CN114516992A - Antistatic composite gas film material and preparation method thereof - Google Patents
Antistatic composite gas film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antistatic composite gas film material and a preparation method thereof, wherein the preparation method comprises the following steps: stirring and mixing polyvinylidene fluoride resin, poly (butylene succinate), polyvinyl alcohol or a polyvinyl alcohol/graphite composite, a plasticizer, a stabilizer, an ultraviolet absorbent, a flame retardant and a functionalized 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 gas film material; and cooling and shaping the preformed gas film material, and cutting and coiling to obtain the finished product. The antistatic composite gas film material prepared by the invention has good antistatic performance, fireproof performance and ultraviolet radiation resistance, is green and environment-friendly, 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 gas membrane material and a preparation method thereof.
Background
The air film building is a building structure system which takes a building film material as a shell and provides air positive pressure for the interior of the air film building by intelligent electromechanics so as to support the interior space. The air film building can make full use of outdoor sunlight and surrounding natural environment, realizes control of air pressure, temperature, humidity, fresh air volume, illumination and the like of an internal space as required, provides a comfortable and spacious indoor environment, and can be applied to sports stadiums such as tennis, basketball, badminton and the like. The used building film material is of an inflatable film structure, has the characteristics of light weight, good plasticity and light transmittance, accords with the concepts of green, low carbon and cost saving, and is common film materials of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, ethylene-tetrafluoroethylene copolymer and the like. Chinese patent CN201710105575.3 discloses a composite membrane structure for building skin and its application, which is composed of two layers of materials, wherein the ethylene-tetrafluoroethylene copolymer film and the polyethylene film are connected by hot melting or bonding layer to form the first layer of material, the polyvinyl chloride film surface is coated with polyvinylidene fluoride to form the second layer of material, and the surface of the first layer of material is provided with an anti-ultraviolet coating which comprises polyvinylpyrrolidone, water, ceria aqueous solution, siloxane, isopropanol, diacetone alcohol and sodium acetate; the composite film structure gas tightness and waterproof nature of this patent are good, can also improve the anti ultraviolet performance of membrane material through anti ultraviolet coating simultaneously, but the anti-static performance of membrane material is not good, also is difficult in degradation processing after the abandonment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antistatic composite gas film material and a preparation method thereof.
An antistatic composite gas 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 absorbent, 1-4 parts of flame retardant and 20-35 parts of filler.
The plasticizer is one or more of dimethyl phthalate, dioctyl adipate, epoxy octyl stearate and trioctyl phosphate.
Further, the plasticizer is a mixture of dimethyl phthalate and epoxy stearic acid octyl ester according to the mass ratio of 3 (1-2).
The stabilizer is one or more of calcium stearate, dibutyltin 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 nano-cellulose, a nano-cellulose/silicon dioxide composite material or a functionalized nano-cellulose/silicon dioxide composite material.
At present, most of the most widely applied gas film materials are mainly traditional high polymer materials, and although the gas film materials have the characteristics of good flexibility, light weight, good insulativity and the like, the development speed is slowed down along with the rising of cost caused by the gradual reduction of petroleum resources, and meanwhile, the problem of environmental pollution generated by the high polymer materials is increasingly highlighted, so that the environment-friendly and easily degradable gas film material is provided while the use requirements of gas film buildings are met. The nanocellulose is rigid rodlike cellulose with the one-dimensional space size smaller than 100nm formed after the amorphous region of natural cellulose is removed, belongs to biodegradable green biomass materials, is rich in source, environment-friendly, large in specific surface area and high in length-diameter ratio, contains a large amount of hydroxyl on the surface, is high in chemical reaction activity, can be used for self-assembly, is good in biodegradability and excellent in 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 is directly added into the hydrophobic matrix, so that the intermolecular binding force is weak, and the excellent reinforcing effect of the nano-cellulose cannot be fully exerted. In order to solve the problem, the invention adopts a series of surface functionalization strategies to carry out surface modification treatment on the nano-cellulose 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 gas 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, small size effect, surface and boundary effect, and has volume effect and quantum tunnel effect to generate free permeation effect, can penetrate into the vicinity of pi bonds of a high molecular compound and overlap with electron clouds of the high molecular compound to form a space network structure, thereby promoting the performance improvement of the high molecular material.
The preparation method of the nano-cellulose/silicon dioxide composite material comprises the following steps:
adding 25-40 parts by weight of nano-cellulose into 100-150 parts by weight of 75-85 wt% organic solvent aqueous solution, stirring at the rotation speed of 400-600rpm at room temperature for 15-30min, then adding 2-5 parts by weight of 20-30 wt% ammonia water solution, continuing stirring for 25-40min, then adding 2-5 parts by weight of ethyl orthosilicate, continuing stirring and reacting for 8-15h, after that, centrifuging at the rotation speed of 800-1500rpm for 4-8min, washing with anhydrous ethanol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material.
The surface of the nano-cellulose is rich in a large amount of hydroxyl groups, and molecular chains have larger interaction force. After the surface of the nano-cellulose is modified by the inorganic nano-material-silicon dioxide, spherical nano-particles with high specific surface area and narrow particle size distribution exist on the surface of the generated nano-cellulose/silicon dioxide composite material, so that the filler can have better dispersibility in a matrix, the interface between the filler and the matrix is more tightly combined, 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 nano-cellulose into 150 parts by weight of 75-85 wt% organic solvent aqueous solution, stirring at the rotating speed of 400-600rpm at room temperature for 15-30min, then adding 2-5 parts by weight of 20-30 wt% ammonia water solution, continuing to stir for 25-40min, adding 2-5 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 8-15h, after that, centrifuging at the rotating speed of 800-1500rpm for 4-8min, washing with anhydrous ethanol for three times, and freeze-drying to obtain the nano-cellulose/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 modification solution, adjusting the pH to 2.0-4.0, stirring and reacting at 75-90 ℃ at a rotation speed of 300-1500 rpm for 8-16h, centrifuging at a rotation speed of 800-1500rpm for 4-8min 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 60-75 wt% ethanol water solution, stirring at the temperature of 85-105 ℃ for 15-40min at the rotation speed of 300-500rpm, then adding 0.2 part by weight of catalyst, setting the reaction temperature at 130-160 ℃ under the protection of nitrogen and the reaction time at 12-24h, pouring out, adding 80-120 parts by weight of trichloromethane, stirring at the rotation speed of 600-1000rpm at room temperature for 20-40min, then adding 150-200 parts by weight of anhydrous ethanol, continuing stirring for 20-40min, filtering, washing the precipitate with anhydrous ethanol for three times, vacuum drying at the temperature of 70-85 ℃ for 8-16h, obtaining the functionalized nano-cellulose/silicon dioxide composite material.
The polylactic acid is thermoplastic aliphatic polyester polymerized by micromolecular 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, better processability and better chemical inertness. The invention takes D-lactic acid as a monomer raw material, generates cyclic dimer lactide and hydrolytic hydroxyl at the tail end of a silane coupling agent on the surface of a nano-cellulose/silicon dioxide composite material to perform a grafting reaction under the action of a catalyst, and generates polylactic acid with high molecular weight by high-temperature polymerization. The polylactic acid grafted on the surface of the functionalized nano-cellulose/silicon dioxide composite material can promote the uniform distribution of molecular chains of a matrix polymer, so that the mechanical property and the degradation property of the air film material are further improved.
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 a smaller dielectric constant, the increased alkyl chain length brings larger steric hindrance to the isopropanol, can provide a lower hydrolysis rate, limits the nucleation rate of silicon dioxide, and directly promotes the uniform growth of the silicon dioxide on the surface of the 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 mixed solution of absolute ethyl alcohol and water according to the volume ratio of (1-3) to 1, and uniformly mixing to obtain the modified polyvinyl alcohol.
The modifier is one or more of vinyl trimethoxy silane, gamma-glycidyl ether oxygen propyl trimethoxy silane and 3-aminopropyl triethoxy silane.
Preferably, the modifier is a mixture of vinyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane, wherein the mass ratio of the vinyltrimethoxysilane to the gamma-glycidoxypropyltrimethoxysilane is (1-3): (2-5).
The invention adopts silane coupling agent-vinyl trimethoxy silane and gamma-glycidyl ether oxygen propyl trimethoxy silane as modifier simultaneously for surface modification of nano cellulose/silicon dioxide composite material, and mainly comprises the following steps: on one hand, the vinyl trimethoxy silane and the gamma-glycidyl 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 the matrix is improved, and the performance of the air film material is improved; on the other hand, the gamma-glycidyl ether oxypropyl trimethoxysilane contains epoxy groups which can be hydrolyzed to generate hydroxyl groups, the hydroxyl groups and lactic acid monomers are polymerized to generate polylactic acid, the vinyl trimethoxy silane contains vinyl groups which can react with unsaturated double bonds in the polylactic acid to form a stable spatial structure, and the vinyl trimethoxy silane and the vinyl groups are combined to promote the polylactic acid to be efficiently and stably grafted on the surface of the nano-cellulose/silicon dioxide composite material, 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 favorably 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:
1-2 parts by weight of 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate, 0.5-1 part by weight of 3-aminopropyl methyl diethoxy silane and 5-8 parts by weight of nano copper powder are uniformly mixed and then put into a ball mill for ball milling treatment for 0.5-1h at the rotating speed of 300-500 rpm; then adding 10-20 parts by weight of nano graphite powder, and continuing ball milling for 2-3h to obtain a graphite compound; and (3) putting the graphite compound and polyvinyl alcohol into a mixer according to the mass ratio of 1 (3-5), and stirring and mixing for 1-2h at the rotating speed of 200-300rpm to obtain the polyvinyl alcohol/graphite compound.
The compound obtained by coating the nano-copper powder with the nano-graphite and the 1-hexyl-2, 3-dimethylimidazole tetrafluoroborate under the modification action of the 3-aminopropylmethyldiethoxysilane avoids the problems of easy agglomeration and poor dispersibility when each component is used independently; the nano graphite can form a conductive electron transmission network in a film material matrix, and the nano graphite can synergistically act with the 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate and the nano copper powder to improve the antistatic performance of the film material; the molecular chain of the polyvinyl alcohol contains a large amount of hydroxyl, and besides a certain antistatic property, when the polyvinyl alcohol is used together with the graphite compound, the dispersibility of the graphite compound can be increased, the polyvinyl alcohol can also play a role in stabilizing, the probability of migration and precipitation caused by poor compatibility in the using process can be reduced, and the antistatic durability of the composite gas film material can be improved.
The preparation method of the antistatic composite gas film material comprises the following steps:
(1) putting the polyvinylidene fluoride resin, the polybutylene succinate, the polyvinyl alcohol or the polyvinyl alcohol/graphite compound, the plasticizer, the stabilizer, the ultraviolet absorbent, the flame retardant and the filler which are weighed according to the parts by weight into a mixer, stirring and mixing at the rotating speed of 250-400rpm for 8-15min 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) feeding the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed gas film material; wherein the temperature of the calender is 170-210 ℃;
(4) and (4) cooling and shaping the preformed gas film material obtained in the step (3) at the temperature of 10-20 ℃, and then cutting edges and coiling according to the size requirement to obtain the antistatic composite gas film material.
The invention has the beneficial effects that: the antistatic composite gas film material prepared by the invention has good antistatic property, fireproof property and ultraviolet radiation resistance, is green and environment-friendly, has good mechanical strength, and can be used as a building film material. According to the invention, the polybutylene succinate, the polyvinyl alcohol and the polyvinylidene fluoride resin are used as main raw materials, and the functional nano-cellulose/silicon dioxide composite material is added, so that the degradability of the air film material is improved while the excellent mechanical property is ensured; the preparation method comprises the steps of utilizing nano-cellulose as a carrier, generating nano-silica hybrid modification on the surface in situ, modifying by a silane coupling agent, and finally grafting polylactic acid to obtain the 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 with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
polyvinylidene fluoride resin, grade: 761, available from arkema chemical co.
Polyvinyl alcohol, molecular weight: 85000, supplied by Shanghai Rong Europeania Kogyo Co., Ltd.
Polybutylene succinate, density: 1.26g/cm3Melting point: 114 ℃, crystallinity: 40% by Jinan However chemical Co., Ltd.
The invention relates to nano-crystalline cellulose, which is prepared from nano-crystalline cellulose and has the following diameter: 10nm, length: 200nm, available from western treasure biotechnology (shanghai) ltd.
Chlorinated paraffin, CAS No.: 63449-39-8.
1-hexyl-2, 3-dimethylimidazolium tetrafluoroborate, CAS No.: 384347-21-1.
3-aminopropylmethyldiethoxysilane, CAS No.: 3179-76-8.
Example 1
An antistatic composite gas 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, 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 in a mass ratio of 3: 2.
The stabilizer is dibutyltin dilaurate.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The flame retardant is chlorinated paraffin.
The filler is nano-cellulose.
The preparation method of the antistatic composite gas film material comprises the following steps:
(1) putting the polyvinylidene fluoride resin, the polybutylene succinate, the polyvinyl alcohol, the plasticizer, the stabilizer, the ultraviolet absorbent, the flame retardant and the filler which are weighed according to the parts by weight into a mixer, and stirring and mixing the materials at the rotating speed of 350rpm for 10min 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) feeding the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed gas film material; wherein the temperature of the calender is 190 ℃;
(4) and (4) cooling and shaping the preformed gas film material obtained in the step (3) at the temperature of 15 ℃, and then cutting edges and coiling according to the size requirement to obtain the antistatic composite gas film material.
Example 2
An antistatic composite gas 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, 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 in a mass ratio of 3: 2.
The stabilizer is dibutyltin 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 nano-cellulose/silicon dioxide composite material comprises the following steps:
adding 30 parts by weight of nano-cellulose into 120 parts by weight of 82 wt% aqueous isopropanol, stirring at the room temperature for 20min at the rotating speed of 500rpm, then adding 2.8 parts by weight of 28 wt% aqueous ammonia, continuing to stir for 30min, then adding 3 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 12h, after the reaction is finished, centrifuging at the rotating speed of 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material.
The preparation method of the antistatic composite gas film material is the same as that of the example 1.
Comparative example 1
Essentially the same as example 2, except that: the preparation method of the nano-cellulose/silicon dioxide composite material comprises the following steps:
adding 30 parts by weight of nano-cellulose into 120 parts by weight of 82 wt% methanol aqueous solution, stirring at the room temperature for 20min at the rotating speed of 500rpm, then adding 2.8 parts by weight of 28 wt% ammonia aqueous solution, continuing stirring for 30min, then adding 3 parts by weight of ethyl orthosilicate, continuing stirring for reaction for 12h, after the reaction is finished, centrifuging at the rotating speed of 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material.
Example 3
An antistatic composite gas 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, 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 in a mass ratio of 3: 2.
The stabilizer is dibutyltin 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 nano-cellulose into 120 parts by weight of 82 wt% isopropanol aqueous solution, stirring at room temperature at a rotating speed of 500rpm for 20min, then adding 2.8 parts by weight of 28 wt% ammonia aqueous solution, continuing to stir for 30min, then adding 3 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 12h, after the reaction is finished, centrifuging at a rotating speed of 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of nano-cellulose/silicon dioxide composite material into 50 parts by weight of modification liquid, adjusting the pH to 3.0, stirring and reacting at 80 ℃ at a rotating speed of 400rpm for 12 hours, centrifuging at a rotating speed of 1000rpm for 5min 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 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 70 wt%, stirring at 100 ℃ for 30min at the rotating 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 room temperature for 30min at the rotating speed of 800rpm, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol for three times, and drying at 80 ℃ for 12h in vacuum to obtain the functionalized 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 polyvinyl alcohol.
The modifier is gamma-glycidol ether oxygen propyl trimethoxy silane.
The preparation method of the antistatic composite gas film material is the same as that of the example 1.
Example 4
Essentially the same as example 3, except that: the preparation method of the functionalized nano-cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nano-cellulose into 120 parts by weight of 82 wt% isopropanol aqueous solution, stirring at room temperature at a rotating speed of 500rpm for 20min, then adding 2.8 parts by weight of 28 wt% ammonia aqueous solution, continuing to stir for 30min, then adding 3 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 12h, after the reaction is finished, centrifuging at a rotating speed of 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of nano-cellulose/silicon dioxide composite material into 50 parts by weight of modification liquid, adjusting the pH to 3.0, stirring and reacting at 80 ℃ at a rotating speed of 400rpm for 12 hours, centrifuging at a rotating speed of 1000rpm for 5min 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 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 70 wt%, stirring at the rotation speed of 350rpm for 30min at the temperature of 100 ℃, 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 rotation speed of 800rpm for 30min at room temperature, adding 170 parts by weight of absolute ethanol, stirring for 30min continuously, filtering, washing the precipitate with absolute ethanol for three times, and drying in vacuum at the temperature of 80 ℃ for 12h to obtain the functionalized 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 polyvinyl alcohol.
The modifier is vinyl trimethoxy silane.
Example 5
Essentially the same as example 3, except that: the preparation method of the functionalized nano-cellulose/silicon dioxide composite material comprises the following steps:
s1, adding 30 parts by weight of nano-cellulose into 120 parts by weight of 82 wt% isopropanol aqueous solution, stirring at room temperature at a rotating speed of 500rpm for 20min, then adding 2.8 parts by weight of 28 wt% ammonia aqueous solution, continuing to stir for 30min, then adding 3 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 12h, after the reaction is finished, centrifuging at a rotating speed of 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of nano-cellulose/silicon dioxide composite material into 50 parts by weight of modification liquid, adjusting the pH to 3.0, stirring and reacting at 80 ℃ at a rotating speed of 400rpm for 12 hours, centrifuging at a rotating speed of 1000rpm for 5min 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 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 70 wt%, stirring at 100 ℃ for 30min at the rotating 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 room temperature for 30min at the rotating speed of 800rpm, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol for three times, and drying at 80 ℃ for 12h in vacuum to obtain the functionalized 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 polyvinyl alcohol.
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 2: 3.
example 6
An antistatic composite gas 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/graphite composite, 22 parts of plasticizer, 4 parts of stabilizer, 2 parts of ultraviolet absorbent, 2 parts of flame retardant and 25 parts of filler.
The plasticizer is a mixture of dimethyl phthalate and epoxy octyl stearate in a mass ratio of 3: 2.
The stabilizer is dibutyltin 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-dimethyl imidazole tetrafluoroborate, 0.5 part by weight of 3-aminopropyl methyl diethoxy silane and 6 parts by weight of nano copper powder, putting the mixture into a ball mill, and carrying out ball milling treatment for 0.5h at the 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 (2) putting the graphite composite and polyvinyl alcohol into a mixer according to the mass ratio of 1:4, and stirring and mixing for 1h at the rotating speed of 200rpm to obtain the polyvinyl alcohol/graphite composite. Wherein the nano graphite powder has the particle size of 50nm and the product number XT-0801-24-1; the nanometer copper powder with the grain diameter of 80nm and the commodity number of XT-0801-5-2 is purchased from Shanghai lane field nanometer material Co.
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 nano-cellulose into 120 parts by weight of 82 wt% isopropanol aqueous solution, stirring at 500rpm for 20min at room temperature, then adding 2.8 parts by weight of 28 wt% ammonia aqueous solution, continuing stirring for 30min, adding 3 parts by weight of ethyl orthosilicate, continuing stirring and reacting for 12h, after the reaction is finished, centrifuging at 1000rpm for 5min, washing with absolute ethyl alcohol for three times, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material;
s2, adding 8 parts by weight of nano-cellulose/silicon dioxide composite material into 50 parts by weight of modification liquid, adjusting the pH to 3.0, stirring and reacting at 80 ℃ at a rotating speed of 400rpm for 12 hours, centrifuging at a rotating speed of 1000rpm for 5min 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 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 70 wt%, stirring at 100 ℃ for 30min at the rotating 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 room temperature for 30min at the rotating speed of 800rpm, adding 170 parts by weight of absolute ethyl alcohol, stirring for 30min, filtering, washing the precipitate with absolute ethyl alcohol for three times, and drying at 80 ℃ for 12h in vacuum to obtain the functionalized 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 polyvinyl alcohol.
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 2: 3.
the preparation method of the antistatic composite gas film material comprises the following steps:
(1) putting the polyvinylidene fluoride resin, the polybutylene succinate, the polyvinyl alcohol/graphite compound, the plasticizer, the stabilizer, the ultraviolet absorbent, the flame retardant and the filler which are weighed according to the parts by weight into a mixer, and stirring and mixing the materials at the rotating speed of 350rpm for 10min 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) feeding the plasticized material obtained in the step (2) into a calender for calendering to obtain a preformed gas film material; wherein the temperature of the calender is 190 ℃;
(4) and (4) cooling and shaping the preformed gas film material obtained in the step (3) at the temperature of 15 ℃, and then cutting edges and coiling according to the size requirement to obtain the antistatic composite gas film material.
Test example 1
And (3) degradation performance evaluation: the anti-static composite air film material prepared in the example is subjected to degradation performance test by referring to national standard GB/T19811-2005 'determination of disintegration degree of plastic material under defined composting conditions'. The specific experimental method comprises the following steps: the specimens having a size of 25 mm. times.25 mm were dried in a vacuum drying oven at 60 ℃ for 12 hours before testing, then removed and weighed immediately, and recorded as m0. And embedding the sample into a self-made paper box filled with commercially available flower-growing nutrient soil, wherein the depth is 5cm, the distance is 5cm, placing the paper box into a forced air drying box after embedding, and performing degradation experiments under the conditions that the temperature is 60 ℃ and the relative humidity of the soil is kept at 60%. Sampling is carried out 30 days and 90 days after the compost degradation experiment, the sample is washed clean, dried for 12 hours in a vacuum oven at 60 ℃, then taken out and weighed, and recorded as mn(n is 30 or 90). Calculated weight loss ratio (%) (m)0-mn)/m0X 100%. The degradation performance of the material takes the average weight loss rate (%) of mass change as an evaluation standard, and the higher the value, the better the degradation performance. Each set of samples was run in parallel five times and averaged.
TABLE 1 degradation Performance test results
| 30 days of weight loss rate% | 90 days weight loss rate% | |
| 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 gas film material has better degradation performance. Compared with examples 3-5, the degradation performance of example 2 is significantly poor, probably because the functionalized nanocellulose/silica composite material adopted in examples 3-5 is grafted with high molecular weight polylactic acid with 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, promotes the uniform distribution of the filler in the matrix, increases the degradation active sites, and thus improves the degradation performance of the material.
Test example 2
And (3) evaluating the mechanical property: the mechanical properties of the antistatic composite gas film materials prepared in examples and comparative examples were tested using a TA-X2i physical property tester according to the method of ASTM-D882-18. 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 chamber (25 ℃, RH ═ 53%) for 48 hours before the test. 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 is parallelly measured for 6 times, and the average value is taken.
TABLE 2 mechanical Property 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, which is probably because the surface of the nanocellulose is modified by the inorganic nanomaterial-silica, and a large number of spherical nanoparticles with high specific surface area and narrow particle size distribution exist on the surface of the generated nanocellulose/silica composite, so that the filler can have better dispersibility in the matrix, the interface between the filler and the matrix is more tightly combined, the interface interaction is increased, and the mechanical properties of the gas film material are improved. Compared with the comparative example 1, the mechanical property of the example 2 is slightly improved, probably because compared with the organic solvent methanol, isopropanol has a smaller dielectric constant, the increased alkyl chain length brings larger steric hindrance to the isopropanol, can provide a lower hydrolysis rate and limit the nucleation rate of silicon dioxide, directly promotes the uniform growth of the silicon dioxide on the surface of the nanocellulose, leads the combination between the filler and the matrix to be tighter, and is beneficial to the improvement of the mechanical property. Compared with the embodiment 2, the mechanical property of the embodiment 3 is obviously improved, mainly probably because the high molecular weight polylactic acid with good mechanical property and processing property is grafted on the surface of the nano-cellulose/silicon dioxide composite material, long molecular chains of the polylactic acid can be intertwined with matrix resin, the uniform distribution of the filler in the matrix is promoted, the compatibility between the filler and the matrix is increased, and the mechanical property of the material is greatly improved. Embodiment 5 adopts two vinyl trimethoxy silane and gamma-glycidyl ether oxypropyl trimethoxy silane as modifier, the mechanical property is better than that of embodiments 3 and 4, the single modifier is mainly used, the epoxy group contained in the gamma-glycidyl ether oxypropyl trimethoxy silane can be hydrolyzed to generate hydroxyl, the hydroxyl and lactic acid monomer are polymerized to generate polylactic acid, the vinyl group contained in the vinyl trimethoxy silane can react with unsaturated double bond in the polylactic acid to form stable space structure, the two jointly act to promote the polylactic acid to be grafted on the surface of the nano-cellulose/silicon dioxide composite material efficiently and stably, the functional modification of the nano-cellulose/silicon dioxide composite material is realized, and the mechanical property of the gas film material is improved.
Test example 3
Evaluation of antistatic Properties: the antistatic composite air film material prepared in the example was subjected to a surface resistance test using an ACL-800 type surface resistance tester (Model, usa) at a temperature of 20 ℃ and a relative humidity of 65%. Each set of samples was run in parallel five times and averaged.
TABLE 3 antistatic Property test results
| Surface resistance, Ω | |
| Example 5 | 3.75×108 |
| Example 6 | 1.32×107 |
From the above results, it can be seen that the polyvinyl alcohol/graphite composite used in example 6 further improves the antistatic performance of the composite gas film material, and the main reason may be that the polyvinyl alcohol/graphite composite is used to avoid the problems of easy agglomeration and poor dispersibility when each component is used alone; the nano graphite can form a conductive electron transmission network in a film material matrix, and the nano graphite can synergistically act with 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate and nano copper powder to improve the antistatic property of the film material; besides certain antistatic performance, when the polyvinyl alcohol is used together with the graphite compound, the dispersibility of the graphite compound can be improved, the polyvinyl alcohol also has a stabilizing effect, the probability of migration and precipitation caused by poor compatibility in the using process can be reduced, and the antistatic durability of the compound gas film material can be improved.
Claims (8)
1. An antistatic composite gas 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 or a polyvinyl alcohol/graphite compound, 20-30 parts of plasticizer, 3-6 parts of stabilizer, 1-5 parts of ultraviolet absorbent, 1-4 parts of flame retardant and 20-35 parts of functionalized nano-cellulose/silicon dioxide composite material.
2. The antistatic composite gas film material of claim 1, wherein the preparation method of the polyvinyl alcohol/graphite composite comprises the following steps:
1-2 parts by weight of 1-hexyl-2, 3-dimethyl imidazole tetrafluoroborate, 0.5-1 part by weight of 3-aminopropyl methyl diethoxy silane and 5-8 parts by weight of nano copper powder are uniformly mixed and then are subjected to ball milling treatment for 0.5-1h at the rotating speed of 300-500 rpm; then adding 10-20 parts by weight of nano graphite powder, and continuing ball milling for 2-3h to obtain a graphite compound; and (3) 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.
3. The antistatic composite gas film material of claim 1, wherein the preparation method of the functionalized nanocellulose/silica composite material comprises the following steps:
s1, adding 25-40 parts by weight of nano-cellulose into 100-150 parts by weight of 75-85 wt% of organic solvent aqueous solution, stirring for 15-30min, then adding 2-5 parts by weight of 20-30 wt% of ammonia water solution, continuing to stir for 25-40min, then adding 2-5 parts by weight of ethyl orthosilicate, continuing to stir for reaction for 8-15h, centrifuging after the reaction is finished, washing, and freeze-drying to obtain the nano-cellulose/silicon dioxide composite material;
s2, adding 6-10 parts by weight of nano-cellulose/silicon dioxide composite material into 40-60 parts by weight of modification liquid, adjusting the pH to 2.0-4.0, then reacting at 75-90 ℃ for 8-16h, 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 60-75 wt% ethanol water solution, stirring at 85-105 ℃ for 15-40min, adding 0.2 part by weight of catalyst, setting the reaction temperature at 130-160 ℃ under the protection of nitrogen, stirring for 12-24h, pouring out after the reaction is finished, adding 80-120 parts by weight of trichloromethane, stirring for 20-40min, adding 200 parts by weight of anhydrous ethanol, continuing stirring for 20-40min, filtering, washing and drying to obtain the functionalized nano-cellulose/silicon dioxide composite material.
4. The antistatic composite gas film material of claim 3, wherein the organic solvent is one or more of isopropanol, ethanol, methanol.
5. The antistatic composite gas film material of claim 3, wherein the modifier is one or more of vinyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
6. The antistatic composite gas film material of claim 1 wherein the plasticizer is one or more of dimethyl phthalate, dioctyl adipate, octyl epoxy stearate, trioctyl phosphate.
7. The antistatic composite gas film material of claim 1, wherein the stabilizer is one or more of calcium stearate, dibutyltin dilaurate, and dibasic lead stearate.
8. The method for preparing the antistatic composite gas film material according to any one of claims 1 to 7, comprising the steps of:
(1) stirring and mixing polyvinylidene fluoride resin, poly (butylene succinate), polyvinyl alcohol or a polyvinyl alcohol/graphite composite, a plasticizer, a stabilizer, an ultraviolet absorbent, a flame retardant and a functionalized 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 gas film material;
(4) and (4) cooling and shaping the preformed air film material obtained in the step (3), and cutting edges and coiling to obtain the antistatic composite air film material.
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| WO2014186802A1 (en) * | 2013-05-17 | 2014-11-20 | Biotectix, LLC | Impregnation of a non-conductive material with an intrinsically conductive polymer |
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