CN107365482A - A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design - Google Patents
A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design Download PDFInfo
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Abstract
The present invention is to belong to biodegradated polymer materal field, a kind of more particularly to special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design, the master batch is mainly by polyadipate/butylene terephthalate, PLA and activeness and quietness transparent agent, stability auxiliary agent is prepared, its preparation method is simple, it is easy to operate, the special master batch of gained can be degradable, good dispersion, the appropriate master batch of addition can blow less than 6 μm ultra-thin Biodegradable mulch, ultra-thin mulch film blow molding process diaphragm is easily open, processing stability and processing efficiency improve, the mulch film mechanical performance enhancing being processed into, improve the light transmittance of mulch film, reduce mist degree, significantly improve mulch film weatherability simultaneously；The master batch is combined with the multiple functions such as enhancing, toughness reinforcing, anti-reflection, lubrication, and application method is simple, improves the processing characteristics of ultra-thin whole life cycle design, reduces whole life cycle design use cost.
Description
Technical field
The invention belongs to Agricultural Materials field, and in particular to a kind of plastic master batch, particularly a kind of ultra-thin complete biodegradable
The special reinforced toughened anti-reflection master batch of mulch film.
Background technology
Plastic film plays great function in agricultural production, but the currently used plastic film overwhelming majority is difficult
With the TPO mulch film of short-term degraded or it with the addition of the incomplete degradation polyolefin class mulch film of starch and photodegradable aid.This
The use of a little film materials, causes " white pollution " of environment, and potential safety hazard is brought for human kind sustainable development.Full biology drop
It is to be process by complete biodegradable plastics by being blow molded or being cast to solve mulch film, can be decomposed completely by microorganism, and it is degraded
Final product be carbon dioxide and water, can be entirely nature consumption, therefore replaced with whole life cycle design current poly-
Olefinic product, it is the important means for solving farmland white pollution.
Whole life cycle design is mainly by PLA, polycaprolactone, aliphatic polyester, fatty poly-ester carbonate, poly- at present
Hydroxyl esters, starch etc. form, but because the own characteristic and defect of above-mentioned polymer, single polymers are difficult to as mulch film
Materials'use.Current research mainly by blending and modifying, modification by copolymerization, plasticization and modification and composite modified improves mulch film
Combination property.Patent CN 103589124B disclose a kind of complete biodegradable PLA/PBAT composite mulching films and preparation method thereof；
Patent CN 104744898A disclose a kind of whole life cycle design and preparation method thereof, the mulch film be have PLA (PLA),
Poly (propylene carbonate) (PPC), polyadipate/butylene terephthalate (PBAT) and heat stabilizer composition, but these mulch films
Universal thickness is higher, is 6um-50um, and the cost of mulch film remains high, and translucency is poor, low intensity, and causing in a short time can not business
Change and promote；Different from the TPO mulch film for being difficult to degrade, for whole life cycle design, as long as easy to process, function admirable,
Ground membrane product gets over Bao Yuehao, and inventor is also dedicated to solve the above problems in the work of early stage, wherein Shen in 2013
A kind of please patent 201310749460.X whole life cycle design master batches and its preparation method and application, but we are in reality
When finding that the master batch is used to blow ultra-thin whole life cycle design in, the ultra-thin mulch film process film bubble less than 6 μm is opened
Mouth difficulty, tensile strength and tearing strength are greatly reduced, mist degree is big, while because illumination triggers resin point during the use of field
Son crosslinking, ground film toughness reduce fragility increase, and mulch film easily ftractures in advance, therefore the technology has the defects of certain, and such as
What overcomes this defect to provide a kind of more balanced ground film master batch of performance needs to solve the problems, such as us.
The content of the invention
The present invention is directed to many weak points existing for prior art, there is provided a kind of ultra-thin whole life cycle design is special
Activeness and quietness is anti-reflection master batch, the master batch is mainly anti-reflection by polyadipate/butylene terephthalate, PLA and activeness and quietness
Agent, stability auxiliary agent are prepared, and its preparation method is simple, easy to operate, the special master batch of gained can degradable, good dispersion,
The appropriate master batch of addition can blow less than 6 μm ultra-thin Biodegradable mulch, and ultra-thin mulch film blow molding process diaphragm is easily open, processing
Stability and processing efficiency improve, the mulch film mechanical performance enhancing being processed into, while improve the light transmittance of mulch film, reduce mist
Degree；The master batch is combined with the multiple functions such as enhancing, toughness reinforcing, anti-reflection, lubrication, and application method is simple, improves ultra-thin full biology drop
The processing characteristics of mulch film is solved, reduces whole life cycle design use cost.
The present invention concrete technical scheme be：
A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design, its key component are calculated as by weight：
Polyadipate/butylene terephthalate 65-85 parts, PLA 1-20 parts, activeness and quietness transparent agent 10-20 parts,
Lubricant 5-30 parts, dispersant 1-5 parts, stability auxiliary agent 1-5 parts；
Wherein described polyadipate/butylene terephthalate and PLA are as vector resin, both melt flows
Dynamic speed is 2-5g/10min, and hydroxyl value is less than 15.Polyadipate/the butylene terephthalate and PLA pair that the present invention uses
The preparation of the ultra-thin special master batch of degradable mulch film and performance are extremely important, should merge all materials, but also to be resistant to
High temperature does not volatilize and decomposed, when preparing ultra-thin whole life cycle design with master batch of the present invention in the later stage, will also and its
His complete biodegradable resin has preferable compatibility, and will not induce the degraded of mulch film, therefore inventor is in numerous alternative resins
In preferably employ vector resin of the above-mentioned resin as master batch, and its specific dosage is defined as above, in the amount ranges
The various functions of lower master batch reach optimum balance.
Described activeness and quietness transparent agent is inorganic activeness and quietness transparent agent, one kind or several of organic activeness and quietness transparent agent
Kind：Described inorganic activeness and quietness transparent agent, selected from hydrophobic nano silica, wherein the hydrophobic nano silica
Size is 5-25nm；Described organic activeness and quietness transparent agent is Acker agate AX-8900 or ADX-1200s resin compatilizer or Hangzhoupro
Like the one or more of gram CE-AZ01 bulking agents in state；
Activeness and quietness transparent agent is no more than 20 parts, is to ensure powder with losing few, distribution in resin hybrid process
Uniformly, and it is easy to be granulated；The various kinds of resin compatibility in later stage processing film is also improved simultaneously, again will not be because of excessive increase-volume
The addition of agent and reduce the mechanical performance of film.
Above-mentioned activeness and quietness transparent agent is selected, there is good comixing compatibility with vector resin, high concentration mother can be made
Grain；In later stage film manufacturing process, nucleator and compatibilization can be played, beneficial to the stability of ultrathin membrane processing, is used simultaneously
In the mechanical property for strengthening ultra-thin full-biodegradable film.
Described lubricant is one or both of polymer microballoon PMMA, silicon dioxide microsphere.Described polymer
Microsphere Size is 0.5-5 μm, and described silicon dioxide microsphere size is 1-5 μm；Can directly it buy from the market；
Above-mentioned lubricant mainly plays lubrication openings in the present invention, film when being processed beneficial to ultra-thin full-biodegradable film
Piece opening, while microspherulite diameter is respectively less than 5 μm, ensures that the later stage prepares the mechanical performance and printing opacity of ultra-thin full-biodegradable film
Property；
Described dispersant is selected from epoxidized soybean oil, the one or two of organic silicon diffusing oil, from above-mentioned dispersant
Afterwards, preferably can coordinate with activeness and quietness transparent agent, it is scattered in vector resin beneficial to activeness and quietness transparent agent；
Described stability auxiliary agent is ultra-violet absorber, the one or two of ultra-violet stabilizer, described ultraviolet
Absorbent is low volatility benzotriazole ultraviolet absorber Tinuvin 234；Described ultra-violet stabilizer is steric hindrance
Amines stabilizer5050H。
Above-mentioned auxiliary agent can avoid and improve the light during ultra-thin whole life cycle design process and field use from dropping
Solution problem, extend its service life；
The above-mentioned all auxiliary agents used of the present invention are environment-friendly reagent and material, can all be degraded in nature.
It is special reinforced toughened anti-reflection that another feature of the present invention just there is provided the ultra-thin whole life cycle design
The preparation method of master batch, comprises the following steps：(1) the activeness and quietness transparent agent of prescription amount, dispersant dissolving are dispersed in tetrachloro
Change in carbon, after stirring, distill out carbon tetrachloride and obtain mixture；(2) mixture that obtains step (1), polyadipate/right
Terephtha-late and PLA, stability auxiliary agent, lubricant put into homogenizer by weight successively, 700~
1000r/min stirrings are kneaded 10-30 minutes；(3) in the mixture input double screw extruder being well mixed step (2), in
135-160 DEG C of extrusion, air-cooled granulation, obtain the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design.
In above-mentioned preparation method, inventor carries out dissolving point to activeness and quietness agent from carbon tetrachloride as solvent first
Dissipate, and dispersant is uniformly wrapped on activeness and quietness agent surface by solvent flashing, be advantageous to activeness and quietness transparent agent in carrier
It is scattered in resin.It is more preferable than present conventional hybrid mode effect.
In summary, the suitable of ultra-thin whole life cycle design processing can be kept using this master batch provided by the present invention
Smooth property, and can ensure the mechanical property and stability in use of ultra-thin whole life cycle design product, while original can be greatly lowered
Material cost.The master batch production process is simple, is easily mastered.The master batch property of this method production is stable, can be complete without any moisture
Degradable, good dispersion, the appropriate master batch of complete biodegradable resin addition can blow 4-6 μm of ultra-thin Biodegradable mulch, surpass
Unfertile land film blow molding process diaphragm is easily open, and processing stability improves.The ultra-thin whole life cycle design of the present invention is special reinforced toughened
Anti-reflection master batch is combined with the multiple functions such as enhancing, toughness reinforcing, anti-reflection, lubrication, light is steady, and application method is simple, can improve ultra-thin complete raw
The processing characteristics of thing degradative plastic film, at the same solve super mulch film bad mechanical strength, mist degree degrade greatly and during the use of field it is too fast
The problem of.
Embodiment
Embodiment 1
The ultra-thin special reinforced toughened anti-reflection master batch of whole life cycle design, in parts by weight, including following components：
It is prepared as steps described below：
Hydrophobic nano silica, epoxidized soybean oil dissolving are scattered in carbon tetrachloride, stirs, distills out four
Chlorination carbon, obtain mixture 1；Again by the mixture 1, polyadipate/butylene terephthalate, PLA, ultra-violet absorber
Tinuvin 234, polymer microballoon PMMA put into 700~1000r/min of homogenizer stirrings successively, are kneaded 10-30 minutes,
Obtain mixture 2；Mixture 2 is put into double screw extruder, in 135-160 DEG C of extrusion, air-cooled granulation, obtains ultra-thin full biology drop
Solve the special reinforced toughened anti-reflection master batch of mulch film.
Embodiment 2
The ultra-thin special reinforced toughened anti-reflection master batch of whole life cycle design, in parts by weight, including following components：
It is prepared as steps described below：
Hydrophobic nano silica, the dissolving of organosilicon diffusing oil are scattered in carbon tetrachloride, stirs, distills out
Carbon tetrachloride, obtain mixture 1；Again by the mixture, polyadipate/butylene terephthalate, PLA, love gram CE-AZ01,
Ultra-violet absorber Tinuvin 234, ultra-violet stabilizer5050H, silicon dioxide microsphere put into high-speed stirring successively
Mix 700~1000r/min of machine stirrings and be kneaded 10-30 minutes, obtain mixture 2；Mixture 2 is put into double screw extruder, in
135-160 DEG C of extrusion, air-cooled granulation, obtain the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design.
Embodiment 3
The ultra-thin special reinforced toughened anti-reflection master batch of whole life cycle design, in percentage by weight, including following components：
It is prepared as steps described below：
Hydrophobic nano silica, the dissolving of organosilicon diffusing oil are scattered in carbon tetrachloride, stirs, distills out
Carbon tetrachloride, obtain mixture 1；Again by the mixture, polyadipate/butylene terephthalate, ultra-violet stabilizer5050H, Acker agate AX-8900, silicon dioxide microsphere put into 700~1000r/min of homogenizer stirrings successively
10-30 minutes are kneaded, obtain mixture 2；Mixture 2 is put into double screw extruder, in 135-160 DEG C of extrusion, air-cooled granulation, is obtained
To the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design.
Experimental example
The ultra-thin special reinforced toughened anti-reflection master batch of whole life cycle design of the present invention is applied in the blowing of super mulch film, mainly
There are two kinds of feed postitions, a kind of is directly to mix master batch with blown film material according to the 1-5% of super ground membrane component ratio, and addition is blown
Film machine extrusion-blown modling；Another kind be by master batch according to the 1-5% of super ground membrane component together with other components again after blended granulation,
Add inflation film manufacturing machine extrusion-blown modling.
Application example 1
Component and dosage (number)
90 parts of PBAT
5 parts of PLA
Special reinforced toughened anti-reflection 5 parts of the master batch of ultra-thin whole life cycle design prepared by embodiment 1
Preparation technology：Various raw materials are weighed by above-mentioned formula, are placed in stirring 5 minutes in high-speed mixer.Through uniform
After mixing, by double-screw extruding pelletizing, compound is placed in the hopper of extrusion inflation film manufacturing machine, extrusion-blown modling is into uniform tubular
Film (film thickness be 4-5 μm, mulch film width 90-200cm), ultra-thin whole life cycle design is made in cut, bundling.
Application example 2
92 parts of PBAT
5 parts of PPC
Special reinforced toughened anti-reflection 3 parts of the master batch of ultra-thin whole life cycle design prepared by embodiment 1
Preparation technology：Various raw materials are weighed by above-mentioned formula, are placed in stirring 5 minutes in high-speed mixer.Through uniform
After mixing, by compound be placed in extrusion inflation film manufacturing machine hopper in, extrusion-blown modling into uniform tubular mulch film (film thickness be 4-5 μm
, mulch film width 90-200cm), ultra-thin whole life cycle design is made in cut, bundling.
According to the measure third portion of GB/T1040.3 plastic tensile performances：The experimental condition of film and thin slice, rate of extension
200mm/min.Each performance of gained mulch film is as shown in table 1.Comparative example is to use equal resin, with not adding ultra-thin complete biodegradable
The mulch film of the special reinforced toughened anti-reflection master batch of film.
| Application example 1 | Comparative example 1 | Application example 2 | Comparative example 2 | |
| Resin | PBAT、PLA | PBAT、PLA | PBAT、PPC | PBAT、PPC |
| Thickness (μm) | 5 | 8 | 5 | 8 |
| Light transmittance (%) | 91 | 90 | 88 | 85 |
| Tensile strength (MPa) | 30 | 25 | 28 | 17 |
| Elongation at break (%) | 706 | 550 | 560 | 386 |
| Angle tear strength (MPa) | 117 | 108 | 93 | 85 |
| Degradability | Degradable | Degradable | Degradable | Degradable |
| Blown film steeps Kekelé structure count | + | - | + | +- |
+：It is open smooth, not film breakage ,+-：It can be open, easy film breakage ,-：It is too embarrassed to say, easy film breakage
It can be seen that the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design prepared by using the present invention, blowing is ultra-thin
Whole life cycle design, its light transmittance, tensile strength and elongation at break etc. is superior to the higher whole life cycle design of thickness,
There is good processing characteristics simultaneously.
Claims (5)
- A kind of 1. special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design, it is characterised in that：Its key component is by weight Part is calculated as：Polyadipate/butylene terephthalate 65-85 parts, PLA 1-20 parts, activeness and quietness transparent agent 10-20 parts, lubrication Agent 5-30 parts, dispersant 1-5 parts, stability auxiliary agent 1-5 parts；Wherein described polyadipate/butylene terephthalate melt flow rate (MFR) is 2-5g/10min, and hydroxyl value is less than 15；Its Described in PLA, its melt flow rate (MFR) is 2-5g/10min, and hydroxyl value is less than 15；Described activeness and quietness transparent agent is inorganic activeness and quietness transparent agent, the one or more of organic activeness and quietness transparent agent：Described lubricant is one or both of polymer microballoon PMMA, silicon dioxide microsphere；Described dispersant is selected from epoxidized soybean oil, the one or two of organic silicon diffusing oil；Described stability auxiliary agent is ultra-violet absorber, the one or two of ultra-violet stabilizer.
- 2. the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design according to claim 1, it is characterised in that：Described inorganic activeness and quietness transparent agent, selected from hydrophobic nano silica, wherein the hydrophobic nano titanium dioxide Silicon size is 5-25nm；Described organic activeness and quietness transparent agent be Acker agate AX-8900 or ADX-1200s resin compatilizer or One or more in the love gram CE-AZ01 bulking agents of Hangzhou.
- 3. the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design according to claim 1, it is characterised in that：Described polymer microballoon size is 1-5 μm；Described silicon dioxide microsphere size is 1-5 μm.
- 4. the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design according to claim 1, it is characterised in that：Institute The ultra-violet absorber stated is low volatility benzotriazole ultraviolet absorber Tinuvin 234.Described ultra-violet stabilizer For steric hindrance amine stabilizer5050H。
- 5. the preparation method of the ultra-thin special reinforced toughened anti-reflection master batch of whole life cycle design, its feature exist described in claim 1 In：Comprise the following steps that：(1) the activeness and quietness transparent agent of prescription amount, dispersant dissolving are dispersed in carbon tetrachloride, after stirring, distilled out Carbon tetrachloride obtains mixture；(2) mixture that obtains step (1), polyadipate/butylene terephthalate, PLA, stability auxiliary agent, lubrication Agent puts into homogenizer by weight successively, and 700~1000r/min stirrings are kneaded 10-30 minutes；(3) in the mixture input double screw extruder being well mixed step (2), extruded in 135-160 DEG C, air-cooled granulation, Obtain the special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710572629.7A CN107365482B (en) | 2017-07-13 | 2017-07-13 | A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design |
| PCT/CN2018/094176 WO2019011152A1 (en) | 2017-07-13 | 2018-07-03 | Master batch with enhanced strength, toughness and transmittance, preparation method therefor and use thereof |
| JP2019563811A JP6942323B2 (en) | 2017-07-13 | 2018-07-03 | Manufacturing method and application of reinforced toughening and permeable masterbatch |
| ZA2019/05793A ZA201905793B (en) | 2017-07-13 | 2019-09-02 | Master batch with enhanced strength, toughness and transmittance, preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710572629.7A CN107365482B (en) | 2017-07-13 | 2017-07-13 | A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design |
Publications (2)
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| WO2019011152A1 (en) * | 2017-07-13 | 2019-01-17 | 山东农业大学 | Master batch with enhanced strength, toughness and transmittance, preparation method therefor and use thereof |
| CN113429757A (en) * | 2021-07-08 | 2021-09-24 | 东莞市金富亮塑胶科技有限公司 | Biodegradable anti-fogging master batch for mulching film and preservative film |
| CN115044175A (en) * | 2021-03-08 | 2022-09-13 | 中国农业科学院农业环境与可持续发展研究所 | Degradable master batch, preparation method thereof and mulching film containing degradable master batch |
| CN116239874A (en) * | 2023-02-24 | 2023-06-09 | 大禾科技发展(南京)有限公司 | Special hydrophobic biodegradable agricultural mulching film for rice as well as preparation method and application thereof |
| CN117382285A (en) * | 2023-10-10 | 2024-01-12 | 山东农业大学 | Multifunctional controllable multilayer co-extrusion biodegradable mulching film and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019011152A1 (en) * | 2017-07-13 | 2019-01-17 | 山东农业大学 | Master batch with enhanced strength, toughness and transmittance, preparation method therefor and use thereof |
| CN115044175A (en) * | 2021-03-08 | 2022-09-13 | 中国农业科学院农业环境与可持续发展研究所 | Degradable master batch, preparation method thereof and mulching film containing degradable master batch |
| CN113429757A (en) * | 2021-07-08 | 2021-09-24 | 东莞市金富亮塑胶科技有限公司 | Biodegradable anti-fogging master batch for mulching film and preservative film |
| CN113429757B (en) * | 2021-07-08 | 2023-03-14 | 东莞市金富亮塑胶科技有限公司 | Biodegradable anti-fogging master batch for mulching film and preservative film |
| CN116239874A (en) * | 2023-02-24 | 2023-06-09 | 大禾科技发展(南京)有限公司 | Special hydrophobic biodegradable agricultural mulching film for rice as well as preparation method and application thereof |
| CN116239874B (en) * | 2023-02-24 | 2024-01-23 | 大禾科技发展(南京)有限公司 | Special hydrophobic biodegradable agricultural mulching film for rice as well as preparation method and application thereof |
| CN117382285A (en) * | 2023-10-10 | 2024-01-12 | 山东农业大学 | Multifunctional controllable multilayer co-extrusion biodegradable mulching film and preparation method thereof |
| CN117382285B (en) * | 2023-10-10 | 2024-05-17 | 山东农业大学 | Multifunctional controllable multilayer co-extrusion biodegradable mulching film and preparation method thereof |
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Application publication date: 20171121 Assignee: Jinan AoYa Wanhe New Material Co.,Ltd. Assignor: Shandong Agricultural University Contract record no.: X2021370000036 Denomination of invention: A special strengthening, toughening and antireflection masterbatch for ultra-thin fully biodegradable plastic film Granted publication date: 20191105 License type: Common License Record date: 20211210 |