CN111269510A - Compatible ethylene-tetrafluoroethylene copolymer nano composite material and preparation method thereof - Google Patents
Compatible ethylene-tetrafluoroethylene copolymer nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a compatible ethylene-tetrafluoroethylene copolymer nano composite material and a preparation method thereof, wherein the method comprises the following steps: pretreating montmorillonite nanoparticles (MMT) by adopting organic quaternary phosphonium salt to obtain OMMT; activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT; grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT; mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material; the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12. The nano composite material has better mechanical property; the composite system has a stable homogeneous structure.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a compatible ethylene-tetrafluoroethylene copolymer nano composite material and a preparation method thereof.
Background
Ethylene-tetrafluoroethylene (ETFE) is prepared from ethylene monomer (CH)2＝CH2) With tetrafluoroethylene monomer (CF)2＝CF2) The copolymer obtained by copolymerization has a plurality of excellent performances. However, the two-component copolymer has the defects of too low processing viscosity, narrow processing temperature zone and the like in the actual production process, so that the ETFE is difficult to process and produce. In addition, the ETFE composite is an incompatible system, and when the tensile strength of the ETFE composite is greater than 15MPa during the stretching process, the material yields, which is caused by the fact that ETFE is a semi-crystalline polymer and the crystal structure in the crystal region deforms during the stretching process, such as deformation of spherulites, bending of platelets, and the like. Air bags made from ETFE film materials with lower yield strengths suffer from surface stress relaxation and creep after prolonged use of the film material, which greatly limits the field of application of ETFE materials.
Mechanical research on the ETFE material in the stretching deformation process finds that when the stretching temperature is lower than the phase transition temperature, the stretching deformation of the ETFE material is mainly related to micro gaps in the material and can be similar to the stretching process of hard plastics; above the phase transition temperature, the deformation process is mainly influenced by the state of the wafer inside the material, and the stretching process of the material is similar to that of elastomers such as rubber. Therefore, the crystallinity of the ETFE composite system is increased to enhance the tensile yield strength of the material, and the defect that the material is easy to yield in use is improved to a certain extent.
The crystallinity of the polymer can be improved by introducing nano particles into the system to form a nano composite material so as to improve the mechanical property. The polymer-based nano composite system has a plurality of properties, but the research on the nano composite system of the ETFE material is less at present, mainly the particularity of the ETFE material, and the nano particles are poor in compatibility with an ETFE matrix and easy to agglomerate in the system.
Disclosure of Invention
In view of the above, the present invention provides a compatible ethylene-tetrafluoroethylene copolymer nanocomposite and a preparation method thereof, wherein the nanocomposite prepared by the method has good compatibility between nanoparticles and ETFE and good mechanical properties.
The invention provides a preparation method of a compatible ethylene-tetrafluoroethylene copolymer nano composite material, which comprises the following steps:
pretreating montmorillonite nanoparticles by adopting organic quaternary phosphonium salt to obtain OMMT;
activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT;
grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT;
mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material;
the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12.
Preferably, the organic quaternary phosphonium salt is selected from one or more of tetraphenylphosphonium bromide, tetraphenylphosphonium chloride and tributyltetradecylphosphonium chloride.
Preferably, the silane coupling agent is selected from vinyl-terminated gamma-methacryloxymethyltrisilane.
Preferably, the fluorine-containing monomer is selected from one or more of dodecafluoroheptyl methacrylate, hexafluoroisopropyl methacrylate and perfluorooctyl methacrylate.
Preferably, the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.5-3: 88-92: 8 to 12.
Preferably, the speed of the extrusion granulation is 60-80 rpm; the temperature of extrusion granulation is 250-280 ℃.
Preferably, the fluorinated modified OMMT is ultrasonically dispersed in 1, 4-dioxane and freeze-dried to obtain fluffy fluorinated OMMT;
the fluffy fluorinated OMMT is mixed with ethylene-tetrafluoroethylene copolymer and polyvinylidene fluoride.
Preferably, the temperature for grafting the fluorine-containing monomer to the activated OMMT is 70-80 ℃ and the time is 7.5-8.5 h;
the grafting is carried out in the presence of an initiator and under a nitrogen atmosphere.
Preferably, the hot pressing temperature during the compression molding is 270-280 ℃, the hot pressing pressure is 8-10 MPa, and the hot pressing time is 5-10 minutes;
the cold pressing temperature is 15-30 ℃, the cold pressing pressure is 8-10 MPa, and the cold pressing time is 10-30 minutes.
The invention provides a compatible ethylene-tetrafluoroethylene copolymer nano composite material which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a compatible ethylene-tetrafluoroethylene copolymer nano composite material, which comprises the following steps: pretreating montmorillonite nanoparticles (MMT) by adopting organic quaternary phosphonium salt to obtain OMMT; activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT; grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT; mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material; the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12. Compared with the traditional inorganic filler type polymer system, the MMT nano particles and the polymer matrix are compounded on the microscopic nano-scale size, but not simply mixed with inorganic phase, and the organically modified montmorillonite nano particles and the polymer matrix are interacted or reacted through groups on the modifier, so that the interaction between MMT lamella and polymer molecular chains is enhanced, the stripping degree of the MMT is increased, and the polymer/montmorillonite nano composite material has stronger mechanical property; the surface of the MMT is coated by a large amount of long fluorine-containing chains by grafting the fluorine-containing monomer on the surface of the MMT, so that the compatibility and the dispersibility of the MMT in a polymer matrix are improved, the interface strength of two fluorine-containing materials in an original composite system is enhanced, and a stable homogeneous structure is formed.
Drawings
FIG. 1 is a synthetic route for the preparation of montmorillonite-based fluorinated nanoparticles having the structure PDFMA-g-OMMT according to one embodiment of the present invention;
FIG. 2 is a XPS energy spectrum and a C1s binding energy shift plot of PDFMA-g-OMMT prepared in example 1 of the present invention;
FIG. 3 shows diffraction peaks and interlayer spacings of PDFMA-g-OMMT prepared in example 1 of the present invention;
FIG. 4 is a cross-sectional profile of a compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 2 according to the present invention;
FIG. 5 is a cross-sectional profile of a compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 3 according to the present invention;
FIG. 6 is a cross-sectional profile of a compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 4 according to the present invention;
FIG. 7 is a cross-sectional profile of a compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 5 according to the present invention;
FIG. 8 is a cross-sectional profile of a compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 6 according to the present invention;
FIG. 9 is a cross-sectional profile of an incompatible ethylene-tetrafluoroethylene copolymer composite prepared according to comparative example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a compatible ethylene-tetrafluoroethylene copolymer nano composite material, which comprises the following steps:
pretreating montmorillonite nanoparticles by adopting organic quaternary phosphonium salt to obtain OMMT;
activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT;
grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT;
mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material;
the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12.
The invention pretreats montmorillonite nanoparticles with organic quaternary phosphonium salt to obtain OMMT. In the present invention, the organic quaternary phosphonium salt is preferably selected from one or more of tetraphenylphosphonium bromide, tetraphenylphosphonium chloride and tributyltetradecylphosphonium chloride. The montmorillonite nanoparticles and organic quaternary phosphonium salt TPB undergo an ion exchange reaction to obtain OMMT, and the interlayer spacing of the MMT is enlarged after modification, so that polymer molecular chains can more easily enter the interlamellar space of the MMT in the extrusion process to form an intercalation or stripping state. The montmorillonite may be a sodium montmorillonite. The temperature of the montmorillonite nanoparticles subjected to pretreatment by organic quaternary phosphonium salt is 75-85 ℃, and the time is 7.5-8.5 h. Montmorillonite nanoparticles and organic quaternary phosphonium salt are mixed, after the reaction is finished, the unreacted organic quaternary phosphonium salt is washed away by using a mixed solution of deionized water and ethanol, the mixture is centrifuged for 5-10 min at a rotating speed of 8000rpm, supernatant liquid is removed, and residues are dried for 10h in vacuum at a temperature of 60-80 ℃ to obtain the MMT nanoparticles modified by the quaternary phosphonium salt, namely OMMT.
After obtaining OMMT, the invention adopts silane coupling agent to carry out activation modification on the surface of the OMMT to obtain activated OMMT; the silane coupling agent is preferably vinyl-terminated gamma-methacryloxymethyltrisilane (KH-570); KH-570 CH3O-reacts with Si-OH on the OMMT surface, so that the OMMT surface is coated with C ═ C. The invention preferably stirs OMMT and silane coupling agent in water-ethanol mixed solvent under air atmosphere to obtain activated OMMT; the stirring speed is 500 rpm; the stirring time is 2 h; the volume ratio of the water-ethanol mixed solution is 1:9 water and ethanol. After the activation is finished, the invention preferably uses ethanol to wash out unreacted materialsThe silane coupling agent of (2) is centrifuged, the supernatant is removed and the residue is dried to obtain activated OMMT. The activated OMMT is OMMT nano-particles with vinyl coating on the surface. In the specific embodiment, after the activation is finished, unreacted KH-570 is washed away by ethanol, the mixture is centrifuged at 8000rpm for 5min, supernatant is removed, and the remainder is dried in vacuum at 60 ℃ for 4h to obtain OMMT nano particles with vinyl-coated surfaces.
After obtaining the activated OMMT, the invention grafts a fluoromonomer to the activated OMMT to obtain a fluorinated modified OMMT. In the present invention, the fluorine-containing monomer is preferably selected from one or more of dodecafluoroheptyl methacrylate (DFMA), hexafluoroisopropyl methacrylate, and perfluorooctyl methacrylate. The invention preferably puts fluorine-containing monomer and activated OMMT into N, N-dimethyl acetamide (DMF) solvent, and then adds initiator to graft; the mass of the initiator accounts for 1-2% of the total mass of the fluorine-containing monomer and the activated OMMT. The temperature of the fluorine-containing monomer grafted to the activated OMMT is 70-80 ℃, and the time is 5.5-8.5 h; the grafting is carried out in the presence of an initiator and under a nitrogen atmosphere; the initiator is recrystallized dibenzoyl peroxide (BPO). After the grafting reaction is finished, removing the polymerized fluorine-containing monomer in the system by using DMF, centrifuging, washing by using ethanol, centrifuging again, and washing by using 1, 4-dioxane to obtain the fluorinated OMMT.
The invention mixes the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extrudes and granulizes, and carries out compression molding to obtain the compatible ethylene-tetrafluoroethylene copolymer nano composite material. In the invention, the fluorinated OMMT and the polymer matrix are preferably subjected to freeze-drying treatment before being mixed; ultrasonically dispersing the fluorinated modified OMMT in 1, 4-dioxane, and freeze-drying to obtain fluffy fluorinated OMMT; the fluffy fluorinated OMMT is mixed with ethylene-tetrafluoroethylene copolymer and polyvinylidene fluoride. Liquid nitrogen freeze-drying is preferably adopted in the invention; the freeze-drying time is preferably 23-25 h, and more preferably 24 h.
In the invention, the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8-12, preferably 0.5-3: 88-92: 8 to 12. In a specific embodiment, the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1:90: 10; or 0.5:90: 10; or 1:90: 10; or 2:90: 10; or 4:90: 10.
The invention adopts a double-screw extruder to carry out extrusion granulation; through the shearing action of the double screws, the polymer matrix and the nano particles are mixed more fully, and the molecular chains can enter between the fluorinated OMMT sheets. The fluorinated OMMT prepared by the method has the characteristics of large interlayer spacing, easy dispersion, large amount of long fluorine-containing chains on the surface and the like, and can be uniformly dispersed on a two-phase interface after being melted, blended and extruded with ETFE and PVDF, so that the phase interface state of the ETFE and the PVDF is changed into a homogeneous structure from an original 'sea-island' structure. Meanwhile, as the phase interface strength is increased, the fluorinated OMMT is tightly combined with the matrix, and polymer molecular chains enter the middle of a fluorinated OMMT lamella, the physical entanglement strength and the crystallinity of the system are improved, the yield strength of the ETFE composite material can be effectively enhanced, and the defect that the conventional ETFE composite material is easy to yield is overcome. In the specific embodiment of the invention, during extrusion granulation, the extrusion temperature of each zone is 1 zone 250 ℃, 2 zone 265 ℃, 3 zone 280 ℃,4 zone 285 ℃, 5 zone 280 ℃, 6 zone 275 ℃ and neck mold 280 ℃; the rate of extrusion granulation was 80 rpm.
In the invention, after extrusion granulation, compression molding is carried out by a flat vulcanizing machine; the hot pressing temperature during compression molding is 270-280 ℃, the hot pressing pressure is 8-10 MPa, and the hot pressing time is 5-10 minutes;
the cold pressing temperature is 15-30 ℃, the cold pressing pressure is 8-10 MPa, and the cold pressing time is 10-30 minutes. In a specific embodiment, the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 20 minutes or 30 minutes.
The invention provides a compatible ethylene-tetrafluoroethylene copolymer nano composite material which is prepared by the preparation method of the technical scheme.
The invention adopts the following test method to test the performance of the compatible ethylene-tetrafluoroethylene copolymer nano composite material:
the interlayer spacing of the nanoparticles and the crystal structure of the sample are measured by an X-ray diffractometer of D8 ADVANCE model of German Bruker; the surface element composition of the nano particles is characterized by adopting an ESCALB 250 type X-ray photoelectron spectrometer of the thermal Scientific company in the United states; observing the section morphology of the composite material by adopting a Japanese HITACHI S-4800 type field emission scanning electron microscope; the dynamic mechanical property of the composite material is measured by adopting DMA Q800 series of TA company in the United states; the yield strength and elongation at break of the composite material were measured on an Instron model 5896 static electric tensile machine in the United states.
In order to further illustrate the present invention, the following examples are provided to describe a compatible ethylene-tetrafluoroethylene copolymer nanocomposite and a preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
A fluorinated nanoparticle based on montmorillonite with structure of PDFMA-g-OMMT, the synthetic route is shown in figure 1;
(1) preparation of OMMT: in a 500ml flask, 20g of montmorillonite (MMT), 200ml of deionized water, and 20g of tetraphenylphosphonium bromide (TPB) were placed under an air atmosphere, and heated to 80 ℃ to react for 8 hours. After the reaction, cooling to room temperature, removing unreacted TPB with a water/ethanol (1: 1) mixture, centrifuging at 8000rpm for 5min, removing supernatant, and vacuum drying the residue at 80 deg.C for 10h to obtain OMMT nanoparticles.
(2) Preparation of OMMT-2: a250 ml flask was charged with 2g of OMMT and 75ml of a water/ethanol (1: 9) mixture under an air atmosphere, and stirred at high speed (500rpm) for 30 min. Adding 30ml of gamma-methacryloxypropyltrimethylsiloxane (KH-570), stirring at high speed (500rpm) for 2h, ultrasonically dispersing for 1h, washing unreacted KH-570 with ethanol after the reaction is finished, centrifuging at 8000rpm for 5min, removing supernatant, completely volatilizing the solvent at 60 ℃, and vacuum drying at 60 ℃ for 4h to obtain OMMT-2 nanoparticles.
(3) Preparation of PDFMA-g-OMMT: a250 ml flask was charged with 1g of OMMT-2, 100ml of N, N-Dimethylformamide (DMF), 2g of dodecafluoroheptyl methacrylate (DFMA) and 0.016g of recrystallized dibenzoyl peroxide (BPO) under a nitrogen atmosphere, and heated to 70 ℃ to react for 6 hours. After the reaction, DMF was added to wash off the remaining DFMA, centrifuged, ultrasonically washed with ethanol, centrifuged again, and the supernatant was removed. And cleaning with 1, 4-dioxane, performing ultrasonic treatment, fully dispersing, freezing with liquid nitrogen, putting into a freeze dryer, and performing vacuum freeze-drying for 24h to obtain fluffy PDFMA-g-OMMT nanoparticles.
The prepared PDFMA-g-OMMT was measured by an X-ray photoelectron spectrometer, and the results are shown in FIG. 2. As can be seen in FIG. 2, the PDFMA-g-OMMT surface contained F and DFMA was successfully grafted onto the OMMT surface.
The prepared PDFMA-g-OMMT was measured by an X-ray diffractometer, and the results are shown in FIG. 3. FIG. 3 shows diffraction peaks and interlayer spacings of the prepared PDFMA-g-OMMT in example 1 of the present invention. As can be seen from FIG. 3, after multiple modifications, the interlayer spacing of MMT is enlarged, and the intercalation structure is easier to form.
Example 2:
0.1g of PDFMA-g-OMMT nanoparticles prepared in example 1, 90g of ETFE and 10g of PVDF were weighed, pre-blended by means of mechanical stirring, and then extruded using a twin-screw extruder at the following extrusion temperature in each zone: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the mixture in a flat vulcanizing machine, wherein the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 20 minutes, so that the partially compatible ethylene-tetrafluoroethylene copolymer nano composite material is obtained. The measured phase interface is shown in fig. 4, and fig. 4 is a cross-sectional profile of the compatible ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 2 of the present invention. The sample at this time had a yield strength of 16.5MPa and an elongation at break of 463% at room temperature.
Example 3:
0.5g of PDFMA-g-OMMT nanoparticles prepared in example 1, 90g of ETFE and 10g of PVDF were weighed, pre-blended by means of mechanical stirring and then extruded using a twin-screw extruder at the following extrusion temperature in each zone: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the mixture in a flat vulcanizing machine, wherein the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 20 minutes, so as to obtain the compatible ethylene-tetrafluoroethylene copolymer nano composite material. The measured phase interface is shown in FIG. 5, and FIG. 5 is a cross-sectional profile of the compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 3 according to the present invention. At this time, the sample has a yield strength of 20.5MPa and an elongation at break of 430% at room temperature.
Example 4
1g of PDFMA-g-OMMT nanoparticles prepared in example 1, 90g of ETFE and 10g of PVDF were weighed, pre-blended by means of mechanical stirring, and then extruded by means of a twin-screw extruder, the extrusion temperature in each zone was as follows: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the mixture in a flat vulcanizing machine, wherein the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 20 minutes, so as to obtain the compatible ethylene-tetrafluoroethylene copolymer nano composite material. The measured phase interface is shown in fig. 6, and fig. 6 is a cross-sectional profile of the compatible ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 4 of the present invention. At this time, the sample had a yield strength of 21.3MPa and an elongation at break of 420% at room temperature.
Example 5
Weighing 2g of PDFMA-g-OMMT nano particles, 90g of ETFE and 10g of PVDF, pre-blending in a mechanical stirring manner, and then extruding by adopting a double-screw extruder, wherein the extrusion temperature of each zone is as follows: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the mixture in a flat vulcanizing machine, wherein the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 20 minutes, so as to obtain the compatible ethylene-tetrafluoroethylene copolymer nano composite material. The measured phase interface is shown in FIG. 7, and FIG. 7 is a cross-sectional profile of the compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 5 according to the present invention. At this point the sample had a yield strength of 20.1MPa and an elongation at break of 395% at room temperature.
Example 6
Weighing 4g of PDFMA-g-OMMT nano particles, 90g of ETFE and 10g of PVDF, pre-blending in a mechanical stirring manner, and then extruding by adopting a double-screw extruder, wherein the extrusion temperature of each zone is as follows: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the mixture in a flat vulcanizing machine, wherein the hot pressing temperature is 280 ℃, the hot pressing pressure is 8MPa, the time is 5 minutes, the cold pressing temperature is 25 ℃, the cold pressing pressure is 10MPa, and the time is 30 minutes, so that the partially compatible ethylene-tetrafluoroethylene copolymer nano composite material is obtained. The measured phase interface is shown in FIG. 8, and FIG. 8 is a cross-sectional profile of the compatibilized ethylene-tetrafluoroethylene copolymer nanocomposite prepared in example 6 according to the present invention. At this point the sample has a yield strength of 19.5MPa and an elongation at break of 178% at room temperature.
Comparative example 1:
weighing 90g of ETFE and 10g of PVDF, pre-blending by a mechanical stirring mode, and then extruding by a double-screw extruder, wherein the extrusion temperature of each zone is as follows: zone 1 250 deg.C, zone 2 deg.C, zone 3, zone 280 deg.C, zone 4, zone 5, zone 280 deg.C, zone 6, die 280 deg.C, extrusion rate 80 rpm. And finally, performing compression molding on the raw materials in a flat vulcanizing press at the hot pressing temperature of 280 ℃ and the hot pressing pressure of 8MPa for 2 minutes, at the cold pressing temperature of 25 ℃ and the cold pressing pressure of 10MPa for 30 minutes to obtain the ETFE composite material. The measured phase interface is shown in FIG. 9, and FIG. 9 is a cross-sectional profile of an incompatible ethylene-tetrafluoroethylene copolymer composite prepared according to comparative example 1 of the present invention. The sample at this point had a yield strength of 15.1MPa and an elongation at break of 480% at room temperature.
As can be seen from the comparison between the above examples 1-6 and the comparative example 1, the comparative example 1 is an ETFE composite material without introduction of PDFMA-g-OMMT, the system is an incompatible system, the yield strength is low, the material is affected to use, as the content of PDFMA-g-OMMT is increased from 0 to 4 wt%, the phase interface of the ETFE nano composite material is transformed from island-compatibility-partial compatibility, and the yield strength is increased from 15.1MPa to 21.3 MPa.
From the above examples, the present invention provides a method for preparing a compatible ethylene-tetrafluoroethylene copolymer nanocomposite, comprising the following steps: pretreating montmorillonite nanoparticles (MMT) by adopting organic quaternary phosphonium salt to obtain OMMT; activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT; grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT; mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material; the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12. Compared with the traditional inorganic filler type polymer system, the MMT nano particles and the polymer matrix are compounded on the microscopic nano-scale size, but not simply mixed with inorganic phase, and the organically modified montmorillonite nano particles and the polymer matrix are interacted or reacted through groups on the modifier, so that the interaction between MMT lamella and polymer molecular chains is enhanced, the stripping degree of the MMT is increased, and the polymer/montmorillonite nano composite material has stronger mechanical property; the surface of the MMT is coated by a large amount of long fluorine-containing chains by grafting the fluorine-containing monomer on the surface of the MMT, so that the compatibility and the dispersibility of the MMT in a polymer matrix are improved, the interface strength of two fluorine-containing materials in an original composite system is enhanced, and a stable homogeneous structure is formed. The experimental results show that: at room temperature, when the content of PDFMA-g-OMMT is 0.1-2 wt%, the phase interface of the ETFE nano composite material disappears, the ETFE nano composite material is in a compatible type, the yield strength of the nano composite material is 16.5-21.3 MPa, and the elongation at break is 395-463%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing a compatible ethylene-tetrafluoroethylene copolymer nano composite material comprises the following steps:
pretreating montmorillonite nanoparticles by adopting organic quaternary phosphonium salt to obtain OMMT;
activating and modifying the OMMT surface by adopting a silane coupling agent to obtain activated OMMT;
grafting a fluorine-containing monomer onto the activated OMMT to obtain a fluorinated modified OMMT;
mixing the fluorinated modified OMMT, the ethylene-tetrafluoroethylene copolymer and the polyvinylidene fluoride, extruding, granulating and carrying out compression molding to obtain a compatible ethylene-tetrafluoroethylene copolymer nano composite material;
the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.1-4: 88-92: 8 to 12.
2. The method according to claim 1, wherein the organic quaternary phosphonium salt is one or more selected from the group consisting of tetraphenylphosphonium bromide, tetraphenylphosphonium chloride and tributyltetradecylphosphonium chloride.
3. The method of claim 1, wherein the silane coupling agent is selected from vinyl terminated gamma-methacryloxymethyltrisilane.
4. The method of claim 1, wherein the fluorine-containing monomer is selected from one or more of dodecafluoroheptyl methacrylate, hexafluoroisopropyl methacrylate, and perfluorooctyl methacrylate.
5. The preparation method according to claim 1, wherein the mass ratio of the fluorinated modified OMMT to the ethylene-tetrafluoroethylene copolymer to the polyvinylidene fluoride is 0.5-3: 88-92: 8 to 12.
6. The method according to claim 1, wherein the extrusion granulation speed is 60 to 80 rpm; the temperature of extrusion granulation is 250-280 ℃.
7. The method of claim 1, wherein the fluorinated modified OMMT is ultrasonically dispersed in 1, 4-dioxane, and lyophilized to provide a fluffy fluorinated OMMT;
the fluffy fluorinated OMMT is mixed with ethylene-tetrafluoroethylene copolymer and polyvinylidene fluoride.
8. The method of claim 1, wherein the fluoromonomer is grafted onto the activated OMMT at a temperature of from 70 to 80 ℃ for a period of from 7.5 to 8.5 hours;
the grafting is carried out in the presence of an initiator and under a nitrogen atmosphere.
9. The preparation method according to claim 1, wherein the hot pressing temperature during the compression molding is 270 to 280 ℃, the hot pressing pressure is 8 to 10MPa, and the hot pressing time is 5 to 10 minutes;
the cold pressing temperature is 15-30 ℃, the cold pressing pressure is 8-10 MPa, and the cold pressing time is 10-30 minutes.
10. A compatible ethylene-tetrafluoroethylene copolymer nanocomposite material prepared by the preparation method of any one of claims 1 to 9.
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