CN108357171A - A kind of Green Polymer packaging film and preparation method thereof having vapor and the double excellent barriers of oxygen - Google Patents

A kind of Green Polymer packaging film and preparation method thereof having vapor and the double excellent barriers of oxygen Download PDF

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Publication number
CN108357171A
CN108357171A CN201810108972.0A CN201810108972A CN108357171A CN 108357171 A CN108357171 A CN 108357171A CN 201810108972 A CN201810108972 A CN 201810108972A CN 108357171 A CN108357171 A CN 108357171A
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layer
film
oxygen
vapor
cupric oxide
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Inventor
顾文秀
方波
何志毅
邹路易
孙余凭
顾瑾
滕跃
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WUXI FANGCHENG COLOR PRINTING PACKING CO Ltd
Jiangnan University
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WUXI FANGCHENG COLOR PRINTING PACKING CO Ltd
Jiangnan University
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Priority to CN201810108972.0A priority Critical patent/CN108357171A/en
Publication of CN108357171A publication Critical patent/CN108357171A/en
Priority to CN201910051385.7A priority patent/CN109551846A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

A kind of Green Polymer packaging film and preparation method thereof having vapor and the double excellent barriers of oxygen, belongs to the packing film technical field of composite polymer material technology.The present invention is on existing three-layer co-extruded polyethylene film Process ba- sis, using hydrophobically modified polyethylene as outer layer, polyethylene, the ethylene-vinyl alcohol copolymer of high obstructing performance and modified compatilizer are as middle level, hydrophilic modifying polyureas porous material coats nano cupric oxide analogue enztme as oxidation prevention layer filler blended and modified polyethylene as internal layer, by three-layer co-extruded curtain coating, the Green Polymer packaging film of vapor and the double excellent barriers of oxygen is made.Gained film is at low cost, simple production process while having both excellent vapor and oxygen-barrier property and having preferable degradability.

Description

A kind of Green Polymer packaging film having the double excellent barriers of vapor and oxygen and Preparation method
Technical field
The present invention relates to a kind of Green Polymer packaging film having vapor and the double excellent barriers of oxygen and its preparations A kind of method, and in particular to high-barrier, degradable three-layer co-extruded packaging film and preparation method thereof belong to composite high-molecular material The packing film technical field of material technology.
Background technology
Using high barrier film, the microbial reproduction caused by the infiltration of the gases such as oxygen can be prevented；Prevent by The oxidation of content is permeated and causes in oxygen；The exudation for preventing fragrance, solvent etc. improves the storage characteristics of content.High-barrier Property film, should also have stronger water vapor barrier property, prevent from causing going mouldy for content due to the infiltration of steam.It is mainly used for The packaging of the food such as ham, sausage, fresh fish, flesh of fish thin slice, raw meat, cheese, mayonnaise, sauce class, agricultural product and marine product.
Up to the present, although barrier packaging film various types, including multilayer complex films（Such as five-layer co-squeezing film）, altogether Mixed film, copolymerization film, evaporated film etc., but the degradability for reducing cost, simplifying technique, realizing high-isolation film material It is still the research direction of barrier film with safety in utilization.The three-layer co-extruded polyethylene film of tradition is at low cost, production technology Simply, but barrier property and degradation property difference are its technical bottlenecks.
In addition, enzyme is efficient biocatalyst, the chemical change of various complexity can be fast in a mild condition in organism Speed carries out, and basic reason is the catalytic action that various forms of enzymes rise in organism, and reaction rate is usually than common It is inorganic, organic catalyst is high by 107~1013Times.The experimental results show that the catalytic activity of enzyme depends on the activated centre of enzyme, The activated centre of a variety of enzymes shows related to elemental copper, and nano cupric oxide not only has the function of mimetic enzyme catalysis and excellent Visible light catalyst.
Invention content
It is an object of the present invention to overcome the above deficiencies, provides one kind and having vapor and the double excellent barriers of oxygen Green Polymer packaging film and preparation method thereof.
According to technical solution provided by the invention, a kind of Green Polymer having vapor and the double excellent barriers of oxygen Packaging film can be achieved through the following technical solutions：On existing three-layer co-extruded polyethylene film Process ba- sis, using polycyclic in oneself The polyethylene blend of ester and glyceryl tristearate hydrophobically modified is as outer layer；Using polyethylene, the ethylene-of high obstructing performance Ethenol copolymer and methyl vinyl ether-maleic acid copolymer are as middle level；Wherein methyl vinyl ether-maleic acid is total Effect of the polymers as compatilizer and photodegradation promoter；Using the cladding nano cupric oxide simulation of hydrophilic modifying polyureas porous material For enzyme as oxidation prevention layer filler blended and modified polyethylene as internal layer, nanoscale porous material not only acts as multilayer physical blocking oxygen The effect of access, while the oxygen penetrated on a small quantity can be made to be consumed by the copper oxide analogue enztme of inside cladding, altogether by three layers Squish flow is prolonged, and the Green Polymer packaging film of vapor and the double excellent barriers of oxygen is made.
A kind of Green Polymer packaging film having the double excellent barriers of vapor and oxygen comprising outer membrane, in Layer film and internal layer membrane are made by three-layer co-extruded curtain coating；
Meter formula in mass ratio is as follows：
The outer membrane is that Di Mi degree Ju Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates are 1 ︰ 7~8 ︰, 1 ︰ 0.1~0.5；
The middle layer film is that the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acids of degree of line are total Polymers is 4~5 ︰, 4~5 ︰ 1；
The internal layer membrane group is divided into the low close low close poly- second alkene ︰ hydrophilic modifying polyureas porous materials of degree of poly- second alkene ︰ lines of spending and coats Nano cupric oxide analogue enztme is 1 ︰, 7~8 ︰ 1~2.
The preparation method of the Green Polymer packaging film for having vapor and the double excellent barriers of oxygen, step is such as Under：
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 10~15 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates Than first by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole being added dropwise to institute while stirring It states in copper nitrate solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, in 100 ~120 DEG C reaction 8~12h, 6000~8000r/min centrifuge 20~40min, washing, vacuum degree be 5~20kPa, 60~ 80 DEG C, it is dried in vacuo 30~60min, obtains nano cupric oxide analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio dispensings that tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰, which intend enzyme ︰ water ︰ acetone quality ratios, Under conditions of 100~200r/min, 25 DEG C of water-baths, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added dropwise To nano cupric oxide analogue enztme water and acetone mixed solution in, be added dropwise in 40~60min, react 1h after, 6000 ~8000r/min, centrifuge 20~40min, vacuum degree be 5~20kPa, 40~60 DEG C vacuum drying 30~60min, obtain close Water modified polyurea porous material coats nano cupric oxide analogue enztme；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ hydrophilic modifying polyureas porous materials coat nano cupric oxide analog-quality than 1 ︰ of enzyme, 7~8 ︰ 1 ~2 carry out dispensing mixing, and mixture is put into melt pelletization in double screw extruder, extruder each section operation temperature Fen Bie Wei ︰ 170~180 DEG C, 180~200 DEG C, 190~210 DEG C, 190~200 DEG C, 180~190 DEG C；
（4）Has the preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By Di Mi degree Ju Yi Xi ︰ lines Property Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates 1 ︰ of mass ratio, 7~8 ︰ 1 ︰ 0.1~0.5 prepare outer layer mixing Material；By the mass ratio 4 of the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymers of degree of line 4~5 ︰ 1 of~5 ︰ prepare middle level mixture；Outer layer mixture and middle level mixture is uniform in stirrer for mixing respectively, then On three-layer co-extruded cast film machine, outer layer mixture, middle level mixture and internal layer master batch are subjected to fusion plastification, operation temperature respectively Degree is 200~220 DEG C, is coextruded and is cast by three-layer co-extruded cast film machine, and the extrusion rotating ratio of Wai Ceng ︰ Zhong Ceng ︰ internal layers is 1 ︰ 1 ︰ 1, co-extrusion output are 10~15kg/h, and rolling speed is 2~10m/min；Extruder die head is T-shaped mould head, the behaviour of T-shaped mould head It is 220~230 DEG C to make temperature, and chill roll cooling temperature is 15~25 DEG C, must have vapor and oxygen pair excellent barriers Green Polymer packaging film, 0.12~0.90mm of film thickness, width 150mm.
The internal layer of the three-layer co-extruded cast film machine, extrusion screw rod a diameter of 20mm, draw ratio L/D in middle level and outer layer are 30 ︰ 1, internal layer, middle level are consistent with the setting of the operating parameter of outer layer, when needing to change, three layers of operating parameter synchronous change.
Beneficial effects of the present invention：The present invention is on existing three-layer co-extruded polyethylene film Process ba- sis, with hydrophobically modified Polyethylene is as outer layer；Polyethylene, the ethylene-vinyl alcohol copolymer of high obstructing performance and modified compatilizer are as middle level；It is hydrophilic Modified polyurea porous material coats nano cupric oxide analogue enztme as oxidation prevention layer filler blended and modified polyethylene as internal layer；Pass through The Green Polymer packaging film of vapor and the double excellent barriers of oxygen is made in three-layer co-extruded curtain coating.Gained film is at low cost, produces It is simple for process while having both excellent vapor and oxygen-barrier property, and there is excellent degradability.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the application of the present invention is without being limited thereto.Used in embodiment Parallel dual-screw extruding machine：KS20, Kunshan Kesun Rubber ＆ Plastic Machinery Co., Ltd.（Diameter=20mm, draw ratioL/D=36 ︰ 1）；It is small-sized Cast film machine（Diameter=20mm, draw ratioL/D=30 ︰ 1, Shanghai Pu Zhan instruments Science and Technology Ltd., D-20）；Planetary ball mill： XQM-2L types, Bei Jing Xin Biao rise experimental instruments and equipment limited；Universal testing machine：1185, Instron companies of Britain；First Base vinyl ether-maleic acid copolymer（Average molecular weight 130000, lark prestige Science and Technology Ltd.）；
Low density polyethylene (LDPE) (trade mark 2426H, Maoming Petrochemical)；Low density polyethylene (LDPE)（The trade mark 2420D, Lan Hua）；Ethylene-vinyl alcohol Copolymer（Trade mark E105B, Kuraray）；Linear low density polyethylene（The trade mark 7042, Qilu Petrochemical）；Linea low density Polyethylene（The trade mark 1801, Yangtze petrochemical industry）；Unless otherwise instructed, raw materials used is commercial goods.
Embodiment 1 has the preparation of the macromolecule packaging film of vapor and the double excellent barriers of oxygen
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 10 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, First by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole is added dropwise to the nitre while stirring In sour copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, it is anti-in 100 DEG C 8h, 6000r/min is answered to centrifuge 20min, washing, vacuum degree 5kPa, 60 DEG C of vacuum drying 30min obtain nano cupric oxide Analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates Under conditions of the quasi- enzyme ︰ water ︰ acetone quality ratios of tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰ are 5 ︰, 1 ︰, 5 ︰, 3 ︰, 4,100 r/min, water Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme by 25 DEG C of bath temperature respectively It in the mixed solution of water and acetone, is added dropwise in 40 min, after reacting 1h, 6000r/min centrifuges 20min, vacuum 5kPa, 40 DEG C of vacuum drying 30min are spent, hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme is obtained；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Ethylene (trade mark 2426H, Maoming Petrochemical) ︰ linear low density polyethylene（The trade mark 7042, Qilu Petrochemical）︰ hydrophilic modifying polyureas is porous 1 ︰ of mass ratio, 7 ︰ 1 that material coats nano cupric oxide analogue enztme carry out dispensing mixing, and mixture, which is put into double screw extruder, to be melted Melt granulation, 170 DEG C, 180 DEG C, 190 DEG C, 190 DEG C, 180 DEG C of extruder each section operation temperature Fen other Wei ︰；
（4）Has the preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By low density polyethylene (LDPE) (board Number 2426H, Maoming Petrochemical) ︰ linear low density polyethylene（The trade mark 7042, Qilu Petrochemical）Tri- glycerol stearates of ︰ polycyclic Ji Nei Zhi ︰ 1 ︰ of mass ratio, 7 ︰, 1 ︰ 0.1 of ester prepare outer layer mixture；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl second of degree of line 4 ︰ of mass ratio, 4 ︰ 1 of alkene ether-copolymer-maleic anhydride prepare middle level mixture；Respectively in stirrer for mixing, then three On layer coextrusion casting film machine, outer layer mixture, middle level mixture and internal layer master batch are subjected to fusion plastification, each section operation respectively Temperature is：200、220、200℃；The extrusion rotating ratio of layer ︰ internal layers is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 12 kg/h, winding Speed is 3 m/min；Extruder die head is T-shaped mould head, the operation temperature on the width of T-shaped mould head be 230,225,220,220, 220,225,230 DEG C, chill roll cooling temperature is 15 DEG C, must have the Green Polymer of vapor and the double excellent barriers of oxygen Packaging film, film thickness 0.48mm, width 150mm.
Embodiment 2 has the preparation of the macromolecule packaging film of vapor and the double excellent barriers of oxygen
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 15 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, First by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole is added dropwise to the nitre while stirring In sour copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, it is anti-in 120 DEG C 12h, 8000r/min is answered to centrifuge 40min, washing, vacuum degree 12kPa, 80 DEG C of vacuum drying 60min are obtained nano oxidized Copper analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates It is water under conditions of 8 ︰, 1 ︰, 12 ︰ 5 ︰ 9,200r/min that tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰, which intend enzyme ︰ water ︰ acetone quality ratios, Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme by 25 DEG C of bath temperature respectively It in the mixed solution of water and acetone, is added dropwise in 60min, after reacting 1h, 8000r/min centrifuges 40min, vacuum degree 20kPa, 60 DEG C of vacuum drying 60min, obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：By 1 ︰, 8 ︰, 2 mass The low density polyethylene (LDPE) of ratio（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）︰ hydrophilic modifyings Polyureas porous material coats nano cupric oxide analogue enztme, carries out dispensing mixing, and mixture is put into melting in double screw extruder and makes Grain, extruder each section operation temperature are respectively：180 DEG C, 200 DEG C, 210 DEG C, 200 DEG C, 190 DEG C；
（4）The preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By low density polyethylene (LDPE)（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）The matter of ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates Amount prepares outer layer mixture than 1 ︰, 8 ︰, 1 ︰ 0.5；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl ethylenes of degree of line 5 ︰ of mass ratio, 5 ︰ 1 of ether-copolymer-maleic anhydride prepare middle level mixture；Respectively in stirrer for mixing, then altogether at three layers It squeezes on cast film machine, outer layer mixture, middle level mixture and internal layer master batch is subjected to fusion plastification, each section operation temperature respectively For：200、220、200℃；The extrusion rotating ratio of layer ︰ internal layers is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 10 kg/h, rolling speed For 2 m/min；Extruder die head is T-shaped mould head, the operation temperature on the width of T-shaped mould head be 230,225,220,220,220, 225,230 DEG C, chill roll cooling temperature is 25 DEG C, must have the Green Polymer packaging of vapor and the double excellent barriers of oxygen Film, film thickness 0.59mm, width 150mm.
Embodiment 3 has the preparation of the macromolecule packaging film of vapor and the double excellent barriers of oxygen
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 11 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, First by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole is added dropwise to the nitre while stirring In sour copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, it is anti-in 110 DEG C 9h, 7000r/min is answered to centrifuge 30min, washing, vacuum degree 10kPa, 70 DEG C of vacuum drying 50min obtain nano cupric oxide Analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates It is water-bath under conditions of 6 ︰, 1 ︰, 7 ︰ 4 ︰ 6,100r/min that tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰, which intend enzyme ︰ water ︰ acetone quality ratios, 25 DEG C of temperature, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to the water of nano cupric oxide analogue enztme It in the mixed solution of acetone, is added dropwise in 50min, after reacting 1h, 7000r/min centrifuges 30min, vacuum degree 8kPa, 40 DEG C of vacuum drying 40min, obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Ethylene (trade mark 2426H, Maoming Petrochemical) ︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）︰ hydrophilic modifying polyureas is porous Material coats 1 ︰ of mass ratio, 7.5 ︰ 1.5 of nano cupric oxide analogue enztme, carries out dispensing mixing, and mixture is put into double screw extruder Middle melt pelletization, 175 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C of extruder each section operation temperature Fen other Wei ︰；
（4）The preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By the low density polyethylene (LDPE) (trade mark 2426H, Maoming Petrochemical) ︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates 1 ︰ of mass ratio, 7.5 ︰ 1 ︰ 0.3 prepare outer layer mixture；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl second of degree of line 4.5 ︰ of mass ratio, 4.5 ︰ 1 of alkene ether-copolymer-maleic anhydride prepare middle level mixture；Respectively in stirrer for mixing, then On three-layer co-extruded cast film machine, outer layer mixture, middle level mixture and internal layer master batch are subjected to mixed melting plasticizing respectively, respectively Section operating temperature is：200、220、200℃；Outer layer：Middle level：The extrusion rotating ratio of internal layer is 1 ︰, 1 ︰ 1, and co-extrusion output is 15 Kg/h, rolling speed are 2 m/min；Extruder die head is T-shaped mould head, the operation temperature of T-shaped mould head is 230,225,220, 220,220,225,230 DEG C, chill roll cooling temperature is 20 DEG C, and the green that must have vapor and the double excellent barriers of oxygen is high Molecule packaging film, film thickness 0.90mm, width 150mm.
Embodiment 4 has the preparation of the macromolecule packaging film of vapor and the double excellent barriers of oxygen
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 15 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, First by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole is added dropwise to the nitre while stirring In sour copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, it is anti-in 100 DEG C 11h, 8000r/min is answered to centrifuge 35min, washing, vacuum degree 15kPa, 65 DEG C of vacuum drying 40min are obtained nano oxidized Copper analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates It is water-bath under conditions of 8 ︰, 1 ︰, 7 ︰ 4 ︰ 8,100r/min that tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰, which intend enzyme ︰ water ︰ acetone quality ratios, 25 DEG C of temperature, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to the water of nano cupric oxide analogue enztme It in the mixed solution of acetone, is added dropwise in 50min, after reacting 1h, 6000r/min centrifuges 25min, vacuum degree 15kPa, 45 DEG C of vacuum drying 45min, obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Ethylene（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）︰ hydrophilic modifying polyureas porous materials 1 ︰ of mass ratio, 8 ︰ 1 of nano cupric oxide analogue enztme are coated, dispensing mixing is carried out, mixture is put into melting in double screw extruder and makes Grain, extruder each section operation temperature Fen Bie 180 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 190 DEG C of Wei ︰；
（4）The preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By low density polyethylene (LDPE)（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）The matter of ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates Amount prepares outer layer mixture than 1 ︰, 8 ︰, 1 ︰ 0.4；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl ethylenes of degree of line 4 ︰ of mass ratio, 4.5 ︰ 1 of ether-copolymer-maleic anhydride prepare middle level mixture；Respectively in stirrer for mixing, then at three layers On coextrusion casting film machine, outer layer mixture, middle level mixture and internal layer master batch are subjected to mixed melting plasticizing, each section behaviour respectively It is as temperature：200、220、200℃；The extrusion rotating ratio of layer ︰ internal layers is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 10 kg/h, is received Volume speed is 10 m/min；Extruder die head is T-shaped mould head, the operation temperature of T-shaped mould head is 230,225,220,220,220, 225,230 DEG C, chill roll cooling temperature is 18 DEG C, must have the Green Polymer packaging of vapor and the double excellent barriers of oxygen Film, film thickness 0.12mm, width 150mm.
Embodiment 5 has the preparation of the macromolecule packaging film of vapor and the double excellent barriers of oxygen
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 10 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, first It is added dropwise to the nitric acid while stirring by copper nitrate and water wiring solution-forming, then by the saturated solution of the sodium citrate of required mole In copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, in 110 DEG C of reactions 11h, 7000r/min centrifuge 35min, washing, and vacuum degree 8kPa, 75 DEG C of vacuum drying 35min obtain nano oxidized copper mold Quasi- enzyme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates Under conditions of the quasi- enzyme ︰ water ︰ acetone quality ratios of tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰ are 7 ︰, 1 ︰, 10 ︰, 4.5 ︰, 7,200 r/min, Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme by 25 DEG C of bath temperature respectively Water and acetone mixed solution in, be added dropwise in 60min, react 1h after, 6000r/min centrifuge 35min, vacuum 17kPa, 55 DEG C of vacuum drying 35min are spent, hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme is obtained；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Ethylene（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）︰ hydrophilic modifying polyureas porous materials 1 ︰ of mass ratio, 7 ︰ 2 of nano cupric oxide analogue enztme are coated, dispensing mixing is carried out, mixture is put into melting in double screw extruder and makes Grain, extruder each section operation temperature Fen Bie 180 DEG C, 180 DEG C, 210 DEG C, 200 DEG C, 190 DEG C of Wei ︰；
（4）The preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By low density polyethylene (LDPE)（The trade mark 2420D, Lan Hua）︰ linear low density polyethylene（The trade mark 1801, Yangtze petrochemical industry）The matter of ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates Amount prepares outer layer mixture than 1 ︰, 7 ︰, 1 ︰ 0.2；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl ethylenes of degree of line 5 ︰ of mass ratio, 4 ︰ 1 of ether-copolymer-maleic anhydride prepare middle level mixture；Respectively in stirrer for mixing, then altogether at three layers It squeezes on cast film machine, outer layer mixture, middle level mixture and internal layer master batch is subjected to mixed melting plasticizing, each section operation respectively Temperature is：200、220、200℃；The extrusion rotating ratio of layer ︰ internal layers is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 15 kg/h, winding Speed is 10 m/min；Extruder die head is T-shaped mould head, the operation temperature of T-shaped mould head is 230,225,220,220,220, 225,230 DEG C, chill roll cooling temperature is 22 DEG C, must have the Green Polymer packaging of vapor and the double excellent barriers of oxygen Film, film thickness 0.18mm, width 150mm.
The Mechanics Performance Testing of film article obtained by 1 Examples 1 to 5 of Application Example
The tensile strength of film presses standard GB/T/T 4456-2008, is tested using universal testing machine, test speed Degree is 10 mm/min, the results are shown in Table 1.
The mechanical property of 1 film of table
The light degradation property test of film article obtained by 2 Examples 1 to 5 of Application Example
In air at room temperature, ultraviolet lamp box（130cm×45cm×20cm）Reactor, 6 40W ultraviolet lamps（Centre wavelength is 340nm, UVA340, Q-lab Co.）, test specimens are cut into the disk of a diameter of 10cm, and the distance of sample and ultraviolet lamp is 5cm, The intensity of ultraviolet lamp is 14mW/cm2.It is measured using U.S.'s NICOLET companies Nexus870 type Fourier transformation infrared spectrometers The infrared spectrogram of sample, and carbonyl base index ︰ CI=A are calculated as follows1720cm-1/ A1465cm-1, the results are shown in Table 2.
The light degradation property of 2 film of table
The landfill weightlessness of film obtained by 3 Examples 1 to 5 of Application Example and barrier property test
Landfill weightless test is carried out according to the degradation property of GB/T 20197-2006 films；With pressure differential gas permeameter device （VAC-V1 types, Labthink Instruments Co., Ltd.）The moisture-vapor transmission and OTR oxygen transmission rate of film are tested, It the results are shown in Table 3.
The landfill weightlessness and barrier property of 3 film of table
The above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art, Under the premise of not departing from present inventive concept, several improvements and modifications can also be made, these improvements and modifications also should be regarded as this hair In bright protection domain.

Claims (3)

1. a kind of Green Polymer packaging film having vapor and the double excellent barriers of oxygen, it is characterised in that：It includes outer Layer film, middle layer film and internal layer membrane are made by three-layer co-extruded curtain coating；
Meter formula in mass ratio is as follows：
The outer membrane is that Di Mi degree Ju Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates are 1 ︰ 7~8 ︰, 1 ︰ 0.1~0.5；
The middle layer film is that the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acids of degree of line are total Polymers is 4~5 ︰, 4~5 ︰ 1；
The internal layer membrane group is divided into the low close low close poly- second alkene ︰ hydrophilic modifying polyureas porous materials of degree of poly- second alkene ︰ lines of spending and coats Nano cupric oxide analogue enztme is 1 ︰, 7~8 ︰ 1~2.
2. have the preparation method of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen described in claim 1, It is characterized in that steps are as follows：
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 10~15 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates Than first by copper nitrate and water wiring solution-forming, then the saturated solution of the sodium citrate of required mole being added dropwise to institute while stirring It states in copper nitrate solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, in 100 ~120 DEG C reaction 8~12h, 6000~8000r/min centrifuge 20~40min, washing, vacuum degree be 5~20kPa, 60~ 80 DEG C of 30~60min of vacuum drying, obtain nano cupric oxide analogue enztme；
（2）Hydrophilic modifying polyureas porous material coats the preparation of nano cupric oxide analogue enztme：According to Toluene-2,4-diisocyanate, 4- diisocyanates It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio dispensings that tri- ethylene of ester ︰, the four nano oxidized copper molds of amine ︰, which intend enzyme ︰ water ︰ acetone quality ratios, Under conditions of 100~200r/min, 25 DEG C of water-baths, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added dropwise To nano cupric oxide analogue enztme water and acetone mixed solution in, be added dropwise in 40~60min, react 1h after, 6000 ~8000r/min centrifuge 20~40min, vacuum degree be 5~20kPa, 40~60 DEG C vacuum drying 30~60min, obtain close Water modified polyurea porous material coats nano cupric oxide analogue enztme；
（3）The porous material of polyureas containing hydrophilic modifying coats the preparation of the internal layer master batch of nano cupric oxide analogue enztme：It is poly- by low-density Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ hydrophilic modifying polyureas porous materials coat 1 ︰ of mass ratio, 7~8 ︰ of nano cupric oxide analogue enztme 1~2 carries out dispensing mixing, and mixture is put into melt pelletization in double screw extruder, and extruder each section operation temperature is respectively： 170~180 DEG C, 180~200 DEG C, 190~210 DEG C, 190~200 DEG C, 180~190 DEG C；
（4）Has the preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen：By Di Mi degree Ju Yi Xi ︰ lines Property Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearates 1 ︰ of mass ratio, 7~8 ︰ 1 ︰ 0.1~0.5 prepare outer layer mixing Material；By the mass ratio 4 of the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymers of degree of line 4~5 ︰ 1 of~5 ︰ prepare middle level mixture；Outer layer mixture and middle level mixture is uniform in stirrer for mixing respectively, then On three-layer co-extruded cast film machine, outer layer mixture, middle level mixture and internal layer master batch are subjected to fusion plastification, operation temperature respectively Degree is 200~220 DEG C, is coextruded and is cast by three-layer co-extruded cast film machine, and the extrusion rotating ratio of Wai Ceng ︰ Zhong Ceng ︰ internal layers is 1 ︰ 1 ︰ 1, co-extrusion output are 10~15kg/h, and rolling speed is 2~10m/min；Extruder die head is T-shaped mould head, the behaviour of T-shaped mould head It is 220~230 DEG C to make temperature, and chill roll cooling temperature is 15~25 DEG C, is made and has vapor and the double excellent barriers of oxygen Green Polymer packaging film, 0.12~0.90mm of film thickness, width 150mm.
3. having the preparation side of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen according to claim 2 Method, it is characterised in that：The internal layer of three-layer co-extruded cast film machine, extrusion screw rod a diameter of 20mm, draw ratio L/D in middle level and outer layer For 30 ︰ 1, internal layer, middle level are consistent with the setting of the operating parameter of outer layer, when needing to change, three layers of operating parameter synchronous change.
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CN111590988A (en) * 2020-05-07 2020-08-28 合肥佛斯德新材料科技有限公司 Processing method of NY/RCPP composite film for high-temperature steaming bag

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CN108263061B (en) * 2018-02-05 2019-11-29 高源� A kind of degradable green package film of high-barrier and preparation method thereof
CN108456352A (en) * 2018-02-05 2018-08-28 江南大学 A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111590988A (en) * 2020-05-07 2020-08-28 合肥佛斯德新材料科技有限公司 Processing method of NY/RCPP composite film for high-temperature steaming bag
CN111590988B (en) * 2020-05-07 2022-04-01 合肥佛斯德新材料科技有限公司 Processing method of NY/RCPP composite film for high-temperature steaming bag

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Application publication date: 20180803