CN109306536B - Graphene-dispersed white oil slurry and preparation method thereof, and preparation method of UHMWPE fiber - Google Patents
Graphene-dispersed white oil slurry and preparation method thereof, and preparation method of UHMWPE fiber Download PDFInfo
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- CN109306536B CN109306536B CN201710623500.4A CN201710623500A CN109306536B CN 109306536 B CN109306536 B CN 109306536B CN 201710623500 A CN201710623500 A CN 201710623500A CN 109306536 B CN109306536 B CN 109306536B
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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Abstract
The invention discloses a preparation method of white oil slurry with graphene dispersed therein, which comprises the following steps: 1) Mixing a component A, a component B, graphene powder and white oil, and ball-milling the mixed materials to fully mix the components, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent; 2) Adding the mixed material obtained in the step 1) into white oil, heating the white oil at a first temperature under stirring, preserving heat for 0.2-3h, then heating to a second temperature, and preserving heat for 2-15h under stirring continuously to form a uniform solution; wherein the second temperature is 30-62 ℃ higher than the first temperature.
Description
Technical Field
The invention relates to a graphene-dispersed white oil slurry and a preparation method thereof, in particular to a graphene-dispersed white oil slurry for improving UHMWPE fiber performance and a preparation method thereof, and belongs to the technical field of organic-inorganic composite materials.
Background
Ultra-high molecular weight polyethylene (UHMWPE) fibers, also known as ultra-high strength polyethylene (UHMWPE) fibers, ultra-high modulus polyethylene (UHMWPE) fibers. Because UHMWPE has the necessary structural characteristics of oriented stretching, the UHMWPE has the ultra-high tensile strength which is comparable or not, so that the fiber with ultra-high elastic modulus and strength can be prepared by a gel spinning method, the tensile strength is up to 3-3.5GPa, and the tensile elastic modulus is up to 100-125GPa; the specific strength of the fiber is the highest of all the fibers commercialized so far, 4 times larger than that of the carbon fiber, 10 times larger than that of the steel wire, and 50% larger than that of the aramid fiber. It is widely used in the fields of military equipment, aerospace, marine operation, sports equipment and the like.
In the UHMWPE fiber production process, the white oil acts as a solvent in production, and forms a spinning solution with UHMWPE, and then spinning is carried out; however, white oil only acts as a solvent and cannot improve the performance of the fiber. Since 2004, graphene has been a research hotspot of people, has excellent mechanical, electrical, thermal and optical properties, and has a wide application prospect in the fields of battery materials, energy storage materials, electronic devices, composite materials and the like. However, graphene has extremely high chemical stability, and aggregation is easily generated due to the action of van der Waals force between graphene sheets, so that a stable dispersion system is difficult to form in water and an organic solvent. Therefore, how to maintain the effective dispersion of graphene at the time of application is a challenge to be solved.
However, if graphene powder is directly added in the spinning process, a large amount of graphene is agglomerated to obtain a spinning solution with poor dispersibility, and in the composite material, the dispersion of the reinforcing phase in the matrix has an important influence on the performance of the material. Researchers have transformed the thinking that the production process of UHMWPE fibers is influenced by graphene/white oil slurry, and the performance of UHMWPE fibers is improved. However, the stable dispersibility of the graphene/white oil slurry plays a crucial role in the continuous production of the final product graphene/UHMWPE composite fiber. However, the high-solid-content graphene/white oil slurry prepared in the traditional process has poor dispersibility, serious agglomeration, difficulty in maintaining stable and uniform dispersion for a long time and short shelf life, so that in the actual production of the composite fiber, the phenomenon of hole blocking of a spinneret plate occurs after continuous operation for 7-8 hours, the production is forced to stop, and the spinneret plate is cleaned and replaced, so that the method does not meet the technological requirements of continuous production of the super fiber. Based on the technical background, the invention improves the old process of the graphene/white oil slurry to prepare the slurry with excellent dispersion stability, and is expected to solve the problem of hole blocking in continuous production of the super fiber.
Disclosure of Invention
Aiming at the technical defects at present, the invention provides a preparation method of graphene-dispersed white oil slurry with excellent dispersibility;
another object of the present invention is to provide the graphene-dispersed white oil slurry prepared by the above method;
it is a further object of the present invention to provide a method for preparing a composite fiber of UHMWPE using the above-mentioned white oil slurry.
The aim of the invention is realized by the following technical scheme:
a graphene-dispersed white oil slurry, which comprises, based on 100wt% of the total mass of the white oil slurry: 0.01-1wt% of component A, 0.01-1wt% of component B and 0.01-0.5wt% of graphene, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent.
As a preferable embodiment of the above-described graphene-dispersed white oil slurry, the white oil slurry contains, based on 100wt% of the total mass of the white oil slurry: 0.1-0.5wt% of component A, 0.1-0.5wt% of component B and 0.1-0.2wt% of graphene.
The above-described graphene-dispersed white oil slurry necessarily contains component a (antioxidant), component B (dispersant and/or modifier), graphene, and white oil, but does not exclude impurities or additives that do not affect the performance of the graphene-dispersed white oil slurry of the present disclosure. Wherein the white oil content is 97.5-99.7wt%.
According to one aspect of the disclosure, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP, preferably one or more of antioxidant 1010, antioxidant 164 or antioxidant DNP.
The numbers and letters in the antioxidant 1010, the antioxidant 1076, the antioxidant CA, the antioxidant 164, the antioxidant DNP, the antioxidant DLTP and the antioxidant TNP represent the types of the antioxidants, and the physicochemical properties of the antioxidants in different types are different.
The antioxidant 1010 is white flowable powder, has a melting point of 120-125 ℃ and low toxicity, and is a good antioxidant. The polypropylene resin has a plurality of applications, is an auxiliary agent with high thermal stability and is very suitable for being used under high temperature conditions, and the service life of the product can be prolonged.
Antioxidant 1076 is white or yellowish crystal powder with melting point of 50-55deg.C, and is nontoxic, insoluble in water, and soluble in benzene, acetone, ethane and esters. Can be used as antioxidant for polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, ABS, acrylic acid and other resins. Has the characteristics of good oxidation resistance, small volatility, washing resistance and the like.
The antioxidant CA is white crystal powder with melting point of 180-188 deg.C, low toxicity, and is dissolved in acetone, ethanol, toluene and ethyl acetate. Is suitable for the antioxidant auxiliary agent in polypropylene, polyethylene, polyvinyl chloride, ABS and polyamide resin, and can be used for wires and cables contacted with copper.
Antioxidant 164 in the form of a white or pale yellow crystalline powder or tablet. The melting point is 70 ℃, the boiling point is about 260 ℃, and the product is nontoxic. Is more suitable for being used in food package molding materials (polypropylene, polyethylene, polyvinyl chloride, ABS, polyester and polystyrene) resin.
The antioxidant DNP is light gray powder, has a melting point of about 230 ℃, is easily dissolved in aniline and nitrobenzene, and is insoluble in water. Is suitable for polyethylene, polypropylene, impact polystyrene and ABS resin, and has better heat stabilization effect and inhibition of the influence of copper and manganese metal besides the antioxidant effect.
The antioxidant DLTP is white crystal powder, has a melting point of about 40 ℃, has low toxicity, is insoluble in water, and can be dissolved in benzene, carbon tetrachloride and acetone. Auxiliary antioxidants for polyethylene, polypropylene, ABS and polyvinyl chloride resins can alter the heat and oxygen resistance of the article. The above materials are generally used in amounts of 0.05% to 1.5%.
Antioxidant TNP, light yellow transparent liquid, solidifying point 19-24 deg.C, boiling point 220 deg.C, and dissolving in alcohol, benzene and acetone. Is suitable for polyvinyl chloride, polystyrene, polypropylene and ABS resin.
According to one aspect of the invention, the dispersant and/or modifier is a polyolefin, such as PE, PVC, PP, etc.; or one or more of PSS, SDBS, SDS, commercial BYK or commercial AFCONA, preferably PE, PP, PSS, SDBS or SDS, or a combination of two or more.
Polyethylene (PE) is one of the simplest molecular structures in plastics, has excellent electrical insulation property and good chemical corrosion resistance, and is easy to process and shape. The LDPE density of the low-density polyethylene is 0.910-0.925g/cm 3 The HDPE of the high-density polyethylene is 0.941-0.965g/cm 3 。
PVC is white powder with an amorphous structure and has small branching degree. The molecular weight of the PVC produced in industry is generally in the range of 5 ten thousand to 12 ten thousand, the PVC has larger dispersity, and the molecular weight is increased along with the reduction of the polymerization temperature; softening at 80-85deg.C without fixed melting point, changing 130 deg.C into viscoelastic state, and changing 160-180deg.C into viscous state; has good mechanical properties, about 60MPa of tensile strength and 5-10kJ/m of impact strength 2 The method comprises the steps of carrying out a first treatment on the surface of the Has excellent dielectric properties. But has poor stability to light and heat, can decompose to generate hydrogen chloride after being exposed to sunlight at a temperature above 100 ℃ or for a long time, and further automatically catalyzes the decomposition to cause discoloration, and the physical and mechanical properties are also rapidly reduced, so that a stabilizer is required to be added in practical application to improve the stability to heat and light. PVC is very hard and has poor solubility, and can only be dissolved in a few solvents such as cyclohexanone, dichloroethane, tetrahydrofuran and the like, is stable to organic and inorganic acids, alkalis and salts, and the chemical stability is reduced with the increase of the use temperature.
Polypropylene PP is a non-toxic, odorless, milky highly crystalline polymer with a density of only 0.90-0.91g/cm 3 Is one of the lightest varieties in all plastics at present. It is especially stable to water, and has water absorption rate of only 0.01% in water for 24 hr and molecular weight of 8-15 ten thousand. Good formability but high shrinkageThick wall articles are prone to dent. The product has good surface luster and is easy to color.
The sodium polystyrene sulfonate PSS is light amber liquid, has no odor and is easy to dissolve in water. The sodium polystyrene sulfonate solution is a water-soluble polymer with unique function and is applied to the aspects of reactive emulsifying agents, water-soluble polymers (coagulants, dispersing agents, container cleaning agents, cosmetics and the like), water treatment agents (dispersing agents, flocculating agents), sulfur exchange resins (films), true writing agents (films), semiconductors, image films, heat conduction products and the like.
SDBS is white or light yellow powdery or flaky solid and is dissolved in water to form semitransparent solution. Mainly used as anionic surfactant. The hydrophilic-lipophilic balance (HLB value) is 10.638, the decomposition temperature is 450 ℃, and the weight loss rate is 60%. Is easy to dissolve in water and easy to absorb moisture and agglomerate.
Sodium Dodecyl Sulfate (SDS) is a white or pale yellow powdery substance, soluble in water, and insensitive to alkali and hard water. Has the advantages of decontamination, emulsification and excellent foaming power. Is an anionic surfactant slightly toxic to human body. Its biodegradability is >90%. The prior application comprises the following steps: it can be used as emulsifier, fire extinguishing agent, foaming agent and textile auxiliary agent, and also as foaming agent for toothpaste, paste, powder and shampoo.
Commercial BYK is a series of dispersants manufactured by the company pick chemical auxiliary in germany. For example, BYK-P104S is chemically composed of a solution of a low molecular weight unsaturated polycarboxylic acid polymer and a polysiloxane copolymer, and the solvent is xylene/diisobutanone, a wetting and dispersing agent for improving pigment wetting and stabilizing pigment dispersion, which produces controlled flocculation of pigments and extender pigments, thus preventing flooding/bloom and hard settling.
Commercial AFCONA is a high molecular weight dispersant, including polyurethane, polyacrylate, and polyester dispersants. For example, AFCONA 4010 is a polyurethane dispersant, the molecular structure of the dispersant contains a special anchoring group with an elastic structure, the anchoring efficiency is much higher than that of a dispersant with a general rigid structure, the dispersant can be well wetted and dispersed on the surface of pigment, and meanwhile, the polymer chain of the dispersant can well prevent aggregation among pigment particles, so that the ideal flocculation preventing effect is achieved. For the dispersion of the matte powder, it is generally recommended to add 3-5%. AFCONA 4700 is a three-level block polyacrylate type high molecular dispersant. The appearance is transparent to very slightly turbid liquid, the density is 1.028-1.038g/cm3, the amine value is 25-31mg KOH/g, the flash point is 24 ℃, the color is not more than 18, the solvent is propylene glycol methyl ether acetate, and the activity content is 49-52%. The organic pigment is generally added with 20-40% and the carbon black is added with 20-60% by weight of the active ingredient of the auxiliary agent to the pigment.
According to one aspect of the disclosure, the graphene is a graphene powder with a single-layer or multi-layer structure, the sheet diameter is 0.5-5um, the thickness is 0.5-30nm, and the specific surface area is 170-320m 2 And/g. According to the invention, through freely controlling the production of the graphene powder, any graphene powder with different morphology requirements and different specific surface area requirements can be realized, and on the basis, the characteristics of the morphology and the specific surface area of the graphene, namely that the sheet diameter is 0.5-5um, the thickness is 0.5-30nm and the specific surface area is 170-320m are obtained through a plurality of factors such as the morphology and the specific surface area of the graphene and influencing factors in the actual production of the slurry for UHMWPE fibers 2 According to the graphene powder of/g', when the obtained white oil slurry is applied to UHMWPE fibers, the phenomenon of spinning hole plugging can be avoided to the greatest extent.
The preparation method of the white oil slurry with the graphene dispersed therein comprises the following steps of:
1) Mixing a component A, a component B, graphene powder and white oil, and ball-milling the mixed materials to fully mix the components, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent;
2) Adding the mixed material obtained in the step 1) into white oil, heating to a first temperature under stirring, preserving heat for 0.2-3h, then heating to a second temperature, and preserving heat for 2-15h under stirring to form a uniform solution;
wherein the second temperature is 30-62 ℃ higher than the first temperature.
According to one aspect of the disclosure, the amount of white oil in step 1) is 1/10 of the total amount of white oil.
The method adopts a method of adding white oil twice, adding a small amount of white oil for the first time, adding the rest white oil, and reacting under the specific temperature and other conditions, thus the purposes are as follows:
1. the powder is infiltrated, so that the graphene powder is prevented from drifting, and is well mixed in the ball milling process;
2. and the particle size of the graphene is controlled, so that the subsequent spinning is facilitated.
According to one aspect of the disclosure, in the step 1), the rotation speed of ball milling is 300-1000rpm, the ball mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1.
According to one aspect of the disclosure, ball milling is performed for 10min-2h.
According to one aspect of the disclosure, the first temperature is 80-130 ℃, preferably 110-130 ℃; the second temperature is 120-180 ℃, preferably 130-160 ℃.
According to one aspect of the disclosure, the first temperature is maintained for 0.5-1h; and/or, the second temperature is used for heat preservation reaction for 4-8h.
According to one aspect of the present disclosure, the heating rate from the first temperature to the second temperature is 20-30 ℃/h.
The inventor has repeatedly studied intensively and found that, when the temperature is directly heated to a set target temperature, the viscosity of the obtained slurry is too high to be truly applied to the production of UHMWPE fibers, so that the problem of hole blocking is caused, or the dispersion degree of graphene in the obtained slurry is insufficient, a little more than a little, the problem of serious agglomeration is caused, the mechanical property of the UHMWPE fibers is finally improved, the stability of the mechanical property of the UHMWPE fibers is not guaranteed, and the slurry loses the value of real industrialized application. However, the temperature condition is critical, and the increase of the temperature on the one hand is favorable for better swelling of the dispersing agent in the white oil, and the dispersing agent is precipitated from the mixed solution at normal temperature due to lower temperature or shorter time; on the other hand, the equipment has limited tolerance to high temperature, and the temperature is increased after reaching 180 ℃, so that the effect is improved generally, and the energy waste is caused. Based on the research, in order to realize the true better dispersion of the graphene in the slurry, the invention adopts a method of setting two heating sections through ingenious improvement of the process, and the purpose of setting a temperature zone of the first temperature is to ensure that the material is primarily decomposed and adsorbed under the condition of having a constant fluidity, and simultaneously reduce the chain breakage of the dispersing agent at a high temperature; the temperature zone of the second temperature is set so that the viscosity of the system can be reduced along with the temperature rise, and the dispersion is more fully and uniformly facilitated.
According to one aspect of the disclosure, the graphene powder has a diameter of 0.5-5um, a thickness of 0.5-30nm, and a specific surface area of 170-320m 2 /g。
According to one aspect of the disclosure, the amount of white oil in step 1) is 1/10 of the total amount of white oil.
The white oil slurry of the graphene is prepared according to the method.
The UHMWPE fiber comprises graphene and UHMWPE, wherein the graphene accounts for 0.1-3 wt% of the UHMWPE.
As a preferable scheme of UHMWPE fiber, the graphene is graphene powder with a single-layer or multi-layer structure, the sheet diameter is 0.5-5um, the thickness is 0.5-30nm, and the specific surface area is 170-320m 2 /g。
Further preferably, the UHMWPE has an average molecular weight of (1-6) x 10 6 Preferably 4X 10 6 . Preferably 4X 10 6 。
The preparation method of the UHMWPE fiber comprises the steps of preparing white oil slurry with graphene dispersed therein by adopting the method, adding UHMWPE powder and white oil into the white oil slurry to prepare a pre-spinning solution, preparing gel filaments by the pre-spinning solution, and extracting, drying and drafting the gel filaments to obtain the composite fiber of the graphene and the UHMWPE.
According to one aspect of the disclosure, the amount of UHMWPE powder and white oil is added such that the graphene in the pre-dope is 0.1% -3% of the UHMWPE; preferably, the UHMWPE powder and the white oil are added in amounts such that the mass ratio of UHMWPE to white oil in the pre-dope is 9:91.
According to one aspect of the disclosure, the pre-spinning solution is firstly heated to 100 ℃ in a swelling kettle, then is extruded by a dissolution kettle, a feeding kettle and a double-screw extruder, is stepped heated to 268 ℃ from 100 ℃, is stepped to 100/130/160/210/240/268 and is quenched into gel filaments, wherein the length-diameter ratio of the double-screw extruder is 54:70, and the double-screw extruder consists of a feeding section, a heating section, a dissolution section and a uniformly mixing section.
According to one aspect of the present disclosure, the extraction adopts a continuous multistage closed ultrasonic extractor and a hydrocarbon extraction high-power stretching device, the extraction temperature is 40 ℃, and the extraction rate is more than or equal to 99%; further preferably, the extraction adopts a multistage multi-tank quantitative liquid supplementing and draining process. By adopting the process, the aim is to more accurately control the oil content of the gel silk after extraction.
Preferably, the extractor is additionally provided with an ultrasonic generator for full extraction, a water circulation die temperature controller is arranged for accurately controlling the temperature of the extracting solution, the temperature difference is less than or equal to +/-1 ℃, and the extraction rate is more than or equal to 99%;
and/or, the drafting adopts 4-level super hot drafting, and the hot drafting temperature is 130-150 ℃.
Graphene agglomeration is a direct cause of hole plugging of a spinneret plate in the production of graphene/UHMWPE composite fibers, and moreover, the agglomerated graphene also affects the performance of a final product. The invention aims to overcome the defects of the prior art, and provides slurry with good dispersibility and high stability of graphene and a preparation process thereof. The defects of easy aggregation and poor dispersibility of graphene are overcome by adjusting and improving the dispersion process of the graphene in the white oil, the problem of hole blocking of a spinneret plate in the production of graphene/UHMWPE composite fibers is effectively prevented, and meanwhile, the application performance of products such as wear resistance and cutting resistance are improved to a certain extent. The main aspects are as follows:
(1) By utilizing the distribution of ball milling steel balls, the particle size of the materials can be reduced by ball milling treatment of graphene powder, a dispersing agent and an antioxidant, the materials are fully ground and uniformly mixed, and then a small amount of white oil is added to moisten the surface of the powder, so that the graphene is adsorbed and uniformly mixed.
(2) The preparation of the graphene/white oil slurry is subjected to formula adjustment and technological parameter improvement, namely: adding the ball-milled mixture into a white oil solvent, heating to 8-130 ℃ while stirring, preserving heat for 0.2-3h, then gradually heating to 130-160 ℃, preserving heat for 2-15h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
The dispersion stability of the graphene/white oil slurry has obvious improvement effect (see figure 2), the graphene/white oil slurry can pass through a 650-mesh screen at room temperature, and the screen is basically free of screen residues, so that a foundation is laid for the subsequent preparation of high-strength graphene/UHMWPE composite fibers, the problem of hole blocking of a spinneret plate in continuous production of the super fibers is solved, the tensile strength of the prepared composite fibers can reach 40cN/dtex, the tensile modulus can reach 1620cN/dtex, the cutting strength is 600, and the international authentication level 2 is reached.
In addition, in the method disclosed by the invention, the adopted new process does not change the traditional gel spinning process, the preparation process is simple, the cost of limited graphene is only increased in the aspect of production cost, the cost performance is higher, and compared with the method of adding inorganic metal, glass fiber and other hard reinforcing materials, the composite fiber prepared by adding graphene has better hand feeling, and the prepared product is more comfortable to wear.
Drawings
FIG. 1 is a process flow of the white oil composite slurry preparation process of the invention;
fig. 2 is an optical microscope image (magnification: 10 x 5) of a white oil composite slurry obtained by the method of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
In one embodiment of the present disclosure, there is provided a white oil paste in which graphene is dispersed, the white oil paste including, in terms of 100wt% of the total mass of the white oil paste: 0.01-1wt% of component A, 0.01-1wt% of component B and 0.01-0.5wt% of graphene, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent. The above-described graphene-dispersed white oil slurry necessarily contains component a (antioxidant), component B (dispersant and/or modifier), graphene, and white oil, but does not exclude impurities or additives that do not affect the performance of the graphene-dispersed white oil slurry of the present disclosure. Wherein the white oil content is 97.5-99.7wt%. For example: the slurry contains 0.02-0.9wt%, 0.03-0.8wt%, 0.04-0.7wt%, 0.05-0.6wt%, 0.08-0.4wt%, 0.1-0.3wt%, 0.2-1wt%, 0.5-0.8wt%, 0.2wt%, 0.5wt%, etc; the slurry contains 0.02-0.9wt%, 0.03-0.8wt%, 0.04-0.7wt%, 0.05-0.6wt%, 0.08-0.4wt%, 0.1-0.3wt%, 0.2-1wt%, 0.5-0.8wt%, 0.2wt%, etc. of dispersant and/or modifier; the slurry contains 0.01-0.4wt%, 0.02-0.3wt%, 0.03-0.2wt%, 0.05-0.1wt%, 0.08-0.1wt%, 0.1-0.5wt%, 0.2-0.3wt%,0.1wt%, 0.15wt%, 0.2wt%, etc.
As a preferable embodiment of the above-described graphene-dispersed white oil slurry, the white oil slurry contains, based on 100wt% of the total mass of the white oil slurry: 0.1 to 0.5 weight percent of antioxidant, 0.1 to 0.5 weight percent of dispersing agent and/or modifier, 0.1 to 0.2 weight percent of graphene and the balance of white oil. For example: the slurry contains 0.1-0.4wt%, 0.12-0.3wt%, 0.15-0.2wt%, 0.18-0.35wt%, 0.2-0.5wt%, 0.23-0.45wt%, 0.3-0.4wt%, 0.25-0.3wt%, and the like of antioxidant; the slurry contains 0.1-0.4wt%, 0.12-0.3wt%, 0.15-0.2wt%, 0.18-0.35wt%, 0.2-0.5wt wt%, 0.23-0.45wt%, 0.3-0.4wt%, 0.25-0.3wt%, etc. of dispersant and/or modifier; the amount of graphene contained in the slurry is 0.1wt%, 0.11wt%, 0.12wt%, 0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.17wt%, 0.18wt%, 0.19wt%, 0.2wt%, etc.
According to one aspect of the invention, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP, preferably one or more of antioxidant 1010, antioxidant 164 or antioxidant DNP. The numbers and letters in the antioxidant 1010, the antioxidant 1076, the antioxidant CA, the antioxidant 164, the antioxidant DNP, the antioxidant DLTP and the antioxidant TNP represent the types of the antioxidants, and the physicochemical properties of the antioxidants in different types are different. The antioxidant 1010 is white flowable powder, has a melting point of 120-125 ℃ and low toxicity, and is a good antioxidant. The polypropylene resin has a plurality of applications, is an auxiliary agent with high thermal stability and is very suitable for being used under high temperature conditions, and the service life of the product can be prolonged. Antioxidant 1076 is white or yellowish crystal powder with melting point of 50-55deg.C, and is nontoxic, insoluble in water, and soluble in benzene, acetone, ethane and esters. Can be used as antioxidant for polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, ABS, acrylic acid and other resins. Has the characteristics of good oxidation resistance, small volatility, washing resistance and the like. The antioxidant CA is white crystal powder with melting point of 180-188 deg.C, low toxicity, and is dissolved in acetone, ethanol, toluene and ethyl acetate. Is suitable for the antioxidant auxiliary agent in polypropylene, polyethylene, polyvinyl chloride, ABS and polyamide resin, and can be used for wires and cables contacted with copper. Antioxidant 164 in the form of a white or pale yellow crystalline powder or tablet. The melting point is 70 ℃, the boiling point is about 260 ℃, and the product is nontoxic. Is more suitable for being used in food package molding materials (polypropylene, polyethylene, polyvinyl chloride, ABS, polyester and polystyrene) resin. The antioxidant DNP is light gray powder, has a melting point of about 230 ℃, is easily dissolved in aniline and nitrobenzene, and is insoluble in water. Is suitable for polyethylene, polypropylene, impact polystyrene and ABS resin, and has better heat stabilization effect and inhibition of the influence of copper and manganese metal besides the antioxidant effect. The antioxidant DLTP is white crystal powder, has a melting point of about 40 ℃, has low toxicity, is insoluble in water, and can be dissolved in benzene, carbon tetrachloride and acetone. Auxiliary antioxidants for polyethylene, polypropylene, ABS and polyvinyl chloride resins can change the heat resistance and the oxidation resistance of the product. The above materials are generally used in amounts of 0.05% to 1.5%. Antioxidant TNP, light yellow transparent liquid, solidifying point 19-24 deg.C, boiling point 220 deg.C, and dissolving in alcohol, benzene and acetone. Is suitable for polyvinyl chloride, polystyrene, polypropylene and ABS resin.
According to one aspect of the invention, the dispersant and/or modifier is a polyolefin, such as PE, PVC, PP, etc.; or one or more of PSS, SDBS, SDS, commercial BYK or commercial AFCONA, preferably PE, PP, PSS, SDBS or SDS, or a combination of two or more. Polyethylene (PE) is one of the simplest molecular structures in plastics, has excellent electrical insulation property and good chemical corrosion resistance, and is easy to process and shape. The LDPE density of the low-density polyethylene is 0.910-0.925g/cm 3 The HDPE of the high-density polyethylene is 0.941-0.965g/cm 3 . PVC is white powder with an amorphous structure and has small branching degree. The molecular weight of the PVC produced in industry is generally in the range of 5 ten thousand to 12 ten thousand, the PVC has larger dispersity, and the molecular weight is increased along with the reduction of the polymerization temperature; softening at 80-85deg.C without fixed melting point, changing 130 deg.C into viscoelastic state, and changing 160-180deg.C into viscous state; has good mechanical properties, about 60MPa of tensile strength and 5-10kJ/m of impact strength 2 The method comprises the steps of carrying out a first treatment on the surface of the Has excellent dielectric properties. But has poor stability to light and heat, can decompose to generate hydrogen chloride after being exposed to sunlight at a temperature above 100 ℃ or for a long time, and further automatically catalyzes the decomposition to cause discoloration, and the physical and mechanical properties are also rapidly reduced, so that a stabilizer is required to be added in practical application to improve the stability to heat and light. PVC is very hard and has poor solubility, and can only be dissolved in a few solvents such as cyclohexanone, dichloroethane, tetrahydrofuran and the like, is stable to organic and inorganic acids, alkali and salts, and the chemical stability is reduced with the increase of the use temperature. Polypropylene PP is a non-toxic, odorless, milky highly crystalline polymer with a density of only 0.90-0.91g/cm 3 Is one of the lightest varieties in all plastics at present. It is especially stable to water, and has water absorption rate of only 0.01% in water for 24 hr and molecular weight of 8-15 ten thousand. The molding property is good, but the thick-wall product is easy to be sunk due to the large shrinkage rate. The product has good surface luster and is easy to color. The sodium polystyrene sulfonate PSS is light amber liquid, has no odor and is easy to dissolve in water. Sodium polystyrene sulfonate solution is a water-soluble polymer with unique function and is applied to reactive emulsifierWater-soluble polymers (coagulants, dispersants, container cleaners, cosmetics, etc.), water treatment agents (dispersants, flocculants), sulfur exchange resins (membranes), writing agents (membranes), semiconductors, imaging films, heat transfer products, etc. SDBS is white or light yellow powdery or flaky solid and is dissolved in water to form semitransparent solution. Mainly used as anionic surfactant. The hydrophilic-lipophilic balance (HLB value) is 10.638, the decomposition temperature is 450 ℃, and the weight loss rate is 60%. Is easy to dissolve in water and easy to absorb moisture and agglomerate. Sodium Dodecyl Sulfate (SDS) is a white or pale yellow powdery substance, soluble in water, and insensitive to alkali and hard water. Has the advantages of decontamination, emulsification and excellent foaming power. Is an anionic surfactant slightly toxic to human body. Degree of biodegradation thereof >90%. The prior application comprises the following steps: it can be used as emulsifier, fire extinguishing agent, foaming agent and textile auxiliary agent, and also as foaming agent for toothpaste, paste, powder and shampoo. Commercial BYK is a series of dispersants manufactured by the company pick chemical auxiliary in germany. For example, BYK-P104S is chemically composed of a solution of a low molecular weight unsaturated polycarboxylic acid polymer and a polysiloxane copolymer, and the solvent is xylene/diisobutanone, a wetting and dispersing agent for improving pigment wetting and stabilizing pigment dispersion, which produces controlled flocculation of pigments and extender pigments, thus preventing flooding/bloom and hard settling. Commercial AFCONA is a high molecular weight dispersant, including polyurethane, polyacrylate, and polyester dispersants. For example, AFCONA 4010 is a polyurethane dispersant, the molecular structure of the dispersant contains a special anchoring group with an elastic structure, the anchoring efficiency is much higher than that of a dispersant with a general rigid structure, the dispersant can be well wetted and dispersed on the surface of pigment, and meanwhile, the polymer chain of the dispersant can well prevent aggregation among pigment particles, so that the ideal flocculation preventing effect is achieved. For the dispersion of the matte powder, it is generally recommended to add 3-5%. AFCONA 4700 is a three-level block polyacrylate type high molecular dispersant. The appearance is transparent to very slightly turbid liquid, the density is 1.028-1.038g/cm3, the amine value is 25-31mg KOH/g, the flash point is 24 ℃, the color is not more than 18, the solvent is propylene glycol methyl ether acetate, and the activity content is 49-52%. In the organic pigment, the weight percentage of the active component of the auxiliary agent to the weight of the pigment is calculated as one Typically 20-40% is added to the carbon black 20-60%.
According to one aspect of the embodiment, the graphene is a graphene powder with a single-layer or multi-layer structure, the sheet diameter is 0.5-5um, the thickness is 0.5-30nm, and the specific surface area is 170-320m 2 And/g. According to the invention, through freely controlling the production of the graphene powder, any graphene powder with different morphology requirements and different specific surface area requirements can be realized, and on the basis, the characteristics of the morphology and the specific surface area of the graphene, namely that the sheet diameter is 0.5-5um, the thickness is 0.5-30nm and the specific surface area is 170-320m are obtained through a plurality of factors such as the morphology and the specific surface area of the graphene and influencing factors in the actual production of the slurry for UHMWPE fibers 2 According to the graphene powder of/g', when the obtained white oil slurry is applied to UHMWPE fibers, the phenomenon of spinning hole plugging can be avoided to the greatest extent.
In another embodiment of the present disclosure, a method for preparing a white oil slurry in which graphene is dispersed is provided, according to the above components and ratio relationship,
1) Ball milling premixing
Mixing the component A (antioxidant), the component B (dispersing agent and/or modifier), graphene powder and white oil, and ball-milling the mixed materials to fully mix the components;
2) Heating reaction
Adding the mixed material obtained in the step 1) into white oil, heating to a temperature under stirring, preserving heat for 0.2-3h, then heating to a second temperature, and preserving heat for 2-15h under continuous stirring to form a uniform solution, thus obtaining uniformly dispersed graphene/white oil slurry;
wherein the second temperature is 30-62 ℃ higher than the first temperature.
The amount of the white oil in the step 1) accounts for 1/10 of the total amount of the white oil.
The invention adopts a method of adding white oil twice, adding a small amount of white oil for the first time, adding the rest white oil, and reacting under the specific temperature and other conditions, thus the purposes are as follows:
1. the powder is infiltrated, so that the graphene powder is prevented from drifting, and is well mixed in the ball milling process;
2. and the particle size of the graphene is controlled, so that the subsequent spinning is facilitated.
According to one aspect of the embodiment, in the step 1), the rotational speed of the ball milling is 300-1000rpm, the ball mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1.
According to one aspect of this embodiment, the ball milling is performed for 10min-2h.
According to one aspect of this embodiment, the first temperature is 80-130 ℃, preferably 110-130 ℃; the second temperature is 120-180 ℃, preferably 130-160 ℃.
According to one aspect of this embodiment, the first temperature is maintained for 0.5-1h; and/or, the second temperature is used for heat preservation reaction for 4-8h.
According to one aspect of this embodiment, the heating rate from the first temperature to the second temperature is 20-30 ℃/h.
The inventor has repeatedly studied intensively and found that no matter how high the heating temperature is, the viscosity of the obtained slurry is too high to be truly applied to the production of UHMWPE fibers, so that the problem of hole blocking is caused, or the problem of severe agglomeration is caused by insufficient dispersity and slightly more graphene in the obtained slurry, so that the mechanical property of UHMWPE fibers is not improved sufficiently, the stability of the mechanical property of UHMWPE fibers is not guaranteed, and the slurry loses the value of real industrialized application. However, the temperature condition is critical, on the one hand, the temperature rise is favorable for better swelling of the dispersing agent in the white oil, and the dispersing agent is separated out from the mixed solution at normal temperature due to lower temperature or shorter time; on the other hand, the equipment has limited tolerance to high temperature, and the temperature is increased after reaching 180 ℃, so that the effect is improved generally, and energy waste is caused. Based on the research, in order to realize the true better dispersion of the graphene in the slurry, the invention adopts a method of setting two heating sections through ingenious improvement of the process, and the purpose of setting a temperature zone of a first temperature is to ensure that the material is primarily decomposed and adsorbed under the condition of having certain fluidity, and meanwhile, the chain breakage of a dispersing agent at high temperature is reduced; the temperature zone of the second temperature is set so that the viscosity of the system can be reduced along with the temperature rise, and the dispersion is more fully and uniformly facilitated.
According to one aspect of the embodiment, the graphene powder has a diameter of 0.5-5um, a thickness of 0.5-30nm, and a specific surface area of 170-320m 2 /g。
According to one aspect of this embodiment, the amount of white oil in step 1) is 1/10 of the total amount of white oil.
The white oil slurry of the graphene is prepared according to the method.
The UHMWPE fiber comprises graphene and UHMWPE, wherein the graphene accounts for 0.1-3 wt% of the UHMWPE.
As a preferable scheme of UHMWPE fiber, the graphene is graphene powder with a single-layer or multi-layer structure, the sheet diameter is 0.5-5um, the thickness is 0.5-30nm, and the specific surface area is 170-320m 2 /g。
Further preferably, the UHMWPE has an average molecular weight of (1-6) x 10 6 Preferably 4X 10 6 . Preferably 4X 10 6 。
According to one embodiment of the disclosure, a preparation method of UHMWPE fiber is provided, the method is adopted to prepare a white oil slurry with graphene dispersed therein, UHMWPE powder and white oil are added into the white oil slurry to prepare a pre-spinning solution, the pre-spinning solution is then prepared into gel filaments, and the gel filaments are subjected to extraction, drying and drawing to obtain the composite fiber of graphene and UHMWPE.
According to one aspect of this embodiment, the UHMWPE powder and white oil are added in amounts such that the graphene in the pre-dope comprises 0.1wt% to 3wt% of the UHMWPE, for example: 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.1wt%, 2.5wt%, 2.7wt%, 2.9wt%, 3wt%, etc.; preferably 0.2% wt% to 2% by weight, for example: 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, etc.
According to one aspect of this embodiment, the UHMWPE powder and the white oil are added in amounts such that the mass ratio of UHMWPE to white oil in the pre-dope is 9:91.
According to one aspect of the embodiment, the pre-spinning solution is firstly heated to 100 ℃ in a swelling kettle, then is extruded by a dissolution kettle, a feeding kettle and a double-screw extruder, is stepped heated to 268 ℃ from 100 ℃, is stepped to 100/130/160/210/240/268 and is quenched into gel filaments, wherein the length-diameter ratio of the double-screw extruder is 54:70, and the double-screw extruder consists of a feeding section, a heating section, a dissolution section and a uniformly mixing section.
According to one aspect of the embodiment, the extraction adopts a continuous multistage closed ultrasonic extractor and a hydrocarbon extraction high-power stretching device, the extraction temperature is 40 ℃, and the extraction rate is more than or equal to 99%; further preferably, the extraction adopts a multistage multi-tank quantitative liquid supplementing and draining process. By adopting the process, the aim is to more accurately control the oil content of the gel silk after extraction.
Preferably, the extractor is additionally provided with an ultrasonic generator for full extraction, a water circulation die temperature controller is arranged for accurately controlling the temperature of the extracting solution, the temperature difference is less than or equal to +/-1 ℃, and the extraction rate is more than or equal to 99%;
and/or, the drafting adopts 4-level super hot drafting, and the hot drafting temperature is 130-150 ℃.
Graphene agglomeration is a direct cause of hole plugging of a spinneret plate in the production of graphene/UHMWPE composite fibers, and moreover, the agglomerated graphene also affects the performance of a final product. The invention aims to overcome the defects of the prior art, and provides slurry with good dispersibility and high stability of graphene and a preparation process thereof. The defects of easy aggregation and poor dispersibility of graphene are overcome by adjusting and improving the dispersion process of the graphene in the white oil, the problem of hole blocking of a spinneret plate in the production of graphene/UHMWPE composite fibers is effectively prevented, and meanwhile, the application performance of products such as wear resistance and cutting resistance are improved to a certain extent. The main aspects are as follows:
(1) By utilizing the distribution of ball milling steel balls, the particle size of the materials can be reduced by ball milling treatment of graphene powder, a dispersing agent and an antioxidant, the materials are fully ground and uniformly mixed, and then a small amount of white oil is added to moisten the surface of the powder, so that the graphene is adsorbed and uniformly mixed.
(2) The preparation of the graphene/white oil slurry is subjected to formula adjustment and technological parameter improvement, namely: adding the ball-milled mixture into a white oil solvent, heating to 8-130 ℃ while stirring, preserving heat for 0.2-3h, then gradually heating to 130-160 ℃, preserving heat for 2-15h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
The graphene/white oil slurry prepared by the novel process has obvious improvement effect (see figure 2), can pass through a 650-mesh screen at room temperature quickly, and basically has no screen residues on the screen, thereby laying a foundation for the subsequent preparation of high-strength graphene/UHMWPE composite fibers, solving the problem of hole blocking of a spinneret plate in continuous production of the super fibers, wherein the tensile strength of the prepared composite fibers can reach 40cN/dtex, the tensile modulus can reach 1620cN/dtex, the cutting strength is 600, and the international authentication level 2 is reached.
In addition, the novel process adopted by the invention does not change the traditional gel spinning process, the preparation process is simple, the cost of limited graphene is only increased in the aspect of production cost, the cost performance is higher, and compared with the process of adding inorganic metal, glass fiber and other hard reinforcing materials, the composite fiber prepared by adding graphene has better hand feeling, and the prepared product is more comfortable to wear.
Example 1:
preparation of the slurry, see fig. 1:
mixing antioxidant 1010 (0.01 kg), PSS (0.01 kg), graphene powder (0.01 kg) and 9.997kg of white oil, completely soaking the antioxidant 1010, PSS and graphene powder, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 500rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and the ball milling is performed for 1h;
The above mixture was added to 89.973kg of white oil, heated to 80 ℃ with stirring for 0.5h, and then gradually warmed to 120 ℃ for 4h to form a uniform solution, i.e., a uniformly dispersed graphene/white oil slurry (dispersibility see fig. 2).
Use of a slurry in fibers of UHMWPE:
adding 10kg of UHMWPE powder (graphene accounting for 0.1% of UHMWPE) and 1.14kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolving kettle, a feeding kettle and a double-screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 2:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (1 kg), SDS (1 kg), graphene powder (0.01 kg) and 9.799kg of white oil, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 1000rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and the ball milling is performed for 10min;
adding the mixed material into 88.191kg of white oil, heating to 110 ℃ while stirring, preserving heat for 0.6h, and then gradually heating to 138 ℃ and preserving heat for 5h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
adding 10kg of UHMWPE powder (graphene accounting for 0.1% of UHMWPE) and 3.12kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double-screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 3
Preparation of composite slurry, see fig. 1:
mixing antioxidant 1076 (1 kg), SDBS (0.01 kg), graphene powder (0.015 kg) and 9.898kg of white oil, ball milling the mixture to fully mix the components, wherein the ball milling speed is 300rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1, and ball milling is carried out for 2 hours;
the above mixture was added to 89.078kg of white oil, heated to 118 ℃ with stirring for 0.7h, and then gradually heated to 140 ℃ for 6h to form a uniform solution, i.e. a uniformly dispersed graphene/white oil slurry (dispersibility see fig. 2).
Further preparation of UHMWPE composite fibers:
Adding 10kg of UHMWPE powder (graphene accounting for 0.15% of UHMWPE) and 2.14kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double-screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying, and carrying out 4-level super heat drawing on the gel silk subjected to standing and balancing, wherein the temperature is 140 ℃ to obtain the composite fiber.
Example 4:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1076 (1 kg), SDBS (0.01 kg), graphene powder (0.5 kg) and 9.849kg of white oil, ball milling the mixture to fully mix the components, wherein the ball milling speed is 800rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and ball milling is carried out for 30min;
adding the mixed material into 88.641kg of white oil, heating to 130 ℃ while stirring, preserving heat for 0.8h, and then gradually heating to 160 ℃ and preserving heat for 7h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
200kg of UHMWPE powder (graphene accounting for 0.25% of UHMWPE) and 1923.73kg of white oil are added into the obtained slurry to prepare a pre-spinning solution, the pre-spinning solution enters a swelling kettle to be heated to 100 ℃, and then the pre-spinning solution is subjected to stepped heating from 100 ℃ to 268 ℃ through a dissolution kettle, a feeding kettle and a double screw extruder, and is quenched into gel filaments. And (3) extracting, drying, and carrying out 4-level super heat drawing on the gel silk subjected to standing and balancing, wherein the temperature is between 150 ℃ to obtain the composite fiber.
Example 5:
preparation of composite slurry, see fig. 1:
mixing an antioxidant CA (1 kg), PE (1 kg), graphene powder (0.5 kg) and 9.75kg of white oil, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 600rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and the ball milling is performed for 90min;
the mixture is added into 87.75kg of white oil, heated to 118 ℃ while stirring for 0.5h, and then gradually heated to 180 ℃ for 8h to form a uniform solution, namely the uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
333.33kg of UHMWPE powder (graphene accounting for 0.15% of UHMWPE) and 3272.84kg of white oil are added into the obtained slurry to prepare a pre-spinning solution, the pre-spinning solution enters a swelling kettle to be heated to 100 ℃, then the pre-spinning solution passes through a dissolution kettle, a feeding kettle and a double screw extruder to be stepped heated to 268 ℃ from 100 ℃, and then the pre-spinning solution is quenched into gel filaments. And (3) extracting, drying, and carrying out 4-level super heat drawing on the gel silk subjected to standing and balancing, wherein the temperature is between 150 ℃ to obtain the composite fiber.
Example 6:
preparation of composite slurry, see fig. 1:
Mixing antioxidant 1010 (1 kg), BYK (1 kg), graphene powder (0.03 kg) and 9.797kg of white oil, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 1000rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and the ball milling is performed for 10min;
adding the mixed material into 88.173kg of white oil, heating to 80 ℃ while stirring, preserving heat for 0.6h, and then gradually heating to 130 ℃ and preserving heat for 5h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
30kg of UHMWPE powder (graphene accounting for 0.1% of UHMWPE) and 205.36kg of white oil are added into the obtained slurry to prepare a pre-spinning solution, the pre-spinning solution enters a swelling kettle to be heated to 100 ℃, and then the pre-spinning solution is subjected to stepped heating from 100 ℃ to 268 ℃ through a dissolution kettle, a feeding kettle and a double screw extruder, and is quenched into gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 7:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (0.1 kg), PSS (0.5 kg), graphene powder (0.1 kg) and 9.93kg of white oil, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 1000rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1, and performing ball milling for 10min;
The mixture is added into 89.37kg of white oil, heated to 110 ℃ while stirring for 0.8h, and then gradually heated to 130 ℃ for 15h to form a uniform solution, namely the uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
adding 100kg of UHMWPE powder (graphene accounting for 0.1% of UHMWPE) and 911.81kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 8:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (0.5 kg), PVC (0.1 kg), graphene powder (0.5 kg) and 9.89kg of white oil, ball-milling the mixture to fully mix the components, wherein the ball-milling speed is 1000rpm, the ball-milling mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1, and ball-milling is carried out for 10min;
the mixture is added into 89.01kg of white oil, heated to 130 ℃ while stirring for 0.6h, and then gradually heated to 180 ℃ for 2h to form a uniform solution, namely the uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
adding 16.67kg of UHMWPE powder (graphene accounts for 3% of UHMWPE) and 69.65kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 9:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (0.5 kg), commercial AFCONA (0.5 kg), graphene powder (0.2 kg) and 9.88kg of white oil, ball milling the mixture to fully mix the components, wherein the ball milling speed is 1000rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, the volume ratio of the three is 3:1:1, and ball milling is carried out for 10min;
adding the mixed material into 88.92kg of white oil, heating to 118 ℃ while stirring, preserving heat for 2 hours, and then gradually heating to 160 ℃ and preserving heat for 8 hours to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
Adding 100kg of UHMWPE powder (graphene accounting for 0.2% of UHMWPE) and 912.31kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 10:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (0.3 kg), PP (0.25 kg), graphene powder (0.15 kg) and 9.93kg of white oil, ball-milling the mixture to fully mix the components, wherein the ball-milling speed is 1000rpm, the ball-milling mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1, and ball-milling is carried out for 10min;
adding the mixed material into 89.37kg of white oil, heating to 80 ℃ while stirring, preserving heat for 3 hours, and then gradually heating to 160 ℃ and preserving heat for 2 hours to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
150kg of UHMWPE powder (graphene accounting for 0.1% of UHMWPE) and 1417.37kg of white oil are added into the obtained slurry to prepare a pre-spinning solution, the pre-spinning solution enters a swelling kettle to be heated to 100 ℃, and then the pre-spinning solution is subjected to stepped heating from 100 ℃ to 268 ℃ through a dissolution kettle, a feeding kettle and a double screw extruder, and is quenched into gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
Example 11:
preparation of composite slurry, see fig. 1:
mixing antioxidant 1010 (0.2 kg), PE (0.2 kg), graphene powder (0.2 kg) and 9.94kg of white oil, performing ball milling on the mixed materials to fully mix the components, wherein the ball milling speed is 1000rpm, the ball material mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1, and performing ball milling for 10min;
adding the mixed material into 89.46kg of white oil, heating to 118 ℃ while stirring, preserving heat for 1h, and then gradually heating to 138 ℃ and preserving heat for 8h to form a uniform solution, namely uniformly dispersed graphene/white oil slurry.
Further preparation of UHMWPE composite fibers:
adding 100kg of UHMWPE powder (graphene accounting for 0.2% of UHMWPE) and 911.71kg of white oil into the obtained slurry to prepare a pre-spinning solution, heating to 100 ℃ in a swelling kettle, heating to 268 ℃ from 100 ℃ in a stepped way through a dissolution kettle, a feeding kettle and a double screw extruder, and quenching to obtain gel filaments. And (3) extracting, drying and 4-level super hot drawing the gel silk after standing and balancing, wherein the temperature is 130 ℃, and thus the composite fiber is obtained.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (25)
1. The preparation method of the graphene-dispersed white oil slurry is characterized by comprising the following steps of: comprising the following steps:
1) Mixing a component A, a component B, graphene powder and white oil, and ball-milling the mixed materials to fully mix the components, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent;
2) Adding the mixed material obtained in the step 1) into white oil, heating the white oil at a first temperature under stirring, preserving heat for 0.2-3h, then heating to a second temperature, and preserving heat for 2-15h under stirring continuously to form a uniform solution;
wherein the second temperature is 30-62 ℃ higher than the first temperature, and the first temperature is 80-130 ℃; the second temperature is 120-180 ℃;
the white oil slurry comprises 0.01-1wt% of a component A, 0.01-1wt% of a component B and 0.01-0.5wt% of graphene, wherein the component A is an antioxidant, and the component B is a dispersing agent and/or a modifying agent; the stone isThe graphene powder has a single-layer or multi-layer structure, and has a sheet diameter of 0.5-5 um, a thickness of 0.5-30 nm, and a specific surface area of 170-320 m 2 /g。
2. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: in the step 1), the rotation speed of ball milling is 300-1000rpm, the ball mass ratio is 10:1, the grinding balls are formed by mixing grinding balls with diameters of 5mm, 12mm and 15mm, and the volume ratio of the three is 3:1:1.
3. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: in the step 1), ball milling is carried out for 10min-2h.
4. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: the first temperature is 110-130 ℃; the second temperature is 130-160 ℃.
5. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: preserving the temperature at the first temperature for 0.5-1h; and/or, the second temperature is used for heat preservation reaction for 4-8h.
6. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: the heating rate from the first temperature to the second temperature is 20-30 ℃/h.
7. The method for preparing the graphene-dispersed white oil slurry according to claim 1, wherein: the amount of the white oil in the step 1) accounts for 1/10 of the total amount of the white oil.
8. A white oil slurry having graphene dispersed therein, characterized in that: the preparation method according to any one of claims 1 to 7.
9. The graphene-dispersed white oil slurry according to claim 8, wherein: the white oil slurry contains 0.1-0.5wt% of component A, 0.1-0.5wt% of component B and 0.1-0.2wt% of graphene based on 100wt% of the total mass of the white oil slurry.
10. The graphene-dispersed white oil slurry according to claim 8, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP.
11. The graphene-dispersed white oil slurry according to claim 10, wherein: the antioxidant is one or the combination of more than two of antioxidant 1010, antioxidant 164 or antioxidant DNP.
12. The graphene-dispersed white oil slurry according to claim 8, wherein: the dispersing agent and/or the modifier is a polyolefin compound; or one or more of PSS, SDBS, SDS, commercial BYK or commercial AFCONA.
13. The graphene-dispersed white oil slurry according to claim 12, wherein: the dispersant and/or modifier is PE, PVC, PP.
14. The graphene-dispersed white oil slurry according to claim 12, wherein: the dispersing agent and/or the modifying agent is one or a combination of more than two of PSS, SDBS or SDS.
15. A process for the preparation of UHMWPE fibers, characterized in that: the preparation method of the graphene-dispersed white oil slurry comprises the steps of preparing a white oil slurry with graphene dispersed therein by adopting the preparation method of any one of claims 1-7, adding UHMWPE powder and white oil into the white oil slurry to prepare a pre-spinning solution, preparing gel filaments from the pre-spinning solution, and extracting, drying and drafting the gel filaments to obtain the composite fiber of graphene and UHMWPE.
16. The method for preparing UHMWPE fibers according to claim 15, characterized in that: the amount of UHMWPE powder and white oil is added to make graphene in the pre-spinning solution account for 0.1% -3% of UHMWPE.
17. The method for producing UHMWPE fibers according to claim 16, characterized in that: the amount of UHMWPE powder and white oil added was such that the mass ratio of UHMWPE to white oil in the pre-dope was 9:91.
18. The method for preparing UHMWPE fibers according to claim 15, characterized in that: the pre-spinning solution firstly enters a swelling kettle to be heated to 100 ℃, then is extruded by a dissolution kettle, a feeding kettle and a double-screw extruder, is heated stepwise from 100 ℃ to 268 ℃, is 100/130/160/210/240/268 stepwise, and is quenched into gel filaments, wherein the length-diameter ratio of the double-screw extruder is 54:70, and the double-screw extruder consists of a feeding section, a heating section, a dissolution section and a uniformly mixing section.
19. The method for preparing UHMWPE fibers according to claim 15, characterized in that: the extraction adopts a continuous multistage closed ultrasonic extractor, the extraction temperature is 40+/-1 ℃, and the extraction rate is more than or equal to 99 percent.
20. The method for preparing UHMWPE fibers according to claim 19, characterized in that: the extraction adopts a multistage multi-tank quantitative liquid supplementing and draining process.
21. The method for preparing UHMWPE fibers according to claim 15, characterized in that: the drafting adopts 4-level super hot drafting, and the hot drafting temperature is 130-150 ℃.
22. An UHMWPE fiber characterized in that: the fiber is prepared according to the preparation method of any one of claims 15-21, wherein the fiber contains graphene and UHMWPE, and the graphene accounts for 0.1-3 wt% of the UHMWPE.
23The UHMWPE fiber according to claim 22, characterized in that: the graphene is graphene powder with a single-layer or multi-layer structure, the sheet diameter is 0.5-5 um, the thickness is 0.5-30 nm, and the specific surface area is 170-320 m 2 /g。
24. The UHMWPE fiber according to claim 22, characterized in that: the UHMWPE has an average molecular weight of (1-6) x 10 6 。
25. The UHMWPE fiber according to claim 24, characterized in that: the UHMWPE has an average molecular weight of 4×10 6 。
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