CN115490940B - Anti-fog breathable anti-aging transparent polyethylene composite material and preparation method thereof - Google Patents

Anti-fog breathable anti-aging transparent polyethylene composite material and preparation method thereof Download PDF

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CN115490940B
CN115490940B CN202110671736.1A CN202110671736A CN115490940B CN 115490940 B CN115490940 B CN 115490940B CN 202110671736 A CN202110671736 A CN 202110671736A CN 115490940 B CN115490940 B CN 115490940B
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polyethylene composite
polyethylene
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朱文俊
徐彦龙
李胜龙
李允升
蓝程程
张建新
张宏科
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Wanhua Chemical Group Co Ltd
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract

The invention discloses an anti-fog breathable anti-aging transparent polyethylene composite material and a preparation method thereof. According to the invention, through optimizing the formula of the antifogging stabilizer, the phenomenon of migration of the antifogging agent does not exist, the ventilation antifogging performance of the polyethylene is improved, the antifogging aging is longer, and meanwhile, the prepared polyethylene material is low in haze, good in transparency, excellent in aging resistance and weather resistance, and good in mechanical properties under the action of environmental factors for a long time.

Description

Anti-fog breathable anti-aging transparent polyethylene composite material and preparation method thereof
Technical Field
The invention belongs to the field of polyethylene materials, and particularly relates to an anti-fog breathable anti-aging transparent polyethylene composite material and a preparation method thereof.
Background
The raw materials for producing the agricultural greenhouse film are mainly polyethylene, and the greenhouse film is mostly used in winter and spring in northern China. Because of cold climate, the temperature and humidity inside and outside the greenhouse are greatly different, so that a large amount of fog drops are attached to the inner wall of the greenhouse film. Hazard of fog drops: the light is refracted, so that the light transmittance of the film is greatly reduced; the light is refracted to crops after being focused by water drops, and the crops can be burnt; the tiny water drops can be gradually gathered and enlarged, and can drop on flowers, stems, leaves or fruits of crops after reaching a certain quality, so that the crops are dried and rotten, and the yield and quality of the crops are reduced; the fogdrops are easy to spread germs when dripping, so that the humidity in the greenhouse is increased, and a proper environment is created for the occurrence of a plurality of diseases due to proper temperature; the temperature in the greenhouse is reduced along with the evaporation of the fog beads, so that the heat preservation effect of the greenhouse is weakened. Therefore, the harm of fog drops is overcome, and the development of the agricultural non-drip film has extremely important significance.
Some anti-fog drip master batches appear in the prior art, for example: chinese patent CN103881189a discloses an anti-fog drip master batch for polyethylene film in 2014, month 06 and 25, wherein the anti-fog drip master batch comprises one of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and coconut diethanolamide as the added drip agent. The addition of the drip agent prevents the formation of a mist film to influence the transmission of sunlight on one hand; on the other hand, the accumulated water droplets are prevented from forming a so-called "lens" effect which burns the crop. However, the anti-dripping agent is a few small molecules, and the small molecules are easy to migrate and short in aging, have single function, are easy to generate fog drops, are short in aging resistance, are short in service life and cannot meet the requirements of agricultural greenhouse films.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an anti-fog breathable anti-aging transparent polyethylene composite material and a preparation method thereof. According to the invention, the formula of the antifogging stabilizer is optimized, so that the antifogging air permeability of the polyethylene film is improved, the antifogging aging is longer, meanwhile, the prepared polyethylene material is low in haze, good in transparency, excellent in ageing resistance and weather resistance, can be used for a long time under the condition of high Wen Guangshe, does not change color, and is good in mechanical property.
In order to achieve the aim of the invention, the invention adopts the following technical scheme that
The invention provides an anti-fog breathable anti-aging transparent polyethylene composite material which comprises the following raw materials in parts by weight:
60-95 parts of polyethylene resin;
5-40 parts, preferably 15-25 parts, of an anti-fog stabilizer;
wherein the antifogging stabilizer comprises the following components in parts by weight:
5-30 parts, preferably 10-20 parts, of an interface modifier;
20-50 parts of methyl phenyl vinyl silicone rubber, preferably 30-50 parts;
15-25 parts, preferably 15-20 parts, of nano calcium carbonate material;
5-20 parts of coupling agent, preferably 5-10 parts;
3-10 parts of an antioxidant, preferably 3-8 parts;
1 to 10 parts, preferably 2 to 5 parts, of light stabilizer.
Further, the polyethylene resin is selected from low density polyethylene with a density in the range of 0.910-0.928g/cm 3 Low-density polyethylene having a melt flow rate of 0.5 to 2g/10min, such as low-density polyethylene LD150 produced using Yanshan petrochemical industry, having a density of 0.920g/cm 3 The melt flow rate was 0.8g/10min.
Further, the interface modifier is selected from ethylene-chlorotrifluoroethylene copolymer and/or ethylene-vinyl acetate copolymer, preferably a mixture of ethylene-chlorotrifluoroethylene copolymer and ethylene-vinyl acetate copolymer, and the mixing mass ratio is preferably 1:0.8-1.5, such as DuPont ethylene-chlorotrifluoroethylene copolymer HALAR ECTFE (F-30) and ethylene-vinyl acetate copolymer Evaflex40W (VA: 40%, MI: 65). When the mixture is used as an interface modifier to be blended with a polyethylene material to prepare a film material, polar components are preferentially repelled on the outer layer of the surface of the master batch, so that the outer layer of the greenhouse film shows strong polarity and the film is super-hydrophilic; in the case of mist, the water drops immediately flow down along the film before being formed, so that mist drops are not formed, the lens effect is not generated on plants, and damage is not caused.
Further, the methyl phenyl vinyl silicone rubber is selected from the group consisting of medium phenyl silicone rubber; preferably, the phenyl content is 5-40mol%, the methyl content is 3-20mol%, and the vinyl content is 0.1-0.6mol%; more preferably, the molecular weight is 40-80 ten thousand, the phenyl content is 15-25mol%, the methyl content is 8-15mol% and the vinyl content is 0.16-0.23mol%, for example, IOTA-120 methylphenyl vinyl silicone rubber manufactured by Anhui Aijia silicone oil Co., ltd.
Further, the granularity of the nano calcium carbonate material is 10-100nm, preferably 20-40nm ultrafine calcium carbonate, such as Anhui refined active calcium carbonate 303, 305 and 306, light nano ultrafine calcium carbonate of source epitaxial powder and the like; it is also possible to use a coupling agent modified nano calcium carbonate, preferably modified with the coupling agent Y-aminopropyl triethoxysilane (APTES), for example activated light calcium carbonate from the major mineral of the major stone family: CCR-4 superfine extra-white active nano calcium carbonate. The modifying effect of the coupling agent reduces the surface energy and hydrophilicity of the calcium carbonate particles and improves the dispersibility of the nano calcium carbonate in the polyethylene matrix.
Further, the coupling agent is selected from any one or a combination of at least two of silane coupling agents and siloxane coupling agents, preferably any one or a combination of at least two of 7-isocyanatopropyltriethoxysilane, gamma-2-propyltrimethoxysilane, Y-aminopropyltriethoxysilane and octamethyl cyclotetrasiloxane. The coupling agent has the function of enhancing the compatibility of the antifogging stabilizer and the matrix.
Further, the antioxidant is selected from any one or a combination of at least two of phenolic antioxidants and phosphite antioxidants; preferably a compound agent formed by a phenolic antioxidant 1010 and a phosphite antioxidant (tris [2, 4-di-tert-butylphenyl ] phosphite) according to a mass ratio of 1:0.5-1.5, preferably 1:0.8-1.
Further, the light stabilizer is selected from hindered amine light stabilizers, and specific light stabilizers are preferably light stabilizers 770, 944 such as basf.
The invention adds the mixture of high molecular ethylene-trifluoro vinyl chloride block copolymer and ethylene-vinyl acetate block copolymer into low density polyethylene to prepare the anti-fog stabilizer. The polar block part in the block copolymer is easy to combine with the silicon-oxygen main chain structure in the silicon rubber due to larger electronegativity, and the nonpolar polyethylene block part has strong compatibility with methyl, phenyl and vinyl, so that the addition of the silicon rubber is easy to form an 'oriented' network structure in the integral structure of the film, so that the hydrophilic side block copolymer chains are distributed on the wall side of the film. Therefore, the structure not only has stronger combination effect, promotes the stability of the film, but also promotes the hydrophilic performance of the inner side of the greenhouse film through the directional effect, promotes the anti-fog effect, and the obtained greenhouse film can not form fog drops, can not drop on flowers, stems, leaves or fruits of crops to make the crops bitter and rotten, simultaneously, does not influence the light transmittance of the greenhouse film, can not spread germs, does not influence the heat preservation effect of the greenhouse, and achieves the good anti-fog effect.
According to the invention, by adding the methyl phenyl vinyl silicone rubber, the good compatibility with the LDPE matrix and the space dispersion effect of the phenyl vinyl thereof, the more sufficient dispersibility is provided for the nano calcium carbonate modified by the Y-aminopropyl triethoxysilane, and the methyl phenyl vinyl silicone resin can be subjected to side group fracture crosslinking after being continuously irradiated by light, so that the nano calcium carbonate is further fixed to prevent migration, the mechanical stability of the film is improved, and the persistence of the ventilation effect of the nano calcium carbonate is ensured.
The nano calcium carbonate material and the matrix can keep good compatibility and dispersibility, and the film has good air permeability to maintain the respiration and prevent fogdrops from forming. When the nano calcium carbonate material is used for modifying PE, the crystallization effect of PE is changed, so that the size of PE spherulites is reduced, the crystallization integrity is reduced, the haze of a product film is improved, and the transmittance of the film is improved. Meanwhile, the nano calcium carbonate powder also solves the problem of reduced film strength caused by the addition of an antioxidant, a light stabilizer and the like.
In the invention, 7-isocyanatopropyl triethoxysilane and the like are added into the polyethylene composite material as coupling agents: on the one hand, the coupling agent such as 7-isocyanatopropyl triethoxysilane has groups with higher permeability, so that the coupling agent has better wettability to a polyethylene substrate and can better permeate into tiny micropores on the surface of the polyethylene; on the other hand, the ethoxy contained in the coupling agent generates silicon hydroxyl after hydrolysis, and the silicon hydroxyl is condensed with each other or with the hydroxyl in the silicon rubber to form a firm chemical bond, so that the coupling agent has better compatibility and osmotic fusion with the silicon rubber, and enhances the interaction force with the matrix.
The invention also provides a preparation method of the anti-fog breathable anti-aging transparent polyethylene composite material, which comprises the following steps in one embodiment:
1) Uniformly mixing polyethylene resin, an interface modifier, methyl phenyl vinyl silicone rubber, a nano calcium carbonate material, a coupling agent, an antioxidant and a light stabilizer, wherein the mixing temperature is 90-100 ℃, and the mixing time is 5-10min, so as to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite material.
In the method step 1), the mixing is performed in a high-speed mixer, and the mixing speed of the high-speed mixer is 800-1500r/min.
In the step 2) of the method, the mixture is extruded by an extruder, the temperature setting range of the extruder is 150-190 ℃, and the method comprises the following specific steps: the temperatures of the first zone, the second zone and the third zone of the extruder are set to 160 ℃ to 165 ℃, the fourth zone is 165 ℃ to 170 ℃, the fifth zone is 170 ℃ to 180 ℃, the sixth zone and the seventh zone are 175 ℃ to 180 ℃, the eighth zone and the ninth zone are 180 ℃ to 190 ℃, and the machine head is 170 ℃ to 175 ℃. The host machine is set to 80-100r/min, and the feeding is set to 6-8r/min.
The anti-fog breathable anti-aging transparent polyethylene composite material can be used for preparing polyethylene film materials and is applied to the fields of agricultural greenhouse films, agricultural mulching films, food bags, medicine bags and the like.
The invention relates to a method for preparing a film from an anti-fog breathable anti-aging transparent polyethylene composite material, which comprises the following steps:
putting the anti-fog breathable anti-aging transparent polyethylene composite master batch into a biaxially oriented film machine for film making;
preferably, in the film-forming process, the longitudinal stretching temperature is 96-106 ℃, the stretching ratio is 4-4.5, the transverse stretching temperature is 148-156 ℃, and the stretching ratio is 7-9.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention optimizes the formula of the antifogging stabilizer, and adds a plurality of auxiliary agents such as high molecular ethylene-chlorotrifluoroethylene copolymer, ethylene-vinyl acetate copolymer and the like into low density polyethylene to prepare the antifogging stabilizer. The antifogging stabilizer can inhibit the formation of fog drops on the surface of the film, enhance the air permeability of the matrix and reduce the haze of the film, effectively reduce the degradation reaction of polyethylene in the outdoor environment use process and improve the optical and mechanical properties of the polyethylene composite material.
2. The invention has the advantages of good anti-fog drop effect, long aging time, comprehensive functions, hydrophilic property, aging resistance and weather resistance, long service life and fully meets the requirements of agricultural greenhouse films because the anti-fog drop containing no small molecules and the anti-fog drop agent is not migrated out, and the low-density polyethylene matrix is combined with the copolymer and the silicone rubber through strong chemical bonds.
3. The methyl phenyl vinyl silicone rubber is added into the formula, so that on one hand, the dispersibility of the auxiliary agent is improved by a synergistic effect to improve the anti-fog air permeability of the polyethylene, and on the other hand, the impact resistance and other properties of the polyethylene composite material can be effectively improved.
4. The granularity of the nano calcium carbonate material ensures that the film has better air permeability to maintain the respiration, and further prevents the formation of fog drops. The obtained greenhouse film can not form fog drops, can not drop on flowers, stems, leaves or fruits of crops to make the crops bitter and rotten, and meanwhile, the light transmittance of the greenhouse film is not affected, germs are not transmitted, the heat preservation effect of the greenhouse is not affected, and a good long-acting fog drop prevention effect is achieved.
Under the synergistic effect of the copolymer, the silicon rubber, the nano calcium carbonate, the coupling agent and other auxiliary agents in the antifogging stabilizer, the dispersibility, the stability and the mechanical property of the greenhouse film are improved. The polyethylene composite material has excellent ageing resistance and excellent transparency after long-time environmental illumination, and the mechanical property is not reduced.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Main raw material information in the examples and comparative examples of the present invention:
low density polyethylene resin: low density polyethylene LD150 produced by Yanshan petrochemical industry and having density of 0.920g/cm 3 The melt flow rate was 0.8g/10min.
Interface modifier: ethylene-chlorotrifluoroethylene copolymer was HALAR ECTFE (F-30) from DuPont and ethylene-vinyl acetate copolymer was DuPont Evaflex40W (VA: 40%, MI: 65) and the two were added in the proportions given in the examples.
Methyl phenyl vinyl silicone rubber: IOTA-120 methyl phenyl vinyl silicone rubber produced by Anhui Ai Yaoda silicone oil Co., ltd, has a molecular weight of 40-80 ten thousand, a methyl content of 10%, a phenyl content of 20mol% and a vinyl content of 0.20%.
Nano calcium carbonate: anhui refined activated calcium carbonate 303, Y-aminopropyl triethoxysilane used in morning photoperiod chemical CG-A110.
The preparation method of the Y-aminopropyl triethoxysilane modified nano calcium carbonate comprises the following steps: mixing prepared 25g nano calcium carbonate with 50ml distilled water and 10g Y-aminopropyl triethoxysilane; 200ml of distilled water and 50ml of absolute ethanol were added to a 500ml beaker, stirred well with a glass rod, and further stirred well with 10g of the coupling agent Y-aminopropyl triethoxysilane. The beaker containing the mixed solution is placed in a constant temperature water bath kettle, and the solution is stirred by a precise pressurizing electric stirrer until the horizontal scale mark of the solution is 100ml. Drying in a drying oven (60deg.C) until the water is completely evaporated to solid, and grinding into powder with a mortar.
Coupling agent: hangzhou jercad chemical 7-isocyanatopropyl triethoxysilane KH-907.
An antioxidant: the compound agent is formed by phenolic antioxidant 1010 of Shandong Sanfeng and phosphite antioxidant (tris [2, 4-di-tert-butylphenyl ] phosphite) according to the mass ratio of 1:1.
Light stabilizers: light stabilizer 770 of basf.
Other materials or reagents are commercially available, unless otherwise specified.
Example 1
1) Taking 15085 parts of low-density polyethylene LD, 15 parts of anti-fog stabilizer, adding 20 parts of polyethylene-polytrifluoroethylene copolymer and polyethylene-vinyl acetate copolymer in the anti-fog stabilizer, 40 parts of methyl phenyl vinyl silicone rubber, 20 parts of Y-aminopropyl triethoxysilane modified nano calcium carbonate, 10 parts of 7-isocyanatopropyl triethoxysilane coupling agent, 1010 5 parts of antioxidant and 770 5 parts of light stabilizer into a high-speed mixer, uniformly mixing at the mixing speed of 1200r/min and the mixing temperature of 100 ℃ for 5min to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, wherein the temperature of the extruder is set as follows: the temperatures of the first, second and third zones of the extruder were set to 160 ℃, the fourth zone was 165 ℃, the fifth zone was 170 ℃, the sixth and seventh zones were 175 ℃, the eighth and ninth zones were 180 ℃, and the head was 170 ℃. The main machine is set at 80r/min, and the feeding is set at 6r/min. Extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite master batch.
Putting the anti-fog breathable anti-aging transparent polyethylene composite master batch into a biaxially oriented film machine for film making; in the film making process, the longitudinal stretching temperature is 100 ℃, the stretching ratio is 4.5, the transverse stretching temperature is 150 ℃, and the stretching ratio is 8, so that the polyethylene plastic film is obtained.
Example 2
1) Taking 15075 parts of low-density polyethylene LD and 25 parts of anti-fog stabilizer, wherein 10 parts of polyethylene-poly (chlorotrifluoroethylene) copolymer, 50 parts of methyl phenyl vinyl silicone rubber, 15 parts of prepared nano calcium carbonate, 10 parts of 7-isocyanatopropyl triethoxysilane coupling agent, 1010 8 parts of antioxidant and 770 7 parts of light stabilizer are added according to a ratio of 1:1, and uniformly mixed in a high-speed mixer at a mixing speed of 1200r/min at a mixing temperature of 95 ℃ for 8min to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, wherein the temperature of the extruder is set as follows: the temperatures of the first, second and third zones of the extruder were set to 160 ℃, the fourth zone was 165 ℃, the fifth zone was 170 ℃, the sixth and seventh zones were 175 ℃, the eighth and ninth zones were 180 ℃, and the head was 170 ℃. The main machine is set at 80r/min, and the feeding is set at 6r/min. And extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite master batch.
Putting the anti-fog breathable anti-aging transparent polyethylene composite master batch into a biaxially oriented film machine for film making; in the film making process, the longitudinal stretching temperature is 105 ℃, the stretching ratio is 4.5, the transverse stretching temperature is 155 ℃, and the stretching ratio is 9, so that the polyethylene plastic film is obtained.
Example 3
1) Taking 60 parts of low-density polyethylene LD150 and 40 parts of antifogging stabilizer, wherein 15 parts of polyethylene-poly (chlorotrifluoroethylene) copolymer and polyethylene-vinyl acetate copolymer, 50 parts of methyl phenyl vinyl silicone rubber, 23 parts of prepared nano calcium carbonate, 8 parts of 7-isocyanatopropyl triethoxysilane coupling agent, 1010 parts of antioxidant and 770 2 parts of light stabilizer are added according to a ratio of 1:1, and uniformly mixed in a high-speed mixer at a mixing speed of 1200r/min at a mixing temperature of 90 ℃ for 10min to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, wherein the temperature of the extruder is set as follows: the temperatures of the first, second and third zones of the extruder were set to 160 ℃, the fourth zone was 165 ℃, the fifth zone was 170 ℃, the sixth and seventh zones were 175 ℃, the eighth and ninth zones were 180 ℃, and the head was 170 ℃. The main machine is set at 80r/min, and the feeding is set at 6r/min. And extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite master batch.
Putting the anti-fog breathable anti-aging transparent polyethylene composite master batch into a biaxially oriented film machine for film making; in the film making process, the longitudinal stretching temperature is 96 ℃, the stretching ratio is 4, the transverse stretching temperature is 148 ℃, and the stretching ratio is 7, so that the polyethylene plastic film is obtained.
Example 4
1) Taking 95 parts of low-density polyethylene LD150 and 5 parts of anti-fog stabilizer, wherein 20 parts of polyethylene-poly (chlorotrifluoroethylene) copolymer, 30 parts of methyl phenyl vinyl silicone rubber, 25 parts of prepared nano calcium carbonate, 18 parts of 7-isocyanatopropyl triethoxysilane coupling agent, 1010 parts of antioxidant and 770 4 parts of light stabilizer are added according to a ratio of 1:1, and uniformly mixed in a high-speed mixer at a mixing speed of 1200r/min at a mixing temperature of 100 ℃ for 10min to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, wherein the temperature of the extruder is set as follows: the temperatures of the first, second and third zones of the extruder were set to 160 ℃, the fourth zone was 165 ℃, the fifth zone was 170 ℃, the sixth and seventh zones were 175 ℃, the eighth and ninth zones were 180 ℃, and the head was 170 ℃. The main machine is set at 80r/min, and the feeding is set at 6r/min. And extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite master batch.
Putting the anti-fog breathable anti-aging transparent polyethylene composite master batch into a biaxially oriented film machine for film making; in the film making process, the longitudinal stretching temperature is 120 ℃, the stretching ratio is 3.5, the transverse stretching temperature is 120 ℃, and the stretching ratio is 2.5, so that the polyethylene plastic film is obtained.
Example 5
Based on the raw materials and the formula proportion thereof in the embodiment 1, the interface modifier polyethylene-poly (trifluoroethylene) vinyl acetate copolymer and the polyethylene-vinyl acetate copolymer in the embodiment 1 are replaced by the polyethylene-poly (trifluoroethylene) vinyl acetate copolymer with equal mass, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Example 6
Based on the raw materials and the formula proportion thereof in the embodiment 1, the interface modifier polyethylene-polytrifluoro vinyl acetate copolymer and the polyethylene-vinyl acetate copolymer in the embodiment 1 are replaced by the polyethylene-vinyl acetate copolymer with equal quality, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Example 7
Based on the raw materials and the formula proportion thereof in the embodiment 1, the modified nano calcium carbonate material in the embodiment 1 is replaced by the unmodified nano calcium carbonate (namely the Anhui refined active calcium carbonate 303) with equal mass, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 1
Based on the raw materials and the formula proportion of the raw materials in the example 1, equal mass of the polyoxyethylene sorbitan monolaurate is used for replacing the methyl phenyl vinyl silicone rubber in the example 1, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 2
Based on the raw materials and the formula proportion of the raw materials in the example 1, the equal mass of the dripping agent polyethylene glycol 400 monolaurate is used for replacing the methyl phenyl vinyl silicone rubber in the example 1, and other raw materials, the proportion and the processing condition are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 3
Based on the raw materials and the formula proportion of the raw materials in the example 1, equal mass of drip sorbitan monooleate is used for replacing the methyl phenyl vinyl silicone rubber in the example 1, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 4
Based on the raw materials and the formula proportion of the raw materials in the example 1, the equal mass of the coconut diethanolamide is used for replacing the methyl phenyl vinyl silicone rubber in the example 1, and other raw materials, the proportion and the processing condition are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 5
Based on the raw materials and the formula proportion in example 1, the mixture of polyoxyethylene sorbitan monolaurate and coconut diethanolamide is used as a mixture of 1:1 equivalent replacement of methyl phenyl vinyl silicone rubber in example 1, other raw materials, proportion and processing conditions are all unchanged, and the polyethylene plastic film is obtained.
Comparative example 6
Based on the raw materials and the formula proportion of the raw materials in the embodiment 1, the methyl phenyl vinyl silicone rubber in the embodiment 1 is not added, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 7
Based on the raw materials and the formula proportion thereof in the embodiment 1, the interface modifier polyethylene-polytrifluoro-vinyl acetate copolymer and the polyethylene-vinyl acetate copolymer in the embodiment 1 are not added, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Comparative example 8
Based on the raw materials and the formula proportion of the raw materials in the embodiment 1, the modified nano calcium carbonate material in the embodiment 1 is not added, and other raw materials, proportions and processing conditions are unchanged, so that the polyethylene plastic film is obtained.
Seven parts of anti-fog breathable anti-aging transparent polyethylene composite material master batches obtained in the examples 1 to 7 and eight parts of polyethylene composite material master batches obtained in the comparative examples 1 to 8 are respectively subjected to anti-fog performance test experiments, and the anti-fog drop polyethylene composite material films are compared according to ISO527-1 test standards and are placed in a thermo-oxidative aging box (140 ℃ for 200 hours) before and after mechanical performance tests such as tensile breaking strength, breaking elongation, falling standard impact strength and the like are completed.
The main test equipment is as follows:
co-rotating parallel double-screw mixing extrusion water bracing granulation experimental line, nanjing poly-power chemical machinery Co., ltd;
a small biaxially oriented film machine, guangzhou general instruments and equipment limited company;
light transmittance haze meter, shanghai precision scientific instruments Co., ltd;
dart impact tester, jinan blue opto-mechanical technology limited company;
intelligent tensile testing machine, jinan blue optical mechanical and electrical technology Co., ltd;
film breathability tester, atanan opto-mechanical and electro-mechanical technology limited company;
antifogging properties include antifogging property test, film contact angle. Film antifogging property measurement refers to GB/T31726-2015 "Plastic film antifogging property test method", and the antifogging property of the test film mainly comprises a water bath hot fogging method and a rapid hot fogging method; contact angles were performed according to the procedure specified in ASTM D5725-1999 (R2008);
the test results of the polyethylene films prepared in examples and comparative examples are shown in tables 1 and 2:
TABLE 1 antifogging property test results
TABLE 2 mechanical test results
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (26)

1. The anti-fog breathable anti-aging transparent polyethylene composite material is characterized by comprising the following raw materials in parts by weight:
60-95 parts of polyethylene resin, wherein the polyethylene resin is selected from low-density polyethylene;
5-40 parts of an anti-fog stabilizer;
wherein the antifogging stabilizer comprises the following components in parts by weight:
5-30 parts of an interface modifier selected from ethylene-chlorotrifluoroethylene copolymer and/or ethylene-vinyl acetate copolymer;
20-50 parts of methyl phenyl vinyl silicone rubber;
15-25 parts of nano calcium carbonate material;
5-20 parts of a coupling agent;
3-10 parts of an antioxidant;
1-10 parts of light stabilizer.
2. The polyethylene composite material according to claim 1, comprising the following raw materials in parts by weight:
60-95 parts of polyethylene resin;
15-25 parts of an anti-fog stabilizer;
wherein the antifogging stabilizer comprises the following components in parts by weight:
10-20 parts of interface modifier;
30-50 parts of methyl phenyl vinyl silicone rubber;
15-20 parts of nano calcium carbonate material;
5-10 parts of a coupling agent;
3-8 parts of an antioxidant;
2-5 parts of light stabilizer.
3. The polyethylene composite material of claim 1, wherein the polyethylene resin density is in the range of 0.910-0.928g/cm 3 。
4. The polyethylene composite material according to claim 1, wherein the polyethylene resin is selected from low density polyethylene having a melt flow rate of 0.5-2g/10 min.
5. The polyethylene composite material according to claim 1, wherein the interfacial modifier is selected from the group consisting of a mixture of ethylene-chlorotrifluoroethylene copolymer and ethylene-vinyl acetate copolymer, the mixing mass ratio being 1:0.8-1.5;
the interface modifier is a mixture of an ethylene-chlorotrifluoroethylene copolymer HALAR ECTFE F-30 and an ethylene-vinyl acetate copolymer Evaflex40W of DuPont company.
6. The polyethylene composite material according to claim 1, wherein the interfacial modifier is selected from the group consisting of a mixture of dupont ethylene-chlorotrifluoroethylene copolymer HALAR ECTFE F-30 and ethylene-vinyl acetate copolymer Evaflex 40W.
7. The polyethylene composite material according to claim 1, wherein: the methyl phenyl vinyl silicone rubber is selected from medium phenyl silicone rubber.
8. The polyethylene composite material according to claim 1, wherein: the methyl phenyl vinyl silicone rubber has the phenyl content of 5-40mol%, the methyl content of 3-20mol% and the vinyl content of 0.1-0.6mol%.
9. The polyethylene composite material according to claim 8, wherein: the methyl phenyl vinyl silicone rubber has a molecular weight of 40-80 ten thousand, a phenyl content of 15-25mol%, a methyl content of 8-15mol% and a vinyl content of 0.16-0.23mol%.
10. The polyethylene composite material according to claim 1, wherein: the granularity of the nano calcium carbonate material is 10-100nm.
11. The polyethylene composite material according to claim 10, wherein: the granularity of the nano calcium carbonate material is 20-40nm of ultrafine calcium carbonate.
12. The polyethylene composite material according to claim 11, wherein: the nano calcium carbonate material is Anhui refined active calcium carbonate 303, 305, 306 and light nano superfine calcium carbonate of source epitaxial powder.
13. The polyethylene composite material according to claim 1, wherein: the nano calcium carbonate material is nano calcium carbonate modified by a coupling agent.
14. The polyethylene composite material according to claim 13, wherein: the nano calcium carbonate material is nano calcium carbonate modified by coupling agent Y-aminopropyl triethoxysilane.
15. The polyethylene composite material according to claim 1, wherein: the coupling agent is selected from any one or a combination of at least two of silane coupling agents and siloxane coupling agents;
the antioxidant is selected from any one or a combination of at least two of phenolic antioxidants and phosphite antioxidants;
the light stabilizer is selected from hindered amine light stabilizers.
16. The polyethylene composite material according to claim 15, wherein: the coupling agent is selected from any one or a combination of at least two of 7-isocyanatopropyl triethoxysilane, gamma-2-propyl trimethoxysilane, Y-aminopropyl triethoxysilane and octamethyl cyclotetrasiloxane.
17. The polyethylene composite material according to claim 15, wherein: the antioxidant is a compound agent formed by a phenolic antioxidant 1010 and a phosphite antioxidant according to a mass ratio of 1:0.5-1.5.
18. The polyethylene composite material according to claim 17, wherein: the antioxidant is a compound agent formed by a phenolic antioxidant 1010 and a phosphite antioxidant according to a mass ratio of 1:0.8-1.
19. The polyethylene composite material according to claim 15, wherein: the light stabilizer is selected from light stabilizers 770, 944 of basf.
20. A method for preparing the anti-fog, breathable and ageing-resistant transparent polyethylene composite material according to any one of claims 1-19, comprising the steps of:
1) Uniformly mixing polyethylene resin, an interface modifier, methyl phenyl vinyl silicone rubber, a nano calcium carbonate material, a coupling agent, an antioxidant and a light stabilizer, wherein the mixing temperature is 90-100 ℃, and the mixing time is 5-10min, so as to obtain a mixture;
2) Adding the mixture obtained in the step 1) into a double-screw extruder, and extruding and granulating to obtain the anti-fog breathable anti-aging transparent polyethylene composite material.
21. The method of manufacturing according to claim 20, wherein:
in the step 1), the mixing is completed in a high-speed mixer, and the mixing speed of the high-speed mixer is 800-1500r/min;
in the step 2), the mixture is extruded by an extruder, and the temperature of the extruder is set to be 150-190 ℃; the host machine is set to 80-100r/min, and the feeding is set to 6-8r/min.
22. The method of manufacturing according to claim 21, wherein: temperature of the extruder: the temperatures of the first area, the second area and the third area are set to 160 ℃ to 165 ℃, the fourth area is 165 ℃ to 170 ℃, the fifth area is 170 ℃ to 180 ℃, the sixth area and the seventh area are 175 ℃ to 180 ℃, the eighth area and the ninth area are 180 ℃ to 190 ℃, and the machine head is 170 ℃ to 175 ℃.
23. Use of an anti-fog breathable ageing-resistant transparent polyethylene composite material according to any of claims 1 to 19 for the preparation of polyethylene film materials.
24. The use according to claim 23, in the field of agricultural greenhouse films, agricultural mulch films, food bags, pharmaceutical packs.
25. The method for preparing the anti-fog breathable ageing-resistant transparent polyethylene composite material film is characterized by comprising the following steps of:
the anti-fog breathable anti-aging transparent polyethylene composite master batch according to any one of claims 1-19 is placed into a biaxially oriented film machine for film forming.
26. The method for producing a transparent polyethylene composite material according to claim 25, wherein the longitudinal stretching temperature is 96-106 ℃, the stretching ratio is 4-4.5, the transverse stretching temperature is 148-156 ℃, and the stretching ratio is 7-9.
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