℃ under the test conditions with a load weight of 2.16kg, 6500 from Perstorp, sweden.
The three-arm star-shaped ionic chain extender is as follows: a three-arm star-shaped compound containing a quaternary ammonium ion ring structure and an epoxy group is prepared by the following steps:
step a, adding an ammonium hydroxide aqueous solution into a flask provided with a thermometer and a stirring device, then dropwise adding propargyl bromide into the aqueous solution, reacting at room temperature for 3 hours, and precipitating ammonium bromide, wherein the solution is yellow in color; then stirring the mixture at room temperature for 24 hours, raising the temperature to 50 ℃, continuing stirring for 48 hours, and finishing the reaction after the propargyl bromide completely reacts; the product is subsequently extracted 3 times with diethyl ether and dried over sodium sulfate, and finally the residue is purified by column chromatography with a diethyl ether/hexane volume ratio of 1:1;
and b, adding the tripropargylamine prepared in the step a into a flask containing a mixed solvent of N, N, N' -pentamethyl divinyl triamine (PMDETA) and N, N-dimethyl formamide (DMF), heating to 90 ℃, slowly dropwise adding 3- (azidomethyl) -2, 2-dimethyl-ethylene oxide, and reacting for 48 hours. After the reaction is finished, cooling the reactant to room temperature, pouring the reactant into deionized water, extracting the reactant with DMF for multiple times, extracting the reactant twice with deionized water and saturated NaCl solution respectively, extracting and washing the reactant with anhydrous Na 2 SO 4 Drying overnight, filtering, and evaporating the solvent under reduced pressure to obtain a compound (I);
Figure BDA0003217648760000091
step c, slowly dropwise adding dimethyl sulfate into the compound (I) prepared in the step b, and stirring and reacting at the constant temperature of 60 ℃ for 24 hours; and (3) cooling to room temperature after the reaction is finished, adding deionized water, standing, precipitating a solid, performing suction filtration, washing with deionized water, recrystallizing with methanol-water, and drying. Preparing a compound (II), namely the three-arm star-shaped ionic chain extender;
Figure BDA0003217648760000101
the ionomers used were:
surlyn 8920: is an ethylene-methacrylic acid copolymer containing sodium ions: the density was 0.95g/cm 3 The MFR is 0.9g/10min at 190 ℃ under the test conditions of a load weight of 2.16kg, the melting point is 88 ℃ and 8920 from DuPont, USA is selected.
The multi-walled carbon nanotubes used were:
MWCNTs: the purity is 95%, the length is 10-20 microns, and XFM01 of Jiangsu Xiancheng nano material science and technology Limited is selected.
MWCNT-COOH: 95% purity, 10-20 micron length, and adopting XFM33 of Jiangsu Xiancheng nanometer material science and technology Limited.
MWCNT-OH: 98 percent of purity and 10 to 20 microns of length, and XFM68 of Jiangsu Xiancheng nano material science and technology Limited company is selected.
The hydrolysis resistant agent is:
hyadimide 100: the chemical component is polymeric carbodiimide with the density of 1.05g/cm 3 The melting temperature is 100 ℃, and Hyadimide 100 of Rhein-Schafer Germany is selected.
Hyadimide 1001: the chemical component is an imine compound with the density of 1.02g/cm 3 The melting temperature is 60-80 ℃, and Hyadimide 1001 of Rhein-Schafer Germany is selected.
The traditional chain extenders used were:
ADR: the molar mass is 5500g/mol, the epoxy equivalent is 445g/mol, the glass transition temperature is 56 ℃, and German BASF 4300 is selected.
The mass percent ratio of each raw material in the following examples is shown in table 1.
TABLE 1 materials and amounts (in weight percent) of PLA-based blended composites
Figure BDA0003217648760000111
Figure BDA0003217648760000121
Example 1
In this embodiment, the materials and formulation of the PLA-based blended composite material are shown in table 1, and the preparation method comprises the following steps:
firstly, performing vacuum drying on PLA, a biodegradable polyester elastomer and an ionomer at 60 ℃ for 12 hours to remove water, controlling the water content of all materials to be lower than 200ppm, then adding the PLA, a multi-wall carbon nano tube and a three-arm star-shaped ionic chain extender into a high-speed mixer in proportion, blending at the rotating speed of 4000r/min, stopping blending when the surface of the PLA is softened and slightly melted and the carbon nano tube and the three-arm star-shaped ionic chain extender are coated on the surface of the PLA, then adding the mixture into a double-screw extruder at the temperature of 140-210 ℃ for melt blending extrusion, and granulating after air cooling at the temperature of 40-50 ℃ to obtain the blended filler master batch. And then fully mixing the master batch with a biodegradable polyester elastomer, an ionomer, an anti-hydrolysis agent and the like in a high-speed mixer at the rotating speed of 3000r/min, then performing melt extrusion in a twin-screw extruder at the temperature of 130-200 ℃, and performing air cooling granulation at the temperature of 30-40 ℃ to obtain the PLA-based blending composite material with an ionic and chemical double-crosslinking structure.
Example 2
In this example, the materials and formulation of PLA-based blended composite material are shown in Table 1, and the preparation process is the same as that of example 1
Example 3
The materials and formulation of the PLA-based blended composite material of this example are shown in Table 1, and the preparation process is the same as that of example 1
Comparative example 1
The materials and formulation of PLA-based blended composite material of this comparative example are shown in Table 1, and the preparation process is the same as that of example 1
Comparative example 2
The materials and formulation of PLA-based blended composite material of this comparative example are shown in Table 1, and the preparation process is the same as that of example 1
Comparative example 3
The materials and formulation of PLA-based blended composite material of this comparative example are shown in Table 1, and the preparation process is the same as that of example 1
Comparative example 4
The materials and the formula of the PLA-based blended composite material in the comparative example are shown in Table 1, and the preparation method comprises the following steps:
PLA, biodegradable polyester elastomer, ionomer were first vacuum dried at 60 ℃ for 12 hours to remove water, controlling the water content of all materials below 200ppm. PLA, biodegradable polyester elastomer, ionomer, carbon nano tube, chain extender and anti-hydrolysis agent are added into a high-speed mixer with the rotating speed of 2000r/min in proportion for full mixing, and then melt extrusion granulation is carried out in a double-screw extruder with the temperature of 130-200 ℃ to prepare the material.
Comparative example 5
The materials and formulation of PLA-based blended composite material of this comparative example are shown in Table 1, and the preparation process is the same as that of comparative example 4.
Test and results
The materials prepared in the above examples and comparative examples were cut to prepare test specimens, wherein the test methods were:
tensile strength: testing according to ISO527 standard, wherein the speed is 50mm/min;
elongation at break: testing according to ASTM D638, with a speed of 10mm/min;
notched impact strength: the pendulum mass is 0.668kg, the speed is 0.46m/s and the pendulum energy is 4J according to the test of the ASTM D256 standard;
conductivity: testing according to GB/T11007 standard;
dielectric constant: the frequency range is 20Hz-2 MHz and the temperature range is 30-80 ℃ according to the test of ASTM A893 standard.
The test results are shown in table 2, with example 3 having the best overall performance. The performance of example 1 is inferior to that of example 3 under the condition of the same content of the carbon nanotubes, because the content of the three-arm star-shaped ionic chain extender is lower than that of example 3, and the regulation effect on the carbon nanotubes is not obvious. In example 2, compared with example 3, the reduction of the content of the carbon nanotubes not only reduces the electrical property, but also reduces the mechanical property of the material, which shows that the filler carbon nanotubes have a reinforcing effect on the material. Comparative example 1 does not use any chain extender and is inferior in performance. Comparative example 3 only uses the traditional chain extender ADR, and finds that the interfacial dispersion state is difficult to regulate and control, and the comprehensive performance of the material is poor. Comparative example 2 introduces a three-arm star-shaped ionic chain extender on the basis of the above, and the effect of regulating and controlling is found to be achieved, but the performance is poorer than that of example 3. In conclusion, the superiority of the formulation designed in example 3 is shown.
The examples 2 and 3 have the same formula as the comparative examples 4 and 5 but have different preparation processes and have larger performance difference. The reason is that the traditional blending method is difficult to realize the controllable dispersion of the carbon tube in the matrix, and embodies the superiority of the preparation process.
The TEM appearances of different samples are shown in FIG. 3, and in example 3, the carbon nanotubes are uniformly dispersed at the interface of two phases to play a role in adhesion and increase the interaction between the two phases. In example 1, the content of the three-arm star-shaped ionic chain extender is less, so that the three-arm star-shaped ionic chain extender has a certain regulation and control effect on the carbon nanotubes, but a small amount of aggregation can still be seen. In example 2, the reinforcing effect was insufficient because the adhesion effect to the two phases at the interface was insufficient due to the small content of the carbon nanotubes. Comparative example 1a large amount of agglomeration of carbon nanotubes in the polyester elastomer was seen because no chain extender was added. Comparative example 3 using a conventional chain extender ADR, it was found that carbon nanotubes were dispersed in a polyester elastomer, but it was difficult to play a role in migration control. In comparative example 2, a part of the three-arm star-shaped ionic chain extender is added on the basis, and the carbon nano tube is found to begin to migrate, but the effect is not obvious enough. In conclusion, the formulation of example 3 is superior.
The carbon nanotubes in comparative examples 4 and 5, which use the conventional blending process, are dispersed randomly, and can be agglomerated both inside the polyester elastomer and at the interface of two phases, which has adverse effects on the properties of the material. Thereby showing the superiority of the material preparation process.
The analysis of the test data shows that the mechanical property of the PLA-based blended composite material is greatly improved, and the following reasons exist: (1) The epoxy group in the chain extender reacts with hydroxyl and carboxyl in PLA and the elastomer, the quaternary ammonium ion and the ionomer play a role in promoting the reaction, the compatibility between the two phases is improved, and the force is uniformly transmitted when the chain extender is acted by the force. (2) After the chain extender is added, the material forms chemical crosslinking, the interaction between ions forms ionic crosslinking, and the two have synergistic action, so that a large amount of energy is absorbed when force is applied to the material, and meanwhile, the rigidity and the toughness of the material are improved. (3) The space structure contains a large number of annular structures, and the strength of the material is improved.
According to analysis of combined test data, the electrical property of the PLA-based blended composite material is greatly improved, and the PLA-based blended composite material has the following reasons: (1) The ions and the carbon nano tubes form ionic interaction, so that the carbon nano tubes are uniformly dispersed; (2) A specific processing technology induces the carbon nano tube to migrate between two phases, so as to achieve the purposes of thermodynamics and kinetic regulation and control; (3) The presence of the ionic crosslinked network in the matrix further improves the electrical properties of the material.
Therefore, as can be seen from the tensile strength, elongation at break, notch impact strength, conductivity and dielectric constant results in each embodiment and the comparative example, the biodegradable polyester elastomer, the three-arm star-shaped ionic chain extender, the ionomer, the multi-wall carbon nanotube and the anti-hydrolysis agent are added for compound use, so that the problem of material strength reduction during toughening of polylactic acid is solved, the material is endowed with excellent electrical property, the application range and the field of the polylactic acid composite material are expanded, and the polylactic acid composite material has wide prospects in special fields such as electrode materials, electromagnetic shielding materials, sensor materials, electrochromic materials and even stealth materials.
TABLE 2 Performance test results for each PLA-based blended composite example
Figure BDA0003217648760000151
Figure BDA0003217648760000161
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.

Claims (8)

1. A PLA-based blending composite material with an ion and chemical double-crosslinking structure is characterized in that the PLA-based blending composite material comprises the following raw materials in percentage by mass:
PLA 60%-64%;
20% -22% of biodegradable polyester elastomer; the biodegradable polyester elastomer is one or more polymers with high toughness of polybutylene terephthalate adipate (PBAT), polycaprolactone (PCL) and polypropylene carbonate (PPC);
2% -5% of a three-arm star-shaped ionic chain extender;
4% -5% of an ionic polymer; the ionic polymer is one or a mixture of ethylene-methacrylate copolymer with cation of sodium, potassium, magnesium or zinc;
3% -6% of multi-wall carbon nano-tubes; the multi-walled carbon nanotube is one or a mixture of more of a carbon nanotube with hydroxyl, amino and carboxyl grafted on the surface and a conventional multi-walled carbon nanotube without surface treatment;
2% -4% of an anti-hydrolysis agent; the main component of the hydrolysis resistant agent is polycarbodiimide;
the three-arm star-shaped ionic chain extender is a three-arm star-shaped compound containing a quaternary ammonium ion ring structure and an epoxy group as shown in a formula II;
Figure DEST_PATH_IMAGE001
the PLA-based blended composite material is prepared by the following method, and the method comprises the following steps: firstly, PLA, a biodegradable polyester elastomer and an ionomer are dried in vacuum at 60 ℃ for 12 hours to remove water, the water content of all materials is controlled to be lower than 200ppm, then the PLA, a multi-wall carbon nano tube and a three-arm star-shaped ionic chain extender are proportionally added into a high-speed mixer and blended at the rotating speed of 4000-5000r/min, softening and micro-melting are carried out on the surface of the PLA, the carbon nano tube and the three-arm star-shaped ionic chain extender are coated on the surface of the PLA, blending is stopped, then the mixture is added into a double-screw extruder at the temperature of 140-210 ℃ to carry out melt blending extrusion, air cooling and granulation are carried out at 40-50 ℃ to obtain a blended filler master batch, then the master batch, the biodegradable polyester elastomer, the ionomer and the hydrolysis-resistant agent are fully mixed in the high-speed mixer at the rotating speed of 2000-4000r/min, then melt extrusion is carried out in the double-screw extruder at the temperature of 130-200 ℃, and air cooling and granulation is carried out at 30-40 ℃ to obtain the PLA-based blended composite material with an ionic and a dual-chemical cross-linking structure.
2. The PLA-based blended composite of claim 1, wherein: the melt mass flow rate of the PLA is 2g/10min-40g/10min under the test conditions that the temperature is 210 ℃ and the load weight is 2.16kg, the flexural modulus is 100-150MPa, the elastic modulus is 3000-4000MPa, the tensile strength is 40-60MPa, the elongation at break is 4-10%, the melting point is 155-180 ℃, and the density is 1.2-1.3g/cm 3
3. The PLA-based blended composite according to any one of claims 1-2, wherein: the density of the biodegradable polyester elastomer is 0.9-1.3g/cm 3 The melt mass flow rate is 3g/10min-43g/10min under the test conditions of the temperature of 190 ℃ and the load weight of 2.16kg, the crystallization temperature is 50-115 ℃, the melting point is 60-130 ℃, the crystallinity is 25-40 percent, and the Shore hardness (A) is 40-90.
4. The PLA-based blended composite of claim 1, wherein: the ionic polymer is one or a mixture of ethylene-methacrylate copolymer with cation of sodium, potassium, magnesium or zinc; the density of the ionic polymer is 0.92-1.22g/cm 3 The melt mass flow rate is 0.5g/10min-10g/10min under the test conditions of the temperature of 190 ℃ and the load weight of 2.16kg, and the melting point is 60-110 ℃.
5. The PLA-based blended composite material according to claim 1, wherein: the multi-wall carbon nano tube is one or a mixture of several of a carbon nano tube with hydroxyl, carboxyl and amino grafted on the surface and a conventional multi-wall carbon nano tube without surface treatment, the diameter is 4-6 nanometers, the purity is more than 98 percent, and the length is 10-20 micrometers.
6. The PLA-based blended composite of claim 1, wherein: the main component of the hydrolysis resistant agent is polycarbodiimide, the molecular weight is 360-400g/mol, and the density is 1.02-1.05g/cm 3 The melting temperature is 60-100 ℃, and the content of carbodiimide is more than 12%.
7. A process for preparing a PLA-based blended composite as claimed in any one of claims 1-6, the process comprising the steps of: firstly, performing vacuum drying on PLA, a biodegradable polyester elastomer and an ionomer at 60 ℃ for 12 hours to remove water, controlling the water content of all materials to be lower than 200ppm, then adding the PLA, a multi-walled carbon nanotube and a three-arm star-shaped ionic chain extender into a high-speed mixer in proportion, blending at the rotating speed of 4000-5000r/min, stopping blending when the surface of the PLA is softened and micro-melted, and the carbon nanotube and the three-arm star-shaped ionic chain extender are coated on the surface of the PLA, then adding the mixture into a double-screw extruder at the temperature of 140-210 ℃ for melt blending extrusion, performing air cooling at 40-50 ℃ for granulation to obtain a blended filler master batch, then fully mixing the master batch, the biodegradable polyester elastomer, the ionomer and the anti-hydrolysis agent in the high-speed mixer at the rotating speed of 2000-4000r/min, performing melt extrusion in the double-screw extruder at the temperature of 130-200 ℃, and performing air cooling granulation at 30-40 ℃ to obtain the PLA-based blended composite material with an ionic and chemical double cross-linked structure.
8. The method of claim 7, further comprising the step of preparing the three-arm star ionic chain extender, specifically comprising the steps of:
step a, adding an ammonium hydroxide aqueous solution into a flask provided with a thermometer and a stirring device, then dropwise adding propargyl bromide into the aqueous solution, reacting at room temperature for 3 hours, and precipitating ammonium bromide, wherein the solution is yellow in color; then stirring the mixture at room temperature for 24 hours, raising the temperature to 50 ℃, continuing stirring for 48 hours, and finishing the reaction after the propargyl bromide completely reacts; the product is subsequently extracted 3 times with diethyl ether and dried over sodium sulfate, and finally the residue is purified by column chromatography with a diethyl ether/hexane volume ratio of 1:1;
b, adding the tripropargylamine prepared in the step a into a flask containing a mixed solvent of N, N, N ', N ' ', N ' ' -pentamethyl divinyl triamine (PMDETA) and N, N-dimethyl formamide (DMF), heating to 90 ℃, slowly dropwise adding 3- (azidomethyl) -2, 2-dimethyl-ethylene oxide, reacting for 48 hours, cooling the reactant to room temperature after the reaction is finished, pouring the reactant into deionized water, extracting the reactant with DMF for multiple times, extracting the reactant twice with the deionized water and saturated NaCl solution respectively, extracting and washing the reactant with anhydrous Na 2 SO 4 Drying overnight, filtering, and evaporating the solvent under reduced pressure to obtain a compound (I);
Figure 602337DEST_PATH_IMAGE002
step c, slowly dropwise adding dimethyl sulfate into the compound (I) prepared in the step b, and stirring and reacting at the constant temperature of 60 ℃ for 24 hours; cooling to room temperature after the reaction is finished, adding deionized water, standing, precipitating a solid, performing suction filtration, washing with deionized water, recrystallizing with methanol-water, and drying to obtain a compound (II), namely the three-arm star-shaped ionic chain extender;
Figure DEST_PATH_IMAGE003
CN202110948334.1A 2021-08-18 2021-08-18 PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof Active CN113817299B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110948334.1A CN113817299B (en) 2021-08-18 2021-08-18 PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110948334.1A CN113817299B (en) 2021-08-18 2021-08-18 PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113817299A CN113817299A (en) 2021-12-21
CN113817299B true CN113817299B (en) 2022-12-13

Family

ID=78922893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110948334.1A Active CN113817299B (en) 2021-08-18 2021-08-18 PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113817299B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116355373A (en) * 2023-04-20 2023-06-30 四川大学 Polylactic acid-based composite material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1076306A (en) * 1965-04-28 1967-07-19 Hoffmann La Roche A process for the manufacture of isocryptoxanthin and echinenone
EP0197432A2 (en) * 1985-03-29 1986-10-15 Merck & Co. Inc. Enantioselective process for producing 1-beta-methylcarbapenem antibiotic intermediates
WO1994006863A1 (en) * 1992-09-11 1994-03-31 Eastman Chemical Company A process for preparing high impact strength poly(1,4-cyclohexylenedimethylene terephthalate)/ionomer blends
CN109679162A (en) * 2018-11-30 2019-04-26 长春安旨科技有限公司 A kind of water lubricating bearing material and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150361258A1 (en) * 2013-01-22 2015-12-17 University Of Guelph Poly (lactic acid)-based biocomposite materials having improved toughness and heat distortion temperature and methods of making and using thereof
CN105623214B (en) * 2016-01-13 2018-01-12 广州市海珥玛植物油脂有限公司 One kind plasticising Biodegradable polyester film and preparation method thereof
WO2019105413A1 (en) * 2017-12-01 2019-06-06 江南大学 Polyester composite material and preparation method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1076306A (en) * 1965-04-28 1967-07-19 Hoffmann La Roche A process for the manufacture of isocryptoxanthin and echinenone
EP0197432A2 (en) * 1985-03-29 1986-10-15 Merck & Co. Inc. Enantioselective process for producing 1-beta-methylcarbapenem antibiotic intermediates
WO1994006863A1 (en) * 1992-09-11 1994-03-31 Eastman Chemical Company A process for preparing high impact strength poly(1,4-cyclohexylenedimethylene terephthalate)/ionomer blends
CN109679162A (en) * 2018-11-30 2019-04-26 长春安旨科技有限公司 A kind of water lubricating bearing material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
弹性体共混改性聚乳酸(PLA)高韧性共混物研究进展;赵西坡等;《材料导报》;20191125;第590-598页 *
聚己二酸对苯二甲酸丁二酯(PBAT)共混改性聚乳酸(PLA)高性能全生物降解复合材料研究进展;王鑫等;《材料导报》;20190610(第11期);第1897-1909页 *

Also Published As

Publication number Publication date
CN113817299A (en) 2021-12-21

Similar Documents

Publication Publication Date Title
Liu et al. Properties of rosin-based waterborne polyurethanes/cellulose nanocrystals composites
US20150104642A1 (en) Production method of electrically conductive graphene composite fiber
CN108166095B (en) Hydrophilic antistatic graphene modified polyester chip and preparation method thereof
EP3202848B1 (en) Composite polyester material, composite polyester fibre, preparation method therefor and use thereof
CN105002595A (en) Polymer composite function fibers containing partial graphene, and preparation method thereof
CN113445154B (en) Flame-retardant low-melting-point polyester fiber and preparation method thereof
CN111690240A (en) Polylactic acid/nano cellulose composite material and preparation method thereof
CN105504713B (en) A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere
CN109233230B (en) Organic/inorganic hybrid modified polylactic acid membrane material and preparation method thereof
CN104177696A (en) Filling material master batch used for non-woven fabrics and preparing process thereof
CN113817299B (en) PLA-based blended composite material with ion and chemical double-crosslinking structure and preparation method thereof
Xia et al. Effects of chain extender and uniaxial stretching on the properties of PLA/PPC/mica composites
CN108912659B (en) Preparation method of crosslinked three-dimensional carbon nano composite polyurethane material
CN109913965B (en) In-situ self-assembly cellulose/graphene composite fiber of co-alkali system and preparation method thereof
CN113337087B (en) High-performance polyester alloy material and preparation method thereof
CN112266592B (en) High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof
CN107163519B (en) High-strength and droplet-resistant graphene/PET composite board and preparation method thereof
CN104017346A (en) Method for preparing high-ductility polymer blend alloy by melt blending
CN113214591A (en) Phosphorus-doped graphene modified ABS/PET alloy material and preparation method thereof
CN109853065B (en) Graphene composite fiber and preparation method thereof
CN104974423A (en) Diatomite/polypropylene composite material and preparation method thereof
CN109440219B (en) Regenerated polyester fiber containing metal modified cross-shaped esterified substance and preparation method thereof
CN107326474B (en) Graphene and polyester composite fiber for cord and preparation method thereof
CN112898750B (en) Full-biodegradable toughened polylactic acid composite material and preparation method thereof
CN110982232A (en) Antistatic PET/nano carbon fiber composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant