CN108276644A - A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof - Google Patents
A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof Download PDFInfo
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Abstract
A kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof, belongs to the preparing technical field of macromolecule new material.The present invention is using polyethylene as macromolecule matrix, high molecular modification of graft is caused using cold grinding stress, simultaneously it will be seen that light filler, porous filler and microbial nutrition additive homogeneous reaction cladding are wherein, form stable multi-functional degradable polymer composite, realize the autoxidation degradation of composite material, thermal oxidative degradation, natural photodegradation, the function of hydrophilic degradation and biodegradable multiple-factor synergy, gained composite material is granulated by one-step method melting extrusion, Fully-degradable ethylene master batch is made, the degradable generation carbon dioxide of energy and water, it can directly blown film finished product use, masterbatch is can also be used as to be added in other macromolecule matrixes, realize the multiple degrading function of mixing high molecular material.Present invention process is simple, energy-efficient, green non-pollution.
Description
Technical field
The present invention relates to a kind of toughenings to enhance Fully-degradable ethylene master batch and preparation method thereof, belongs to macromolecule new material
Preparing technical field.
Background technology
With the improvement of people's living standards, while disposable plastic packing articles bring health, facilitate, also result in
Serious environmental pollution.For this purpose, developing low-cost, the full-degradable disposable plastic packaging materials being readily produced, as refuse bag,
There is important practical significance and environmental protecting commonweal to be worth for shopping bag and cutlery box etc..
Degradation plastic currently on the market includes Biodegradable polyester, as polylactic acid, polybutylene succinate-are sour
The compound etc. of ester, polyhydroxybutyrate-valerate, polyethylene succinate, polyester acid amide and pla-pcl separately has containing degradation
Other composite polymer materials of accelerating agent.But since current degradable plastic product is substantially more expensive, and existing can
Palliating degradation degree and machining property are difficult to the defect balanced, it is difficult to which the existing plastic product with long-term occuping market competes, are
Biodegradable plastic enters the major obstacle in market.But in recent years, with the continuous increase of pollution pressure, to environmentally-friendly plastic
Demand gradually increase, novel degradable environmentally-friendly plastic and new technology are developed in market in urgent need, to reduce the production of degradation plastic
Cost promotes the use attraction to user.
High-energy ball milling method generates lattice defect, crystal phase transition and decrystallized effect using reaction particle during Ultrafine Grinding
And make the raising of crystal interior energy, substance inside constantly focused energy that can be broken to form in surface chemistry key with priming reaction particle
It is final to realize reaction under the action of unsaturated bond, free ion and electronics.Macromolecule can produce under the inducing action of stress
Raw macromolecular radical, to which degradation, grafting, block, crosslinking can be realized under room temperature cold grinding state and introduce other functions
The reactions such as group.In addition, solid phase stress field, which can induce, causes the chemical reaction that conventional chemical processes are difficult to or can not carry out, prepare
General chemical method and the not getable material with property of manufacturing process become hot spot skill in investigation of materials field
Art is a kind of environmentally protective, energy-efficient new technology of the preparation and the modified field of application of high molecular material.
Invention content
The purpose of the present invention is overcoming the defect difficult to degrade of vinyon in the prior art, it is complete to provide a kind of toughening enhancing
Degrading polyethylene master batch and preparation method thereof, by add efficient photosensitizer, oxidant, biological inducing agent, degradation of promoter,
Toughening enhances modifier and stabilizer etc., and the technological means that co-extrusion is further modified is modified and repeatedly melted by a step cold grinding,
Realize the combination of the degradable and excellent mechanical property of vinyon.
Technical scheme of the present invention, a kind of toughening enhancing Fully-degradable ethylene master batch and preparation method thereof, with polyethylene
For macromolecule matrix, increase intensity by adding a small amount of polyacrylonitrile and nylon；Add the nanometer three of hydrophilic modifying polyurea coating
Molybdenum oxide carries out porous modification and promotes Visible Light Induced Photocatalytic activity；Nanometer hydroxyapatite filler plays enhancing modifying function；Three second
Alkene tetramine and epoxy silane coupling play the role of appropriate cross-linked network hydrophilic modifying jointly, while amino and epoxy group can
Improve thermooxidative degradation；The effect of polyvingl ether and propylgallate reacting property photodissociation accelerating agent；Ethylene-acrylic acid
Methyl esters-glycidyl methacrylate terpolymer and sorbeth play the work of toughening compatilizer and stress release agent
With；Carboxymethyl chitosan and citric acid provide Louis acid catalysis effect and biological degradability；Acetyl tri-n-butyl citrate and
The polynary ester admixture of amyl-based polyol is as plasticizer；It is modified by a step cold grinding method and repeatedly melting co-extrusion is further modified
Technological means, be made toughening enhance Fully-degradable ethylene master batch, the multiple drop such as light, vapor, microorganism, thermal oxide can be caused
Factor synergistic effect is solved, after validity period, can be degraded rapidly, while there is preferable intensity and toughness.
A kind of toughening enhancing Fully-degradable ethylene master batch, formula are counted as follows in mass ratio：Ju Yi Xi ︰ Ju Bing Xi Jing ︰ Ni Long ︰
Na meters of Qiang base Lin Hui Shi ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ of nanometer San Yangization Mu ︰ of hydrophilic modifying polyurea coating are poly-
The Gong Ju Wu ︰ sorbierites of Yi alkenyl Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate San members are poly-
Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer proportions are：10~30 ︰, 0.1~0.5 ︰, 0.2~0.6 ︰, 0.01~0.03 ︰, 1 ︰ 0.1
1~2 ︰ of~0.5 ︰ 0.1~0.3 ︰, 0.01~0.05 ︰, 0.002~0.005 ︰, 0.02~0.08 ︰, 0.01~0.05 ︰, 1~2 ︰ 1~3；
Further, the nylon is nylon 6 or nylon 4；
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 toughening enhancing Fully-degradable ethylene master batch, steps are as follows：
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An be 5~8 ︰, 1 ︰, 5~12 ︰ 3~5 ︰ 4~9,100~200r/min under conditions of,
25 DEG C of bath temperature, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly dropped to the water of nano-sized molybdenum oxide
In the mixed solution of acetone, it is added dropwise in 40~60min, after reacting 1h, 6000~8000r/min centrifugations 20~
40min, washing, vacuum degree be 5~20kPa, 60~80 DEG C vacuum drying 30~60min, obtain receiving for hydrophilic modifying polyurea coating
Rice molybdenum trioxide；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, Ju Yi Xi ︰ Ju Bing Xi Jing ︰ Ni Long ︰ are hydrophilic
Na meters of Qiang base Lin Hui Shi ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene of nanometer San Yangization Mu ︰ of modified polyurea cladding
The Gong Ju Wu ︰ sorbierites Ju Mi ︰ of Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate San members
The mass ratio of Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：10~30 ︰, 0.1~0.5 ︰, 0.2~0.6 ︰, 0.01~0.03 ︰, 1 ︰
0.1~0.5 ︰, 0.1~0.3 ︰, 0.01~0.05 ︰, 0.002~0.005 ︰, 0.02~0.08 ︰, 0.01~0.05 ︰, 1~2 ︰, 1~2 ︰ 1~
3；By the component in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating in homogenizer, with 800~1000 r/
Min is sufficiently mixed 10 min, obtains mixture, adds mixture into planetary ball mill, in material ball ratio 1 ︰ 2~5 and 1 ︰ 1.5
Under rotating ratio, after 10~30 min of vibration hybrid reaction, the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating is added, continues vibration
Modified poly ethylene mixture is made in 30~60min；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, the operation temperature of double screw extruder is：180~200 DEG C, 50~80 r/min of screw speed
Under, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2~3 times, be granulated, and obtains toughening enhancing degradable
Polyethylene master batch.
Further, a diameter of 20mm of the double screw extruder, draw ratioL/D It is 36:1.
Beneficial effects of the present invention：The present invention is by adding efficient photosensitizer, oxidant, biological inducing agent, degradation promotion
Agent, toughening enhancing modifier, stabilizer etc., a step cold grinding is modified and repeatedly melting co-extrusion is further modified, and realizes polyethylene
Plastics degradable and and excellent mechanical property combination, 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）；Planet
Qiu Mo Ji ︰ XQM-2L types, Bei Jing Xin Biao rise experimental instruments and equipment limited；Machine ︰ 1185, Britain Instron are tested in Wan Nengcai material examinations
Company；
Nano-sized molybdenum oxide（Hubei Zhong Ao nano material technologies Co., Ltd, grain size are less than 50nm）；Ethylene-methyl acrylate-
Glycidyl methacrylate terpolymer（The trade mark 16 MA 003, French A Kema）；Sorbeth（Trade mark HK-
6305S, Jining Hua Kai resin Co., Ltd）；Carboxymethyl chitosan（Degree of substitution>80%, the limited public affairs of the emerging biotechnology of Zhejiang Australia
Department）；Amyl-based polyol polyester（Liaocheng Rui Jie Chemical Co., Ltd.s）；Polyvingl ether, propylgallate, acetyl lemon
Sour tri-n-butyl, maleic anhydride and polylactic acid are purchased from Chinese medicines group Shanghai Co., Ltd；KH-560（γ-（2,3- epoxies third
Oxygen）Propyl trimethoxy silicane, Nanjing Pin Ning coupling agents Co., Ltd）；High density polyethylene (HDPE)（The trade mark, EGDA-6888, section's prestige
Special petrochemical industry）；Low density polyethylene (LDPE)（Trade mark 2100TN00, Iranian petrochemical industry）；Low density polyethylene (LDPE) (trade mark 2426H, Maoming Petrochemical)；
Linear low density polyethylene（The trade mark 7042, Yangtze petrochemical industry）；Linear low density polyethylene（The trade mark 7042, Qilu Petrochemical）；Such as nothing
Illustrate, it is other it is raw materials used be commercial goods.
1 toughening of embodiment enhances the preparation of Fully-degradable ethylene master batch
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
Under conditions of ︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An are 5 ︰, 1 ︰, 5 ︰, 3 ︰, 4,100 r/min, 25 DEG C of bath temperature, respectively
By Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise in the water of nano-sized molybdenum oxide and the mixed solution of acetone
It goes, is added dropwise in 40min, after reacting 1h, 6000r/min centrifuges 20min, washing, vacuum degree 5kPa, 60 DEG C of vacuum
Dry 30min, obtains the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, high density polyethylene (HDPE)（The trade mark, EGDA-
6888, Kuwait's petrochemical industry）The nanometer San Yangization Mu ︰ nano-hydroxy-apatites of 6 ︰ hydrophilic modifying polyurea coatings of ︰ Ju Bing Xi Jing ︰ nylon
Shi ︰ tri- ethylene Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylates-Glycidyl methacrylate is sweet
The mass ratio of the Gong Ju Wu ︰ sorbierites Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer of grease San members is：10 ︰, 0.1 ︰, 0.2 ︰
0.01 ︰, 1 ︰, 0.1 ︰, 0.1 ︰, 0.01 ︰, 0.002 ︰, 0.02 ︰, 0.01 ︰, 1 ︰, 1 ︰ 1；It will be except the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating
Component in addition is sufficiently mixed 10min in homogenizer, with 800r/min, obtains mixture, adds mixture into planet
In ball mill, under the rotating ratio of material ball ratio 1 ︰ 2 and 1 ︰ 1.5, after vibration hybrid reaction 10min, hydrophilic modifying polyureas packet is added
The nano-sized molybdenum oxide covered continues vibration 30min, and modified poly ethylene mixture is made；
The plasticizer is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, double screw extruder each section operation temperature is：180,190,200,200,190 DEG C, screw rod turns
Under fast 50r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2 times, be granulated, obtains toughening enhancing
Fully-degradable ethylene master batch.
2 toughening of embodiment enhances the preparation of Fully-degradable ethylene master batch
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An are 25 DEG C of bath temperature under conditions of 8 ︰, 1 ︰, 12 ︰ 5 ︰ 9,200r/min, respectively
By Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise in the water of nano-sized molybdenum oxide and the mixed solution of acetone
Go, be added dropwise in 60min, react 1h after, 8000r/min centrifuge 40min, washing, vacuum degree 20kPa, 80 DEG C very
The dry 60min of sky, obtains the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, low density polyethylene (LDPE)（Trade mark 2100TN00,
Iranian petrochemical industry）Na meters of Qiang base Lin Hui Shi ︰ triethylenes of nanometer San Yangization Mu ︰ of 4 ︰ hydrophilic modifying polyurea coatings of ︰ Ju Bing Xi Jing ︰ nylon
Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate ternarys
The mass ratio of Gong Ju Wu ︰ sorbierites Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：30 ︰, 0.5 ︰, 0.6 ︰, 0.03 ︰, 1 ︰, 0.5 ︰
0.3 ︰, 0.05 ︰, 0.005 ︰, 0.08 ︰, 0.05 ︰, 2 ︰, 2 ︰ 3；Component in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating is existed
In homogenizer, 10min is sufficiently mixed with 1000r/min, obtains mixture, is added mixture into planetary ball mill,
Under the rotating ratio of material ball ratio 1 ︰ 5 and 1 ︰ 1.5, after vibration hybrid reaction 30min, three oxygen of nanometer of hydrophilic modifying polyurea coating is added
Change molybdenum, continue vibration 60min, modified poly ethylene mixture is made；
The plasticizer is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, double screw extruder each section operation temperature is：190,200,200,200,180 DEG C, screw rod turns
Under 80 r/min of speed, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated, obtains toughening increasing
Strong Fully-degradable ethylene master batch.
3 toughening of embodiment enhances the preparation of Fully-degradable ethylene master batch
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An are 6:1:7:4:Under conditions of 5,200r/min, 25 DEG C of bath temperature respectively will
Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise in the water of nano-sized molybdenum oxide and the mixed solution of acetone
Go, be added dropwise in 50min, react 1h after, 7000r/min centrifuge 25min, washing, vacuum degree 10kPa, 70 DEG C very
The dry 40min of sky, obtains the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, linear low density polyethylene（The trade mark 7042,
Yangtze petrochemical industry）Na meters of Qiang base Lin Hui Shi ︰ triethylenes of nanometer San Yangization Mu ︰ of 6 ︰ hydrophilic modifying polyurea coatings of ︰ Ju Bing Xi Jing ︰ nylon
Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate ternarys
The mass ratio of Gong Ju Wu ︰ sorbierites Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：20 ︰, 0.2 ︰, 0.3 ︰, 0.02 ︰, 1 ︰, 0.3 ︰
0.2 ︰, 0.03 ︰, 0.003 ︰, 0.04 ︰, 0.02 ︰, 1 ︰, 1 ︰ 2；Component in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating is existed
In homogenizer, 10min is sufficiently mixed with 900r/min, obtains mixture, is added mixture into planetary ball mill, expected
Ball is than under the rotating ratio of 1 ︰ 3 and 1 ︰ 1.5, after vibration hybrid reaction 20min, the nanometer three that hydrophilic modifying polyurea coating is added aoxidizes
Molybdenum continues vibration 40min, and modified poly ethylene mixture is made；
The plasticizer is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, double screw extruder each section operation temperature is：180℃、180℃、190℃、190℃、180
DEG C, under 60 r/min of screw speed, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated,
Obtaining toughening enhances Fully-degradable ethylene master batch.
4 toughening of embodiment enhances the preparation of Fully-degradable ethylene master batch
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An are under conditions of 6 ︰, 1 ︰, 8 ︰ 3 ︰ 6,100r/min, and 25 DEG C of bath temperature respectively will
Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise in the water of nano-sized molybdenum oxide and the mixed solution of acetone
Go, be added dropwise in 40min, react 1h after, 6000r/min centrifuge 30min, washing, vacuum degree 15kPa, 65 DEG C very
The dry 50min of sky, obtains the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, low density polyethylene (LDPE) (trade mark 2426H, cyclopentadienyl
Na meters of Qiang base Lin Hui Shi ︰ triethylenes four of nanometer San Yangization Mu ︰ of 4 ︰ hydrophilic modifying polyurea coatings of name petrochemical industry) ︰ Ju Bing Xi Jing ︰ nylon
An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate ternarys are total
The mass ratio of Ju Wu ︰ sorbierite Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：15 ︰, 0.4 ︰, 0.5 ︰, 0.02 ︰, 1 ︰, 0.4 ︰
0.2 ︰, 0.04 ︰, 0.003 ︰, 0.07 ︰, 0.04 ︰, 1.5 ︰, 1.5 ︰ 2.5；It will be in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating
Component is sufficiently mixed 10min in homogenizer, with 900r/min, obtains mixture, adds mixture into planetary ball mill
In, under the rotating ratio of material ball ratio 1 ︰ 4 and 1 ︰ 1.5, after vibration hybrid reaction 25min, receiving for hydrophilic modifying polyurea coating is added
Rice molybdenum trioxide, continues vibration 50min, and modified poly ethylene mixture is made；
The plasticizer is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, double screw extruder each section operation temperature is：190℃、190℃、200℃、200℃、190
DEG C, under screw speed 70r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2 times, be granulated,
Obtaining toughening enhances Fully-degradable ethylene master batch.
5 toughening of embodiment enhances the preparation of Fully-degradable ethylene master batch
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An are 25 DEG C of bath temperature under conditions of 7 ︰, 1 ︰, 10 ︰ 4 ︰ 8,200r/min, respectively
By Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly added drop-wise in the water of nano-sized molybdenum oxide and the mixed solution of acetone
Go, be added dropwise in 45min, react 1h after, 8000r/min centrifuge 35min, washing, vacuum degree 17kPa, 75 DEG C very
The dry 45min of sky, obtains the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, linear low density polyethylene（The trade mark 7042,
Qilu Petrochemical）Na meters of Qiang base Lin Hui Shi ︰ triethylenes of nanometer San Yangization Mu ︰ of 6 ︰ hydrophilic modifying polyurea coatings of ︰ Ju Bing Xi Jing ︰ nylon
Si An ︰ KH-560 ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate ternarys
The mass ratio of Gong Ju Wu ︰ sorbierites Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：25 ︰, 0.3 ︰, 0.2 ︰, 0.02 ︰, 1 ︰, 0.3 ︰
0.1 ︰, 0.05 ︰, 0.002 ︰, 0.08 ︰, 0.01 ︰, 2 ︰, 1 ︰ 3；Component in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating is existed
In homogenizer, 10min is sufficiently mixed with 800r/min, obtains mixture, is added mixture into planetary ball mill, expected
Ball is than under the rotating ratio of 1 ︰ 5 and 1 ︰ 1.5, after vibration hybrid reaction 10min, the nanometer three that hydrophilic modifying polyurea coating is added aoxidizes
Molybdenum continues vibration 60min, and modified poly ethylene mixture is made；
The plasticizer is the mixture that three positive Ding Zhi ︰ amyl-based polyol polyester mass ratioes of acetyl tributyl citrate are 1 ︰ 1；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, double screw extruder each section operation temperature is：180℃、180℃、200℃、180℃、180
DEG C, under screw speed 70r/min, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 3 times, be granulated,
Obtaining toughening enhances Fully-degradable ethylene master batch.
The Mechanics Performance Testing of master batch product obtained by 1 Examples 1 to 5 of Application Example
Using R-3202 type experiment compact hot press（Wuhan Qi En developments in science and technology Co., Ltd）With with sleeving plastic standard specimen mold
Standardized test specimen is prepared, sample tensile strength is pressed GB/T 1040.3-2006, is tested using universal testing machine,
Test speed is 10 mm/min, the results are shown in Table 1.
The mechanical property of 1 master batch product of table
Master batch product obtained by 2 Examples 1 to 5 of Application Example under field conditions (factors) test by multiple-factor degradation property
Using R-3202 type experiment compact hot press（Wuhan Qi En developments in science and technology Co., Ltd）With with sleeving plastic standard specimen mold
Prepare standardized test specimen.Plastic film mulch experiment is carried out in Jiangsu Province Localities In Southwest farmland.After 3 months, film starts to burst apart, 6
2~3 cm are resolved into after month2Fragment is easily twisted powder after 12 months.
The biological degradability test of master batch product obtained by 3 Examples 1 to 5 of Application Example
Using R-3202 type experiment compact hot press（Wuhan Qi En developments in science and technology Co., Ltd）With with sleeving plastic standard specimen mold
Prepare standardized test specimen.Assay method is implemented according to ISO14855-1 (2005), and test sample decomposes the titanium dioxide generated
Carbon is measured using gas-chromatography (Agilent, 7820A), the results are shown in Table 2.
2 biodegradability 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 (7)
1. a kind of toughening enhances Fully-degradable ethylene master batch, it is characterised in that formula is counted as follows in mass ratio：Ju Yi Xi ︰ polypropylene
Na meters of Qiang base Lin Hui Shi ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydrides of nanometer San Yangization Mu ︰ of Jing ︰ Ni Long ︰ hydrophilic modifying polyurea coatings are even
The Gong Ju Wu ︰ of Lian Ji ︰ polyethylene Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate San members
Sorbierite Ju Mi ︰ Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer proportions are：10~30 ︰, 0.1~0.5 ︰, 0.2~0.6 ︰ 0.01~
0.03 ︰, 1 ︰, 0.1~0.5 ︰, 0.1~0.3 ︰, 0.01~0.05 ︰, 0.002~0.005 ︰, 0.02~0.08 ︰, 0.01~0.05 ︰, 1~2 ︰ 1
~2 ︰ 1~3.
2. toughening enhances Fully-degradable ethylene master batch according to claim 1, it is characterised in that：The nylon be nylon 6 or
Nylon 4.
3. toughening enhances Fully-degradable ethylene master batch according to claim 1, it is characterised in that：The polyethylene is high density
Polyethylene, low density polyethylene (LDPE) or linear low density polyethylene.
4. toughening enhances Fully-degradable ethylene master batch according to claim 1, it is characterised in that：The epoxy radicals silicone hydride coupling
Agent is KH-560, i.e. γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane.
5. toughening enhances Fully-degradable ethylene master batch according to claim 1, it is characterised in that：The plasticizer is acetyl lemon
The mixture that lemon three positive Ding Zhi ︰ neopentyl polyol ester mass ratioes of acid are 1 ︰ 1.
6. the preparation method of one of the claim 1-5 toughening enhancing Fully-degradable ethylene master batches, it is characterised in that step is such as
Under：
（1）The preparation of the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating：According to Toluene-2,4-diisocyanate, 4- bis- Yi Qing Suan Zhi ︰ triethylenes four
︰ nanometers of San Yangization Mu ︰ Shui ︰ acetone quality ratios of An be 5~8 ︰, 1 ︰, 5~12 ︰ 3~5 ︰ 4~9,100~200r/min under conditions of,
25 DEG C of bath temperature, respectively by Toluene-2,4-diisocyanate, 4- diisocyanate and triethylene tetramine are slowly dropped to the water of nano-sized molybdenum oxide
In the mixed solution of acetone, it is added dropwise in 40~60min, after reacting 1h, 6000~8000r/min centrifugations 20~
40min, washing, vacuum degree be 5~20kPa, 60~80 DEG C vacuum drying 30~60min, obtain receiving for hydrophilic modifying polyurea coating
Rice molybdenum trioxide；
（2）Cold grinding modified poly ethylene mixture：By raw material components dispensing in mass ratio, Ju Yi Xi ︰ Ju Bing Xi Jing ︰ Ni Long ︰ are hydrophilic
Na meters of Qiang base Lin Hui Shi ︰ tri- ethylene Si An ︰ epoxy radicals silicone hydride Ou Lian Ji ︰ polyethylene of nanometer San Yangization Mu ︰ of modified polyurea cladding
The Gong Ju Wu ︰ sorbierites Ju Mi ︰ of Ji Mi ︰ nutgall acid Bing Zhi ︰ ethylene-methyl acrylate-glyceryl methacrylate San members
The mass ratio of Suo methyl Ke Ju Tang ︰ Ning Meng Suan ︰ plasticizer is：10~30 ︰, 0.1~0.5 ︰, 0.2~0.6 ︰, 0.01~0.03 ︰, 1 ︰
0.1~0.5 ︰, 0.1~0.3 ︰, 0.01~0.05 ︰, 0.002~0.005 ︰, 0.02~0.08 ︰, 0.01~0.05 ︰, 1~2 ︰, 1~2 ︰ 1~
3；By the component in addition to the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating in homogenizer, with 800~1000 r/
Min is sufficiently mixed 10 min, obtains mixture, adds mixture into planetary ball mill, in material ball ratio 1 ︰ 2~5 and 1 ︰ 1.5
Under rotating ratio, after 10~30 min of vibration hybrid reaction, the nano-sized molybdenum oxide of hydrophilic modifying polyurea coating is added, continues vibration
Modified poly ethylene mixture is made in 30~60min；
（3）Toughening enhances the preparation of Fully-degradable ethylene master batch：By step（2）Gained modified poly ethylene mixture is squeezed in twin-screw
Go out and carry out melt modification in machine, the operation temperature of double screw extruder is：180~200 DEG C, 50~80 r/min of screw speed
Under, melt blending squeezes out, and under identical operating condition, repeats melt blending and squeezes out 2~3 times, be granulated, and obtains toughening enhancing degradable
Polyethylene master batch.
7. the preparation method of toughening enhancing Fully-degradable ethylene master batch according to claim 6, it is characterised in that：Step（3）
The a diameter of 20mm of double screw extruder, draw ratioL/D It is 36:1.
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| CN111234357A (en) * | 2020-04-09 | 2020-06-05 | 苏州清之绿新材料有限公司 | Biodegradable nano plastic sheet and manufacturing method thereof |
| CN111333803A (en) * | 2018-12-19 | 2020-06-26 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material and application thereof |
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| CN111333803A (en) * | 2018-12-19 | 2020-06-26 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material and application thereof |
| CN111333803B (en) * | 2018-12-19 | 2022-02-18 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material and application thereof |
| CN111234357A (en) * | 2020-04-09 | 2020-06-05 | 苏州清之绿新材料有限公司 | Biodegradable nano plastic sheet and manufacturing method thereof |
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