CN114516992B - Antistatic composite air film material and preparation method thereof - Google Patents
Antistatic composite air film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antistatic composite air film material and a preparation method thereof, comprising the following steps: stirring and mixing polyvinylidene fluoride resin, polybutylene succinate, polyvinyl alcohol or a polyvinyl alcohol/graphite compound, a plasticizer, a stabilizer, an ultraviolet absorber, a flame retardant and a functional nano cellulose/silicon dioxide composite material to obtain a mixture; plasticizing the mixture to obtain a plasticized material; calendering the plasticized material to obtain a preformed air film material; and cooling and shaping the preformed air film material, trimming and coiling to obtain the air film. The antistatic composite air film material prepared by the invention has good antistatic performance, fireproof performance and ultraviolet radiation resistance, is environment-friendly and has good mechanical strength, and can be used as a building film material.
Description
Technical Field
The invention relates to the technical field of building membrane materials, in particular to an antistatic composite membrane material and a preparation method thereof.
Background
The air film building is a building structure system which takes building film materials as a shell and provides air positive pressure for the inside of the building film materials by an intelligent machine, so that the internal space is supported. The air film building can fully utilize outdoor sunlight and surrounding natural environments, realize the on-demand control of air pressure, temperature, humidity, fresh air quantity, illumination and the like of an inner space, provide comfortable and open indoor environments, and can be applied to sports stadiums such as tennis, basketball and badminton. The building membrane material is of an inflatable membrane structure, has the characteristics of light weight, plasticity and good light transmittance, accords with the concepts of green low carbon and cost saving, and is a common membrane material such as polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, ethylene-tetrafluoroethylene copolymer and the like. Chinese patent CN201710105575.3 discloses a composite film structure for building skin and its application, which is composed of two layers of materials, wherein an ethylene-tetrafluoroethylene copolymer film and a polyethylene film are connected by hot melt or adhesive layer to form a first layer of material, polyvinyl chloride film material surface is coated with polyvinylidene fluoride to form a second layer of material, and at the same time, the first layer of material surface is provided with an ultraviolet-proof coating layer comprising polyvinylpyrrolidone, water, ceria aqueous solution, siloxane, isopropanol, diacetone alcohol and sodium acetate; the composite membrane structure of the patent has good air tightness and waterproof property, and simultaneously can improve the ultraviolet resistance of the membrane material through the ultraviolet-proof coating, but the membrane material has poor antistatic property and is not easy to degrade after being abandoned.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antistatic composite air film material and a preparation method thereof.
An antistatic composite air film material comprises the following raw materials: 50-80 parts of polyvinylidene fluoride resin, 20-40 parts of polybutylene succinate, 10-25 parts of polyvinyl alcohol or a polyvinyl alcohol/graphite compound, 20-30 parts of plasticizer, 3-6 parts of stabilizer, 1-5 parts of ultraviolet absorber, 1-4 parts of flame retardant and 20-35 parts of filler.
The plasticizer is one or more of dimethyl phthalate, dioctyl adipate, octyl epoxy stearate and trioctyl phosphate.
Further, the plasticizer is a mixture of dimethyl phthalate and octyl epoxy stearate according to the mass ratio of 3 (1-2).
The stabilizer is one or more of calcium stearate, dibutyl tin dilaurate and dibasic lead stearate.
The ultraviolet absorbent is one or more of 2-hydroxy-4-methoxybenzophenone, phenyl o-hydroxybenzoate and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
The flame retardant is one or more of chlorinated paraffin, magnesium hydroxide and antimony trioxide.
The filler is one of nanocellulose, nanocellulose/silicon dioxide composite material or functionalized nanocellulose/silicon dioxide composite material.
At present, most of the most widely applied air film materials mainly adopt traditional high polymer materials, and the air film materials have the characteristics of good flexibility, light weight, good insulativity and the like, but the development speed is reduced along with the increasing reduction of petroleum resources, and meanwhile, the environmental pollution problem caused by the high polymer materials is increasingly remarkable, so that the air film material provided by the invention meets the use requirements of air film buildings and is environment-friendly and easy to degrade. The nano cellulose is rigid rod-shaped cellulose with one-dimensional space size smaller than 100nm formed after the amorphous area is removed from the natural cellulose, belongs to a biodegradable green biomass material, has rich sources, is environment-friendly, has large specific surface area, high length-diameter ratio and high chemical reaction activity, contains a large amount of hydroxyl groups on the surface, can be used for self-assembly, has good biodegradability and excellent mechanical property, and is an ideal reinforcing filler for improving the material performance.
The nano cellulose belongs to hydrophilic fillers, has poor compatibility with a hydrophobic organic polymer matrix, and can not fully play the excellent reinforcing effect of the nano cellulose due to weak intermolecular binding force caused by directly adding the nano cellulose filler into the hydrophobic matrix. In order to solve the problem, the invention adopts a series of surface functionalization strategies to carry out surface modification treatment on the nanocellulose so as to obtain the renewable material-based filler with good compatibility with a matrix, and the renewable material-based filler is used for preparing the air film material with high mechanical property, environmental protection and easy degradation.
The nano silicon dioxide is a common inorganic nano filler, has high strength, toughness and thermal stability, also has small-size effect, surface and boundary effect, has volume effect and quantum tunneling effect to generate a migration effect, can penetrate into the vicinity of pi bond of a high polymer compound and overlap with electron cloud of the high polymer compound to form a space network structure, thereby promoting the performance improvement of the high polymer material.
The preparation method of the nanocellulose/silicon dioxide composite material comprises the following steps:
adding 25-40 parts by weight of nanocellulose into 100-150 parts by weight of organic solvent aqueous solution with the mass fraction of 75-85wt%, stirring at the room temperature for 15-30min at the rotating speed of 400-600rpm, then adding 2-5 parts by weight of ammonia water solution with the mass fraction of 20-30wt%, continuing stirring for 25-40min, adding 2-5 parts by weight of tetraethoxysilane, continuing stirring for reacting for 8-15h, centrifuging at the rotating speed of 800-1500rpm for 4-8min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nanocellulose/silicon dioxide composite material.
The surface of the nanocellulose is rich in a large number of hydroxyl groups, and a large interaction force exists between molecular chains, so that the nanocellulose is used as an organic carrier, nano silicon dioxide is generated on the surface of the nanocellulose in situ, the hybridization modification of the nanocellulose is realized, and the nanocomposite with the advantages of both organic and inorganic nanomaterials is prepared. After the surface of the nano-cellulose is modified by inorganic nano-material-silicon dioxide, a large number of spherical nano-particles with high specific surface area and narrow particle size distribution exist on the surface of the nano-cellulose/silicon dioxide composite material, so that the filler can have better dispersibility in a matrix, the interface combination between the filler and the matrix is tighter, and the interface interaction is increased, thereby improving the mechanical property of the air film material and better playing the degradation property brought by the nano-cellulose.
The preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 25-40 parts by weight of nanocellulose into 100-150 parts by weight of organic solvent aqueous solution with the mass fraction of 75-85wt%, stirring at room temperature for 15-30min at the speed of 400-600rpm, then adding 2-5 parts by weight of ammonia water solution with the mass fraction of 20-30wt%, continuing stirring for 25-40min, adding 2-5 parts by weight of tetraethoxysilane, continuing stirring for reacting for 8-15h, centrifuging at the speed of 800-1500rpm for 4-8min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nanocellulose/silicon dioxide composite material;
s2, adding 6-10 parts by weight of the nano cellulose/silicon dioxide composite material into 40-60 parts by weight of the modified liquid, regulating the pH value to 2.0-4.0, stirring at the temperature of 75-90 ℃ at the rotating speed of 300-500rpm for reaction for 8-16 hours, centrifuging at the rotating speed of 800-1500rpm for 4-8 minutes after the reaction is finished, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 4-8 parts by weight of modified nano cellulose/silicon dioxide composite material and 25-40 parts by weight of D-lactic acid into 45-60 parts by weight of ethanol water solution with the mass fraction of 60-75%, stirring for 15-40min at the temperature of 85-105 ℃ at the rotating speed of 300-500rpm, adding 0.2 part by weight of catalyst, setting the reaction temperature at 130-160 ℃ under the protection of nitrogen for 12-24h, pouring out after the reaction, adding 80-120 parts by weight of chloroform, stirring for 20-40min at the rotating speed of 600-1000rpm at room temperature, adding 150-200 parts by weight of absolute ethyl alcohol, continuing stirring for 20-40min, filtering, washing the precipitate with absolute ethyl alcohol for three times, and vacuum drying for 8-16h at 70-85 ℃ to obtain the functionalized nano cellulose/silicon dioxide composite material.
Polylactic acid is thermoplastic aliphatic polyester polymerized by micro-molecular lactic acid obtained by microbial fermentation of renewable plant resources (corn, wheat, sweet potato, cassava, beet, natural fibers and the like), has excellent biocompatibility and biodegradability, can be completely degraded into water and carbon dioxide, and also has good mechanical property, good processability and good chemical inertness. The invention takes D-lactic acid as a monomer raw material, generates cyclic dimer lactide and generates grafting reaction with hydrolytic hydroxyl at the tail end of a silane coupling agent on the surface of a nano cellulose/silicon dioxide composite material under the action of a catalyst, and then high-temperature polymerization is utilized to generate polylactic acid with high molecular weight. The polylactic acid grafted on the surface of the functionalized nano cellulose/silicon dioxide composite material can promote the uniform distribution of the molecular chains of the matrix polymer, thereby further increasing the mechanical property and degradation property of the air film material.
The organic solvent is one or more of isopropanol, ethanol and methanol; preferably, the organic solvent is isopropanol.
Compared with methanol and ethanol, isopropanol has smaller dielectric constant, and the increased alkyl chain length brings larger steric hindrance to isopropanol, can provide lower hydrolysis rate and limit the nucleation rate of silicon dioxide, and directly promotes the uniform growth of silicon dioxide on the surface of nanocellulose.
The preparation method of the modified liquid comprises the following steps: adding 1-5 parts by weight of modifier into 85-110 parts by weight of absolute ethyl alcohol and water according to the volume ratio (1-3): 1, and uniformly mixing the mixture liquid to obtain the product.
The modifier is one or more of vinyl trimethoxy silane, gamma-glycidol ether oxypropyl trimethoxy silane and 3-amino propyl triethoxy silane.
Preferably, the modifier is a mixture of vinyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane, wherein the mass ratio of the vinyl trimethoxy silane to the gamma-glycidoxypropyl trimethoxy silane is (1-3): (2-5).
The invention adopts the silane coupling agent, namely vinyl trimethoxy silane and gamma-glycidol ether oxygen propyl trimethoxy silane, as the modifier for the surface modification of the nano cellulose/silicon dioxide composite material, and the main possibilities are: on one hand, vinyl trimethoxy silane and gamma-glycidol ether oxypropyl trimethoxy silane can be grafted on the surface of the nano cellulose/silicon dioxide composite material through silanol condensation reaction to carry out hydrophobic modification on the nano cellulose/silicon dioxide composite material, so that the compatibility between the filler and a matrix is improved, and the performance of the air film material is improved; on the other hand, the gamma-glycidol ether oxypropyl trimethoxy silane contains epoxy groups which can be hydrolyzed to generate hydroxyl groups and polymerized with lactic acid monomers to generate polylactic acid, the vinyl trimethoxy silane contains vinyl which can react with unsaturated double bonds in the polylactic acid to form a stable space structure, and the two react together to promote the polylactic acid to be grafted on the surface of the nano cellulose/silicon dioxide composite material efficiently and stably, so that the functional modification of the nano cellulose/silicon dioxide composite material is realized, and the mechanical property and the degradation property of the air film material are improved.
The catalyst is one or more of stannous octoate, stannous chloride and p-toluenesulfonic acid.
The preparation method of the polyvinyl alcohol/graphite composite comprises the following steps:
uniformly mixing 1-2 parts by weight of 1-hexyl-2, 3-dimethylimidazole tetrafluoroborate, 0.5-1 part by weight of 3-aminopropyl methyl diethoxysilane and 5-8 parts by weight of nano copper powder, and putting into a ball mill, and performing ball milling treatment for 0.5-1h at a rotating speed of 300-500 rpm; then adding 10-20 parts by weight of nano graphite powder, and continuing ball milling for 2-3 hours to obtain a graphite compound; and (3) adding the graphite compound and polyvinyl alcohol into a mixer according to the mass ratio of 1 (3-5), and stirring and mixing for 1-2 hours at the rotating speed of 200-300rpm to obtain the polyvinyl alcohol/graphite compound.
The composite obtained by coating the nano copper powder with the nano graphite and the 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate under the modification effect of the 3-aminopropyl methyl diethoxy silane avoids the problems of easy agglomeration and poor dispersibility when the components are used independently; the nano graphite can form a conductive electron transmission network in the film substrate to cooperate with the 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate and the nano copper powder, so that the antistatic performance of the film is improved; the polyvinyl alcohol molecular chain contains a large number of hydroxyl groups, and besides certain antistatic performance, when the polyvinyl alcohol molecular chain is used together with the graphite compound, the dispersion of the graphite compound can be increased, the polyvinyl alcohol molecular chain can play a role in stabilizing, the probability of migration and precipitation due to poor compatibility in the use process is reduced, and the antistatic durability of the composite air film material is improved.
The preparation method of the antistatic composite air film material comprises the following steps:
(1) The polyvinylidene fluoride resin, the polybutylene succinate, the polyethylene alcohol or the polyvinyl alcohol/graphite compound, the plasticizer, the stabilizer, the ultraviolet absorber, the flame retardant and the filler which are weighed according to the weight parts are put into a mixer to be stirred and mixed for 8-15min at the rotating speed of 250-400rpm, so as to obtain a mixture;
(2) Putting the mixture obtained in the step (1) into a planetary extruder for plasticizing, wherein the temperature of the extruder is 170-200 ℃ and the extrusion speed is 40-60r/min, so as to obtain a plasticized material;
(3) Delivering the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed air film material; wherein the temperature of the calender is 170-210 ℃;
(4) And (3) cooling and shaping the preformed air film material obtained in the step (3) at the temperature of 10-20 ℃, and then trimming and coiling according to the size requirement to obtain the antistatic composite air film material.
The invention has the beneficial effects that: the antistatic composite air film material prepared by the invention has good antistatic performance, fireproof performance and ultraviolet radiation resistance, is environment-friendly and has good mechanical strength, and can be used as a building film material. According to the invention, the poly (butylene succinate), the polyvinyl alcohol and the polyvinylidene fluoride resin are used as main raw materials, and the degradability of the air film material is improved while the excellent mechanical property is ensured by adding the functionalized nano cellulose/silicon dioxide composite material; the nano-silica hybrid modification is generated on the surface in situ by taking nano-cellulose as a carrier, and then the nano-silica hybrid modification is modified by a silane coupling agent, and finally polylactic acid is grafted to obtain the nano-silica hybrid modified polylactic acid. The raw materials of the invention are green and environment-friendly, and the preparation process is simple.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
polyvinylidene fluoride resin, brand: 761, supplied by the company, vac marc chemical, france.
Polyvinyl alcohol, molecular weight: 85000, supplied by Shanghai Rong Europe chemical technology Co., ltd.
Polybutylene succinate, density: 1.26g/cm 3 Melting point: crystallinity at 114 ℃): 40% by Jinan culvert hundred chemical industry Co.
Nanocellulose, the invention adopts nanocrystalline cellulose, diameter: 10nm, length: 200nm, offered by the West Bao Biotechnology (Shanghai) Inc.
Chlorinated paraffin, CAS number: 63449-39-8.
1-hexyl-2, 3-dimethylimidazole tetrafluoroborate, CAS number: 384347-21-1.
3-aminopropyl methyldiethoxysilane, CAS number: 3179-76-8.
Example 1
An antistatic composite air film material is composed of the following raw materials: 60 parts of polyvinylidene fluoride resin, 25 parts of polybutylene succinate, 15 parts of polyvinyl alcohol, 22 parts of plasticizer, 4 parts of stabilizer, 2 parts of ultraviolet absorber, 2 parts of flame retardant and 25 parts of filler.
The plasticizer is a mixture of dimethyl phthalate and epoxy octyl stearate according to a mass ratio of 3:2.
The stabilizer is dibutyl tin dilaurate.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The flame retardant is chlorinated paraffin.
The filler is nanocellulose.
The preparation method of the antistatic composite air film material comprises the following steps:
(1) The polyvinylidene fluoride resin, the polybutylene succinate, the polyethylene alcohol, the plasticizer, the stabilizer, the ultraviolet absorber, the flame retardant and the filler which are weighed according to the weight parts are put into a mixer to be stirred and mixed for 10 minutes at the rotating speed of 350rpm, so as to obtain a mixture;
(2) Putting the mixture obtained in the step (1) into a planetary extruder for plasticizing, wherein the temperature of the extruder is 180 ℃, and the extrusion speed is 50r/min, so as to obtain a plasticized material;
(3) Delivering the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed air film material; wherein the temperature of the calender is 190 ℃;
(4) And (3) cooling and shaping the preformed air film material obtained in the step (3) at the temperature of 15 ℃, and then trimming and coiling according to the size requirement to obtain the antistatic composite air film material.
Example 2
An antistatic composite air film material is composed of the following raw materials: 60 parts of polyvinylidene fluoride resin, 25 parts of polybutylene succinate, 15 parts of polyvinyl alcohol, 22 parts of plasticizer, 4 parts of stabilizer, 2 parts of ultraviolet absorber, 2 parts of flame retardant and 25 parts of filler.
The plasticizer is a mixture of dimethyl phthalate and epoxy octyl stearate according to a mass ratio of 3:2.
The stabilizer is dibutyl tin dilaurate.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The flame retardant is chlorinated paraffin.
The filler is a nano cellulose/silicon dioxide composite material.
The preparation method of the nanocellulose/silicon dioxide composite material comprises the following steps:
adding 30 parts by weight of nanocellulose into 120 parts by weight of isopropanol water solution with the mass fraction of 82wt%, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of ammonia water solution with the mass fraction of 28wt%, continuing stirring for 30min, adding 3 parts by weight of tetraethoxysilane, continuing stirring for reaction for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nanocellulose/silicon dioxide composite material.
The preparation method of the antistatic composite air film material is the same as that of the embodiment 1.
Comparative example 1
Substantially the same as in example 2, the only difference is that: the preparation method of the nanocellulose/silicon dioxide composite material comprises the following steps:
adding 30 parts by weight of nanocellulose into 120 parts by weight of a methanol water solution with the mass fraction of 82wt%, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of an ammonia water solution with the mass fraction of 28wt%, continuing stirring for 30min, adding 3 parts by weight of tetraethoxysilane, continuing stirring for reacting for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nanocellulose/silicon dioxide composite material.
Example 3
An antistatic composite air film material is composed of the following raw materials: 60 parts of polyvinylidene fluoride resin, 25 parts of polybutylene succinate, 15 parts of polyvinyl alcohol, 22 parts of plasticizer, 4 parts of stabilizer, 2 parts of ultraviolet absorber, 2 parts of flame retardant and 25 parts of filler.
The plasticizer is a mixture of dimethyl phthalate and epoxy octyl stearate according to a mass ratio of 3:2.
The stabilizer is dibutyl tin dilaurate.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The flame retardant is chlorinated paraffin.
The filler is a functionalized nano cellulose/silicon dioxide composite material.
The preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nanocellulose into 120 parts by weight of 82wt% isopropyl alcohol aqueous solution, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of 28wt% ammonia aqueous solution, continuously stirring for 30min, then adding 3 parts by weight of tetraethoxysilane, continuously stirring for reaction for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain a nanocellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of the nano cellulose/silicon dioxide composite material into 50 parts by weight of the modified liquid, adjusting the pH to 3.0, stirring at the temperature of 80 ℃ at the rotation speed of 400rpm for reaction for 12 hours, centrifuging at the rotation speed of 1000rpm for 5 minutes after the reaction is finished, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 5 parts by weight of the modified nano cellulose/silicon dioxide composite material and 30 parts by weight of D-lactic acid into 50 parts by weight of ethanol aqueous solution with the mass fraction of 70wt%, stirring at the temperature of 100 ℃ for 30min at the speed of 350rpm, adding 0.2 part by weight of stannous octoate, setting the reaction temperature to 145 ℃ under the protection of nitrogen, reacting for 16h, pouring out after the reaction is finished, adding 100 parts by weight of trichloromethane, stirring at the room temperature at the speed of 800rpm for 30min, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol three times, and vacuum drying at the temperature of 80 ℃ for 12h to obtain the functional nano cellulose/silicon dioxide composite material.
The preparation method of the modified liquid comprises the following steps: adding 2 parts by weight of modifier into 100 parts by weight of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 2:1, and uniformly mixing to obtain the modified polyethylene.
The modifier is gamma-glycidyl ether oxypropyl trimethoxy silane.
The preparation method of the antistatic composite air film material is the same as that of the embodiment 1.
Example 4
Substantially the same as in example 3, the only difference is that: the preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nanocellulose into 120 parts by weight of 82wt% isopropyl alcohol aqueous solution, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of 28wt% ammonia aqueous solution, continuously stirring for 30min, then adding 3 parts by weight of tetraethoxysilane, continuously stirring for reaction for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain a nanocellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of the nano cellulose/silicon dioxide composite material into 50 parts by weight of the modified liquid, adjusting the pH to 3.0, stirring at the temperature of 80 ℃ at the rotation speed of 400rpm for reaction for 12 hours, centrifuging at the rotation speed of 1000rpm for 5 minutes after the reaction is finished, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 5 parts by weight of the modified nano cellulose/silicon dioxide composite material and 30 parts by weight of D-lactic acid into 50 parts by weight of ethanol aqueous solution with the mass fraction of 70wt%, stirring at the temperature of 100 ℃ for 30min at the speed of 350rpm, adding 0.2 part by weight of stannous octoate, setting the reaction temperature to 145 ℃ under the protection of nitrogen, reacting for 16h, pouring out after the reaction is finished, adding 100 parts by weight of trichloromethane, stirring at the room temperature at the speed of 800rpm for 30min, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol three times, and vacuum drying at the temperature of 80 ℃ for 12h to obtain the functional nano cellulose/silicon dioxide composite material.
The preparation method of the modified liquid comprises the following steps: adding 2 parts by weight of modifier into 100 parts by weight of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 2:1, and uniformly mixing to obtain the modified polyethylene.
The modifier is vinyl trimethoxy silane.
Example 5
Substantially the same as in example 3, the only difference is that: the preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nanocellulose into 120 parts by weight of 82wt% isopropyl alcohol aqueous solution, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of 28wt% ammonia aqueous solution, continuously stirring for 30min, then adding 3 parts by weight of tetraethoxysilane, continuously stirring for reaction for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain a nanocellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of the nano cellulose/silicon dioxide composite material into 50 parts by weight of the modified liquid, adjusting the pH to 3.0, stirring at the temperature of 80 ℃ at the rotation speed of 400rpm for reaction for 12 hours, centrifuging at the rotation speed of 1000rpm for 5 minutes after the reaction is finished, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 5 parts by weight of the modified nano cellulose/silicon dioxide composite material and 30 parts by weight of D-lactic acid into 50 parts by weight of ethanol aqueous solution with the mass fraction of 70wt%, stirring at the temperature of 100 ℃ for 30min at the speed of 350rpm, adding 0.2 part by weight of stannous octoate, setting the reaction temperature to 145 ℃ under the protection of nitrogen, reacting for 16h, pouring out after the reaction is finished, adding 100 parts by weight of trichloromethane, stirring at the room temperature at the speed of 800rpm for 30min, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol three times, and vacuum drying at the temperature of 80 ℃ for 12h to obtain the functional nano cellulose/silicon dioxide composite material.
The preparation method of the modified liquid comprises the following steps: adding 2 parts by weight of modifier into 100 parts by weight of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 2:1, and uniformly mixing to obtain the modified polyethylene.
The modifier is a mixture of vinyl trimethoxy silane and gamma-glycidyl ether oxypropyl trimethoxy silane, wherein the mass ratio of the vinyl trimethoxy silane to the gamma-glycidyl ether oxypropyl trimethoxy silane is 2:3.
example 6
An antistatic composite air film material is composed of the following raw materials: 60 parts by weight of polyvinylidene fluoride resin, 25 parts by weight of polybutylene succinate, 15 parts by weight of polyvinyl alcohol/graphite composite, 22 parts by weight of plasticizer, 4 parts by weight of stabilizer, 2 parts by weight of ultraviolet absorber, 2 parts by weight of flame retardant and 25 parts by weight of filler.
The plasticizer is a mixture of dimethyl phthalate and epoxy octyl stearate according to a mass ratio of 3:2.
The stabilizer is dibutyl tin dilaurate.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The flame retardant is chlorinated paraffin.
The preparation method of the polyvinyl alcohol/graphite composite comprises the following steps:
uniformly mixing 1.5 parts by weight of 1-hexyl-2, 3-dimethylimidazole tetrafluoroborate, 0.5 part by weight of 3-aminopropyl methyl diethoxysilane and 6 parts by weight of nano copper powder, putting into a ball mill, and performing ball milling treatment for 0.5h at a rotating speed of 300 rpm; then adding 15 parts by weight of nano graphite powder, and continuing ball milling for 2.5 hours to obtain a graphite compound; and (3) putting the graphite compound and polyvinyl alcohol into a mixer according to a mass ratio of 1:4, and stirring and mixing for 1h at a rotating speed of 200rpm to obtain the polyvinyl alcohol/graphite compound. Wherein, the particle size of the nano graphite powder is 50nm, and the product number is XT-0801-24-1; nanometer copper powder with the particle size of 80nm and the product number of XT-0801-5-2 is purchased from Shanghai lane field nanometer materials limited company.
The filler is a functionalized nano cellulose/silicon dioxide composite material.
The preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nanocellulose into 120 parts by weight of 82wt% isopropyl alcohol aqueous solution, stirring at room temperature for 20min at a rotating speed of 500rpm, then adding 2.8 parts by weight of 28wt% ammonia aqueous solution, continuously stirring for 30min, then adding 3 parts by weight of tetraethoxysilane, continuously stirring for reaction for 12h, centrifuging at a rotating speed of 1000rpm for 5min after the completion, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain a nanocellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of the nano cellulose/silicon dioxide composite material into 50 parts by weight of the modified liquid, adjusting the pH to 3.0, stirring at the temperature of 80 ℃ at the rotation speed of 400rpm for reaction for 12 hours, centrifuging at the rotation speed of 1000rpm for 5 minutes after the reaction is finished, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 5 parts by weight of the modified nano cellulose/silicon dioxide composite material and 30 parts by weight of D-lactic acid into 50 parts by weight of ethanol aqueous solution with the mass fraction of 70wt%, stirring at the temperature of 100 ℃ for 30min at the speed of 350rpm, adding 0.2 part by weight of stannous octoate, setting the reaction temperature to 145 ℃ under the protection of nitrogen, reacting for 16h, pouring out after the reaction is finished, adding 100 parts by weight of trichloromethane, stirring at the room temperature at the speed of 800rpm for 30min, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol three times, and vacuum drying at the temperature of 80 ℃ for 12h to obtain the functional nano cellulose/silicon dioxide composite material.
The preparation method of the modified liquid comprises the following steps: adding 2 parts by weight of modifier into 100 parts by weight of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 2:1, and uniformly mixing to obtain the modified polyethylene.
The modifier is a mixture of vinyl trimethoxy silane and gamma-glycidyl ether oxypropyl trimethoxy silane, wherein the mass ratio of the vinyl trimethoxy silane to the gamma-glycidyl ether oxypropyl trimethoxy silane is 2:3.
the preparation method of the antistatic composite air film material comprises the following steps:
(1) The polyvinylidene fluoride resin, the polybutylene succinate, the polyethylene alcohol/graphite compound, the plasticizer, the stabilizer, the ultraviolet absorbent, the flame retardant and the filler which are weighed according to the weight parts are put into a mixer to be stirred and mixed for 10 minutes at the rotating speed of 350rpm, so as to obtain a mixture;
(2) Putting the mixture obtained in the step (1) into a planetary extruder for plasticizing, wherein the temperature of the extruder is 180 ℃, and the extrusion speed is 50r/min, so as to obtain a plasticized material;
(3) Delivering the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed air film material; wherein the temperature of the calender is 190 ℃;
(4) And (3) cooling and shaping the preformed air film material obtained in the step (3) at the temperature of 15 ℃, and then trimming and coiling according to the size requirement to obtain the antistatic composite air film material.
Test example 1
Degradation performance evaluation: reference to the national Standard GB/T19811-2005 determination of the degree of disintegration of Plastic Material under defined composting conditions for the examplesAnd the prepared antistatic composite air film material is subjected to degradation performance test. The specific experimental method comprises the following steps: the sample size was 25mm x 25mm, dried in a vacuum drying oven at 60℃for 12 hours before testing, and then taken out and immediately weighed, designated m 0 . Then the test sample is buried in a self-made paper box filled with commercial flower-growing nutrient soil, the depth is 5cm, the distance is 5cm, the paper box is placed in an air blast drying box after the test sample is buried, and a degradation experiment is carried out under the condition that the temperature is 60 ℃ and the relative humidity of soil is kept at 60%. Sampling after 30 days and 90 days of composting degradation experiment, washing the sample, drying in a vacuum oven at 60 ℃ for 12 hours, taking out, weighing and marking as m n (n is 30, 90). Calculate weight loss (%) = (m) 0 -m n )/m 0 X 100%. The degradation performance of the material takes the average weight loss rate (%) of the quality change as an evaluation standard, and the higher the numerical value is, the better the degradation performance is. Each group of samples was measured in duplicate five times and averaged.
TABLE 1 degradation Performance test results
| Weight loss rate of 30 days,% | Weight loss rate of 90 days,% | |
| Example 2 | 17.8 | 60.4 |
| Example 3 | 24.1 | 75.8 |
| Example 4 | 23.9 | 75.5 |
| Example 5 | 25.6 | 80.2 |
The raw materials used in the invention are green and environment-friendly, and the prepared antistatic composite air film material has better degradation performance. The degradation performance of example 2 is significantly inferior to that of examples 3 to 5, probably because the functionalized nanocellulose/silica composite materials employed in examples 3 to 5 are grafted with high molecular weight polylactic acid having excellent biocompatibility and biodegradability, which not only increases the oxygen content in the filler, but also has long molecular chains capable of intertwining with the matrix resin, promoting the uniform distribution of the filler in the matrix, increasing the degradation active sites, thereby improving the degradation performance of the material.
Test example 2
Mechanical property evaluation: the mechanical properties of the antistatic composite air film materials prepared in examples and comparative examples were tested by using a TA-X2i physical property tester according to the ASTM-D882-18 method. The specific experimental method comprises the following steps: the test specification of the sample was 15mm×100mm, and the sample was placed in a constant temperature and humidity oven (25 ℃, rh=53%) for 48 hours before testing. The initial distance between the clamps is set to be 50mm, the moving speed of the probe is set to be 60mm/min, each group of samples are measured in parallel for 6 times, and the average value is obtained.
TABLE 2 mechanical test results
| Tensile strength, MPa | Elongation at break% | |
| Example 1 | 10.2 | 34.81 |
| Example 2 | 13.6 | 39.27 |
| Comparative example 1 | 12.1 | 37.08 |
| Example 3 | 18.9 | 48.73 |
| Example 4 | 18.0 | 48.09 |
| Example 5 | 20.5 | 52.36 |
The above results show that the mechanical properties of example 2 are better than those of example 1, and it is possible that the surface of the nano-cellulose/silica composite material is modified by inorganic nano-material-silica, and a large number of spherical nano-particles with high specific surface area and narrow particle size distribution exist on the surface of the nano-cellulose/silica composite material, so that the filler can have better dispersibility in the matrix, the interface combination between the filler and the matrix is tighter, and the interface interaction is increased, thereby improving the mechanical properties of the air film material. Compared with comparative example 1, the mechanical properties of example 2 are slightly improved, probably because isopropanol has a smaller dielectric constant than the organic solvent methanol, and the increased alkyl chain length brings greater steric hindrance to isopropanol, can provide a lower hydrolysis rate, limit the nucleation rate of silica, directly promote the uniform growth of silica on the surface of nanocellulose, lead to tighter bonding between the filler and the matrix, and are beneficial to the improvement of mechanical properties. Compared with the embodiment 2, the mechanical properties of the embodiment 3 are obviously improved, and the main reason is that the high molecular weight polylactic acid with good mechanical properties and processing properties is grafted on the surface of the nano cellulose/silicon dioxide composite material, and the long molecular chains of the polylactic acid can be intertwined with matrix resin, so that the uniform distribution of the filler in the matrix is promoted, the compatibility between the filler and the matrix is increased, and the mechanical properties of the material are greatly improved. In the embodiment 5, the mechanical properties of the vinyl trimethoxy silane and the gamma-glycidyl ether oxypropyl trimethoxy silane which are used as the modifier are superior to those of the embodiments 3 and 4, and the mechanical properties of the modifier are superior to those of the single modifier, and the main possibility is that the epoxy group contained in the gamma-glycidyl ether oxypropyl trimethoxy silane can be hydrolyzed to generate hydroxyl and polymerize with lactic acid monomers to generate polylactic acid, the vinyl contained in the vinyl trimethoxy silane can react with unsaturated double bonds in the polylactic acid to form a stable space structure, and the two react together to promote the polylactic acid to be grafted on the surface of the nano cellulose/silicon dioxide composite material efficiently and firmly, so that the functional modification of the nano cellulose/silicon dioxide composite material is realized, and the mechanical properties of the air film material are improved.
Test example 3
Antistatic property evaluation: the antistatic composite air film material prepared in the example was subjected to surface resistance test by using ACL-800 type surface resistance tester (American Model) at 20℃and 65% relative humidity. Each group of samples was measured in duplicate five times and averaged.
TABLE 3 antistatic Performance test results
| Surface resistance, Ω | |
| Example 5 | 3.75×10 8 |
| Example 6 | 1.32×10 7 |
The above results show that the use of the polyvinyl alcohol/graphite composite in example 6 further improves the antistatic performance of the composite air film material, and the main reasons are probably that the use of the polyvinyl alcohol/graphite composite avoids the problems of easy agglomeration and poor dispersibility when the components are used independently; the nano graphite can form a conductive electron transmission network in the film substrate to cooperate with the 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate and the nano copper powder, so that the antistatic performance of the film is improved; besides a certain antistatic property, the polyvinyl alcohol can not only increase the dispersibility of the graphite compound, but also play a role in stabilizing, reduce the probability of migration and precipitation due to poor compatibility in the use process and improve the antistatic durability of the composite air film material when being used together with the graphite compound.
Claims (5)
1. An antistatic composite air film material is characterized by comprising the following raw materials: 50-80 parts of polyvinylidene fluoride resin, 20-40 parts of polybutylene succinate, 10-25 parts of polyvinyl alcohol/graphite composite, 20-30 parts of plasticizer, 3-6 parts of stabilizer, 1-5 parts of ultraviolet absorber, 1-4 parts of flame retardant and 20-35 parts of functionalized nano-cellulose/silicon dioxide composite;
the preparation method of the polyvinyl alcohol/graphite composite comprises the following steps:
uniformly mixing 1-2 parts by weight of 1-hexyl-2, 3-dimethylimidazole tetrafluoroborate, 0.5-1 part by weight of 3-aminopropyl methyl diethoxysilane and 5-8 parts by weight of nano copper powder, and performing ball milling treatment for 0.5-1h at a rotating speed of 300-500 rpm; then adding 10-20 parts by weight of nano graphite powder, and continuing ball milling for 2-3 hours to obtain a graphite compound; stirring and mixing the graphite compound and polyvinyl alcohol according to the mass ratio of 1 (3-5) for 1-2h to obtain the polyvinyl alcohol/graphite compound;
the preparation method of the functionalized nano cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 25-40 parts by weight of nanocellulose into 100-150 parts by weight of an organic solvent aqueous solution with the mass fraction of 75-85wt%, stirring for 15-30min, then adding 2-5 parts by weight of an ammonia water solution with the mass fraction of 20-30wt%, continuing stirring for 25-40min, adding 2-5 parts by weight of tetraethoxysilane, continuing stirring for reacting for 8-15h, centrifuging after finishing, washing, and freeze-drying to obtain the nanocellulose/silicon dioxide composite material;
s2, adding 6-10 parts by weight of the nano cellulose/silicon dioxide composite material into 40-60 parts by weight of the modified liquid, adjusting the pH to 2.0-4.0, then reacting for 8-16 hours at the temperature of 75-90 ℃, centrifuging after finishing, washing, and freeze-drying to obtain the modified nano cellulose/silicon dioxide composite material;
s3, adding 4-8 parts by weight of modified nano cellulose/silicon dioxide composite material and 25-40 parts by weight of D-lactic acid into 45-60 parts by weight of ethanol water solution with the mass fraction of 60-75%, stirring for 15-40min at the temperature of 85-105 ℃, adding 0.2 part by weight of catalyst, setting the reaction temperature to 130-160 ℃ under the protection of nitrogen, reacting for 12-24h, pouring out after the reaction is finished, adding 80-120 parts by weight of chloroform, stirring for 20-40min, adding 150-200 parts by weight of absolute ethyl alcohol, continuing stirring for 20-40min, filtering, washing and drying to obtain the functionalized nano cellulose/silicon dioxide composite material;
the preparation method of the modified liquid comprises the following steps: adding 1-5 parts by weight of modifier into 85-110 parts by weight of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio (1-3): 1, and uniformly mixing to obtain the modified aqueous emulsion; the modifier is one or more of vinyl trimethoxy silane, gamma-glycidol ether oxypropyl trimethoxy silane and 3-amino propyl triethoxy silane.
2. The antistatic composite air film material of claim 1 wherein said organic solvent is one or more of isopropanol, ethanol, methanol.
3. The antistatic composite air film material of claim 1 wherein said plasticizer is one or more of dimethyl phthalate, dioctyl adipate, octyl epoxy stearate, trioctyl phosphate.
4. The antistatic composite air film material of claim 1 wherein said stabilizer is one or more of calcium stearate, dibutyl tin dilaurate, dibasic lead stearate.
5. The method for producing an antistatic composite air film material according to any one of claims 1 to 4, comprising the steps of:
(1) Stirring and mixing polyvinylidene fluoride resin, polybutylene succinate, polyvinyl alcohol/graphite composite, plasticizer, stabilizer, ultraviolet absorber, flame retardant and functional nano cellulose/silicon dioxide composite material to obtain a mixture;
(2) Plasticizing the mixture obtained in the step (1) to obtain a plasticized material;
(3) Calendering the plasticized material obtained in the step (2) to obtain a preformed air film material;
(4) And (3) cooling and shaping the preformed air film material obtained in the step (3), trimming and coiling to obtain the antistatic composite air film material.
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