CN117774471B - High-barrier gas-phase rust-proof film and multilayer co-extrusion molding process thereof - Google Patents
High-barrier gas-phase rust-proof film and multilayer co-extrusion molding process thereof Download PDFInfo
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 4
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- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
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- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-barrier gas-phase rust-proof film and a multilayer coextrusion molding process thereof, belonging to the technical field of rust-proof film processing. The invention is used for solving the technical problem that the barrier property of the high-barrier anti-rust film to water vapor and oxygen and the self tensile property of the high-barrier anti-rust film in the prior art are to be further improved, the high-barrier gas-phase anti-rust film comprises a core layer and coating layers positioned at two sides of the core layer, wherein the core layer consists of modified polyolefin, ethylene-vinyl alcohol copolymer, brominated butyl rubber, auxiliary additives, toughening fibers and catalysts, and the two coating layers consist of the modified polyolefin, the ethylene-vinyl alcohol copolymer and the auxiliary additives. According to the invention, the modified polyethylene and polypropylene are matched with the toughening fiber, the ethylene-vinyl alcohol copolymer, the brominated butyl rubber and the like to prepare the three-layer co-extrusion-molded antirust film, so that the barrier property of the antirust film to water vapor and oxygen is effectively improved, and the tensile property of the antirust film is also improved.
Description
Technical Field
The invention relates to the technical field of rust-proof film processing, in particular to a high-barrier gas-phase rust-proof film and a multilayer coextrusion molding process thereof.
Background
With the rapid development of industrial production, metal corrosion problems are increasingly prominent during the manufacture, storage, transportation, etc. of metal products. The rust of the metal product not only seriously affects the service function and service life of the product, but also causes resource waste and environmental pollution. At present, the common rust prevention methods in the market comprise physical rust prevention, electrochemical rust prevention and the like, but the methods often have the problems of unstable effect, high manufacturing cost and the like. The high-barrier gas-phase antirust film is a functional polymer material with good gas permeation resistance.
The high-barrier gas-phase rust-proof film can effectively cut off the contact of the metal product with external oxygen, water vapor, corrosive gas and the like, and delay the chemical reaction of the metal, thereby achieving the aim of rust prevention of the metal product for a long time.
The gas phase barrier capability of polyethylene, polyester and other materials in the prior art is good, but compared with the high barrier material, the gas phase barrier capability of the materials still has a larger gap, the oxygen transmission capacity and the water vapor transmission capacity of the barrier material are required to be further improved, the special requirements of the metal product industry on the performance of the rust-proof film are difficult to be met, the existing high barrier rust-proof film is usually used for rust-proof protection of the metal product, the rust-proof film is required to have good tensile property, the metal product is completely coated, but the tensile property of the existing high barrier rust-proof film is poor, when the high barrier rust-proof film is used for coating the metal product, the phenomenon that the rust-proof film is broken often occurs, and the tensile property of the high barrier rust-proof film is required to be further improved.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a high-barrier gas-phase rust-proof film and a multilayer coextrusion molding process thereof, which are used for solving the technical problems that the high-barrier rust-proof film in the prior art is difficult to meet the special requirements of metal product industry on the performance of the rust-proof film, the oxygen transmission amount and the water vapor transmission amount of the high-barrier gas-phase rust-proof film are required to be further improved, the phenomenon that the rust-proof film is broken frequently occurs when the metal product is coated by the existing high-barrier rust-proof film, and the tensile property of the high-barrier rust-proof film is poor.
The aim of the invention can be achieved by the following technical scheme:
the high-barrier gas-phase antirust film comprises a core layer and coating layers positioned at two sides of the core layer, wherein the core layer consists of modified polyolefin, ethylene-vinyl alcohol copolymer, brominated butyl rubber, auxiliary additives, toughening fibers and catalysts, and the two coating layers consist of the modified polyolefin, the ethylene-vinyl alcohol copolymer and the auxiliary additives;
the modified polyolefin is processed by the following steps:
A1, uniformly mixing polyethylene, polypropylene, maleic anhydride, glycidyl methacrylate, dicumyl peroxide and acetone, adding into a double-screw extruder, and carrying out melt extrusion and granulation to obtain a modified polyolefin crude product;
A2, adding the crude modified polyolefin and the dimethylbenzene into a three-neck flask, stirring, raising the temperature of the three-neck flask to reflux, preserving heat, stirring for 3-5h, filtering while the three-neck flask is hot, naturally cooling filtrate to room temperature, adding butanone into the filtrate, stirring for 30-50min, and performing post-treatment to obtain the modified polyolefin.
Further, the weight ratio of the modified polyolefin to the ethylene-vinyl alcohol copolymer to the brominated butyl rubber to the auxiliary additive to the toughening fiber to the catalyst is 30:60:15:4:8:2, the weight ratio of the modified polyolefin to the ethylene-vinyl alcohol copolymer to the auxiliary additive is 50:50:4, the catalyst is diphenyl disulfide, the auxiliary additive consists of a lubricant, a dispersing agent, an anti-aging agent and an antioxidant according to the dosage ratio of 1g to 1g, wherein the lubricant is one or more of butyl stearate, oleamide and ethylene bis-stearamide, the dispersing agent is one or more of zinc stearate, calcium stearate, magnesium stearate and cadmium stearate, and the anti-aging agent is one or more of an anti-aging agent DPPD, an anti-aging agent PPD and an anti-aging agent H; the antioxidant is one or more of butyl hydroxy anisole, dibutyl hydroxy toluene and tertiary butyl hydroquinone.
Further, in the step A1, the weight ratio of polyethylene, polypropylene, maleic anhydride, glycidyl methacrylate, dicumyl peroxide and acetone is 60:40:3:6:1:10, the temperature of 6 temperature sections from a feeding end to a discharging end of the double-screw extruder is 195 ℃, 200 ℃, 210 ℃ and 210 ℃ in sequence, the main shaft rotating speed of the double-screw extruder is 20r/min, the double-screw extruder is used for melt extrusion, water cooling and cooling molding, the double-screw extruder is used for granulating at the rotating speed of 100r/min, and then the obtained product is transferred into a drying box with the temperature of 80-90 ℃ for vacuum drying to constant weight, so that a modified polyolefin crude product is obtained; the dosage ratio of the crude modified polyolefin to the dimethylbenzene to the butanone in the step A2 is 1g:45mL:30mL, and the post-treatment operation comprises: after stirring, filtering, washing the filter cake with butanone for three times, and then pumping, transferring the filter cake into a drying oven with the temperature of 55-65 ℃, and vacuum drying to constant weight to obtain the modified polyolefin.
Further, the toughening fiber is processed by the following steps:
B1, adding the composite fiber and the activating solution into a beaker, raising the temperature of the beaker to 50-60 ℃, performing ultrasonic dispersion for 50-60min, and performing aftertreatment to obtain modified fibers;
And B2, adding the modified fiber, absolute ethyl alcohol, tetraethoxysilane, allyl triethoxysilane and triethoxy [4- (ethylene oxide-2-yl) butyl ] silane into a conical flask, performing ultrasonic dispersion for 10-15min, adding 10vt percent ammonia water into the conical flask, heating the conical flask to 45-55 ℃, performing heat preservation ultrasonic reaction for 2-3h, and performing post treatment to obtain the toughened fiber.
Further, in the step B1, the dosage ratio of the composite fiber to the activating solution is 1g to 8mL, the activating solution is composed of 1mol/L hydrochloric acid, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water according to the dosage ratio of 10mL to 1g to 4mL to 0.5g to 60g, and the post-treatment operation comprises: after the reaction is finished, the temperature of the beaker is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is dried, the filter cake is transferred into a drying oven with the temperature of 65-75 ℃ and is dried to constant weight, and modified fibers are obtained; the dosage ratio of the modified fiber, the absolute ethyl alcohol, the tetraethoxysilane, the allyltriethoxysilane, the triethoxy [4- (ethylene oxide-2-yl) butyl ] silane and the 10vt percent ammonia water in the step B2 is 10g:50mL:6g:4g:5g:15mL, and the post-treatment operation comprises: after the reaction is finished, the temperature of the conical flask is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is dried, the filter cake is transferred into a drying oven with the temperature of 65-75 ℃ and is dried to constant weight, and the toughened fiber is obtained.
Further, the preparation method of the composite fiber comprises the following steps: nylon 6, poly (m-xylylenediamine adipamide) and an antioxidant are evenly mixed and added into a melt spinning machine for melt spinning, and then the composite fiber is obtained after stretching and cooling.
Further, the weight ratio of nylon 6 to poly (m-xylylenediamine) adipamide to antioxidant is 20:4:0.1, the antioxidant is antioxidant 1010, the spinning temperature of a melt spinning machine is 230-250 ℃, the aperture of a spinneret plate is 0.1mm, and the sprayed spinning fiber is subjected to 3-time stretching, air cooling molding and cutting to obtain the composite fiber with the length of 3-5mm and the diameter of 10-20 mu m.
The multilayer co-extrusion molding process of the high-barrier gas-phase antirust film comprises the following steps of:
S1, adding modified polyolefin and ethylene-vinyl alcohol copolymer into a pulverizer, pulverizing, sieving with a 60-mesh sieve, and adding an auxiliary additive into the sieved powder to obtain mixed powder I;
s2, adding modified polyolefin, ethylene-vinyl alcohol copolymer and brominated butyl rubber into a pulverizer, pulverizing, sieving with a 60-mesh sieve, and adding auxiliary additives, toughening fibers and catalysts into the sieved powder to obtain mixed powder II;
S3, adding the first mixed powder into a first double-screw extruder, adding the second mixed powder into a second double-screw extruder, respectively carrying out melt extrusion on the first mixed powder and the second mixed powder through the first double-screw extruder and the second double-screw extruder, and then injecting the first mixed powder and the second mixed powder into a multilayer co-extrusion film machine, so as to co-extrude the first mixed powder and the second mixed powder into the anti-rust film with two coating layers and a core layer between the two coating layers, wherein the core layer is formed by the second mixed powder.
Further, the temperature of the 6 temperature sections from the feeding end to the discharging end of the twin-screw extruder is 195 ℃, 200 ℃,210 ℃ and 210 ℃ in sequence, the spindle rotation speed of the twin-screw extruder is 15r/min, the temperature of the 6 temperature sections from the feeding end to the discharging end of the twin-screw extruder is 220 ℃,230 ℃ and 15r/min.
The invention has the following beneficial effects:
1. The high-barrier gas-phase rust-proof film is prepared by co-extrusion of the coating layer, the core layer and the coating layer which are arranged from top to bottom, so that an A/B/A sandwich structure is formed, the core layer is modified by the coating layer, a compound effect is formed, and the barrier rust-proof performance of the rust-proof film is improved; in the process of preparing the anti-rust film, acetone is used as a reaction cosolvent, dicumyl peroxide is used as an initiator, glycidyl methacrylate and maleic anhydride are used as modification monomers, a mixing system consisting of polyethylene and polypropylene is modified and subjected to xylene leaching to prepare modified polyolefin modified by maleic anhydride and glycidyl methacrylate, and the polarity and hydrophilicity of the modified polyolefin modified by maleic anhydride and glycidyl methacrylate are effectively improved, so that the modified polyolefin can be fully mixed with an ethylene-vinyl alcohol copolymer and the ethylene-vinyl alcohol copolymer, the compatibility of the modified polyolefin and the ethylene-vinyl alcohol copolymer is improved, the modified polyolefin and the ethylene-vinyl alcohol copolymer form a uniform blending system, and the ethylene-vinyl alcohol copolymer has good hydrophilic property, so that the modified polyolefin is a high-gas-phase barrier material, and the water absorption property of the material can be reduced by the mixed addition of the modified polyolefin, so that the modified polyolefin can keep good barrier property in a high-humidity environment.
2. In the preparation process, the brominated butyl rubber is added into the modified polyolefin and the ethylene-vinyl alcohol copolymer, and the crosslinking reaction of the modified polyolefin and the brominated butyl rubber is initiated under the action of a catalyst to form a three-dimensional network structure, and the brominated butyl rubber has good barrier property and is matched with the modified polyolefin and the ethylene-vinyl alcohol copolymer, so that the barrier property of the anti-rust film is further improved; the core layer and the coating layer both contain modified polyolefin and ethylene-vinyl alcohol copolymer, the coating layer and the core layer have good compatibility, and in the film blowing process, the coating layer can form a tape casting effect in the core layer by controlling the extrusion temperature of the core layer to be higher than that of the coating layer, so that the antirust film with tightly combined core layer and coating layer is prepared.
3. According to the high-barrier gas-phase antirust film, nylon 6 and poly (m-xylylenediamine) are mixed according to a proportion and then melt-spun to prepare the composite fiber mixed by poly (m-xylylenediamine) and nylon 6, the composite fiber is activated and dispersed through an activating solution, the dispersion of the composite fiber is promoted, the modified fiber with active oxygen-containing groups on the surface is prepared, the tetraethoxysilane, the allyl triethoxysilane and the triethoxy [4- (ethylene oxide-2-yl) butyl ] silane are disconnected in an alkaline environment, and self-assembly is carried out on the siloxane piece and the modified fiber, so that the toughened fiber of the polysiloxane-coated modified fiber is obtained, the siloxane has higher gas-phase barrier property, and the surface modified double-bond olefin and the ethylene oxide group can be subjected to crosslinking reaction with the composition of a core layer to form a stable chemical bond crosslinking structure, so that the tensile property of the antirust film can be further improved while the barrier property of the antirust film is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic view of a partially cut-away structure of an anti-rust film prepared according to the present invention.
In the figure: 100. a core layer; 200.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1, the multi-layer co-extrusion process of the high barrier gas phase rust preventive film of the present embodiment includes the following steps:
S1, preparing modified polyolefin
Weighing: 600g of polyethylene, 400g of polypropylene, 30g of maleic anhydride, 60g of glycidyl methacrylate, 10g of dicumyl peroxide and 100g of acetone are uniformly mixed, the mixture is added into a double-screw extruder, the temperatures of 6 temperature sections from a feeding end to a discharging end of the double-screw extruder are 195 ℃, 200 ℃, 210 ℃ and 210 ℃, the main shaft rotation speed of the double-screw extruder is 20r/min, the mixture is subjected to melt extrusion through the double-screw extruder, water cooling and cooling molding, and after being pelletized at the rotation speed of 100r/min by a pelletizer, the mixture is transferred into a drying box with the temperature of 80-90 ℃, and vacuum drying is carried out until the mixture is constant in weight, thus obtaining a modified polyolefin crude product;
Weighing: adding 100g of modified polyolefin crude product and 4500mL of dimethylbenzene into a three-neck flask, stirring, raising the temperature of the three-neck flask to reflux, preserving heat, stirring for 3h, filtering while the mixture is hot, naturally cooling the filtrate to room temperature, adding 3000mL of butanone into the filtrate, stirring for 30min, filtering, washing the filter cake with butanone for three times, pumping, transferring the filter cake into a drying box with the temperature of 55 ℃, and vacuum drying to constant weight to obtain the modified polyolefin.
S2, preparing composite fiber
Weighing: mixing 62000g nylon, 400g poly (m-xylylenediamine) adipamide and 101010g antioxidant, adding into a melt spinning machine, wherein the spinning temperature of the melt spinning machine is 230 ℃, the aperture of a spinneret plate is 0.1mm, carrying out melt spinning, stretching the sprayed spinning fiber 3 times, carrying out air cooling molding, and cutting to obtain the composite fiber with the length of 3-5mm and the diameter of 10-20 mu m.
S3, preparing toughened fiber
Adding 1mol/L hydrochloric acid, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1g:4mL:0.5g:60g, and uniformly mixing to obtain an activation solution;
Weighing: adding 100g of composite fiber and 800mL of activating solution into a beaker, increasing the temperature of the beaker to 50 ℃, performing ultrasonic dispersion for 50min, reducing the temperature of the beaker to room temperature, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying oven with the temperature of 65 ℃, and drying to constant weight to obtain modified fiber;
Weighing: 100g of modified fiber, 500mL of absolute ethyl alcohol, 60g of tetraethoxysilane, 40g of allyl triethoxysilane and 50g of triethoxy [4- (ethylene oxide-2-yl) butyl ] silane are added into a conical flask for ultrasonic dispersion for 10min, 150mL of 10vt percent ammonia water is added into the conical flask, the temperature of the conical flask is increased to 45 ℃, the ultrasonic reaction is carried out for 2h, the temperature of the conical flask is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is dried, the filter cake is transferred into a drying box with the temperature of 65 ℃ and is dried to constant weight, and the toughened fiber is obtained.
S4, preparing mixed powder I
Weighing: 500g of modified polyolefin and 500g of ethylene-vinyl alcohol copolymer are added into a pulverizer, pulverized, screened by a 60-mesh screen, 10g of butyl stearate, 10g of zinc stearate, 10g of antioxidant DPPD and 10g of butyl hydroxy anisole are added into the screened powder, and mixed powder I is obtained;
S5, preparing mixed powder II
Weighing: 300g of modified polyolefin, 600g of ethylene-vinyl alcohol copolymer and 150g of brominated butyl rubber are added into a pulverizer, pulverized, screened by a 60-mesh screen, 10g of butyl stearate, 10g of zinc stearate, 10g of antioxidant DPPD, 10g of butyl hydroxy anisole, 80g of toughening fiber and 20g of diphenyl disulfide are added into the screened powder, and mixed powder II is obtained.
S6, preparing an antirust film
Adding the first mixed powder into a first double-screw extruder, adding the second mixed powder into a second double-screw extruder, sequentially heating the first double-screw extruder from a feeding end to a discharging end at 195 ℃, 200 ℃, 210 ℃ and 210 ℃, sequentially heating the second double-screw extruder from the feeding end to the discharging end at 220 ℃, 230 ℃ and 230 ℃ at 15r/min, respectively melting and extruding the first mixed powder and the second mixed powder through the first double-screw extruder and the second double-screw extruder, and then injecting the first mixed powder and the second mixed powder into a multilayer co-extrusion film machine, and co-extruding to form an anti-rust film with two coating layers 200 consisting of the first mixed powder and a core layer 100 consisting of the second mixed powder between the two coating layers 200.
Example 2
Referring to fig. 1, the multi-layer co-extrusion process of the high barrier gas phase rust preventive film of the present embodiment includes the following steps:
S1, preparing modified polyolefin
Weighing: 600g of polyethylene, 400g of polypropylene, 30g of maleic anhydride, 60g of glycidyl methacrylate, 10g of dicumyl peroxide and 100g of acetone are uniformly mixed, the mixture is added into a double-screw extruder, the temperatures of 6 temperature sections from a feeding end to a discharging end of the double-screw extruder are 195 ℃, 200 ℃, 210 ℃ and 210 ℃, the main shaft rotation speed of the double-screw extruder is 20r/min, the mixture is subjected to melt extrusion through the double-screw extruder, water cooling and cooling molding, and after being pelletized at the rotation speed of 100r/min by a pelletizer, the mixture is transferred into a drying box with the temperature of 80-90 ℃, and vacuum drying is carried out until the mixture is constant in weight, thus obtaining a modified polyolefin crude product;
weighing: adding 100g of modified polyolefin crude product and 4500mL of dimethylbenzene into a three-neck flask, stirring, raising the temperature of the three-neck flask to reflux, preserving heat, stirring for 4h, filtering while the mixture is hot, naturally cooling the filtrate to room temperature, adding 3000mL of butanone into the filtrate, stirring for 40min, filtering, washing the filter cake with butanone for three times, pumping, transferring the filter cake into a drying box with the temperature of 60 ℃, and vacuum drying to constant weight to obtain the modified polyolefin.
S2, preparing composite fiber
Weighing: mixing 62000g nylon, 400g poly (m-xylylenediamine) adipamide and 101010g antioxidant, adding into a melt spinning machine, spinning at 240 deg.C, with a hole diameter of 0.1mm, melt spinning, stretching the spun fiber 3 times, air cooling to form, cutting to obtain composite fiber with a length of 3-5mm and a diameter of 10-20 μm.
S3, preparing toughened fiber
Adding 1mol/L hydrochloric acid, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1g:4mL:0.5g:60g, and uniformly mixing to obtain an activation solution;
Weighing: adding 100g of composite fiber and 800mL of activating solution into a beaker, increasing the temperature of the beaker to 55 ℃, performing ultrasonic dispersion for 55min, reducing the temperature of the beaker to room temperature, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying oven with the temperature of 70 ℃, and drying to constant weight to obtain modified fiber;
Weighing: 100g of modified fiber, 500mL of absolute ethyl alcohol, 60g of tetraethoxysilane, 40g of allyl triethoxysilane and 50g of triethoxy [4- (ethylene oxide-2-yl) butyl ] silane are added into a conical flask for ultrasonic dispersion for 13min, 150mL of 10vt percent ammonia water is added into the conical flask, the temperature of the conical flask is increased to 50 ℃, the ultrasonic reaction is carried out for 2.5h, the temperature of the conical flask is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is dried, the filter cake is transferred into a drying box with the temperature of 70 ℃ and is dried to constant weight, and the toughened fiber is obtained.
S4, preparing mixed powder I
Weighing: 500g of modified polyolefin and 500g of ethylene-vinyl alcohol copolymer are added into a pulverizer, pulverized, screened by a 60-mesh screen, and 10g of oleamide, 10g of calcium stearate, 10g of antioxidant PPD and 10g of dibutyl hydroxy toluene are added into the screened powder to obtain mixed powder I;
S5, preparing mixed powder II
Weighing: 300g of modified polyolefin, 600g of ethylene-vinyl alcohol copolymer and 150g of brominated butyl rubber are added into a pulverizer, pulverized, screened by a 60-mesh screen, and 10g of oleamide, 10g of calcium stearate, 10g of antioxidant PPD, 10g of dibutyl hydroxy toluene, 80g of toughening fiber and 20g of diphenyl disulfide are added into the screened powder to obtain mixed powder II.
S6, preparing an antirust film
Adding the first mixed powder into a first double-screw extruder, adding the second mixed powder into a second double-screw extruder, sequentially heating the first double-screw extruder from a feeding end to a discharging end at 195 ℃, 200 ℃, 210 ℃ and 210 ℃, sequentially heating the second double-screw extruder from the feeding end to the discharging end at 220 ℃, 230 ℃ and 230 ℃ at 15r/min, respectively melting and extruding the first mixed powder and the second mixed powder through the first double-screw extruder and the second double-screw extruder, and then injecting the first mixed powder and the second mixed powder into a multilayer co-extrusion film machine, and co-extruding to form an anti-rust film with two coating layers 200 consisting of the first mixed powder and a core layer 100 consisting of the second mixed powder between the two coating layers 200.
Example 3
Referring to fig. 1, the multi-layer co-extrusion process of the high barrier gas phase rust preventive film of the present embodiment includes the following steps:
S1, preparing modified polyolefin
Weighing: 600g of polyethylene, 400g of polypropylene, 30g of maleic anhydride, 60g of glycidyl methacrylate, 10g of dicumyl peroxide and 100g of acetone are uniformly mixed, the mixture is added into a double-screw extruder, the temperatures of 6 temperature sections from a feeding end to a discharging end of the double-screw extruder are 195 ℃, 200 ℃, 210 ℃ and 210 ℃, the main shaft rotation speed of the double-screw extruder is 20r/min, the mixture is subjected to melt extrusion through the double-screw extruder, water cooling and cooling molding, and after being pelletized at the rotation speed of 100r/min by a pelletizer, the mixture is transferred into a drying box with the temperature of 80-90 ℃, and vacuum drying is carried out until the mixture is constant in weight, thus obtaining a modified polyolefin crude product;
weighing: adding 100g of modified polyolefin crude product and 4500mL of dimethylbenzene into a three-neck flask, stirring, raising the temperature of the three-neck flask to reflux, preserving heat, stirring for 5h, filtering while the mixture is hot, naturally cooling the filtrate to room temperature, adding 3000mL of butanone into the filtrate, stirring for 50min, filtering, washing the filter cake with butanone for three times, pumping, transferring the filter cake into a drying box with the temperature of 65 ℃, and vacuum drying to constant weight to obtain the modified polyolefin.
S2, preparing composite fiber
Weighing: mixing 62000g nylon, 400g poly (m-xylylenediamine) adipamide and 101010g antioxidant, adding into a melt spinning machine, wherein the spinning temperature of the melt spinning machine is 250 ℃, the aperture of a spinneret plate is 0.1mm, carrying out melt spinning, stretching the sprayed spinning fiber 3 times, carrying out air cooling molding, and cutting to obtain the composite fiber with the length of 3-5mm and the diameter of 10-20 mu m.
S3, preparing toughened fiber
Adding 1mol/L hydrochloric acid, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1g:4mL:0.5g:60g, and uniformly mixing to obtain an activation solution;
Weighing: adding 100g of composite fiber and 800mL of activating solution into a beaker, increasing the temperature of the beaker to 60 ℃, performing ultrasonic dispersion for 60min, reducing the temperature of the beaker to room temperature, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying oven with the temperature of 75 ℃, and drying to constant weight to obtain modified fiber;
Weighing: 100g of modified fiber, 500mL of absolute ethyl alcohol, 60g of tetraethoxysilane, 40g of allyl triethoxysilane and 50g of triethoxy [4- (ethylene oxide-2-yl) butyl ] silane are added into a conical flask for ultrasonic dispersion for 15min, 150mL of 10vt percent ammonia water is added into the conical flask, the temperature of the conical flask is increased to 55 ℃, the ultrasonic reaction is carried out for 3h, the temperature of the conical flask is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is dried, the filter cake is transferred into a drying box with the temperature of 75 ℃ and is dried to constant weight, and the toughened fiber is obtained.
S4, preparing mixed powder I
Weighing: 500g of modified polyolefin and 500g of ethylene-vinyl alcohol copolymer are added into a pulverizer, pulverized, screened by a 60-mesh screen, and 10g of ethylene bis stearamide, 10g of magnesium stearate, 10g of anti-aging agent H and 10g of tertiary butyl hydroquinone are added into the screened powder to obtain mixed powder I;
S5, preparing mixed powder II
Weighing: 300g of modified polyolefin, 600g of ethylene-vinyl alcohol copolymer and 150g of brominated butyl rubber are added into a pulverizer, pulverized, screened by a 60-mesh screen, and 10g of ethylene bis stearamide, 10g of magnesium stearate, 10g of anti-aging agent H, 10g of tertiary butyl hydroquinone, 80g of toughening fiber and 20g of diphenyl disulfide are added into the screened powder to obtain mixed powder II.
S6, preparing an antirust film
Adding the first mixed powder into a first double-screw extruder, adding the second mixed powder into a second double-screw extruder, sequentially heating the first double-screw extruder from a feeding end to a discharging end at 195 ℃, 200 ℃, 210 ℃ and 210 ℃, sequentially heating the second double-screw extruder from the feeding end to the discharging end at 220 ℃, 230 ℃ and 230 ℃ at 15r/min, respectively melting and extruding the first mixed powder and the second mixed powder through the first double-screw extruder and the second double-screw extruder, and then injecting the first mixed powder and the second mixed powder into a multilayer co-extrusion film machine, and co-extruding to form an anti-rust film with two coating layers 200 consisting of the first mixed powder and a core layer 100 consisting of the second mixed powder between the two coating layers 200.
Comparative example 1
The difference between this comparative example and example 1 is that step S1 is eliminated and the modified polyolefin of step S4 and step S5 is replaced by a mixture of polyethylene and polypropylene in a weight ratio of 3:2.
Comparative example 2
The difference between this comparative example and example 1 is that step S3 is eliminated and the same amount of conjugate fibers is used to replace the toughening fibers in step S5.
Comparative example 3
The present comparative example differs from example 1 in that no toughening fiber was added in step S5.
Performance test:
The barrier properties and tensile properties of the antirust films prepared in examples 1 to 3 and comparative examples 1 to 3 were tested, wherein the barrier properties and mechanical properties were measured with reference to the standard GB/T40266-2021 for oxide barrier transparent plastic composite film for food packaging, general rule for bag quality, for oxygen transmission and water vapor transmission of test samples, and the tensile properties were measured with reference to the standard GB/T528-2009 for measurement of tensile stress strain properties of vulcanized rubber or thermoplastic rubber, for tensile strength and elongation at break, and the specific test results are shown in the following table:
Data analysis:
by comparing and analyzing the data in the table, the oxygen transmission capacity of the anti-rust film prepared by the invention is reduced to 0.12cm 3·(m2·24h·0.1MPa)-1, the water vapor transmission capacity is reduced to 0.06g (m 2·24h)-1, the tensile strength reaches 3.58MPa, the stretch-break elongation reaches 254.2%, and all detection data are superior to those of the comparative example, so that the anti-rust film prepared by the invention has good oxygen and water vapor barrier properties, can play a good anti-rust effect on materials, and also improves the tensile strength and the stretch-break elongation of the anti-rust film.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (3)
1. The high-barrier gas-phase antirust film comprises a core layer (100) and cladding layers (200) positioned on two sides of the core layer (100), and is characterized in that the core layer (100) consists of modified polyolefin, ethylene-vinyl alcohol copolymer, brominated butyl rubber, auxiliary additives, toughening fibers and catalysts, the two cladding layers (200) consist of modified polyolefin, ethylene-vinyl alcohol copolymer and auxiliary additives, the weight ratio of the modified polyolefin, ethylene-vinyl alcohol copolymer, brominated butyl rubber, auxiliary additives, toughening fibers and catalysts is 30:60:15:4:8:2, the weight ratio of the modified polyolefin, ethylene-vinyl alcohol copolymer and the auxiliary additives is 50:50:4, the catalysts are diphenyl disulfide, the auxiliary additives consist of lubricants, dispersants, antioxidants and the proportions of 1g to 1g, wherein the lubricants are one or more of butyl stearate, oleamide and ethylene bis stearamide, the dispersants are one or more of zinc stearate, cadmium stearate, magnesium stearate, one or more antioxidants are one or more of DPPPD and one or more antioxidants are DPH; the antioxidant is one or more of butyl hydroxy anisole, dibutyl hydroxy toluene and tertiary butyl hydroquinone;
the modified polyolefin is processed by the following steps:
Uniformly mixing polyethylene, polypropylene, maleic anhydride, glycidyl methacrylate, dicumyl peroxide and acetone, adding into a double-screw extruder, carrying out melt extrusion and granulation to obtain a modified polyolefin crude product, wherein the weight ratio of polyethylene, polypropylene, maleic anhydride, glycidyl methacrylate, dicumyl peroxide and acetone is 60:40:3:6:1:10, the temperature of 6 temperature sections of the double-screw extruder from a feeding end to a discharging end is 195 ℃,200 ℃, 210 ℃ and 210 ℃, the main shaft rotating speed of the double-screw extruder is 20r/min, carrying out melt extrusion through the double-screw extruder, carrying out water cooling and forming, and transferring into a drying box with the temperature of 80-90 ℃ after granulating through a granulator, and carrying out vacuum drying to constant weight to obtain the modified polyolefin crude product;
A2, adding the modified polyolefin crude product and the dimethylbenzene into a three-neck flask, stirring, heating the three-neck flask until the system flows back, preserving heat, stirring for 3-5h, filtering while the three-neck flask is hot, naturally cooling the filtrate to room temperature, adding the butanone into the filtrate, stirring for 30-50min, and performing aftertreatment to obtain the modified polyolefin, wherein the dosage ratio of the modified polyolefin crude product to the dimethylbenzene to the butanone is 1g:45mL:30mL;
the toughening fiber is processed by the following steps:
B1, adding the composite fiber and an activating solution into a beaker, raising the temperature of the beaker to 50-60 ℃, performing ultrasonic dispersion for 50-60min, and performing post-treatment to obtain a modified fiber, wherein the dosage ratio of the composite fiber to the activating solution is 1 g/8 mL, and the activating solution consists of 1mol/L hydrochloric acid, sodium nitrate, 15vt% hydrogen peroxide, sodium dodecyl sulfate and purified water according to the dosage ratio of 10mL:1 g/4 mL:0.5 g/60 g;
Adding modified fiber, absolute ethyl alcohol, tetraethoxysilane, allyl triethoxysilane and triethoxy [4- (ethylene oxide-2-yl) butyl ] silane into a conical flask, performing ultrasonic dispersion for 10-15min, adding 10vt percent ammonia water into the conical flask, heating the conical flask to 45-55 ℃, performing ultrasonic reaction for 2-3h, and performing post-treatment to obtain toughened fiber, wherein the dosage ratio of the modified fiber to the absolute ethyl alcohol to the tetraethoxysilane to the allyl triethoxysilane to the triethoxy [4- (ethylene oxide-2-yl) butyl ] silane to the 10vt percent ammonia water is 10g:50mL:6g:4g:5g:15mL;
The preparation method of the composite fiber comprises the following steps: uniformly mixing nylon 6, poly (m-xylylenediamine) adipamide and an antioxidant, adding the mixture into a melt spinning machine, carrying out melt spinning, stretching and cooling to obtain composite fibers, wherein the weight ratio of the nylon 6 to the poly (m-xylylenediamine) adipamide to the antioxidant is 20:4:0.1, the antioxidant is antioxidant 1010, the spinning temperature of the melt spinning machine is 230-250 ℃, the aperture of a spinneret plate is 0.1mm, and the sprayed spinning fibers are subjected to air cooling molding and cutting after 3 times stretching, so that the composite fibers with the length of 3-5mm and the diameter of 10-20 mu m are obtained.
2. The multilayer co-extrusion process of a high barrier vapor phase rust inhibitive film according to claim 1, comprising the steps of:
S1, adding modified polyolefin and ethylene-vinyl alcohol copolymer into a pulverizer, pulverizing, sieving with a 60-mesh sieve, and adding an auxiliary additive into the sieved powder to obtain mixed powder I;
s2, adding modified polyolefin, ethylene-vinyl alcohol copolymer and brominated butyl rubber into a pulverizer, pulverizing, sieving with a 60-mesh sieve, and adding auxiliary additives, toughening fibers and catalysts into the sieved powder to obtain mixed powder II;
S3, adding the mixed powder I into a double-screw extruder I, adding the mixed powder II into a double-screw extruder II, respectively carrying out melt extrusion on the mixed powder I and the mixed powder II through the double-screw extruder I and the double-screw extruder II, and then injecting the mixed powder I and the mixed powder II into a multilayer coextrusion film machine, and carrying out coextrusion to form the antirust film with two coating layers (200) composed of the mixed powder I and a core layer (100) composed of the mixed powder II between the two coating layers (200).
3. The multilayer coextrusion process according to claim 2, wherein the temperature of the 6 temperature sections from the feed end to the discharge end of the twin-screw extruder I is 195 ℃, 200 ℃, 210 ℃ and 210 ℃, the main shaft rotation speed of the twin-screw extruder is 15r/min, the temperature of the 6 temperature sections from the feed end to the discharge end of the twin-screw extruder II is 220 ℃, 230 ℃, and the main shaft rotation speed of the twin-screw extruder is 15r/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329586A (en) * | 2018-01-30 | 2018-07-27 | 苏州赛伍应用技术股份有限公司 | A kind of three-decker water vapor rejection film and preparation method thereof |
| CN114855444A (en) * | 2022-04-18 | 2022-08-05 | 南京工业大学 | Surface coating modification method for ultra-high molecular weight polyethylene fiber |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113045789A (en) * | 2021-04-15 | 2021-06-29 | 江南大学 | Polyolefin-based high-barrier film with renewable structure and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329586A (en) * | 2018-01-30 | 2018-07-27 | 苏州赛伍应用技术股份有限公司 | A kind of three-decker water vapor rejection film and preparation method thereof |
| CN114855444A (en) * | 2022-04-18 | 2022-08-05 | 南京工业大学 | Surface coating modification method for ultra-high molecular weight polyethylene fiber |
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