CN111548606B - High-strength super-toughness modified graphene/PET barrier composite material, preparation and application - Google Patents
High-strength super-toughness modified graphene/PET barrier composite material, preparation and application Download PDFInfo
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Abstract
The invention relates to the field of high polymer materials, in particular to a high-strength and super-toughness silane coupling agent modified graphene/polyethylene terephthalate barrier composite material and a preparation method thereof, wherein a nanoscale crystal structure exists in the microstructure of the barrier composite material, and the barrier composite material is prepared from the following raw materials: modified graphene serving as a filling material and polyethylene terephthalate serving as a matrix resin, wherein the modified graphene is prepared from the following raw materials: original graphene and a silane coupling agent. The preparation method of the barrier composite material provided by the invention is based on the principle of limited crystallization, utilizes a multi-stage stretching extrusion process to combine heterogeneous nucleation and space limitation of lamellar graphene, induces the formation of a nano-stage crystalline phase amorphous phase separation bionic microstructure in the microstructure of the composite material, obviously improves the toughness of the composite material, obviously improves the strength, and has excellent barrier property.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength super-toughness silane coupling agent modified graphene/polyethylene terephthalate barrier composite material, and preparation and application thereof.
Background
In recent years, with the rapid rise of emerging industries such as flexible lighting, flexible wearable photoelectric devices and the like, polymer film materials with high strength, high ductility and high fracture toughness show wide application prospects. However, because of the different molecular mechanisms of action, the toughness and strength of polymer composites are often mutually exclusive, and most current studies inevitably result in reduced strength of the materials while attempting to improve toughness and ductility of the polymer composites. Therefore, developing polymer composites that integrate high strength, ductility and versatility remains a significant challenge in the field of material science.
In order to solve the problem of considering the toughness of polymer composite materials, current researches are focused on the construction of bionic structures, wherein the construction of spider silk and mussel foot silk microstructures is a hot spot of the researches. Research has found that the superior toughness of spider silks and mussel foot silks is due to the multi-layer assembled nanophase separation structure and the dense ordered dynamic hydrogen bonding within the limited region of the nanophase phase. The dynamic hydrogen bond is used as an efficient energy sacrificial bond, can be dynamically broken and reconstructed in the stretching process and is accompanied with the deformation of the nanoparticle phase, so that energy is dissipated on a molecular scale, the material is endowed with excellent toughness, and the preparation of the polymer composite material with high strength, high ductility and high fracture toughness is realized.
Disclosure of Invention
The invention solves the technical problems that the preparation process of the bionic material in the prior art is complex, the cost is high, and the large-scale application is difficult to realize.
In order to solve the problems, the inventor has studied intensively, and utilizes a silane coupling agent to graft and modify graphene, and mixes the modified graphene with PET, and the silane coupling agent organic molecular chain on the surface of the graphene ensures that the graphene has better compatibility and dispersibility in a PET matrix; and the principle of polymer limited crystallization is adopted, and the heterogeneous nucleation effect and the space limitation effect of lamellar Graphene (GNs) are combined by utilizing the strong orientation stress of a multistage stretching extrusion process, so that a large number of crystal nuclei can be formed in the PET matrix, and the crystal nuclei are mutually limited to form limited nanocrystalline in the growing process, so that a bionic microstructure with separated nanoscale crystalline phase and amorphous phase is constructed, and the polymer composite material with high strength, high ductility and high fracture toughness is obtained. The invention provides a method for preparing a high-strength, high-ductility and high-fracture-toughness polymer composite material, which has simple process, high production efficiency, no toxicity, environmental protection and good industrial application prospect, and can be realized by using the existing processing equipment.
From the above, the barrier composite material provided by the invention is based on the principle of limited crystallization, and the heterogeneous nucleation and the space limitation of lamellar graphene are combined by using a multistage stretching extrusion process, so that a nano-scale crystalline phase-amorphous phase-separation bionic microstructure is formed in the microstructure of the composite material, the toughness of the composite material is obviously improved, the strength of the composite material is obviously improved, and meanwhile, the barrier composite material has excellent barrier property.
Specifically, in order to solve the technical problems, the invention provides the following technical scheme:
the silane coupling agent modified graphene/polyethylene terephthalate barrier composite material is characterized in that a nanoscale crystal structure exists in a microstructure of the barrier composite material, and the barrier composite material is prepared from the following raw materials: modified graphene as a filler and polyethylene terephthalate as a matrix resin;
the modified graphene is prepared from the following raw materials: original graphene and a silane coupling agent.
Preferably, for the barrier composite, wherein the graphene is modified in the raw material for preparing the barrier composite: the mass ratio of the polyethylene terephthalate is 0.01-0.1: 100, preferably 0.03 to 0.1:100, more preferably 0.05 to 0.1:100.
preferably, for the barrier composite material, raw graphene in the raw material for preparing the modified graphene: the mass ratio of the silane coupling agent is 1:5-15, preferably 1:10-15.
Preferably, for the barrier composite, the sheet diameter of the original graphene is 10 μm to 19 μm, preferably 13 μm;
the number of the original graphene layers is 3-8, preferably 5-6;
the specific surface area of the original graphene is more than or equal to 400m 2 /g。
Preferably, for the barrier composite, the intrinsic viscosity of the polyethylene terephthalate is 0.7850 to 0.815dl/g.
Preferably, for the barrier composite, the silane coupling agent is a silane coupling agent containing a general formula: y (CH) 2 )nSiX 3 Wherein n is 0-3, X is one or more selected from chlorine group, methoxy group, ethoxy group and acetoxy group, and Y is one selected from vinyl group, amino group, epoxy group, methacryloxy group and ureido group;
preferably one or more selected from gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma- (methacryloyloxy) propyl trimethoxysilane; further preferred is gamma-glycidoxypropyl trimethoxysilane.
Preferably, for the barrier composite, the particle size of the imperfect nanocrystals present in the barrier composite is from 10 to 40nm.
The preparation method of the silane coupling agent modified graphene/PET barrier composite material in any section comprises the following steps:
(1) Adopting a silane coupling agent to stir and react original graphene in a reaction medium, and carrying out surface grafting modification;
(2) And (3) mixing the modified graphene obtained by the reaction in the step (1) with polyethylene terephthalate, and carrying out multistage stretching extrusion.
Preferably, for the preparation method, the reaction medium in step (1) is: supercritical carbon dioxide;
preferably, the reaction temperature of the grafting modification in the step (1) is 40-70 ℃, and more preferably, the reaction temperature is 40 ℃;
preferably, the reaction time of the grafting modification in the step (1) is 1 to 5 hours, and more preferably the reaction time is 2 hours;
preferably, the reaction pressure of the grafting modification in the step (1) is 10-25 MPa, and more preferably, the reaction pressure is 20MPa;
preferably, the stirring rate of the stirring reaction in the step (1) is 120 to 180r/min, and more preferably the stirring rate is 180r/min.
Preferably, for the preparation method, the number of dividing-laminating units used in the multi-stage stretching extrusion performed in the step (2) is: 5 (2048 layers),
preferably, the multistage stretching extrusion employs a draw rate of 80 to 100r/min, more preferably 90 to 100r/min.
A silane coupling agent modified graphene/polyethylene terephthalate barrier composite material is prepared by the preparation method in any section.
The application of the barrier composite material in the fields of flexible lighting, flexible wearable photoelectric devices and artificial ligaments.
The beneficial effects of the invention include:
(1) The invention introduces a silane coupling agent organic molecular chain to the graphite surface. The compatibility and the dispersibility of the modified graphene in the matrix are improved;
(2) The toughness and the strength of the composite material provided by the invention are mutually exclusive, and the super-tough high-strength polymer composite material cannot be obtained at the same time;
(3) The invention has simple process, can be realized by adopting the existing processing equipment, can realize continuous production, has high production efficiency and has good industrial application prospect.
Drawings
FIG. 1 is an SEM photograph of a barrier composite prepared in comparative example 1 after etching with a 10% KOH (mass concentration) aqueous solution;
FIG. 2 is an SEM photograph of the barrier composite prepared in comparative example 2 after etching with a 10% KOH (mass concentration) aqueous solution;
FIG. 3 is an SEM photograph of the barrier composite prepared in comparative example 3 after etching with a 10% KOH (mass concentration) aqueous solution;
FIG. 4 is an SEM photograph of the barrier composite prepared in example 1 after etching with a 10% KOH (mass concentration) aqueous solution;
FIG. 5 is an SEM photograph of the barrier composite prepared in example 2 after etching with 10% KOH (mass concentration) aqueous solution;
FIG. 6 is an SEM photograph of a barrier composite prepared in example 3 after etching with a 10% KOH (mass concentration) aqueous solution;
FIG. 7 is a stress-strain curve of the products obtained in comparative example 1, comparative example 2, example 1, example 2 and example 3;
FIG. 8 is a stress-strain curve of the products obtained in comparative example 1, comparative example 2, example 1, example 2 and example 3;
fig. 9 is an infrared spectrum of graphene before and after KH550 modification in example 1;
FIG. 10 is an infrared spectrum of graphene before and after KH560 modification in example 2;
FIG. 11 is an infrared spectrum of graphene before and after KH570 modification in example 3;
FIG. 12 shows WAXD (wide angle X-ray diffraction) curves for the products obtained in comparative example 1, comparative example 2 and examples 1, example 2, and example 3;
FIG. 13 is a schematic structural diagram of a multi-stage drawing extrusion system used in the present invention, comprising the following specific components: a hopper, a heating unit, a dividing-folding unit, a stretching roller, and a sheet; wherein the dividing-folding unit includes: the process of dividing, stretching and folding.
Detailed Description
The invention aims to provide a silane coupling agent modified graphene/polyethylene terephthalate barrier composite material (hereinafter polyethylene terephthalate is abbreviated as 'PET', and graphene is abbreviated as 'GNs') which has a nano-scale crystalline phase and an amorphous phase separation microstructure and has high strength, high ductility and high fracture toughness, and the inventor finds that after intensive research: firstly, by utilizing a surface grafting modification principle, a silane coupling agent molecular chain is introduced to the surface of original graphene, so that the modified graphene has more excellent compatibility and dispersibility in a polymer PET matrix; and then according to the principle of polymer limited crystallization, the heterogeneous nucleation and space limitation of the multi-stage stretching extrusion process are utilized, and simultaneously, the heterogeneous nucleation and space limitation of the combined layer lamellar Graphene (GNs) are utilized to induce the formation of a large number of crystal nuclei in the PET matrix added with the modified graphene, and the crystal nuclei are mutually limited to form limited nanocrystalline in the growing process, so that a microstructure with separated nanoscale crystalline phase and amorphous phase is constructed, and finally, the polymer barrier composite material with high strength, high ductility and high fracture toughness is obtained.
On the other hand, the invention also provides a method for preparing the polymer composite material with high strength, high ductility and high fracture toughness, which has simple process, can be realized by using the existing processing equipment, has high production efficiency, is nontoxic and environment-friendly, and has good industrial application prospect.
In a preferred embodiment of the invention, the preparation method comprises the steps of:
(1) Silane coupling agent modified graphene: dispersing silane coupling agent in ethanol/water mixed solution, regulating pH value of the mixed solution with acid, hydrolyzing, adding supercritical carbon dioxide (Sc-CO) into hydrolyzed silane coupling modifier solution and GNs 2 ) Reacting in a reaction kettle for a certain time, repeatedly washing graphene with water, and vacuum drying to obtain silane coupling agent modified graphene;
(2) Preparing a modified GNs/PET barrier composite material: and (3) mixing the silane coupling agent modified graphene obtained in the step (1) with PET, and then putting the mixture into a multistage stretching extrusion system (by utilizing repeated shearing and superposition actions of a segmentation-superposition unit) (see figure 13) for melt extrusion to obtain the sheet-shaped modified GNs/PET barrier composite material.
Wherein the temperatures of a feeding section, a conveying section, a melting section, a homogenizing section, a melt pump, a dividing-superposing unit and a die of the double-screw extruder are 180 ℃, 240 ℃, 255 ℃, 260 ℃, 255 ℃, the traction speed is 80-100r/min, and the thickness of the sheet is controlled to be 0.6+/-0.1 mm.
Wherein the Sc-CO used in the invention 2 The reaction kettle and the double-screw extruder are respectively: GSH type reaction kettle produced by chemical machinery Co., ltd is built in Taixing city;
the twin-screw extruder is a TE-20 extruder of Nanjia extrusion equipment limited company;
the split-stack unit is self-designed for the subject group, the split-stack unit, also called multiplier, is manufactured for self-design, and the specific structure is shown in figure 13.
Instruments, devices, etc., not illustrated herein are commercially available to those of ordinary skill in the art.
The present invention will be described in further detail by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as will be apparent to those skilled in the art upon examination of the present disclosure.
Examples
In the following examples of the present invention, the sources of the raw materials used are respectively:
original graphene: high-activity graphene of 1000 meshes (13 mu m), 5-6 layers and specific surface area of 400m in Shanxi institute of coal chemistry of China academy of sciences 2 /g and above;
silane coupling agent: gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidoxypropyl trimethoxysilane (KH 560), gamma- (methacryloyloxy) propyl trimethoxysilane (KH 570) are commercially available from jetty chemical technology, inc;
PET: the model is CB602, which is produced by Shanghai, inc., and the intrinsic viscosity is 0.800+ -0.015 dl/g.
Example 1
Table 1 example 1 raw material composition
(1) Silane coupling agent modified graphene
First 10g gamma-aminopropyl triethoxysilane (KH 550) are dispersed in 40g ethanol: in the mixed solution with the water mass ratio of 9:1 (w/w), regulating the PH value to 4 by acetic acid, and stirring and hydrolyzing for 2 hours at the room temperature of 25 ℃;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO 2 In the reaction kettle, the reaction product is taken out after the reaction is carried out for 2 hours at the temperature of 40 ℃ and the pressure of 20MPa and the stirring speed of 180r/min, and is repeatedly washed by deionized water and dried for 12 hours at the temperature of 80 ℃ by a vacuum drying oven to obtain the modified graphene: GNs-1.
(2) Preparation of modified GNs/PET Barrier composite Material
Uniformly mixing 10.3g of modified GNs prepared in the step (1) with 1000g of PET resin (the weight ratio is 0.03:100), and then putting the mixture into a multistage stretching extrusion system containing 5 dividing-overlapping units (2048 layers) for melt extrusion to prepare a sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material A).
Wherein, the temperatures of the feeding section, the conveying section, the melting section, the homogenizing section, the melt pump, the dividing-superposing unit and the mouth die of the double-screw extruder are 180 ℃, 240 ℃, 255 ℃, 260 ℃, 255 ℃, the traction speed is 90r/min, and the thickness of the sheet is controlled to be 0.6+/-0.1 mm.
Example 2
Table 2 example 2 raw material composition
(1) Silane coupling agent modified graphene: the addition amount is the same as that of the step (1) of the example 1, and the modified graphene is obtained: GNs-2;
(2) Preparing a modified GNs/PET composite material: the same experimental procedure as in step (2) of example 1 was followed to produce a sheet-like modified GNs/PET barrier composite (denoted composite B).
Example 3
TABLE 3 example 3 raw material composition
(1) Silane coupling agent modified graphene: the addition amount is the same as that of the step (1) of the example 1, and the modified graphene is obtained: GNs-3;
(2) Preparing a modified GNs/PET composite material: the same experimental procedure as in step (2) of example 1 was followed to produce a sheet-like modified GNs/PET barrier composite (denoted composite C).
Example 4
TABLE 4 example 4 raw material composition
(1) Silane coupling agent modified graphene
First (weight of GNs) (5% wt) 0.05g gamma-aminopropyl triethoxysilane (KH 560) was dispersed in 40g ethanol: in the mixed solution with the water mass ratio of 7:3 (w/w), regulating the PH value to 4 by acetic acid, and stirring and hydrolyzing for 2 hours at the room temperature of 25 ℃;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO 2 In the reaction kettle, the reaction product is taken out after the reaction is carried out for 4 hours at the temperature of 60 ℃ and the pressure of 25MPa and the stirring rate of 150r/min, repeatedly washed by deionized water, and dried for 12 hours at the temperature of 80 ℃ by a vacuum drying oven to obtain the modified graphene: GNs-4.
(2) Preparing a modified GNs/PET composite material:
uniformly mixing 0.3g of modified GNs-4 prepared in the step (1) with 1000g of PET (the weight ratio is 0.03:100), and then putting the mixture into a multi-stage stretching extrusion system containing 5 splitting-overlapping units (2048 layers) for melt extrusion to prepare a sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material D).
Wherein, the temperatures of the feeding section, the conveying section, the melting section, the homogenizing section, the melt pump, the dividing-superposing unit and the mouth die of the double-screw extruder are 180 ℃, 240 ℃, 255 ℃, 260 ℃, 255 ℃, the traction speed is 100r/min, and the thickness of the sheet is controlled to be 0.6+/-0.1 mm.
Example 5
TABLE 5 example 5 raw material composition
(1) Silane coupling agent modified graphene
First (weight of GNs) (15% wt) 0.15g gamma-aminopropyl triethoxysilane (KH 560) was dispersed in a 7:3 (w/w) ethanol and water mixed solution and hydrolyzed with acetic acid with stirring at room temperature 25 ℃ to PH 4 for 2 hours;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO 2 In a reaction kettle, taking out a reaction product after reacting for 1 hour at the temperature of 70 ℃ and the pressure of 10MPa and the stirring rate of 180r/min, repeatedly washing with deionized water, and drying for 12 hours at the temperature of 80 ℃ by using a vacuum drying oven to obtain modified graphene: GNs-5.
(2) Preparation of modified GNs/PET composite Material
Uniformly mixing 0.3g of modified GNs-5 prepared in the step (1) with 1000g of PET (the weight ratio is 0.03:100), and then putting the mixture into a multi-stage stretching extrusion system containing 5 splitting-overlapping units (2048 layers) for melt extrusion to prepare a sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material E).
Wherein, the temperatures of the feeding section, the conveying section, the melting section, the homogenizing section, the melt pump, the dividing-superposing unit and the mouth die of the double-screw extruder are 180 ℃, 240 ℃, 255 ℃, 260 ℃, 255 ℃, the traction speed is 90r/min, and the thickness of the sheet is controlled to be 0.6+/-0.1 mm.
Example 6
TABLE 6 example 6 raw material composition
(1) Silane coupling agent modified graphene: the same amount and operation parameters as those of the step (1) in the example 5 are adopted to obtain modified graphene: GNs-6;
(2) Preparation of modified GNs/PET composite Material
After 0.1g of the modified GNs-6 prepared in the step (1) and 1000g of PET (weight ratio of 0.01:100) are uniformly mixed, the rest operation and parameters are the same as those of the step (2) in the example 5, and finally the sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material F) is prepared.
Example 7
TABLE 7 example 7 raw material composition
(1) Silane coupling agent modified graphene: the same amount and operation parameters as those of the step (1) in the example 5 are adopted to obtain modified graphene: GNs-7;
(2) Preparation of modified GNs/PET Barrier composite Material
After 0.5G of the modified GNs-7 prepared in the step (1) and 1000G of PET (weight ratio of 0.05:100) are uniformly mixed, the rest operation and parameters are the same as those of the step (2) of the example 5, and finally the sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material G) is prepared.
Example 8
TABLE 8 example 8 raw material composition
(1) Silane coupling agent modified graphene: the same amount and operation parameters as those of the step (1) in the example 5 are adopted to obtain modified graphene: GNs-8;
(2) Preparation of modified GNs/PET composite Material
After uniformly mixing 1g of the modified GNs-8 prepared in the step (1) with 1000g of PET (weight ratio of 0.1:100), the rest operation and parameters are the same as those of the step (2) in the example 5, and finally the sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material H) is prepared.
Comparative example 1
Preparing a pure PET sheet: 1000g of the dried PET is directly put into a multistage stretching extrusion system for melt extrusion to prepare the PET sheet. Wherein the twin screw extruder operating parameters were the same as in example 1.
Comparative example 2
Preparation of unmodified GNs/PET composites: after mixing unmodified GNs and PET in a weight ratio of 0.03:100, a sheet-like raw GNs/PET composite was prepared according to the process of comparative example 1, with the thickness of the sheet being controlled at 0.6±0.1mm.
Comparative example 3
After 0.3g of unmodified GNs and 1000g of PET resin (weight ratio of 0.03:100) are uniformly mixed, the mixture is put into a multistage stretching extrusion system containing 3 splitting-overlapping units (256 layers) for melt extrusion to prepare the modified GNs/PET barrier composite material. Wherein, the temperatures of the feeding section, the conveying section, the melting section, the homogenizing section, the melt pump, the dividing-superposing unit and the mouth die of the double-screw extruder are 180 ℃, 240 ℃, 255 ℃, 260 ℃, 255 ℃, the traction speed is 100r/min, and the thickness of the sheet is controlled to be 0.6+/-0.1 mm.
To verify the properties of the products obtained in examples 1 to 8 and comparative examples 1 to 3 above, the following tests were carried out:
(1) Infrared spectrum testing: fig. 9 shows infrared spectrum tests of graphene before and after KH550 modification in example 1, graphene before and after KH560 modification in example 2, and graphene before and after KH570 modification in example 3, using the following instruments: NEXUS 570 of Nicolet Inc. of America.
(2) And (3) observing the crystal morphology: the sheet materials obtained in examples 1 to 8 and comparative examples 1 to 3 were etched with a 10% aqueous solution of KOH (mass concentration) for 1 hour, and then subjected to scanning electron microscopy to observe the crystal morphology, wherein the types of the scanning electron microscopy are as follows: quanta FEG250 scanning electron microscope of FEI company of America.
(3) Oxygen permeability and water vapor permeability test: an Ox-Tran Model 2/21 type oxygen permeameter (gas: high purity oxygen, temperature: 23.+ -. 1 ℃ C., sample size: 50 cm) from MOCON was used 2 ) And PERMATRAN-W3/33 type moisture permeation instrument (gas: water vapor, temperature: 23+ -1deg.C, humidity: 100%, sample size: 50cm 2 ) According to ASTMD3985-2005 standardThe oxygen permeability and the water vapor permeability are quasi-separately tested.
(4) Mechanical property test: preparing a standard dumbbell sample from the prepared sheet material by using a dumbbell sample making machine, and then testing the tensile strength and the elongation at break of the sheet material by using a Shenzhen Sanzhen material detection Co., ltd., CMA6104 type universal testing machine according to GB/T1040-2006, wherein the tensile speed is 50mm/min.
(5) WAXD (wide angle X-ray diffraction) test: bruker-xrf type polycrystalline X-ray diffractometer (WAXD, bruck, germany), cuK.alpha.40 kV/30mA, 2.theta.=5-60 degrees.
The above detection results were analyzed as follows:
(1) Infrared spectrogram analysis: FIG. 9 shows that the original graphene is compared with the graphene modified by KH550 in example 1, since the original graphene is 1100cm in length -1 The characteristic peak is nearby, and the Si-O bond characteristic peak in the silane coupling agent is also 1000cm -1 Nearby, so that Si-O bond characteristic peak is covered, and modified graphene is 1450cm -1 N-H group characteristic peaks appear nearby, which proves that a silane coupling agent KH550 is introduced into the graphene;
as shown in FIG. 10, at 900cm -1 A characteristic peak of CN (O) CH appears nearby, which proves that a silane coupling agent KH560 is introduced on the graphene;
as shown in FIG. 11, at 1800cm -1 A c=o characteristic peak appears nearby, demonstrating the introduction of a silane coupling agent KH570 on graphene.
(2) SEM scanning electron microscope analysis: as shown in fig. 1 to 6, fig. 1 is a scanning electron microscope image of a pure PET sheet of comparative example 1, fig. 2 is a scanning electron microscope image of an unmodified GNs/PET composite sheet of comparative example 2, fig. 3 is a scanning electron microscope image of a sheet of a product obtained in comparative example 3, and fig. 4 to 6 are scanning electron microscope images of modified GNs/PET composite sheets of example 1, example 2 and example 3, respectively.
As can be seen from the scanning electron microscope image: pure PET has a relatively large grain size, as determined by Nano Measurer software statistics, the grain size of pure PET (comparative example 1) in FIG. 1 is about 100-180nm, while the modified GNs/PET sheets and unmodified CNs/PET composite sheets of FIG. 2, prepared using 5 split-fold units (2048 layers), in FIGS. 4-6, form a large number of grains of about 10-40nm in size;
in contrast, the composite sheet prepared using 3 split-fold units (256 layers) in FIG. 3, resulted in a grain size of about 200-400nm, significantly greater than the CNs/PET composite sheet prepared using 5 split-fold units (2048 layers);
in addition, as can be seen from fig. 4-6, the prepared modified GNs/PET composite sheet has imperfect crystallization, and a nano-scale crystalline phase and amorphous phase separation structure is formed in the system.
(2) - (3): the oxygen permeability and water vapor permeability tests and the mechanical properties test results are shown in the following table:
TABLE 9 results of Material Performance test for examples 1-8 and comparative examples 1-3
As can be seen from table 8 above, compared with the pure PET sheet prepared in comparative example 1, the water vapor permeability, oxygen permeability and mechanical properties of the composite sheet can be significantly improved by adding a small amount of the silane coupling agent modified graphene prepared in examples 1 to 8 of the present invention;
wherein, the modified CNs/PET barrier composite material sheet prepared in the example 1 has the lowest oxygen permeability, and compared with the oxygen permeability of a pure PET resin sheet, the oxygen barrier property is improved by more than 60 percent; the modified CNs/PET composite material sheet of the embodiment 5 has the lowest water vapor permeability, and compared with the pure PET resin sheet, the water vapor barrier property is improved by more than 93 percent, so that the modified CNs/PET barrier composite material sheet prepared by the invention has good oxygen and water vapor barrier properties; compared with the mechanical properties (tensile strength and elongation at break) of the pure PET resin sheet, the mechanical properties of the modified CNs/PET barrier composite sheet are improved, wherein the tensile strength can reach more than 70MPa, the elongation at break can reach 722%, and the modified CNs/PET barrier composite sheet is far higher than the pure PET sheet, and has higher strength and excellent toughness.
The invention is trueThe oxygen permeability of the modified CNs/PET barrier composite sheets of examples 1-8 ranged from 2.7 to 4.6 (cc/m) 2 Day) with a water vapor permeability of 0.07-4.3 (gm/m) 2 Day), a tensile strength of 52-75MPa, an elongation at break of 614-722%; wherein the products prepared in examples 1-2 and 6-8 have the best combination of properties, oxygen permeability of 2.7-4.3 (cc/m 2 Day) with a water vapor permeability of 0.07-0.5 (gm/m) 2 Day), tensile strength of 60-75MPa and elongation at break of 620-670%.
The mechanism is as follows: the barrier properties of CNs/PET barrier composites are closely related to the interfacial bonding of CNs to PET matrix, e.g., example 2, GNs modified with KH560, although the water vapor permeability is lowest, the oxygen permeability is not optimal, mainly because the bond formed by the reaction of KH560 epoxy groups with hydroxyl and carboxyl end groups in the PET molecular chain is with O 2 The molecules have affinity, so that the improvement of oxygen barrier performance is not obvious, and in addition, the composite material prepared from the KH570 modified GNs has similar reasons for the unobvious water barrier performance due to the affinity of the water vapor molecules and the bonding bonds. The barrier properties of the composite are determined by the dispersion distribution of GNs in the matrix, the interfacial properties, and the affinity of the interface with water vapor and oxygen molecules.
And, the tensile strength and elongation at break of the modified CNs/PET barrier composite sheet of the present invention are improved compared to the properties of the unmodified CNs/PET barrier composite sheets of comparative examples 2 and 3, mainly because the silicone-modified CNs have better compatibility and dispersibility in PET matrix due to the organic molecules on the surface thereof compared to the original CNs.
Claims (26)
1. The application of the silane coupling agent modified graphene/polyethylene terephthalate barrier composite material in the fields of flexible lighting, flexible wearable photoelectric devices and artificial ligaments is characterized in that a nanoscale crystal structure exists in the microstructure of the barrier composite material, wherein the barrier composite material is prepared from the following raw materials: modified graphene as a filler and polyethylene terephthalate as a matrix resin;
the modified graphene is prepared from the following raw materials: original graphene and a silane coupling agent; raw graphene in raw materials for preparing the modified graphene comprises the following steps: the mass ratio of the silane coupling agent is 1:5-15;
modified graphene in raw materials for preparing the barrier composite material: the mass ratio of the polyethylene terephthalate is 0.01-0.1: 100;
the preparation method of the barrier composite material comprises the following steps:
(1) Adopting a silane coupling agent to stir and react original graphene in a reaction medium, and carrying out surface grafting modification;
(2) Mixing the modified graphene obtained by the reaction in the step (1) with polyethylene terephthalate, and carrying out multistage stretching extrusion;
wherein, the number of the splitting-folding units used in the multi-stage stretching extrusion in the step (2) is as follows: 5 (2048 layers);
the reaction medium in the step (1) is as follows: supercritical carbon dioxide; the reaction time of grafting modification in the step (1) is 1-5 h, and the stirring rate of stirring reaction in the step (1) is 120-180 r/min.
2. The use of claim 1, wherein the raw materials for preparing the barrier composite material comprise modified graphene: the mass ratio of the polyethylene terephthalate is 0.03-0.1: 100.
3. the use of claim 1, wherein the raw materials for preparing the barrier composite material comprise modified graphene: the mass ratio of the polyethylene terephthalate is 0.05-0.1: 100.
4. the use according to claim 1, wherein the raw graphene in the raw material for preparing the modified graphene: the mass ratio of the silane coupling agent is 1:10-15.
5. The use according to claim 2, wherein the raw graphene in the raw material for preparing the modified graphene: the mass ratio of the silane coupling agent is 1:10-15.
6. The use according to claim 1, wherein the sheet diameter of the original graphene is 10-19 μm, the number of the original graphene layers is 3-8, and the specific surface area of the original graphene is more than or equal to 400m 2 /g。
7. The use according to claim 6, wherein the original graphene has a sheet diameter of 13 μm.
8. The use according to claim 6, wherein the number of original graphene layers is 5-6.
9. The use according to claim 2, wherein the sheet diameter of the original graphene is 10-19 μm, the number of layers of the original graphene is 3-8, and the specific surface area of the original graphene is equal to or larger than 400m 2 /g。
10. The application of claim 4, wherein the sheet diameter of the original graphene is 10-19 μm, the number of the original graphene layers is 3-8, and the specific surface area of the original graphene is more than or equal to 400m 2 /g。
11. Use according to any one of claims 1 to 10 wherein the polyethylene terephthalate has an intrinsic viscosity of 0.7850 to 0.815dl/g.
12. The use according to any one of claims 1 to 10, wherein the silane coupling agent is a silane coupling agent comprising a compound represented by the general formula: y (CH) 2 )nSiX 3 Wherein n is 0-3, X is one or more selected from chloro, methoxy, ethoxy and acetoxy, and Y is one selected from vinyl, amino, epoxy, methacryloxy and ureido.
13. The use according to claim 12, wherein X is selected from one or more of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma- (methacryloyloxy) propyl trimethoxysilane.
14. The use according to claim 12, wherein X is γ -glycidoxypropyl trimethoxysilane.
15. The use according to claim 11, wherein the silane coupling agent is a silane coupling agent comprising the general formula: y (CH) 2 )nSiX 3 Wherein n is 0-3, X is one or more selected from chloro, methoxy, ethoxy and acetoxy, and Y is one selected from vinyl, amino, epoxy, methacryloxy and ureido.
16. Use according to any one of claims 1 to 10, wherein the imperfect nanocrystals present in the barrier composite have a particle size of 10 to 40nm.
17. The use according to claim 11, wherein the imperfect nanocrystals present in the barrier composite have a particle size of 10-40 nm.
18. The use according to claim 12, wherein the imperfect nanocrystals present in the barrier composite have a particle size of 10-40 nm.
19. The use according to any one of claims 1 to 10, wherein the reaction temperature of the graft modification in step (1) is 40 to 70 ℃.
20. The use according to claim 19, wherein the reaction temperature of the graft modification in step (1) is 40 ℃.
21. The use according to any one of claims 1 to 10, wherein the reaction time of the graft modification in step (1) is 2h.
22. The use according to any one of claims 1 to 10, wherein the reaction pressure of the graft modification in step (1) is 10 to 25MPa.
23. The use according to claim 22, wherein the reaction pressure of the graft modification in step (1) is 20MPa.
24. The use according to any one of claims 1 to 10, wherein the stirring rate of the stirring reaction in step (1) is 180r/min.
25. Use according to any one of claims 1-10, wherein multistage stretch extrusion is carried out with a draw rate of 80-100r/min.
26. Use according to claim 25, wherein multistage stretching extrusion is carried out with a draw rate of 90-100r/min.
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