CN112266592B - High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof - Google Patents
High-conductivity nano-mineral modified fully-degradable polymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-conductivity nano-mineral modified fully-degradable polymer composite material, which comprises the following steps: adding attapulgite and a surface treatment agent into water, mixing, and placing into a microwave reaction kettle to obtain an aqueous dispersion liquid containing an intermediate; continuously adding pyrrole monomer, dopant and oxidant into the microwave reaction kettle in sequence to obtain the aqueous dispersion liquid of the functionalized attapulgite; spray drying the functionalized attapulgite dispersion to obtain functionalized attapulgite microparticles; putting the functionalized attapulgite micro-particles, the degradable polymer, the compatilizer and the processing aid into mixing equipment for melt blending to obtain functional master batches containing the functionalized attapulgite; and mixing the functional master batches and the degradable polymers, and putting the mixture into melt blending equipment for melt blending to obtain the degradable antistatic composite material. The invention realizes the surface functionalization and high conductivity of the mineral filler, and greatly improves the processability, conductivity and mechanical property of the composite material.
Description
Technical Field
The invention relates to an antistatic functional nano composite material of a degradable polymer modified by functionalized attapulgite, in particular to a high-conductivity nano mineral modified fully-degradable polymer composite material with high strength, high toughness and excellent conductivity and a preparation method thereof, belonging to the technical field of high performance and multi-functionalization of degradable polymer materials.
Background
The application of the traditional non-degradable plastics in a large amount not only consumes a large amount of petroleum and resources, but also causes huge environmental pollution and ecological damage. Although part of the plastic is recycled and reused, most of the waste plastic is buried and incinerated, especially the plastic packaging waste in the household garbage. Statistically, more than 41% of the total plastic yield is used in the packaging industry, and 47% of the total plastic yield is used in food packaging. Conventional plastic packaging materials, almost all petroleum-based products, are discarded to the environment after consumption, creating tremendous environmental pressure. In order to solve the global problem, the development of green polymer materials is urgently needed, and the research and development of degradable polymer materials draw extensive attention and attention.
The industrial and academic circles pay great attention to the production and research of degradable high polymer materials, and the successfully developed varieties reach dozens of varieties, mainly including polylactic acid (PLA), Polycaprolactone (PCL), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), polyvinyl alcohol (PVA) and the like. However, some intrinsic property defects of degradable high polymer materials, such as brittleness, poor heat resistance, low melt strength, etc., limit their wider application in packaging materials. The specific defects are as follows: (1) environmental pollution pressure of petroleum-based traditional materials: although high-power spinning can obviously improve the orientation degree of polypropylene molecular chains and crystals, the high-power spinning can cause fiber surface quality defects (such as hairiness and holes), and becomes a main obstacle for hindering the improvement of fiber performance and application thereof. (2) Conventional conductive materials are not degradable and the color of the article is limited: the nucleation capability of polypropylene can be improved by adding ordinary micron-grade/nanometer-grade talcum powder or mica powder conventionally, and a certain reinforcing effect is given to polypropylene fibers; however, the fillers are easy to agglomerate in the matrix, which causes difficult processing of the fiber material and also often becomes a stress concentration failure point of the polypropylene fiber. (3) The filler dispersion effect in the conventional melt processing form is poor: the introduction of nucleating agents and other fillers or glass fiber and other reinforcing phases has great damage to production environment or processing equipment, influences the environment and is difficult to realize low-cost and sustainable production and supply. Therefore, the degradable polymer is usually modified with a specific property (such as mechanical property, barrier property, electrical property, etc.) to meet a specific application scenario.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide a fully-degradable polymer composite material which can overcome the defects in the material technology in the field of the prior packaging industry and has high strength, high conductivity and high toughness.
The attapulgite is an aqueous magnesium-rich aluminosilicate clay mineral with a chain layered structure, the crystal of the attapulgite is fibrous, acicular or fiber-aggregated, the diameter of single fiber crystal is about 20 nm, and the length can reach several microns. As a natural one-dimensional nano material, the attapulgite has good colloidal properties of unique dispersion, high temperature resistance, saline-alkali resistance and the like and higher adsorption decoloration capacity. Higher surface activity (specific surface area 9.6 ‒ 36 m)2The/g) endows the attapulgite with good surface modification potential, and is beneficial to implementing quick, simple and convenient functionalization modification, thereby obtaining good electrical conductivity, thermal conductivity or barrier property.
In order to solve the technical problems, the preparation method of the high-conductivity nano-mineral modified fully-degradable polymer composite material provided by the invention comprises the following steps:
s1 preparation of intermediate: adding attapulgite and a surface treating agent into water, uniformly mixing, putting into a microwave reaction kettle, heating to 50 ‒ 120 ℃ under a stirring state, reacting for 30 seconds ‒ 5 minutes, and cooling after the reaction is finished to obtain an aqueous dispersion liquid containing an intermediate;
s2, preparing the functionalized attapulgite: continuously adding pyrrole monomer, dopant and oxidant into the microwave reaction kettle in turn under the stirring state, and carrying out thermal insulation oxidative polymerization reaction at 25 ‒ 60 ℃ for 5 minutes ‒ 30 minutes to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s3, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S2, wherein the inlet air temperature is 200 ‒ 350 ℃, and the water evaporation capacity is 1 ‒ 800 kg/h, thereby obtaining fully dried functionalized attapulgite microparticles;
s4, preparing the attapulgite functional master batch: putting the functionalized attapulgite micro-particles obtained in the step S3, the degradable polymer, the compatilizer and the processing aid into mixing equipment in proportion for melt blending, cooling and granulating or directly granulating after mixing uniformly to obtain functional master batches containing the functionalized attapulgite;
s5, preparing the fully-degradable polymer composite material: and (3) mixing the functional master batch obtained in the step S4 with the degradable polymer, uniformly stirring the mixture according to a certain proportion, and putting the mixture into a melt blending device for melt blending to obtain the fully degradable polymer composite material.
In the improvement, in step S1, the mass fraction of the attapulgite in water is 1% ‒ 25%, the surface treatment agent is at least one of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, methyl orange and amino silane coupling agent, and the mass ratio of the surface treatment agent to the attapulgite is 1:99 ‒ 3: 7.
As an improvement, the mass ratio of the pyrrole monomer to the attapulgite in the step S2 is 1:5 ‒ 1: 2; the dopant is at least one of naphthalene sulfonic acid, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyethylene glycol p-isooctyl phenyl ether, sodium benzene sulfonate and p-toluenesulfonic acid, and the molar ratio of the dopant to the pyrrole monomer is 1:7 ‒ 1: 1.4; the oxidant is at least one of potassium persulfate, sodium persulfate and ammonium persulfate, and the molar ratio of the oxidant to the pyrrole monomer is 1:2 ‒ 1: 0.6.
As an improvement, the attapulgite micro-particles obtained in the step S3 have the size of 10 ‒ 500 μm and the moisture content of less than 0.1 percent.
As an improvement, in the step S4, the mass fraction of the functionalized attapulgite micro-particles in the functional master batch is 5% ‒ 50%.
As an improvement, in step S4, the degradable polymer is at least one of polylactic acid (PLA), Polycaprolactone (PCL), polyvinyl alcohol (PVA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA), and polybutylene adipate terephthalate (PBAT), and the mass fraction of the degradable polymer in the functional masterbatch is 40% ‒ 90%.
In the improvement, in step S4, the compatibilizer is at least one of maleic anhydride grafted polyolefin elastomer (MAH-g-POE), maleic anhydride grafted ethylene-methyl acrylate copolymer (MAH-g-EMA), maleic anhydride grafted ethylene-ethyl acrylate copolymer (MAH-g-EEA), maleic anhydride grafted ethylene-butyl acrylate copolymer (MAH-g-EBA), and glycidyl methacrylate, and the mass fraction of the compatibilizer in the functional masterbatch is 2% ‒ 5%.
In the improvement, in step S4, the compatibilizer is at least one of tetrabutyl titanate, a reactive polyepoxy compatibilizer, and acetyl tri-n-butyl citrate, and the mass fraction of the compatibilizer in the functional masterbatch is 0.2% ‒ 1.5.5%.
In the step S4, the processing aid is at least one of a chain extender, a toughening agent, a flow modifier, a coupling agent, an antioxidant and a stabilizer, and the mass fraction of the processing aid in the functional masterbatch is 1% ‒ 10%.
As an improvement, in the step S4, the mixing device is at least one of a high-speed mixer, an open mill, a turnover type internal mixer, a continuous type internal mixer, a reciprocating screw extruder, a twin-screw extruder, a single-screw extruder, a Z-type kneader, a screw kneader, a vacuum kneader and a horizontal twin-screw mixer; the mixing temperature is 100 ‒ 250 ℃, and the energy consumption per unit mass in the mixing process is 0.1 ‒ 5 kWh/kg.
In the step S5, the melt blending equipment is at least one of a turn-over type internal mixer, a continuous type internal mixer, a reciprocating type screw extruder, a twin-screw extruder and a single-screw extruder, the melt blending temperature is 120 ‒ 250 ℃, and the mass ratio of the functional master batch to the degradable macromolecule is 1:19 ‒ 1: 4.
The invention also provides a high-conductivity nano-mineral modified fully-degradable polymer composite material, which consists of polypyrrole-modified attapulgite, a degradable polymer, a compatilizer and a processing aid; the functionalized mineral is polypyrrole modified attapulgite synthesized by microwave assistance; the degradable polymer is at least one of polylactic acid (PLA), Polycaprolactone (PCL), polyvinyl alcohol (PVA), polybutylene succinate (PBS), Polyhydroxyalkanoate (PHA) and polybutylene adipate terephthalate (PBAT); the compatilizer is maleic anhydride grafted polyolefin elastomer (MAH-g-POE)At least one of maleic anhydride grafted ethylene-methyl acrylate copolymer (MAH-g-EMA), maleic anhydride grafted ethylene-ethyl acrylate copolymer (MAH-g-EEA), maleic anhydride grafted ethylene-butyl acrylate copolymer (MAH-g-EBA), glycidyl methacrylate (the mass fraction in the functional master batch is 2% ‒ 5%), tetrabutyl titanate, reactive polyepoxy compatibilizer or acetyl tributyl citrate; the processing aid is at least one of a chain extender, a toughening agent, a flow modifier, a coupling agent, an antioxidant and a stabilizer. The surface resistance of the composite material was 104‒109Omega, volume resistivity of 103‒108Omega.m. Therefore, a good antistatic effect can be obtained, and the application range in the field of packaging materials is expanded.
The invention has the beneficial effects that: (1) the microwave-assisted synthetic route promotes the formation and anchoring of the conductive modification layer on the surface of the attapulgite, thereby improving the conductivity of the nano attapulgite and the dispersibility in a polymer matrix and fully exerting the unique functions of the one-dimensional high-conductivity nano attapulgite (such as forming an enhanced network and a conductive network); (2) the solution containing the functionalized nano-grade attapulgite is directly dried into high-conductivity attapulgite microparticles (the diameter is 10-500 mu m) by adopting a spray drying process, so that the high-conductivity attapulgite microparticles are endowed with good dispersibility and processability, and the good processability and function realization of the conductive filler are realized; (3) the in-situ modification realizes the surface treatment of the nano-scale mineral filler, effectively improves the interaction between the filler and a matrix and improves the interface bonding force in a composite system; (4) the masterbatching technical route forces the nanoscale high-conductivity mineral filler to be fully stripped and uniformly dispersed in a high-molecular matrix to form a relatively perfect network structure, so that the composite material is endowed with good reinforcing effect and conductivity; (5) the high shear rate melting compounding process effectively peels off and uniformly disperses the functionalized attapulgite micro-particles and other processing aids in the degradable polymer to obtain functional master batches containing the functionalized high-conductivity attapulgite and endow the master batches with good dispersibility and processability; (6) directly and uniformly mixing the functional master batch containing the functionalized high-conductivity attapulgite with the degradable polymer, and carrying out melt blending to obtain the composite material with high conductivity and high mechanical property; (7) the composite material has the characteristics of high strength, high modulus, high ductility, high toughness and the like, and the preparation method reflects the characteristics of environmental protection, low cost and the like, and is favorable for expanding the application and development of the degradable high polymer material in the field of high-end packaging materials. The method has the advantages of simple production process, easy large-scale production, low production cost and various product functions.
Drawings
FIG. 1 is a flow chart of the preparation method of the high-conductivity nano-mineral modified fully-degradable polymer composite material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the preparation method of the high-conductivity nano-mineral modified fully-degradable polymer composite material provided by the invention comprises the following steps:
s11 preparation of intermediate: adding 25 parts by mass of attapulgite and 10.7 parts by mass of hexadecyl trimethyl ammonium bromide into 75 parts by mass of water, uniformly mixing, putting into a microwave reaction kettle, heating to 50 ℃ under a stirring state, reacting for 5 minutes, and then finishing and cooling to obtain an aqueous dispersion liquid containing an intermediate;
s12, preparing the functionalized attapulgite: continuously adding pyrrole monomers, sodium benzenesulfonate and sodium persulfate into a microwave reaction kettle in sequence under the stirring state, wherein the pyrrole monomers account for 12.5 parts by mass, the molar ratio of the sodium benzenesulfonate to the pyrrole monomers is 1:1.4, and the molar ratio of the sodium persulfate to the pyrrole monomers is 1:2, and carrying out thermal insulation oxidative polymerization at 60 ℃ for 5 minutes to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s13, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S12, wherein the inlet air temperature is 200 ℃, and the water evaporation capacity is 1 kg/h, so that the functionalized attapulgite micro-particles which are dried fully can be obtained;
s14, preparing the attapulgite functional master batch: carrying out melt blending on 5 parts by mass of functionalized attapulgite microparticles obtained in S13, 40 parts by mass of PBS, 50 parts by mass of PLA, 2 parts by mass of MAH-g-POE, 1 part by mass of antioxidant and 2 parts by mass of flow modifier in a double-screw extruder (at the interval temperature of 100 ‒ 250 ℃), and cooling and granulating after the unit mass energy consumption reaches 0.1 kWh/kg to obtain functionalized attapulgite-containing functional master batches;
s15, preparing the fully-degradable polymer composite material: and (3) uniformly stirring 20 parts of the functional master batch obtained in the step S14 and 80 parts of PLA, and carrying out melt blending by using a reciprocating single-screw extruder (the interval temperature is 120 ‒ 250 ℃) to obtain the fully-degradable polymer composite material.
Example 2
A high-conductivity nano-mineral modified fully-degradable polymer composite material and a preparation method thereof comprise the following steps:
s21 preparation of intermediate: adding 1 part by mass of attapulgite and 0.011 part by mass of aminosilane coupling agent into 99 parts by mass of water, uniformly mixing, putting into a microwave reaction kettle, heating to 120 ℃ in a stirring state, reacting for 30 seconds, and then finishing and cooling to obtain aqueous dispersion containing an intermediate;
s22, preparing the functionalized attapulgite: continuously adding pyrrole monomer, sodium dodecyl sulfate and potassium persulfate into the microwave reaction kettle in sequence under the stirring state, wherein the pyrrole monomer accounts for 0.2 part by mass, the molar ratio of the sodium dodecyl sulfate to the pyrrole monomer is 1:7, the molar ratio of the potassium persulfate to the pyrrole monomer is 1:0.6, and carrying out thermal insulation oxidative polymerization reaction at 25 ℃ for 30 minutes to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s23, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S22, wherein the inlet air temperature is 350 ℃, and the water evaporation capacity is 800 kg/h, so that the functionalized attapulgite micro-particles which are dried fully can be obtained;
s24, preparing the attapulgite functional master batch: carrying out melt blending on 50 parts by mass of functionalized attapulgite microparticles obtained in S23, 43.5 parts by mass of PBS, 1.5 parts by mass of tetrabutyl titanate, 1 part by mass of antioxidant, 2 parts by mass of chain extender and 2 parts by mass of flow modifier in a turnover type internal mixer (at the interval temperature of 180 ‒ 210 ℃), and cooling and granulating after the unit mass energy consumption reaches 5 kWh/kg to obtain functionalized attapulgite-containing functional master batches;
s25, preparing the fully-degradable polymer composite material: and (3) uniformly stirring 5 parts of the functional master batch obtained in the step S24, 40 parts of PLA and 55 parts of PCL, and carrying out melt blending by using a double-screw extruder (the interval temperature is 140 ‒ 230 ℃) to obtain the fully-degradable polymer composite material.
Example 3
The invention provides a high-conductivity nano-mineral modified fully-degradable polymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s31 preparation of intermediate: adding 10 parts by mass of attapulgite and 1 part by mass of hexadecyl trimethyl ammonium bromide into 90 parts by mass of water, uniformly mixing, putting into a microwave reaction kettle, heating to 80 ℃ under a stirring state, reacting for 2 minutes, and then finishing and cooling to obtain an aqueous dispersion liquid containing an intermediate;
s32, preparing the functionalized attapulgite: continuously adding 2.5 parts by mass of pyrrole monomer, 1:5 of molar ratio of polyethylene glycol to isooctyl phenyl ether to pyrrole monomer and 1:1 of molar ratio of ammonium persulfate to pyrrole monomer into a microwave reaction kettle in sequence under the stirring state, and carrying out thermal insulation oxidative polymerization reaction for 10 minutes at 50 ℃ to obtain aqueous dispersion liquid of the functionalized attapulgite;
s33, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S32, wherein the inlet air temperature is 220 ℃, and the water evaporation capacity is 150 kg/h, so that the functionalized attapulgite micro-particles which are dried fully can be obtained;
s34, preparing the attapulgite functional master batch: carrying out melt blending on 40 parts by mass of functionalized attapulgite micro-particles obtained in S33, 19 parts by mass of PHA, 30 parts by mass of PBAT, 1 part by mass of reactive multi-epoxy compatibilizer, 2 parts of antioxidant, 2 parts of chain extender and 6 parts of flow modifier in a continuous internal mixer (at the interval temperature of 120 ‒ 200 ℃), and cooling and granulating after the unit mass energy consumption reaches 0.5 kWh/kg to obtain functional master batches containing functionalized attapulgite;
s35, preparing the fully-degradable polymer composite material: and (3) uniformly stirring 10 parts of the functional master batch obtained in the step S34 and 90 parts of PLA, and carrying out melt blending by using a double-screw extruder (the interval temperature is 140 ‒ 230 ℃) to obtain the fully-degradable polymer composite material.
Example 4
The invention provides a high-conductivity nano-mineral modified fully-degradable polymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s41 preparation of intermediate: adding 15 parts by mass of attapulgite and 2 parts by mass of dodecyl trimethyl ammonium bromide into 85 parts by mass of water, uniformly mixing, putting into a microwave reaction kettle, heating to 120 ℃ under a stirring state, reacting for 1 minute, finishing, and cooling to obtain an aqueous dispersion liquid containing an intermediate;
s42, preparing the functionalized attapulgite: continuously adding pyrrole monomers, polyethylene glycol p-isooctyl phenyl ether and ammonium persulfate into the microwave reaction kettle in sequence under the stirring state, wherein the pyrrole monomers account for 5 parts by mass, the molar ratio of the polyethylene glycol p-isooctyl phenyl ether to the pyrrole monomers is 1:2, the molar ratio of the ammonium persulfate to the pyrrole monomers is 1:1.5, and carrying out thermal insulation oxidative polymerization reaction for 20 minutes at 40 ℃ to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s43, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S42, wherein the inlet air temperature is 200 ℃, and the water evaporation capacity is 100 kg/h, thereby obtaining fully dried functionalized attapulgite microparticles;
s44, preparing the attapulgite functional master batch: carrying out melt blending on 35 parts by mass of functionalized attapulgite microparticles obtained in S43, 25 parts by mass of PHA, 32 parts by mass of PBS, 1 part by mass of acetyl tri-n-butyl citrate, 1 part of antioxidant, 2 parts of chain extender and 4 parts of flow modifier in a reciprocating single-screw extruder (at the interval temperature of 120 ‒ 200 ℃), and cooling and granulating after the unit mass energy consumption reaches 3 kWh/kg to obtain functional master batches containing functionalized attapulgite;
s45, preparing the fully-degradable polymer composite material: and (3) uniformly stirring 15 parts of the functional master batch obtained in the step S44 and 85 parts of PLA, and carrying out melt blending by using a continuous internal mixer (the interval temperature is 120 ‒ 210 ℃) to obtain the fully-degradable polymer composite material.
Example 5
The invention provides a high-conductivity nano-mineral modified fully-degradable polymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
s51 preparation of intermediate: adding 20 parts by mass of attapulgite and 4 parts by mass of methyl orange into 80 parts by mass of water, uniformly mixing, putting into a microwave reaction kettle, heating to 90 ℃ under a stirring state, reacting for 2 minutes, finishing, and cooling to obtain an aqueous dispersion liquid containing an intermediate;
s52, preparing the functionalized attapulgite: continuously adding pyrrole monomer, p-toluenesulfonic acid and sodium persulfate into the microwave reaction kettle in sequence under the stirring state, wherein the pyrrole monomer is 6 parts by mass, the molar ratio of the p-toluenesulfonic acid to the pyrrole monomer is 1:4, the molar ratio of the sodium persulfate to the pyrrole monomer is 1:1, and carrying out thermal insulation oxidative polymerization at 45 ℃ for 15 minutes to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s53, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite obtained in S52, wherein the inlet air temperature is 210 ℃, and the water evaporation capacity is 200 kg/h, thereby obtaining fully dried functionalized attapulgite microparticles;
s54, preparing the attapulgite functional master batch: carrying out melt blending on 45 parts by mass of functionalized attapulgite micro-particles obtained in S53, 17 parts by mass of PHA, 30 parts by mass of PCL, 1 part by mass of acetyl tri-n-butyl citrate, 2 parts of antioxidant, 2 parts of chain extender and 3 parts of flow modifier in a reciprocating single-screw extruder (at the interval temperature of 100 ‒ 180 ℃) and then cooling and pelletizing after the unit mass energy consumption reaches 1.5 kWh/kg to obtain functional master batches containing functionalized attapulgite;
s55, preparing the fully-degradable polymer composite material: and (3) uniformly stirring 10 parts of the functional master batch obtained in the step S54, 40 parts of PLA and 50 parts of PBS, and carrying out melt blending by using a double-screw extruder (the interval temperature is 130 ‒ 190 ℃) to obtain the fully-degradable polymer composite material.
Comparative example 1
Basically, the method of example 1 is adopted to prepare master batches and composite materials, except that in the example, the attapulgite is not modified at all, but 5 parts by mass of the attapulgite, 40 parts of PBS, 50 parts of PLA, 2 parts of MAH-g-POE, 1 part of antioxidant and 2 parts of flow modifier are directly subjected to melt blending in a double-screw extruder (the interval temperature is 100 ‒ 250 ℃), and the master batches containing the attapulgite are obtained by cooling and granulating after the unit mass energy consumption reaches 0.1 kWh/kg; and then uniformly stirring the obtained 20 parts of attapulgite filling master batch and 80 parts of PLA, and blending by a reciprocating single-screw extruder (the interval temperature is 120 ‒ 250 ℃) to obtain the composite material.
Comparative example 2
The method of example 2 is basically adopted to prepare the functionalized attapulgite and the microparticles thereof, except that the present example does not prepare the functional master batch, but directly blends to prepare the composite material, namely, 2.5 parts by mass of the functionalized attapulgite microparticles, 2.175 parts by mass of PBS, 0.075 parts by mass of tetrabutyl titanate, 0.05 part by mass of antioxidant, 0.1 part by mass of chain extender, 0.1 part by mass of flow modifier, 40 parts by mass of PLA and 55 parts by mass of PCL are uniformly stirred, and the composite material is obtained by blending through a double screw extruder (interval temperature 140 ‒ 230 ℃).
Comparative example 3
Basically, the method of example 3 is adopted to prepare master batches and composite materials, except that in the present example, the attapulgite is not modified at all, but 40 parts by mass of the attapulgite, 19 parts by mass of PHA, 30 parts by mass of PBAT, 1 part by mass of a reactive multi-epoxy compatibilizer, 2 parts of an antioxidant, 2 parts of a chain extender and 6 parts of a flow modifier are subjected to melt blending in a continuous internal mixer (the interval temperature is 120 ‒ 200 ℃), and the master batches containing the attapulgite are obtained by cooling and granulating after the unit mass energy consumption reaches 0.5 kWh/kg; then, the 10 parts of attapulgite filling master batch and 90 parts of PLA are uniformly stirred and blended by a double-screw extruder (interval temperature 140 ‒ 230 ℃) to obtain the composite material.
Structural characterization and Performance testing
And (3) testing tensile property: the resulting composite was subjected to injection molding (molding temperatures of 160 ‒ 220 ℃ C. and 220 ℃ C.) to obtain tensile and impact test specimens, and the tensile properties of the composite were measured using a universal tensile machine (model 5900) of Instron, USA, according to the tensile properties test standards for plastics in ASTM D638-2003, American society for testing materials; the impact properties of the composite material were tested according to ASTM D256-1997 Standard test method for Izod impact testing of plastics, of the American society for testing materials. At least 3 parallel test specimens were guaranteed per group and the results were averaged.
Electrical Performance testing: and testing the surface resistance and the volume resistivity of the composite material according to the national standard GB/T1410-2006 test method for the volume resistivity and the surface resistivity of the solid insulating material. At least 5 replicates of each group were tested and the results averaged.
TABLE 1 mechanical and electrical property test results of the composite materials
The experimental results are as follows: table 1 compares the tensile test results of the high-conductivity nano-mineral modified fully-degradable polymer composite material, and examples 1 ‒ 5 all have higher yield strength (42.3 ‒ 68.9.9 MPa), elongation at break (29 ‒ 154%) and impact strength (7.8 ‒ 28.4.4 kJ/m)2) The composite material embodies excellent comprehensive mechanical properties and meets the basic performance requirements of the packaging material. However, comparative example 1 ‒ 3 had an elongation at break of only about 10% and an impact strength of only 4 kJ/m2On the other hand, it is difficult to satisfy the requirements of the packaging material for toughness and ductility.
Also of significance, example 1 ‒ 5 all exhibited good antistatic properties, with surface resistance in the range of E04 ‒ E07 Ω and volume resistivity in the range of E03 ‒ E06 Ω · m, being a good antistatic material. In particular, the surface resistance of example 5 was as low as 8X 104Omega and volume resistivity as low as 9 x 103Omega.m, the conductive performance of the composite material is the same as that of the conventional conductive filler modified composite material such as carbon black. However, comparative examples 1 and 3, which used only unmodified attapulgite, both exhibited an insulating state and could not be used as antistatic packing materials. Comparative example 2, which did not adopt the masterbatching technical route, had significantly reduced mechanical properties and conductivity compared to example 2, and could not give full play to conductivityReinforcing effect and multi-functionalization of the electro-mineral nano-filler.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (12)
1. A preparation method of a high-conductivity nano-mineral modified fully-degradable polymer composite material is characterized by comprising the following steps: the method comprises the following steps:
s1 preparation of intermediate: adding attapulgite and a surface treating agent into water, mixing, putting into a microwave reaction kettle, heating to 50 ‒ 120 ℃ under a stirring state, and reacting for 30 seconds ‒ 5 minutes to obtain an aqueous dispersion liquid containing an intermediate;
s2, preparing the functionalized attapulgite: continuously adding pyrrole monomer, dopant and oxidant into the microwave reaction kettle under the stirring state, and carrying out thermal insulation oxidative polymerization reaction at 25 ‒ 60 ℃ for 5 ‒ 30 minutes to obtain the aqueous dispersion liquid of the functionalized attapulgite;
s3, preparing the functionalized attapulgite micro-particles: spray drying the aqueous dispersion of the functionalized attapulgite, wherein the inlet air temperature is 200 ‒ 350 ℃, and the water evaporation capacity is 1 ‒ 800 kg/h, so as to obtain functionalized attapulgite micro-particles;
s4, preparing the attapulgite functional master batch: putting the functionalized attapulgite micro-particles, the degradable polymer, the compatilizer and the processing aid into mixing equipment for melt blending to obtain functional master batches containing the functionalized attapulgite; the processing aid is at least one of a chain extender, a flexibilizer, a flow modifier, a coupling agent, an antioxidant and a stabilizer;
s5, preparing the fully-degradable polymer composite material: and mixing the functional master batches with the degradable polymers, and putting the mixture into melt blending equipment for melt blending to obtain the high-conductivity nano mineral modified fully-degradable polymer composite material.
2. The method of claim 1, wherein: in the step S1, the mass fraction of the attapulgite in the water is 1% ‒ 25%, the surface treatment agent is at least one of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, methyl orange and amino silane coupling agent, and the mass ratio of the surface treatment agent to the attapulgite is 1:99 ‒ 3: 7.
3. The method of claim 1, wherein: in the step S2, the mass ratio of the pyrrole monomer to the attapulgite is 1:5 ‒ 1: 2; the dopant is at least one of naphthalene sulfonic acid, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyethylene glycol p-isooctyl phenyl ether, sodium benzene sulfonate and p-toluenesulfonic acid, and the molar ratio of the dopant to the pyrrole monomer is 1:7 ‒ 1: 1.4; the oxidant is at least one of potassium persulfate, sodium persulfate and ammonium persulfate, and the molar ratio of the oxidant to the pyrrole monomer is 1:2 ‒ 1: 0.6.
4. The method of claim 1, wherein: the functionalized attapulgite micro-particles in the step S3 have the size of 10 ‒ 500 μm and the moisture content of less than 0.1 percent.
5. The method of claim 1, wherein: in the step S4, the mass fraction of the functionalized attapulgite micro-particles in the functional master batch is 5% to ‒ 50%.
6. The method of claim 1, wherein: in the step S4, the degradable polymer is at least one of polylactic acid, polycaprolactone, polyvinyl alcohol, polybutylene succinate, polyhydroxyalkanoate, and polybutylene adipate terephthalate, and the mass fraction of the degradable polymer in the functional masterbatch is 40% ‒ 90%.
7. The method of claim 1, wherein: in the step S4, the compatibilizer is at least one of a maleic anhydride grafted polyolefin elastomer, a maleic anhydride grafted ethylene-methyl acrylate copolymer, a maleic anhydride grafted ethylene-ethyl acrylate copolymer, a maleic anhydride grafted ethylene-butyl acrylate copolymer, and glycidyl methacrylate, and the mass fraction of the compatibilizer in the functional masterbatch is 2% ‒ 5%.
8. The method of claim 1, wherein: the compatilizer in the step S4 is at least one of tetrabutyl titanate, reactive polyepoxy compatilizer and acetyl tri-n-butyl citrate; the mass fraction of the compatilizer in the functional master batch is 0.2 percent ‒ 1.5.5 percent.
9. The method of claim 1, wherein: in the step S4, the mass fraction of the processing aid in the functional master batch is 1% ‒ 10%.
10. The method of claim 1, wherein: the mixing equipment in the step S4 is at least one of an open mill, a turnover internal mixer, a continuous internal mixer, a reciprocating screw extruder, a twin-screw extruder, a single-screw extruder, a Z-type kneader, a screw kneader and a vacuum kneader, the mixing temperature is 100 ‒ 250 ℃, and the energy consumption per unit mass in the mixing process is 0.1 ‒ 5 kWh/kg.
11. The method of claim 1, wherein: the melt blending equipment in the step S5 is at least one of a turnover internal mixer, a continuous internal mixer, a reciprocating screw extruder, a double screw extruder and a single screw extruder, the melt blending temperature is 120 ‒ 250 ℃, and the mass ratio of the functional master batch to the degradable polymer is 1:19 ‒ 1: 4.
12. The high-conductivity nano-mineral modified fully-degradable polymer composite material prepared by the preparation method according to any one of claims 1 to 11, which is characterized in that: the surface resistance of the high-conductivity nano-mineral modified fully-degradable polymer composite material is 104‒109Omega, volume resistivity of 103‒108 Ω·m。
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