CN111234366B - Ultraviolet-resistant antifogging polyethylene greenhouse film and preparation method thereof - Google Patents
Ultraviolet-resistant antifogging polyethylene greenhouse film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-ultraviolet antifogging polyethylene greenhouse film and a preparation method thereof, wherein raw materials comprise LLDPE resin, LDPE resin, EVA plastic and an anti-ultraviolet antifogging agent; putting the raw materials into a high-speed mixing stirrer in proportion, mixing and stirring for 10min at the temperature of 60 ℃ at the speed of 300r/min, extruding and granulating at the extrusion temperature of 170 ℃, and then carrying out extrusion casting, cooling, trimming, pressurizing and rolling to obtain the ultraviolet-resistant antifogging polyethylene greenhouse film. The invention covalently grafts the glyceryl monooleate on rGO/SiO by free radical reaction2Obtaining an anti-ultraviolet antifogging agent on the surface; glyceryl monooleate and hybrid material rGO-SiO2Surface active functional groups such as hydroxyl and carboxyl are subjected to better chemical reaction, so that the poly glyceryl monooleate is not easy to continuously reduce along with the movement of molecules to the surface of the film; the method of inorganic grafting and the combination of the dripping agent and the high molecular main chain grafting further prolongs the precipitation speed of the dripping agent and controls the precipitation amount.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an ultraviolet-resistant antifogging polyethylene greenhouse film and a preparation method thereof.
Background
Polyethylene (PE) is a thermoplastic resin obtained by polymerizing ethylene. In industry, copolymers of ethylene with small amounts of alpha-olefins are also included. The polyethylene is odorless and nontoxic, feels like wax, has excellent low-temperature resistance (the lowest use temperature can reach-100 to-70 ℃), has good chemical stability, and can resist most of acid and alkali erosion (cannot resist acid with oxidation property). Is insoluble in common solvents at room temperature, has low water absorption and excellent electrical insulation.
The surface tension of the polyethylene is 3.0 x 10-2Newton/m, and the surface tension of water is 7.2X 10-2Newton/m, the surface tension difference is too large, thus causing dew drops to be gathered on the surface of the common polyethylene greenhouse film. The essence of the antifogging agent is a surfactant which has two functional groups of hydrophile and lipophile, the oleophylic group extends to the interior of the greenhouse film, and the hydrophilic group faces to the exterior of the film.
The surface of the inorganic nano particle has special performance, and the extremely strong surface activity enables the inorganic nano particle to easily have a bonding effect with oxygen in resin, so that the effect of changing weak bond electron cloud is achieved, and the bonding force of molecules is improved; in addition, the compounding of the inorganic nanoparticles is also beneficial to improving the dispersion degree of the inorganic nanoparticles, and the nanoscale dispersion as small as possible is obtained by obtaining the existence state of ideal nanoparticles in a polymer, so that the generation of the nano effect of the nanoparticles is ensured; the acting force between the nano-material and the polymer chain segment can be strengthened, weak bonds in the polymer chain segment are protected, the service life of the material is prolonged, and the long-acting property of the nano-effect is ensured; meanwhile, the nano-particles have strong light scattering characteristics, and the light scattering is the main optical property of the nano-particles. If inorganic nano particles with strong reflection to ultraviolet rays are selected, the nano particles can have obvious blocking effect on ultraviolet rays in a range and do not influence the light transmittance of the agricultural film after being compounded with the agricultural film base material, and the inorganic nano material has a certain crystallization nucleation effect and can promote the refinement of polymer grains.
The nanometer sweet osmanthus dioxide is amorphous white powder, unsaturated residual bonds and light groups in different bonding states exist on the surface, the molecular state of the nanometer sweet osmanthus dioxide is a three-dimensional chain structure or a three-dimensional cassiterite structure with a three-dimensional net structure, and the like, and the free permeation effect of the nanometer sweet osmanthus dioxide is that the nanometer sweet osmanthus dioxide can penetrate into the vicinity of the unsaturated bonds of the material due to the small-size effect and the macroscopic quantum channel effect and acts with electron clouds to be combined with macromolecules of the material into a three-dimensional net structure; in addition, the bay oxide tetrahedron of the cinnamon dioxide is an electrovalence unsaturated structure, has good activity, particularly has stronger specific surface area and activity after the particle size reaches a nanometer level, and can be chemically combined with a polymer matrix, thereby achieving the effects of improving and improving degrees, strength and stability of the material. The nanometer cinnamon dioxide has special optical performance which is not possessed by the conventional doll dioxide, the extremely small particle size enables the nanometer cinnamon dioxide to be well dispersed in materials, simultaneously, the nanometer cinnamon dioxide also has the function of scattering ultraviolet rays, has extremely strong ultraviolet absorption and infrared reflection characteristics, and has good intermiscibility with linear low-density polyethylene.
The antifogging agent for greenhouse film is non-ionic surfactant comprising two parts of hydrophilic group and lipophilic group. Hydrophilic groups such as carboxyl (-COOH), hydroxyl (-OH), amino (-NH)2-ether linkage (-CH)2─CH2O-or the like, the lipophilic group generally being a long-chain alkyl group CnH2n+1. The polarity of the hydrophilic group determines the hydrophilicity, and the length of the lipophilic carbon chain determines the compatibility with the resin. The antifogging agent with strong hydrophilicity and long oleophylic group has good compatibility with resin, slow migration rate and good lasting antifogging effect; the antifogging agent with strong hydrophilicity and short lipophilic group has high migration rate and good initial antifogging effect.
The antifogging agent is added into the film and gradually migrates to the surface of the greenhouse film along with molecular motion to cover on the low-energy surface of the polyethylene greenhouse film, so that the surface tension of the greenhouse film is increased, the hydrophilic end of the antifogging agent is compatible with water, the surface tension of water drops is reduced, the water is close to the surface tension of the greenhouse film, the water drops attached to the inner surface of the greenhouse film are spread to form a thin water film, and the antifogging effect is achieved by considering the flowing-down of the greenhouse film, which is an important mechanism of the antifogging agent. However, the amount of the antifogging agent is reduced continuously along with the movement of molecules to the surface of the film, and the antifogging effect cannot be achieved when a certain time period is reached. (rGO/SiO)2The g-PGMO can be bonded into the LLDPE matrix, making it difficult for the antifogging agent to be extracted from the LLDPE matrix (to play a major role), on the one hand, and the rGO/SiO2g-PGMO can prevent the ungrafted antifogging agent from being separated out, so that the antifogging time is prolonged.
Disclosure of Invention
In order to make up for the defects in the background art, the invention provides an anti-ultraviolet antifogging polyethylene greenhouse film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an anti-ultraviolet antifogging polyethylene greenhouse film comprises the following components in parts by weight;
LLDPE resin: 100 parts of (A);
LDPE resin: 30 parts of (1);
EVA plastics: 30 parts of (1);
anti-ultraviolet antifogging agent rGO/SiO2-g-PGMO: 5-15 parts;
the LLDPE resin is a linear low density polyethylene, LLDPE is typically produced by copolymerizing ethylene and a higher alpha olefin, such as butene, hexene or octene, at lower temperatures and pressures. The copolymerization process produces LLDPE polymers having a narrower molecular weight distribution than typical LDPE's, while having a linear structure that imparts different rheological characteristics. The melt flow characteristics of LLDPE are adapted to the requirements of new processes, especially film extrusion processes, to yield high quality LLDPE products.
The LDPE resin is low-density polyethylene, the low-density polyethylene usually takes ethylene as a monomer, oxygen or organic peroxide as an initiator under the high pressure of 98.0-294 MPa, and the density of the polymer obtained by polymerization is 0.910-0.9259 g/cm3. The low density polyethylene molecular chain has long and short branched chains. The crystallinity is low, the molecular weight is generally 5-50 ten thousand, and the resin is milky semitransparent waxy solid resin and is non-toxic. The softening point is lower, the material is melted when the softening point is exceeded, and the material has good heat fusion property, good forming and processing properties, good flexibility, good impact toughness and good low temperature resistance.
The EVA plastic is an ethylene-vinyl acetate copolymer. The content of the Vinyl Acetate (VA) is 5-40%, compared with Polyethylene (PE), the EVA has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, and the toughness, the impact resistance, the filler compatibility and the heat sealing performance are improved. EVA products with the vinyl acetate content of 5-10% are elastic films and the like. EVA has the characteristics of good flexibility, rubber elasticity, good flexibility, transparency, surface gloss, good chemical stability, good aging resistance and ozone resistance, and no toxicity at the temperature of-50 ℃. Has good mixing property with the filler, coloring property and molding processability.
The anti-ultraviolet antifogging agent rGO/SiO2The preparation method of the-g-PGMO comprises the following steps:
（1）rGO/SiO2the preparation of (1): dissolving 2g of CTAB (cetyl trimethyl ammonium bromide) in 280ml of deionized water at room temperature, adding 50ml of 1, 4-dioxane, 40ml of ethanol and a certain amount of ammonia water, and magnetically stirring; after 30min, 10ml of TEOS (tetraethyl orthosilicate) and a certain amount of graphene oxide ethanol solution are dripped into the solution and stirred to react for 4 h; after 4h hydrochloric acid was added to ph 7 and stirred for 15 min. Washing and centrifuging with ethanol and deionized water to obtain graphene oxide modified nano silicon dioxide (GO-SiO)2) In N2Calcining at the high temperature of 800 ℃ for 4h under the protection of atmosphere to obtain the graphene modified nano silicon dioxide composite material rGO/SiO2。
（2）rGO/SiO2-g-PGMO: the glycerol monooleate is weighed and added into a three-neck flask, and the mixture is heated in a constant-temperature water bath kettle at 60 ℃ to be melted. After the glyceryl monooleate is completely melted, slowly adding the mesoporous silicon dioxide modified by the graphene oxide and the initiator BPO while stirring. Then, in N2Reacting for 4 hours in a protected environment to obtain rGO/SiO2g-PGMO, washed several times by filtration with acetone until the upper liquid is clear. Finally, evaporating the residual acetone by using a rotary evaporator, and drying in a vacuum drying oven to obtain purified rGO/SiO2g-PGMO (mass ratio of SiO2 to glycerol monooleate 1: 3).
The preparation method of the ultraviolet-resistant antifogging polyethylene greenhouse film comprises the following steps: the LLDPE resin, the LDPE resin, the EVA plastic and the anti-ultraviolet antifogging agent are put into a high-speed mixing stirrer in proportion, mixed and stirred for 10min at the temperature of 60 ℃ at 300r/min in the stirrer to be uniformly mixed, and extruded and granulated at the extrusion temperature of 170 ℃; and extruding, casting, cooling, trimming, pressurizing and rolling the obtained particles to obtain the ultraviolet-resistant antifogging polyethylene cast film product.
Further, the casting process is direct casting, the casting roller is a chromium-plated steel roller, the thickness of the chromium-plated layer is 0.01-0.015 mm, the diameter of the steel roller is 500mm, and the middle height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
Further, the pressurizing and rolling process comprises pressurizing and rolling on a 60-65A liquid silica gel rubber roll, wherein the pressurizing pressure is 5-8 Kgf.
Has the advantages that:
(1) the mesoporous silica is inorganic nano particle with relatively high light scattering characteristic and light scattering as its main optical property. After the mesoporous silicon dioxide and the polyethylene agricultural film are compounded, the compound film has obvious blocking effect on ultraviolet rays in a range and does not influence the light transmittance of the agricultural film, and the inorganic nano material has certain crystallization and nucleation effects and can promote the refinement of polymer grains;
(2) the invention carries out surface modification on mesoporous silicon dioxide by cetyl trimethyl ammonium bromide, and leads SiO to be ionized after the introduced amino2The surface of the particle is positively charged; reacting negatively charged GO with positively charged SiO2The particles are combined together by electrostatic action to form GO-SiO2A hybrid material; in addition, the high-temperature calcination is used for removing redundant organic cetyl trimethyl ammonium bromide during the preparation of silicon dioxide on one hand, and is used for facilitating the growth of crystal grains and improving the crystallinity on the other hand; secondly, the obtained hybrid material rGO-SiO is calcined2The composite material is prepared by blending the rGO and the PE matrix, so that the rGO and the SiO can be fully utilized2The mutual blocking effect of the particles inhibits the agglomeration of the particles in a matrix, and simultaneously, the synergistic enhancement, toughening and modification effects of the particles and the PE are fully exerted. Glyceryl monooleate GMO is covalently grafted on reduced graphene oxide modified nano silicon dioxide (rGO/SiO) through free radical reaction2) Surface formation of rGO/SiO2-g-PGMO; glyceryl monooleate GMO and hybrid material rGO-SiO2The surface active functional groups such as hydroxyl and carboxyl have better chemical reaction, so that the PGMO is not easy to reduce continuously along with the movement of molecules to the surface of the film. By combining inorganic grafting and the grafting of the dripping agent and the high molecular main chain, the precipitation speed of the dripping agent is further prolonged andcontrolling the precipitation amount.
Drawings
FIG. 1 shows the anti-UV antifogging agent rGO/SiO prepared in example 12-ir spectrum of g-PGMO;
FIG. 2 shows the anti-UV antifogging agent rGO/SiO prepared in example 12SEM picture of g-PGMO.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
An ultraviolet-resistant antifogging polyethylene greenhouse film comprises the following components in parts by weight:
LLDPE resin: 100 parts of (A);
LDPE resin: 30 parts of (1);
EVA plastics: 30 parts of (1);
anti-ultraviolet antifogging agent rGO/SiO2-g-PGMO: 5 parts of a mixture;
the LLDPE resin is a linear low density polyethylene, LLDPE is typically produced by copolymerizing ethylene and a higher alpha olefin, such as butene, hexene or octene, at lower temperatures and pressures. The copolymerization process produces LLDPE polymers having a narrower molecular weight distribution than typical LDPE's, while having a linear structure that imparts different rheological characteristics. The melt flow characteristics of LLDPE are adapted to the requirements of new processes, especially film extrusion processes, to yield high quality LLDPE products.
The LDPE resin is low-density polyethylene, the low-density polyethylene usually takes ethylene as a monomer, oxygen or organic peroxide as an initiator under the high pressure of 98.0-294 MPa, and the density of the polymer obtained by polymerization is 0.910-0.9259 g/cm3. The low density polyethylene molecular chain has long and short branched chains. The crystallinity is low, the molecular weight is generally 5-50 ten thousand, and the resin is milky semitransparent waxy solid resin and is non-toxic. The softening point is lower, the material is melted when the softening point is exceeded, and the material has good heat fusion property, good forming and processing properties, good flexibility, good impact toughness and good low temperature resistance.
The EVA plastic is an ethylene-vinyl acetate copolymer. The content of the Vinyl Acetate (VA) is 5-40%, compared with Polyethylene (PE), the EVA has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, and the toughness, the impact resistance, the filler compatibility and the heat sealing performance are improved. EVA products with the vinyl acetate content of 5-10% are elastic films and the like. EVA has the characteristics of good flexibility, rubber elasticity, good flexibility, transparency, surface gloss, good chemical stability, good aging resistance and ozone resistance, and no toxicity at the temperature of-50 ℃. Has good mixing property with the filler, coloring property and molding processability.
The anti-ultraviolet antifogging agent rGO/SiO2The preparation method of the-g-PGMO comprises the following steps:
rGO/SiO2the preparation of (1): dissolving 2g of CTAB (cetyl trimethyl ammonium bromide) in 280ml of deionized water at room temperature, adding 50ml of 1, 4-dioxane, 40ml of ethanol and a certain amount of ammonia water, and magnetically stirring; after 30min, 10ml of TEOS (tetraethyl orthosilicate) and a certain amount of graphene oxide ethanol solution are dripped into the solution and stirred to react for 4 h; after 4h hydrochloric acid was added to ph 7 and stirred for 15 min. Washing and centrifuging with ethanol and deionized water to obtain graphene oxide modified nano silicon dioxide (GO-SiO)2) In N2Calcining at the high temperature of 800 ℃ for 4h under the protection of atmosphere to obtain the graphene modified nano silicon dioxide composite material rGO/SiO2。
rGO/SiO2-g-PGMO: the glycerol monooleate is weighed and added into a three-neck flask, and the mixture is heated in a constant-temperature water bath kettle at 60 ℃ to be melted. After the glyceryl monooleate is completely melted, slowly adding the mesoporous silicon dioxide modified by the graphene oxide and the initiator BPO while stirring. Then, in N2Reacting for 4 hours in a protected environment to obtain rGO/SiO2g-PGMO, washed several times by filtration with acetone until the upper liquid is clear. Finally, evaporating the residual acetone by using a rotary evaporator, and drying in a vacuum drying oven to obtain purified rGO/SiO2-g-PGMO（SiO2The mass ratio of the glycerol monooleate to the glycerol monooleate is 1: 3).
The preparation method comprises the following steps: the LLDPE resin, the LDPE resin, the EVA plastic and the ultraviolet-resistant antifogging agent are put into a high-speed mixing stirrer in proportion, mixed and stirred for 10min at the temperature of 60 ℃ at the speed of 300r/min in the stirrer to be uniformly mixed, and extruded and granulated at the extrusion temperature of 170 ℃. And extruding, casting, cooling, trimming, pressurizing and rolling the obtained particles to obtain the ultraviolet-resistant antifogging polyethylene cast film product.
The casting process is direct casting, the casting roller is a chromium-plated steel roller, the thickness of the chromium plating layer is 0.01-0.015 mm, the diameter of the steel roller is 500mm, and the height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
The pressurizing and rolling process comprises the step of pressurizing and rolling on a 60-65A liquid silica gel rubber roller, wherein the pressurizing pressure is 5 Kgf.
Example 2
An ultraviolet-resistant antifogging polyethylene greenhouse film comprises the following components in parts by weight:
LLDPE resin: 100 parts of (A);
LDPE resin: 30 parts of (1);
EVA plastics: 30 parts of (1);
anti-ultraviolet antifogging agent rGO/SiO2-g-PGMO: 10 parts of (A);
the LLDPE resin is a linear low density polyethylene, LLDPE is typically produced by copolymerizing ethylene and a higher alpha olefin, such as butene, hexene or octene, at lower temperatures and pressures. The copolymerization process produces LLDPE polymers having a narrower molecular weight distribution than typical LDPE's, while having a linear structure that imparts different rheological characteristics. The melt flow characteristics of LLDPE are adapted to the requirements of new processes, especially film extrusion processes, to yield high quality LLDPE products.
The LDPE resin is low-density polyethylene, the low-density polyethylene usually takes ethylene as a monomer, oxygen or organic peroxide as an initiator under the high pressure of 98.0-294 MPa, and the density of the polymer obtained by polymerization is 0.910-0.9259 g/cm3. The low density polyethylene molecular chain has long and short branched chains. The crystallinity is low, the molecular weight is generally 5-50 ten thousand, and the resin is milky semitransparent waxy solid resin and is non-toxic. Lower softening point, aboveThe softening point is melting, and the hot melt adhesive property and the molding processability are good, the flexibility is good, and the impact toughness and the low temperature resistance are good.
The EVA plastic is an ethylene-vinyl acetate copolymer. The content of the Vinyl Acetate (VA) is 5-40%, compared with Polyethylene (PE), the EVA has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, and the toughness, the impact resistance, the filler compatibility and the heat sealing performance are improved. EVA products with the vinyl acetate content of 5-10% are elastic films and the like. EVA has the characteristics of good flexibility, rubber elasticity, good flexibility, transparency, surface gloss, good chemical stability, good aging resistance and ozone resistance, and no toxicity at the temperature of-50 ℃. Has good mixing property with the filler, coloring property and molding processability.
The anti-ultraviolet antifogging agent rGO/SiO2The preparation method of the-g-PGMO comprises the following steps:
rGO/SiO2the preparation of (1): dissolving 2g of CTAB (cetyl trimethyl ammonium bromide) in 280ml of deionized water at room temperature, adding 50ml of 1, 4-dioxane, 40ml of ethanol and a certain amount of ammonia water, and magnetically stirring; after 30min, 10ml of TEOS (tetraethyl orthosilicate) and a certain amount of graphene oxide ethanol solution are dripped into the solution and stirred to react for 4 h; after 4h hydrochloric acid was added to ph 7 and stirred for 15 min. Washing and centrifuging with ethanol and deionized water to obtain graphene oxide modified nano silicon dioxide (GO-SiO)2) In N2Calcining at the high temperature of 800 ℃ for 4h under the protection of atmosphere to obtain the graphene modified nano silicon dioxide composite material rGO/SiO2。
rGO/SiO2-g-PGMO: the glycerol monooleate is weighed and added into a three-neck flask, and the mixture is heated in a constant-temperature water bath kettle at 60 ℃ to be melted. After the glyceryl monooleate is completely melted, slowly adding the mesoporous silicon dioxide modified by the graphene oxide and the initiator BPO while stirring. Then, in N2Reacting for 4 hours in a protected environment to obtain rGO/SiO2g-PGMO, washed several times by filtration with acetone until the upper liquid is clear. Finally, the remaining residue was evaporated off using a rotary evaporatorAcetone is put into a vacuum drying oven for drying to obtain purified rGO/SiO2-g-PGMO（SiO2The mass ratio of the glycerol monooleate to the glycerol monooleate is 1: 3).
The preparation method comprises the following steps: the LLDPE resin, the LDPE resin, the EVA plastic and the ultraviolet-resistant antifogging agent are put into a high-speed mixing stirrer in proportion, mixed and stirred for 10min at the temperature of 60 ℃ at the speed of 300r/min in the stirrer to be uniformly mixed, and extruded and granulated at the extrusion temperature of 170 ℃. And extruding, casting, cooling, trimming, pressurizing and rolling the obtained particles to obtain the ultraviolet-resistant antifogging polyethylene cast film product.
The casting process is direct casting, the casting roller is a chromium-plated steel roller, the thickness of the chromium plating layer is 0.01-0.015 mm, the diameter of the steel roller is 500mm, and the height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
The pressurizing and rolling process comprises the step of pressurizing and rolling on a 60-65A liquid silica gel rubber roller, wherein the pressurizing pressure is 5 Kgf.
Example 3
An ultraviolet-resistant antifogging polyethylene greenhouse film comprises the following components in parts by weight:
LLDPE resin: 100 parts of (A);
LDPE resin: 30 parts of (1);
EVA plastics: 30 parts of (1);
anti-ultraviolet antifogging agent rGO/SiO2-g-PGMO: 15 parts of (1);
the LLDPE resin is a linear low density polyethylene, LLDPE is typically produced by copolymerizing ethylene and a higher alpha olefin, such as butene, hexene or octene, at lower temperatures and pressures. The copolymerization process produces LLDPE polymers having a narrower molecular weight distribution than typical LDPE's, while having a linear structure that imparts different rheological characteristics. The melt flow characteristics of LLDPE are adapted to the requirements of new processes, especially film extrusion processes, to yield high quality LLDPE products.
The LDPE resin is low-density polyethylene, the low-density polyethylene usually takes ethylene as a monomer, oxygen or organic peroxide is used as an initiator under the high pressure of 98.0-294 MPa, and the density of the polymer obtained by polymerization is 0.910-0.9259/cm 3. The low density polyethylene molecular chain has long and short branched chains. The crystallinity is low, the molecular weight is generally 5-50 ten thousand, and the resin is milky semitransparent waxy solid resin and is non-toxic. The softening point is lower, the material is melted when the softening point is exceeded, and the material has good heat fusion property, good forming and processing properties, good flexibility, good impact toughness and good low temperature resistance.
The EVA plastic is an ethylene-vinyl acetate copolymer. The content of the Vinyl Acetate (VA) is 5-40%, compared with Polyethylene (PE), the EVA has the advantages that the vinyl acetate monomer is introduced into the molecular chain, so that the high crystallinity is reduced, and the toughness, the impact resistance, the filler compatibility and the heat sealing performance are improved. EVA products with the vinyl acetate content of 5-10% are elastic films and the like. EVA has the characteristics of good flexibility, rubber elasticity, good flexibility, transparency, surface gloss, good chemical stability, good aging resistance and ozone resistance, and no toxicity at the temperature of-50 ℃. Has good mixing property with the filler, coloring property and molding processability.
The anti-ultraviolet antifogging agent rGO/SiO2The preparation method of the-g-PGMO comprises the following steps:
rGO/SiO2the preparation of (1): dissolving 2g of CTAB (cetyl trimethyl ammonium bromide) in 280ml of deionized water at room temperature, adding 50ml of 1, 4-dioxane, 40ml of ethanol and a certain amount of ammonia water, and magnetically stirring; after 30min, 10ml of TEOS (tetraethyl orthosilicate) and a certain amount of graphene oxide ethanol solution are dripped into the solution and stirred to react for 4 h; after 4h hydrochloric acid was added to ph 7 and stirred for 15 min. Washing and centrifuging with ethanol and deionized water to obtain graphene oxide modified nano silicon dioxide (GO-SiO)2) In N2Calcining at the high temperature of 800 ℃ for 4 hours under the protection of atmosphere to obtain the graphene modified nano silicon dioxide composite material rGO/SiO2。
rGO/SiO2-g-PGMO: the glycerol monooleate is weighed and added into a three-neck flask, and the mixture is heated in a constant-temperature water bath at 60 ℃ to be melted. After the glyceryl monooleate is completely melted, slowly adding the mesoporous silicon dioxide modified by the graphene oxide and the initiator BPO while stirring. Then, in N2In a protected environmentReacting for 4 hours to obtain rGO/SiO2g-PGMO, washed several times by filtration with acetone until the upper liquid is clear. Finally, evaporating the residual acetone by using a rotary evaporator, and drying in a vacuum drying oven to obtain purified rGO/SiO2-g-PGMO（SiO2The mass ratio of the glycerol monooleate to the glycerol monooleate is 1: 3).
The preparation method comprises the following steps: the LLDPE resin, the LDPE resin, the EVA plastic and the ultraviolet-resistant antifogging agent are put into a high-speed mixing stirrer in proportion, mixed and stirred for 10min at the temperature of 60 ℃ at the speed of 300r/min in the stirrer to be uniformly mixed, and extruded and granulated at the extrusion temperature of 170 ℃. And extruding, casting, cooling, trimming, pressurizing and rolling the obtained particles to obtain the ultraviolet-resistant antifogging polyethylene cast film product.
The casting process is direct casting, the casting roller is a chromium-plated steel roller, the thickness of the chromium plating layer is 0.01-0.015 mm, the diameter of the steel roller is 500mm, and the height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
The pressurizing and rolling process comprises the step of pressurizing and rolling on a 60-65A liquid silica gel rubber roller, wherein the pressurizing pressure is 5 Kgf.
FIG. 1 is rGO/SiO2IR spectrum of g-PGMO, 1100 cm-1And 800 cm-1The near peak is SiO2Respectively represents the antisymmetric stretching vibration peak and the symmetric stretching vibration peak of Si-O-Si. rGO/SiO2With rGO/SiO2-g-PGMO except at 2916cm-1And 2849cm-1Different peaks appear at the positions, which are respectively the symmetric and asymmetric stretching vibration characteristic peaks of C-H bond, 1378cm-1Is the peak of C-H bond bending vibration, from which rGO/SiO is visible2PGMO has been successfully grafted.
FIG. 2 shows the anti-UV antifogging agent rGO/SiO prepared in example 12SEM picture of g-PGMO; SiO thereof2The dispersion on rGO and PGMO is more uniform, the agglomeration phenomenon is less, and SiO is more favorably realized2The film has more excellent performance by combining with the matrix resin.
Performance analysis: table 1 shows examples 1-3 and blanks tested according to GB 4455-2LLDPE100 parts of g-PGMOFilms prepared from 30 parts of LDPE and 30 parts of EVA); table 2 shows antifog duration and contact angle test results.
Table 1: mechanical properties
It can be seen from table 1 that the addition of the anti-uv antifogging agent improves the mechanical properties of the film, and does not adversely affect the mechanical properties of the film.
TABLE 2 anti-fog duration and contact angle
The data in table 2 show that: anti-ultraviolet antifogging agent rGO/SiO2The anti-fog duration of the film is obviously improved by adding the g-PGMO, the anti-fog duration is improved by 5 to 6 days compared with the effect of simple physical blending of SiO2 and glycerol monooleate, and the anti-fog effect is improved by 18 to 19 days compared with the common polyethylene film without the anti-fog agent.
The contact angle of the film without the anti-ultraviolet antifogging agent is 87.5 degrees, and B is SiO2The contact angle of the simple physical blend film of glycerol monooleate was 51.5 degrees, and the contact angles of examples 1-3 were 30.3 degrees, 28.1 degrees, and 27.2 degrees, respectively. Visible, rGO/SiO2The addition of the-g-PGMO improves the hydrophilic capability of the film, so that the contact angle of the film is reduced, and the antifogging property is greatly improved.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made within the scope of the present invention should be covered by the present invention.
Claims (4)
1. The utility model provides an anti ultraviolet antifog polyethylene canopy film which characterized in that: the composition comprises the following components in parts by weight;
LLDPE resin: 100 parts of (A);
LDPE resin: 30 parts of (1);
EVA plastics: 30 parts of (1);
anti-ultraviolet antifogging agent rGO/SiO2-g-PGMO: 5-15 parts;
the anti-ultraviolet antifogging agent rGO/SiO2The preparation method of the-g-PGMO comprises the following steps:
（1）rGO/SiO2the preparation of (1): dissolving 2g CTAB in 280ml of deionized water at room temperature, adding 50ml of 1, 4-dioxane, 40ml of ethanol and a certain amount of ammonia water, and magnetically stirring; after 30min, dripping 10ml of TEOS and a certain amount of graphene oxide ethanol solution into the mixture, and stirring the mixture to react for 4 h; after 4h, adding hydrochloric acid until the pH value is 7, and stirring for 15 min; washing and centrifuging by using ethanol and deionized water to obtain graphene oxide modified nano silicon dioxide, and adding the graphene oxide modified nano silicon dioxide into N2Calcining at the high temperature of 800 ℃ for 4h under the protection of atmosphere to obtain the graphene modified nano silicon dioxide composite material rGO/SiO2；
（2）rGO/SiO2-g-PGMO: weighing glycerol monooleate, adding into a three-neck flask, heating at 60 deg.C in a constant temperature water bath to melt the glycerol monooleate, and slowly adding graphene modified nano-silica composite material rGO/SiO while stirring after the glycerol monooleate is completely melted2And initiator BPO, then, in N2Reacting for 4 hours in a protected environment to obtain rGO/SiO2And (4) filtering and washing the (g) -PGMO by using acetone for multiple times until the upper layer liquid is transparent, and finally evaporating the residual acetone by using a rotary evaporator and putting the evaporated residual acetone into a vacuum drying oven for drying to obtain the purified rGO/SiO 2-g-PGMO.
2. A method for preparing the ultraviolet-resistant antifogging polyethylene greenhouse film as claimed in claim 1, which is characterized in that: LLDPE resin, LDPE resin, EVA plastic and anti-ultraviolet antifogging agent rGO/SiO2Putting the-g-PGMO into a high-speed mixing stirrer in proportion, mixing and stirring for 10min at the temperature of 60 ℃ in the stirrer at 300r/min to uniformly mix the materials, extruding and granulating at the extrusion temperature of 170 ℃, and finally, carrying out extrusion casting, cooling, trimming and pressure rolling on the obtained particles to obtain the ultraviolet-resistant antifogging polyethylene greenhouse film.
3. The method of claim 2, wherein: the casting is direct casting, the casting roller is a chromium-plated steel roller, the thickness of the chromium-plated layer is 0.01-0.015 mm, the diameter of the steel roller is 500mm, and the height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
4. The method of claim 2, wherein: the pressurizing and rolling are specifically as follows: and (3) pressurizing and rolling on a 60-65A liquid silica gel rubber roller, wherein the pressurizing pressure is 5-8 Kgf.
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|---|---|---|---|---|
| CN1035310A (en) * | 1988-02-23 | 1989-09-06 | 石家庄市东风塑料厂 | Anti-aging and dropless agricultural film |
| CN103021662A (en) * | 2012-12-11 | 2013-04-03 | 常州大学 | Nanometer multilayer mesoporous metal nitride/graphene composite materials for super capacitor and preparation method thereof |
| CN103450546A (en) * | 2013-08-23 | 2013-12-18 | 吴江市英力达塑料包装有限公司 | Anti-fogging and non-dropping film and preparation method thereof |
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| CN1035310A (en) * | 1988-02-23 | 1989-09-06 | 石家庄市东风塑料厂 | Anti-aging and dropless agricultural film |
| CN103021662A (en) * | 2012-12-11 | 2013-04-03 | 常州大学 | Nanometer multilayer mesoporous metal nitride/graphene composite materials for super capacitor and preparation method thereof |
| CN103450546A (en) * | 2013-08-23 | 2013-12-18 | 吴江市英力达塑料包装有限公司 | Anti-fogging and non-dropping film and preparation method thereof |
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