CN114806458B - Anti-slip antistatic coiled material and preparation method thereof - Google Patents

Anti-slip antistatic coiled material and preparation method thereof Download PDF

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CN114806458B
CN114806458B CN202210528636.8A CN202210528636A CN114806458B CN 114806458 B CN114806458 B CN 114806458B CN 202210528636 A CN202210528636 A CN 202210528636A CN 114806458 B CN114806458 B CN 114806458B
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coiled material
stirring
temperature
mass
slip
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CN114806458A (en
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庞胜全
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Suzhou Yudeshui Electric Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/006—Presence of epoxy resin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate

Abstract

The invention discloses an anti-slip antistatic coiled material and a preparation method thereof, and relates to the technical field of building materials. In the preparation of the anti-slip antistatic coiled material, polyethylene glycol is reacted with succinic anhydride, thionyl chloride and p-aminophenol in sequence, then reacted with p-aminophenol again, then reacted with toluene diisocyanate to prepare polyurethane, a metal organic framework and polyacrylonitrile are spun and carbonized, then reacted with ferric chloride and polyamic acid solution to prepare modified carbon nano fibers, an ethylene-vinyl acetate copolymer, phenolic resin and talcum powder are prepared into an adhesive layer through tape casting and rolling, a polyethylene film and the adhesive layer are pressed to obtain a semi-isolated adhesive layer, epoxy resin, polyurethane and modified carbon nano fibers are coated and cured on the non-isolated surface of the semi-isolated adhesive layer, and the anti-slip antistatic coiled material is prepared through double hot pressing. The anti-slip antistatic coiled material prepared by the invention has excellent anti-slip, anti-static and anti-stripping properties.

Description

Anti-slip antistatic coiled material and preparation method thereof
Technical Field
The invention relates to the technical field of building materials, in particular to an anti-slip antistatic coiled material and a preparation method thereof.
Background
The waterproof coiled material is mainly used for building walls, roofs, tunnels, roads, landfill sites and the like, plays a role in resisting external rainwater and groundwater leakage, is a flexible coiled building material product, is used as a non-leakage connection between an engineering foundation and a building, is a first waterproof barrier of the whole engineering, and plays a vital role in the whole engineering.
The prior art usually uses synthetic rubber, synthetic resin or a blend of the synthetic rubber and the synthetic resin as base materials, and adds a proper amount of chemical auxiliary agents and filling materials, and the coiled sheet waterproof coiled material is manufactured through a certain procedure. The coiled material has the advantages of high tensile strength, high tearing strength, high elongation at break, good heat resistance, good low-temperature flexibility, corrosion resistance, aging resistance, cold construction and the like. Although good waterproof effect is achieved, water is easy to stay to cause slipping, meanwhile, the resistivity is large, static electricity is easy to generate, and the coiled material prepared by the method has good anti-slip and antistatic effects.
Disclosure of Invention
The invention aims to provide an anti-skid antistatic coiled material and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the anti-skid antistatic coiled material is characterized in that the anti-skid antistatic coiled material is prepared by double hot pressing of a semi-finished coiled material; the semi-finished coiled material sequentially comprises an isolation layer, an adhesive layer and a surface layer from bottom to top.
As optimization, the isolation layer is a polyethylene film; the adhesive layer is prepared from ethylene-vinyl acetate copolymer, phenolic resin and talcum powder by tape casting and rolling; the surface layer is prepared by coating and curing epoxy resin, polyurethane and modified carbon nano fibers.
As optimization, the polyurethane is prepared by reacting polyethylene glycol with succinic anhydride, thionyl chloride and para-aminophenol in sequence, then reacting the polyethylene glycol with the para-aminophenol again to prepare modified polyethylene glycol, and reacting the modified polyethylene glycol with toluene diisocyanate; the modified carbon nanofiber is prepared by spinning a metal organic framework and polyacrylonitrile to obtain a nanofiber, carbonizing the nanofiber, and mixing the nanofiber with ferric chloride and polyamide acid solution for reaction.
As optimization, the double hot pressing is to firstly perform stripe hot pressing, and then to raise the temperature and the pressure for full hot pressing.
As optimization, the preparation method of the anti-slip antistatic coiled material comprises the following preparation steps:
(1) The modified polyethylene glycol and ethyl acetate are mixed according to the mass of 1:1 to 1:2, uniformly mixing, adding toluene diisocyanate with the mass of 2-3 times of that of modified polyethylene glycol in nitrogen atmosphere, stirring for 10-15 min at the temperature of 10-30 ℃ and at the speed of 300-500 r/min, heating to the temperature of 40-50 ℃, continuously stirring for 25-30 min, adding dibutyl tin dilaurate with the mass of 0.003-0.005 time of that of modified polyethylene glycol, continuously reacting for 2-3 h under the condition of constant temperature stirring, and standing for 6-8 h at the temperature of 20-30 ℃ and the pressure of 1-2 kPa to obtain polyurethane;
(2) The metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1: 6-1: 1:8, uniformly mixing, and stirring for 6-8 hours at 70-80 ℃ and 800-1000 r/min to obtain spinning solution; carrying out electrostatic spinning on the spinning solution to obtain nanofiber; preheating the nanofiber at 100-120 ℃ for 30-40 min in nitrogen atmosphere, heating to 250-300 ℃ at the speed of 5-6 ℃/min, standing for 60-80 min, heating to 800-900 ℃ at the same speed, and standing for 2-3 h to obtain the carbon nanofiber; the carbon nanofiber, ferric chloride and polyamic acid solution are mixed according to the mass ratio of 4:1: 40-6: 1:60, uniformly mixing, and carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the frequency of 30-40 kHz for 40-50 min to obtain modified carbon nanofibers;
(3) The ethylene-vinyl acetate copolymer and phenolic resin are mixed according to the mass ratio of 1:1 to 1:2, uniformly mixing, stirring at the temperature of 170-180 ℃ for 10-15 min at the speed of 300-500 r/min, adding talcum powder with the mass of 0.01-0.03 times that of the ethylene-vinyl acetate copolymer, continuously stirring for 50-60 min, placing in a casting roller press, rolling to the thickness of 0.5-0.7 mm at the temperature of 120-130 ℃, naturally cooling to room temperature to obtain an adhesive layer, attaching the adhesive layer to a polyethylene film with the thickness of 0.1-0.5 mm in an area such as the like, and rolling at the pressure-bonding speed of 0.1-0.2 m/s at the temperature of 40-50 ℃ at the pressure of 1.3-1.5 MPa to obtain the semi-isolated adhesive layer;
(4) Epoxy resin, polyurethane, modified carbon nanofiber, a curing agent, a coupling agent, a plasticizer, cyclohexanone, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 50:30:30:5:3:8:20:10: 2-70: 40:40:7:5:12:30:15:4, uniformly mixing, stirring for 2-3 min at 30-40 ℃ at 500-700 r/min, uniformly coating on the non-isolated surface of the semi-isolated adhesive layer, standing for 20-24 h in a room temperature environment to form a surface layer with the thickness of 2-3 mm, and preparing a semi-finished coiled material;
(5) Carrying out stripe hot-pressing treatment on the semi-finished coiled material, wherein the stripe interval is 2-3 cm, the stripe thickness is 1-2 cm, the hot-pressing temperature is 120-130 ℃, the hot-pressing pressure is 0.3-0.5 MPa, the hot-pressing time is 1-2 h, after naturally cooling to room temperature, the surface is cleaned with pure water and absolute ethyl alcohol for 3-5 times, after naturally drying, carrying out full hot-pressing again, the hot-pressing temperature is 130-150 ℃, the hot-pressing pressure is 1.5-2.0 MPa, the hot-pressing time is 30-40 min, the pressure is reduced to 0.3-0.5 MPa, the pressure is kept unchanged, the temperature is reduced to room temperature at a speed of 3-5 ℃/min, the surface is cleaned with pure water and absolute ethyl alcohol for 3-5 times, and the anti-slip antistatic coiled material is obtained after naturally drying.
As optimization, the preparation method of the modified polyethylene glycol in the step (1) comprises the following steps: succinic anhydride and polyethylene glycol are mixed according to the mass ratio of 1: 3-1: 4, uniformly mixing, stirring for 3-4 hours at 70-80 ℃ and 800-1000 r/min, and mixing with thionyl chloride and tetrahydrofuran according to the mass ratio of 15:100: 1-40: 300:1, uniformly mixing, stirring and reacting for 2-3 hours at 40-50 ℃ and 300-500 r/min, heating to 60-70 ℃, continuously stirring and reacting for 2-3 hours, and standing for 30-40 minutes at 10-30 ℃ and 60-100 Pa to obtain the pre-modified polyethylene glycol; the method comprises the following steps of (1) mixing p-aminophenol and dichloromethane: 10 to 1:12, uniformly mixing at 0-5 ℃, adding triethylamine with the mass of 0.3-0.4 times of para-aminophenol, stirring for 3-5 min at 0-5 ℃ at 300-500 r/min, continuously stirring and dropwise adding pre-modified ethylene glycol with the mass of 3-5 times of para-aminophenol at the rate of 1-2 mL/min, stirring for 40-50 min at 0-5 ℃ at 300-500 r/min, standing for 6-8 h at 20-30 ℃ at 1-2 kPa, reducing the temperature to 0-5 ℃, adding para-aminophenol with the mass of 0.2-0.3 times of pre-modified ethylene glycol, hydrochloric acid with the mass fraction of 10-15% of 3-4 times of pre-modified ethylene glycol and sodium nitrite aqueous solution with the mass fraction of 10-15% of 3-4 times of pre-modified ethylene glycol, stirring for 20-30 min, adding strong sodium oxide to adjust the pH to 6.8-7.2, standing for 6-8 h at 1-2 kPa, adding absolute ethyl alcohol with the mass of 3-4 times of pre-modified ethylene glycol, separating at-1 Pa to 10Pa, and drying for 1-10 Pa to 10 h.
As optimization, the preparation method of the metal-organic framework in the step (2) comprises the following steps: zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:10: 100-1: 5:20:120 are evenly mixed, stirred and reacted for 3 to 5 hours at the temperature of between 30 and 40 ℃ and the speed of between 300 and 500r/min, centrifugally separated and washed for 3 to 5 times by absolute ethyl alcohol, and the product is prepared.
As optimization, the electrostatic spinning process parameters in the step (2) are as follows: humidity of 25-35%, voltage of 15-18 kV, receiving distance of 15-20 cm and flow rate of 3-5 mL/h.
As an optimization, the preparation method of the polyamic acid solution in the step (2) comprises the following steps: biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:3: 40-5: 4:50 are evenly mixed and stirred for 20 to 24 hours at the temperature of between 5 and 15 ℃ and the speed of between 800 and 1000r/min in a nitrogen atmosphere.
As optimization, the epoxy resin in the step (4) is bisphenol A type epoxy resin; the curing agent is ethylenediamine; the coupling agent is vinyl trimethoxy silane; the plasticizer is one or more of di (2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate.
Compared with the prior art, the invention has the following beneficial effects:
when the anti-skid antistatic coiled material is prepared, firstly, an adhesive layer is prepared by tape casting and rolling of an ethylene-vinyl acetate copolymer, phenolic resin and talcum powder, a polyethylene film and the adhesive layer are pressed to obtain a semi-isolated adhesive layer, epoxy resin, polyurethane and modified carbon nano fibers are coated and cured on the non-isolated surface of the semi-isolated adhesive layer, stripe hot pressing is carried out firstly, and then the temperature and the pressure are increased to carry out comprehensive hot pressing to obtain the anti-skid antistatic coiled material.
Firstly, polyethylene glycol is reacted with succinic anhydride, thionyl chloride and para-aminophenol in sequence and then reacted with para-aminophenol again to prepare modified polyethylene glycol, the modified polyethylene glycol is reacted with toluene diisocyanate to prepare polyurethane, azo bonds are generated after the polyethylene glycol is modified, the azo bonds are broken under the hot-pressing condition to form free radicals, and the free radical polymerization of carbon-carbon double bonds is initiated to form a crosslinked network structure, so that the stripping resistance of the anti-skid antistatic coiled material is improved; the stripe hot pressing makes polyurethane azo bond fracture and forms soft section free radical and hard section free radical, and soft section free radical is more easy to remove to not stripe hot pressing region under the pressure and improves elasticity and form elasticity region, and when the object moves on the surface, the concave convex department on object surface can be filled to elasticity region, improves frictional force through unsmooth meshing to the antiskid performance of anti-static coiled material has been improved.
Secondly, zinc nitrate and 2-methylimidazole are reacted to prepare a metal organic framework, the metal organic framework and polyacrylonitrile are spun to obtain nanofibers, biphenyl tetracarboxylic dianhydride and 3, 5-diaminostyrene are reacted to prepare a polyamide acid solution, the nanofibers are carbonized and then mixed with ferric chloride and polyamide acid solution to prepare modified carbon nanofibers, the metal organic framework can be carbonized to enable the modified carbon nanofibers to have a metal porous embedded structure and have nitrogen infiltration, the nitrogen infiltration improves the adsorption complexing performance of the modified carbon nanofibers on metal ions, the carbon nanofibers are modified to enable the carbon nanofibers to load metal ions and enable polyamide acid to be combined on the surface, breakage of the carbon nanofibers and loss of the loaded metal ions are prevented, and therefore the antistatic performance of the anti-slip antistatic coiled material is improved; the hard segment free radical formed by the adsorption of the metal porous embedded structure and the polyurethane fracture is formed by the stripe hot-pressing, so that the hard segment free radical is hardened, the whole hot-pressing is performed, the whole body is smooth, when an object moves on the surface, the pressure of the object makes the hardened stripe stand out, and the hardened stripe can buffer the movement, so that the anti-skid property of the anti-skid antistatic coiled material is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test method of each index of the anti-slip antistatic coiled material manufactured in the following examples is as follows:
antistatic properties: the anti-slip antistatic coiled material obtained in each example was measured for antistatic property by measuring volume resistivity according to GB/T15662 standard by taking the same size, shape and thickness as those of the comparative example material.
Anti-skid properties: the anti-slip antistatic coiled material obtained in each example and the material of the comparative example are taken to have the same size, shape and thickness, and the dynamic friction factor is tested according to the GB/T10006 standard.
Peel resistance: the anti-slip antistatic coiled material obtained in each example and the material of the comparative example are taken to have the same size, shape and thickness, the isolation layer is removed, the anti-slip antistatic coiled material is used on the same substrate at the same pressure and the same temperature, and the peeling strength is tested according to the GB/T2792 standard method.
Example 1
The preparation method of the anti-skid antistatic coiled material mainly comprises the following preparation steps:
(1) Succinic anhydride and polyethylene glycol are mixed according to the mass ratio of 1:4, uniformly mixing, stirring at 70 ℃ for 4 hours at 800r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 15:100:1, uniformly mixing, stirring at 40 ℃ and 300r/min for reaction for 3 hours, heating to 60 ℃ for continuous stirring for reaction for 2 hours, and standing at 10 ℃ and 60Pa for 40 minutes to obtain the pre-modified polyethylene glycol; the method comprises the following steps of (1) mixing p-aminophenol and dichloromethane: 10, uniformly mixing at 0 ℃, adding triethylamine with the mass of 0.3 times of that of the para-aminophenol, stirring at 300r/min for 5min, continuously stirring, dripping 3 times of that of the para-aminophenol into the mixture at a rate of 1mL/min, stirring at 0 ℃ for 50min at 300r/min, standing at 20 ℃ for 8h at 1kPa, reducing the temperature to 0 ℃, adding 0.2 times of that of the para-aminophenol, 10% of hydrochloric acid with the mass fraction of 3 times of that of the pre-modified ethylene glycol and 10% of sodium nitrite aqueous solution with the mass fraction of 4 times of that of the pre-modified ethylene glycol, stirring at 800r/min for 30min, adding strong sodium oxide to adjust the pH value to 6.8, standing at 20 ℃ for 8h at 1kPa, adding 3 times of absolute ethyl alcohol with the mass of the pre-modified ethylene glycol, centrifugally separating, and drying at-1 ℃ for 8h at 1Pa to prepare the modified polyethylene glycol; the modified polyethylene glycol and ethyl acetate are mixed according to the mass of 1:1, uniformly mixing, adding toluene diisocyanate with the mass 2 times of that of the modified polyethylene glycol in a nitrogen atmosphere, stirring for 15min at 10 ℃ and 300r/min, heating to 40 ℃, continuously stirring for 30min, adding dibutyltin dilaurate with the mass 0.003 time of that of the modified polyethylene glycol, continuously reacting for 2h under the condition of keeping the temperature stirring unchanged, and standing for 8h at 20 ℃ and 1kPa to prepare polyurethane;
(2) Zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:10:100, stirring and reacting for 5 hours at 30 ℃ and 300r/min, centrifugally separating, and washing with absolute ethyl alcohol for 5 times to obtain a metal organic framework; the metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1:6, uniformly mixing, and stirring at 70 ℃ and 800r/min for 8 hours to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions of 25% humidity, 15kV voltage, 15cm receiving distance and 3mL/h flow rate to obtain nanofiber; preheating the nanofiber at 100 ℃ for 40min in a nitrogen atmosphere, heating to 250 ℃ at the speed of 5 ℃/min, standing for 80min, heating to 800 ℃ at the same speed, and standing for 3h to obtain the carbon nanofiber; biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:3:40, uniformly mixing, and stirring at 5 ℃ and 800r/min for 24 hours in a nitrogen atmosphere to obtain a polyamic acid solution; the carbon nanofiber, ferric chloride and polyamic acid solution are mixed according to the mass ratio of 4:1:40, uniformly mixing, and carrying out ultrasonic treatment at 20 ℃ and 30kHz for 50min to obtain modified carbon nanofibers;
(3) The ethylene-vinyl acetate copolymer and phenolic resin are mixed according to the mass ratio of 1:1, uniformly mixing, stirring at the temperature of 170 ℃ for 15min at 300r/min, adding talcum powder with the mass of 0.01 times of that of ethylene-vinyl acetate copolymer, continuously stirring for 50min, rolling to the thickness of 0.6mm at the temperature of 120 ℃ in a tape casting roller press, naturally cooling to room temperature to obtain an adhesive layer, bonding the adhesive layer with a polyethylene film with the thickness of 0.3mm in equal area, and rolling at the pressure of 0.1m/s at the temperature of 40 ℃ under the pressure of 1.3MPa to obtain a semi-isolated adhesive layer;
(4) The preparation method comprises the following steps of mixing bisphenol A epoxy resin, polyurethane, modified carbon nanofibers, ethylenediamine, vinyl trimethoxy silane, dibutyl phthalate, cyclohexanone, absolute ethyl alcohol and pure water according to a mass ratio of 50:30:30:5:3:8:20:10:2, uniformly mixing, stirring at 30 ℃ for 3min at 500r/min, uniformly coating on the non-isolated surface of the semi-isolated adhesive layer, standing for 20h in a room temperature environment to form a surface layer with the thickness of 2.5mm, and preparing a semi-finished coiled material;
(5) Carrying out stripe hot-pressing treatment on the semi-finished coiled material, wherein the stripe interval is 2cm, the stripe thickness is 1cm, the hot-pressing temperature is 120 ℃, the hot-pressing pressure is 0.3MPa, the hot-pressing time is 2h, after natural cooling to room temperature, cleaning the surface with pure water and absolute ethyl alcohol for 3 times, after natural drying, carrying out full hot-pressing again, the hot-pressing temperature is 130 ℃, the hot-pressing pressure is 1.5MPa, the hot-pressing time is 40min, after the pressure is reduced to 0.3MPa, the pressure is kept unchanged, cooling to room temperature at a speed of 3 ℃/min, taking out, cleaning the surface with pure water and absolute ethyl alcohol for 3 times, and after natural drying, obtaining the anti-skidding antistatic coiled material.
Example 2
The preparation method of the anti-skid antistatic coiled material mainly comprises the following preparation steps:
(1) Succinic anhydride and polyethylene glycol are mixed according to the mass ratio of 1:3.5, stirring for 3.5 hours at the temperature of 75 ℃ at 900r/min, and mixing with thionyl chloride and tetrahydrofuran according to the mass ratio of 27:200:1, uniformly mixing, stirring at 45 ℃ and 400r/min for reaction for 2.5 hours, heating to 65 ℃ and continuously stirring for reaction for 2.5 hours, and standing at 20 ℃ and 80Pa for 35 minutes to obtain pre-modified polyethylene glycol; the method comprises the following steps of (1) mixing p-aminophenol and dichloromethane: 11, uniformly mixing at 3 ℃, adding triethylamine with the mass of 0.35 times of that of the para-aminophenol, stirring at 400r/min for 4min, continuously stirring, dripping pre-modified ethylene glycol with the mass of 4 times of the para-aminophenol at the speed of 1.5mL/min, stirring at 3 ℃ for 45min at 400r/min, standing at 25 ℃ for 7h at 1.5kPa, reducing the temperature to 3 ℃, adding para-aminophenol with the mass of 0.25 times of that of the pre-modified ethylene glycol, hydrochloric acid with the mass fraction of 12% with the mass of 3.5 times of that of the pre-modified ethylene glycol and sodium nitrite aqueous solution with the mass fraction of 12% with the mass of 3.5 times of that of the pre-modified ethylene glycol, stirring at 900r/min for reacting for 25min, adding strong sodium oxide to adjust the pH to 7, standing at 25 ℃ for 7h at 1.5kPa, adding absolute ethyl alcohol with the mass of 3.5 times of that of the pre-modified ethylene glycol, centrifuging, and drying at-5 Pa for 7h to prepare modified polyethylene glycol; the modified polyethylene glycol and ethyl acetate are mixed according to the mass of 1:1.5, adding toluene diisocyanate with the mass of 2.5 times of that of the modified polyethylene glycol into the nitrogen atmosphere, stirring for 12min at 20 ℃ and 400r/min, heating to 45 ℃, continuously stirring for 28min, adding dibutyltin dilaurate with the mass of 0.004 times of that of the modified polyethylene glycol, continuously reacting for 2.5h under the condition of keeping the temperature stirring, and standing for 4h at 25 ℃ and 1.5kPa to obtain polyurethane;
(2) Zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:15:110, stirring at 35 ℃ and 400r/min for reaction for 4 hours, centrifugally separating, and washing with absolute ethyl alcohol for 4 times to obtain a metal organic framework; the metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1:7, uniformly mixing, and stirring at 75 ℃ for 7 hours at 900r/min to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions of 30% humidity, 16kV voltage, 18cm receiving distance and 4mL/h flow rate to obtain nanofiber; preheating the nanofiber at 110 ℃ for 35min in a nitrogen atmosphere, heating to 280 ℃ at the speed of 5 ℃/min, standing for 70min, heating to 850 ℃ at the same speed, and standing for 2.5h to obtain the carbon nanofiber; biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:3:45, uniformly mixing, and stirring for 22 hours at the temperature of 10 ℃ and the speed of 900r/min in a nitrogen atmosphere to prepare a polyamic acid solution; the preparation method comprises the following steps of (1) mixing carbon nanofibers, ferric chloride and polyamide acid solution according to a mass ratio of 5:1:50, uniformly mixing, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 45min to obtain modified carbon nanofibers;
(3) The ethylene-vinyl acetate copolymer and phenolic resin are mixed according to the mass ratio of 1:1.5, uniformly mixing, stirring at 175 ℃ for 12min at 400r/min, adding talcum powder with the mass of 0.02 times of that of the ethylene-vinyl acetate copolymer, continuously stirring for 55min, rolling to the thickness of 0.6mm at 125 ℃ in a casting rolling machine, naturally cooling to room temperature to obtain an adhesive layer, attaching the adhesive layer to a polyethylene film with the thickness of 0.3mm in an area, and rolling at 45 ℃ and 1.4MPa at the pressing speed of 0.15m/s to obtain a semi-isolated adhesive layer;
(4) Bisphenol A epoxy resin, polyurethane, modified carbon nanofiber, ethylenediamine, vinyl trimethoxy silane, dibutyl phthalate, cyclohexanone, absolute ethyl alcohol and pure water are mixed according to a mass ratio of 60:35:35:6:4:10:25:12:3, uniformly mixing, stirring at 35 ℃ and 600r/min for 2.5min, uniformly coating on the non-isolated surface of the semi-isolated adhesive layer, standing for 22h in a room temperature environment to form a surface layer with the thickness of 2.5mm, and preparing a semi-finished coiled material;
(5) Carrying out stripe hot-pressing treatment on the semi-finished coiled material, wherein the stripe interval is 2cm, the stripe thickness is 1cm, the hot-pressing temperature is 125 ℃, the hot-pressing pressure is 0.4MPa, the hot-pressing time is 1.5h, after natural cooling to room temperature, cleaning the surface for 4 times by using pure water and absolute ethyl alcohol, after natural drying, carrying out full hot-pressing, the hot-pressing temperature is 140 ℃, the hot-pressing pressure is 1.8MPa, the hot-pressing time is 35min, keeping the pressure unchanged after the pressure is reduced to 0.4MPa, cooling to room temperature at the speed of 4 ℃/min, taking out, cleaning the surface for 4 times by using pure water and absolute ethyl alcohol, and naturally drying to obtain the anti-skidding antistatic coiled material.
Example 3
The preparation method of the anti-skid antistatic coiled material mainly comprises the following preparation steps:
(1) Succinic anhydride and polyethylene glycol are mixed according to the mass ratio of 1:4, uniformly mixing, stirring at 80 ℃ for 3 hours at 1000r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 40:300:1, uniformly mixing, stirring at 50 ℃ for reaction for 2 hours at 500r/min, heating to 70 ℃ for continuous stirring for reaction for 2 hours, and standing at 30 ℃ for 30min at 100Pa to obtain pre-modified polyethylene glycol; the method comprises the following steps of (1) mixing p-aminophenol and dichloromethane: 12, uniformly mixing at 5 ℃, adding triethylamine with the mass which is 0.4 times of that of the para-aminophenol, stirring at 500r/min for 3min, continuously stirring, dripping pre-modified ethylene glycol with the mass which is 5 times of that of the para-aminophenol at the rate of 2mL/min, stirring at 5 ℃ for 40min at 500r/min, standing at 30 ℃ for 6h at 2kPa, reducing the temperature to 5 ℃, adding para-aminophenol with the mass which is 0.3 times of that of the pre-modified ethylene glycol, hydrochloric acid with the mass fraction which is 115% of that of the pre-modified ethylene glycol and sodium nitrite with the mass fraction which is 15% of that of the pre-modified ethylene glycol, stirring at 1000r/min for 20min, adding strong sodium oxide to adjust the pH to 7.2, standing at 30 ℃ for 6h at 2kPa, adding absolute ethanol with the mass which is 4 times of that of the pre-modified ethylene glycol, centrifugally separating, and drying at 10Pa for 6h at-10 ℃ to prepare modified polyethylene glycol; the modified polyethylene glycol and ethyl acetate are mixed according to the mass of 1:2, uniformly mixing, adding toluene diisocyanate with the mass 3 times of that of the modified polyethylene glycol in a nitrogen atmosphere, stirring for 10min at 30 ℃ and 500r/min, heating to 50 ℃, continuously stirring for 30min, adding dibutyltin dilaurate with the mass 0.005 time of that of the modified polyethylene glycol, continuously reacting for 2h under the condition of keeping the temperature stirring unchanged, and standing for 6h at 30 ℃ and 2kPa to obtain polyurethane;
(2) Zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:5:20:120, stirring at 40 ℃ and 500r/min for reaction for 3 hours, centrifugally separating, and washing with absolute ethyl alcohol for 5 times to obtain a metal organic framework; the metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1:8, uniformly mixing, and stirring at 80 ℃ and 1000r/min for 6 hours to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions of 35% humidity, 18kV voltage, 20cm receiving distance and 5mL/h flow rate to obtain nanofiber; preheating the nanofiber at 120 ℃ for 30min in a nitrogen atmosphere, heating to 300 ℃ at the speed of 6 ℃/min, standing for 60min, heating to 900 ℃ at the same speed, and standing for 2h to obtain the carbon nanofiber; biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:4:50, uniformly mixing, and stirring for 20 hours at 15 ℃ and 1000r/min in a nitrogen atmosphere to prepare a polyamic acid solution; the carbon nanofiber, ferric chloride and polyamic acid solution are mixed according to the mass ratio of 6:1:60, uniformly mixing, and carrying out ultrasonic treatment at 30 ℃ and 40kHz for 40min to obtain modified carbon nanofibers;
(3) The ethylene-vinyl acetate copolymer and phenolic resin are mixed according to the mass ratio of 1:1, uniformly mixing, stirring at the temperature of 170 ℃ for 15min at 300r/min, adding talcum powder with the mass of 0.01 times of that of ethylene-vinyl acetate copolymer, continuously stirring for 50min, rolling to the thickness of 0.6mm at the temperature of 120 ℃ in a tape casting roller press, naturally cooling to room temperature to obtain an adhesive layer, bonding the adhesive layer with a polyethylene film with the thickness of 0.3mm in equal area, and rolling at the pressure of 0.2m/s at the temperature of 40 ℃ under the pressure of 1.3MPa to obtain a semi-isolated adhesive layer;
(4) Bisphenol A epoxy resin, polyurethane, modified carbon nanofiber, ethylenediamine, vinyl trimethoxy silane, dibutyl phthalate, cyclohexanone, absolute ethyl alcohol and pure water are mixed according to a mass ratio of 70:40:40:7:5:12:30:15:4, uniformly mixing, stirring at 40 ℃ and 700r/min for 2min, uniformly coating on the non-isolated surface of the semi-isolated adhesive layer, standing for 20h in a room temperature environment to form a surface layer with the thickness of 2.5mm, and preparing a semi-finished coiled material;
(5) Carrying out stripe hot-pressing treatment on the semi-finished coiled material, wherein the stripe interval is 2cm, the stripe thickness is 1cm, the hot-pressing temperature is 130 ℃, the hot-pressing pressure is 0.5MPa, the hot-pressing time is 1h, after natural cooling to room temperature, cleaning the surface for 5 times by using pure water and absolute ethyl alcohol, after natural drying, carrying out full hot-pressing, the hot-pressing temperature is 130 ℃, the hot-pressing pressure is 1.5MPa, the hot-pressing time is 30min, after the pressure is reduced to 0.5MPa, the pressure is kept unchanged, cooling to room temperature at a speed of 5 ℃/min, taking out, cleaning the surface for 5 times by using pure water and absolute ethyl alcohol, and naturally drying to obtain the anti-skidding antistatic coiled material.
Comparative example 1
The method for producing the anti-slip antistatic roll of comparative example 1 is different from example 2 only in the step (1), and the step (1) is modified as follows: polyethylene glycol and ethyl acetate are mixed according to the mass of 1:1.5, adding toluene diisocyanate with the mass of 2.5 times of that of polyethylene glycol in a nitrogen atmosphere, stirring for 12min at 20 ℃ and 400r/min, heating to 45 ℃, continuously stirring for 28min, adding dibutyltin dilaurate with the mass of 0.004 times of that of polyethylene glycol, continuously reacting for 2.5h under the condition of keeping the temperature stirring, and standing for 4h at 25 ℃ and 1.5kPa to obtain polyurethane. The remaining steps are as in example 2.
Comparative example 2
The method for preparing the anti-slip antistatic roll of comparative example 2 is different from example 2 only in the step (2), and the step (2) is modified as follows: polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:7, uniformly mixing, and stirring at 75 ℃ for 7 hours at 900r/min to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions of 30% humidity, 16kV voltage, 18cm receiving distance and 4mL/h flow rate to obtain nanofiber; preheating the nanofiber at 110 ℃ for 35min in a nitrogen atmosphere, heating to 280 ℃ at the speed of 5 ℃/min, standing for 70min, heating to 850 ℃ at the same speed, and standing for 2.5h to obtain the carbon nanofiber; biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:3:45, uniformly mixing, and stirring for 22 hours at the temperature of 10 ℃ and the speed of 900r/min in a nitrogen atmosphere to prepare a polyamic acid solution; the preparation method comprises the following steps of (1) mixing carbon nanofibers, ferric chloride and polyamide acid solution according to a mass ratio of 5:1:50, and carrying out ultrasonic treatment at 25 ℃ and 35kHz for 45min to obtain the modified carbon nanofiber. The remaining steps are as in example 2.
Comparative example 3
The method for preparing the anti-slip antistatic roll of comparative example 3 is different from example 2 only in the step (2), and the step (2) is modified as follows: zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:15:110, stirring at 35 ℃ and 400r/min for reaction for 4 hours, centrifugally separating, and washing with absolute ethyl alcohol for 4 times to obtain a metal organic framework; the metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1:7, uniformly mixing, and stirring at 75 ℃ for 7 hours at 900r/min to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions of 30% humidity, 16kV voltage, 18cm receiving distance and 4mL/h flow rate to obtain nanofiber; in nitrogen atmosphere, preheating the nanofiber at 110 ℃ for 35min, heating to 280 ℃ at the speed of 5 ℃/min, standing for 70min, heating to 850 ℃ at the same speed, and standing for 2.5h to obtain the carbon nanofiber. And "carbon nanofibers" are used in the subsequent steps.
Comparative example 4
The process for producing the anti-slip antistatic roll of comparative example 4 was different from example 2 only in the step (5), and the step (5) was modified as follows: and (3) carrying out overall hot pressing treatment on the semi-finished coiled material, wherein the hot pressing temperature is 125 ℃, the hot pressing pressure is 0.4MPa, the hot pressing time is 1.5h, after natural cooling to room temperature, cleaning the surface for 4 times by using pure water and absolute ethyl alcohol, after natural drying, carrying out overall hot pressing again, wherein the hot pressing temperature is 140 ℃, the hot pressing pressure is 1.8MPa, the hot pressing time is 35min, the pressure is reduced to 0.4MPa, the pressure is kept unchanged, the temperature is reduced to room temperature at the speed of 4 ℃/min, the surface is cleaned for 4 times by using pure water and absolute ethyl alcohol, and the anti-skid antistatic coiled material is obtained after natural drying. The remaining steps are as in example 2.
Comparative example 5
The manufacturing method of the anti-slip antistatic roll of comparative example 5 is different from example 2 only in that step (5) is not performed and the anti-slip antistatic roll is directly manufactured from step (4).
Effect example
The following table 1 shows the results of performance analysis of antistatic properties, anti-slip properties, and peeling resistance of the anti-slip antistatic rolls of examples 1 to 3 and comparative examples 1 to 5 according to the present invention.
TABLE 1
As can be seen from the comparison of the experimental data of examples 1 to 3 and comparative examples 1 to 5 in Table 1, the anti-slip antistatic coiled material prepared by the invention has good antistatic performance, anti-slip performance and peeling resistance.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1, the dynamic friction factors and the peel strength of the examples 1, 2 and 3 compared with those of comparative example 1 are high, which shows that polyurethane prepared from the modified polyethylene glycol and toluene diisocyanate breaks azo bonds on the polyethylene glycol under the hot-pressing condition to form free radicals, initiates free radical polymerization of carbon-carbon double bonds to form a crosslinked network structure, thereby improving the peeling resistance of the anti-slip antistatic coiled material, secondly breaks the modified polyethylene glycol to form soft free radicals, forms hard free radicals on the rest, combines with stripe hot pressing to form hardened stripes, and further improves the anti-slip performance of the anti-slip antistatic coiled material; from comparison of experimental data of examples 1, 2 and 3 and comparative example 2, examples 1, 2 and 3 have low volume resistivity and high dynamic friction factor and peeling strength, and the fact that a metal organic framework is used in the preparation of the modified carbon nanofiber is demonstrated that the modified carbon nanofiber has a metal porous embedded structure after carbonization and nitrogen permeation, the nitrogen permeation improves the adsorption complexing performance of the modified carbon nanofiber on metal ions, so that the antistatic performance of the anti-skid antistatic coiled material is improved, and the metal porous embedded structure is easy to adsorb hard segment free radicals formed by polyurethane under the hot-pressing condition, so that the bonding effect is improved, and the formation of hardened stripes is improved, so that the anti-skid performance and the peeling resistance of the anti-skid antistatic coiled material are improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 3, it can be found that the volume resistivity of the comparative example 3 is low and the peel strength is high in the examples 1, 2 and 3, which shows that after the carbon nanofibers are modified, the carbon nanofibers are loaded with metal ions and polyamide acid is combined on the surface, so that the breakage of the carbon nanofibers and the loss of the loaded metal ions are prevented, and the antistatic performance of the anti-slip antistatic coiled material is improved, and meanwhile, the carbon-carbon double bonds on the polyamide acid can participate in the polymerization of free radicals to form a crosslinked network, so that the peeling resistance of the anti-slip antistatic coiled material is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative examples 4 and 5, it can be found that the dynamic friction factors of examples 1, 2 and 3 and comparative examples 4 and 5 are high, which indicates that the better anti-slip effect is obtained by performing dual thermal energy, stripe hot pressing is performed first, polyurethane azo bond is broken to form soft segment free radicals and hard segment free radicals, the soft segment free radicals are easier to move to a non-stripe hot pressed region under pressure to improve elasticity to form an elastic region, the hard segment free radicals are easy to be adsorbed and combined by modified carbon nano fibers to form hardened stripes, and then comprehensive hot pressing is performed, so that the whole is smooth, when an object moves on the surface, the elastic region can fill concave and convex parts of the surface of the object, friction force is improved by concave-convex meshing, and meanwhile, the hardened stripes can buffer movement, so that the anti-slip performance of the anti-slip antistatic coiled material is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (8)

1. The preparation method of the anti-skid antistatic coiled material is characterized in that the anti-skid antistatic coiled material is prepared by double hot pressing of a semi-finished coiled material; the semi-finished coiled material sequentially comprises an isolation layer, an adhesive layer and a surface layer from bottom to top;
the isolating layer is a polyethylene film; the adhesive layer is prepared from ethylene-vinyl acetate copolymer, phenolic resin and talcum powder by tape casting and rolling; the surface layer is prepared by coating and curing epoxy resin, polyurethane and modified carbon nano fibers;
the polyurethane is prepared by sequentially reacting polyethylene glycol with succinic anhydride, thionyl chloride and para-aminophenol, then reacting with para-aminophenol again to prepare modified polyethylene glycol, and reacting the modified polyethylene glycol with toluene diisocyanate; the modified carbon nanofiber is prepared by spinning a metal organic framework and polyacrylonitrile to obtain a nanofiber, carbonizing the nanofiber, and mixing the nanofiber with ferric chloride and polyamide acid solution for reaction.
2. The method for producing an anti-slip and anti-static web according to claim 1, wherein the double hot pressing is a stripe hot pressing first, and then a full hot pressing is performed by raising the temperature and the pressure.
3. The method for preparing the anti-slip antistatic coiled material according to claim 1, wherein the method for preparing the anti-slip antistatic coiled material comprises the following preparation steps:
(1) The modified polyethylene glycol and ethyl acetate are mixed according to the mass of 1: 1-1: 2, uniformly mixing, adding toluene diisocyanate with the mass of 2-3 times of that of modified polyethylene glycol into nitrogen atmosphere, stirring for 10-15 min at the temperature of 10-30 ℃ and 300-500 r/min, heating to 40-50 ℃, continuously stirring for 25-30 min, adding dibutyl tin dilaurate with the mass of 0.003-0.005 times of that of modified polyethylene glycol, continuously reacting for 2-3 h under the condition of constant temperature stirring, and standing for 6-8 h at the temperature of 20-30 ℃ and 1-2 kPa to obtain polyurethane;
(2) The metal organic framework, polyacrylonitrile and N, N-dimethylformamide are mixed according to the mass ratio of 1:1: 6-1: 1:8, uniformly mixing, and stirring for 6-8 hours at 70-80 ℃ and 800-1000 r/min to obtain spinning solution; carrying out electrostatic spinning on the spinning solution to obtain nanofiber; preheating the nanofiber at 100-120 ℃ for 30-40 min in a nitrogen atmosphere, heating to 250-300 ℃ at the speed of 5-6 ℃/min, standing for 60-80 min, heating to 800-900 ℃ at the same speed, and standing for 2-3 h to obtain the carbon nanofiber; the carbon nanofiber, ferric chloride and polyamic acid solution are mixed according to the mass ratio of 4:1: 40-6: 1:60, uniformly mixing, and carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the frequency of 30-40 kHz for 40-50 min to obtain modified carbon nanofibers;
(3) The ethylene-vinyl acetate copolymer and phenolic resin are mixed according to the mass ratio of 1: 1-1: 2, uniformly mixing, stirring at the temperature of 170-180 ℃ for 10-15 min at 300-500 r/min, adding talcum powder with the mass of 0.01-0.03 times of that of the ethylene-vinyl acetate copolymer, continuously stirring for 50-60 min, placing in a casting roller press, rolling to the thickness of 0.5-0.7 mm at the temperature of 120-130 ℃, naturally cooling to room temperature to obtain an adhesive layer, attaching the adhesive layer to a polyethylene film with the thickness of 0.1-0.5 mm in an area such as the like, and rolling at the pressure-bonding speed of 0.1-0.2 m/s at the temperature of 40-50 ℃ at 1.3-1.5 MPa to obtain a semi-isolated adhesive layer;
(4) Epoxy resin, polyurethane, modified carbon nanofiber, a curing agent, a coupling agent, a plasticizer, cyclohexanone, absolute ethyl alcohol and pure water are mixed according to the mass ratio of 50:30:30:5:3:8:20:10: 2-70: 40:40:7:5:12:30:15:4, uniformly mixing, stirring for 2-3 min at 30-40 ℃ at 500-700 r/min, uniformly coating on the non-isolated surface of the semi-isolated adhesive layer, standing for 20-24 h in a room temperature environment to form a surface layer with the thickness of 2-3 mm, and preparing a semi-finished coiled material;
(5) Carrying out stripe hot-pressing treatment on the semi-finished coiled material, wherein the stripe interval is 2-3 cm, the stripe thickness is 1-2 cm, the hot-pressing temperature is 120-130 ℃, the hot-pressing pressure is 0.3-0.5 MPa, the hot-pressing time is 1-2 h, after natural cooling to room temperature, the surface is cleaned with pure water and absolute ethyl alcohol for 3-5 times, after natural drying, carrying out full hot-pressing, the hot-pressing temperature is 130-150 ℃, the hot-pressing pressure is 1.5-2.0 MPa, the hot-pressing time is 30-40 min, the pressure is reduced to 0.3-0.5 MPa, the pressure is kept unchanged, the temperature is reduced to the room temperature at the speed of 3-5 ℃/min, the surface is cleaned with pure water and absolute ethyl alcohol for 3-5 times, and the anti-slip antistatic coiled material is obtained after natural drying.
4. The method for preparing an anti-slip and antistatic coiled material according to claim 3, wherein the method for preparing the modified polyethylene glycol in the step (1) comprises the following steps: succinic anhydride and polyethylene glycol are mixed according to the mass ratio of 1: 3-1: 4, uniformly mixing, stirring for 3-4 hours at 70-80 ℃ and 800-1000 r/min, and mixing with thionyl chloride and tetrahydrofuran according to a mass ratio of 15:100: 1-40: 300:1, uniformly mixing, stirring at the temperature of 40-50 ℃ for reaction for 2-3 hours at the speed of 300-500 r/min, heating to the temperature of 60-70 ℃, continuously stirring for reaction for 2-3 hours, and standing at the temperature of 10-30 ℃ for 30-40 minutes at the pressure of 60-100 Pa to obtain pre-modified polyethylene glycol; the method comprises the following steps of (1) mixing p-aminophenol and dichloromethane: 10-1: 12 uniformly mixing at 0-5 ℃, adding triethylamine with the mass of 0.3-0.4 times of that of the para-aminophenol, stirring for 3-5 min at 0-5 ℃ at 300-500 r/min, continuously stirring, dripping pre-modified glycol with the mass of 3-5 times of that of the para-aminophenol at a rate of 1-2 mL/min, stirring for 40-50 min at 0-5 ℃ at 300-500 r/min, standing for 6-8 h at 20-30 ℃ at 1-2 kPa, reducing the temperature to 0-5 ℃, adding p-aminophenol with the mass of 0.2-0.3 times of that of the pre-modified ethylene glycol, hydrochloric acid with the mass fraction of 10-15% with the mass fraction of 3-4 times of that of the pre-modified ethylene glycol and sodium nitrite aqueous solution with the mass fraction of 10-15% with the mass fraction of 3-4 times of that of the pre-modified ethylene glycol, stirring and reacting for 20-30 min at 800-1000 r/min, adding strong sodium oxide to adjust the pH value to 6.8-7.2, standing for 6-8 h at 20-30 ℃ at 1-2 kPa, adding absolute ethyl alcohol with the mass fraction of 3-4 times of that of the pre-modified ethylene glycol, centrifuging, and drying for 6-8 h at-1 to-10 Pa.
5. The method for preparing an anti-slip and anti-static coiled material according to claim 3, wherein the method for preparing the metal-organic framework in the step (2) comprises the following steps: zinc nitrate, 2-methylimidazole, pure water and absolute ethyl alcohol are mixed according to the mass ratio of 1:4:10: 100-1: 5:20:120, stirring and reacting for 3-5 hours at the temperature of 30-40 ℃ and the speed of 300-500 r/min, centrifugally separating, and washing with absolute ethyl alcohol for 3-5 times.
6. The method for preparing an anti-slip and anti-static coiled material according to claim 3, wherein the electrostatic spinning process parameters in the step (2) are as follows: the humidity is 25-35%, the voltage is 15-18 kV, the receiving distance is 15-20 cm, and the flow rate is 3-5 mL/h.
7. The method for preparing an anti-slip and anti-static coiled material according to claim 3, wherein the method for preparing the polyamic acid solution in the step (2) comprises the following steps: biphenyl tetracarboxylic dianhydride, 3, 5-diaminostyrene and dimethylacetamide are mixed according to the mass ratio of 5:3: 40-5: 4:50, and stirring for 20-24 hours at the temperature of 5-15 ℃ and the speed of 800-1000 r/min in a nitrogen atmosphere.
8. The method for producing an anti-slip and anti-static coil according to claim 3, wherein the epoxy resin in the step (4) is bisphenol a type epoxy resin; the curing agent is ethylenediamine; the coupling agent is vinyl trimethoxy silane; the plasticizer is one or more of di (2-ethylhexyl) phthalate, dibutyl phthalate and diethyl phthalate.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633490A (en) * 2016-11-10 2017-05-10 周荣 Preparation method of polyvinyl chloride antistatic film
CN110845827A (en) * 2019-11-26 2020-02-28 萧县金虹新型防水建材有限公司 Preparation method of high-strength tear-resistant waterproof coiled material
CN111483199A (en) * 2020-03-26 2020-08-04 合肥中通防水工程有限公司 Pre-laid anti-sticking macromolecule self-adhesive film waterproof coiled material and construction process thereof
AU2020103171A4 (en) * 2020-11-02 2021-01-14 Inner Mongolia Agricultural University Preparation method and application of graphene/carbon fiber composite material
CN114381212A (en) * 2021-12-27 2022-04-22 合肥中科凯辰新材料有限公司 Polyurethane self-adhesive film waterproof coiled material, preparation method and application thereof
CN114479716A (en) * 2021-12-30 2022-05-13 盐城市瑞龙塑业有限公司 Environment-friendly modified high-molecular hot-melt pressure-sensitive adhesive and processing technology thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106633490A (en) * 2016-11-10 2017-05-10 周荣 Preparation method of polyvinyl chloride antistatic film
CN110845827A (en) * 2019-11-26 2020-02-28 萧县金虹新型防水建材有限公司 Preparation method of high-strength tear-resistant waterproof coiled material
CN111483199A (en) * 2020-03-26 2020-08-04 合肥中通防水工程有限公司 Pre-laid anti-sticking macromolecule self-adhesive film waterproof coiled material and construction process thereof
AU2020103171A4 (en) * 2020-11-02 2021-01-14 Inner Mongolia Agricultural University Preparation method and application of graphene/carbon fiber composite material
CN114381212A (en) * 2021-12-27 2022-04-22 合肥中科凯辰新材料有限公司 Polyurethane self-adhesive film waterproof coiled material, preparation method and application thereof
CN114479716A (en) * 2021-12-30 2022-05-13 盐城市瑞龙塑业有限公司 Environment-friendly modified high-molecular hot-melt pressure-sensitive adhesive and processing technology thereof

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