CN110777534B - PET industrial filament-based tire cord and preparation method thereof - Google Patents
PET industrial filament-based tire cord and preparation method thereof Download PDFInfo
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- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to a PET industrial silk-based tire cord and a preparation method thereof, wherein the preparation method comprises the following steps: covalently grafting a ligand of MOF on the surface of the PET industrial yarn, and growing MOF in situ on the surface of the PET industrial yarn by taking the ligand of MOF as a nucleation site to prepare the PET industrial yarn-based tire cord; the prepared PET industrial silk-based tire cord mainly comprises PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk. The preparation method of the PET industrial silk-based tire cord provided by the invention has the advantages of simple and feasible process and low cost, increases the roughness and surface energy of the fiber surface and the interface bonding strength between the fiber surface and rubber, can be used for various rubber products, can also be used in the fields of resin, plastics and the like, and has wide application prospects.
Description
Technical Field
The invention belongs to the technical field of polyester industrial yarns, and relates to a PET industrial yarn-based tire cord and a preparation method thereof.
Background
The automobile tire uses a large number of tire cords compounded with rubber to enhance its strength and dimensional stability, and the tire cords are one of the important factors determining the safety performance and life of the tire. Since the successful development of polyester cords by the american goodyear company in 1962, the development of the polyester cords has been rapidly progressed due to its excellent properties. The polyester industrial yarn has the advantages of high strength, large initial modulus, good thermal shrinkage and dimensional stability, but has high axial height orientation, high crystallinity, smooth surface and large chemical inertia, can not form chemical bonds with rubber and can not be easily wetted by the rubber, and the interfacial bonding force between the polyester industrial yarn and the rubber is low. In practical application, the excellent interface bonding strength between the tire cord and the rubber is required to ensure that the load can be uniformly and effectively transmitted before the fiber is damaged. Therefore, in order to improve the interface bonding strength, the surface modification of the polyester fiber is required.
The method for introducing active or polar groups on the surface of the polyester fiber mainly comprises 3 methods: firstly, surface heat treatment is carried out, so that spherulites appear on the surface of the material, and the roughness is increased; secondly, carrying out chemical reaction through functional groups such as benzene rings, ester groups and the like on the surface of the polyester fiber; and thirdly, active groups are directly introduced to the surface of the fiber through the action of high-energy plasmas such as plasmas and ultraviolet rays, or further chemical reaction or graft polymerization is initiated by using active centers such as active radicals and free radicals generated by high-energy particles (electron beams and cobalt sources). Among these methods, radiation-induced graft polymerization is a very effective method mainly due to its strong penetration ability into the substrate, the formation of uniform active sites on the substrate for grafting, no significant change in the properties obtained by graft polymerization, easy control of the reaction conditions, and no residue of any initiator in the reaction. In addition, radiation graft polymerization is very suitable for laboratory and industrial mass production. After the polyester industrial yarn is subjected to grafting modification, the polyester industrial yarn can be further treated by one or more of RFL (resorcinol-formaldehyde-latex), isocyanate or epoxy impregnation liquid, and the influence of the grafting treatment on the interface bonding strength is not only related to the grafting rate and the structure of a grafting group, but also related to the roughness of the surface of a material.
Conventional methods for increasing the surface roughness of fiber materials include etching the surface with strong acid or strong alkali (Tincotic Response of Recycled PET Fibers to Chemical modification of the resin and reactions, Ind. Eng. chem. Res.2014,53,16652 16663) or adhering inorganic nanoparticles to the surface of fiber materials by means of adhesives (Synthesis of a fluorine-free polymeric water-recycling agent for the creation of a hydrophobic fabric, application. rf. Sci.2017,426, 694-703), which both increase the surface energy while increasing the roughness. However, the former method causes damage to the inherent strength of the fiber, and both methods cause a decrease in the interfacial bonding strength between the fiber and the rubber because improper handling causes excessive processing and a decrease in the fiber volume fraction in the composite material, and the latter method does not allow the binder to firmly fix the nanoparticles to the surface of the fiber material.
Therefore, it is very important to research a method capable of simultaneously improving the roughness, the surface energy and the interfacial bonding strength between the PET industrial yarn and the rubber.
Disclosure of Invention
The invention aims to solve the problem that the roughness, the surface energy and the interface bonding strength between the polyester industrial yarn and rubber cannot be simultaneously improved by a method for modifying the polyester industrial yarn in the prior art, and provides a PET industrial yarn-based tire cord and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of a PET industrial silk-based tire cord comprises the steps of covalently grafting ligands of MOF on the surface of a PET industrial silk, and growing MOF in situ on the surface of the PET industrial silk by taking the ligands of MOF as nucleation sites to prepare the PET industrial silk-based tire cord.
Because the original fiber has smooth surface and lacks effective functional groups, crystal nucleus of the MOF can not grow on the surface of the fiber, so that the direct modification of the MOF on the surface of the fiber can not be realized, and the original fiber must be modifiedAnd (5) decorating. There are many methods for modifying the surface of the fiber, such as first depositing a layer of Al on the surface of the fiber by atomic deposition2O3ZnO or TiO2And then growing the UiO-66-NH in situ by heterogeneous nucleation2MOF of structure (UiO-66-NH2 Metal-Organic Framework (MOF) Nuclear TiO (MoF)2,ZnO,and Al2O3Atomic Layer Deposition-Treated Polymer Fibers, namely, Role of Metal Oxide on MOF Growth and catalysis Hydrolysis of Chemical Water Agent Simulans. ACS appl. Mat. interfaces 2017,9(51),44847 and 44855), but the MOF prepared in this way has poor durability of functional coatings due to lack of covalent bonds between the deposited layers and Fibers, easily falls off the Atomic deposited layers and the UiO-66-NH2 Layer, and in addition, Atomic Deposition equipment is expensive and the reaction conditions are harsh; for example, by oxidation, carboxyl groups (or acrylic acid grafts) are present on the surface of Fibers such as PET (Building Nanoporous metals-Organic framework "Armor" on Fibers for High-Performance Composite materials. ACS Appl. Mat. Interfaces 2017,9(6),5590-5599.) because the introduced carboxyl groups are not able to enter the UiO-66-NH2The crystal lattice of MOF, so there is a limit to the improvement of the interface bonding strength, while not enabling UiO-66-NH2A uniform coating layer is formed on the surface of the fiber, and the mechanical property of the fiber is greatly influenced by chemical oxidation; for example, the surface of the fiber is coated with a layer of dopamine as a binder ("MOF-cloth" for via Supramolecula arrangement of NH)2MIL-101(Cr) crystals on subpamine modified polyimide fiber for high temperature function paper-based filter, composites Part B: Engineering 2019,168,406-2Or the fibers are not connected by covalent bonds, and UiO-66-NH can appear after being used for many times2And the dopamine is expensive, so that large-scale application cannot be realized.
The invention introduces grafting chain with strong durability to the surface of PET fiber through covalent bond, then the ligand of MOF reacts with functional group on the grafting chain with strong durability, thereby realizing covalent bond linkage, then 3D MOF structure is constructed in situ on the fiber surface by taking MOF ligand as nucleation site, the roughness of the fiber surface can be improved by 3D MOF growth in situ on the fiber surface, thereby enhancing the mechanical anchoring force when the fiber is compounded with rubber, MOF has higher specific surface area and contains a large amount of polar organic ligand, which is beneficial to improving the fiber surface energy and wettability, the introduction of three-dimensional structure, and the high surface energy of MOF can simultaneously improve the roughness and surface energy of the fiber, on one hand, the influence on the inherent strength of the fiber is less due to the treatment mode, on the other hand, after the treatment by the treatment mode, when the fiber is compounded with glue solution, uncured small glue solution is easy to diffuse into the MOF or gaps, and the fiber is solidified in the MOF pore canal or the gap, so that the interface bonding force is improved, the interface bonding strength between the fiber and the rubber is greatly improved, and the method has good practical application value.
As a preferred technical scheme:
in the preparation method of the PET industrial silk-based tire cord, the ligand of the MOF is ATA (amino terephthalic acid), and the MOF is UiO-66-NH2；UiO-66-NH2The organic ligand contains active groups such as carboxyl, amino and the like, is easy to react with components in the glue solution, can further improve the interface bonding force with the fiber, and can also react with a polymer to form a mixed matrix membrane, so that the fiber functionalized surface in-situ grows UO-66-NH2Is an ideal means for improving the binding force.
The preparation method of the PET industrial silk-based tire cord comprises the following specific steps:
(1) GMA (glycidyl methacrylate) is grafted on the surface of the PET industrial yarn by radiation through a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, GMA is directionally grafted on the surface of the PET yarn by initiating free radical polymerization in the process of gamma-ray co-radiation grafting, and polymerization is carried out;
(2) initiating the amino group of ATA and the epoxy group of PET-g-PGMA to carry out ring-opening reaction to obtain PET-g-PGMA/ATA;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2Obtaining the PET industrial silk-based tire cord.
The invention firstGMA is grafted onto the surface of the fibres by irradiation (in order to introduce epoxide groups) and then by introducing UiO-66-NH2The amino group and the epoxy group in the ligand are subjected to ring-opening reaction, the ligand is introduced to the fiber surface in an in-situ covalent manner, and finally the MOF is loaded to the fiber surface in situ through subsequent reaction, and the process has the advantage that the grafted ligand can directly enter UiO-66-NH2Lattice sites which will maximize the interfacial bonding between the fibers and the MOF and enable UiO-66-NH2The MOF is uniformly coated on the surface of the fiber, so that the binding force of the MOF and the fiber is greatly improved, and the MOF has practical application value.
The preparation method of the PET industrial silk-based tire cord comprises the following steps of (1): firstly, extracting PET industrial yarn in alcohol I (specifically methanol or ethanol) at the temperature of 60-65 ℃ for 12-24 hours, drying (the drying temperature is 50-60 ℃ for 0.5-1 hour), then mixing the PET industrial yarn with alcohol II (specifically methanol and/or ethanol) and GMA, introducing nitrogen for 20-40 minutes at the temperature of 20-25 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 5-50 kGy, and then carrying out post-treatment (the post-treatment specific process comprises the steps of firstly ultrasonically cleaning the PET industrial yarn for 1-1.5 hours by using acetone and then drying in an oven at the temperature of 60 ℃) to obtain PET-g-PGMA.
According to the preparation method of the PET industrial silk-based tire cord, in the step (1), the weight part ratio of the PET industrial silk, the alcohol II and the GMA is 100: 1500-2500: 150-280.
The preparation method of the PET industrial silk-based tire cord comprises the following specific steps of (2): adding ATA into a DMSO aqueous solution, stirring for 10-15 min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1-1.5 h, reacting for 8-12 h at 75-90 ℃, and performing post-treatment (treating for 1-3 h with boiling water, then performing ultrasonic cleaning, and drying at 60 ℃) to obtain PET-g-PGMA/ATA.
In the preparation method of the PET industrial silk-based tire cord, in the step (2), the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 1-100: 1000-4500, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 1-15: 90-100: 80-110.
The preparation method of the PET industrial silk-based tire cord comprises the following specific steps of (3): firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1-2 hours to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 10-30 hours in a closed environment (specifically, the internal environment of a hydrothermal reaction kettle) at the temperature of 70-130 ℃, and finally performing post-treatment (namely performing ultrasonic cleaning treatment in water for 1-3 hours and drying at the temperature of 60 ℃) to obtain the PET industrial yarn-based tire cord.
According to the preparation method of the PET industrial silk-based tire cord, in the step (3), the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 20-100: 18-90: 9000-1100: 100-220.
The invention also provides a PET industrial silk-based tire cord prepared by the preparation method of the PET industrial silk-based tire cord, which mainly comprises the PET industrial silk, a ligand of MOF (metal organic framework) connected with the PET industrial silk through a covalent bond and MOF formed by taking the ligand of MOF as a nucleation site, wherein the MOF is wrapped on the surface of the PET industrial silk.
Has the advantages that:
(1) according to the preparation method of the PET industrial silk-based tire cord, GMA is grafted by adopting a co-irradiation grafting means at a lower dosage, so that the influence of irradiation on the degradation of a base material is reduced to the greatest extent;
(2) according to the preparation method of the PET industrial silk-based tire cord, the frame organic monomer is introduced through the ring-opening reaction, so that the fiber and the UiO-66-NH are improved2The interface bonding force between the fiber and the fiber increases the roughness of the fiber;
(3) the preparation method of the PET industrial silk-based tire cord has the advantages of simple and feasible process and lower cost;
(4) the PET industrial silk-based tire cord prepared by the method can be used for various rubber products, and can also be used in the fields of resin, plastics and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing a PET industrial filament-based tire cord of the present invention;
FIG. 2 shows virgin PET fibers (a) and PET/UiO-66-NH2(b) Scanning electron microscope images of;
FIG. 3 shows PET, PET-g-PGMA/ATA, and PET/UiO-66-NH2An infrared spectrum of (1);
FIG. 4 shows PET, PET/UiO-66-NH2And UiO-66-NH2XRD spectrum of (1).
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims. Example 1
A preparation method of PET industrial silk-based tire cord comprises the following specific steps, and the specific preparation process flow is shown in figure 1:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in methanol at the temperature of 60 ℃ for 24 hours, then drying the PET industrial yarn at the temperature of 50 ℃ for 1 hour, then mixing the PET industrial yarn, the methanol and GMA in a weight ratio of 100:1500:150, introducing nitrogen for 40 minutes at the temperature of 20 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 5kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of firstly ultrasonically cleaning the PET industrial yarn for 1 hour by using acetone, and then drying the PET industrial yarn in an oven at the temperature of 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 10min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1h, reacting for 12h at 75 ℃, performing post-treatment, treating for 1h with boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 1:1000, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 1:90: 80;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 30h in a sealed environment in a hydrothermal reaction kettle at the temperature of 70 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 1h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 20:18:9000: 100;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, ligands of MOF which are connected with the PET industrial silk through covalent bonds and MOF which is formed by taking the ligands of the MOF as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk; mixing the original PET fiber with PET/UiO-66-NH2The scanning electron microscope test was performed, and the results are shown in FIG. 2, where a is the original PET fiber and b is PET/UiO-66-NH2(ii) a Mixing PET, PET-g-PGMA/ATA and PET/UiO-66-NH2Infrared spectrum test is carried out, and the result is shown in figure 3; mixing PET, PET/UiO-66-NH2And UiO-66-NH2XRD testing was performed and the results are shown in FIG. 4.
The PET industrial yarn-based tire cord was compounded with rubber and then tested to have an average value of adhesion peel strength of 11.9N/mm.
Comparative example 1
A PET industrial yarn, which is the PET industrial yarn in the step (1) in the embodiment 1 without other steps in the embodiment 1; after the PET industrial yarn was compounded with rubber, the average value of the adhesion peel strength was measured to be 7.8N/mm.
Comparing the comparative example 1 with the example 1, it can be seen that the adhesive peel strength in the comparative example 1 is significantly lower than that in the example 1, because the MOF in the example 1 grows in situ on the fiber surface to improve the roughness of the fiber surface, thereby enhancing the mechanical anchoring force when the fiber is compounded with rubber, the MOF has a higher specific surface area and contains a large amount of polar organic ligands, which is beneficial to improving the fiber surface energy and wettability, the introduction of three-dimensional structure, and the MOF high surface energy simultaneously improves the roughness and surface energy of the fiber, on one hand, because the treatment mode has less influence on the inherent strength of the fiber, on the other hand, because after the treatment mode, when the MOF is compounded with glue, the uncured glue solution small molecules are easy to diffuse into the MOF or gaps, and are cured in the MOF pore channels or gaps, thereby improving the interface bonding force, therefore, the method greatly improves the interface bonding strength between the fiber and the rubber.
Example 2
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in ethanol at 65 ℃ for 12 hours, drying at 55 ℃ for 0.7 hour, then mixing the PET industrial yarn, the ethanol and GMA at a weight ratio of 100:2000:200, introducing nitrogen for 30 minutes at 24 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with an absorbed dose of 20kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of firstly ultrasonically cleaning the PET industrial yarn by using acetone for 1.2 hours, and then drying in an oven at 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 12min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.2h, reacting for 10h at 80 ℃, performing post-treatment, treating for 2h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 20:2000, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 10:95: 100;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 2h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 25h in a closed environment in a hydrothermal reaction kettle at the temperature of 80 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 2h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 50:40:4000: 150;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 3
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in methanol at the temperature of 64 ℃ for 14 hours, then drying the PET industrial yarn at the temperature of 60 ℃ for 0.5 hour, then mixing the PET industrial yarn with the weight portion ratio of 100:2500:280, a mixture of methanol and ethanol with the mass ratio of 1:1 and GMA, introducing nitrogen for 20 minutes at the temperature of 25 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 40kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of ultrasonically cleaning the PET industrial yarn for 1.3 hours by using acetone, and then drying the PET industrial yarn in an oven at the temperature of 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 14min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.3h, reacting for 8h at 90 ℃, performing post-treatment, treating for 3h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 40:4500, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 15:100: 110;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 20h in a closed environment in a hydrothermal reaction kettle at the temperature of 100 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 3h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 100:50:1100: 220;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 4
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in ethanol at the temperature of 60 ℃ for 24 hours, drying at the temperature of 53 ℃ for 0.6 hour, then mixing the PET industrial yarn with methanol and GMA at the weight ratio of 100:1800:180, introducing nitrogen for 30 minutes at the temperature of 23 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 30kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of firstly ultrasonically cleaning the PET industrial yarn by using acetone for 1.5 hours, and then drying in an oven at the temperature of 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 15min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.5h, reacting for 12h at 75 ℃, performing post-treatment, treating for 2h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 50:2000, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 1:90: 100;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1.5h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 10h in a sealed environment in a hydrothermal reaction kettle at the temperature of 130 ℃, and finally performing post-treatment, namely firstly performing ultrasonic cleaning treatment for 2h in water, and then drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 80:70:6000: 150;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 5
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: extracting PET industrial yarn in methanol at 65 ℃ for 12 hours, drying at 57 ℃ for 0.6 hour, mixing the PET industrial yarn with ethanol and GMA at a weight ratio of 100:2000:220, introducing nitrogen for 20 minutes at 22 ℃, irradiating the mixture for 17 hours by using a cobalt source with an absorbed dose of 50kGy, performing post-treatment, wherein the post-treatment comprises the specific steps of ultrasonically cleaning the PET industrial yarn by using acetone for 1.2 hours, and drying in an oven at 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 12min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.4h, reacting for 10h at 85 ℃, performing post-treatment, treating for 1h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 100:3000, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 10:100: 100;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 15h in a closed environment in a hydrothermal reaction kettle at the temperature of 120 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 1h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 60:50:5500: 180;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 6
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in methanol at the temperature of 62 ℃ for 16 hours, drying at the temperature of 55 ℃ for 0.8 hour, then mixing the PET industrial yarn with the weight portion ratio of 100:2300:250, a mixture of methanol and ethanol with the mass ratio of 1:1 and GMA, introducing nitrogen for 40 minutes at the temperature of 20 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 20kGy, and performing post-treatment, wherein the post-treatment comprises the specific steps of ultrasonically cleaning the PET industrial yarn for 1.4 hours by using acetone, and then drying in an oven at the temperature of 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 13min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.2h, reacting for 9h at 90 ℃, performing post-treatment, treating for 2h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 80:4000, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 5:95: 95;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1.5h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 23h in a closed environment in a hydrothermal reaction kettle at the temperature of 110 ℃, and finally performing post-treatment, namely firstly performing ultrasonic cleaning treatment for 2h in water, and then drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 20:30:2200: 120;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 7
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in methanol at 63 ℃ for 15 hours, drying at 55 ℃ for 0.8 hour, then mixing the PET industrial yarn with methanol and GMA at a weight ratio of 100:1600:170, introducing nitrogen for 20 minutes at 25 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with an absorbed dose of 30kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of firstly ultrasonically cleaning the PET industrial yarn by using acetone for 1.3 hours, and then drying in an oven at 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 14min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.2h, reacting for 11h at 75 ℃, performing post-treatment, treating for 2h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 10:1500, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 5:100: 90;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 2h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 25h in a closed environment in a hydrothermal reaction kettle at the temperature of 100 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 2h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 100:85:1500: 200;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Example 8
A preparation method of PET industrial silk-based tire cord comprises the following specific steps:
(1) the method comprises the following steps of (1) carrying out radiation grafting on GMA on the surface of a PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA, wherein the method specifically comprises the following steps: firstly, extracting PET industrial yarn in ethanol at the temperature of 60 ℃ for 24 hours, drying at the temperature of 60 ℃ for 0.5 hour, then mixing the PET industrial yarn with ethanol and GMA in a weight ratio of 100:1900:200, introducing nitrogen for 40 minutes at the temperature of 20 ℃, finally irradiating the mixture for 17 hours by using a cobalt source with the absorption dose of 40kGy, and then carrying out post-treatment, wherein the post-treatment comprises the specific steps of firstly ultrasonically cleaning the PET industrial yarn for 1.2 hours by using acetone, and then drying in an oven at the temperature of 60 ℃ to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and carrying out ring-opening reaction on the epoxy group of PET-g-PGMA to obtain PET-g-PGMA/ATA, which specifically comprises the following steps: adding ATA into a DMSO aqueous solution, stirring for 15min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1.2h, reacting for 10h at 80 ℃, performing post-treatment, treating for 2h by using boiling water, performing ultrasonic cleaning, and drying at 60 ℃ to obtain PET-g-PGMA/ATA; wherein the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 30:2500, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 5:95: 95;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2The PET industrial silk-based tire cord is obtained by the following steps: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1h to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 20h in a closed environment in a hydrothermal reaction kettle at the temperature of 90 ℃, and finally performing aftertreatment, namely performing ultrasonic cleaning treatment for 2h in water, and drying at the temperature of 60 ℃ to obtain the PET industrial silk-based tire cord, namely PET/UiO-66-NH2(ii) a Wherein the weight part ratio of zirconium tetrachloride to ATA to DMF to PET-g-PGMA/ATA is 50:45:5000: 150;
the prepared PET industrial silk-based tire cord consists of PET industrial silk, MOF ligands connected with the PET industrial silk through covalent bonds and MOF formed by taking the MOF ligands as nucleation sites, wherein the MOF is coated on the surface of the PET industrial silk.
Claims (8)
1. A preparation method of PET industrial silk-based tire cord is characterized by comprising the following steps: covalently grafting a ligand of MOF on the surface of the PET industrial yarn, and growing MOF in situ on the surface of the PET industrial yarn by taking the ligand of MOF as a nucleation site to prepare the PET industrial yarn-based tire cord;
the ligand of the MOF is ATA, and the MOF is UiO-66-NH2；
The preparation method of the PET industrial silk-based tire cord comprises the following specific steps:
(1) carrying out radiation grafting on GMA on the surface of the PET industrial yarn by a gamma-ray co-radiation grafting method to obtain PET-g-PGMA;
(2) initiating the amino group of ATA and the epoxy group of PET-g-PGMA to carry out ring-opening reaction to obtain PET-g-PGMA/ATA;
(3) in-situ growth of UiO-66-NH on the surface of PET-g-PGMA/ATA by using a solvothermal method2Obtaining the PET industrial silk-based tire cord.
2. The method for preparing the PET industrial silk-based tire cord as claimed in claim 1, wherein the step (1) is specifically as follows: firstly, extracting PET industrial yarn in alcohol I at the temperature of 60-65 ℃ for 12-24 h, drying, then mixing the PET industrial yarn with alcohol II and GMA, introducing nitrogen for 20-40 min at the temperature of 20-25 ℃, finally irradiating the mixture for 17h by using a cobalt source with the absorption dose of 5-50 kGy, and then carrying out post-treatment to obtain PET-g-PGMA.
3. The method for preparing the PET industrial silk-based tire cord as claimed in claim 2, wherein in the step (1), the weight part ratio of the PET industrial silk, the alcohol II and the GMA is 100: 1500-2500: 150-280.
4. The method for preparing the PET industrial silk-based tire cord as claimed in claim 1, wherein the step (2) is specifically as follows: adding ATA into a DMSO aqueous solution, stirring for 10-15 min to obtain an ATA water/DMSO solution, adding PET-g-PGMA into the ATA water/DMSO solution, stirring for 1-1.5 h, reacting for 8-12 h at the temperature of 75-90 ℃, and finally performing post-treatment to obtain PET-g-PGMA/ATA.
5. The method for preparing the PET industrial silk-based tire cord according to claim 4, wherein in the step (2), the weight part ratio of the PET-g-PGMA to the ATA water/DMSO solution is 1-100: 1000-4500, and the weight part ratio of the ATA, the water and the DMSO in the ATA water/DMSO solution is 1-15: 90-100: 80-110.
6. The method for preparing the PET industrial silk-based tire cord as claimed in claim 1, wherein the step (3) is specifically as follows: firstly, adding zirconium tetrachloride and ATA into DMF (dimethyl formamide) for ultrasonic treatment for 1-2 hours to obtain a solution, then mixing the solution with PET-g-PGMA/ATA, reacting for 10-30 hours in a closed environment at the temperature of 70-130 ℃, and finally performing post-treatment to obtain the PET industrial silk-based tire cord.
7. The method for preparing the PET industrial silk-based tire cord according to claim 6, wherein in the step (3), the weight part ratio of zirconium tetrachloride, ATA, DMF and PET-g-PGMA/ATA is 20-100: 18-90: 9000-1100: 100-220.
8. The PET industrial silk-based tire cord prepared by the preparation method of the PET industrial silk-based tire cord as claimed in any one of claims 1 to 7 is characterized in that: the MOF is coated on the surface of the PET industrial filament.
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