CN106854283A - A kind of nanometer barrier additive and preparation method thereof and Related product - Google Patents
A kind of nanometer barrier additive and preparation method thereof and Related product Download PDFInfo
- Publication number
- CN106854283A CN106854283A CN201611200521.7A CN201611200521A CN106854283A CN 106854283 A CN106854283 A CN 106854283A CN 201611200521 A CN201611200521 A CN 201611200521A CN 106854283 A CN106854283 A CN 106854283A
- Authority
- CN
- China
- Prior art keywords
- pla
- nanometer barrier
- nanometer
- barrier additive
- additive
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- 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 provide a kind of nanometer barrier additive, it has the structure as shown in formula I, and 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 the component that a kind of nanometer barrier PLA master batch includes following mass percent：PLA 73%~80.9%, nanometer barrier additive 13%~17%, antioxidant 0.1%~1%, dispersant 0.5%~2%, compatilizer 3%~10%.The invention further relates to a kind of preparation method of PLA packaging film, first by PLA, nanometer barrier additive, antioxidant, dispersant, compatilizer mixes extruding pelletization, and nanometer barrier PLA master batch is obtained, again by nanometer barrier PLA master batch and PLA, extrusion and blow molding, then thermal finalization.Nanometer barrier additive of the invention can effectively intercept steam, and the PLA master batch using the nanometer barrier additive has excellent mechanical property.
Description
Technical field
The present invention relates to a kind of hyperbranched POSS property-modifying additives, and the additive preparation method, belong to macromolecule
Field of material technology.
Background technology
At present, we belong to petrochemicals using more plastics such as polyethylene, polypropylene etc., although due to matter
The characteristic such as gently, intensity is high, convenient, inexpensive is very popular, but these plastics are the arch-criminals for producing white pollution,
And with the scarcity of oil, the price of these plastics is also rising steadily.The development of biodegradable plastic is to administer and solve in vain
The important channel of color pollution, biodegradation material is that a class can be decomposed by microorganisms such as the bacterium in environment, mould, algae, most
Throughout one's life into the plastics of environmentally safe material.Biodegradation material raw material sources are in renewable resource, such as corn and soybean
Deng being conducive to the mankind to break away from the dependence to petroleum resources.
In the biodegradation material of production and application at present, PLA (PLA) is that people's research and industrialized production should
Use widest material.PLA is a kind of thermoplastic polyester, can be inhaled with good biological degradability, biocompatibility and biology
The property received, and have the advantage of the plastics such as PP, PE, PST concurrently, most rising environmentally friendly packing material is considered by industrial circle.It is poly-
Lactic acid applies the performance for mainly needing that solve problem is its obstruct steam on environmentally friendly packing material.Although, existing commercialization
PLA packaging materials for food are applied to market, but its barrier property is still poor, and the protective effect time to food still needs
Increase.For example, first produced using Nature Works PLA bottle carries out the public affairs of All Pure Nature organic fruit drink packaging in the world
Department Blue Lake, it only can guarantee that 60 days shelf lifes of product, still can not meet guaranteeing the quality for current fruit drink at least half a year
Phase.
Therefore, the efficient barrier that research and development one kind can be used for PLA (PLA) is those skilled in the art urgently to be resolved hurrily
Problem.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind and can effectively intercept steam nanometer barrier additive and its system
Preparation Method, it is a kind of that there is PLA master batch of excellent mechanical property and preparation method thereof, one using the nanometer barrier additive
Plant the preparation method using the PLA packaging film of the PLA master batch.
The present invention is that a kind of technical scheme for solving above-mentioned technical problem proposition is：A kind of nanometer barrier additive, has
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.
The present invention is that another technical scheme for solving above-mentioned technical problem proposition is：A kind of system of nanometer barrier additive
Preparation Method, appropriate cage modle polysilsesquioxane and POCl3 are reacted using acidic catalyst, and generation nanometer barrier adds
Plus agent finished product, the cage modle polysilsesquioxane has structure as shown in formula II,
Wherein, R is that have the structure as shown in formula III,
Above-mentioned cage modle polysilsesquioxane is 3 with the mol ratio of POCl3:2 to 2:1；The reaction temperature is 110 DEG C
~150 DEG C (preferably 135 DEG C), the reaction time 18h~36h (preferably 24h), the reaction is using nitrogen protection, the acid
Property catalyst is hydrochloric acid.
After above-mentioned reaction terminates, ethanol is added as solvent, add triethylamine up to the smog of hydrochloric acid disappears, then mistake
Filter, washing, 85 DEG C~95 DEG C of vacuum (preferably 90 DEG C) is dried, so as to obtain solid additive.
The present invention is that another technical scheme for solving above-mentioned technical problem proposition is：A kind of nanometer barrier PLA is female
Grain, including following mass percent component：PLA 73%~80.9%, nanometer barrier additive 13%~17%, antioxygen
Agent 0.1%~1%, dispersant 0.5%~2%, compatilizer 3%~10%.
Above-mentioned antioxidant is one or more in antioxidant 1010, irgasfos 168 and antioxidant TNP；The dispersant
It is the one kind or many in calcium stearate, polyethylene wax micro mist, polytetrafluoroethylwax wax micro mist and the wax powders of Licocene PE MA 4351
Kind；The compatilizer is one or two in the copolymer and ethylene-vinyl acetate copolymer of ethene and butyl acrylate.It is anti-
The composite antioxidant of the preferred antioxidant 1010 of oxygen agent and irgasfos 168.The preferred calcium stearate of dispersant and Licocene PE MA
4351 composition.
The present invention is that another technical scheme for solving above-mentioned technical problem proposition is：A kind of preparation of PLA packaging film
Method, comprises the following steps：
A. by the component of following mass percent：PLA 73%~80.9%, nanometer barrier additive 13%~17%,
Antioxidant 0.1%~1%, dispersant 0.5%~2%, compatilizer 3%~10% mixes extruding pelletization, nanometer barrier is obtained and gathers
Lactic acid master batch,
B. by the component of following mass percent：Nanometer barrier PLA master batch 5%~10% (preferably 7%), remaining is
PLA, extrusion and blow molding, then thermal finalization.
PLA in above-mentioned steps A and step B dries 8h~15h at a temperature of 80 DEG C~100 DEG C in advance；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 rotating speed is 40r/min~60r/min (preferably 50r/min), each section of temperature respectively be 140 DEG C, 150 DEG C, 170 DEG C, 180
℃、180℃；It is the single screw rod blow moulding machine of 125mm that extrusion and blow molding in the step B uses screw diameter, and single screw rod turns
Speed is 20r/min~50r/min, and each section of temperature 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 is 110 DEG C~130 DEG C (preferably 120 DEG C).
The present invention has positive effect：Nanometer barrier additive of the invention is the hyperbranched POSS with special construction
Modifying agent, with heat endurance and barrier properties for gases higher, to surface, formation more connects meeting fast transferring in heat-setting process
The siliceous obstruct network structure of continuousization, the consumption of additive is less.Its production that can be used for PLA packagings for foodstuff and PLA packaging films
The aspect such as printing, will not substantially reduce the transparency and printing performance of PLA packaging films, not only reduce packaging film into
This, also improves the combination property of packaging film.It is high by the additive agent modified PLA of nanometer barrier of the invention under natural environment
Intercept packaging for foodstuff or packaging film can be degradable, the petrochemical industry material such as alternative traditional polyethylene, be a kind of environment friend
Good type product, with important environment protection significance, and product combination property is high, and production is simple, it is easy to popularization and application, with very wide
General application prospect.
Brief description of the drawings
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 PLA packaging film thermal finalization of application examples 1；
Fig. 6 is the natural fracture face optical microscope image of the nanometer barrier PLA master batch of application examples 1；
Fig. 7 is the natural fracture face optical microscope image of the nanometer barrier PLA master batch of application examples 2；
Fig. 8 is the reaction scheme figure of the nanometer barrier additive in the present invention.
Specific embodiment
Raw material and reagent used by the embodiment of the present invention are the common product of in the market, wherein：
PLA (PLA) the preferably polylactic acid slice with certain melt viscosity, when test condition is 210 DEG C of 2.16Kg
Melt flow rate (MFR) be 6g/10min~60g/10min；Density is:1.20g/cm3~1.25g/cm3, further preferred melt
Flow rate is 20g/10min, and density is 1.20g/cm3Polylactic acid slice.The polylactic acid slice of suitable melt flow speed
Reliability of the PLA in process can be improved, it is ensured that Product processing is smoothed out, improve product quality.
The preferred Germany road of the copolymer (EBA) of ethene and butyl acrylate is comparable1400MN types ethene and third
The copolymer of olefin(e) acid butyl ester.
With ethylene-vinyl acetate copolymer (EVA) the preferably type ethylene-vinyl acetate copolymers of Du Pont Elvax 3165.
Embodiment 1
The structural formula of the nanometer barrier additive of the present embodiment is A3B2Phosphorylated T8 type silsesquioxane alkyl structures, have
Structure as shown in formula I,
Wherein, POSS is γ-aminopropyl silsesquioxane, and with the structure as shown in formula II, silicon atom number is 8.
Wherein, R is the third amino, with 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 there-necked flask with reflux condensate device of 500ml, 120 DEG C are heated in the case of mechanical agitation, protected in nitrogen
Under conditions of shield, then by a certain amount of POCl3 addition there-necked flask, it is subsequently adding the salt that a certain amount of concentration is 34%
After acid continues to react 24h at 135 DEG C, ethanol is added as solvent, be slowly added triethylamine until the smog of hydrochloric acid disappears.Finally
Through filtering, and with water cyclic washing until infrared spectrum 2700cm-1Peak disappears, and 90 DEG C of vacuum is dried to obtain solid product.γ-ammonia
Propylsilsesquioxane is 1.75 with the mol ratio of POCl3:1.γ-aminopropyl silsesquioxane is according to document《γ-ammonia third
The hydrolytic polymerization study mechanism and product structure of base silsesquioxane are characterized》(Gu Zheming etc., the national academic report of macromolecule in 2005
Accuse meeting) disclosed in method synthesize.
As shown in Figures 1 to 4, to solid product by carrying out infrared spectrum detection, magnetic resonance detection respectively, showing that difference is swept
Retouch calorimetry detection, thermogravimetric detection.The infrared spectrogram for obtaining is as shown in figure 1, the infrared structure for obtaining characterizes spectral data such as
Shown in table 1, the proton nmr spectra for obtaining is as shown in Fig. 2 the DSC curve figure for obtaining is as shown in figure 3, the thermogravimetric curve for obtaining
As shown in Figure 4.
The structural characterization spectral data of table 1
Infrared spectrum 3421cm-1(NH2, N-H stretching vibrations), 3064cm-1(O=C-NH2, N-H stretching vibrations),
2800cm-1(CH2Stretching vibration), 1595cm-1(C=O stretching vibrations), 1477cm-1(CH2Rocking vibration), 1410cm-1(C-N
Stretching vibration), 1206cm-1(C-N stretch and N-H flexural vibrations), 1000-1130cm-1(Si-O-Si stretching vibrations), 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 collection of illustrative plates, 166.2 DEG C of crystallization temperature, 260 DEG C of fusing point.
The weightlessness of thermogravimetric curve 1% is at 150 DEG C, and 269 DEG C obvious weightlessness occur, it can be seen that have in PLA well
Heat endurance and similar processing characteristics.
So as to verify that product is the nanometer barrier additive with the structure as shown in formula I.
Embodiment 2
The preparation method of the nanometer barrier additive of the present embodiment, remainder is same as Example 1, and difference exists
In：γ-aminopropyl silsesquioxane is 3 with the mol ratio of POCl3:2, reaction temperature is 140 DEG C, and the reaction time is 20h.
Embodiment 3
The preparation method of the nanometer barrier additive of the present embodiment, remainder is same as Example 1, and difference exists
In：γ-aminopropyl silsesquioxane is 2 with the mol ratio of POCl3:1, reaction temperature is 130 DEG C, and the reaction time is 27h.
Application examples 1
The preparation method of the nanometer barrier additive PLA packaging film of the application example, including step in detail below：
A. by the component of following mass percent：PLA 73%, nanometer barrier additive 15%, antioxidant 1%, dispersion
Agent 1%, compatilizer 10% mixes extruding pelletization, and nanometer barrier PLA master batch is obtained.Antioxidant is antioxidant 1010 and antioxygen
The mass ratio of agent 168 is 1:1 composite antioxidant.Dispersant is calcium stearate and the mass ratioes of Licocene PE MA 4351 are 4:1
Composition.Compatilizer is the type ethylene-vinyl acetate copolymers (EVA) of Du Pont Elvax 3165.
PLA dries 12h at a temperature of 100 DEG C in advance.Then content accurately weighs each raw material by mass percentage.
The raw material that will be weighed up carries out dry blending process in disposably all putting into super mixer.Raw material after again will be well mixed is added to
Double screw extruder melt blending extruding pelletization, obtains nanometer barrier PLA master batch.
Dry blending process use vertical double helical ribbon mixer, driving power 3KW~120KW, incorporation time is 5min.Extruder
Using extruding machine with two screw rods engaging in the same direction, the twin-screw rotating speed of extruding machine with two screw rods engaging in the same direction is 50r/min, each section of temperature according to
It is secondary to be respectively 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C.
B. the nanometer barrier PLA master batch that mass percent is 7% and the PLA that mass percent is 93% are cut
Piece, extrusion-blown modling is into packaging film, then thermal finalization.
It is the single screw rod blow moulding machine of 125mm that blow molding uses screw diameter, and single screw rod rotating 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 is 120 DEG C.
Application examples 2 to 8 of the invention is with the difference of application examples 1：Component proportion is different, refers to table 2.
The PLA packaging film component table of table 2
As shown in figure 5, nanometer barrier additive during thermal finalization to the surface migration of PLA packaging film, nanometer
Intercept the little addition of additive and just can reach good barriering effect.Nanometer barrier additive enrichment shape in heat-setting process
Into after the protection network of serialization, nanometer barrier additive is meeting stable existence, and the surface silicone content for showing film keeps not
Become.In PLA packaging film long-term use, its barriering effect will not be varied over.Nanometer barrier additive is to carry
The main additive of PLA barrier property high, its dispersed serialization protection network structure is remarkably improved PLA
Obstruct steam ability.Compatilizer has cooperative effect with the correct selection of dispersant, can improve POSS property-modifying additives
While dispersiveness and compatibility, the processing characteristics of PLA is improved.
The morphology characterization of the nanometer barrier PLA master batch in application examples of the present invention can be using light microscope to master batch
Natural fracture face carries out observation of taking pictures.For analyzing dispersiveness and compatibility of the additive in lactic acid matrix, light microscope
After being taken pictures to natural fracture face, the analysis method carried using instrument carries out dispersed analysis.Fig. 6 and Fig. 7 are respectively
The natural fracture face optical microscope image of the nanometer barrier PLA master batch of application examples 1 and application examples 2.Can from Fig. 6 and Fig. 7
To see, the POSS property-modifying additives in application examples 1 and application examples 2 are uniformly dispersed in PLA matrixes, and soilless sticking phenomenon,
Realized with PLA matrixes preferably compatible.
The tensile property test of PLA packaging film uses GB13022-91《Stretched plastic film method for testing performance》Make
It is experimental technique.Barrier property test uses GB/T1037-1988《Plastic sheeting and sheet material water vapor permeability test method are cup type
Method》And GB/T1038-2000《Plastic sheeting and thin slice gas-premeable test method pressure differential method》As experimental technique.
Test the water vapor transmittance of PLA packaging film, mechanical property, light transmittance, mist degree and surface dynes value, test knot
It is really as shown in table 3 below：
The PLA packaging film performance data of table 3
Data in analytical table 2 understand that the water vapor transmittance of each application examples is more excellent compared with pure PLA, illustrates this hair
Bright nanometer barrier PLA master batch has excellent mechanical property and barrier property.Suitable thermal finalization treatment can accelerate nanometer
Migration of the additive to surface is intercepted, increases its enrichment on film surface, make its barrier property more preferably, this is also from another side
The barrier property for demonstrating the barrier package film of nanometer barrier PLA master batch preparation can be with the extension of use time more
It is good.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to of the invention
The restriction of implementation method.For those of ordinary skill in the field, it can also be made on the basis of the above description
The change or variation of its multi-form.There is no need and unable to be exhaustive to all of implementation method.And these belong to this hair
Obvious change that bright spirit is extended out or among changing still in protection scope of the present invention.
Claims (10)
1. a kind of nanometer barrier additive, it is characterised in that：With the structure as shown in formula I,
Wherein, POSS is cage modle polysilsesquioxane.
2. a kind of nanometer barrier additive according to claim 1, it is characterised in that：The cage modle polysilsesquioxane tool
Just like the structure shown in formula II,
Wherein, R is the functional group with amino.
3. a kind of nanometer barrier additive according to claim 2, it is characterised in that：The R has as shown in formula III
Structure,
4. a kind of preparation method of nanometer barrier additive, it is characterised in that appropriate cage modle polysilsesquioxane and trichlorine oxygen
Phosphorus is reacted using acidic catalyst, generates nanometer barrier additive finished product, and the cage modle polysilsesquioxane has such as formula
Structure shown in II,
Wherein, R is that have the structure as shown in formula III,
5. the preparation method of a kind of nanometer barrier additive according to claim 4, it is characterised in that：Poly- times of the cage modle
Half siloxanes is 3 with the mol ratio of POCl3:2 to 2:1；The reaction temperature is 110 DEG C~150 DEG C, the reaction time
18h~36h, the reaction is protected using nitrogen, and the acidic catalyst is hydrochloric acid.
6. the preparation method of a kind of nanometer barrier additive according to claim 5, it is characterised in that：The reaction terminates
Afterwards, ethanol is added as solvent, adds triethylamine until the smog disappearance of hydrochloric acid, then filters, washes, vacuum 85 DEG C~95
DEG C drying, so as to obtain solid additive.
7. a kind of nanometer barrier PLA master batch, it is characterised in that the component including following mass percent：PLA 73%~
80.9%, nanometer barrier additive 13%~17%, antioxidant 0.1%~1%, dispersant 0.5%~2%, compatilizer 3%~
10%.
8. a kind of nanometer barrier PLA master batch according to claim 7, it is characterised in that：The antioxidant is antioxidant
1010th, one or more in irgasfos 168 and antioxidant TNP；The dispersant is calcium stearate, polyethylene wax micro mist, gathers
One or more in tetrafluoroethene wax micro mist and the wax powders of Licocene PE MA 4351；The compatilizer is ethene and propylene
One or two in the copolymer and ethylene-vinyl acetate copolymer of acid butyl ester.
9. a kind of preparation method of PLA packaging film, it is characterised in that：Comprise the following steps：
A. by the component of following mass percent：PLA 73%~80.9%, nanometer barrier additive 13%~17%, antioxygen
Agent 0.1%~1%, dispersant 0.5%~2%, compatilizer 3%~10% mixes extruding pelletization, and nanometer barrier PLA is obtained
Master batch,
B. by the component of following mass percent：Nanometer barrier PLA master batch 5%~10%, remaining is PLA, and extrusion is blown
Type is moulded, then thermal finalization.
10. the preparation method of a kind of PLA packaging film according to claim 9, it is characterised in that：The step A and step
PLA in rapid B dries 8h~15h at a temperature of 80 DEG C~100 DEG C in advance；Mixing in step A uses vertical pair of ribbon
Mixer, driving power 3KW~120KW, incorporation time is 3min~10min；Extruder in the step A is used to be nibbled in the same direction
Close double screw extruder, the twin-screw rotating speed of extruding machine with two screw rods engaging in the same direction is 40r/min~60r/min, each section of temperature according to
It is secondary to be respectively 140 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 180 DEG C；Extrusion and blow molding in the step B use screw diameter for
The single screw rod blow moulding machine of 125mm, single screw rod rotating speed is 20r/min~50r/min, each section of temperature respectively be 140 DEG C, 150
℃、170℃、180℃、180℃；Heat-setting time 2s~10s in the step B, heat setting temperature is 110 DEG C~130 DEG C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643041.5A CN110256827A (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier polylactic acid master batch |
| CN201910643033.0A CN110204878A (en) | 2016-12-22 | 2016-12-22 | A kind of preparation method of polylactic acid packaging film |
| CN201611200521.7A CN106854283B (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier additive and preparation method thereof and Related product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611200521.7A CN106854283B (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier additive and preparation method thereof and Related product |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910643041.5A Division CN110256827A (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier polylactic acid master batch |
| CN201910643033.0A Division CN110204878A (en) | 2016-12-22 | 2016-12-22 | A kind of preparation method of polylactic acid packaging film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106854283A true CN106854283A (en) | 2017-06-16 |
| CN106854283B CN106854283B (en) | 2019-08-06 |
Family
ID=59126376
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910643033.0A Pending CN110204878A (en) | 2016-12-22 | 2016-12-22 | A kind of preparation method of polylactic acid packaging film |
| CN201910643041.5A Pending CN110256827A (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier polylactic acid master batch |
| CN201611200521.7A Active CN106854283B (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier additive and preparation method thereof and Related product |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910643033.0A Pending CN110204878A (en) | 2016-12-22 | 2016-12-22 | A kind of preparation method of polylactic acid packaging film |
| CN201910643041.5A Pending CN110256827A (en) | 2016-12-22 | 2016-12-22 | A kind of nanometer barrier polylactic acid master batch |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN110204878A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955172A (en) * | 2017-10-25 | 2018-04-24 | 浙江大学宁波理工学院 | Photosensitive nanoparticles, intelligent light-controlled nanometer gas barrier composite material containing the particle and preparation method thereof |
| CN111607203A (en) * | 2020-07-09 | 2020-09-01 | 山东农业大学 | Reinforced and toughened poly (butylene adipate)/terephthalate-polylactic acid) composite film and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090036589A1 (en) * | 2007-08-01 | 2009-02-05 | Chang Gung University | Polymer-blend nanocomposites using nanocompatibilizer and method of manufacture thereof |
| JP2009542836A (en) * | 2006-07-07 | 2009-12-03 | アプライド・ナノテック・ホールディングス・インコーポレーテッド | Nanocomposite and method for producing the same |
| US7951310B2 (en) * | 2006-03-28 | 2011-05-31 | East China University Of Science And Technology | Nanophase carbon black grafted with organic compound in situ |
| CN103602048A (en) * | 2013-11-28 | 2014-02-26 | 四川大学 | Polylactic acid film blowing processing aid and preparation method and application thereof |
| CN103724957A (en) * | 2013-12-17 | 2014-04-16 | 浙江普利特新材料有限公司 | Novel polylactic acid thin film material and preparation method thereof |
| CN105440611A (en) * | 2015-05-03 | 2016-03-30 | 湖南工业大学 | High-strength and high-toughness polylactic acid composite film with antimicrobial and barrier properties |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI413659B (en) * | 2010-10-05 | 2013-11-01 | Ind Tech Res Inst | Bio-based material composition and optical device employing the same |
| CN103232689B (en) * | 2013-04-03 | 2015-06-03 | 西安理工大学 | Preparation method for polylactic acid film with toughness |
| US10112150B2 (en) * | 2014-07-17 | 2018-10-30 | The Research Foundation For The State University Of New York | Porous graphene based composite membranes for nanofiltration, desalination, and pervaporation |
-
2016
- 2016-12-22 CN CN201910643033.0A patent/CN110204878A/en active Pending
- 2016-12-22 CN CN201910643041.5A patent/CN110256827A/en active Pending
- 2016-12-22 CN CN201611200521.7A patent/CN106854283B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7951310B2 (en) * | 2006-03-28 | 2011-05-31 | East China University Of Science And Technology | Nanophase carbon black grafted with organic compound in situ |
| JP2009542836A (en) * | 2006-07-07 | 2009-12-03 | アプライド・ナノテック・ホールディングス・インコーポレーテッド | Nanocomposite and method for producing the same |
| US20090036589A1 (en) * | 2007-08-01 | 2009-02-05 | Chang Gung University | Polymer-blend nanocomposites using nanocompatibilizer and method of manufacture thereof |
| CN103602048A (en) * | 2013-11-28 | 2014-02-26 | 四川大学 | Polylactic acid film blowing processing aid and preparation method and application thereof |
| CN103724957A (en) * | 2013-12-17 | 2014-04-16 | 浙江普利特新材料有限公司 | Novel polylactic acid thin film material and preparation method thereof |
| CN105440611A (en) * | 2015-05-03 | 2016-03-30 | 湖南工业大学 | High-strength and high-toughness polylactic acid composite film with antimicrobial and barrier properties |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955172A (en) * | 2017-10-25 | 2018-04-24 | 浙江大学宁波理工学院 | Photosensitive nanoparticles, intelligent light-controlled nanometer gas barrier composite material containing the particle and preparation method thereof |
| 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 |
| CN111607203A (en) * | 2020-07-09 | 2020-09-01 | 山东农业大学 | Reinforced and toughened poly (butylene adipate)/terephthalate-polylactic acid) composite film and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106854283B (en) | 2019-08-06 |
| CN110204878A (en) | 2019-09-06 |
| CN110256827A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106854283A (en) | A kind of nanometer barrier additive and preparation method thereof and Related product | |
| CN105419193B (en) | A kind of fast degradation type soybean protein simulation plastic film and preparation method thereof | |
| Castaño et al. | Physical, chemical and mechanical properties of pehuen cellulosic husk and its pehuen-starch based composites | |
| CN102532837A (en) | Preparation method for high molecular weight polylactic acid steric composite | |
| CN103980548A (en) | Starch-based degradable agricultural mulching film and preparation method thereof | |
| CN102529056A (en) | Preparation method for high melt strength poly lactic acid, and extruder thereof | |
| CN111944287A (en) | Preparation method of high-transparency easy-tearing polylactic acid blown film | |
| CN103642181B (en) | High permeability to water vapour casting films | |
| CN110628087B (en) | Polyion liquid plasticized thermoplastic starch and preparation method thereof | |
| CN101792539B (en) | Method for preparing full-starch full-biodegradable thermoplastic plastic | |
| CN111378261A (en) | Processing method of disposable lunch box | |
| CN108395607A (en) | A kind of ultraviolet light turns blue light resin and its preparation method and application | |
| CN102093682A (en) | Light polylactic acid composite material and preparation method thereof | |
| CN109705446A (en) | A kind of modified polyolefin mother material and its preparation method and application | |
| CN111073123B (en) | Polyethylene master batch, preparation method thereof and polyethylene composition | |
| CN102443269B (en) | Radiation modified soybean isolated protein/starch plastic and preparation method thereof | |
| CN102174179A (en) | Preparation method of heat-resistant polylactic acid biodegradable material | |
| CN102604308B (en) | Preparation method of blow molding type thermoplastic konjak glucomannan/poly-caprolactone composite resin | |
| CN101722654A (en) | Method for preparing polylactic acid-based resin film by liquid phase medium heat conduction double-membrane soaking method | |
| CN115216093A (en) | Environment-friendly degradable plastic bag and preparation method thereof | |
| CN107366038A (en) | It is crosslinked the preparation method and product of dextrorotation PLA/PLLA blended fiber | |
| CN202367928U (en) | Extruding machine | |
| CN104098824A (en) | Filling master batch for degradable plastic film | |
| CN111057350A (en) | Full-biodegradable composite material with excellent mechanical property and preparation method thereof | |
| CN109161177A (en) | A kind of lined polymethyl ethylene carbonate base high barrier material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 213000 industrial concentration area of Lijia Town, Wujin District, Jiangsu, Changzhou Applicant after: Changzhou film Polytron Technologies Inc Address before: 213000 industrial concentration area of Lijia Town, Wujin District, Jiangsu, Changzhou Applicant before: Changzhou Baijia Film Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Nano-barrier additive and its preparation method and related products Effective date of registration: 20200722 Granted publication date: 20190806 Pledgee: Changzhou Jiawei technology new material Co.,Ltd. Pledgor: CHANGZHOU BBETTER FILM TECHNOLOGIES Co.,Ltd. Registration number: Y2020980004269 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20201229 Granted publication date: 20190806 Pledgee: Changzhou Jiawei technology new material Co.,Ltd. Pledgor: CHANGZHOU BBETTER FILM TECHNOLOGIES Co.,Ltd. Registration number: Y2020980004269 |