阅读说明：本技术 一种抗静电防震缠绕膜及其生产工艺 (Antistatic shockproof winding film and production process thereof ) 是由 崔文进 吴仁秀 邹晓俊 于 2021-07-29 设计创作，主要内容包括：本发明提供一种抗静电防震缠绕膜及其生产工艺,缠绕膜包括了防护层、防静电层、防震层、基材；缠绕膜的生产工艺包括选用改性聚乳酸和聚己二酸-对苯二甲酸丁二酯复合材料作为基材,基材中用杂化纳米晶纤维素进行改性,无毒,易降解；将无溶剂发泡聚氨酯刮涂在基材上作为防震层,然后水浴加热,发泡聚氨酯内含有的端异氰酸酯基和水反应,在基材表面形成致密的微孔,达到减震的效果,添加纳米二氧化钼增加了防震层的机械强度；防震层上涂覆有抗静电涂料作为抗静电层,抗静电层上涂覆有改性酚醛树脂作为防护层,防护层中用氧化石墨烯对酚醛树脂进行改性。(The invention provides an antistatic shockproof winding film and a production process thereof, wherein the winding film comprises a protective layer, an antistatic layer, a shockproof layer and a base material; the production process of the winding film comprises the steps of selecting a composite material of modified polylactic acid and poly (butylene adipate-terephthalate) as a base material, and modifying the base material by using hybrid nanocrystalline cellulose, so that the winding film is non-toxic and easy to degrade; the solvent-free foamed polyurethane is coated on a base material to serve as a shockproof layer, then water bath heating is carried out, terminal isocyanate groups contained in the foamed polyurethane react with water, compact micropores are formed on the surface of the base material, the shock absorption effect is achieved, and the mechanical strength of the shockproof layer is increased by adding the nano molybdenum dioxide; and the anti-vibration layer is coated with antistatic coating as an antistatic layer, the antistatic layer is coated with modified phenolic resin as a protective layer, and the phenolic resin is modified by graphene oxide in the protective layer.)

1. The production process of the antistatic shockproof winding film is characterized by comprising the following steps of: the production process of the winding film comprises the following steps:

s1: preparation of the substrate

(1) Mixing and stirring nanocrystalline cellulose, glucose, a dispersing agent and deionized water, performing ultrasonic dispersion, then adding a silver ammonia solution, performing hydrothermal reaction at 65-95 ℃, continuously stirring for 10-60min, cooling, centrifuging, washing to be neutral, performing vacuum drying, and performing crushing and refining treatment to obtain hybrid nanocrystalline cellulose;

(2) ultrasonically dispersing polylactic acid and succinic anhydride, mixing and stirring, and repeatedly granulating for 2-3 times by using an extrusion granulator to obtain polylactic acid master batches;

(3) uniformly mixing polybutylene adipate-terephthalate, polylactic acid master batches and hybrid nanocrystalline cellulose, repeatedly granulating for 2-5 times through an extrusion granulator, and forming a film through a curtain coating stretching device to obtain a base material;

s2: preparation of the vibration-damping layer

(1) Carrying out ultrasonic treatment on polyester glycol, toluene diisocyanate, pentaerythritol oleate, nano molybdenum dioxide and a catalyst at 25-50 ℃, mixing and stirring, heating to 60-90 ℃, and carrying out hydrothermal reaction for 1.5-4h to obtain foamed polyurethane;

(2) blade-coating the foamed polyurethane on the substrate layer in the step S1, performing hydrothermal reaction at 30-60 ℃, and performing vacuum drying to obtain a shockproof layer;

s3: preparation of antistatic layer

(1) Dissolving titanium sulfate in deionized water, adding ammonia water to adjust the pH value to 8-10, centrifuging, repeatedly washing, then adding hydrogen peroxide, aging for 20-36h to obtain titanium peroxide sol, soaking glass fibers and activated carbon fibers in the sol for 24-36h, then performing vacuum drying at 90-110 ℃, taking out, soaking in silver nitrate, performing ultraviolet irradiation treatment, performing vacuum drying, calcining at the temperature of 450-600 ℃ for 1.5-3h under the protection of nitrogen, cooling to 20-25 ℃, and then crushing and refining to obtain mixed powder;

(2) mixing and stirring the mixed powder and the polyester modified epoxy resin powder coating under ultrasonic treatment to obtain an antistatic coating, coating the antistatic coating on the shockproof layer in the step S3, and drying in vacuum to obtain an antistatic layer;

s4: preparation of protective layer

(1) Mixing and stirring phenol, formaldehyde and graphene oxide, performing ultrasonic dispersion at 40-60 ℃ for 20-60min, adding sodium hydroxide, heating to 55-75 ℃ for reaction for 1-3h, performing reduced pressure dehydration, adding boric acid under the stirring condition, heating to 80-95 ℃ for reaction for 1-2h, cooling, performing vacuum drying at 55-70 ℃, and performing crushing and refining treatment to obtain modified powder; mixing and stirring modified powder, hollow glass beads, nano silicon dioxide and distilled water, and performing ultrasonic treatment to obtain a modified solution;

(2) and (4) coating the modified solution on the antistatic layer in the step S3, and performing vacuum drying to obtain a protective layer, thus obtaining the antistatic shockproof winding film.

2. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in the step S1(1), the mass ratio of the nanocrystalline cellulose to the dispersing agent to the glucose is (9-11) to (3) to (1-5); the dispersing agent is one or more of methyl amyl alcohol, polyacrylamide, sodium dodecyl sulfate and fatty acid polyglycol ester.

3. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in the step S1(2), the content of the hybridized nanocrystalline cellulose in the base material is 1-8%; in the step S1(3), the mass part ratio of the polylactic acid, the polybutylene adipate-terephthalate and the succinic anhydride is 12:38 (0.1-0.3).

4. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in the step S2(1), the mass parts of the polyester glycol, the toluene diisocyanate and the catalyst are (10-30): (15-50): 0.02-0.1); the content of the nano molybdenum dioxide in the shockproof layer is 1-6%; the catalyst is one or more of stannous octoate, dimethylethanolamine and dibutyltin dilaurate.

5. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in step S3(1), the molar ratio of hydrogen peroxide to titanium sulfate is 4:1.

6. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: the mass ratio of the mixed powder to the polyester modified epoxy resin powder coating in the step S3(2) is 3: 1.

7. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in the step S4(1), the decompression dehydration is carried out for 1-2h at the temperature of 105-.

8. The production process of the antistatic shockproof winding film as claimed in claim 1, wherein: in the step S4(1), the molar ratio of the formaldehyde to the phenol to the boric acid is (1.2-1.6): 0.8-1.2): 0.4; the mass ratio of the sodium hydroxide to the phenol is 2-4%; the mass ratio of the modified powder to the hollow glass beads to the nano silicon dioxide is 30:2 (2-8).

9. An antistatic shockproof winding film is characterized in that: produced by the process of any one of claims 1 to 8.

Technical Field

The invention relates to the field of packaging materials, in particular to an antistatic shockproof winding film and a production process thereof.

Background

The winding film, also called stretch film or heat shrink film, is usually made by using high polymer materials such as PE, PP and the like as main materials, adding auxiliary agents and carrying out casting molding or blow molding. The winding film has the advantages of high tensile strength, good tear strength and the like, and is widely applied to the field of packaging materials.

At present, the winding film is mainly applied to the sale and transportation of products, the raw material is polyethylene which is a linear structure and thermoplastic engineering plastic with excellent total performance, the development is rapid, the use amount is large, the natural degradation is difficult, and the environment-friendly production requirement is not met. The existing winding film is light and thin, does not have the shockproof effect, has the problems of easy generation of static electricity, poor toughness, easy damage and the like, and cannot play an effective protection role on products.

Therefore, research and development of a winding film having a good antistatic effect, and also having good toughness and a good anti-vibration effect has become a focus of current research.

Disclosure of Invention

The invention aims to provide an antistatic shockproof winding film and a production process thereof, which aim to solve the problems in the prior art.

In order to solve the technical problems, the invention provides the following technical scheme:

the production process of the antistatic shockproof winding film comprises the following steps:

s1: preparation of the substrate

(1) Mixing and stirring nanocrystalline cellulose, glucose, a dispersing agent and deionized water, performing ultrasonic dispersion, then adding a silver ammonia solution with the concentration, performing hydrothermal reaction at 65-95 ℃, continuously stirring for 10-60min, cooling, centrifuging, washing to be neutral, performing vacuum drying, and performing crushing and refining treatment to obtain hybrid nanocrystalline cellulose;

(2) ultrasonically dispersing polylactic acid and succinic anhydride, mixing and stirring, and repeatedly granulating for 2-3 times by using an extrusion granulator to obtain polylactic acid master batches;

(3) uniformly mixing polybutylene adipate-terephthalate, polylactic acid master batches and hybrid nanocrystalline cellulose, repeatedly granulating for 2-5 times through an extrusion granulator, and forming a film through a curtain coating stretching device to obtain a base material;

further, the mass ratio of the nanocrystalline cellulose to the dispersing agent to the glucose is (9-11) to (3) to (1-5); the dispersant is one or more of methyl amyl alcohol, polyacrylamide, sodium dodecyl sulfate and fatty acid polyglycol ester;

further, the content of the hybrid nanocrystalline cellulose in the base material is 1-8%; the mass part ratio of polylactic acid, polybutylene adipate-terephthalate and succinic anhydride is 12:38 (0.1-0.3);

the winding film used at present mostly uses polyethylene which is toxic and difficult to degrade and pollutes the environment, the invention selects the composite material of modified polylactic acid (PLA) and polybutylene adipate-terephthalate (PBAT) as the base material, and the polylactic acid (PLA) and the polybutylene adipate-terephthalate (PBAT) have full biodegradability and meet the requirement of environment-friendly production;

but polylactic acid (PLA) and poly adipic acid-butylene terephthalate (PBAT) are directly blended, the compatibility is poor, the mechanical property of the blend is poor due to the defect of substance crystallinity, and the hybrid nanocrystalline cellulose is used for modifying the PLA and PBAT composite material;

the nanocrystalline cellulose is of a rod-shaped structure, the diameter range is 2-40nm, and silver ions can be reduced into nano silver due to the surface of the nanocrystalline cellulose is provided with carbomethoxy, and the nano silver is promoted to be uniformly dispersed and attached to the surface of the nanocrystalline cellulose;

the nano silver reduces the exposed area of the nanocrystalline cellulose in a polylactic acid (PLA) and polybutylene adipate-terephthalate (PBAT) composite material, and inhibits the heterogeneous nucleation effect of the nanocrystalline cellulose; with the continuous increase of the content of the nano silver, the conductivity of the base material is obviously improved, and the heat transfer in the base material is influenced; interface interaction is generated between the hybridized nanocrystalline cellulose and the PLA and PBAT composite materials to limit the movement of molecular chains;

compared with pure PLA and PBAT blending, after the nanocrystalline cellulose is added, the thermal stability is increased, the uniformly dispersed hybrid nanocrystalline cellulose serves as a heterogeneous nucleating agent in the PLA and PBAT composite material, the crystallization of the PLA and PBAT composite material is accelerated due to the increase of the contact area, the crystallinity and the tortuosity of a transmission path in the PLA and PBAT composite material effectively reduce the water absorption of the base material, and the penetrating power of water vapor in the base material is limited;

the hybrid nanocrystalline cellulose with different polar group (carboxyl and hydroxyl) contents has good dispersibility and biocompatibility in PLA and PBAT, and is beneficial to maintaining the spatial dispersibility and adhesion performance after the hybrid nanocrystalline cellulose is blended with the PLA and the PBAT; succinic anhydride is used as a chain extender and added into PLA for chain extension reaction, and the generated product has higher viscosity; hydroxyl and carboxyl on the surface of the hybridized nanocrystalline cellulose induce the hydroxyl and carboxyl to form a hydrogen bond network with PLA and PBAT, and the tightly interwoven network structure and molecular chains of the PLA and PBAT can be mutually permeated, intertwined and tightly combined, so that the water vapor barrier property and the mechanical property of the base material are further enhanced;

s2: preparation of the vibration-damping layer

(1) Carrying out ultrasonic treatment on polyester glycol, toluene diisocyanate, pentaerythritol oleate, nano molybdenum dioxide and a catalyst at 25-50 ℃, mixing and stirring, heating to 60-90 ℃, and carrying out hydrothermal reaction for 1.5-4h to obtain foamed polyurethane;

(2) coating foamed polyurethane on the substrate layer obtained in the step S1 in a blade mode, then carrying out hydrothermal reaction at the temperature of 30-60 ℃ to enable the foamed polyurethane to be solidified on the surface of the substrate to form a porous polyurethane coating, and carrying out vacuum drying to obtain a shockproof layer;

furthermore, the polyester diol, the toluene diisocyanate, the pentaerythritol oleate and the catalyst are counted by weight parts of (10-30): (15-50): 0.01-0.1): 0.02-0.1, the catalyst is one or more of stannous octoate, dimethylethanolamine and dibutyltin dilaurate, and the content of the nano molybdenum dioxide in the shockproof layer is 1-6%;

at present, N-dimethylformamide solvent is mostly used in the synthesis of foaming polyurethane, and the problems of product safety, easy environmental pollution and the like caused by solvent residue exist; when the modified foaming polyurethane is prepared, the solvent-free foaming polyurethane is coated on a base material as a shockproof layer by scraping, then the water bath heating is carried out, the isocyanate group at the end contained in the foaming polyurethane reacts with water to generate carbon dioxide, and compact micropores are formed on the surface of the base material to achieve the shock absorption effect, and the addition of the nano molybdenum dioxide increases the mechanical strength of the shockproof layer;

s3: preparation of antistatic layer

(1) Dissolving titanium sulfate in deionized water, adding ammonia water to adjust the pH value to 8-10, centrifuging, repeatedly washing, then adding hydrogen peroxide, aging for 20-36h to obtain titanium peroxide sol, soaking glass fibers and activated carbon fibers in the sol for 24-36h, then performing vacuum drying at 90-110 ℃, taking out, soaking in silver nitrate, performing ultraviolet irradiation treatment, performing vacuum drying, calcining at the temperature of 450-600 ℃ for 1.5-3h under the protection of nitrogen, cooling to 20-25 ℃, and then crushing and refining to obtain mixed powder;

(2) mixing and stirring the mixed powder and the polyester modified epoxy resin powder coating under ultrasonic treatment to obtain an antistatic coating, coating the antistatic coating on the shockproof layer obtained in the step S3, and drying in vacuum to obtain an antistatic layer;

further, in step S3(1), the molar ratio of hydrogen peroxide to titanium sulfate is 4: 1;

further, in the step S3(2), the mass ratio of the mixed powder to the polyester modified epoxy resin powder coating is 3: 1;

silver or titanium dioxide is used as an antistatic agent independently and is easy to agglomerate, the antistatic layer is prepared by using silver-titanium dioxide composite glass fiber and activated carbon fiber, the surfaces of the glass fiber and the activated carbon fiber are loaded with titanium dioxide films, and the silver is deposited on the surface of the titanium dioxide in a simple substance form, so that the growth agglomeration of titanium dioxide crystal grains can be inhibited, the antistatic property of the winding film is enhanced, the anti-permeability and the corrosion resistance of the winding film are improved, and the service life of the winding film is prolonged;

s4: preparation of protective layer

(1) Mixing and stirring phenol, formaldehyde and graphene oxide, performing ultrasonic dispersion at 40-60 ℃ for 20-60min, adding sodium hydroxide, heating to 55-75 ℃ for reaction for 1-3h, performing reduced pressure dehydration, adding boric acid under the stirring condition, heating to 80-95 ℃ for reaction for 1-2h, cooling, performing vacuum drying at 55-70 ℃, and performing crushing and refining treatment to obtain modified powder; mixing and stirring modified powder, hollow glass beads, nano silicon dioxide and distilled water, and performing ultrasonic treatment to obtain a modified solution;

(2) and (4) coating the modified solution on the antistatic layer in the step S3, and performing vacuum drying to obtain the antistatic shockproof winding film serving as a protective layer.

Further, the decompression dehydration in the step S4(1) is carried out at 105-115 ℃ and under the vacuum degree of 130-140Pa for reaction for 1-2h, and then the reaction is cooled to 22-45 ℃.

Furthermore, in the step S4(1), the molar ratio of formaldehyde to phenol to boric acid is (1.2-1.6): 0.8-1.2):0.4, and the mass ratio of sodium hydroxide to phenol is 2-4%.

Further, in the step S4(2), the mass ratio of the modified powder to the hollow glass beads to the nano silicon dioxide is 30:2 (2-8).

At present, inorganic particles are added to the phenolic resin for modifying the phenolic resin, so that the thermal property or the mechanical property of the phenolic resin can be only singly improved, and the inorganic particles are easy to agglomerate;

the graphene oxide is uniformly dispersed in the phenolic resin in a folded state, and a large number of cross-linking points are provided, so that the resin network is tighter, and the mechanical property of the winding film is improved; the addition of the hollow glass beads and the nano silicon dioxide strengthens the flame retardance, the self-cleaning property, the bending strength and the tensile strength of the winding film.

The invention has the beneficial effects that:

the invention discloses an antistatic shockproof winding film and a production process thereof, wherein the winding film comprises a base material, a shockproof layer, an antistatic layer and a protective layer;

the composite material of modified polylactic acid (PLA) and poly (butylene adipate-terephthalate) (PBAT) is selected as a base material, is nontoxic and easy to degrade, and meets the requirement of green sustainable development; modifying the PLA and PBAT composite material by using hybridized nanocrystalline cellulose; the sheet structure of the hybrid nanocrystalline cellulose has the effects of increasing the tortuosity of a permeation path and reducing the permeation area for small molecular gas and water vapor, improving the barrier property of the base material for oxygen and water vapor, and simultaneously increasing the antibacterial property for the base material;

the solvent-free foamed polyurethane is coated on a base material to serve as a shockproof layer, then water bath heating is carried out, terminal isocyanate groups contained in the foamed polyurethane react with water to generate carbon dioxide, compact micropores are formed on the surface of the base material, the shock absorption effect is achieved, and the mechanical strength of the shockproof layer is increased due to the addition of the nano molybdenum dioxide;

the antistatic layer is prepared by silver-titanium dioxide composite glass fiber and activated carbon fiber, the surfaces of the glass fiber and the activated carbon fiber are loaded with titanium dioxide films, and silver is deposited on the surface of the titanium dioxide in a simple substance form, so that the growth and agglomeration of titanium dioxide crystal grains can be inhibited;

graphene oxide is used for modifying the phenolic resin, the graphene oxide is uniformly dispersed in the phenolic resin in a folded state, and a large number of cross-linking points are provided to enable a resin network to be tighter, so that the mechanical property of the winding film is improved; the flame retardance, the self-cleaning property, the bending strength and the tensile strength of the winding film are enhanced by adding the hollow glass beads and the nano silicon dioxide; the invention has the advantages of rich raw material sources, easily controlled process conditions and strong operability.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.

Example 1

S1: preparation of the substrate

(1) Mixing and stirring the nanocrystalline cellulose, the methyl amyl alcohol and the glucose with deionized water according to the mass ratio of 9:3:1, performing ultrasonic dispersion, then adding a silver ammonia solution with the concentration of 0.01mol/L, performing hydrothermal reaction at 95 ℃, continuously stirring for 10min, cooling, centrifuging, washing with water to be neutral, performing vacuum drying, and performing crushing and refining treatment to obtain hybrid nanocrystalline cellulose;

(2) ultrasonically dispersing polylactic acid and succinic anhydride with the mass part ratio of 12:0.1, mixing and stirring, and repeatedly granulating for 2 times by using an extrusion granulator to obtain polylactic acid master batches;

(3) the content of the hybrid nanocrystalline cellulose in the base material is 1%, the polylactic acid, the polybutylene adipate-terephthalate and the succinic anhydride are uniformly mixed according to the mass ratio of 12:38:0.1, and the base material is obtained by repeatedly granulating for 2 times through an extrusion granulator and then forming a film through a tape casting stretching device;

s2: preparation of the vibration-damping layer

(1) According to the mass ratio of polyester diol to toluene diisocyanate, pentaerythritol oleate to stannous octoate of 10:15:0.01:0.02 and the content of nano molybdenum dioxide in the shockproof layer of 1%, carrying out ultrasonic treatment on the polyester diol, the toluene diisocyanate, the pentaerythritol oleate, the nano molybdenum dioxide and stannous octoate at 25 ℃, mixing and stirring, heating to 60 ℃, and carrying out hydrothermal reaction for 4 hours to obtain foamed polyurethane;

(2) coating foamed polyurethane on the substrate layer obtained in the step S1 in a blade mode, then carrying out hydrothermal reaction at the temperature of 30 ℃ to enable the foamed polyurethane to be solidified on the surface of the substrate to form a porous polyurethane coating, and carrying out vacuum drying to obtain a shockproof layer;

s3: preparation of antistatic layer

(1) Dissolving titanium sulfate in deionized water, adding ammonia water to adjust the pH value to 8, centrifuging, repeatedly washing, then adding hydrogen peroxide, wherein the molar ratio of hydrogen peroxide to titanium sulfate is 4:1, aging for 36h to obtain titanium peroxide sol, soaking glass fibers and activated carbon fibers in the sol for 36h, then vacuum drying at 110 ℃, taking out, soaking in silver nitrate, irradiating by ultraviolet rays, vacuum drying, calcining at 600 ℃ for 1.5h under the protection of nitrogen, cooling to 20 ℃, crushing and refining to obtain mixed powder;

(2) mixing and stirring the mixed powder and the polyester modified epoxy resin powder coating in a mass ratio of 3:1 under ultrasonic treatment to obtain an antistatic coating, coating the antistatic coating on the shockproof layer in the step S3, and drying in vacuum to obtain an antistatic layer;

s4: preparation of protective layer

(1) Mixing and stirring phenol, formaldehyde and graphene oxide according to the molar ratio of 1.2:0.8:0.4 of formaldehyde to phenol to obtain a mixture, ultrasonically dispersing the mixture for 60min at 40 ℃, adding sodium hydroxide, wherein the mass ratio of the sodium hydroxide to the phenol is 2%, heating to 75 ℃ to react for 1h, reacting for 2h at 105 ℃ and the vacuum degree of 130Pa, cooling to 22 ℃, adding boric acid under the stirring condition, heating to 80 ℃ to react for 1h, cooling, then drying in vacuum at 55 ℃, crushing and refining to obtain modified powder; mixing and stirring the modified powder, the hollow glass beads and the nano silicon dioxide with distilled water according to the mass ratio of 15:1:1, and performing ultrasonic treatment to obtain a modified solution;

(2) and (4) coating the modified solution on the antistatic layer in the step S3, and performing vacuum drying to obtain the antistatic shockproof winding film serving as a protective layer.

Example 2

S1: preparation of the substrate

(1) Mixing nanocrystalline cellulose, polyacrylamide and glucose with deionized water at a mass ratio of 10:3:3, stirring, performing ultrasonic dispersion, adding a silver ammonia solution with a concentration of 0.08mol/L, performing hydrothermal reaction at 80 ℃, continuously stirring for 30min, cooling, centrifuging, washing with water to neutrality, performing vacuum drying, and performing crushing and refining treatment to obtain hybrid nanocrystalline cellulose;

(2) carrying out ultrasonic dispersion on polylactic acid and succinic anhydride with the mass part ratio of 12:0.2, mixing and stirring, and repeatedly granulating for 3 times by using an extrusion granulator to obtain polylactic acid master batches;

(3) the content of the hybrid nanocrystalline cellulose in the base material is 3%, the polylactic acid, the polybutylene adipate-terephthalate and the succinic anhydride are uniformly mixed according to the mass ratio of 12:38:0.2, and the film is formed by a casting stretching device after repeated granulation is carried out for 3 times by an extruder granulator to obtain the base material;

s2: preparation of the vibration-damping layer

(1) According to the mass part ratio of 20:40:0.05:0.08 of polyester diol, toluene diisocyanate, pentaerythritol oleate and stannous octoate, wherein the content of nano molybdenum dioxide in the shockproof layer is 3%, the polyester diol, the toluene diisocyanate, the pentaerythritol oleate, the nano molybdenum dioxide and stannous octoate are subjected to ultrasonic treatment at 40 ℃, mixed and stirred, heated to 80 ℃ and subjected to hydrothermal reaction for 2 hours to obtain foamed polyurethane;

(2) coating foamed polyurethane on the base material layer obtained in the step S1 in a blade mode, then carrying out hydrothermal reaction at 50 ℃ to enable the foamed polyurethane to be solidified on the surface of the base material to form a porous polyurethane coating, and carrying out vacuum drying to obtain a shockproof layer;

s3: preparation of antistatic layer

(1) Dissolving titanium sulfate in deionized water, adding ammonia water to adjust the pH value to 9, centrifuging, repeatedly washing, then adding hydrogen peroxide, wherein the molar ratio of hydrogen peroxide to titanium sulfate is 4:1, aging for 24h to obtain titanium peroxide sol, soaking glass fibers and activated carbon fibers in the sol for 28h, then vacuum drying at 100 ℃, taking out, soaking in silver nitrate, irradiating by ultraviolet rays, vacuum drying, calcining at 500 ℃ for 2h under the protection of nitrogen, cooling to 22 ℃, crushing and refining to obtain mixed powder;

(2) mixing and stirring the mixed powder and the polyester modified epoxy resin powder coating under ultrasonic treatment according to the mass ratio of 3:1 to obtain an antistatic coating, coating the antistatic coating on the shockproof layer in the step S3, and drying in vacuum to obtain an antistatic layer;

s4: preparation of protective layer

(1) Mixing and stirring phenol, formaldehyde and graphene oxide, ultrasonically dispersing for 40min at 50 ℃, adding sodium hydroxide, wherein the mass ratio of the sodium hydroxide to the phenol is 3%, heating to 60 ℃, reacting for 2h, reacting for 1.5h at 110 ℃ and the vacuum degree of 135Pa, cooling to 40 ℃, adding boric acid under the stirring condition, heating to 90 ℃, reacting for 1.5h, cooling, vacuum drying at 60 ℃, crushing and refining to obtain modified powder, wherein the molar ratio of the formaldehyde to the phenol to the boric acid is 1.4:1.1: 0.4; mixing and stirring the modified powder, the hollow glass beads and the nano silicon dioxide with distilled water according to the mass ratio of 30:2:5, and performing ultrasonic treatment to obtain a modified solution;

(2) and (4) coating the modified solution on the antistatic layer in the step S3, and performing vacuum drying to obtain the antistatic shockproof winding film serving as a protective layer.

Example 3

S1: preparation of the substrate

(1) Mixing nanocrystalline cellulose, sodium dodecyl sulfate and glucose with deionized water according to the mass ratio of 11:3:5, stirring, performing ultrasonic dispersion, then adding a silver ammonia solution with the concentration of 0.1mol/L, performing hydrothermal reaction at 65 ℃, continuously stirring for 60min, cooling, centrifuging, washing with water to be neutral, performing vacuum drying, and performing crushing and refining treatment to obtain hybrid nanocrystalline cellulose;

(2) carrying out ultrasonic dispersion on polylactic acid and succinic anhydride with the mass part ratio of 12:0.3, mixing and stirring, and repeatedly granulating for 3 times by using an extrusion granulator to obtain polylactic acid master batches;

(3) the content of the hybrid nanocrystalline cellulose in the base material is 8%, the polylactic acid, the polybutylene adipate-terephthalate and the succinic anhydride are uniformly mixed according to the mass part ratio of 12:38:0.3, and the film is formed by a casting stretching device after repeated granulation is carried out for 5 times by an extruder granulator to obtain the base material;

s2: preparation of the vibration-damping layer

(1) Carrying out ultrasonic treatment on polyester diol, toluene diisocyanate, pentaerythritol oleate and stannous octoate at the mass ratio of 30:50:0.1:0.1 at 50 ℃, mixing and stirring, heating to 90 ℃, and carrying out hydrothermal reaction for 1.5h to obtain foamed polyurethane;

(2) blade-coating the foamed polyurethane in the step S2(1) on the substrate layer in the step S1, then carrying out hydrothermal reaction at 60 ℃ to solidify the foamed polyurethane on the surface of the substrate to form a porous polyurethane coating, and carrying out vacuum drying to obtain a shockproof layer;

s3: preparation of antistatic layer

(3) Dissolving titanium sulfate in deionized water, adding ammonia water to adjust the pH value to 10, centrifuging, repeatedly washing, then adding hydrogen peroxide, aging for 20-36h with the molar ratio of hydrogen peroxide to titanium sulfate being 4:1 to obtain titanium peroxide sol, soaking glass fiber and activated carbon fiber in the sol for 24h, then vacuum drying at 90 ℃, taking out, soaking in silver nitrate, carrying out ultraviolet irradiation treatment, vacuum drying, calcining at 450 ℃ for 3h under the protection of nitrogen, cooling to 25 ℃, crushing and refining to obtain mixed powder;

(4) mixing and stirring the mixed powder and the polyester modified epoxy resin powder coating in a mass ratio of 3:1 under ultrasonic treatment to obtain an antistatic coating, coating the antistatic coating on the shockproof layer in the step S3, and drying in vacuum to obtain an antistatic layer;

s4: preparation of protective layer

(2) Mixing and stirring phenol, formaldehyde and graphene oxide according to the molar ratio of 1.6:1.2:0.4 of formaldehyde to boric acid and the mass ratio of sodium hydroxide to phenol of 4%, ultrasonically dispersing for 20-60min at 40-60 ℃, adding sodium hydroxide, heating to 55 ℃ for reaction for 3h, reacting for 1h at 115 ℃ and the vacuum degree of 140Pa, cooling to 45 ℃, adding boric acid under the stirring condition, heating to 95 ℃ for reaction for 1h, cooling, vacuum drying at 55 ℃, crushing and refining to obtain modified powder; mixing and stirring the modified powder, the hollow glass beads and the nano silicon dioxide with distilled water according to the mass ratio of 30:2:8, and performing ultrasonic treatment to obtain a modified solution;

(2) and (3) coating the modified solution in the step S4(1) on the antistatic layer in the step S3, and performing vacuum drying to obtain an antistatic shockproof winding film serving as a protective layer.

Example 4

In example 3, in step S3(2), the stannous octoate was replaced with dimethylethanolamine, and the other steps were performed normally.

Example 5

In example 3, in step S3(2), stannous octoate was replaced with dibutyltin dilaurate, and the other steps were carried out in a normal reaction.

Example 6

In the step S1(1) in example 3, the reaction was carried out normally in the other steps, wherein the polyacrylamide was replaced with fatty acid polyglycol ester.

And (3) performance testing: the winding films produced in examples 1 to 6 were subjected to an antistatic property test, the winding films produced in examples 1 to 6 were cut into a size of 10 × 10mm, and the volume resistance was measured on a high resistance meter (model: SME-8310); the wrapping films produced in examples 1-6 were tested with reference to BB/T0024-; the performance of the winding films produced in examples 1-6 were tested as shown in table 1;

TABLE 1

As can be seen from the above tests, the volume resistivity of the wound films of examples 1 to 6 was less than 10⁵(omega.cm), indicating that the produced winding film has excellent antistatic property;

in examples 1 to 6, the longitudinal elongation at break of the wrapping films is more than 500%, the transverse elongation thereof is more than 600%, and the puncture rupture resistance thereof is more than 20.0N, which indicates that the produced wrapping films have excellent tensile properties, puncture resistance and mechanical properties;

in addition, the winding film disclosed by the invention has excellent shock resistance, wear resistance, self-cleaning property, ultraviolet resistance and long service life.

The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.