CN109467791A - 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
- Publication number
- CN109467791A CN109467791A CN201910051359.4A CN201910051359A CN109467791A CN 109467791 A CN109467791 A CN 109467791A CN 201910051359 A CN201910051359 A CN 201910051359A CN 109467791 A CN109467791 A CN 109467791A
- Authority
- CN
- China
- Prior art keywords
- modified poly
- poly ethylene
- high strength
- preparation
- suan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/08—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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-bisacrylamide, triethylene tetramine, epoxy silane coupling, polyvingl ether, propylgallate, glycidyl methacrylate graft octene ethylene copolymer, maleic anhydride, polylactic acid, carboxymethyl starch, citric acid, bis- (3,4- dimethylbenzylidene) sorbierite, glycerol and plasticizer；Promote to be modified by the compatibility, hydrophily, activeness and quietness, photocatalysis and the thermal oxide that carry out green low-energy consumption to polyethylene, nano-powder, pass through the technological means modified and that repeatedly melting co-extrusion is further modified of a step cold grinding, prepare modified poly ethylene, gained modified poly ethylene have synchronous enhancing mechanical property and good degradation property, it is simple process, low in cost, 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 technique
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 is widely used in production polybag, milk container, beverage bottle, food package film, toy and irrigation water
Pipe etc. is the 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, will 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 separate with the solid waste that other are degradable, and followed by recycling properties of product are not achieved
It is required that being of limited application, the economic benefit for causing recycling to generate is unobvious；Burning disposal then will lead to serious environment and ask
Topic.The plastics produced at present by natural biodegradable polymer material, there are the problem of for it is at high cost, intensity is inadequate, 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 have oxygen-containing functional group in degradable macromolecular structure, so that the digestion of microorganism is degraded；Its
It is secondary, there is certain hydrophily, heat sensitivity and reasonable textural porosity, in favor of the entrance of vapor, oxygen and light,
To being easy to cause hydrophilic degradation, thermal degradation, photocatalytic degradation and oxidative degradation, make macromolecular structure be degraded to largely 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 reaction 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 reaction, 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.
Summary of the invention
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 compatibility, hydrophily, activeness and quietness, photocatalysis and the heat of green low-energy consumption to polyethylene, nano-powder
Oxidation promotes to be modified, by the technological means modified and that repeatedly melting co-extrusion is further modified of a step cold grinding, so that modified poly- second
Alkene has the synchronous mechanical property enhanced and good degradation property.
Technical solution 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, being mentioned
It is high-intensitive；The nano cupric oxide analogue enztme and calcium octahate phosphate for adding hydrophilic modifying polyurea coating carry out porous modification and provide 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 modified effect of water, while thermooxidative degradation can be improved in amino and epoxy group；Polyvingl ether and propylgallate rise anti-
The effect of answering property photodissociation promotor；Glycidyl methacrylate graft octene ethylene copolymer and the poly- cream 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；Bis- (3,4- dimethyl benzenes
Methylene) sorbierite and glycerol as anti-reflection increases soft modified conditioner, by a step cold grinding it is modified and repeatedly melting co-extrusion into one
Modified technological means is walked, high strength easy-to-degrade modified poly ethylene film is made, there is mechanical property, the aesthetic appearance of synchronous enhancing
It can be with 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: bis- (3,4- bis-
Methyl benzylidene) the Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ hydrophilic modifying polyurea coating of Shan Li Chun ︰ Gan You ︰ Ju Yi Xi ︰
Nano oxidized copper mold intends eight calcium ︰ of enzyme ︰ phosphoric acid and receives meter tri- ethylene of oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰, a four amine ︰ epoxy group silicon
The Malaysia Ju Wu ︰ Gong alkane Ou Lian Ji ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer proportions be 0.002~0.005 ︰, 0.02~0.08 ︰, 10~30 ︰ 1~
2 ︰, 1~5 ︰, 0.02~0.05 ︰, 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-(2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane；
Further, the plasticizer is the mixing that the positive Ding Zhi ︰ neopentyl polyol ester mass ratio of acetyl tributyl citrate three is 1 ︰ 1
Object；
The preparation method of the high strength easy-to-degrade modified poly ethylene film, steps are as follows:
(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, vacuum degree be 5~20kPa, 60~
80 DEG C of 30~60min of vacuum drying, obtain nano cupric oxide analogue enztme；
(2) 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 ︰
The four nano oxidized copper mold of amine ︰ of alkene intend enzyme ︰ water ︰ acetone quality ratio be 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio ingredient, 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 is centrifugated 20~40min, and vacuum degree is 5~20kPa, and 40~60 DEG C of 30~60min of vacuum drying are obtained hydrophilic
The nano cupric oxide analogue enztme of modified polyurea cladding；
(3) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
The nano oxidized copper mold that the super high point of son of the sweet poly- second alkene ︰ of oil ︰ of alcohol ︰ measures poly- second alkene ︰ glass glass fibre dimension ︰ hydrophilic modifying polyurea coating intends enzyme ︰
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyvinyls of phosphoric acid Ba Gai ︰
The Gong Ju Wu ︰ Ma of Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi carrys out Suan Gan ︰ Ju Ru Suan ︰ carboxymethyl
The mass ratio of Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.002~0.005 ︰, 0.02~0.08 ︰, 10~30 ︰, 1~2 ︰, 1~5 ︰ 0.02~
0.05 ︰, 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
2~5 ︰ 1~3 of~3 ︰；
By the component in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating in high-speed mixer, with 800~
1000r/min is sufficiently mixed 10min, obtains mixture, adds mixture into planetary ball mill, in 1 ︰ of ︰ 2~5 and 1 of material ball ratio
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
Continuous 30~60min of vibration, is made modified poly ethylene；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by step (3) described modified poly ethylene in double screw extruder
Middle carry out melt modification, the operation temperature of double screw extruder are 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 rod and squeezes out 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 twin-screw in step (4)
Extruder diameter of phi is 20mm, draw ratioL/DFor 36 ︰ 1；It is 25mm that single screw rod, which squeezes out inflation film manufacturing machine diameter of phi, in step (4), long
Diameter ratioL/D For 28 ︰ 1.
Beneficial effects of the present invention: the present invention is by carrying out the compatibility of green low-energy consumption, parent to polyethylene, nano-powder
Aqueous, activeness and quietness, photocatalysis and thermal oxide promote to be modified, and are further modified by the modified and multiple melting co-extrusion of a step cold grinding
Technological means, prepare modified poly ethylene, gained modified poly ethylene has the mechanical property of synchronous enhancing, appearance property and good
Degradation property, it is simple process, low in cost, easy to industrialized production.
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
Tong is to Shuan Luo bar Ji Chu Ji ︰ KS20, Kunshan Kesun Rubber & Plastic Machinery Co., Ltd. (Zhi Jing ︰ Φ=20mm, draw ratioL/D=36:1)；
Single screw rod squeezes out Chui Mo Ji ︰ hartek, HTBS-25, (Zhi Jing ︰ Φ=25mm, draw ratioL/D=28:1)；Row star ball mill ︰ XQM-
2L type, Bei Jing Xin Biao rise experimental instruments and equipment limited；Machine ︰ 1185, Instron company, Britain are tested in Wan Nengcai material examination；
Neopentyl polyol ester (Liaocheng Rui Jie Chemical Co., Ltd.)；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.)；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- epoxy
Third oxygen) propyl trimethoxy silicane, Nanjing Pin Ning coupling agent Co., Ltd)；Nano-ZnO (30nm, Shanghai Mike's woods biochemical technology
Co., Ltd)；High density polyethylene (HDPE) (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 (trade mark 9085, Tianjin connection
It closes)；Linear low density polyethylene (trade mark 7042, Yangtze petrochemical industry)；Bis- (3,4- dimethylbenzylidenes) (Hubei is suitable in fact for sorbierite
Biotechnology Co., Ltd)；Unless otherwise instructed, it is other it is raw materials used be commercial goods.
The preparation of 1 high strength easy-to-degrade modified poly ethylene film of embodiment
(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 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 are centrifugated 20min, washing, and vacuum degree 5kPa, 60 DEG C of vacuum drying 30min obtain nano cupric oxide simulation
Enzyme；
(2) 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 ingredient that the four nano oxidized copper mold of amine ︰ of alkene, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 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) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
(trade mark, the Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ of TR-144, Maoming Petrochemical) ︰ is hydrophilic to be changed Chun ︰ Gan You ︰ high density polyethylene (HDPE)
Property polyurea coating nano oxidized copper mold intend eight calcium ︰ of enzyme ︰ phosphoric acid and receive a meter oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰ triethylene
The Gong Ju Wu ︰ horse of Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Carry out the mass ratio of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.002 ︰, 0.02 ︰, 10 ︰, 1 ︰, 1 ︰, 0.02 ︰, 1 ︰, 1 ︰
0.1 ︰, 0.1 ︰, 0.1 ︰, 0.2 ︰, 0.002 ︰, 1 ︰, 1 ︰, 1 ︰, 1 ︰, 2 ︰ 1；It will be in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating
Component in high-speed mixer, be sufficiently mixed 10 min with 800 r/min, obtain mixture, add mixture into planet ball
In grinding machine, under the rotating ratio of 1 ︰ of ︰ 2 and 12 of material ball ratio after 30 min of vibration hybrid reaction, hydrophilic modifying polyurea coating is added
Nano cupric oxide analogue enztme continues 30 min of vibration, and modified poly ethylene is made；The plasticizer is the positive fourth of acetyl tributyl citrate three
Zhi ︰ neopentyl polyol ester mass ratio is the mixture of 1 ︰ 1；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by modified poly ethylene obtained by step (3) in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are as follows: 150,160,170,180,160 DEG C, screw speed 60
Under r/min, melt blending is squeezed out, and under identical operating condition, is repeated melt blending and is squeezed out 2 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into single screw rod and squeezes out inflation film manufacturing machine, each section operation temperature are as follows: hot-melt extruded at 180,200,200,180 DEG C
Blown Film, obtains the high strength easy-to-degrade modified poly ethylene film, and 45 microns of film thickness.
The preparation of 2 high strength easy-to-degrade modified poly ethylene film of embodiment
(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
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, reacted in 120 DEG C
12h, 8000r/min are centrifugated 40min, and washing, vacuum degree 20kPa, 80 DEG C of vacuum drying 60min obtain nano cupric oxide
Analogue enztme；
(2) 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 ingredient that the four nano oxidized copper mold of amine ︰ of alkene, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 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) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
(the Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ of trade mark 2100TN00, Qilu Petrochemical) ︰ is hydrophilic to be changed Chun ︰ Gan You ︰ low density polyethylene (LDPE)
Property polyurea coating nano oxidized copper mold intend eight calcium ︰ of enzyme ︰ phosphoric acid and receive a meter oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰ triethylene
The Gong Ju Wu ︰ horse of Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Carry out the mass ratio of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.005 ︰, 0.08 ︰, 30 ︰, 2 ︰, 5 ︰, 0.05 ︰, 1 ︰, 2 ︰
0.5 ︰, 0.5 ︰, 0.5 ︰, 0.5 ︰, 0.008 ︰, 3 ︰, 2 ︰, 5 ︰, 3 ︰, 5 ︰ 3；It will be in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating
Component in high-speed mixer, be sufficiently mixed 10 min with 1000 r/min, obtain mixture, add mixture into planet ball
In grinding machine, under the rotating ratio of 1 ︰ of ︰ 5 and 12 of material ball ratio after 60 min of vibration hybrid reaction, hydrophilic modifying polyurea coating is added
Nano cupric oxide analogue enztme continues vibration 60min, and modified poly ethylene is made；The plasticizer is the positive Ding Zhi ︰ of acetyl tributyl citrate three
Neopentyl polyol ester mass ratio is the mixture of 1:1；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by modified poly ethylene obtained by step (3) in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are as follows: 160,170,180,180,160 DEG C, screw speed 80
Under r/min, melt blending is squeezed out, and under identical operating condition, is repeated melt blending and is squeezed out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into single screw rod and squeezes out inflation film manufacturing machine, each section operation temperature are as follows: hot-melt extruded at 190,200,190,180 DEG C
Blown Film, obtains the high strength easy-to-degrade modified poly ethylene film, and 45 microns of film thickness.
The preparation of 3 high strength easy-to-degrade modified poly ethylene film of embodiment
(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
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 are centrifugated 30min, washing, and vacuum degree 8kPa, 70 DEG C of vacuum drying 40min obtain nano cupric oxide simulation
Enzyme；
(2) 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 ingredient that the four nano oxidized copper mold of amine ︰ of alkene, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 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) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
(trade mark 9085, the Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ of) ︰ is hydrophilic changes for Tianjin joint for Chun ︰ Gan You ︰ linear low density polyethylene
Property polyurea coating nano oxidized copper mold intend eight calcium ︰ of enzyme ︰ phosphoric acid and receive a meter oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰ triethylene
The Gong Ju Wu ︰ horse of Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Carry out the mass ratio of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.003 ︰, 0.05 ︰, 20 ︰, 1 ︰, 2 ︰, 0.03 ︰, 1 ︰, 1 ︰
0.4 ︰, 0.3 ︰, 0.4 ︰, 0.3 ︰, 0.006 ︰, 2 ︰, 1 ︰, 3 ︰, 2 ︰, 3 ︰ 2；It will be in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating
Component in high-speed mixer, be sufficiently mixed 10 min with 900 r/min, obtain mixture, add mixture into planet ball
In grinding machine, under the rotating ratio of 1 ︰ of ︰ 3 and 12 of material ball ratio after 40 min of vibration hybrid reaction, hydrophilic modifying polyurea coating is added
Nano cupric oxide analogue enztme continues vibration 50min, and modified poly ethylene is made；The plasticizer is the positive Ding Zhi ︰ of acetyl tributyl citrate three
Neopentyl polyol ester mass ratio is the mixture of 1:1；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by modified poly ethylene obtained by step (3) in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are as follows: 150,180,180,170,160 DEG C, screw speed 70
Under r/min, melt blending is squeezed out, and under identical operating condition, is repeated melt blending and is squeezed out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into single screw rod and squeezes out inflation film manufacturing machine, each section operation temperature are as follows: hot-melt extruded at 180,200,190,190 DEG C
Blown Film, obtains the high strength easy-to-degrade modified poly ethylene film, and 45 microns of film thickness.
The preparation of 4 high strength easy-to-degrade modified poly ethylene film of embodiment
(1) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 12 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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, reacted in 115 DEG C
11h, 6000r/min are centrifugated 25min, and washing, vacuum degree 15kPa, 65 DEG C of vacuum drying 50min obtain nano cupric oxide
Analogue enztme；
(2) 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 ingredient that the four nano oxidized copper mold of amine ︰ of alkene, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 35min, and vacuum degree is
18kPa, is dried in vacuo 55min, obtains the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating by 55 DEG C；
(3) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
The super high point son of the sweet oil ︰ low density polyethylene (LDPE) of alcohol ︰ (trade mark 2100TN00, Iranian petrochemical industry) ︰, which measures poly- second alkene ︰ glass glass fibre dimension ︰ is hydrophilic, to be changed
Property polyurea coating nano oxidized copper mold intend eight calcium ︰ of enzyme ︰ phosphoric acid and receive a meter oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰ triethylene
The Gong Ju Wu ︰ horse of Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Carry out the mass ratio of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.004 ︰, 0.07 ︰, 15 ︰, 1.5 ︰, 3 ︰, 0.04 ︰, 1 ︰
1.5 ︰, 0.4 ︰, 0.3 ︰, 0.3 ︰, 0.4 ︰, 0.006 ︰, 2 ︰, 1.5 ︰, 3 ︰, 2 ︰, 3 ︰ 2；It will be simulated except the nano cupric oxide of hydrophilic modifying polyurea coating
Component other than enzyme is sufficiently mixed 10 min in high-speed mixer, with 800 r/min, obtains mixture, adds mixture into
In planetary ball mill, under the rotating ratio of 1 ︰ of ︰ 4 and 12 of material ball ratio after 50 min of vibration hybrid reaction, hydrophilic modifying polyureas is added
The nano cupric oxide analogue enztme of cladding continues vibration 50min and is made, modified poly ethylene；The plasticizer is acetyl tributyl citrate three
The mixture that positive Ding Zhi ︰ amyl-based polyol polyester mass ratio is 1:1；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by modified poly ethylene obtained by step (3) in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are as follows: 170,180,180,170,160 DEG C, screw speed 60
Under r/min, melt blending is squeezed out, and under identical operating condition, is repeated melt blending and is squeezed out 2 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into single screw rod and squeezes out inflation film manufacturing machine, each section operation temperature are as follows: hot-melt extruded at 180,200,200,190 DEG C
Blown Film, obtains the high strength easy-to-degrade modified poly ethylene film, and 45 microns of film thickness.
5 the present embodiment of embodiment is the preparation of high strength easy-to-degrade modified poly ethylene film
(1) preparation of nano cupric oxide analogue enztme: being that 1 ︰, 14 ︰ 1 is matched by the molar ratio of Xiao Suan Tong ︰ Shui ︰ sodium citrate, 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 are centrifugated 35min, and washing, vacuum degree 18kPa, 75 DEG C of vacuum drying 45min obtain nano oxidized copper mold
Quasi- enzyme；
(2) 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 ingredient that the four nano oxidized copper mold of amine ︰ of alkene, which intends enzyme ︰ water ︰ acetone quality ratio, 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 is centrifugated 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) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
(trade mark 7042, the Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ of Yangtze petrochemical industry) ︰ is hydrophilic to be changed Chun ︰ Gan You ︰ linear low density polyethylene
Property polyurea coating nano oxidized copper mold intend eight calcium ︰ of enzyme ︰ phosphoric acid and receive a meter oxygen zinc ︰ N, N- methylene bisacrylamide acyl amine ︰ triethylene
The Gong Ju Wu ︰ horse of Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Carry out the mass ratio of Suan Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.005 ︰, 0.03 ︰, 10 ︰, 2 ︰, 1 ︰, 0.05 ︰, 1 ︰, 1 ︰
0.5 ︰, 0.1 ︰, 0.5 ︰, 0.2 ︰, 0.008 ︰, 1 ︰, 2 ︰, 1 ︰, 3 ︰, 2 ︰ 3；It will be in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating
Component in high-speed mixer, be sufficiently mixed 10 min with 800 r/min, obtain mixture, add mixture into planet ball
In grinding machine under the rotating ratio of 1 ︰ of ︰ 5 and 12 of material ball ratio after 30 min of vibration hybrid reaction, receiving for hydrophilic modifying polyurea coating is added
Rice copper oxide analogue enztme, continues vibration 60min, and modified poly ethylene is made；The plasticizer is that the positive Ding Zhi ︰ of acetyl tributyl citrate three is new
Amyl polyalcohol polyester mass ratio is the mixture of 1 ︰ 1；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by modified poly ethylene obtained by step (3) in double screw extruder
Middle carry out melt modification, double screw extruder each section operation temperature are as follows: 150,160,170,180,150 DEG C, screw speed 70
Under r/min, melt blending is squeezed out, and under identical operating condition, is repeated melt blending and is squeezed out 3 times, be granulated, obtain composite master batch；It will
The composite master batch is sent into single screw rod and squeezes out inflation film manufacturing machine, each section operation temperature are as follows: hot-melt extruded at 180,190,200,180 DEG C
Blown Film, obtains the high strength easy-to-degrade modified poly ethylene film, and 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, (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
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 film, 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 scope.
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: bis- (3,4- diformazans
Base benzylidene) the Shan Li Chun ︰ Gan You ︰ Ju Yi Xi Chao Gao Fen amount Ju Yi Xi ︰ Bo glass Xian Wei ︰ hydrophilic modifying polyurea coating of ︰ receives
Rice copper oxide Mo Ni Mei ︰ phosphoric acid Ba Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydrides of Gai ︰
The Gong Ju Wu ︰ maleic acid of Ou Lian Ji ︰ polyethylene Ji Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi
Gan ︰ Ju Ru Suan ︰ Suo methyl Dian Fen ︰ Ning Meng Suan ︰ plasticizer proportions are 0.002~0.005 ︰, 0.02~0.08 ︰, 10~30 ︰, 1~2 ︰ 1
0.002~0.008 ︰ of~5 ︰ 0.02~0.05 ︰, 1 ︰, 1~2 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.1~0.5 ︰, 0.2~0.5 ︰, 1~3 ︰ 1
1~5 ︰ of~2 ︰, 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-(2,3- the third oxygen of epoxy) 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
The positive Ding Zhi ︰ neopentyl polyol ester mass ratio of citric acid three is the mixture of 1 ︰ 1.
5. the preparation method of high strength easy-to-degrade modified poly ethylene film described in one of claim 1-4, it is characterised in that step
It is as follows:
(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, vacuum degree be 5~20kPa, 60~
80 DEG C of 30~60min of vacuum drying, obtain nano cupric oxide analogue enztme；
(2) 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 ︰
The four nano oxidized copper mold of amine ︰ of alkene intend enzyme ︰ water ︰ acetone quality ratio be 5~8 ︰, 1 ︰, 5~12 ︰, 3~5 ︰, 4~9 ratio ingredient, 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 is centrifugated 20~40min, and vacuum degree is 5~20kPa, 40~60 DEG C of 30~60min of vacuum drying, obtains hydrophilic
The nano cupric oxide analogue enztme of modified polyurea cladding；
(3) preparation of cold grinding modified poly ethylene: by raw material components ingredient in mass ratio, bis- (3,4- dimethylbenzylidene) sorbs
The nano oxidized copper mold that the super high point of son of the sweet poly- second alkene ︰ of oil ︰ of alcohol ︰ measures poly- second alkene ︰ glass glass fibre dimension ︰ hydrophilic modifying polyurea coating intends enzyme ︰
Na meters of Yangization Xin ︰ N, N- methylene bisacrylamide Xian An ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyvinyls of phosphoric acid Ba Gai ︰
The Gong Ju Wu ︰ Ma of Mi ︰ galla turcica acid Bing Zhi ︰ glycidyl methacrylate graft octene Yi Xi carrys out Suan Gan ︰ Ju Ru Suan ︰ carboxymethyl
The mass ratio of Dian Fen ︰ Ning Meng Suan ︰ plasticizer are as follows: 0.002~0.005 ︰, 0.02~0.08 ︰, 10~30 ︰, 1~2 ︰, 1~5 ︰ 0.02~
0.05 ︰, 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
2~5 ︰ 1~3 of~3 ︰；
By the component in addition to the nano cupric oxide analogue enztme of hydrophilic modifying polyurea coating in high-speed mixer, with 800~
1000r/min is sufficiently mixed 10min, obtains mixture, adds mixture into planetary ball mill, in 1 ︰ of ︰ 2~5 and 1 of material ball ratio
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
Continuous 30~60min of vibration, is made modified poly ethylene；
(4) preparation of high strength easy-to-degrade modified poly ethylene film: by step (3) described modified poly ethylene in double screw extruder
Middle carry out melt modification, the operation temperature of double screw extruder are 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 rod and squeezes out 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) double screw extruder diameter of phi is 20mm, draw ratio inL/DFor 36 ︰ 1；Single screw rod squeezes out inflation film manufacturing machine diameter in step (4)
Φ is 25mm, draw ratioL/D For 28 ︰ 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810109064.3A CN108456352A (en) | 2018-02-05 | 2018-02-05 | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof |
| CN2018101090643 | 2018-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109467791A true CN109467791A (en) | 2019-03-15 |
Family
ID=63239539
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810109064.3A Pending CN108456352A (en) | 2018-02-05 | 2018-02-05 | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof |
| CN201910051359.4A Pending CN109467791A (en) | 2018-02-05 | 2019-01-21 | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810109064.3A Pending CN108456352A (en) | 2018-02-05 | 2018-02-05 | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108456352A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108357171A (en) * | 2018-02-05 | 2018-08-03 | 江南大学 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN102321353A (en) * | 2011-07-26 | 2012-01-18 | 成都市新津事丰医疗器械有限公司 | Degradable material for preparing outside sleeve of disposable injector |
| WO2016038110A2 (en) * | 2014-09-09 | 2016-03-17 | Imerys Minerals Limited | Polymer compositions |
| 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 |
-
2018
- 2018-02-05 CN CN201810109064.3A patent/CN108456352A/en active Pending
-
2019
- 2019-01-21 CN CN201910051359.4A patent/CN109467791A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415651A (en) * | 2002-12-10 | 2003-05-07 | 中国科学院长春应用化学研究所 | Method for preparing amylaceous fully degradable plastic |
| CN102321353A (en) * | 2011-07-26 | 2012-01-18 | 成都市新津事丰医疗器械有限公司 | Degradable material for preparing outside sleeve of disposable injector |
| WO2016038110A2 (en) * | 2014-09-09 | 2016-03-17 | Imerys Minerals Limited | Polymer compositions |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108456352A (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109467791A (en) | A kind of high strength easy-to-degrade modified poly ethylene film and preparation method thereof | |
| CN101805463B (en) | Starch filled biodegradable polypropylene and preparation method thereof | |
| CN106633722B (en) | Tear-resistant high-toughness biodegradable material and preparation method thereof | |
| CN102746629B (en) | Degradable masterbatch and preparation method thereof | |
| CN109467792A (en) | A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof | |
| Sabathini et al. | Mechanical Physicial properties of chlorella-PVA based bioplastic with ultrasonic homogenizer | |
| CN112920565B (en) | High-melt-strength biodegradable polyester material and preparation method thereof | |
| CN112111119A (en) | Polyvinyl alcohol nanocomposite with excellent performance and preparation method thereof | |
| CN109320816A (en) | A kind of polyethylene wood plastic micro foaming composite material and preparation method thereof | |
| CN107141564A (en) | A kind of PE expanded materials and preparation method thereof | |
| CN107365482B (en) | A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design | |
| CN106336634B (en) | A kind of improved biodegradable shopping bag and preparation method thereof | |
| CN106589539A (en) | Biodegradable additive and plastic products with addition of additive | |
| CN109206727A (en) | A kind of degradable polyethylene agricultural film and preparation method thereof | |
| CN113788900B (en) | Modified cellulose nanocrystal with high thermal stability and preparation method thereof | |
| CN108373560A (en) | A kind of degradable polymeric packaging material of the transparency and preparation method thereof | |
| CN109467865A (en) | A kind of degradable green plastic master batch and preparation method thereof | |
| CN108395583A (en) | A kind of degradable starch-based fresh food package sheet material raw material and preparation method thereof | |
| Sun et al. | Effect of poly-methyltriethoxysilane on the waterproof property of starch/fiber composites with open cell structures | |
| CN115679474A (en) | Hydrolysis-resistant polylactic acid fiber composite material and preparation method thereof | |
| CN112795154B (en) | Foaming-grade biodegradable polyester material and preparation method thereof | |
| CN105385120B (en) | A kind of preparation method of PET organic intercalations α ZrP composites | |
| CN109467793A (en) | A kind of transparent multiple-factor degradation modification polyethylene film and preparation method thereof | |
| CN114292501A (en) | Biodegradable material and preparation method and application thereof | |
| CN106674740A (en) | Polypropylene (PP) composite material specially used for packaging bags, and preparation method of PP composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190315 |
|
| RJ01 | Rejection of invention patent application after publication |