CN116178765B - Tape-casting low-water-vapor-permeability polyethylene film and preparation method thereof - Google Patents
Tape-casting low-water-vapor-permeability polyethylene film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tape-casting low-water-vapor-permeability polyethylene film and a preparation method thereof. According to the invention, the polyethylene film is prepared by adopting a tape casting molding process, the surface glossiness of the prepared polyethylene film is good, the raw material for preparing the polyethylene film is linear low-density polyethylene resin, the prepared polyethylene film has high tensile strength, the linear low-density polyethylene resin is modified by adding the nucleating agent, the crystallization rate of the polyethylene is high, the crystallinity is increased, the grain size is refined under the action of the nucleating agent, the tensile strength of the polyethylene film can be further improved, and the molding period of the polyethylene film is shortened; in addition, the crystallinity is increased, the grain size is thinned, and the compactness of the crystal is improved, so that the barrier property of the polyethylene film is improved, and the water vapor transmittance of the polyethylene film is reduced.
Description
Technical Field
The invention relates to the field of packaging, and particularly provides a tape-casting low-water-vapor-permeability polyethylene film and a preparation method thereof.
Background
LLDPE (Linear Low Density polyethylene) films have the characteristics of higher tensile strength, good tear resistance and puncture resistance, relatively low production cost and the like, and are widely applied to various fields of packaging films. In the field of polyethylene film production, "blow molding" and "casting" are two processes that are relatively common. The blow molding process has the characteristics of high production efficiency, low equipment investment and low material consumption, and the surface glossiness, flatness, thickness uniformity, flexibility, transparency and other properties of the polyethylene film produced by the casting process are better than those of the polyethylene film produced by the blow molding process. However, the polyethylene film produced by the casting process has poor mechanical properties because the polyethylene film is not subjected to biaxial stretching.
Chinese patent CN103012937B discloses a method for preparing a polyethylene cast film, in which a nucleating agent and polyethylene particles are mixed into an organic solvent respectively, the organic solvent is distilled off to crystallize the polyethylene particles, thereby obtaining polyethylene particles with improved crystallization, and finally the crystallized polyethylene particles are extruded and cast into a film, so as to prepare the polyethylene cast film. By adding the nucleating agent and matching with the crystallization step, the crystallization speed of the polyethylene in the process of processing the cast film is improved. However, when the nucleating agent is an inorganic nucleating agent such as talcum powder, the compatibility with the polyethylene matrix is poor, and the inorganic nucleating agent is unevenly dispersed in the polyethylene matrix, so that the uniformity of nucleation crystallization is affected, and the strength of the polyethylene film is further affected.
In addition, since LLDPE has a large apparent melt viscosity and poor flowability, it causes poor melt flow continuity in extrusion from a die, affects the stability of a cast-molded polyethylene film, and has high extrusion energy consumption and poor processability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low water vapor transmission rate polyethylene film formed by tape casting and a preparation method thereof, which are used for solving the problems of poor tensile strength, high apparent melt viscosity of LLDPE and the like of polyethylene film products produced by large apparent melt viscosity of LLDPE in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a tape-cast low water vapor transmission polyethylene film, comprising the steps of:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, heating and refluxing for reaction, filtering to remove the cuprous cyanide after the reaction is finished, and performing rotary evaporation to remove the N, N-dimethylformamide to obtain nitrile-substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyl trimethoxysilane and a nickel catalyst into methanol, introducing hydrogen for reaction, filtering to remove the nickel catalyst after the reaction is finished, and removing the methanol by rotary evaporation to obtain amino-substituted dodecyl trimethoxysilane;
s13, 1,3: adding 2, 4-dibenzylidene sorbitol and copper powder into acetone, introducing oxygen, heating for reaction, filtering to remove copper powder after the reaction is completed, and performing rotary evaporation to remove acetone to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3: adding 2, 4-dibenzylidene sorbitol and triethylamine into carbon tetrachloride, heating and refluxing for reaction, and removing carbon tetrachloride by rotary evaporation after the reaction is completed to obtain a reaction product;
s15, adding a reaction product into an ethanol water solution to obtain a mixed solution, adding nano silicon dioxide into the mixed solution, heating for reaction under stirring, filtering to obtain a filtered residue after the reaction is completed, and drying to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100: (0.1-1) melt blending to obtain a melt, and preparing the melt into the low water vapor transmission polyethylene film through a tape casting process.
Preferably, in S11, the mass ratio of 11-bromoundecyl trimethoxysilane, cuprous cyanide and N, N-dimethylformamide is 355:100: (2250-4500), the temperature of the heating reflux reaction is 110-130 ℃, the time of the heating reflux reaction is 10-15h, and the rotary steaming temperature is 140 ℃.
Preferably, in S12, the mass ratio of the nitrile group substituted undecyltrimethoxysilane, the nickel catalyst and the methanol is 300: (8-12): (1500-3000), the hydrogen gas is introduced into the reaction system at a pressure of 3-5MPa, a reaction temperature of 40-50 ℃, a reaction time of 10-15h and a rotary evaporation temperature of 55 ℃.
Preferably, in S13, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: (6-10): (1500-3000), the oxygen inlet amount is 10-20mL/min, the heating reaction condition is that the temperature is 60-80 ℃ for reaction for 1-3h, and the rotary evaporation temperature is 50 ℃.
Preferably, in S14, the amino group is substituted with dodecyl trimethoxysilane, and the aldehyde groups are 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300: (355-365): (10-20): (3000-5000), the temperature of the heating reflux reaction is 70-80 ℃, the time of the heating reflux reaction is 8-10h, and the rotary evaporation temperature is 65 ℃.
Preferably, in S15, the concentration of the ethanol aqueous solution is 95% (the mass percentage of ethanol in the ethanol aqueous solution is 95%), and the mass ratio of the reaction product, the nano silica and the ethanol is (650-670): 60: (2000-4000), stirring speed is 300-500r/min, heating reaction temperature is 40-60 ℃, and heating reaction time is 1-2h.
Preferably, in S15, the drying temperature is 40-60 ℃ and the drying time is 5-10h.
Preferably, in the step S2, the melt blending is performed in a single screw extruder, the screw speed is 30r/min, and the temperature of the melt blending is 170-200 ℃.
Preferably, in S2, the casting process specifically includes: and extruding and casting the melt to a casting roller through a die head, and cooling the melt through a cooling roller to obtain the cast low-water-vapor-permeability polyethylene film.
Preferably, the temperature of the die is 180 ℃, the temperature of the casting roll is 80 ℃, the drawing speed of the casting roll is 7m/min, and the temperature of the cooling roll is 25 ℃.
Preferably, in said S2, the LLDPE has a density of from 0.91 to 0.93g/cm 3 。
Preferably, the invention discloses a cast low water vapor transmission polyethylene film prepared by the preparation method of the cast low water vapor transmission polyethylene film.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a tape casting molding process is adopted to prepare the polyethylene film, the surface glossiness of the prepared polyethylene film is good, the raw material for preparing the polyethylene film is linear low-density polyethylene resin, the prepared polyethylene film has high tensile strength, the linear low-density polyethylene resin is modified by adding the nucleating agent, the crystallization nucleation process of the polyethylene is changed into heterogeneous nucleation from the original homogeneous nucleation under the action of the nucleating agent, the nucleating agent is used as a crystal nucleus of heterogeneous nucleation, so that the crystallization rate of the polyethylene is fast, the crystallinity is increased, the grain size is refined, the crystallization is more perfect, the stress of the polyethylene film is more uniform, the tensile strength of the polyethylene film can be further improved, and the molding cycle of the polyethylene film is shortened; in addition, the crystallinity is increased, the grain size is thinned, and the compactness of the crystal is improved, so that the barrier property of the polyethylene film is improved, and the water vapor transmittance of the polyethylene film is reduced.
The nucleating agent in the invention is an organic-inorganic composite nucleating agent, wherein nano silicon dioxide is used as an inorganic nucleating agent part in the organic-inorganic composite nucleating agent, and the ratio of 1,3: the 2, 4-dibenzylidene sorbitol is used as an organic nucleating agent part, and the inorganic nucleating agent nano silicon dioxide can be used as a crystal nucleus for heterogeneous nucleation of polyethylene, can be filled in a polyethylene molecular gap, so that the compactness of the polyethylene film is improved, and the barrier property of the polyethylene film is further improved; organic nucleating agent 1,3:2, 4-dibenzylidene sorbitol has good compatibility with polyethylene resin, can promote the rapid completion of the polyethylene crystallization process, shortens the molding period, and ensures the dimensional stability of the polyethylene film; the organic nucleating agent is connected with the inorganic nucleating agent through 11-bromoundecyl trimethoxysilane, so that the dispersion compatibility of the inorganic nucleating agent in the polyethylene resin is improved, and the barrier property of the polyethylene film is further improved; in the preparation process of the organic-inorganic composite nucleating agent, 11-bromoundecyl trimethoxysilane is firstly substituted by nitrile (-CN), then nitrile is converted into amino through hydrogenation addition to obtain amino substituted dodecyl trimethoxysilane, 1,3: catalytic oxidation of 2, 4-dibenzylidene sorbitol gives hydroformylation 1,3:2, 4-dibenzylidene sorbitol, amino-substituted dodecyl trimethoxysilane with hydroformylation 1,3:2, 4-dibenzylidene sorbitol reacts to connect two substances through stable chemical bonds, and siloxane in molecules is hydrolyzed into silanol to react with hydroxyl on the surface of nano silicon dioxide to prepare the organic-inorganic composite nucleating agent; wherein, as nitrile group is hydrogenated and added into amino, the number of straight-chain alkyl groups is changed into dodecyl, and when the number of carbon atoms in the straight-chain alkyl molecular chain reaches 12, the straight-chain alkyl groups can have lubricating effect on the resin after being added into the resin, so that the interfacial friction between resin molecules can be reduced, the viscosity of LLDPE melt is reduced, the fluidity is improved, and the stability of the polyethylene film prepared by a tape casting forming process is improved; amino-substituted dodecyl trimethoxysilane with hydroformylation 1,3: the stable chemical bond formed by the reaction of the 2, 4-dibenzylidene sorbitol is a carbon-nitrogen double bond (-C=N-), so that the Schiff base compound is prepared, and the Schiff base compound can inhibit and sterilize, so that the polyethylene film has the effects of inhibiting bacteria and preserving freshness when being reused in food packaging.
Drawings
FIG. 1 is a schematic illustration of the reaction of 11-bromoundecyl trimethoxysilane with cyanided to produce nitrile substituted undecyl trimethoxysilane according to the present invention;
FIG. 2 is a schematic illustration of the reaction of a nitrile substituted undecyltrimethoxysilane with hydrogen to produce an amino substituted dodecyltrimethoxysilane according to the present invention;
FIG. 3 shows the structure of the present invention 1,3: reaction of 2, 4-dibenzylidene sorbitol with oxygen to produce hydroformylation 1,3: schematic of the reaction of 2, 4-dibenzylidene sorbitol;
FIG. 4 shows amino-substituted dodecyl trimethoxysilane and hydroformylation 1,3 in accordance with the present invention: a reaction scheme for the reaction of 2, 4-dibenzylidene sorbitol;
FIG. 5 is a schematic molecular structure of the organic-inorganic composite nucleating agent prepared in the present invention;
FIG. 6 is a plot of tensile properties of the cast low water vapor transmission polyethylene films prepared in examples 1-5 and comparative examples 1-2 of the present invention;
FIG. 7 is a line graph of the results of melt flow property tests obtained by melt blending in examples 1-5 and comparative examples 1-2 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of a tape-casting low-water vapor-permeability polyethylene film, which comprises the following steps:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, wherein the mass ratio of the 11-bromoundecyl trimethoxysilane to the cuprous cyanide to the N, N-dimethylformamide is 355:100:2250 Heating and refluxing at 110 ℃ for 15 hours, filtering to remove cuprous cyanide after the reaction is completed, and performing rotary evaporation at 140 ℃ to remove N, N-dimethylformamide to obtain nitrile substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyltrimethoxysilane and a nickel catalyst into methanol, wherein the mass ratio of the nitrile-substituted undecyltrimethoxysilane to the nickel catalyst to the methanol is 300:8:1500, introducing hydrogen to react for 15h at 40 ℃, wherein the introducing amount of the hydrogen is that the pressure of a reaction system is 3MPa, filtering to remove a nickel catalyst after the reaction is finished, and performing rotary evaporation at 55 ℃ to remove methanol to obtain amino-substituted dodecyl trimethoxy silane;
s13, 1,3:2, 4-dibenzylidene sorbitol, copper powder were added to acetone, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: 6:1500, introducing oxygen, wherein the oxygen inlet amount is 10mL/min, heating at 60 ℃ for reaction for 3h, filtering to remove copper powder after the reaction is completed, and performing rotary evaporation at 50 ℃ to remove acetone to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3:2, 4-dibenzylidene sorbitol, triethylamine are added into carbon tetrachloride, amino-substituted dodecyl trimethoxy silane and hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300:355:10:3000 Heating and refluxing at 70 ℃ for reaction for 10 hours, and removing carbon tetrachloride by rotary evaporation at 65 ℃ after the reaction is completed to obtain a reaction product;
s15, adding the reaction product into a 95% ethanol water solution to obtain a mixed solution, and adding nano silicon dioxide into the mixed solution, wherein the mass ratio of the reaction product to the nano silicon dioxide to the ethanol water solution is 650:60:2000 Heating at 40 ℃ for reaction for 2 hours at the stirring speed of 300r/min, filtering to obtain a filtered residue after the reaction is completed, and drying at 40 ℃ for 10 hours to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100:0.1, melt blending in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 170 ℃, a melt is obtained, the melt is extruded and cast on a casting roller through a die head, and then cooled by a cooling roller, so that a low water vapor transmittance polyethylene film formed by casting is obtained; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Example 2
The embodiment discloses a preparation method of a tape-casting low-water vapor-permeability polyethylene film, which comprises the following steps:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, wherein the mass ratio of the 11-bromoundecyl trimethoxysilane to the cuprous cyanide to the N, N-dimethylformamide is 355:100:4500 Heating and refluxing at 130 ℃ for reaction for 10 hours, filtering to remove cuprous cyanide after the reaction is completed, and performing rotary evaporation at 140 ℃ to remove N, N-dimethylformamide to obtain nitrile substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyltrimethoxysilane and a nickel catalyst into methanol, wherein the mass ratio of the nitrile-substituted undecyltrimethoxysilane to the nickel catalyst to the methanol is 300:12:3000, introducing hydrogen to react for 10 hours at 50 ℃, wherein the introducing amount of the hydrogen is that the pressure of a reaction system is 5MPa, filtering to remove a nickel catalyst after the reaction is finished, and performing rotary evaporation at 55 ℃ to remove methanol to obtain amino-substituted dodecyl trimethoxy silane;
s13, 1,3:2, 4-dibenzylidene sorbitol, copper powder were added to acetone, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: 10:3000, introducing oxygen, wherein the oxygen introducing amount is 20mL/min, heating at 80 ℃ for reaction for 1h, filtering to remove copper powder after the reaction is completed, and performing rotary evaporation at 50 ℃ to remove acetone to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3:2, 4-dibenzylidene sorbitol, triethylamine are added into carbon tetrachloride, amino-substituted dodecyl trimethoxy silane and hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300:365:20:5000 Heating and refluxing at 80 ℃ for reaction for 8 hours, and removing carbon tetrachloride by rotary evaporation at 65 ℃ after the reaction is completed to obtain a reaction product;
s15, adding the reaction product into a 95% ethanol water solution to obtain a mixed solution, and adding nano silicon dioxide into the mixed solution, wherein the mass ratio of the reaction product to the nano silicon dioxide to the ethanol water solution is 670:60:4000 Heating at 60 ℃ for reaction for 1h at the stirring speed of 500r/min, filtering to obtain a filtered residue after the reaction is completed, and drying at 60 ℃ for 5h to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100:1, melt blending in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 200 ℃, a melt is obtained, the melt is extruded and cast on a casting roller through a die head, and then cooled by a cooling roller, so that a low water vapor transmittance polyethylene film formed by casting is obtained; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Example 3
The embodiment discloses a preparation method of a tape-casting low-water vapor-permeability polyethylene film, which comprises the following steps:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, wherein the mass ratio of the 11-bromoundecyl trimethoxysilane to the cuprous cyanide to the N, N-dimethylformamide is 355:100:2800 Heating and refluxing at 120 ℃ for 13 hours, filtering to remove cuprous cyanide after the reaction is completed, and performing rotary evaporation at 140 ℃ to remove N, N-dimethylformamide to obtain nitrile substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyltrimethoxysilane and a nickel catalyst into methanol, wherein the mass ratio of the nitrile-substituted undecyltrimethoxysilane to the nickel catalyst to the methanol is 300:9:1800, introducing hydrogen at 45 ℃ for reaction for 13 hours, wherein the pressure of a reaction system is 4MPa, filtering to remove a nickel catalyst after the reaction is finished, and performing rotary evaporation at 55 ℃ to remove methanol to obtain amino-substituted dodecyl trimethoxy silane;
s13, 1,3:2, 4-dibenzylidene sorbitol, copper powder were added to acetone, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: 7:1900, introducing oxygen with the oxygen inlet amount of 15mL/min, heating at 70 ℃ for 2h, filtering to remove copper powder after the reaction is completed, and performing rotary evaporation at 50 ℃ to remove acetone to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3:2, 4-dibenzylidene sorbitol, triethylamine are added into carbon tetrachloride, amino-substituted dodecyl trimethoxy silane and hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300:357.5:12.5:3500 Heating and refluxing at 75 ℃ for reaction for 9 hours, and removing carbon tetrachloride by rotary evaporation at 65 ℃ after the reaction is completed to obtain a reaction product;
s15, adding the reaction product into a 95% ethanol water solution to obtain a mixed solution, and adding nano silicon dioxide into the mixed solution, wherein the mass ratio of the reaction product to the nano silicon dioxide to the ethanol water solution is 655:60:2500 Heating at 45 ℃ for reaction for 2 hours at the stirring speed of 400r/min, filtering to obtain a filtered residue after the reaction is completed, and drying at 45 ℃ for 10 hours to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100:0.3, melt blending in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 180 ℃ to obtain a melt, extruding and casting the melt through a die head onto a casting roller, and cooling through a cooling roller to obtain a low water vapor transmittance polyethylene film formed by casting; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Example 4
The embodiment discloses a preparation method of a tape-casting low-water vapor-permeability polyethylene film, which comprises the following steps:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, wherein the mass ratio of the 11-bromoundecyl trimethoxysilane to the cuprous cyanide to the N, N-dimethylformamide is 355:100:3350 Heating and refluxing at 120 ℃ for 13 hours, filtering to remove cuprous cyanide after the reaction is completed, and performing rotary evaporation at 140 ℃ to remove N, N-dimethylformamide to obtain nitrile substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyltrimethoxysilane and a nickel catalyst into methanol, wherein the mass ratio of the nitrile-substituted undecyltrimethoxysilane to the nickel catalyst to the methanol is 300:10:2200, introducing hydrogen at 45 ℃ for reaction for 13 hours, wherein the introducing amount of the hydrogen is that the pressure of a reaction system is 4MPa, filtering to remove a nickel catalyst after the reaction is finished, and performing rotary evaporation at 55 ℃ to remove methanol to obtain amino-substituted dodecyl trimethoxy silane;
s13, 1,3:2, 4-dibenzylidene sorbitol, copper powder were added to acetone, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: 8:2300, introducing oxygen with the oxygen inlet amount of 15mL/min, heating at 70 ℃ for 2 hours, filtering to remove copper powder after the reaction is completed, and removing acetone by rotary evaporation at 50 ℃ to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3:2, 4-dibenzylidene sorbitol, triethylamine are added into carbon tetrachloride, amino-substituted dodecyl trimethoxy silane and hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300:360:15:4000 Heating and refluxing at 75 ℃ for reaction for 9 hours, and removing carbon tetrachloride by rotary evaporation at 65 ℃ after the reaction is completed to obtain a reaction product;
s15, adding the reaction product into a 95% ethanol water solution to obtain a mixed solution, and adding nano silicon dioxide into the mixed solution, wherein the mass ratio of the reaction product to the nano silicon dioxide to the ethanol water solution is 660:60:300 Heating at 50 ℃ for reaction for 1.5 hours at the stirring speed of 400r/min, filtering to obtain a filtered residue after the reaction is completed, and drying at 50 ℃ for 8 hours to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100:0.6, melt blending in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 185 ℃ to obtain a melt, extruding and casting the melt through a die head onto a casting roller, and cooling through a cooling roller to obtain a low water vapor transmittance polyethylene film formed by casting; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Example 5
The embodiment discloses a preparation method of a tape-casting low-water vapor-permeability polyethylene film, which comprises the following steps:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, wherein the mass ratio of the 11-bromoundecyl trimethoxysilane to the cuprous cyanide to the N, N-dimethylformamide is 355:100:3900 Heating and refluxing at 120 ℃ for 13 hours, filtering to remove cuprous cyanide after the reaction is completed, and performing rotary evaporation at 140 ℃ to remove N, N-dimethylformamide to obtain nitrile substituted undecyl trimethoxysilane;
s12, adding nitrile-substituted undecyltrimethoxysilane and a nickel catalyst into methanol, wherein the mass ratio of the nitrile-substituted undecyltrimethoxysilane to the nickel catalyst to the methanol is 300:11:2600, introducing hydrogen at 45 ℃ for reaction for 13 hours, wherein the pressure of a reaction system is 4MPa, filtering to remove a nickel catalyst after the reaction is finished, and performing rotary evaporation at 55 ℃ to remove methanol to obtain amino-substituted dodecyl trimethoxy silane;
s13, 1,3:2, 4-dibenzylidene sorbitol, copper powder were added to acetone, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: 9:2700, introducing oxygen with the oxygen inlet amount of 15mL/min, heating at 70 ℃ for 2h, filtering to remove copper powder after the reaction is completed, and removing acetone by rotary evaporation at 50 ℃ to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3:2, 4-dibenzylidene sorbitol, triethylamine are added into carbon tetrachloride, amino-substituted dodecyl trimethoxy silane and hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300:362.5:17.5:4500 Heating and refluxing at 75 ℃ for reaction for 9 hours, and removing carbon tetrachloride by rotary evaporation at 65 ℃ after the reaction is completed to obtain a reaction product;
s15, adding the reaction product into a 95% ethanol water solution to obtain a mixed solution, and adding nano silicon dioxide into the mixed solution, wherein the mass ratio of the reaction product to the nano silicon dioxide to the ethanol water solution is 665:60:3500 Heating at 55 ℃ for reaction for 1h at the stirring speed of 400r/min, filtering to obtain a filtered residue after the reaction is completed, and drying at 55 ℃ for 5h to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film: LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100:0.8, melt blending in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 190 ℃ to obtain a melt, extruding and casting the melt through a die head onto a casting roller, and cooling through a cooling roller to obtain a cast low-water-vapor-permeability polyethylene film; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Comparative example 1
A method for preparing a tape-cast low water vapor transmission polyethylene film, comprising the steps of:
melt blending LLDPE in a single screw extruder, wherein the screw rotating speed is 30r/min, the melt blending temperature is 185 ℃ to obtain a melt, extruding and casting the melt to a casting roller through a die head, and cooling the melt through a cooling roller to obtain a cast low-water-vapor-permeability polyethylene film; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
Comparative example 2
A method for preparing a tape-cast low water vapor transmission polyethylene film, comprising the steps of:
LLDPE, 11-bromoundecyltrimethoxysilane, 1,3:2, 4-dibenzylidene sorbitol and nano silicon dioxide according to the mass ratio of 100:0.28:0.28:0.04 in a single screw extruder, wherein the screw rotating speed is 30r/min, the temperature of the melt blending is 185 ℃ to obtain a melt, the melt is extruded and cast on a casting roller through a die head, and then cooled by a cooling roller to obtain a low water vapor transmittance polyethylene film formed by casting; wherein the temperature of the die head is 180 ℃, the temperature of the casting roller is 80 ℃, the traction speed of the casting roller is 7m/min, and the temperature of the cooling roller is 25 ℃.
In examples 1-5 and comparative examples 1-2, cuprous cyanide was purchased from national pharmaceutical systems chemical reagent limited, specification: AR (Shanghai test) is more than or equal to 99.0%; nickel catalysts were purchased from national pharmaceutical group chemicals, inc., specification: alfa-031276; copper powder was purchased from national pharmaceutical group chemical reagent limited, specifications: 2.7N 250-300 mesh (Shanghai test) more than or equal to 99.7%; the nano silicon dioxide is purchased from Shanghai Naieou nanotechnology Co., ltd, the average grain diameter is 500nm, and the product number is NO-O-001-2; LLDPE is purchased from China petrochemical, yangzhi petrochemical Co., ltd., trade mark: DFDA-7042, melt index: 2.2g/10min, density 0.92g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyethylene films produced were all 60 μm thick.
Test examples
(1) Tensile property test: the polyethylene films prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to tensile properties test, the test method being referred to the standard GB13022-91 "tensile properties test method for Plastic film", the tensile speed being 250.+ -. 25mm/min, and the test results being shown in Table 1:
as is clear from Table 1, the polyethylene film produced by the present invention has high tensile strength. In the comparative example, since no nucleating agent was added, the tensile strength of the produced polyethylene film was low, and in comparative example 2, the tensile strength was improved as compared with comparative example 1, but the inorganic nucleating agent, the organic nucleating agent and the coupling agent were added to the LLDPE in the form of physical mixture only, and the crystallization promoting effect was reduced and the reinforcing effect on the tensile strength of the polyethylene film was weakened as compared with the dispersion phase of the inorganic nucleating agent nanosilicon dioxide in the LLDPE in example 4, in which the inorganic nucleating agent and the organic nucleating agent were connected by a stable chemical bond through the coupling agent;
(2) Barrier performance test: the polyethylene films prepared in examples 1-5 and comparative examples 1-2 were subjected to barrier property testing by referring to the standard ASTM F1249-2020, with the test results shown in Table 2:
as is clear from Table 2, the polyethylene film produced by the present invention has low water vapor permeability. In comparative example 1, the water vapor transmission rate was higher because no nucleating agent was added, whereas in comparative example 2, the water vapor transmission rate was lower than in comparative example, but higher than that of the polyethylene film produced in examples, because the inorganic nucleating agent nano silica was added;
(3) Antibacterial performance test: the polyethylene films prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to antibacterial property test by referring to the standard QB/T2591-2003 "antibacterial property test method and antibacterial effect of antibacterial plastics", and the test structures are shown in Table 3:
as can be seen from Table 3, the polyethylene film prepared by the invention has good antibacterial effect. In comparative example 1, since no organic-inorganic composite nucleating agent, i.e., no Schiff base, was added, the antibacterial effect was greatly reduced; in comparative example 2, although an inorganic nucleating agent and an organic nucleating agent were added, the inorganic nucleating agent and the organic nucleating agent did not react to form schiff base, and thus the antibacterial effect was comparable to comparative example 1;
(4) Melt blending in examples 1-5 and comparative examples 1-2 gave melt flow property tests: test methods reference to the determination of the Plastic thermoplastic melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) section 1, standard GB/T3682.1-2018: standard method, test temperature 190 ℃, test results are shown in Table 4:
as can be seen from Table 4, under the action of the organic-inorganic composite nucleating agent, LLDPE has high melt mass flow rate and good flow property, and can be applied to the preparation of polyethylene films by a tape casting process. In the comparative example, since the alkyl straight chain having a lubricating effect is not formed, the melt viscosity of LLDPE cannot be reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for preparing a tape-cast low water vapor transmission polyethylene film, comprising the steps of:
s1, preparing an organic-inorganic composite nucleating agent, which specifically comprises the following steps:
s11, adding 11-bromoundecyl trimethoxysilane and cuprous cyanide into N, N-dimethylformamide, heating and refluxing for reaction, and filtering and rotary steaming after the reaction is finished to obtain cyano-substituted undecyl trimethoxysilane;
s12, adding cyano-substituted undecyl trimethoxysilane and a nickel catalyst into methanol, introducing hydrogen for reaction, and filtering and steaming after the reaction is finished to obtain amino-substituted dodecyl trimethoxysilane;
s13, 1,3: adding 2, 4-dibenzylidene sorbitol and copper powder into acetone, introducing oxygen, heating for reaction, filtering after the reaction is completed, and performing rotary evaporation to obtain hydroformylation 1,3:2, 4-dibenzylidene sorbitol;
s14, amino-substituted dodecyl trimethoxy silane is subjected to hydroformylation 1,3: adding 2, 4-dibenzylidene sorbitol and triethylamine into carbon tetrachloride, heating and refluxing for reaction, and performing rotary evaporation after the reaction is completed to obtain a reaction product;
s15, adding a reaction product into an ethanol water solution to obtain a mixed solution, adding nano silicon dioxide into the mixed solution, heating for reaction under stirring, filtering after the reaction is completed, and drying to obtain the organic-inorganic composite nucleating agent;
s2, preparing a polyethylene film:
LLDPE and an organic-inorganic composite nucleating agent are mixed according to the mass ratio of 100: (0.1-1) melt blending to obtain a melt, and preparing the melt into the low water vapor transmission polyethylene film through a tape casting process.
2. The method for preparing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S11, the mass ratio of 11-bromoundecyl trimethoxysilane, cuprous cyanide, and N, N-dimethylformamide is 355:100: (2250-4500), the temperature of the heating reflux reaction is 110-130 ℃, the time of the heating reflux reaction is 10-15h, and the rotary steaming temperature is 140 ℃.
3. The method for preparing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S12, the mass ratio of cyano-substituted undecyltrimethoxysilane, nickel catalyst, and methanol is 300: (8-12): (1500-3000), the hydrogen gas is introduced into the reaction system at a pressure of 3-5MPa, a reaction temperature of 40-50 ℃, a reaction time of 10-15h and a rotary evaporation temperature of 55 ℃.
4. The method for producing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S13, 1,3: mass ratio 358 of 2, 4-dibenzylidene sorbitol, copper powder and acetone: (6-10): (1500-3000), the oxygen inlet amount is 10-20mL/min, the heating reaction condition is that the temperature is 60-80 ℃ for reaction for 1-3h, and the rotary evaporation temperature is 50 ℃.
5. The method for producing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S14, amino-substituted dodecyl trimethoxysilane, hydroformylation 1,3: the mass ratio of the 2, 4-dibenzylidene sorbitol to the triethylamine to the carbon tetrachloride is 300: (355-365): (10-20): (3000-5000), the temperature of the heating reflux reaction is 70-80 ℃, the time of the heating reflux reaction is 8-10h, and the rotary evaporation temperature is 65 ℃.
6. The method for preparing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S15, the mass ratio of the reaction product, nano silica, and ethanol is (650-670): 60: (2000-4000), stirring speed is 300-500r/min, heating reaction temperature is 40-60 ℃, and heating reaction time is 1-2h.
7. The method for producing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S2, the melt blending is performed in a single screw extruder at a screw speed of 30r/min and at a temperature of 170 to 200 ℃.
8. The method for preparing a low water vapor transmission rate polyethylene film according to claim 1, wherein in S2, the casting process specifically comprises:
and extruding and casting the melt to a casting roller through a die head, and cooling the melt through a cooling roller to obtain the cast low-water-vapor-permeability polyethylene film.
9. The method for producing a low water vapor transmission rate polyethylene film according to claim 8, wherein the die temperature is 180 ℃, the casting roll temperature is 80 ℃, the drawing speed of the casting roll is 7m/min, and the cooling roll temperature is 25 ℃.
10. A cast low water vapor transmission polyethylene film produced by the method for producing a cast low water vapor transmission polyethylene film according to any one of claims 1 to 9.
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