CN109845540B - Agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances - Google Patents
Agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances Download PDFInfo
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- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
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Abstract
The invention relates to the field of agricultural greenhouse films, in particular to an agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant properties. The agricultural greenhouse film is composed of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence. The agricultural greenhouse film prepared by the invention has the long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances, and is particularly characterized by good dripping performance, long dripping duration, fast temperature rise, strong heat preservation, obvious yield-increasing effect, strong weather resistance and wind resistance, better antifogging function and light transmittance, capability of reducing or eliminating fog in a greenhouse, contribution to photosynthesis of crops and reduction of crop diseases, and suitability for overwintering cultivation of various leaf vegetables, flowers and fruits in various large and medium-sized arched sheds and sunlight greenhouses.
Description
Technical Field
The invention belongs to the field of agricultural greenhouse films, and particularly relates to an agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances.
Background
The greenhouse is one of important facilities of modern agriculture, and changes the dependence of the traditional planting method on natural conditions. Effectively improves the yield and the quality of crops in unit area and relatively reduces the production cost. Therefore, the greenhouse planting technology is gradually replacing the traditional planting technology in agriculture and planting industry and is accepted by people, and the covered area of the greenhouse film in China exceeds 16000km according to statistics2The annual usage amount of the greenhouse film is about 1500kt/a, the annual updating demand amount is about 700kt, and the greenhouse film is gradually usedThe trend is increasing year by year. A huge industry has been formed. The raw materials for producing the agricultural greenhouse film are mainly polyethylene resin, and a layer of white reflective water drops are condensed on the inner surface of the greenhouse film when the common polyethylene greenhouse film is used, so that the light transmission is influenced; moreover, water drops drip, so that the humidity in the greenhouse is increased, and the crops are easy to suffer from diseases; the water drops drop on the crops and are easy to rot, thereby causing the reduction of yield. The problem of dripping water in the use of the polyethylene greenhouse film is solved by two methods: one is an internal addition method, which is to mix and blow-mold a substance with surface activity and polyethylene resin to prepare a dripping greenhouse film, wherein the hydrophilic end migrates to the surface of the film, so that water drops are changed into a water film to achieve the effect of preventing water drops; the other method is an external coating method, namely, the dripping agent is coated on the surface of the film to ensure that the film has hydrophilicity so as to achieve the effect of preventing dripping.
The flow drop fog dissipation duration of the flow drop fog dissipation greenhouse film prepared by the internal addition method is short, generally about 3-4 months, and the growth requirement of crops cannot be met. The coating type dripping fog reduction shed film has longer lasting period of dripping fog dissipation, generally more than 8 months. The preparation method is to directly coat a layer of dripping fog-reducing agent on the surface of the polyethylene greenhouse film, and the polyethylene and the coating type dripping fog-reducing agent have great polarity difference, so that the coating is difficult and the adhesion between the coating and the polyethylene surface is poor, so that the greenhouse film has short dripping fog-reducing lasting period and can not meet the requirements. Therefore, the invention aims to solve the problem that the conventional anti-dropping agent cannot play a role in defogging due to low surface activity ratio, and simultaneously solve the problem that the anti-dropping function is gradually lost and the onset period is short due to the fact that auxiliary agent molecules such as the anti-dropping agent, the anti-fog agent and the like continuously migrate to the surface of the film and are lost along with water drops.
Disclosure of Invention
In order to solve the problems, the invention provides an agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence.
As a preferable technical scheme, the agricultural greenhouse film comprises the following components in parts by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer.
As a preferred technical scheme, the inner layer comprises the following components in parts by weight: 20-30 parts of POE, 15-20 parts of LLDPE-1, 10-20 parts of LDPE-1 and 5-10 parts of anti-aging dripping master batch.
As a preferred technical scheme, the inner two layers comprise the following components in parts by weight: 25-35 parts of POE, 10-15 parts of mLLDPE-1 and 3-7 parts of ageing-resistant dripping master batch.
As a preferred technical scheme, the middle layer comprises the following components in parts by weight: 20-30 parts of EVA (ethylene-vinyl acetate), 15-25 parts of POE (polyolefin elastomer), 10-15 parts of LDPE-2 and 4-7 parts of heat-insulating master batch.
As a preferred technical scheme, the outer two layers comprise the following components in parts by weight: 20-30 parts of mLLDPE-2, 30-50 parts of POE, 30-40 parts of LLDPE-2 and 3-5 parts of anti-aging master batch.
As a preferred technical solution, the outer layer comprises, in parts by weight: 30-40 parts of mLLDPE-3, 30-40 parts of POE, 10-20 parts of LLDPE-3 and 5-10 parts of anti-aging master batch.
As a preferable technical scheme, the anti-aging dripping master batch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.5-1.5 parts of anti-aging agent, 1-1.5 parts of hindered amine light stabilizer, 1-3 parts of functional assistant and 0.3-0.8 part of dripping agent.
As a preferred technical scheme, the heat-preservation master batch comprises the following components in parts by weight: 20-30 parts of LDPE, 10-15 parts of talcum powder and 3-5 parts of basic magnesium carbonate.
As a preferred technical scheme, the anti-aging masterbatch comprises the following components in parts by weight: 20-30 parts of LLDPE, 0.5-1.5 parts of hindered amine light stabilizer and 1-3 parts of composite antioxidant.
Has the advantages that: the agricultural greenhouse film prepared by the invention has the long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances, and is particularly characterized by good dripping performance, the formed water drops can flow down along the film, the dripping duration is long, the temperature rise is fast, the heat preservation is strong, the yield-increasing effect is obvious, the weather resistance and the wind resistance are strong, the agricultural greenhouse film also has good fog-preventing function and light transmittance, the fog in the greenhouse can be reduced or eliminated, the photosynthesis of crops is facilitated, the crop diseases are reduced, and the agricultural greenhouse film is suitable for overwintering cultivation of various leaf vegetables, flowers and fruits in various large and medium arched sheds and sunlight greenhouses in sunlight greenhouses.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the problems, the invention provides an agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence.
In a preferred embodiment, the agricultural greenhouse film comprises, in parts by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer.
< inner layer >
In a preferred embodiment, the inner layer of the present invention comprises, in parts by weight: 20-30 parts of POE, 15-20 parts of LLDPE-1, 10-20 parts of LDPE-1 and 5-10 parts of anti-aging dripping master batch.
(POE)
The POE is a polyolefin elastomer, has a molecular structure similar to Ethylene Propylene Diene Monomer (EPDM), has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is widely applied to the fields of the automobile industry, wire and cable sheaths, plastic toughening agents and the like.
The POE of the inner layer is not particularly limited, and may be any of those conventionally used in the art, and may be commercially available, for example, commercially available POE includes, but is not limited to, products available from dupont dow under the designation 1881G or 8201.
(LLDPE-1)
The LLDPE, i.e., linear low density polyethylene, is a copolymer formed by polymerizing ethylene and a small amount of higher alpha-olefin (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) under the action of a catalyst and under high pressure or low pressure.
The LLDPE-1 of the invention preferably has the density of 0.912-0.918 g/cm3For example, commercially available LLDPE-1 includes, but is not limited to, the product available from Exxon Mobil under the designation FL201XV, having a density of 0.916g/cm3。
(LDPE-1)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The preferred density of the LDPE-1 is 0.912-0.918 g/cm3For example, commercially available LDPE-1 includes, but is not limited to, the product available from Exxon Mobil under the designation 350D65, having a density of 0.917g/cm3。
(anti-aging dripping masterbatch)
In a preferred embodiment, the aging-resistant dripping masterbatch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.5-1.5 parts of anti-aging agent, 1-1.5 parts of hindered amine light stabilizer, 1-3 parts of functional assistant and 0.3-0.8 part of dripping agent.
LDPE
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The LDPE in the aging-resistant dripping master batch is not particularly limited in the invention, can be various LDPE which is conventionally used in the field and can be obtained commercially, for example, the commercially available LDPE comprises but is not limited to the product which is obtained from Exxon Mobil and has the trademark of LD171 BA.
Anti-aging agent
The anti-aging agent is a substance capable of delaying the chemical combination aging of high polymers. Most of them can inhibit the action of oxygen, and some can inhibit the action of heat or light, so that the service life of the product can be prolonged. Generally divided into natural antioxidants, physical antioxidants and chemical antioxidants. They can be classified into antioxidants, antiozonants and copper inhibitors according to their action, or into antioxidants which change color and do not change color, stain and do not stain, are resistant to heat or flexural aging, and prevent aging such as cracking.
The anti-aging agent in the anti-aging dripping master batch is selected from one or more of amine anti-aging agents, phenol (derivative) anti-aging agents and benzimidazole anti-aging agents.
Examples of amine antioxidants include, but are not limited to: n, N '-bis (2-octyl) -p-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylenediamine, N '-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine organic complexes.
Examples of phenolic (derivative) antioxidants include, but are not limited to: octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2' -thiobis (4-methyl-6-tert-butylphenol).
Examples of benzimidazole antioxidants include, but are not limited to: 2-mercaptobenzimidazole.
In a preferred embodiment, the antioxidant of the aging resistant dripping masterbatch of the present invention is Irganox1010, which is commercially available from Basff.
Hindered amine light stabilizers
The hindered amine light stabilizer is an organic amine compound with steric hindrance. The hindered amine has good inhibition effect on the photo-oxidative degradation reaction (see the photo-degradation of high polymers) and organic compounds, and is a light stabilizer with excellent performance.
The hindered amine light stabilizer in the aging-resistant dripping master batch is selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ].
In a preferred embodiment, the hindered amine light stabilizer in the aging resistant dripper of the present invention is TH9944, available from Ank chemical Limited, Zheng.
Functional auxiliary agent
In some embodiments, the functional additive in the aging-resistant dripping master batch is prepared from L-lysine triisocyanate, behenyl alcohol and a functional monomer.
In a more preferred embodiment, the functional monomers of the present invention are propylene diamine and imidazoline acetate.
In some embodiments, the functional additives of the present invention are prepared by steps comprising: adding L-lysine triisocyanate into a reaction kettle provided with a thermometer and a reflux device, diluting with acetone, dropwise adding behenyl alcohol and an acetone solution containing dibutyltin dilaurate serving as a catalyst, stirring at 55 ℃ for reacting for 1-2 hours, dropwise adding a functional monomer, and reacting for 2-3 hours under heat preservation to obtain the functional auxiliary agent.
In a preferred embodiment, the preparation step of the imidazoline acetate of the present invention comprises: adding acetic acid and diethylenetriamine into a three-neck flask at the temperature of 80 ℃, adding toluene, stirring and refluxing for 30min, then heating to 140 ℃ for reaction for 1 hour, then heating to 180 ℃ for reaction for 2 hours, cooling reactants to 110 ℃ when no water drop occurs in a condensation tube, distilling out the toluene and the excessive diethylenetriamine, and cooling to room temperature to obtain the imidazoline acetate monomer.
In a preferred embodiment, the molar ratio of L-lysine triisocyanate to behenyl alcohol in the process of preparing the functional additive according to the present invention is 1: (1.8-2.2); the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: (0.5 to 1.2); the functional monomer is propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is (1-3): 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
The inventor of the application finds that the drip effect of the greenhouse film can be improved by controlling the selection and the dosage proportion of the monomer components prepared from the functional additives, so that the acting period of the greenhouse film is prolonged, and the fog reducing effect of the greenhouse film can be improved at the same time. The possible reason is that the functional assistant is helpful to improve the activity of one layer of the inner surface of the greenhouse film under the synergistic action of dripping agent, other components of the master batch and the like, so that water molecules are quickly adsorbed and condensed on the inner surface of the greenhouse film, and simultaneously, the surface tension of the water molecules is reduced, so that the water molecules flow into the ground along the film wall. In addition, the applicant unexpectedly found that the interaction between the functional assistant and the drip agent can improve the service life of the greenhouse film, and the drip and fog reducing effects do not disappear in a short time without causing the greenhouse explosion even under the condition of a large amount of pesticides containing chlorine, sulfur and the like. When pesticides containing chlorine, sulfur and other elements are used in the conventional greenhouse film, the elements can accelerate the precipitation of assistants such as dripping agents and the like and shorten the acting period of fog reduction and dripping effects of the greenhouse film, and the problems are solved under the synergistic action of the functional assistants, the dripping agents and the like in the invention. The probable reason is that amino groups and other groups in the molecules of the functional auxiliary agent are basic to a certain extent, and can be combined with elements such as chlorine, sulfur and the like of pesticide, so that the elements are prevented from damaging light stabilizers, anti-aging agents and the like in the greenhouse film, and the acceleration of the migration speed of related components caused by the degradation of the greenhouse film is avoided.
Drip agent
The dripping agent is a surfactant which is an aid for destroying the interfacial tension between water drops and a film and preventing the water drops from forming on the surface. Generally, the surfactant is added in the polymer processing process, so that condensed water drops can be distributed into a continuous transparent thin layer, and the function of the thin layer is to reduce the contact angle between water and the surface of the polymer and prevent the surface from forming water drops.
In a preferred embodiment, the drip-forming agent in the aging-resistant drip-forming concentrate of the present invention is selected from polyol fatty acid esters.
In a more preferred embodiment, the drip-off agent of the present invention is FWD650, available from shanghai' an yi chemical company, ltd.
In a more preferred embodiment, the functional aid and the drip agent of the present invention are used in a ratio of 1 part by weight: (0.2-0.4).
The inventor finds that the combination of the functional additive and the drip agent in a certain weight proportion can prolong the fog reduction and drip effect time of the greenhouse film and can be matched with the service life of the greenhouse film. The inventors speculate that the functional aid has a long aliphatic chain structure, the cohesive energy density of the functional aid is not greatly different from that of other polyethylene components, and the functional aid can be well compatible and dispersed, and the functional aid has poor compatibility due to strong polarity of groups such as urethane bonds and the like, and large difference with polyolefin components, so that partial chain segments (polar parts) of the functional aid can migrate to the surface of a film, and the functional aid plays a dripping role under the action of water in a greenhouse. Due to the mutual entanglement between the long fatty chain in the functional auxiliary and other components of the system, the loss of the functional auxiliary is effectively avoided, and the onset time is prolonged. Meanwhile, due to the fact that the irregular random molecular chain structure of the functional auxiliary agent hinders the orderly arrangement of the raw materials for preparing the greenhouse film, crystallization of the raw materials in the preparation process is avoided, light refraction and reflection are avoided, and improvement of the light transmittance and the low-temperature resistance of the greenhouse film is facilitated.
< inner two layers >
In a preferred embodiment, the inner two layers of the present invention comprise, in parts by weight: 25-35 parts of POE, 10-15 parts of mLLDPE-1 and 3-7 parts of ageing-resistant dripping master batch.
(POE)
The POE is a polyolefin elastomer, has a molecular structure similar to Ethylene Propylene Diene Monomer (EPDM), has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is widely applied to the fields of the automobile industry, wire and cable sheaths, plastic toughening agents and the like.
The POE of the inner two layers is not particularly limited in the present invention, and may be any of various POE conventionally used in the art, and may be commercially available, for example, commercially available POE includes, but is not limited to, products available from dupont dow under the designation 1881G or 8201.
(mLLDPE-1)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-1 is 0.919-0.935 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-1 includes, but is not limited to, products available from Exxon Mobil under the trade designations 1327CA, 1327ED, having a density of 0.927g/cm3。
(anti-aging dripping masterbatch)
The anti-aging dripping master batch of the inner two layers is the same as the anti-aging dripping master batch of the inner layer.
< middle layer >
In a preferred embodiment, the middle layer of the present invention comprises, in parts by weight: 20-30 parts of EVA (ethylene-vinyl acetate), 15-25 parts of POE (polyolefin elastomer), 10-15 parts of LDPE-2 and 4-7 parts of heat-insulating master batch.
(EVA)
The EVA is prepared by copolymerizing ethylene and acetic acid, and has the Chinese cultural name: ethylene-vinyl acetate copolymer (ethylene-vinyl acetate copolymer), the content of general Vinyl Acetate (VA) is 5% -40%, compared with Polyethylene (PE), EVA because introduce vinyl acetate monomer in the molecular chain, thus has reduced the high degree of crystallinity, has improved toughness, impact resistance, filler intermiscibility and heat sealability, is used in fields such as foaming shoe material, functional shed membrane, packaging mould, hot melt adhesive, wire and cable and toy extensively.
The content of VA in the EVA is preferably 8-18 wt%, and the melt index at 190 ℃ and 2.16kg is 0.5-2 g/10 min; more preferably, the content of VA in the EVA is preferably 10-16 wt%, and the melt index at 190 ℃ under 2.16kg is 0.5-1 g/10 min; commercially available EVA can be obtained, for example, commercially available EVA includes but is not limited to products available from Yangzhini Pasteur under the trade name V4110F, the VA content is 12.6-15.4 wt%, and the melt index is 0.6-0.9 g/10 min.
The inventor finds that the VA with specific content in the EVA can cause the polarity and cohesive energy density of the component to be high, and improves the material molecular internal acting force, thereby improving the strength of the greenhouse film and avoiding premature wear and damage of the greenhouse film in the using process. However, the VA content cannot be too high, otherwise incompatible regions and interfaces exist between materials due to the polarity difference between the VA content and other components, and the strength of the greenhouse film is reduced. Secondly, the applicant finds that the content of VA is in the range of 8-18 wt%, which is beneficial to improving the heat preservation effect of the greenhouse film, and the probable reason is that the EVA with specific VA content increases the density of the middle layer of the greenhouse film and reduces heat loss in the greenhouse film on the premise of not influencing the compatibility among various materials, thereby improving the heat preservation effect. In addition, applicants have unexpectedly discovered that the use of EVA with the above specified VA content also helps to prolong the haze reduction, drip reduction effect of the greenhouse film. The possible reason is that the EVA has a relatively compact structure and relatively high density, so that functional additives, dripping agents and other ingredients in the inner two layers are prevented from migrating to the middle layer or the outer layer, and the functional additives are slowly migrated to the inner layer under the extrusion of the EVA component, namely, the functional additives are slowly released, the corresponding effect of the greenhouse film is prevented from disappearing along with the loss of time, and the corresponding effect of the greenhouse film can be fully exerted.
(POE)
The POE is a polyolefin elastomer, has a molecular structure similar to Ethylene Propylene Diene Monomer (EPDM), has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is widely applied to the fields of the automobile industry, wire and cable sheaths, plastic toughening agents and the like.
The POE of the middle layer is not particularly limited in the present invention, and may be any of various POE conventionally used in the art, and may be commercially available, for example, commercially available POE includes, but is not limited to, products available from dupont dow under the designations 1881G or 8201.
(LDPE-2)
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The optimized density of the LDPE-2 is 0.912-0.935 g/cm3The LDPE of (A) can be obtained commercially, for example commercially available LDPE includes but is not limited to that purchased from Exxon Mobil under the trademark LD171BA and has a density of 0.929g/cm3。
(Heat-insulating Master batch)
In a preferred embodiment, the insulation masterbatch comprises the following components in parts by weight: 20-30 parts of LDPE, 10-15 parts of talcum powder and 3-5 parts of basic magnesium carbonate.
LDPE
The LDPE, namely the low-density polyethylene, also called high-pressure polyethylene, is a plastic material, is suitable for various molding processes of thermoplastic molding and processing, and has good molding processability.
The LDPE in the insulation masterbatch is not particularly limited in the invention, can be various LDPE which is conventionally used in the field, and can be obtained commercially, for example, the commercially available LDPE includes but is not limited to the product which is obtained from Exxon Mobil and has the trademark LD171 BA.
Talcum powder
The talcum powder is magnesium silicate mineral talc, the main component of which is hydrous magnesium silicate, and the talcum powder is prepared by crushing, then treating with hydrochloric acid, washing with water and drying. The coating has excellent physical and chemical properties such as lubricity, anti-sticking property, flow aid property, fire resistance, acid resistance, insulativity, high melting point, chemical inactiveness, good covering power, softness, good luster, strong adsorption power and the like.
The talcum powder in the heat-insulating master batch is not particularly limited, can be various talcum powders which are conventionally used in the field and can be obtained commercially, and is purchased from Changxing Huayang plastic material Co.
Basic magnesium carbonate
The basic magnesium carbonate is white monoclinic crystal or amorphous powder, is pentatoxic and tasteless, and is stable in air. It is used as excellent filler and reinforcing agent for rubber products, and can be used as heat-insulating, high-temp. resisting, fire-resisting and heat-insulating material.
The basic magnesium carbonate in the heat-preservation master batch is not particularly limited, can be various basic magnesium carbonates conventionally used in the field, and can be obtained commercially.
< outer two layers >
In a preferred embodiment, the outer two layers of the present invention comprise, in parts by weight: 20-30 parts of mLLDPE-2, 30-50 parts of POE, 30-40 parts of LLDPE-2 and 3-5 parts of anti-aging master batch.
(mLLDPE-2)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-2 is 0.919-0.935 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-2 includes, but is not limited to, products available from Exxon Mobil under the trade designations 1327CA, 1327ED, having a density of 0.927g/cm3。
(POE)
The POE is a polyolefin elastomer, has a molecular structure similar to Ethylene Propylene Diene Monomer (EPDM), has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is widely applied to the fields of the automobile industry, wire and cable sheaths, plastic toughening agents and the like.
The POE of the outer two layers is not particularly limited in the present invention, and may be any of various POE conventionally used in the art, and may be commercially available, for example, commercially available POE includes, but is not limited to, products available from dupont dow under the designation 1881G or 8201.
(LLDPE-2)
The LLDPE, i.e., linear low density polyethylene, is a copolymer formed by polymerizing ethylene and a small amount of higher alpha-olefin (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) under the action of a catalyst and under high pressure or low pressure.
The LLDPE-2 of the invention preferably has the density of 0.919-0.935 g/cm3LLDPE of (a), can be obtained commercially, for example, LLDPE-2 available commercially includes, but is not limited to, the product available from Exxon Mobil under the trademark LL1107X95, having a density of 0.922g/cm3。
(antiaging agent)
In a preferred embodiment, the anti-aging masterbatch comprises, in parts by weight: 20-30 parts of LLDPE, 0.5-1.5 parts of hindered amine light stabilizer and 1-3 parts of composite antioxidant.
LLDPE
The LLDPE, i.e., linear low density polyethylene, is a copolymer formed by polymerizing ethylene and a small amount of higher alpha-olefin (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) under the action of a catalyst and under high pressure or low pressure.
The LLDPE in the antioxidant masterbatch of the present invention is not particularly limited, and may be any LLDPE conventionally used in the art, and may be commercially available, for example, commercially available LLDPE includes, but is not limited to, those purchased from exxonmobil under the designation JB-512.
Hindered amine light stabilizers
The hindered amine light stabilizer is an organic amine compound with steric hindrance. The hindered amine has good inhibition effect on the photo-oxidative degradation reaction (see the photo-degradation of high polymers) and organic compounds, and is a light stabilizer with excellent performance.
The hindered amine light stabilizer in the anti-aging master batch is not particularly limited, and can be various anti-aging agents conventionally used in the field, for example, the hindered amine light stabilizer can be selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, tris (1,2,2,6, 6-pentamethyl-4-piperidyl) phosphite, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidyl) imine ] ] ].
In a preferred embodiment, the hindered amine light stabilizer in the age resistor masterbatch of the present invention is TH9944, available from zheng akm chemical ltd.
Composite antioxidant
The antioxidants of the present invention are a class of chemicals which, when present in only small amounts in a polymer system, retard or inhibit the progress of the polymer oxidation process, thereby retarding polymer aging and extending its useful life.
The composite antioxidant in the anti-aging master batch is selected from at least two of amine antioxidant, ester antioxidant and phenol antioxidant; wherein the amine antioxidant is selected from hindered amine antioxidants; the ester antioxidant is selected from phosphite ester antioxidants; the phenolic antioxidant is selected from hindered phenolic antioxidants.
Examples of amine antioxidants include, but are not limited to: antioxidant 445, hindered amine 5057, hindered amine 944.
Examples of phenolic antioxidants include, but are not limited to: BHT, antioxidant 1010, antioxidant 1076, antioxidant DLTDP, antioxidant 1135 and antioxidant 245.
Examples of phosphite antioxidants include, but are not limited to: antioxidant 168, antioxidant 3010, and antioxidant 626.
In a preferred embodiment, the antioxidant in the antioxidant masterbatch is antioxidant 1010 and antioxidant 168, wherein the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 1 is obtained by compounding.
< outer layer >
In a preferred embodiment, the outer layer of the present invention comprises, in parts by weight: 30-40 parts of mLLDPE-3, 30-40 parts of POE, 10-20 parts of LLDPE-3 and 5-10 parts of anti-aging master batch.
(mLLDPE-3)
The mLLDPE is metallocene linear low-density polyethylene, has the characteristics of narrow relative molecular mass distribution and uniform comonomer distribution, and has the advantages of high toughness, good transparency, pollution resistance, puncture resistance, wide heat sealing temperature range and the like, so that the mLLDPE is widely applied.
The preferred density of the mLLDPE-3 is 0.912-0.918 g/cm3The mLLDPE of (a) can be obtained commercially, for example, commercially available mLLDPE-3 includes, but is not limited to, the product available from Exxon Mobil under the trademark E1012HA, and has a density of 0.912g/cm3。
(POE)
The POE is a polyolefin elastomer, has a molecular structure similar to Ethylene Propylene Diene Monomer (EPDM), has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like, and is widely applied to the fields of the automobile industry, wire and cable sheaths, plastic toughening agents and the like.
The POE of the outer layer is not particularly limited, and may be any of those conventionally used in the art, and may be commercially available, for example, commercially available POE includes, but is not limited to, products available from dupont dow under the designation 1881G or 8201.
(LLDPE-3)
The LLDPE, i.e., linear low density polyethylene, is a copolymer formed by polymerizing ethylene and a small amount of higher alpha-olefin (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) under the action of a catalyst and under high pressure or low pressure.
The LLDPE-3 of the invention preferably has the density of 0.912-0.918 g/cm3For example, commercially available LLDPE-3 includes, but is not limited to, the product available from Exxon Mobil under the designation FL201XV, having a density of 0.916g/cm3。
(antiaging agent)
The anti-aging master batch of the outer layer is the same as the anti-aging master batches of the outer two layers.
The applicant finds that a density gradient is formed between the inner layer and the inner two layers and between the outer layer and the outer two layers, and under the extrusion of high-density and relatively compact materials of the inner two layers and the outer two layers, the functional core layers in the inner two layers and the outer two layers are respectively and slowly migrated to the inner layer and the outer layer, so that the functional components are slowly released, and the effect of the components is fully exerted and the onset time of the functional core layers is prolonged.
The second aspect of the invention provides a preparation method of the aging-resistant dripping master batch, which comprises the following steps: and putting the LDPE, the anti-aging agent, the hindered amine light stabilizer, the functional assistant and the dripping agent into a high-speed mixer, mixing for 10-15 min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 150-200 ℃, and performing air cooling to obtain the anti-aging dripping master batch.
The third aspect of the invention provides a preparation method of the heat preservation master batch, which comprises the following steps: and (2) putting the LDPE, the talcum powder and the basic magnesium carbonate into a high-speed mixer, mixing for 10-15 min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 150-200 ℃, and air cooling to obtain the heat-preservation master batch.
The fourth aspect of the invention provides a preparation method of the anti-aging masterbatch, which comprises the following steps: and putting the LLDPE, the hindered amine light stabilizer and the composite antioxidant into a high-speed mixer, mixing for 10-15 min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 150-200 ℃, and air cooling to obtain the anti-aging master batch.
The fifth aspect of the invention provides a preparation method of the agricultural greenhouse film, which comprises the following steps:
(1) mixing the preparation raw materials of the inner layer, the inner two layer, the middle layer, the outer two layer and the outer layer of the greenhouse film, stirring for 15min, and then respectively putting into five main machine hoppers of the inner layer, the inner two layer, the middle layer, the outer two layer and the outer layer for extrusion by an extruder;
(2) continuously putting raw materials in five main machine hoppers into an extruder, melting and extruding the raw materials into a composite die head with five spiral runners, namely an inner layer, a middle layer, an outer layer and an outer layer, wherein the molten raw materials flow out according to respective spiral and converge in the die head to form a five-layer composite tube blank, wherein the temperature of a machine barrel of the extruder is 160-190 ℃, the temperature of a connecting pipe is 180-210 ℃, and the temperature of a machine head is 180-200 ℃;
(3) and blowing the stretched pipe blank to a required size by a fan, and then cooling, shaping and post-treating to obtain the pipe blank.
The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 20 parts of POE, 15 parts of LLDPE-1, 10 parts of LDPE-1 and 5 parts of anti-aging dripping master batch.
The sources of the components of the inner layer are as follows:
the inner layer of POE is a product which is purchased from DuPont Dow company and has the trademark of 1881G;
the LLDPE-1 is a product purchased from Exxon Mobil and having the mark number FL201XV, and the density is 0.916g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
Wherein, by weight, the anti-aging dripping master batch comprises: 10 parts of LDPE, 0.5 part of anti-aging agent, 1 part of hindered amine light stabilizer, 1 part of functional assistant and 0.3 part of dripping agent;
wherein the LDPE in the aging-resistant dripping master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the model of the anti-aging agent in the anti-aging dripping master batch is Irganox1010 and is purchased from Pasteur;
the hindered amine light stabilizer in the aging-resistant dripper is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the functional auxiliary agent in the anti-aging dripping master batch is prepared from L-lysine triisocyanate, behenyl alcohol and a functional monomer; wherein the functional monomers are propane diamine and imidazoline acetate;
wherein the preparation steps of the functional auxiliary agent comprise: adding L-lysine triisocyanate into a reaction kettle provided with a thermometer and a reflux device, diluting with acetone, then dropwise adding behenyl alcohol and an acetone solution containing a catalyst dibutyltin dilaurate, stirring at 55 ℃ for reacting for 2 hours, then dropwise adding a functional monomer, and carrying out heat preservation reaction for 2 hours to obtain the functional auxiliary agent;
the preparation method of the imidazoline acetate comprises the following steps: adding acetic acid and diethylenetriamine into a three-neck flask at the temperature of 80 ℃, adding toluene, stirring and refluxing for 30min, then heating to 140 ℃ for reaction for 1 hour, then heating to 180 ℃ for reaction for 2 hours, cooling reactants to 110 ℃ when no water drops appear in a condensation tube, distilling out the toluene and excessive diethylenetriamine, and cooling to room temperature to obtain the imidazoline acetate monomer;
in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 1.8; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 0.5; the functional monomer is propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is 1: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8;
the drip agent was FWD650, purchased from shanghai' an yi chemical company, ltd.
The preparation method of the anti-aging dripping master batch comprises the following steps: and putting the LDPE, the anti-aging agent, the hindered amine light stabilizer, the functional assistant and the dripping agent into a high-speed mixer, mixing for 15min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 180 ℃, and performing air cooling to obtain the anti-aging dripping master batch.
The inner two layers comprise the following components in parts by weight: 25 parts of POE, 10 parts of mLLDPE-1 and 3 parts of ageing-resistant dripping master batch.
The sources of the components of the inner two layers are as follows:
the inner two-layer POE is a product which is purchased from DuPont Dow company and has the mark number of 1881G or 8201;
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3；
The anti-aging dripping master batches of the inner two layers are the same as the anti-aging dripping master batches of the inner layer.
According to the weight portion, the middle layer comprises: 20 parts of EVA, 15 parts of POE, 10 parts of LDPE-2 and 4 parts of heat-insulating master batch.
The sources of the components of the middle layer are as follows:
the EVA is a product purchased from Yangzi petrochemical BASF and having a mark of V4110F, the content of the VA is 12.6-15.4 wt%, and the melt index is 0.6-0.9 g/10 min;
the POE of the middle layer is a product which is purchased from DuPont Dow and has the trademark of 1881G;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 20 parts of LDPE, 10 parts of talcum powder and 3 parts of basic magnesium carbonate;
the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the talc powder is purchased from chang huayang plastic materials ltd;
the basic magnesium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.
The preparation method of the heat preservation master batch comprises the following steps: and (2) putting the LDPE, the talcum powder and the basic magnesium carbonate into a high-speed mixer, mixing for 15min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 180 ℃, and air cooling to obtain the heat-preservation master batch.
The outer two layers of the invention comprise, by weight: 20 parts of mLLDPE-2, 30 parts of POE, 30 parts of LLDPE-2 and 3 parts of anti-aging master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3；
The outer two layers of POE are products purchased from DuPont Dow company under the trademark 1881G;
the LLDPE-2 is a product purchased from Exxon Mobil under the brand number LL1107X95 and has the density of 0.922g/cm 3;
wherein, by weight, the anti-aging master batch comprises: 20 parts of LLDPE, 0.5 part of hindered amine light stabilizer and 1 part of composite antioxidant;
LLDPE in the anti-aging master batch is a product purchased from Exxon Mobil and having the brand number of JB-512;
the hindered amine light stabilizer in the anti-aging master batch is TH9944, and is purchased from Zhengzhou Akhm chemical industry Co., Ltd;
the antioxidant in the anti-aging master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1 is obtained by compounding.
The preparation method of the anti-aging master batch comprises the following steps: and putting the LLDPE, the hindered amine light stabilizer and the composite antioxidant into a high-speed mixer, mixing for 15min, transferring to a double-screw extruder, melting and extruding at the extrusion temperature of 180 ℃, and air cooling to obtain the anti-aging master batch.
The outer layer comprises the following components in parts by weight: 30 parts of mLLDPE-3, 30 parts of POE, 10 parts of LLDPE-3 and 5 parts of anti-aging master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The outer layer of POE is a product which is purchased from DuPont Dow and has the trademark of 1881G;
the LLDPE-3 is a product purchased from Exxon Mobil and having the mark number FL201XV, and the density is 0.916g/cm3；
The anti-aging master batches on the outer layer are the same as the anti-aging master batches on the outer two layers.
The preparation method of the agricultural greenhouse film comprises the following steps:
(1) mixing the preparation raw materials of the inner layer, the inner two layer, the middle layer, the outer two layer and the outer layer of the greenhouse film, stirring for 15min, and then respectively putting into five main machine hoppers of the inner layer, the inner two layer, the middle layer, the outer two layer and the outer layer for extrusion by an extruder;
(2) continuously putting raw materials in five main machine hoppers into an extruder, melting and extruding the raw materials into a composite die head with five spiral runners, namely an inner layer, a middle layer, an outer layer and an outer layer, wherein the molten raw materials flow out according to respective spiral and converge in the die head to form a five-layer composite tube blank, wherein the temperature of a machine barrel of the extruder is 160-190 ℃, the temperature of a connecting pipe is 180-210 ℃, and the temperature of a machine head is 180-200 ℃;
(3) and blowing the stretched pipe blank to a required size by a fan, and then cooling, shaping and post-treating to obtain the pipe blank.
Example 2
Embodiment 2 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 30 parts of POE, 20 parts of LLDPE-1, 20 parts of LDPE-1 and 10 parts of ageing-resistant dripping master batch.
The sources of the components of the inner layer are as follows:
the inner layer of POE is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LLDPE-1 is a product purchased from Exxon Mobil and having the mark number FL201XV, and the density is 0.916g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
Wherein, by weight, the anti-aging dripping master batch comprises: 20 parts of LDPE, 1.5 parts of anti-aging agent, 1.5 parts of hindered amine light stabilizer, 3 parts of functional assistant and 0.8 part of dripping agent;
wherein the LDPE in the aging-resistant dripping master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the model of the anti-aging agent in the anti-aging dripping master batch is Irganox1010 and is purchased from Pasteur;
the hindered amine light stabilizer in the aging-resistant dripper is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the functional auxiliary agent in the aging-resistant dripping master batch is the same as that in the embodiment 1;
the drip agent was FWD650, purchased from shanghai' an yi chemical company, ltd.
The preparation method of the aging-resistant dripping master batch is the same as that of the example 1.
The inner two layers comprise the following components in parts by weight: 35 parts of POE, 15 parts of mLLDPE-1 and 7 parts of ageing-resistant dripping master batch.
The sources of the components of the inner two layers are as follows:
the POE of the inner two layers is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327ED, and the density is 0.927g/cm3；
The anti-aging dripping master batches of the inner two layers are the same as the anti-aging dripping master batches of the inner layer.
According to the weight portion, the middle layer comprises: 30 parts of EVA, 25 parts of POE, 15 parts of LDPE-2 and 7 parts of heat-insulating master batch.
In the middle ofThe component sources of the layers are as follows:
the EVA is a product purchased from Yangzi petrochemical BASF and having a mark of V4110F, the content of the VA is 12.6-15.4 wt%, and the melt index is 0.6-0.9 g/10 min;
the POE of the middle layer is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 30 parts of LDPE, 15 parts of talcum powder and 5 parts of basic magnesium carbonate;
the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the talc powder is purchased from chang huayang plastic materials ltd;
the basic magnesium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.
The preparation method of the heat preservation master batch is the same as that of the example 1.
The outer two layers of the invention comprise, by weight: 30 parts of mLLDPE-2, 50 parts of POE, 40 parts of LLDPE-2 and 5 parts of anti-aging master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having the brands of 1327CA and 1327ED, and the density is 0.927g/cm3；
The POE of the outer two layers is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LLDPE-2 is a product purchased from Exxon Mobil under the trademark LL1107X95 and has the density of 0.922g/cm3；
Wherein, by weight, the anti-aging master batch comprises: 30 parts of LLDPE, 1.5 parts of hindered amine light stabilizer and 3 parts of composite antioxidant;
LLDPE in the anti-aging master batch is a product purchased from Exxon Mobil and having the brand number of JB-512;
the hindered amine light stabilizer in the anti-aging master batch is TH9944, and is purchased from Zhengzhou Akhm chemical industry Co., Ltd;
the antioxidant in the anti-aging master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1 is obtained by compounding.
The preparation method of the anti-aging masterbatch is the same as that of example 1.
The outer layer comprises the following components in parts by weight: 40 parts of mLLDPE-3, 40 parts of POE, 20 parts of LLDPE-3 and 10 parts of anti-aging master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The outer layer of POE is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LLDPE-3 is a product purchased from Exxon Mobil and having the mark number FL201XV, and the density is 0.916g/cm3；
The anti-aging master batches on the outer layer are the same as the anti-aging master batches on the outer two layers.
The preparation method of the agricultural greenhouse film is the same as that of the embodiment 1.
Example 3
Embodiment 3 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
The inner layer comprises the following components in parts by weight: 25 parts of POE, 18 parts of LLDPE-1, 15 parts of LDPE-1 and 8 parts of ageing-resistant dripping master batch.
The sources of the components of the inner layer are as follows:
the inner layer of POE is a product which is purchased from DuPont Dow company and has the trademark of 1881G;
the LLDPE-1 is commercially availableAvailable from Exxon Mobil under the trademark FL201XV, and has a density of 0.916g/cm3；
The LDPE-1 is a product purchased from Exxon Mobil and having a grade of 350D65 and has a density of 0.917g/cm3；
Wherein, by weight, the anti-aging dripping master batch comprises: 15 parts of LDPE, 1 part of anti-aging agent, 1.2 parts of hindered amine light stabilizer, 2 parts of functional assistant and 0.5 part of dripping agent;
wherein the LDPE in the aging-resistant dripping master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the model of the anti-aging agent in the anti-aging dripping master batch is Irganox1010 and is purchased from Pasteur;
the hindered amine light stabilizer in the aging-resistant dripper is TH9944 purchased from Zhengzhou Akhm chemical Co., Ltd;
the functional auxiliary agent in the aging-resistant dripping master batch is the same as that in the embodiment 1;
the drip agent was FWD650, purchased from shanghai' an yi chemical company, ltd.
The preparation method of the aging-resistant dripping master batch is the same as that of the example 1.
The inner two layers comprise the following components in parts by weight: 30 parts of POE, 12 parts of mLLDPE-1 and 5 parts of ageing-resistant dripping master batch.
The sources of the components of the inner two layers are as follows:
the POE of the inner two layers is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the mLLDPE-1 is a product purchased from Exxon Mobil and having a grade of 1327ED, and the density is 0.927g/cm3；
The anti-aging dripping master batches of the inner two layers are the same as the anti-aging dripping master batches of the inner layer.
According to the weight portion, the middle layer comprises: 25 parts of EVA, 20 parts of POE, 13 parts of LDPE-2 and 6 parts of heat-insulating master batch.
The sources of the components of the middle layer are as follows:
the EVA is a product purchased from Yangzi petrochemical BASF and having a mark of V4110F, the content of the VA is 12.6-15.4 wt%, and the melt index is 0.6-0.9 g/10 min;
the POE of the middle layer is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LDPE-2 is a product purchased from Exxon Mobil and having the trademark LD171BA and the density of the LDPE-2 is 0.929g/cm3；
Wherein, by weight, the heat preservation master batch comprises: 25 parts of LDPE, 12 parts of talcum powder and 4 parts of basic magnesium carbonate;
the LDPE in the heat-insulating master batch is a product purchased from Exxon Mobil and having the grade of LD171 BA;
the talc powder is purchased from chang huayang plastic materials ltd;
the basic magnesium carbonate is purchased from Shanghai Yangtze titanium white chemical products, Co.
The preparation method of the heat preservation master batch is the same as that of the example 1.
The outer two layers of the invention comprise, by weight: 25 parts of mLLDPE-2, 40 parts of POE, 35 parts of LLDPE-2 and 4 parts of anti-aging master batch.
The sources of the components of the outer two layers are as follows:
the mLLDPE-2 is a product purchased from Exxon Mobil and having a grade of 1327ED, and the density is 0.927g/cm3；
The outer two layers of POE are products purchased from DuPont Dow company under the trademark 1881G;
the LLDPE-2 is a product purchased from Exxon Mobil under the trademark LL1107X95 and has the density of 0.922g/cm3；
Wherein, by weight, the anti-aging master batch comprises: 25 parts of LLDPE, 1.0 part of hindered amine light stabilizer and 2 parts of composite antioxidant;
LLDPE in the anti-aging master batch is a product purchased from Exxon Mobil and having the brand number of JB-512;
the hindered amine light stabilizer in the anti-aging master batch is TH9944, and is purchased from Zhengzhou Akhm chemical industry Co., Ltd;
the antioxidant in the anti-aging master batch is antioxidant 1010 and antioxidant 168 according to the weight ratio of 1: 1 is obtained by compounding.
The preparation method of the anti-aging masterbatch is the same as that of example 1.
The outer layer comprises the following components in parts by weight: 35 parts of mLLDPE-3, 35 parts of POE, 15 parts of LLDPE-3 and 8 parts of anti-aging master batch.
The sources of the components of the outer layer are as follows:
the mLLDPE-3 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3；
The outer layer of POE is a product which is purchased from DuPont Dow company and has the brand number of 8201;
the LLDPE-3 is a product purchased from Exxon Mobil and having the mark number FL201XV, and the density is 0.916g/cm3；
The anti-aging master batches on the outer layer are the same as the anti-aging master batches on the outer two layers.
The preparation method of the agricultural greenhouse film is the same as that of the embodiment 1.
Example 4
Embodiment 4 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 4 is the same as example 3, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2.2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1.2; the functional monomer is propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is 3: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 5
Embodiment 5 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 5 is the same as example 3, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1; the functional monomers are propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is 2: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 6
Embodiment 6 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 6 is the same as example 5, except that the aging resistant drip masterbatch is different: the anti-aging dripping master batch comprises the following components in parts by weight: 15 parts of LDPE, 1 part of anti-aging agent, 1.2 parts of hindered amine light stabilizer, 0.1 part of functional assistant and 0.5 part of dripping agent.
Example 7
Embodiment 7 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers and an outer layer, wherein the layers are stacked from the inner layer to the outer layer in sequence; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 7 is the same as example 5 except that the aging resistant drip masterbatch is different: the anti-aging dripping master batch comprises the following components in parts by weight: 15 parts of LDPE, 1 part of anti-aging agent, 1.2 parts of hindered amine light stabilizer, 30 parts of functional assistant and 0.5 part of dripping agent.
Example 8
Embodiment 8 provides an agricultural greenhouse film with long-acting dripping, fog-reducing, aging-resistant, and low-temperature-resistant properties, which consists of an inner layer, an inner two layers, a middle layer, an outer two layers, and an outer layer, wherein the layers are stacked in sequence from the inner layer to the outer layer; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 8 is the same as example 5, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1; the functional monomer is propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is 0.1: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 9
Embodiment 9 provides an agricultural greenhouse film having long-acting dripping, fog-reducing, aging-resistant, and low-temperature-resistant properties, the agricultural greenhouse film being composed of an inner layer, an inner two layers, a middle layer, an outer two layers, and an outer layer, and the layers being stacked in order from the inner layer to the outer layer; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 9 is the same as example 5, except that the ratio of the individual raw materials in the functional aid preparation process is different: in the preparation process of the functional auxiliary agent, the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: 2; the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: 1; the functional monomers are propane diamine and imidazoline acetate, and the weight ratio of the propane diamine to the imidazoline acetate is 20: 1; wherein the CAS of the L-lysine triisocyanate is 69878-18-8, and the CAS of the behenyl alcohol is 661-19-8.
Example 10
Embodiment 10 provides an agricultural greenhouse film having long-acting dripping, fog-reducing, aging-resistant, and low-temperature-resistant properties, the agricultural greenhouse film being composed of an inner layer, an inner two layers, a middle layer, an outer two layers, and an outer layer, the layers being stacked in order from the inner layer to the outer layer; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 10 is the same as example 5 except that the EVA was a product purchased from Exxon Mobil under the designation FL00728CC, the VA content was 27.5 wt%, and the melt index was 7g/10 min.
Example 11
Embodiment 11 provides an agricultural greenhouse film having long-acting drip, fog-reducing, aging-resistant, and low-temperature resistant properties, the agricultural greenhouse film being composed of an inner layer, an inner two layers, a middle layer, an outer two layers, and an outer layer, and the layers being stacked in order from the inner layer to the outer layer; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 11 is the same as example 5 except that the EVA was a product purchased from Korea modern under the trade name EF221, the VA content was 3 wt%, and the melt index was 0.6g/10 min.
Example 12
Embodiment 12 provides an agricultural greenhouse film having long-acting drip, fog-reducing, aging-resistant, and low-temperature resistant properties, the agricultural greenhouse film comprising an inner layer, a middle layer, an outer layer, and an outer layer, each layer being stacked in order from the inner layer to the outer layer; wherein, by weight, the agricultural greenhouse film comprises: 12 parts of an inner layer, 10 parts of an inner two-layer, 18 parts of a middle layer, 18 parts of an outer two-layer and 25 parts of an outer layer.
Example 12 is the same as example 5 except that: the mLLDPE-1 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3(ii) a The mLLDPE-2 is a product purchased from Exxon Mobil and having the grade of E1012HA, and the density is 0.912g/cm3(ii) a The mLLDPE-3 is a product purchased from Exxon Mobil and having a grade of 1327CA and the density is 0.927g/cm3。
Evaluation of Performance
1. And (3) artificial accelerated aging test: the test was carried out according to the GB/T16422.3-2014 standard.
2. Testing the flow drop fog dissipation period, the transmittance and the haze: the test was carried out according to the GB/T20202-2006 standard.
3. And (3) mobility testing: the sample was left in a dry environment for six months, and the mobility was determined by measuring the rate of change in weight.
TABLE 1
Claims (1)
1. An agricultural greenhouse film with long-acting dripping, fog-reducing, ageing-resistant and low-temperature-resistant performances is characterized in that the agricultural greenhouse film is composed of an inner layer, an inner two layer, a middle layer, an outer two layer and an outer layer, and the layers are stacked from the inner layer to the outer layer in sequence;
the agricultural greenhouse film comprises the following components in parts by weight: 10-15 parts of an inner layer, 8-12 parts of an inner two layer, 15-20 parts of a middle layer, 15-20 parts of an outer two layer and 20-30 parts of an outer layer;
the inner layer comprises the following components in parts by weight: 20-30 parts of POE, 15-20 parts of LLDPE-1, 10-20 parts of LDPE-1 and 5-10 parts of anti-aging dripping master batch;
the inner two layers comprise the following components in parts by weight: 25-35 parts of POE, 10-15 parts of mLLDPE-1 and 3-7 parts of ageing-resistant dripping master batch; the anti-aging dripping master batch comprises the following components in parts by weight: 10-20 parts of LDPE, 0.5-1.5 parts of anti-aging agent, 1-1.5 parts of hindered amine light stabilizer, 1-3 parts of functional assistant and 0.3-0.8 part of dripping agent; the functional assistant and the dripping agent have the following weight portions of 1: (0.2 to 0.4); the preparation method of the functional auxiliary agent comprises the following steps: adding an appropriate amount of acetone into L-lysine triisocyanate (CAS: 69878-18-8) to dilute, then dropwise adding an acetone solution of behenyl alcohol (CAS: 661-19-8) and a catalyst dibutyltin dilaurate, stirring and reacting for 1-2 hours at 55 ℃, then dropwise adding a functional monomer, and reacting for 2-3 hours under heat preservation to obtain the L-lysine triisocyanate; the molar ratio of the L-lysine triisocyanate to the behenyl alcohol is 1: (1.8-2.2); the molar ratio of the L-lysine triisocyanate to the functional monomer is 1: (0.5 to 1.2); the functional monomers are propane diamine and imidazoline acetate; the weight ratio of the propane diamine to the acetic acid imidazoline is (1-3): 1; the preparation method of the imidazoline acetate comprises the following steps: adding acetic acid and diethylenetriamine into a three-neck flask at the temperature of 80 ℃, adding toluene, stirring and refluxing for 30min, then heating to 140 ℃ for reaction for 1 hour, then heating to 180 ℃ for reaction for 2 hours, cooling reactants to 110 ℃ when no water drops appear in a condensation tube, distilling out the toluene and excessive diethylenetriamine, and cooling to room temperature to obtain the imidazoline acetate monomer;
the middle layer comprises the following components in parts by weight: 20-30 parts of EVA (ethylene-vinyl acetate), 15-25 parts of POE (polyolefin elastomer), 10-15 parts of LDPE-2 and 4-7 parts of heat-insulating master batch; the content of VA in the EVA is 8-18 wt%, and the melt index at 190 ℃ and 2.16kg is 0.5-2 g/10 min; the heat-preservation master batch comprises the following components in parts by weight: 20-30 parts of LDPE, 10-15 parts of talcum powder and 3-5 parts of basic magnesium carbonate;
the outer two layers comprise the following components in parts by weight: 20-30 parts of mLLDPE-2, 30-50 parts of POE, 30-40 parts of LLDPE-2 and 3-5 parts of anti-aging master batch;
the outer layer comprises the following components in parts by weight: 30-40 parts of mLLDPE-3, 30-40 parts of POE, 10-20 parts of LLDPE-3 and 5-10 parts of anti-aging master batch; the anti-aging master batch comprises the following components in parts by weight: 20-30 parts of LLDPE, 0.5-1.5 parts of hindered amine light stabilizer and 1-3 parts of composite antioxidant.
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| CN114763024A (en) * | 2021-05-26 | 2022-07-19 | 江苏智信塑胶科技有限公司 | Diffuse scattering film and preparation method thereof |
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| JP2000280425A (en) * | 1999-03-30 | 2000-10-10 | Sekisui Chem Co Ltd | Agricultural film |
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