CN110283343A - A kind of polylactic acid film material of high-strength high-tractility and preparation method thereof - Google Patents
A kind of polylactic acid film material of high-strength high-tractility and preparation method thereof Download PDFInfo
- Publication number
- CN110283343A CN110283343A CN201910396426.6A CN201910396426A CN110283343A CN 110283343 A CN110283343 A CN 110283343A CN 201910396426 A CN201910396426 A CN 201910396426A CN 110283343 A CN110283343 A CN 110283343A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- film material
- acid film
- preparation
- stretching device
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
Abstract
The invention discloses polylactic acid film materials of a kind of high-strength high-tractility and preparation method thereof, comprising the following steps: (1) raw material drying；(2) preparation polylactic acid cast film is squeezed out；(3) preparation polylactic acid oriented film is stretched；The invention has the advantages that: the polylactic acid oriented films of preparation to have excellent mechanical property, and elongation at break reaches as high as 294.90%, and intensity is up to 170.04 MPa, and compared to pure PLA film, 1743.13% and 277.87% has been respectively increased.And it is also able to maintain the effect of activeness and quietness under cryogenic conditions (- 20 DEG C), has greatly widened the application range of polylactic acid film.This method simple process, mass production easy to accomplish；It does not need that any other component is added in preparation process, only using simple melting extrusion drawing process can realize.
Description
Technical field
The present invention relates to degradable film material and its preparation field, in particular to the poly- cream of a kind of high-strength high-tractility
Sour thin-film material and preparation method thereof.
Background technique
Polylactic acid is a kind of Biodegradable high-molecular, has excellent biocompatibility and higher modulus.Meanwhile it is poly-
Lactic acid can be easily prepared into various products, be expected to replace traditional using general method for melt processing such as extrusion, injection moldings
Petroleum based high molecular.(Journal of Polymer Science Part B:Polymer Physics,2011,49(15),
1051-1083.) still, since molecule chain rigidity is big, crystallizing power is poor, and polylactic acid shows apparent brittleness, limits it extensively
Using.
Currently, copolymerization and blending are to improve the main path of polylactic acid toughness.Modification by copolymerization usually use grafting or
The method of block introduces soft segment, such as polyethylene glycol and polycaprolactone etc. in polylactic acid rigid molecule chain.
(Macromolecules,2009,42(8):3162-3169；Biomaterials, 2005,26 (14): 2121-2128.) although
Toughness can be increased substantially by being copolymerized, but complex process, and process is tediously long, and production efficiency is low, is difficult to apply to industrial production.Together
When, copolymerization not can avoid the use of poisonous and harmful solvent, be unfavorable for environmental protection and production safety.Compared to copolymerization, blending and modifying is more
Add and be simple and efficient, more suitable for large-scale production.(Biomacromolecules, 2006,7 (1), 199-207.) but not phase
The addition for holding component can bring weak phase interface, be readily incorporated defect, be unfavorable for the raising of mechanical property.
In actual production, it usually needs various auxiliary agents are added.Such as a kind of (degradable PLA thin-film materials such as Chen Qiao is strong
And preparation method thereof the Shanghai [P]: CN108276568A, 2018-07-13.) in polylactic acid be added strand modifying agent, degradation
Agent, chain extender, crosslinking agent etc. carry out Screw Extrusion, form the macromolecular main chain for having functional fragment, material is made to show to increase
The characteristic of strong toughening.(the green environmentally friendly toughened strong antibacterial degradable lactic acid composite material of one kind and preparation method thereof such as Fan Weihua
The Henan [P]: CN105001605A, 2015-10-28.) using the nano zine oxide that chlorophyll ketonic acid and coupling agent treatment are crossed as
Complex antimicrobials, while the molecular weight that chain extender improves polylactic acid is added, improve the mechanical property and hot property of material.But
The addition of a variety of auxiliary agents not only makes process flow more complicated, it is also possible to destroy the excellent biological degradability of polylactic acid.
In addition to this, the common issue that polylactic acid toughened system faces at present is: the raising of toughness invariably accompanies intensity
Loss.Therefore, how under the premise of being added without other components, with the increasing that can realize polylactic acid with industrialized simple means
Strong toughening is still a huge challenge.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to prepare a kind of high intensity using melting extrusion drawing process
The polylactic acid film material of high ductibility.Its mechanism is quenching after first squeezing out polylactic acid beads fuse, obtains polylactic acid
Cast film.(60-150 DEG C) stretching in certain temperature range later, the amorphous area and crystalline region for making polylactic acid are along draw direction
Orientation.By changing draw roll revolving speed, elongational flow field intensity is adjusted, the polylactic acid for finally obtaining draw ratio 1.0-50.0 is thin
Film.Wherein, the orientation and crystallization for regulating and controlling stretching induction, may be implemented the activeness and quietness of polylactic acid film.
Advantage of the invention is that need to can only be made using simple process capable of being industrialized it is not necessary that any other component is added
The polylactic acid film material of standby high-strength high-tractility out, mass production easy to accomplish.Elongation at break reaches as high as
294.90%, intensity is up to 170.04MPa, and compared to pure PLA film, 1743.13% and 277.87% has been respectively increased.
And activeness and quietness effect is able to maintain the low temperature environment at -20 DEG C, for widening the application range of poly-lactic acid material
It is of great significance.
The first aspect of the invention provides:
A kind of polylactic acid film material, yield strength range are 54.0~170.0MPa, and breaking strength range is 61.0
~276.0MPa, elongation at break ranges are 25.0~295.0%.
In one embodiment, additive is not contained in the polylactic acid film material.
In one embodiment, tensile strength 60~180MPa of the polylactic acid film material at -20 DEG C, more
It is preferred that 100~180；And elongation at break 10-300%, more preferable 15~300%, further preferably 50~300%；Yield strength is not
Less than 70MPa.
In one embodiment, the polylactic acid film material crystallinity is 0.0%~85.0%；More preferably
10.0%~85.0%.
In one embodiment, the yield strength range of the polylactic acid film material is 54.0~170.0MPa.
In one embodiment, the polylactic acid film material with a thickness of 5~200 μm.
In one embodiment, the amount of orientation 0.0-0.9 of the polylactic acid film material.
The second aspect of the invention provides:
A kind of preparation method of polylactic acid film material includes the following steps: to carry out heating melting simultaneously to poly-lactic acid material
It squeezes out, quenching processing and then progress stretch processing.
In one embodiment, it heating melting and squeezes out using single screw extrusion machine.
In one embodiment, single screw extrusion machine single screw extrusion machine is 185- from feed opening to die temperature range
200 DEG C, screw speed 50-200r/min.
In one embodiment, the cooling procedure of the extrudate of single screw extrusion machine can be used the conduction of low temperature casting roller cold
But and/or it is air-cooled.
In one embodiment, it is 1.0~50.0 that draw ratio is controlled in stretch processing.
In one embodiment, draw roll revolving speed is 1.0~100.0m/min in stretch processing.
In one embodiment, draft temperature is 60~15 DEG C in stretch processing.
The third aspect of the invention provides:
The process units of polylactic acid film material, comprising:
Drying device, for polylactic acid to be dried；
Extrusion device, for carrying out heat fusing to polylactic acid raw material and being extruded into film；
Cooling device, the film for obtaining to extrusion device carry out cooling treatment；
Stretching device, the film for obtaining to cooling device carry out stretch processing.
In one embodiment, the extrusion device is single screw extrusion machine.
It in one embodiment, include draw roll in stretching device, and the revolving speed of draw roll and draw ratio are adjustable.
The fourth aspect of the invention provides:
Stretching device is for improving the application in polylactic acid film material performance.
In one embodiment, stretching device is used to improve the polylactic acid content of the gg conformation of polylactic acid film material；
Preferably, control draw ratio is 1~20, further preferably 3~12, most preferably 7.5.
In one embodiment, stretching device is used to improve the junction degree of orientation of polylactic acid film material；Preferably, it controls
Draw ratio processed is 1~25, further preferably 10~20, most preferably 19.
In one embodiment, stretching device is used to reduce the activity amorphous content in polylactic acid film material；It is excellent
Choosing, control draw ratio is 7.5~25, further preferably 10~25, most preferably 19.
In one embodiment, stretching device is used to improve in the yield strength of polylactic acid film material；Preferably, it controls
Draw ratio processed is 7.5~50, further preferably 20~50.
In one embodiment, stretching device is used to improve the elongation at break of polylactic acid film material；Preferably, it controls
Draw ratio processed is 1~15, further preferably 1~12, most preferably 7.5.
In one embodiment, stretching device is for improving the tensile strength of polylactic acid film material under cryogenic；
Preferably, the cryogenic conditions refer to -20~0 DEG C；Preferably, control draw ratio is 1~12, most preferably 9.8.
Beneficial effect
A kind of preparation method of high-strength and high ductility polylactic acid film provided by the invention is compared to existing other methods, such as altogether
Poly- method and blending method etc., are simple and efficient with preparation method, the advantages such as are convenient for industrialized production.
Compared with the prior art, the invention has the following advantages:
(1) present invention only uses polylactic acid as raw material, is added without any other component, without using any solvent.
Therefore the deterioration of poor compatibility bring performance is avoided, while ensure that the biodegradability and good life of polylactic acid essence
Object compatibility；
(2) the method for the present invention is simple, high production efficiency, using traditional Polymer Processing means, need to only carry out to technique
More accurately controlling can realize, be easy to be generalized to large-scale production；
(3) interaction of control accurate of the present invention orientation and crystallization.The Molecular connectivity indices that amorphous phase orientation generates become
Change, form the gg conformation of a large amount of upper state, can reduce the limit stress that shear yielding occurs, it is tough to significantly improve material
Property.Meanwhile the presence of stretching induction oriented crystalline phenomenon, the effect of similar crosslinking points is play in stress, it can be effectively
Deformation is resisted, so that material shows higher toughness.Therefore activeness and quietness while polylactic acid may be implemented.
(4) polylactic acid film prepared by the present invention, is also able to maintain high-strength high-tractility at low temperature, shows to be applied to
The case where cracking is not present in the great potential of cold environment under -20 DEG C of environment.
Detailed description of the invention
Fig. 1 is reflection absorption ftir spectroscopy (a) and the absorbance statistics of embodiment 4,7,10,13,16,19,22 and comparative example 1
Line chart (b).
Fig. 2 is the two-dimentional WAXD wide angle X ray diffraction pattern of embodiment 4,7,10,13,16,19,22 and comparative example 1.
Fig. 3 is the degree of orientation line chart of embodiment 4,7,10,13,16,19,22 and comparative example 1.
Fig. 4 is a heating curve of embodiment 4,7,10,13,16,19,22 and comparative example 1.
Fig. 5 is the crystallinity of embodiment 4,7,10,13,16,19,22 and comparative example 1, activity amorphous phase and rigid amorphous phase
Content line chart.
Fig. 6 is the yield strength (region a) and elongation at break column of embodiment 4,7,10,13,16,19,22 and comparative example 1
Shape figure (region b).
Fig. 7 is embodiment 7,13,19 and comparative example 1 in 0 DEG C (a) and -20 DEG C (b) of stress-strain diagram.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It is necessarily pointed out that following embodiment is only used
In the present invention is further illustrated, should not be understood as limiting the scope of the invention, field technical staff according to
The nonessential modifications and adaptations that foregoing invention content makes the present invention still fall within protection scope of the present invention.
Embodiment 1-30 (is shown in Table 1)
(1) raw material drying: will be sufficiently dry by particles of polylactic acid.
(2) squeeze out: the polylactic acid pellet after will be dry in step (1) is sent in single screw extrusion machine, is led to after heating melting
Slit die extrusion is crossed, obtains polylactic acid cast film after quenching.Single screw extrusion machine is from feed opening to die temperature range
185-200 DEG C, screw speed 50-200r/min.The cooling procedure of extrudate can be used the conduction of low temperature casting roller cooling and wind
It is cold to combine.
(3) stretch: setting draft temperature is 60-150 DEG C.Polylactic acid cast film obtained in step (2) is sent into and is drawn
Stretch device.Adjusting draw roll revolving speed is 1.0-100.0m/min, obtains the polylactic acid that draw ratio (being abbreviated as DR) is 2.5-50.0
Film.Film thickness is 5-180 μm.
Comparative example 1-3 (is shown in Table 1)
(1) raw material drying: will be sufficiently dry by particles of polylactic acid.
(2) squeeze out: the polylactic acid pellet after will be dry in step (1) is sent in single screw extrusion machine, is led to after heating melting
Slit die extrusion is crossed, obtains polylactic acid cast film after quenching.Single screw extrusion machine is from feed opening to die temperature range
185-200 DEG C, screw speed 50-200r/min.The draw ratio of comparative example is set as 0.The cooling procedure of extrudate can be used
The conduction cooling of low temperature casting roller is combined with air-cooled.Obtained film thickness is 200 μm.
Mechanical property under 1 embodiment 1-30 of table and comparative example 1-3 preparation process condition and different test temperatures
Material characterization experiment
Gg conformation:
In order to compare relative amount of the different stretch than high energy gg conformation in sample, by 1267cm-1Absorbance (the Fig. 1 at place
In the region (a)) region (b) in Fig. 1 of statistics.With the increase of draw ratio, the content of gg conformation first increases to be reduced afterwards, in DR
Reach maximum in 7.5 (embodiments 4).Illustrate that stretching the molecularly oriented generated advantageously forms gg conformation.Then lured due to stretching
Lead the appearance of ordered structure, it is suppressed that gg conformation shows as 1267cm-1Locate the decrease of peak intensity.
Crystal orientation structure:
In order to investigate crystal habit, using the method for WAXD wide angle X ray diffraction.In Fig. 2, DR 0 (comparative example 1) and
DR7.5 (embodiment 4) shows as the annulus signal of Mass, illustrates for complete amorphous phase.When draw ratio is greater than 9.8, in meridian
There is (110/200) crystal face of dotted polylactic acid α crystalline substance and the diffracted signal of (203) crystal face in line direction, it was confirmed that oriented crystal
Formation.
In order to quantify degree of orientation, the degree of orientation of (110/200) crystal face is calculated using Herman formula, as shown in Figure 3.
With the increase of draw ratio, the degree of orientation is gradually increased, and wherein the sample degree of orientation of DR 19.0 (embodiment 19) is up to
0.65.When draw ratio increases to 21.7 (embodiments 22), degree of orientation decrease to some degree is produced when may be excessive with draw ratio
Raw crystal fracture is related.
Thermal behavior:
The thermal behavior of polylactic acid film after being stretched for evaluation, polylactic acid film after being stretched using differential scanning calorimetry measurement
A heating curve.The polylactic acid film sample prepared with embodiment 4,7,10,13,16,19,22 and comparative example 1 it is primary
For heating curve (such as Fig. 4).The sample of comparative example 1 and DR 7.5 (embodiment 4) are fainter due to crystallizing, near 100 DEG C
There is apparent cold crystallization peak.With the increase of draw ratio, crystalline polamer is obvious, and cold crystallization peak gradually weakens, and significant
It is deviated to low temperature direction.When draw ratio reaches 19.0, since broken wafers have occurred, the heat content at cold crystallization peak slightly increases,
But cold crystallization temperature remains unchanged.
In order to quantify different stretch than activity amorphous phase in polylactic acid film, the content of rigid amorphous phase and crystal phase is used
Modulation differential scanning calorimeter characterizes the reversible thermal capacitance and the variation of Non reversing heat flow of film temperature-rise period.It can be obtained by Fig. 5, DR
0 sample (comparative example 1) and 7.5 sample of DR (embodiment 4) crystallinity are almost the diffraction ring signal of complete Mass in 0, with Fig. 1
Unanimously, illustrate only when draw ratio be higher than 7.5 when, be likely to occur stretching induction crystallization.Also, it is living with the increase of draw ratio
The content of dynamic amorphous phase drops sharply to 48.1% from 98.9%, and the content of rigid amorphous phase and crystal phase is continuously increased, and crystallizes
Degree highest can achieve 32.7%.In summary changing rule can obtain, and the orientation texture that stretching induction is formed is originated from movable amorphous
The fixation and crystallization of phase.
Mechanical property:
In order to establish relation be- tween structure and properties, by the yield strength of polylactic acid film and elongation at break statistics in Fig. 6
In table 1.Comparative example 1 shows the typical brittleness of polylactic acid.It is brilliant due to generating orientation for the film after stretching
Body increases with draw ratio, and yield strength is gradually increased.The trend for first increasing and reducing afterwards, main cause is then presented in elongation at break
It is the raising that gg conformation is conducive to toughness.When draw ratio reaches 9.8, oriented crystal starts to occur, it is suppressed that the shape of gg conformation
At being gradually reduced later so elongation at break reaches maximum at DR 7.5 (embodiment 4).
60 DEG C of comparison, 100 DEG C, the mechanical property result (such as table 1) under 120 DEG C of three draft temperatures can obtain, under high temperature more
Height-oriented structure is advantageously formed, so intensity raising is more obvious.
In order to evaluate the service performance of polylactic acid film at low temperature, using with temperature-controlled box universal tensile testing machine into
Row test.Film is pre-chilled at least half an hour in advance in temperature-controlled box first, to simulate true cold environment.The test of selection
Temperature is 0 DEG C and -20 DEG C, and specific data are shown in Table 1.With embodiment 7,13,19 and comparative example 1 in 0 DEG C and -20 DEG C of ess-strain
For curve (such as Fig. 7).
In conclusion the polylactic acid film for preparing of the present invention has the characteristics of high-strength high ductibility, show good
Low temperature use characteristic.Material preparation process is simple, and technique is easy to grasp, and production cost is low, there is the huge latent of large-scale production
Power is expected to be applied to low temperature packaging material.
Claims (10)
1. a kind of polylactic acid film material, which is characterized in that its yield strength range is 54.0~170.0 MPa, and fracture is strong
Degree range is 61.0~276.0 MPa, and elongation at break ranges is 25.0~295.0 %.
2. polylactic acid film material according to claim 1, which is characterized in that be free of in the polylactic acid film material
There is additive；
In one embodiment, tensile strength 60~180MPa of the polylactic acid film material at -20 DEG C, more preferably
100~180；And elongation at break 10-300%, more preferable 15~300%, further preferably 50~300%；Yield strength is not less than
70MPa；
In one embodiment, the polylactic acid film material crystallinity is the % of 0.0 %~85.0；More preferable 10.0 %~
85.0 %。
3. polylactic acid film material according to claim 1, which is characterized in that the surrender of the polylactic acid film material
Strength range is 54.0~170.0 MPa；
In one embodiment, the polylactic acid film material with a thickness of 5~200 μm；
In one embodiment, the amount of orientation 0.0-0.9 of the polylactic acid film material.
4. the preparation method of polylactic acid film material described in claim 1, which comprises the steps of: to poly- cream
Sour material carries out heating melting and squeezes out, quenching processing and then progress stretch processing.
5. the preparation method of polylactic acid film material according to claim 4, which is characterized in that heating melting and squeeze out adopt
Use single screw extrusion machine；
In one embodiment, single screw extrusion machine single screw extrusion machine is 185-from feed opening to die temperature range
200 DEG C, screw speed is 50-200 r/min；
In one embodiment, the conduction cooling of low temperature casting roller can be used in the cooling procedure of the extrudate of single screw extrusion machine
And/or it is air-cooled.
6. the preparation method of polylactic acid film material according to claim 4, which is characterized in that control and draw in stretch processing
It stretches than being 1.0~50.0；
In one embodiment, draw roll revolving speed is 1.0~100.0 m/min in stretch processing；
In one embodiment, draft temperature is 60~15 DEG C in stretch processing.
7. a kind of process units of polylactic acid film material characterized by comprising
Drying device, for polylactic acid to be dried；
Extrusion device, for carrying out heat fusing to polylactic acid raw material and being extruded into film；
Cooling device, the film for obtaining to extrusion device carry out cooling treatment；
Stretching device, the film for obtaining to cooling device carry out stretch processing.
8. the process units of polylactic acid film material according to claim 7, which is characterized in that the extrusion device is
Single screw extrusion machine；It include draw roll in stretching device, and the revolving speed of draw roll and draw ratio are adjustable.
9. stretching device is for improving the application in polylactic acid film material performance.
10. application according to claim 9, which is characterized in that stretching device is used to improve the gg of polylactic acid film material
The polylactic acid content of conformation；Preferably, control draw ratio is 1~20, further preferably 3~12, most preferably 7.5；
In one embodiment, stretching device is used to improve the junction degree of orientation of polylactic acid film material；Preferably, control is drawn
It stretches than being 1~25, further preferably 10~20, most preferably 19；
In one embodiment, stretching device is used to reduce the activity amorphous content in polylactic acid film material；Preferably,
Controlling draw ratio is 7.5~25, further preferably 10~25, most preferably 19；
In one embodiment, stretching device is used to improve in the yield strength of polylactic acid film material；Preferably, control is drawn
It stretches than being 7.5~50, further preferably 20~50；
In one embodiment, stretching device is used to improve the elongation at break of polylactic acid film material；Preferably, control is drawn
It stretches than being 1~15, further preferably 1~12, most preferably 7.5；
In one embodiment, stretching device is for improving the tensile strength of polylactic acid film material under cryogenic；It is preferred that
, the cryogenic conditions refer to -20~0 DEG C；Preferably, control draw ratio is 1~12, most preferably 9.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910396426.6A CN110283343B (en) | 2019-05-14 | 2019-05-14 | High-strength high-ductility polylactic acid film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910396426.6A CN110283343B (en) | 2019-05-14 | 2019-05-14 | High-strength high-ductility polylactic acid film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110283343A true CN110283343A (en) | 2019-09-27 |
| CN110283343B CN110283343B (en) | 2022-02-08 |
Family
ID=68001862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910396426.6A Active CN110283343B (en) | 2019-05-14 | 2019-05-14 | High-strength high-ductility polylactic acid film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283343B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111673969A (en) * | 2020-06-17 | 2020-09-18 | 中国科学技术大学 | Polylactic acid transparent material with high impact strength and preparation method thereof |
| CN113276377A (en) * | 2021-05-26 | 2021-08-20 | 广东工业大学 | Preparation method of high-strength high-toughness polystyrene film |
| CN114350128A (en) * | 2022-01-13 | 2022-04-15 | 中国科学院长春应用化学研究所 | Reinforced and toughened polylactic acid material and preparation method thereof |
| CN114773644A (en) * | 2022-04-26 | 2022-07-22 | 四川大学 | Polylactic acid porous film with low dielectric constant and high toughness and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443780A (en) * | 1992-07-09 | 1995-08-22 | Shimadzu Corporation | Oriented films of polylactic acid and methods of producing same |
| CN104908329A (en) * | 2015-05-27 | 2015-09-16 | 广东工业大学 | Preparation method for high-crystallinity bidirectional high-mechanical strength polylactic acid film |
| CN105479707A (en) * | 2015-11-24 | 2016-04-13 | 四川大学 | Preparation method of reinforced and toughened polylactic acid |
| CN109648881A (en) * | 2018-12-18 | 2019-04-19 | 广东工业大学 | A kind of transparent polylactic acid film and its preparation method and application |
-
2019
- 2019-05-14 CN CN201910396426.6A patent/CN110283343B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443780A (en) * | 1992-07-09 | 1995-08-22 | Shimadzu Corporation | Oriented films of polylactic acid and methods of producing same |
| CN104908329A (en) * | 2015-05-27 | 2015-09-16 | 广东工业大学 | Preparation method for high-crystallinity bidirectional high-mechanical strength polylactic acid film |
| CN105479707A (en) * | 2015-11-24 | 2016-04-13 | 四川大学 | Preparation method of reinforced and toughened polylactic acid |
| CN109648881A (en) * | 2018-12-18 | 2019-04-19 | 广东工业大学 | A kind of transparent polylactic acid film and its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111673969A (en) * | 2020-06-17 | 2020-09-18 | 中国科学技术大学 | Polylactic acid transparent material with high impact strength and preparation method thereof |
| CN113276377A (en) * | 2021-05-26 | 2021-08-20 | 广东工业大学 | Preparation method of high-strength high-toughness polystyrene film |
| CN114350128A (en) * | 2022-01-13 | 2022-04-15 | 中国科学院长春应用化学研究所 | Reinforced and toughened polylactic acid material and preparation method thereof |
| CN114773644A (en) * | 2022-04-26 | 2022-07-22 | 四川大学 | Polylactic acid porous film with low dielectric constant and high toughness and preparation method thereof |
| CN114773644B (en) * | 2022-04-26 | 2023-08-15 | 四川大学 | Polylactic acid porous film with low dielectric constant and high toughness and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110283343B (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110283343A (en) | A kind of polylactic acid film material of high-strength high-tractility and preparation method thereof | |
| Yamane et al. | Mechanical properties and higher order structure of bacterial homo poly (3-hydroxybutyrate) melt spun fibers | |
| CN104004253B (en) | Heavy polymer nucleater modified super-high molecular weight polythene blending material | |
| Luo et al. | Coupling effects of glass fiber treatment and matrix modification on the interfacial microstructures and the enhanced mechanical properties of glass fiber/polypropylene composites | |
| Li et al. | Shape memory effect of polyethylene/nylon 6 graft copolymers | |
| DE69919450T2 (en) | Aromatic liquid crystalline polyesters and resin composition made therefrom | |
| KR20010024527A (en) | Polypropylene composition useful for making solid state oriented film | |
| CN113278268B (en) | High-toughness polyester composite material and preparation method thereof | |
| CN104877317B (en) | A kind of melted after can the preparation method of the quick full bio-based composite material of Stereocomplex | |
| CN113278269B (en) | Preparation method of durable polyglycolic acid-based material | |
| CN103443339A (en) | Biodegradable polyester fiber having excellent thermal stability and strength, and method for producing same | |
| CN105199348B (en) | Preparation method for high-strength high-toughness heatproof polylactic-acid-based membrane material | |
| Tang et al. | Fabrication of low-density poly (lactic acid) microcellular foam by self-assembly crystallization nucleating agent | |
| WO2015029316A1 (en) | Polyester fiber | |
| Run et al. | Influences of hyperbranched poly (amide-ester) on the properties of poly (butylene succinate) | |
| Kim et al. | Effects of annealing on structure and properties of TLCP/PEN/PET ternary blend fibers | |
| Guo et al. | The synergistic effect of heterogeneous nucleation and stress-induced crystallization on supramolecular structure and performances of poly (lactic acid) melt-spun fibers | |
| CN113442401A (en) | High-strength high-barrier PGA/PBAT food packaging film and preparation method thereof | |
| JPH01272814A (en) | Polyvinyl alcohol-based yarn having excellent hot water resistance and production thereof | |
| CN109183191A (en) | A kind of flexibility P3HB4HB/PLA blended fiber and preparation method thereof | |
| KR102506968B1 (en) | A biodegradable polymer resin composition for manufacturing high-performance sutures and high functional suture prepared thereof | |
| CN109456524B (en) | High-barrier PE/LCP/PET resin composition and preparation method thereof | |
| Liu et al. | In-situ constructing highly oriented ductile poly (3-hydroxybutyrate-co-3-hydroxyvalerate) nanoribbons: Towards strong, ductile, and good heat-resistant polylactic-based composites | |
| CN114149668A (en) | Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase | |
| CN114350128B (en) | Reinforced and toughened polylactic acid material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200817 Address after: 211800 Block C, Hatching Building, No. 99 Unity Road, Yanchuang Park, Jiangbei New District, Nanjing City, Jiangsu Province Applicant after: JIANGSU JICUI ADVANCED HIGH-MOLECULAR MATERIAL INSTITUTE Co.,Ltd. Applicant after: Nanjing strand Technology Co., Ltd Address before: 211800 Block C, Hatching Building, No. 99 Unity Road, Yanchuang Park, Jiangbei New District, Nanjing City, Jiangsu Province Applicant before: JIANGSU JICUI ADVANCED HIGH-MOLECULAR MATERIAL INSTITUTE Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |