CN108456352A - A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof - Google Patents
A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof Download PDFInfo
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Abstract
A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof, belongs to degradable modified poly ethylene thin film technique field.Inventive formulation includes nano cupric oxide analogue enztme, calcium octahate phosphate, nano zine oxide, the N of polyethylene, ultra-high molecular weight polyethylene, glass fibre, hydrophilic modifying polyurea coating, N methylene-bisacrylamides, triethylene tetramine, epoxy silane coupling, polyvingl ether, propylgallate, glycidyl methacrylate graft octene ethylene copolymer, maleic anhydride, polylactic acid, carboxymethyl starch, citric acid and plasticizer；Compatibility, hydrophily, activeness and quietness, photocatalysis and thermal oxide by carrying out green low-energy consumption to polyethylene, nano-powder promote to be modified, the technological means that co-extrusion is further modified is modified and repeatedly melted by a step cold grinding, prepare modified poly ethylene, gained modified poly ethylene has the mechanical property of synchronous enhancing and a good degradation property, simple for process, of low cost, be easy to industrialized production.
Description
Technical field
The present invention relates to a kind of high strength easy-to-degrade modified poly ethylene films and preparation method thereof, and it is poly- to belong to degradable modification
Vinyl film technical field.
Background technology
Plastics include the synthesis being made of carbon, hydrogen, oxygen and semi-synthetic macromolecule, because it is easy to get, high intensity, lightweight, tough
Property and it is widely used, the amount of resulting waste is also very huge.Plastics it is random it is discarded result in serious water source and
Soil pollution.Wherein polyethylene, which is widely used in, makes polybag, milk container, beverage bottle, food package film, toy and irrigation water
Pipe etc. is most common solid waste, accounts for about the 60% of total polybag yield.Polyethylene since its molecular weight is big and hydrophobic and
The degradable functional group of inanimate object, it is not degradable, it can be stabilized in the natural environment for quite a long time.Therefore, no limitation
Ground, which is arbitrarily discarded, can lead to serious environmental pollution.Recycling is a kind of method of solution plastic refuse pollution environment, currently, modeling
Main problem in material recycling is to be difficult to detach with the solid waste that other are degradable, followed by recycles properties of product and is not achieved
It is required that be of limited application, the economic benefit unobvious for causing recycling to generate；Burning disposal then can cause serious environment to be asked
Topic.The plastics produced at present by natural biodegradable polymer material, there are the problem of be of high cost, insufficient strength, therefore develop
The novel plastic product of low cost, mechanical property and degradation property equilibrium is the best bet for solving plastic pollution.
In general, to there is oxygen-containing functional group in degradable macromolecular structure, degrade in favor of the digestion of microorganism；Its
It is secondary, there is certain hydrophily, heat sensitivity and rational textural porosity, in favor of the entrance of vapor, oxygen and light,
To be easy to cause hydrophilic degradation, thermal degradation, photocatalytic degradation and oxidative degradation, make macromolecular structure be degraded to it is a large amount of it is oxygen-containing,
Hydrophilic small molecule segment, by the digestion of microorganism, converts completely to form the microenvironment of suitable micro-organisms growth
At carbon dioxide and water.
Solid state mechanochemistry reacts, and is that chemistry then occurs using the variation of mechanical energy inducing materials tissue, structure and performance
It reacts to prepare new material or carry out a kind of technology of surface modification treatment to material.Solid state mechanochemistry reacts, solvent-free, cleaning
It is pollution-free, low energy is efficient.Using the effect of solid phase stress field, it can induce and cause conventional chemical processes and be difficult to or can not carry out
Chemical reaction, prepares the not getable material with property of general chemical method and manufacturing process.
Invention content
The purpose of the present invention is overcoming above-mentioned shortcoming, provide a kind of high strength easy-to-degrade modified poly ethylene film and its
Preparation method carries out polyethylene, nano-powder compatibility, hydrophily, activeness and quietness, photocatalysis and the heat of green low-energy consumption
Oxidation promotes to be modified, and passes through the technological means that a step cold grinding is modified with repeatedly melting co-extrusion is further modified so that modified poly- second
Alkene has the mechanical property of synchronous enhancing and good degradation property.
Technical scheme of the present invention, a kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof, can by with
Lower technical solution is realized：Using polyethylene as macromolecule matrix, by adding a small amount of ultra-high molecular weight polyethylene and glass fibre, carry
High intensity；It adds the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating and calcium octahate phosphate carries out porous modification and provides biology
Enzyme degrading activity and microbial nutrition facilitation；Nano zine oxide filler plays enhancing modifying function and Visible Light Induced Photocatalytic promotes to make
With；N, N- methylene-bisacrylamide, triethylene tetramine and epoxy silane coupling play appropriate cross-linked network parent jointly
The effect that water is modified, while thermooxidative degradation can be improved in amino and epoxy group；Polyvingl ether and propylgallate rise anti-
The effect of answering property photodissociation accelerating agent；Glycidyl methacrylate graft octene ethylene copolymer and the poly- breast of maleic anhydride grafting
Acid plays a part of to be crosslinked toughener and stress release agent；Carboxymethyl starch and citric acid provide Louis acid catalysis effect and biology
Degradability；Acetyl tri-n-butyl citrate and the polynary ester admixture of amyl-based polyol are as plasticizer；Changed by a step cold grinding
Property and the multiple technological means that is further modified of melting co-extrusion, high strength easy-to-degrade modified poly ethylene film is made, has and synchronizes
The mechanical property of enhancing and good degradation property.
A kind of high strength easy-to-degrade modified poly ethylene film, it is characterised in that meter formula in mass ratio is as follows：Ju Yi Xi ︰ are super
It is nano oxidized that the nano oxidized copper mold of the poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings of height point son amount intends eight calcium ︰ of enzyme ︰ phosphoric acid
Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
Agent ratio be 10~30 ︰, 1~2 ︰, 1~5 ︰, 0.01~0.03 ︰, 1 ︰, 1~2 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰ 0.2~
0.5 ︰, 0.002~0.008 ︰, 1~3 ︰, 1~2 ︰, 1~5 ︰, 1~3 ︰, 2~5 ︰ 1~3；
Further, the polyethylene is high density polyethylene (HDPE), low density polyethylene (LDPE) or linear low density polyethylene；
Further, the epoxy silane coupling is KH-560, i.e. γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicon
Alkane；
Further, the plasticizer is the mixing that three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of acetyl tributyl citrate are 1 ︰ 1
Object；
The preparation method of the high strength easy-to-degrade modified poly ethylene film, 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）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, 100~
Under conditions of 200r/min, 25 DEG C of water-baths, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nanometer
In the water of copper oxide analogue enztme and the mixed solution of acetone, it is added dropwise in 40~60min, after reacting 1h, 6000~
8000r/min, centrifuge 20~40min, vacuum degree be 5~20kPa, 40~60 DEG C vacuum drying 30~60min, obtain hydrophilic
The nano cupric oxide analogue enztme of modified polyurea cladding；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, the Chao Gao Fen amounts Ju Yi Xi ︰ glass of Ju Yi Xi ︰
The nano oxidized copper mold of glass fibre dimension ︰ hydrophilic modifying polyurea coatings intends eight calcium ︰ of enzyme ︰ phosphoric acid and receives meter oxygen zinc ︰ N, N- a di-2-ethylhexylphosphine oxide third
Xi Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ methyl propenoic acid glycidyls
The ester grafting Gong Ju Wu ︰ Ma of octene Yi Xi carry out the mass ratioes of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer and are：10~
30 ︰, 1~2 ︰, 1~5 ︰, 0.01~0.03 ︰, 1 ︰, 1~2 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰ 0.002~
0.008 ︰, 1~3 ︰, 1~2 ︰, 1~5 ︰, 1~3 ︰, 2~5 ︰ 1~3；
By the component in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating in homogenizer, with 800~
1000r/min is sufficiently mixed 10min, obtains mixture, adds mixture into planetary ball mill, in material ball ratio 1 ︰ 2~5 and 1 ︰
Under 2 rotating ratio after 30~60min of vibration hybrid reaction, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, after
30~60min of continuous vibration, is made modified poly ethylene；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）The modified poly ethylene is in double screw extruder
The operation temperature of middle carry out melt modification, double screw extruder is 150~180 DEG C, under 60~80r/min of screw speed, melting
Blending extrusion under identical operating condition, repeats melt blending and squeezes out 2~3 times, be granulated, obtain composite master batch；It will be described compound
Master batch is sent into Single screw extrusion inflation film manufacturing machine, and the hot-melt extruded Blown Film at 180~200 DEG C obtains the high strength easy-to-degrade and changes
Property polyethylene film.
Further, the preparation method of the high strength easy-to-degrade modified poly ethylene film, wherein step（4）Middle twin-screw
The a diameter of 20mm of extruder, draw ratioL/DFor 36 ︰ 1；Step（4）The middle a diameter of 25mm of Single screw extrusion inflation film manufacturing machine, draw ratioL/D For 28 ︰ 1.
Beneficial effects of the present invention：The present invention to polyethylene, nano-powder by carrying out the compatibility of green low-energy consumption, parent
Aqueous, activeness and quietness, photocatalysis and thermal oxide promote to be modified, and are modified by a step cold grinding and repeatedly melting co-extrusion is further modified
Technological means, prepare modified poly ethylene, gained modified poly ethylene has the mechanical property of synchronous enhancing and good degradability
Can, it is simple for process, of low cost, be easy to industrialized production.
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
Tong is to Shuan Luo bar Ji Chu Ji ︰ KS20, Kunshan Kesun Rubber ＆ Plastic Machinery Co., Ltd.（Diameter=20mm, draw ratioL/D=36:1）；Single spiral shell
Bar squeezes out Chui Mo Ji ︰ hartek, HTBS-25,（Diameter=25mm, draw ratioL/D=28:1）；Row star ball mill ︰ XQM-2L types, north
Jing Xin Biao rise experimental instruments and equipment limited；Machine ︰ 1185, Instron companies of Britain are tested in Wan Nengcai material examinations；
Neopentyl polyol ester（Liaocheng Rui Jie Chemical Co., Ltd.s）；Ultra-high molecular weight polyethylene（Pai ︰ 9400, Yanshan Mountain stone
Change）；Glycidyl methacrylate graft octene ethylene copolymer（POE-g-GMA, the limited public affairs in good easy appearance compatilizer Jiangsu
Department）；Carboxymethyl starch（Yantai Yong Sheng Chemical Co., Ltd.s）；Acetyl tri-n-butyl citrate, polyvingl ether, gallic acid third
Ester, triethylene tetramine, maleic anhydride and polylactic acid are purchased to Chinese medicines group Shanghai Co., Ltd；KH-560（γ-（2,3- epoxies
Third oxygen）Propyl trimethoxy silicane, Nanjing Pin Ning coupling agents Co., Ltd）；Nano-ZnO（30nm, Shanghai Mike's woods biochemical technology
Co., Ltd）；High density polyethylene (HDPE)（The trade mark, TR-144, Maoming Petrochemical）；Low density polyethylene (LDPE)（Trade mark 2100TN00, Shandong
Petrochemical industry）；Low density polyethylene (LDPE)（Trade mark 2100TN00, Iranian petrochemical industry）；Linear low density polyethylene（The trade mark 9085, Tianjin connection
It closes）；Linear low density polyethylene（The trade mark 7042, Yangtze petrochemical industry）；Unless otherwise instructed, it is other it is raw materials used be commercially available quotient
Product.
The preparation of 1 high strength easy-to-degrade modified poly ethylene film of embodiment
（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 sodium citrate saturated solution of required mole is added dropwise to the nitric acid while stirring
In copper solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, react 8 in 100 DEG C
H, 6000r/min centrifuge 20min, washing, and vacuum degree 5kPa, 60 DEG C of vacuum drying 30min obtain nano cupric oxide simulation
Enzyme；
（2）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 5 ︰, 1 ︰, 5 ︰, 3 ︰, 4 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, under conditions of 100r/min, 25
DEG C water-bath, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine be slowly added drop-wise to nano cupric oxide analogue enztme water and
It in the mixed solution of acetone, is added dropwise in 40min, after reacting 1h, 6000r/min centrifuges 20min, and vacuum degree is
5kPa, 40 DEG C of vacuum drying 30min, obtain the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, high density polyethylene (HDPE)（The trade mark, TR-144,
Maoming Petrochemical）The nano oxidized copper mold that the super high point of son of ︰ measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends enzyme ︰ phosphoric acid eight
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ of Gai ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
The mass ratio of agent is：10 ︰, 1 ︰, 1 ︰, 0.01 ︰, 1 ︰, 1 ︰, 0.1 ︰, 0.1 ︰, 0.1 ︰, 0.2 ︰, 0.002 ︰, 1 ︰, 1 ︰, 1 ︰, 1 ︰, 2 ︰ 1；It will gather except hydrophilic modifying
Component other than the nano cupric oxide analogue enztme of urea cladding is sufficiently mixed 10 min with 800 r/min, obtains in homogenizer
Mixture adds mixture into planetary ball mill, the vibration hybrid reaction 30 under the rotating ratio of material ball ratio 1 ︰ 2 and 1 ︰ 2
After min, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, continues 30 min of vibration, modified poly ethylene is made；Institute
It is the mixture that three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of acetyl tributyl citrate are 1 ︰ 1 to state plasticizer；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）Gained modified poly ethylene is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150,160,170,180,160 DEG C, screw speed 60
Under r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into Single screw extrusion inflation film manufacturing machine, and each section operation temperature is：180, hot-melt extruded at 200,200,180 DEG C
Blown Film obtains the high strength easy-to-degrade modified poly ethylene film, 45 microns of film thickness.
The preparation of 2 high strength easy-to-degrade modified poly ethylene film of embodiment
（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
It is added dropwise to the copper nitrate while stirring by copper nitrate and water wiring solution-forming, then by the sodium citrate saturated solution of required mole
In solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, in 120 DEG C of reactions
12h, 8000r/min centrifuge 40min, washing, and vacuum degree 20kPa, 80 DEG C of vacuum drying 60min obtain nano cupric oxide
Analogue enztme；
（2）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 8 ︰, 1 ︰, 12 ︰, 5 ︰, 9 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, under conditions of 200r/min, 25
DEG C water-bath, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine be slowly added drop-wise to nano cupric oxide analogue enztme water and
It in the mixed solution of acetone, is added dropwise in 60min, after reacting 1h, 8000r/min centrifuges 40min, and vacuum degree is
20kPa, 60 DEG C of vacuum drying 60min, obtain the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, low density polyethylene (LDPE)（Trade mark 2100TN00,
Qilu Petrochemical）The nano oxidized copper mold that the super high point of son of ︰ measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends enzyme ︰ phosphoric acid eight
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ of Gai ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
The mass ratio of agent is：30 ︰, 2 ︰, 5 ︰, 0.03 ︰, 1 ︰, 2 ︰, 0.5 ︰, 0.5 ︰, 0.5 ︰, 0.5 ︰, 0.008 ︰, 3 ︰, 2 ︰, 5 ︰, 3 ︰, 5 ︰ 3；It will gather except hydrophilic modifying
Component other than the nano cupric oxide analogue enztme of urea cladding is sufficiently mixed 10 min in homogenizer with 1000 r/min,
Mixture is obtained, is added mixture into planetary ball mill, the vibration hybrid reaction 60 under the rotating ratio of material ball ratio 1 ︰ 5 and 1 ︰ 2
After min, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, continues vibration 60min, modified poly ethylene is made；Institute
It is 1 that state plasticizer, which be three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of acetyl tributyl citrate,:1 mixture；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）Gained modified poly ethylene is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：160,170,180,180,160 DEG C, screw speed 80
Under r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into Single screw extrusion inflation film manufacturing machine, and each section operation temperature is：190, hot-melt extruded at 200,190,180 DEG C
Blown Film obtains the high strength easy-to-degrade modified poly ethylene film, 45 microns of film thickness.
The preparation of 3 high strength easy-to-degrade modified poly ethylene film of embodiment
（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
It is added dropwise to the copper nitrate while stirring by copper nitrate and water wiring solution-forming, then by the sodium citrate saturated solution of required mole
In solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, react 9 in 110 DEG C
H, 7000r/min centrifuge 30min, washing, and vacuum degree 8kPa, 70 DEG C of vacuum drying 40min obtain nano cupric oxide simulation
Enzyme；
（2）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 6 ︰, 1 ︰, 7 ︰, 4 ︰, 5 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, under conditions of 100r/min, 25
DEG C water-bath, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine be slowly added drop-wise to nano cupric oxide analogue enztme water and
It in the mixed solution of acetone, is added dropwise in 50min, after reacting 1h, 7000r/min centrifuges 30min, and vacuum degree is
10kPa, 50 DEG C of vacuum drying 40min, obtain the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, linear low density polyethylene（The trade mark 9085,
Combine Tianjin）The nano oxidized copper mold that the super high point of son of ︰ measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends enzyme ︰ phosphoric acid eight
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ of Gai ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
The mass ratio of agent is：20 ︰, 1 ︰, 2 ︰, 0.02 ︰, 1 ︰, 1 ︰, 0.4 ︰, 0.3 ︰, 0.4 ︰, 0.3 ︰, 0.006 ︰, 2 ︰, 1 ︰, 3 ︰, 2 ︰, 3 ︰ 2；It will gather except hydrophilic modifying
Component other than the nano cupric oxide analogue enztme of urea cladding is sufficiently mixed 10 min with 900 r/min, obtains in homogenizer
Mixture adds mixture into planetary ball mill, the vibration hybrid reaction 40 under the rotating ratio of material ball ratio 1 ︰ 3 and 1 ︰ 2
After min, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, continues vibration 50min, modified poly ethylene is made；Institute
It is 1 that state plasticizer, which be three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of acetyl tributyl citrate,:1 mixture；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）Gained modified poly ethylene is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150,180,180,170,160 DEG C, screw speed 70
Under r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into Single screw extrusion inflation film manufacturing machine, and each section operation temperature is：180, hot-melt extruded at 200,190,190 DEG C
Blown Film obtains the high strength easy-to-degrade modified poly ethylene film, 45 microns of film thickness.
The preparation of 4 high strength easy-to-degrade modified poly ethylene film of embodiment
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 12 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, first
It is added dropwise to the copper nitrate while stirring by copper nitrate and water wiring solution-forming, then by the sodium citrate saturated solution of required mole
In solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, in 115 DEG C of reactions
11h, 6000r/min centrifuge 25min, washing, and vacuum degree 15kPa, 65 DEG C of vacuum drying 50min obtain nano cupric oxide
Analogue enztme；
（2）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 7 ︰, 1 ︰, 9 ︰, 4 ︰, 6 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, under conditions of 200r/min, 25
DEG C water-bath, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine be slowly added drop-wise to nano cupric oxide analogue enztme water and
It in the mixed solution of acetone, is added dropwise in 45min, after reacting 1h, 6000r/min centrifuges 35min, and vacuum degree is
18kPa, 55 DEG C of vacuum drying 55min, obtain the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, low density polyethylene (LDPE)（Trade mark 2100TN00,
Iranian petrochemical industry）The nano oxidized copper mold that the super high point of son of ︰ measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends enzyme ︰ phosphoric acid eight
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ of Gai ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
The mass ratio of agent is：15 ︰, 1.5 ︰, 3 ︰, 0.01 ︰, 1 ︰, 1.5 ︰, 0.4 ︰, 0.3 ︰, 0.3 ︰, 0.4 ︰, 0.006 ︰, 2 ︰, 1.5 ︰, 3 ︰, 2 ︰, 3 ︰ 2；It will remove hydrophilic
Component other than the nano cupric oxide analogue enztme of modified polyurea cladding is sufficiently mixed 10 in homogenizer with 800 r/min
Min obtains mixture, adds mixture into planetary ball mill, and vibration mixing is anti-under the rotating ratio of material ball ratio 1 ︰ 4 and 1 ︰ 2
After answering 50 min, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, continues vibration 50min and is made, modified poly- second
Alkene；The plasticizer is that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1:1 mixture；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）Gained modified poly ethylene is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：170,180,180,170,160 DEG C, screw speed 60
Under r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into Single screw extrusion inflation film manufacturing machine, and each section operation temperature is：180, hot-melt extruded at 200,200,190 DEG C
Blown Film obtains the high strength easy-to-degrade modified poly ethylene film, 45 microns of film thickness.
The preparation of 5 high strength easy-to-degrade modified poly ethylene film of embodiment
（1）The preparation of nano cupric oxide analogue enztme：It is that 1 ︰, 14 ︰ 1 are matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrates, first
It is added dropwise to the copper nitrate while stirring by copper nitrate and water wiring solution-forming, then by the sodium citrate saturated solution of required mole
In solution, salting liquid must be complexed after being added dropwise, the complexing salting liquid is placed in hydrothermal reaction kettle, react 11 in 105 DEG C
H, 6000r/min centrifuge 35min, washing, and vacuum degree 18kPa, 75 DEG C of vacuum drying 45min obtain nano oxidized copper mold
Quasi- enzyme；
（2）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 5 ︰, 1 ︰, 11 ︰, 4 ︰, 8 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, under conditions of 100r/min, 25
DEG C water-bath, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine be slowly added drop-wise to nano cupric oxide analogue enztme water and
It in the mixed solution of acetone, is added dropwise in 55min, after reacting 1h, 8000r/min centrifuges 25min, and vacuum degree is
8kPa, 45 DEG C of vacuum drying 35min, obtain the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, linear low density polyethylene（The trade mark 7042,
Yangtze petrochemical industry）The nano oxidized copper mold that the super high point of son of ︰ measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends enzyme ︰ phosphoric acid eight
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ of Gai ︰
The Gong Ju Wu ︰ Ma of glycidyl methacrylate graft octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticising
The mass ratio of agent is：10 ︰, 2 ︰, 1 ︰, 0.03 ︰, 1 ︰, 1 ︰, 0.5 ︰, 0.1 ︰, 0.5 ︰, 0.2 ︰, 0.008 ︰, 1 ︰, 2 ︰, 1 ︰, 3 ︰, 2 ︰ 3；It will gather except hydrophilic modifying
Component other than the nano cupric oxide analogue enztme of urea cladding is sufficiently mixed 10 min with 800 r/min, obtains in homogenizer
Mixture adds mixture into planetary ball mill 30 min of vibration hybrid reaction under the rotating ratio of material ball ratio 1 ︰ 5 and 1 ︰ 2
Afterwards, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, continues vibration 60min, modified poly ethylene is made；The increasing
Modeling agent is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）Gained modified poly ethylene is in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are：150,160,170,180,150 DEG C, screw speed 70
Under r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into Single screw extrusion inflation film manufacturing machine, and each section operation temperature is：180, hot-melt extruded at 190,200,180 DEG C
Blown Film obtains the high strength easy-to-degrade modified poly ethylene film, 45 microns of film thickness.
The Mechanics Performance Testing of film article obtained by 1 Examples 1 to 5 of Application Example
The tensile strength of film presses GB/T 1040.3-2006, is tested using universal testing machine, test speed 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 performance 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 films, the results are shown in Table 3.
The landfill weightlessness performance test 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 (6)
1. a kind of high strength easy-to-degrade modified poly ethylene film, it is characterised in that meter formula in mass ratio is as follows：Ju Yi Xi ︰ superelevation
The nano oxidized copper mold that point son measures poly- second alkene ︰ glass glass fibres dimension ︰ hydrophilic modifying polyurea coatings intends eight calcium ︰ of enzyme ︰ phosphoric acid and receives a meter oxygen zinc ︰
N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ methyl
The glycidyl acrylate grafting Gong Ju Wu ︰ Ma of octene Yi Xi carry out Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer ratios
Example is 10~30 ︰, 1~2 ︰, 1~5 ︰, 0.01~0.03 ︰, 1 ︰, 1~2 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰
0.002~0.008 ︰, 1~3 ︰, 1~2 ︰, 1~5 ︰, 1~3 ︰, 2~5 ︰ 1~3.
2. high strength easy-to-degrade modified poly ethylene film according to claim 1, it is characterised in that：The polyethylene is highly dense
Spend polyethylene, low density polyethylene (LDPE) or linear low density polyethylene.
3. high strength easy-to-degrade modified poly ethylene film according to claim 1, it is characterised in that：The epoxy radicals silicone hydride is even
Connection agent is KH-560, i.e. γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane.
4. high strength easy-to-degrade modified poly ethylene film according to claim 1, it is characterised in that：The plasticizer is acetyl
Three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of citric acid are the mixture of 1 ︰ 1.
5. the preparation method of one of the claim 1-4 high strength easy-to-degrade modified poly ethylene films, it is characterised in that step
It is 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）The preparation of the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, tri- second of 4- bis- Yi Qing Suan Zhi ︰
It is 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio dispensings that the four nano oxidized copper molds of amine ︰ of alkene, which intend enzyme ︰ water ︰ acetone quality ratios, 100~
Under conditions of 200r/min, 25 DEG C of water-baths, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise to nanometer
In the water of copper oxide analogue enztme and the mixed solution of acetone, it is added dropwise in 40~60min, after reacting 1h, 6000~
8000r/min centrifuge 20~40min, vacuum degree be 5~20kPa, 40~60 DEG C vacuum drying 30~60min, obtain hydrophilic
The nano cupric oxide analogue enztme of modified polyurea cladding；
（3）The preparation of cold grinding modified poly ethylene：By raw material components dispensing in mass ratio, the Chao Gao Fen amounts Ju Yi Xi ︰ glass of Ju Yi Xi ︰
The nano oxidized copper mold of glass fibre dimension ︰ hydrophilic modifying polyurea coatings intends eight calcium ︰ of enzyme ︰ phosphoric acid and receives meter oxygen zinc ︰ N, N- a di-2-ethylhexylphosphine oxide third
Xi Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ methyl propenoic acid glycidyls
The ester grafting Gong Ju Wu ︰ Ma of octene Yi Xi carry out the mass ratioes of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer and are：10~
30 ︰, 1~2 ︰, 1~5 ︰, 0.01~0.03 ︰, 1 ︰, 1~2 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰ 0.002~
0.008 ︰, 1~3 ︰, 1~2 ︰, 1~5 ︰, 1~3 ︰, 2~5 ︰ 1~3；
By the component in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating in homogenizer, with 800~
1000r/min is sufficiently mixed 10min, obtains mixture, adds mixture into planetary ball mill, in material ball ratio 1 ︰ 2~5 and 1 ︰
Under 2 rotating ratio after 30~60min of vibration hybrid reaction, the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating is added, after
30~60min of continuous vibration, is made modified poly ethylene；
（4）The preparation of high strength easy-to-degrade modified poly ethylene film：By step（3）The modified poly ethylene is in double screw extruder
The operation temperature of middle carry out melt modification, double screw extruder is 150~180 DEG C, under 60~80r/min of screw speed, melting
Blending extrusion under identical operating condition, repeats melt blending and squeezes out 2~3 times, be granulated, obtain composite master batch；It will be described compound
Master batch is sent into Single screw extrusion inflation film manufacturing machine, and the hot-melt extruded Blown Film at 180~200 DEG C obtains the high strength easy-to-degrade and changes
Property polyethylene film.
6. the preparation method of high strength easy-to-degrade modified poly ethylene film according to claim 5, it is characterised in that：Step
（4）The middle a diameter of 20mm of double screw extruder, draw ratioL/DFor 36 ︰ 1；Step（4）Middle Single screw extrusion inflation film manufacturing machine is a diameter of
25mm, draw ratioL/D For 28 ︰ 1.
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| CN109551846A (en) * | 2018-02-05 | 2019-04-02 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof having vapor and the double excellent barriers of oxygen |
| CN114716697A (en) * | 2021-06-21 | 2022-07-08 | 中联融鑫(北京)科技开发有限公司 | Biodegradable plastic master batch and plastic prepared from same |
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| CN102321353B (en) * | 2011-07-26 | 2012-10-03 | 成都市新津事丰医疗器械有限公司 | Degradable material for preparing outside sleeve of disposable injector |
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| CN109551846A (en) * | 2018-02-05 | 2019-04-02 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof having vapor and the double excellent barriers of oxygen |
| CN114716697A (en) * | 2021-06-21 | 2022-07-08 | 中联融鑫(北京)科技开发有限公司 | Biodegradable plastic master batch and plastic prepared from same |
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Application publication date: 20180828 |