CN111548606A - High-strength super-toughness modified graphene/PET barrier composite material, and preparation and application thereof - Google Patents
High-strength super-toughness modified graphene/PET barrier composite material, and preparation and application thereof 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-tough silane coupling agent modified graphene/polyethylene glycol terephthalate barrier composite material and a preparation method thereof, wherein a nano-scale crystal structure exists in a microstructure of the barrier composite material, and the barrier composite material is prepared from the following raw materials: the modified graphene is used as a filler, and the polyethylene terephthalate is used as a matrix resin, wherein the modified graphene is prepared from the following raw materials: pristine 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, and induces the composite material microstructure to form a nano-scale crystalline phase and amorphous phase separation bionic microstructure by using the heterogeneous nucleation effect and the space limitation effect of the laminated graphene combined by a multistage stretching and extruding process, so that the toughness of the composite material is obviously improved, the strength is obviously improved, and the barrier composite material has excellent barrier property.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-strength and super-tough silane coupling agent modified graphene/polyethylene glycol 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, large ductility and high fracture toughness show wide application prospects. However, since the toughness and strength of polymer composites are generally mutually exclusive due to different molecular mechanisms of action, most of the current research is trying to improve the toughness and ductility of polymer composites, and at the same time, the strength of the materials is inevitably reduced. Therefore, the development of polymer composite materials with high strength, high ductility and multiple functionalities remains a great challenge in the field of material science.
In order to solve the problem of considering both the toughness and the toughness of the polymer composite material, the current research mostly focuses on the construction of a bionic structure, wherein the construction of the microstructure of spider silks and mussel byssus is a hot point of research. The excellent obdurability of the spider silk and the mussel byssus is found to be caused by the closely-ordered dynamic hydrogen bonding in a nano phase separation structure and a nano crystal phase limited region assembled in a multi-level mode. 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 a 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, large 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 above problems, the inventors of the present invention have made intensive studies, and have used a silane coupling agent to graft modified graphene, and mixed the modified graphene with PET, wherein the organic molecular chain of the silane coupling agent on the surface of the graphene makes the graphene have better compatibility and dispersibility in the PET matrix; and the method is based on the principle of polymer limited crystallization, and utilizes the heterogeneous nucleation and space limitation of oriented stress bonding layer sheet Graphene (GNs) with strong multistage stretching extrusion process to induce the formation of a large number of crystal nuclei in a PET matrix, the crystal nuclei are mutually limited to form limited nano crystals in the growth process, a nano crystalline phase and amorphous phase separation bionic microstructure is constructed, and the polymer composite material with high strength, large ductility and high fracture toughness is obtained. The invention provides a method for preparing a polymer composite material with high strength, large ductility and high fracture toughness, which has the advantages of simple process, realization by using the existing processing equipment, high production efficiency, no toxicity, environmental protection and good industrial application prospect.
According to the barrier composite material, the principle of limited crystallization is adopted, the heterogeneous nucleation effect and the space limitation effect of the flaky graphene combined with the multi-stage stretching and extruding process are utilized to induce the nano-scale crystalline phase and amorphous phase separation bionic microstructure to be 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 performance.
Specifically, in order to solve the above technical problems, the present invention provides the following technical solutions:
a silane coupling agent modified graphene/polyethylene terephthalate barrier composite material, wherein a nano-scale crystalline structure exists in the 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: pristine graphene and a silane coupling agent.
Preferably, for the barrier composite, the ratio of the modified graphene: the mass ratio of the polyethylene glycol terephthalate is 0.01-0.1: 100, preferably 0.03-0.1: 100, and more preferably 0.05 to 0.1: 100.
preferably, for the barrier composite, the ratio of original graphene: the mass ratio of the silane coupling agent is 1: 5-15, preferably 1: 10-15.
Preferably, for the barrier composite material, the sheet diameter of the original graphene is 10-19 μm, preferably 13 μm;
the number of the original graphene layers is 3-8, and 5-6 layers are preferred;
the specific surface area of the original graphene is more than or equal to 400m2/g。
Preferably, the barrier composite material is characterized in that the intrinsic viscosity of the polyethylene terephthalate is 0.7850-0.815 dl/g.
Preferably, for the barrier composite, the silane coupling agent is a silane coupling agent containing a compound represented by the following general formula: y (CH)2)nSiX3Wherein n is 0 to 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;
preferably one or more selected from gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane; further preferred is gamma-glycidoxypropyltrimethoxysilane.
Preferably, the particle size of the imperfect nano-crystalline existing in the barrier composite material is 10-40 nm.
The preparation method of the silane coupling agent modified graphene/PET barrier composite material in any section comprises the following steps:
(1) stirring and reacting original graphene by adopting a silane coupling agent in a reaction medium, and carrying out surface grafting modification;
(2) and (2) mixing the modified graphene obtained by the reaction in the step (1) with polyethylene glycol terephthalate, and performing multi-stage stretching extrusion.
Preferably, for the preparation method, wherein the reaction medium in step (1) is: supercritical carbon dioxide;
preferably, the reaction temperature of the graft modification in the step (1) is 40-70 ℃, and further preferably is 40 ℃;
preferably, the reaction time of the grafting modification in the step (1) is 1-5 h, and further preferably 2 h;
preferably, the reaction pressure of the grafting modification in the step (1) is 10-25 MPa, and further preferably the reaction pressure is 20 MPa;
preferably, the stirring speed of the stirring reaction in the step (1) is 120-180 r/min, and further preferably 180 r/min.
Preferably, in the preparation method, the number of the split-overlap units used in the multistage drawing extrusion in the step (2) is as follows: 5 (2048 layers) of the composite material,
preferably, the drawing rate for the multistage drawing extrusion is 80 to 100r/min, more preferably 90 to 100 r/min.
A silane coupling agent modified graphene/polyethylene glycol terephthalate barrier composite material is prepared by the preparation method in any one of the above paragraphs.
The barrier composite material in any section is applied to the fields of flexible lighting, flexible wearable photoelectric devices and artificial ligaments.
The beneficial effects of the invention include:
(1) the invention introduces the organic molecular chain of the silane coupling agent to the surface of the graphite. The compatibility and the dispersibility of the modified graphene in a 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
Figure 1 is an SEM photograph of the barrier composite prepared in comparative example 1 after etching with 10% KOH (mass concentration) aqueous solution;
figure 2 is an SEM photograph of the barrier composite prepared in comparative example 2 after etching with 10% KOH (mass concentration) aqueous solution;
figure 3 is an SEM photograph of the barrier composite prepared in comparative example 3 after etching with 10% KOH (mass concentration) aqueous solution;
figure 4 is an SEM photograph of the barrier composite prepared in example 1 after etching with 10% KOH (mass concentration) aqueous solution;
figure 5 is an SEM photograph of the barrier composite prepared in example 2 after etching with 10% KOH (mass concentration) aqueous solution;
figure 6 is an SEM photograph of the barrier composite prepared in example 3 after etching with 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 IR spectrum of graphene before and after KH570 modification in example 3;
FIG. 12 is WAXD (Wide-angle X-ray diffraction) curves of the products obtained in comparative example 1, comparative example 2 and example 1, example 2, example 3;
fig. 13 is a schematic structural view of a multi-stage stretching and extruding system used in the present invention, which comprises the following specific components: a hopper, a heating unit, a splitting-superposing unit, a stretching roller, and a sheet; wherein the dividing-superposing unit includes: the process of cutting, 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) with a nano crystalline phase and amorphous phase separation microstructure, high strength, large ductility and high fracture toughness, and the inventor finds out after intensive research: firstly, by utilizing a surface grafting modification principle, introducing a silane coupling agent molecular chain 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 polymer limited crystallization principle, utilizing the strong orientation stress of the multistage stretching extrusion process and the heterogeneous nucleation and space limitation effects of the bonding layer flaky Graphene (GNs), inducing the PET matrix added with the modified graphene to form a large number of crystal nuclei, mutually limiting the crystal nuclei to form limited nano crystals in the growth process, constructing a microstructure with separated nano crystal phases and amorphous phases, and finally obtaining the polymer barrier composite material with high strength, large ductility and high fracture toughness.
On the other hand, the invention also provides a method for preparing the polymer composite material with high strength, large ductility and high fracture toughness, which has the advantages of simple process, realization by using the existing processing equipment, high production efficiency, no toxicity, environmental protection and good industrial application prospect.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) silane coupling agent modified graphene: dispersing silane coupling agent in ethanol/water mixed solution, adjusting pH value of the mixed solution with acid, hydrolyzing, adding hydrolyzed silane coupling modifier solution and GNs into supercritical carbon dioxide (Sc-CO)2) In a reaction kettleReacting for a certain time, then repeatedly washing graphene with water, and drying in vacuum to obtain silane coupling agent modified graphene;
(2) preparing a modified GNs/PET barrier composite material: and (2) mixing the silane coupling agent modified graphene obtained in the step (1) with PET, and putting the mixture into a multistage stretching and extruding system (by utilizing repeated shearing and superposition 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 segmentation-superposition unit and a neck mold of the double-screw extruder are respectively 180 ℃, 240 ℃, 255 ℃, 260 ℃ and 255 ℃, the traction speed is 80-100r/min, and the thickness of the sheet is controlled to be 0.6 +/-0.1 mm.
Wherein Sc-CO is used in the invention2The reaction kettle and the double-screw extruder are respectively as follows: a GSH type reaction kettle produced by chemical machinery, Inc. is built in Thaixing;
the double-screw extruder is a TE-20 type extruder of Nanjing Jie ya extrusion equipment Co., Ltd;
the dividing-superposing unit is designed for the subject group, and the dividing-superposing unit, also called multiplier, is designed for the subject group to find the person to process, and the specific structure is shown in the attached figure 13.
Instruments, equipment, etc., not listed herein are commercially available to those of ordinary skill in the art.
The present invention will be described in further detail below by way of examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art without departing from the spirit and scope of the invention.
Examples
In the following examples of the present invention, the sources of the raw materials used were respectively:
raw graphene: shanxi institute of coal chemistry, Chinese academy of sciences, high-activity graphene, 1000 meshes (13 mu m), 5-6 layers and 400m of specific surface area2G and/orThe above step (1);
silane coupling agent: gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), gamma- (methacryloyloxy) propyltrimethoxysilane (KH570) were purchased from Jie chemical technologies, Inc., Guangzhou;
PET: manufactured by Yuanzao industries (Shanghai) Co., Ltd., type CB602, and having an intrinsic viscosity of 0.800. + -. 0.015 dl/g.
Example 1
Table 1 example 1 raw material composition
(1) Silane coupling agent modified graphene
First 10g of gamma-aminopropyltriethoxysilane (KH550) were dispersed in 40g of ethanol: adjusting the pH value to 4 with acetic acid in a mixed solution with the water mass ratio of 9:1(w/w), and stirring and hydrolyzing for 2 hours at room temperature and 25 ℃;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO2In a reaction kettle, reacting for 2 hours at the temperature of 40 ℃, the pressure of 20MPa and the stirring speed of 180r/min, taking out a reaction product, 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-1.
(2) Preparation of modified GNs/PET barrier composite material
Uniformly mixing 10.3g of the modified GNs prepared in the step (1) with 1000g of PET resin (the weight ratio is 0.03:100), and putting the mixture into a multistage stretching and extruding system containing 5 splitting-laminating units (2048 layers) for melt extrusion to prepare the sheet-shaped modified GNs/PET barrier composite material (expressed as composite material A).
Wherein the temperatures of a feeding section, a conveying section, a melting section, a homogenizing section, a melt pump, a segmentation-superposition unit and a neck mold of the double-screw extruder are respectively 180 ℃, 240 ℃, 255 ℃, 260 ℃ and 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 and experimental operation were the same as in example 1, step (1), to obtain modified graphene: GNs-2;
(2) preparing a modified GNs/PET composite material: the addition amount and experimental operation are the same as those in the step (2) of the example 1, and finally the sheet-shaped modified GNs/PET barrier composite material (represented by the composite material B) is prepared.
Example 3
Table 3 example 3 raw material composition
(1) Silane coupling agent modified graphene: the addition amount and experimental operation were the same as in example 1, step (1), to obtain modified graphene: GNs-3;
(2) preparing a modified GNs/PET composite material: the addition amount and experimental operation are the same as those in the step (2) of the example 1, and finally the sheet-shaped modified GNs/PET barrier composite material (expressed as the composite material C) is prepared.
Example 4
Table 4 example 4 raw material composition
(1) Silane coupling agent modified graphene
First (by weight of GNs) (5% wt)0.05g of gamma-aminopropyltriethoxysilane (KH560) was dispersed in 40g of ethanol: adjusting the pH value to 4 with acetic acid in a mixed solution with the water mass ratio of 7:3(w/w), and stirring and hydrolyzing for 2 hours at room temperature and 25 ℃;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO2Reacting in a reaction kettle at 60 deg.C and 25MPa at a stirring rate of 150r/min for 4 hr, taking out the reaction product, repeatedly washing with deionized water, and washing with deionized waterDrying in a vacuum drying oven at 80 ℃ for 12h to obtain the modified graphene: GNs-4.
(2) Preparing a modified GNs/PET composite material:
uniformly mixing 40.3 g of the modified GNs prepared in the step (1) with 1000g of PET (weight ratio of 0.03:100), and putting the mixture into a multistage stretching and extruding system containing 5 splitting-laminating units (2048 layers) for melt extrusion to prepare the sheet-shaped modified GNs/PET barrier composite material (expressed as composite material D).
Wherein the temperatures of a feeding section, a conveying section, a melting section, a homogenizing section, a melt pump, a segmentation-superposition unit and a neck mold of the double-screw extruder are respectively 180 ℃, 240 ℃, 255 ℃, 260 ℃ and 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
Firstly, 0.15g (15 wt percent) of gamma-aminopropyltriethoxysilane (KH560) (based on the weight of GNs) is dispersed in a 7:3(w/w) mixed solution of ethanol and water, the pH value is adjusted to 4 by acetic acid, and the mixture is stirred and hydrolyzed at room temperature of 25 ℃ for 2 hours;
adding the hydrolyzed silane modifier solution and 1g of original GNs into Sc-CO2In a reaction kettle, reacting for 1 hour at the temperature of 70 ℃, the pressure of 10MPa and the stirring rate of 180r/min, taking out a reaction product, 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 50.3 g of the modified GNs prepared in the step (1) with 1000g of PET (weight ratio of 0.03:100), and putting the mixture into a multistage stretching and extruding system containing 5 splitting-laminating units (2048 layers) for melt extrusion to prepare the flaky modified GNs/PET barrier composite material (expressed as composite material E).
Wherein the temperatures of a feeding section, a conveying section, a melting section, a homogenizing section, a melt pump, a segmentation-superposition unit and a neck mold of the double-screw extruder are respectively 180 ℃, 240 ℃, 255 ℃, 260 ℃ and 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 addition amount and the operation parameters are the same as those in the step (1) of the example 5, so that the modified graphene is obtained: GNs-6;
(2) preparation of modified GNs/PET composite Material
After uniformly mixing 60.1 g of the modified GNs prepared in the step (1) and 1000g of PET (weight ratio of 0.01:100), the rest of the operation and parameters are the same as those in the step (2) of 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 addition amount and the operation parameters are the same as those in the step (1) of the example 5, so that the modified graphene is obtained: GNs-7;
(2) preparation of modified GNs/PET barrier composite material
And (2) uniformly mixing 70.5G of the modified GNs prepared in the step (1) and 1000G of PET (the weight ratio is 0.05:100), and finally preparing the sheet-shaped modified GNs/PET barrier composite material (expressed as a composite material G) by the same operation and parameters as those in the step (2) in the example 5.
Example 8
Table 8 example 8 raw material composition
(1) Silane coupling agent modified graphene: the addition amount and the operation parameters are the same as those in the step (1) of the example 5, so that the modified graphene is obtained: GNs-8;
(2) preparation of modified GNs/PET composite Material
After uniformly mixing the modified GNs-81 g prepared in the step (1) and 1000g of PET (weight ratio of 0.1:100), the rest of the operation and parameters are the same as those in the step (2) of 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
Preparation of pure PET sheets: the dried PET1000g was directly fed into a multistage stretch extrusion system to be melt-extruded to produce a PET sheet. The twin-screw extruder operating parameters were the same as in example 1.
Comparative example 2
Preparation of unmodified GNs/PET composites: unmodified GNs were mixed with PET in a weight ratio of 0.03:100 and a sheet-like raw GNs/PET composite was prepared according to the procedure of comparative example 1, with the thickness of the sheet controlled at 0.6 ± 0.1 mm.
Comparative example 3
0.3g of unmodified GNs and 1000g of PET resin (weight ratio of 0.03:100) are uniformly mixed, and then put into a multi-stage stretching extrusion system containing 3 split-superposition units (256 layers) for melt extrusion to prepare the 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 segmentation-superposition unit and a neck mold of the double-screw extruder are respectively 180 ℃, 240 ℃, 255 ℃, 260 ℃ and 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 described above, the following tests were carried out:
(1) infrared spectrum test: infrared spectroscopy was performed on 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, as shown in fig. 9, using the following instruments: NEXUS 570 from Nicolet, USA.
(2) And (3) crystal morphology observation: the sheet materials obtained in examples 1 to 8 and comparative examples 1 to 3 were etched with 10% KOH (mass concentration) aqueous solution for 1 hour and then observed for crystal morphology by a scanning electron microscope, the model of which is as follows: quanta FEG model 250 scanning electron microscope (FEI, USA).
(3) Oxygen and water vapor permeability test: an Ox-Tran Model 2/21 Model oxygen permeameter (gas: high purity oxygen, temperature: 23 + -1 deg.C, sample size: 50 cm) from MOCON was used2) And PERMATRAN-W3/33 type moisture vapor permeability apparatus (gas: water vapor, temperature: 23 ± 1 ℃, humidity: 100%, sample size: 50cm2) The oxygen permeability and the water vapor permeability were respectively measured according to the ASTM D3985-2005 standard.
(4) And (3) testing mechanical properties: the prepared sheet material is prepared into a standard dumbbell type sample by using a dumbbell type prototype making machine, and then the tensile strength and the elongation at break are tested by adopting a CMA6104 universal testing machine of Shenzhen New Sansi material detection Limited according to GB/T1040-.
(5) WAXD (wide angle X-ray diffraction) test: model Bruker-xrf polycrystalline X-ray diffractometer (WAXD, brueck, germany) CuK α 40kV/30mA, 2 θ 5-60 °.
The above detection results were analyzed as follows:
(1) infrared spectrogram analysis: fig. 9 shows that the original graphene is 1100cm higher than the graphene modified with KH550 in example 1-1Has a characteristic peak nearby, and the characteristic peak of Si-O bond in the silane coupling agent is also 1000cm-1Nearby, therefore, the characteristic peak of the Si-O bond is covered, and the modified graphene is at 1450cm-1An N-H group characteristic peak appears nearby, and the silane coupling agent KH550 is proved to be introduced into the graphene;
as shown in fig. 10, at 900cm-1A CN (O) CH characteristic peak appears nearby, and the silane coupling agent KH560 is proved to be introduced into the graphene;
as shown in FIG. 11, at 1800cm-1The characteristic peak of C ═ O appears nearby, which proves that the stone is covered withThe graphene is introduced with a silane coupling agent KH 570.
(2) SEM analysis: as shown in the accompanying fig. 1-6, 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 material of a product obtained in comparative example 3, and fig. 4-6 are scanning electron microscope images of modified GNs/PET composite sheets of example 1, example 2 and example 3, respectively.
From the scanning electron micrograph, it can be seen that: pure PET has relatively large grain size, and the grain size of the pure PET (comparative example 1) in the figure 1 is about 100-180nm, and the modified GNs/PET sheet prepared by 5 splitting-superposing units (2048 layers) and the unmodified CNs/PET composite sheet in the figure 2 are adopted in the figures 4-6 to form a large number of grains with the size of about 10-40nm, which are obtained by statistics of Nano Measurer software;
in contrast, the composite sheet prepared by using 3 dividing-laminating units (256 layers) in fig. 3 has a grain size of about 200-400nm, which is significantly larger than that of the CNs/PET composite sheet prepared by using 5 dividing-laminating 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 and water vapor permeability tests and mechanical property test results are shown in the following table:
TABLE 9 results of testing Properties of materials of examples 1 to 8 and comparative examples 1 to 3
As can be seen from table 8 above, compared with the pure PET sheet prepared in comparative example 1, the graphene modified by adding a small amount of silane coupling agent, prepared in examples 1 to 8 of the present invention, can significantly improve the water vapor permeability, oxygen permeability and mechanical properties of the composite sheet;
the modified CNs/PET barrier composite material sheet prepared in the embodiment 1 has the lowest oxygen permeability, and compared with the oxygen permeability of a pure PET resin sheet, the oxygen barrier performance is improved by more than 60%; the modified CNs/PET composite material sheet in the embodiment 5 has the lowest water vapor permeability, and compared with a pure PET resin sheet, the water vapor barrier property is improved by more than 93%, 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 a pure PET resin sheet, the mechanical properties of the modified CNs/PET barrier composite material sheet are improved, wherein the tensile strength can reach more than 70MPa, the elongation at break can reach 722 percent, the modified CNs/PET barrier composite material sheet is far higher than the pure PET sheet, and the modified CNs/PET barrier composite material sheet has higher strength and excellent toughness.
The oxygen permeability of the modified CNs/PET barrier composite material sheets in the embodiments 1-8 of the invention is 2.7-4.6 (cc/m)2Day) and a water vapor permeability of 0.07 to 4.3 (gm/m)2Day), tensile strength of 52-75MPa, elongation at break of 614-722%; the products prepared in examples 1-2 and 6-8 have the best overall performance, with oxygen permeabilities of 2.7-4.3 (cc/m)2Day) and a water vapor permeability of 0.07 to 0.5 (gm/m)2Day), tensile strength of 60-75MPa, elongation at break of 620-670%.
The mechanism is known as follows: the barrier property of the CNs/PET barrier composite material is closely related to the interfacial bonding bond between CNs and PET matrix, for example, in example 2, the GNs modified by KH560 have the lowest water vapor permeability, but the oxygen permeability is not the best, mainly because the bonds generated by the reaction of KH560 epoxy groups and the terminal hydroxyl and carboxyl groups in the PET molecular chain and O2The molecules have an affinity effect and thus the oxygen barrier properties are not significantly improved, and furthermore, the KH 570-modified GNs produce composites with less significant water barrier properties due to the affinity of the water vapor molecules to the binding bonds. The barrier properties of the composite are determined by the dispersion distribution of GNs in the matrix, the nature of the interface, and the affinity of the interface with water vapor and oxygen molecules.
And compared with the performances of the unmodified CNs/PET barrier composite material sheets in the comparative examples 2 and 3, the tensile strength and the elongation at break of the modified CNs/PET barrier composite material sheet are improved, but mainly because the CNs modified by siloxane have better compatibility and dispersibility in a PET matrix due to organic molecules on the surface compared with the original CNs.
Claims (12)
1. The silane coupling agent modified graphene/polyethylene glycol terephthalate barrier composite material is characterized in that a nano-scale crystal structure exists in a 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: pristine graphene and a silane coupling agent.
2. The barrier composite of claim 1, wherein the modified graphene: the mass ratio of the polyethylene glycol terephthalate is 0.01-0.1: 100, preferably 0.03-0.1: 100, and more preferably 0.05 to 0.1: 100.
3. the barrier composite of claim 1 or 2, wherein the raw graphene: the mass ratio of the silane coupling agent is 1: 5-15, preferably 1: 10-15.
4. The barrier composite of any one of claims 1 to 3, wherein the pristine graphene has a platelet diameter of 10 μm to 19 μm, preferably 13 μm;
the number of the original graphene layers is 3-8, and 5-6 layers are preferred;
the specific surface area of the original graphene is more than or equal to 400m2/g。
5. The barrier composite of any one of claims 1 to 4, wherein the polyethylene terephthalate has an intrinsic viscosity of 0.7850 to 0.815 dl/g.
6. The barrier composite of any one of claims 1 to 5, wherein the silane coupling agent is a silane coupling agent comprising the general formula: y (CH)2)nSiX3Wherein n is 0 to 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;
preferably one or more selected from gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane; further preferred is gamma-glycidoxypropyltrimethoxysilane.
7. The barrier composite of any one of claims 1 to 6, wherein the imperfect nanocrystals present in the barrier composite have a particle size of 10 to 40 nm.
8. The preparation method of the silane coupling agent modified graphene/PET barrier composite material of any one of claims 1 to 7, characterized by comprising the following steps:
(1) stirring and reacting original graphene by adopting a silane coupling agent in a reaction medium, and carrying out surface grafting modification;
(2) and (2) mixing the modified graphene obtained by the reaction in the step (1) with polyethylene glycol terephthalate, and performing multi-stage stretching extrusion.
9. The production method according to claim 8, wherein the reaction medium in step (1) is: supercritical carbon dioxide;
preferably, the reaction temperature of the graft modification in the step (1) is 40-70 ℃, and further preferably is 40 ℃;
preferably, the reaction time of the grafting modification in the step (1) is 1-5 h, and further preferably 2 h;
preferably, the reaction pressure of the grafting modification in the step (1) is 10-25 MPa, and further preferably the reaction pressure is 20 MPa;
preferably, the stirring speed of the stirring reaction in the step (1) is 120-180 r/min, and further preferably 180 r/min.
10. The production method according to claim 8 or 9, wherein the number of split-lay units used in the multistage draw extrusion in step (2) is: 5 (2048 layers) of the composite material,
preferably, the drawing rate for the multistage drawing extrusion is 80 to 100r/min, more preferably 90 to 100 r/min.
11. A silane coupling agent modified graphene/polyethylene terephthalate barrier composite material prepared by the preparation method of any one of claims 8-10.
12. Use of the barrier composite of any one of claims 1 to 7, or claim 11 in the field of flexible lighting, flexible wearable optoelectronic devices, artificial ligaments.
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