CN109551846A - 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
CN109551846A
CN109551846A CN201910051385.7A CN201910051385A CN109551846A CN 109551846 A CN109551846 A CN 109551846A CN 201910051385 A CN201910051385 A CN 201910051385A CN 109551846 A CN109551846 A CN 109551846A
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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
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WUXI FANGCHENG COLOR PRINTING PACKING CO Ltd
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    • 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
    • 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
    • B32B27/18—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

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, the anti-reflection soft conditioner and modified compatilizer of increasing are as middle layer, 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, has both excellent vapor and oxygen-barrier property simultaneously and has 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 for 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 technique
Using high barrier film, the microbial reproduction due to caused by the infiltration of oxygen can be prevented；It prevents due to oxygen Permeate and cause the oxidation of content；The exudation for preventing fragrance, solvent etc. improves the storage characteristics of content.High barrier film, Should also have stronger water vapor barrier property, prevent the infiltration due to steam and cause the mildew of content.It is mainly used for ham, perfume (or spice) The packaging of the food such as intestines, 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 reaction of various complexity in organism can be effectively facilitated in temperate condition It is lower to carry out rapidly, reaction rate usually than it is common it is inorganic, organic catalyst is high by 107~1013Times.The experimental results table Bright, the catalytic activity of enzyme depends on the activated centre of enzyme, the activated centre of a variety of enzymes show it is related to elemental copper, it is nano oxidized Copper not only have mimetic enzyme catalysis function and excellent visible light catalyst.
Summary of the invention
It is an object of the present invention to overcome the above deficiencies, provides one kind and has 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, anti-reflection soft bis- (the 3,4- dimethyl benzene methylenes of conditioner of increasing Base) sorbierite and glycerol are as middle layer, and wherein methyl vinyl ether-maleic acid copolymer promotes as compatilizer and light degradation The effect of agent；It is poly- as oxidation prevention layer filler blending and modifying using hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme For ethylene as internal layer, nanoscale porous material not only acts as the effect of multilayer physical blocking oxygen access, while can make a small amount of The oxygen of infiltration is consumed by the copper oxide analogue enztme of inside cladding, by three-layer co-extruded curtain coating, vapor is made and oxygen is double The Green Polymer packaging film of excellent barrier.
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 tristearate is 1 ︰ 7~8 ︰, 1 ︰ 0.1~0.5；
The middle layer film is the low close poly- second alkene ︰ ethylene-second of degree of bis- sweet oil ︰ lines of (3,4- dimethylbenzylidene) mountain pears alcohol ︰ Alkene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer is 0.001~0.005 ︰, 0.001~0.009 ︰, 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 material of degree of poly- second alkene ︰ line of spending and coats Nano cupric oxide analogue enztme is 1 ︰, 7~8 ︰ 2~3.
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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 10~15 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate 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 of reaction 8~12h, 6000~8000r/min are centrifugated 20~40min, washing, and vacuum degree is 5~20kPa, 60~ 80 DEG C, it is dried in vacuo 30~60min, obtains nano cupric oxide analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio ingredient that tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 20~40min, and vacuum degree is 5~20kPa, 40~60 DEG C of 30~60min of vacuum drying, obtains close Water modified polyurea porous material coats nano cupric oxide analogue enztme；
(3) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ hydrophilic modifying polyureas porous material coats 1 ︰ of nano cupric oxide analogue enztme mass ratio, 7~8 ︰ 2 ~3 carry out ingredient 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 ︰ line Property Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearate 1 ︰ of mass ratio, 7~8 ︰, 1 ︰ 0.1~0.5 prepare outer layer mixing Material；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ first of degree of bis- sweet oil ︰ lines of (3,4- dimethylbenzylidene) mountain pears alcohol ︰ During 4~5 ︰ of mass ratio 0.001~0.005 ︰, 0.001~0.009 ︰, 4~5 ︰ 1 of base vinyl ether-maleic acid copolymer is prepared Layer mixture；Outer layer mixture and middle layer mixture is uniform in stirrer for mixing respectively, then in three-layer co-extruded casting films On machine, outer layer mixture, middle layer mixture and internal layer master batch are subjected to fusion plastification respectively, operation temperature is 200~220 DEG C, It is coextruded and is cast by three-layer co-extruded cast film machine, the extrusion rotating ratio of layer ︰ internal layer is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 10 ~15kg/h, rolling speed are 2~10m/min；Extruder die head is T-die, and the operation temperature of T-die is 220~230 DEG C, chill roll cooling temperature is 15~25 DEG C, must have the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 0.12~0.90mm of film thickness, width 150mm.
The extrusion screw rod diameter of the internal layer of the three-layer co-extruded cast film machine, middle layer and outer layer is 20mm, and draw ratio L/D is 30 ︰ 1, internal layer, middle layer 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, the anti-reflection soft modification of increasing Bis- (3,4- dimethylbenzylidene) sorbierites of conditioner and glycerol are as middle layer；Hydrophilic modifying polyureas porous material coats nanometer Copper oxide analogue enztme is as oxidation prevention layer filler blended and modified polyethylene as internal layer；By three-layer co-extruded curtain coating, vapor is made With the Green Polymer packaging film of the double excellent barriers of oxygen.Gained film is at low cost, simple production process, have both simultaneously it is excellent Vapor and oxygen-barrier property, and there is excellent degradability.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but of the invention using 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 instrument Science and Technology Ltd., D-20)；Planetary ball mill: XQM-2L type, Bei Jing Xin Biao rise experimental instruments and equipment limited；Universal testing machine: 1185, Instron company, 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) (trade mark 2420D, orchidization)；Ethylene-vinyl alcohol Copolymer (trade mark E105B, Kuraray)；Linear low density polyethylene (trade mark 7042, Qilu Petrochemical)；Linea low density Polyethylene (trade mark 1801, Yangtze petrochemical industry)；(Hubei is real along the limited public affairs of biotechnology for bis- (3,4- dimethylbenzylidene) sorbierites Department)；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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 10 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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 be centrifugated 20min, washing, vacuum degree 5kPa, 60 DEG C of vacuum drying 30min obtain nano cupric oxide Analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate Under conditions of the quasi- enzyme ︰ water ︰ acetone quality ratio of tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰ is 5 ︰, 1 ︰, 5 ︰, 3 ︰, 4,100 r/min, water 25 DEG C of bath temperature, Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme respectively It in the mixed solution of water and acetone, is added dropwise in 40 min, after reacting 1h, 6000r/min is centrifugated 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) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density ((trade mark 7042, Qilu Petrochemical) ︰ hydrophilic modifying polyureas are porous for trade mark 2426H, Maoming Petrochemical) ︰ linear low density polyethylene for ethylene 1 ︰ of mass ratio, 7 ︰ 2 that material coats nano cupric oxide analogue enztme carries out ingredient mixing, and mixture, which is put into double screw extruder, to be melted Melt granulation, 170 DEG C of ︰ of Wei, 180 DEG C, 190 DEG C, 190 DEG C, 180 DEG C of other of extruder each section operation temperature Fen；
(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 (trade mark 7042, tri- glycerol stearate of Qilu Petrochemical) ︰ polycyclic Ji Nei Zhi ︰ 1 ︰ of mass ratio, 7 ︰, 1 ︰ 0.1 of ester prepares outer layer mixture；It is linearly low by bis- (3,4- dimethylbenzylidene) Shan Li Chun ︰ Gan You ︰ 0.001 ︰ of mass ratio, 0.001 ︰ of the close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer of degree 4 ︰, 4 ︰ 1 prepares middle layer mixture；Respectively in stirrer for mixing, then on three-layer co-extruded cast film machine, by outer layer mixture, Middle layer mixture and internal layer master batch carry out fusion plastification, each section operation temperature respectively are as follows: 200,220,200 DEG C；In Wai Ceng ︰ The extrusion rotating ratio of layer ︰ internal layer is 1 ︰, 1 ︰ 1, and co-extrusion output is 12 kg/h, and rolling speed is 3 m/min；Extruder die head is T Pattern head, the operation temperature on the width of T-die are 230,225,220,220,220,225,230 DEG C, the cooling temperature of chill roll Degree is 15 DEG C, must have the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 15 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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 be centrifugated 40min, washing, vacuum degree 20kPa, 80 DEG C of vacuum drying 60min are obtained nano oxidized Copper analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate It is 8 ︰, 1 ︰, 12 ︰, 5 ︰ 9 that tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰, which intends enzyme ︰ water ︰ acetone quality ratio, under conditions of 200r/min, water 25 DEG C of bath temperature, Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme respectively It in the mixed solution of water and acetone, is added dropwise in 60min, after reacting 1h, 8000r/min is centrifugated 40min, vacuum degree 20kPa, 60 DEG C of vacuum drying 60min obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
(3) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: 1 ︰, 8 ︰, 3 mass is pressed Low density polyethylene (LDPE) (trade mark 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ hydrophilic modifying of ratio Polyureas porous material coats nano cupric oxide analogue enztme, carries out ingredient mixing, and mixture is put into melting in double screw extruder and makes Grain, extruder each section operation temperature are respectively as follows: 180 DEG C, 200 DEG C, 210 DEG C, 200 DEG C, 190 DEG C；
(4) preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen: the low density polyethylene (LDPE) (trade mark is pressed 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ polycyclic ester ︰ glyceryl tristearate in oneself matter Amount prepares outer layer mixture than 1 ︰, 8 ︰, 1 ︰ 0.5；It is poly- by bis- (3,4- dimethylbenzylidene) Shan Li Chun ︰ Gan You ︰ linea low densities 5 ︰ of second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer mass ratio 0.005 ︰, 0.009 ︰, 5 ︰ 1 matches Middle layer mixture processed；Respectively in stirrer for mixing, then on three-layer co-extruded cast film machine, outer layer mixture, middle layer are mixed It closes material and internal layer master batch carries out fusion plastification, each section operation temperature respectively are as follows: 200,220,200 DEG C；Wai Ceng ︰ Zhong Ceng ︰ internal layer Extrusion rotating ratio be 1 ︰, 1 ︰ 1, co-extrusion output be 10 kg/h, rolling speed be 2 m/min；Extruder die head is T-die, T Operation temperature on the width of pattern head is 230,225,220,220,220,225,230 DEG C, and chill roll cooling temperature is 25 DEG C, Must have the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 11 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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 be centrifugated 30min, washing, vacuum degree 10kPa, 70 DEG C of vacuum drying 50min obtain nano cupric oxide Analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate It is 6 ︰, 1 ︰, 7 ︰, 4 ︰ 6 that tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰, which intends enzyme ︰ water ︰ acetone quality ratio, under conditions of 100r/min, water-bath 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 is centrifugated 30min, vacuum degree 8kPa, 40 DEG C of vacuum drying 40min obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
(3) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density ((trade mark 1801, Yangtze petrochemical industry) ︰ hydrophilic modifying polyureas are porous for trade mark 2426H, Maoming Petrochemical) ︰ linear low density polyethylene for ethylene Material coats 1 ︰ of mass ratio, 7.5 ︰ 2.5 of nano cupric oxide analogue enztme, carries out ingredient mixing, and mixture is put into double screw extruder Middle melt pelletization, 175 DEG C of ︰ of Wei, 190 DEG C, 200 DEG C, 200 DEG C, 190 DEG C of other of extruder each section operation temperature Fen；
(4) preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen: the low density polyethylene (LDPE) (trade mark is pressed 2426H, Maoming Petrochemical) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearate 1 ︰ of mass ratio, 7.5 ︰, 1 ︰ 0.3 prepare outer layer mixture；It is linearly low by bis- (3,4- dimethylbenzylidene) Shan Li Chun ︰ Gan You ︰ 0.002 ︰ of mass ratio, 0.005 ︰ of the close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer of degree 4.5 ︰, 4.5 ︰ 1 prepares middle layer mixture；Respectively in stirrer for mixing, then on three-layer co-extruded cast film machine, outer layer is mixed It closes material, middle layer mixture and internal layer master batch and carries out mixed melting plasticizing, each section operation temperature respectively are as follows: 200,220,200 DEG C； Outer layer: middle layer: the extrusion rotating ratio of internal layer is 1 ︰, 1 ︰ 1, and co-extrusion output is 15 kg/h, and rolling speed is 6 m/min；Extruder Die head is T-die, and the operation temperature of T-die is 230,225,220,220,220,225,230 DEG C, chill roll cooling temperature It is 20 DEG C, must has the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 15 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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 be centrifugated 35min, washing, vacuum degree 15kPa, 65 DEG C of vacuum drying 40min are obtained nano oxidized Copper analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate It is 8 ︰, 1 ︰, 7 ︰, 4 ︰ 8 that tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰, which intends enzyme ︰ water ︰ acetone quality ratio, under conditions of 100r/min, water-bath 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 is centrifugated 25min, vacuum degree 15kPa, 45 DEG C of vacuum drying 45min obtain hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme；
(3) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density Ethylene (trade mark 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ hydrophilic modifying polyureas porous material 1 ︰ of mass ratio, 8 ︰ 2 of nano cupric oxide analogue enztme is coated, ingredient 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 of ︰ of Wei, 180 DEG C, 190 DEG C, 200 DEG C, 190 DEG C；
(4) preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen: the low density polyethylene (LDPE) (trade mark is pressed 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ polycyclic ester ︰ glyceryl tristearate in oneself matter Amount prepares outer layer mixture than 1 ︰, 8 ︰, 1 ︰ 0.4；It is poly- by bis- (3,4- dimethylbenzylidene) Shan Li Chun ︰ Gan You ︰ linea low densities 4 ︰ of second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer mass ratio 0.003 ︰, 0.007 ︰, 4.5 ︰ 1 Prepare middle layer mixture；Respectively in stirrer for mixing, then on three-layer co-extruded cast film machine, by outer layer mixture, middle layer Mixture and internal layer master batch carry out mixed melting plasticizing, each section operation temperature respectively are as follows: 200,220,200 DEG C；In Wai Ceng ︰ The extrusion rotating ratio of layer ︰ internal layer is 1 ︰, 1 ︰ 1, and co-extrusion output is 14 kg/h, rolling speed 8m/min；Extruder die head is T-type Die head, the operation temperature of T-die are 230,225,220,220,220,225,230 DEG C, and chill roll cooling temperature is 18 DEG C, are obtained Have the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 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) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 10 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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, reacted in 110 DEG C 11h, 7000r/min are centrifugated 35min, and washing, vacuum degree 8kPa, 75 DEG C of vacuum drying 35min obtain nano oxidized copper mold Quasi- enzyme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate Under conditions of the quasi- enzyme ︰ water ︰ acetone quality ratio of tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰ is 7 ︰, 1 ︰, 10 ︰, 4.5 ︰, 7,200 r/min, 25 DEG C of bath temperature, Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nano cupric oxide analogue enztme respectively Water and acetone mixed solution in, be added dropwise in 60min, react 1h after, 6000r/min be centrifugated 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) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density Ethylene (trade mark 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ hydrophilic modifying polyureas porous material 1 ︰ of mass ratio, 7 ︰ 3 of nano cupric oxide analogue enztme is coated, ingredient 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 of ︰ of Wei, 180 DEG C, 210 DEG C, 200 DEG C, 190 DEG C；
(4) preparation of the Green Polymer packaging film of vapor and the double excellent barriers of oxygen: the low density polyethylene (LDPE) (trade mark is pressed 2420D, Lan Hua) ︰ linear low density polyethylene (trade mark 1801, Yangtze petrochemical industry) ︰ polycyclic ester ︰ glyceryl tristearate in oneself matter Amount prepares outer layer mixture than 1 ︰, 7 ︰, 1 ︰ 0.2；It is poly- by bis- (3,4- dimethylbenzylidene) Shan Li Chun ︰ Gan You ︰ linea low densities 5 ︰ of second alkene ︰ ethylene-ethylene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer mass ratio 0.004 ︰, 0.003 ︰, 4 ︰ 1 matches Middle layer mixture processed；Respectively in stirrer for mixing, then on three-layer co-extruded cast film machine, outer layer mixture, middle layer are mixed It closes material and internal layer master batch carries out mixed melting plasticizing, each section operation temperature respectively are as follows: 200,220,200 DEG C；Wai Ceng ︰ Zhong Ceng ︰ The extrusion rotating ratio of internal layer is 1 ︰, 1 ︰ 1, and co-extrusion output is 13 kg/h, and rolling speed is 10 m/min；Extruder die head is T-type Die head, the operation temperature of T-die are 230,225,220,220,220,225,230 DEG C, and chill roll cooling temperature is 22 DEG C, are obtained Have the Green Polymer packaging film of vapor and the double excellent barriers of oxygen, 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, (central wavelength is for 6 40W ultraviolet lamps 340nm, UVA340, Q-lab Co.), test specimens are cut into diameter as the disk 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 company Nexus870 type Fourier transformation infrared spectrometer The infrared spectrogram of sample, and carbonyl base index ︰ CI=A is calculated as follows1720cm-1/ A1465cm-1, the results are shown in Table 2.
The light degradation property of 2 film of table
Landfill weightlessness and the barrier property test of film obtained by 3 Examples 1 to 5 of Application Example
Landfill weightless test is carried out according to the degradation property of GB/T 20197-2006 film；With pressure differential gas permeameter device (VAC-V1 type, Labthink Instruments Co., Ltd.) tests the moisture-vapor transmission and OTR oxygen transmission rate of film, 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 scope.

Claims (3)

1. a kind of Green Polymer packaging film for 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 tristearate is 1 ︰ 7~8 ︰, 1 ︰ 0.1~0.5；
The middle layer film is the low close poly- second alkene ︰ ethylene-second of degree of bis- sweet oil ︰ lines of (3,4- dimethylbenzylidene) mountain pears alcohol ︰ Alkene alcohol copolymer ︰ methyl vinyl ether-maleic acid copolymer is 0.001~0.005 ︰, 0.001~0.009 ︰, 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 material of degree of poly- second alkene ︰ line of spending and coats Nano cupric oxide analogue enztme is 1 ︰, 7~8 ︰ 2~3.
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 by the following steps:
(1) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 10~15 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate 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 of reactions 8~12h, 6000~8000r/min, are centrifugated 20~40min, washing, and vacuum degree is 5~20kPa, 60 ~80 DEG C of 30~60min of vacuum drying, obtain nano cupric oxide analogue enztme；
(2) preparation of hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme: according to Toluene-2,4-diisocyanate, 4- diisocyanate It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio ingredient that tri- ethylene of ester ︰, the four nano oxidized copper mold of amine ︰, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 20~40min, and vacuum degree is 5~20kPa, 40~60 DEG C of 30~60min of vacuum drying, obtains close Water modified polyurea porous material coats nano cupric oxide analogue enztme；
(3) preparation of the internal layer master batch of the porous material of polyureas containing hydrophilic modifying cladding nano cupric oxide analogue enztme: poly- by low-density 1 ︰ of mass ratio, 7~8 ︰ of Yi Xi ︰ Xian Di Mi degree Ju Yi Xi ︰ hydrophilic modifying polyureas porous material cladding nano cupric oxide analogue enztme 2~3 carry out ingredient mixing, and mixture is put into melt pelletization in double screw extruder, and extruder each section operation temperature is respectively as follows: 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 ︰ line Property Di Mi degree Ju Yi Xi ︰ polycyclic Ji Nei Zhi ︰ glyceryl tristearate 1 ︰ of mass ratio, 7~8 ︰, 1 ︰ 0.1~0.5 prepare outer layer mixing Material；By the low close poly- second alkene ︰ ethylene-ethylene alcohol copolymer ︰ first of degree of bis- sweet oil ︰ lines of (3,4- dimethylbenzylidene) mountain pears alcohol ︰ During 4~5 ︰ of mass ratio 0.001~0.005 ︰, 0.001~0.009 ︰, 4~5 ︰ 1 of base vinyl ether-maleic acid copolymer is prepared Layer mixture；Outer layer mixture and middle layer mixture is uniform in stirrer for mixing respectively, then in three-layer co-extruded casting films On machine, outer layer mixture, middle layer mixture and internal layer master batch are subjected to fusion plastification respectively, operation temperature is 200~220 DEG C, It is coextruded and is cast by three-layer co-extruded cast film machine, the extrusion rotating ratio of layer ︰ internal layer is 1 ︰, 1 ︰ 1 in outer layer ︰, and co-extrusion output is 10 ~15kg/h, rolling speed are 2~10m/min；Extruder die head is T-die, and the operation temperature of T-die is 220~230 DEG C, chill roll cooling temperature is 15~25 DEG C, and the Green Polymer packaging for having vapor and the double excellent barriers of oxygen is made 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 extrusion screw rod diameter of the internal layer of three-layer co-extruded cast film machine, middle layer and outer layer is 20mm, draw ratio L/D For 30 ︰ 1, internal layer, middle layer 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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CN108263061A (en) * 2018-02-05 2018-07-10 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
CN108263061A (en) * 2018-02-05 2018-07-10 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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