CN110256827A - A kind of nanometer barrier polylactic acid master batch - Google Patents
A kind of nanometer barrier polylactic acid master batch Download PDFInfo
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- CN110256827A CN110256827A CN201910643041.5A CN201910643041A CN110256827A CN 110256827 A CN110256827 A CN 110256827A CN 201910643041 A CN201910643041 A CN 201910643041A CN 110256827 A CN110256827 A CN 110256827A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
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- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Abstract
The present invention relates to a kind of nanometer barrier additive is provided, there is the structure as shown in formula I, POSS is that have the structure as shown in formula II, and R has the structure as shown in formula III.The invention further relates to a kind of nanometer barrier polylactic acid master batches to include the following components'mass percentage: polylactic acid 73%~80.9%, nanometer barrier additive 13%~17%, antioxidant 0.1%~1%, dispersing agent 0.5%~2%, compatilizer 3%~10%.The invention further relates to a kind of preparation methods of polylactic acid packaging film, first by polylactic acid, nanometer barrier additive, antioxidant, dispersing agent, compatilizer mix extruding pelletization, and nanometer barrier polylactic acid master batch is made, again by nanometer barrier polylactic acid master batch and polylactic acid, extrusion and blow molding, then thermal finalization.Nanometer barrier additive of the invention can effectively obstruct steam, have excellent mechanical property using the polylactic acid master batch of the nanometer barrier additive.
Description
The application is divisional application, original application application No. is 201611200521.7, the applying date are as follows: 2016.12.22,
Invention and created name: a kind of nanometer barrier additive and preparation method thereof and Related product.
Technical field
The present invention relates to the preparation methods of a kind of hyperbranched POSS modified additive and the additive, belong to macromolecule
Field of material technology.
Background technique
Currently, we belong to petrochemicals using more plastics such as polyethylene, polypropylene etc., although due to matter
Gently, intensity it is high, conveniently, the characteristics such as inexpensive it is very popular, but these plastics are the arch-criminals for generating white pollution,
And with the scarcity of petroleum, the price of these plastics is also rising steadily.The development of biodegradable plastic is to administer and solve white
The important channel of color pollution, biodegradation material be it is a kind of can be by microorganism decompositions such as bacterium, mould, algae in environment, most
Throughout one's life at the plastics of the substance of no pollution to the environment.Biodegradation material raw material sources are in renewable resource, such as corn and soybean
Deng being conducive to the mankind and get rid of dependence to petroleum resources.
In the current biodegradation material for producing and applying, polylactic acid (PLA) is that people's research and industrialized production are answered
With widest material.PLA is a kind of thermoplastic polyester, and there is good biological degradability, biocompatibility and biology can inhale
The property received, and the advantages of have both the plastics such as PP, PE, PST, most promising environmentally friendly packing material is considered by industrial circle.It is poly-
Lactic acid applies mainly need to solve the problems, such as to be its performance for obstructing steam on environmentally friendly packing material.Although having commercialization
PLA packaging material for food is applied to market, but its barrier property is still poor, still needs to the protective effect time of food
Increase.For example, public affairs that first all natural organic fruit drink of PLA bottle progress produced using Nature Works is packed in the world
Blue Lake is taken charge of, 60 days shelf life of product is only can guarantee, still can not meet guaranteeing the quality for current fruit drink at least half a year
Phase.
Therefore, researching and developing one kind to can be used for the efficient barrier of polylactic acid (PLA) is that those skilled in the art is urgently to be resolved
The problem of.
Summary of the invention
The technical problem to be solved by the present invention is to steam nanometer barrier additive and its system can effectively be obstructed by providing one kind
Preparation Method, a kind of polylactic acid master batch and preparation method thereof using the nanometer barrier additive with excellent mechanical property, one
Kind uses the preparation method of the polylactic acid packaging film of the polylactic acid master batch.
A kind of technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of nanometer barrier additive has
The structure as shown in formula I,
Wherein, POSS is cage modle polysilsesquioxane, and the silicon atom number of cage modle polysilsesquioxane is 8.
Above-mentioned cage modle polysilsesquioxane has the structure as shown in formula II,
Wherein, R is the functional group with amino.
Above-mentioned R has the structure as shown in formula III,
Cage modle polysilsesquioxane is γ-aminopropyl silsesquioxane.
Another technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of system of nanometer barrier additive
Preparation Method, suitable cage modle polysilsesquioxane and phosphorus oxychloride are reacted using acidic catalyst, are generated nanometer barrier and are added
Adding agent finished product, the cage modle polysilsesquioxane has the structure as shown in formula II,
Wherein, R is that have the structure as shown in formula III,
The molar ratio of above-mentioned cage modle polysilsesquioxane and phosphorus oxychloride is 3:2 to 2:1；The reaction temperature is 110 DEG C
~150 DEG C (preferably 135 DEG C), the reaction time 18h~36h (preferably for 24 hours), the reaction uses nitrogen protection, the acid
Property catalyst is hydrochloric acid.
It is above-mentioned that ethyl alcohol is added and is used as solvent after reaction, add triethylamine until hydrochloric acid smog disappearance, then mistake
Filter, washing, 85 DEG C~95 DEG C of vacuum (preferably 90 DEG C) is dry, to obtain solid additive.
Another technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of nanometer barrier polylactic acid is female
Grain, includes the following components'mass percentage: polylactic acid 73%~80.9%, nanometer barrier additive 13%~17%, antioxygen
Agent 0.1%~1%, dispersing agent 0.5%~2%, compatilizer 3%~10%.
Above-mentioned antioxidant is one of antioxidant 1010, irgasfos 168 and antioxidant TNP or a variety of；The dispersing agent
It is one of calcium stearate, 4351 wax powder of polyethylene wax micro mist, polytetrafluoroethylwax wax micro mist and Licocene PE MA or more
Kind；The compatilizer is one or both of copolymer and ethylene-vinyl acetate copolymer of ethylene and butyl acrylate.It is anti-
The composite antioxidant of oxygen agent preferred antioxidant 1010 and irgasfos 168.The preferred calcium stearate of dispersing agent and Licocene PE MA
4351 composition.
Another technical solution that the present invention proposes to solve above-mentioned technical problem is: a kind of preparation of polylactic acid packaging film
Method, comprising the following steps:
A. by the component of following mass percent: polylactic acid 73%~80.9%, nanometer barrier additive 13%~17%,
Antioxidant 0.1%~1%, dispersing agent 0.5%~2%, compatilizer 3%~10% mix extruding pelletization, and it is poly- that nanometer barrier is made
Lactic acid master batch,
B. by the component of following mass percent: nanometer barrier polylactic acid master batch 5%~10% (preferably 7%), remaining is
Polylactic acid, extrusion and blow molding, then thermal finalization.
Polylactic acid in above-mentioned steps A and step B is in advance in 80 DEG C~100 DEG C of at a temperature of dry 8h~15h；Step A
In mixing use vertical double helical ribbon mixer, driving power 3KW~120KW, incorporation time be 3min~10min (preferably
5min)；Extruder in the step A uses extruding machine with two screw rods engaging in the same direction, double spiral shells of extruding machine with two screw rods engaging in the same direction
Bar revolving speed is 40r/min~60r/min (preferably 50r/min), and temperature of each section respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180
℃,180℃；Extrusion and blow molding in the step B uses screw diameter for the single screw rod blow moulding machine of 125mm, and single screw rod turns
Speed is 20r/min~50r/min, and temperature of each section respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；The step
Heat-setting time 2s~10s (preferably 5s~7s) in B, heat setting temperature are 110 DEG C~130 DEG C (preferably 120 DEG C).
The present invention has the effect of positive: nanometer barrier additive of the invention is the hyperbranched POSS with special construction
Modifying agent, thermal stability and barrier properties for gases with higher, meeting fast transferring to surface, formation more connects in heat-setting process
The siliceous barrier network structure of continuousization, the dosage of additive are less.Its production that can be used for PLA food packaging and PLA packaging film
Printing etc., will not substantially reduce the transparency and printing performance of PLA packaging film, not only reduce packaging film at
This, also improves the comprehensive performance of packaging film.In a natural environment, the PLA high additive agent modified by nanometer barrier of the invention
It obstructs food packaging or packaging film can be degradable, the petrochemical industries material such as alternative traditional polyethylene, be a kind of environment friend
Good type product has important environment protection significance, and product comprehensive performance is high, and production is simple, application easy to spread, has very wide
General application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the nanometer barrier additive of embodiment 1；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the nanometer barrier additive of embodiment 1；
Fig. 3 is the DSC curve figure of the nanometer barrier additive of embodiment 1；
Fig. 4 is the thermogravimetric curve of the nanometer barrier additive of embodiment 1；
The migration schematic diagram of nanometer barrier additive when Fig. 5 is the polylactic acid packaging film thermal finalization of application examples 1；
Fig. 6 is the natural fracture face optical microscope image of the nanometer barrier polylactic acid master batch of application examples 1；
Fig. 7 is the natural fracture face optical microscope image of the nanometer barrier polylactic acid master batch of application examples 2；
Fig. 8 is the reaction route figure of the nanometer barrier additive in the present invention.
Specific embodiment
Raw materials and reagents used in the embodiment of the present invention are product common in the market, in which:
Polylactic acid (PLA) is preferably with the polylactic acid slice of certain melt viscosity, when test condition is 210 DEG C of 2.16Kg
Melt flow rate (MFR) be 6g/10min~60g/10min；Density are as follows: 1.20g/cm3~1.25g/cm3, further preferred melt
Flow rate is 20g/10min, density 1.20g/cm3Polylactic acid slice.The polylactic acid slice of suitable melt flow rate
Polylactic acid can be improved in the reliability of process, guarantee that product processing is gone on smoothly, improve product quality.
The preferred German road of the copolymer (EBA) of ethylene and butyl acrylate is comparable1400MN type ethylene and
The copolymer of butyl acrylate.
With ethylene-vinyl acetate copolymer (EVA) preferably 3165 type ethylene-vinyl acetate copolymer of Du Pont Elvax.
Embodiment 1
The structural formula of the nanometer barrier additive of the present embodiment is A3B2Phosphorylated T8 type silsesquioxane structure, have
The structure as shown in formula I,
Wherein, POSS is γ-aminopropyl silsesquioxane, has the structure as shown in formula II, silicon atom number is 8.
Wherein, R is the third amino, has the structure as shown in formula III,
The preparation method of the nanometer barrier additive of the present embodiment is to put a certain amount of γ-aminopropyl silsesquioxane
Enter in the three-necked flask with reflux condensate device of 500ml, 120 DEG C are heated in the case where mechanical stirring, is protected in nitrogen
Under conditions of shield, then by a certain amount of phosphorus oxychloride addition three-necked flask, the salt that a certain amount of concentration is 34% is then added
Acid continues after 135 DEG C of reactions for 24 hours, and ethyl alcohol is added as solvent, is slowly added triethylamine until the smog of hydrochloric acid disappears.Finally
It is washed repeatedly through filtering, and with water until infrared spectroscopy 2700cm-1Peak disappears, and 90 DEG C of vacuum are dried to obtain solid product.γ-ammonia
The molar ratio of propylsilsesquioxane and phosphorus oxychloride is 1.75:1.γ-aminopropyl silsesquioxane is according to document " γ-ammonia third
The hydrolytic polymerization mechanism study and product structure of base silsesquioxane characterize " (Gu Zheming etc., national macromolecule science report in 2005
Accuse meeting) disclosed in method synthesize.
As shown in Figures 1 to 4, to solid product by carrying out infrared spectroscopy detection respectively, magnetic resonance detection, showing that difference is swept
Retouch calorimetry detection, thermogravimetric detection.Obtained infrared spectrogram is as shown in Figure 1, obtained infrared structure characterizes spectral data such as
Shown in table 1, obtained nuclear magnetic resonance spectroscopy as shown in Fig. 2, obtained DSC curve figure as shown in figure 3, obtained thermogravimetric curve
As shown in Figure 4.
1 structural characterization spectral data of table
Infrared spectroscopy 3421cm-1(NH2, N-H stretching vibration), 3064cm-1(O=C-NH2, N-H stretching vibration),
2800cm-1(CH2Stretching vibration), 1595cm-1(C=O stretching vibration), 1477cm-1(CH2Rocking vibration), 1410cm-1(C-N
Stretching vibration), 1206cm-1(C-N stretches and N-H bending vibration), 1000-1130cm-1(Si-O-Si stretching vibration), 911cm-1
(CH2Rocking vibration).
Nuclear magnetic resonance-Si-CH2- 0.58~0.61ppm ,-CH2–CH30.85ppm ,-C (O)-CH2–CH2–/–CH2–CH3
(overlapping) 1.52ppm ,-Si-CH2–CH2–/-C(O)–CH2–CH2(overlapping) 1.6ppm ,-C (O)-CH2–
2.05ppm ,-Si-CH2–CH2–CH2–2.6ppm。
In DSC map, 166.2 DEG C of crystallization temperature, 260 DEG C of fusing point.
1% weightlessness of thermogravimetric curve is at 150 DEG C, and 269 DEG C apparent weightlessness occur, it can be seen that has in PLA well
Thermal stability and similar processing performance.
It is the nanometer barrier additive with the structure as shown in formula I to verify product.
Embodiment 2
The preparation method of the nanometer barrier additive of the present embodiment, rest part is same as Example 1, and difference exists
In: the molar ratio of γ-aminopropyl silsesquioxane and phosphorus oxychloride is 3:2, and reaction temperature is 140 DEG C, reaction time 20h.
Embodiment 3
The preparation method of the nanometer barrier additive of the present embodiment, rest part is same as Example 1, and difference exists
In: the molar ratio of γ-aminopropyl silsesquioxane and phosphorus oxychloride is 2:1, and reaction temperature is 130 DEG C, reaction time 27h.
Application examples 1
The preparation method of the nanometer barrier additive polylactic acid packaging film of the application example, comprising the following specific steps
A. by the component of following mass percent: polylactic acid 73%, nanometer barrier additive 15%, antioxidant 1%, dispersion
Agent 1%, compatilizer 10% mix extruding pelletization, and nanometer barrier polylactic acid master batch is made.Antioxidant is antioxidant 1010 and antioxygen
168 mass ratio of agent is the composite antioxidant of 1:1.Dispersing agent is calcium stearate and 4351 mass ratio of Licocene PE MA is 4:1
Composition.Compatilizer is 3165 type ethylene-vinyl acetate copolymer (EVA) of Du Pont Elvax.
Polylactic acid is in advance in 100 DEG C of at a temperature of dry 12h.Then content accurately weighs each raw material by mass percentage.
The raw material weighed up is disposably all put into super mixer and carries out dry blending process.Raw material after mixing is added to again
Double screw extruder melt blending extruding pelletization obtains nanometer barrier polylactic acid master batch.
Dry blending process uses vertical double helical ribbon mixer, driving power 3KW~120KW, incorporation time 5min.Extruder
Using extruding machine with two screw rods engaging in the same direction, the twin-screw revolving speed of extruding machine with two screw rods engaging in the same direction is 50r/min, temperature of each section according to
Secondary is respectively 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C.
B. by mass percent be 7% nanometer barrier polylactic acid master batch and mass percent be 93% polylactic acid cut
Piece, extrusion-blown modling is at packaging film, then thermal finalization.
Blow molding uses screw diameter for the single screw rod blow moulding machine of 125mm, and single screw rod revolving speed is 30r/min, each section of temperature
Degree respectively is 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C.Heat-setting time 5s, heat setting temperature are 120 DEG C.
Application examples 2 to 8 of the invention from application examples 1 the difference is that: component proportion is different, and see Table 2 for details.
2 polylactic acid packaging film component table of table
As shown in figure 5, nanometer barrier additive is during thermal finalization to the surface migration of polylactic acid packaging film, nanometer
The seldom additive amount of barrier additive can reach good barriering effect.Nanometer barrier additive is enriched with shape in heat-setting process
After the protection network of serialization, nanometer barrier additive can be stabilized, and the surface silicone content for showing film is kept not
Become.In the long-time service of polylactic acid packaging film, barriering effect will not be varied over.Nanometer barrier additive is to mention
The main additive of high polylactic acid barrier property, evenly dispersed serialization protect network structure, are remarkably improved polylactic acid
Barrier steam ability.The correct selection of compatilizer and dispersing agent has synergistic effect, can improve POSS modified additive
While dispersibility and compatibility, the processing performance of polylactic acid is improved.
Optical microscopy can be used to master batch in the morphology characterization of nanometer barrier polylactic acid master batch in application examples of the present invention
Natural fracture face carries out observation of taking pictures.For analyzing dispersibility and compatibility of the additive in lactic acid matrix, optical microscopy
After taking pictures to natural fracture face, dispersed analysis is carried out using the analysis method that instrument carries.Fig. 6 and Fig. 7 are respectively
The natural fracture face optical microscope image of the nanometer barrier polylactic acid master batch of application examples 1 and application examples 2.It can from Fig. 6 and Fig. 7
To see, the POSS modified additive in application examples 1 and application examples 2 is uniformly dispersed in PLA matrix, and soilless sticking phenomenon,
It is realized with PLA matrix preferable compatible.
The tensile property test of polylactic acid packaging film is made using GB13022-91 " stretched plastic film method for testing performance "
For experimental method.Using GB/T1037-1988, " plastic film and sheet material water vapor permeability test method are cup type for barrier property test
Method " and GB/T1038-2000 " plastic film and thin slice gas-premeable test method pressure differential method " be used as experimental method.
Test the water vapor transmittance of polylactic acid packaging film, mechanical property, light transmittance, mist degree and surface dynes value, test knot
Fruit is as shown in table 3 below:
3 polylactic acid packaging film performance data of table
Data in analytical table 2 illustrate this hair it is found that the water vapor transmittance of each application examples is more excellent compared with pure PLA
Bright nanometer barrier polylactic acid master batch has excellent mechanical property and barrier property.Suitable thermal finalization processing can accelerate nanometer
Migration of the additive to surface is obstructed, increases it in the enrichment of film surface, keeps its barrier property more preferable, this is also from another side
The barrier property for demonstrating the barrier package film of nanometer barrier polylactic acid master batch preparation can with the extension of use time and more
It is good.
Obviously, the above embodiment is merely an example for clearly illustrating the present invention, and is not to of the invention
The restriction of embodiment.For those of ordinary skill in the art, it can also be made on the basis of the above description
Its various forms of variation or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
The obvious changes or variations that bright spirit is extended out are still in the protection scope of this invention.
Claims (5)
1. a kind of nanometer barrier polylactic acid master batch, which is characterized in that include the following components'mass percentage: polylactic acid 73%~
80.9%, nanometer barrier additive 13%~17%, antioxidant 0.1%~1%, dispersing agent 0.5%~2%, compatilizer 3%~
10%.
2. a kind of nanometer barrier polylactic acid master batch according to claim 1, it is characterised in that:
The nanometer barrier additive has the structure as shown in formula I,
Wherein, POSS is cage modle polysilsesquioxane.
3. a kind of nanometer barrier polylactic acid master batch according to claim 2, it is characterised in that:
The cage modle polysilsesquioxane has the structure as shown in formula II,
Wherein, R is the functional group with amino.
4. a kind of nanometer barrier polylactic acid master batch according to claim 3, it is characterised in that:
The R has the structure as shown in formula III,
5. a kind of nanometer barrier polylactic acid master batch according to claim 1, it is characterised in that: the antioxidant is antioxidant
1010, one of irgasfos 168 and antioxidant TNP or a variety of；The dispersing agent is calcium stearate, polyethylene wax micro mist, gathers
One of 4351 wax powder of tetrafluoroethene wax micro mist and Licocene PE MA is a variety of；The compatilizer is ethylene and propylene
One or both of copolymer and ethylene-vinyl acetate copolymer of acid butyl ester.
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| CN107955172B (en) * | 2017-10-25 | 2020-10-27 | 浙江大学宁波理工学院 | Photosensitive nano particle, intelligent light-operated nano barrier composite material containing photosensitive nano particle and preparation method of intelligent light-operated nano barrier composite material |
| CN110511412B (en) * | 2019-09-11 | 2021-05-25 | 内蒙古农业大学 | High-breathability PLDxL copolymer film, preparation method thereof and application thereof in fruit and vegetable fresh keeping |
| CN111607203B (en) * | 2020-07-09 | 2022-08-23 | 山东农业大学 | Reinforced and toughened poly (butylene adipate)/terephthalate-polylactic acid) composite film and preparation method thereof |
| CN113621146B (en) * | 2021-07-22 | 2024-02-27 | 厦门长塑实业有限公司 | Antifogging, antibacterial and mildew-proof polylactic acid master batch, film thereof and preparation method thereof |
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| CN106854283A (en) | 2017-06-16 |
| CN110204878A (en) | 2019-09-06 |
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