CN111763426A - Bio-based polyamide biaxially oriented film and preparation method thereof - Google Patents
Bio-based polyamide biaxially oriented film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of film materials, and provides a bio-based polyamide biaxially oriented film and a preparation method thereof. According to the invention, the bio-based polyamide film is prepared by adding inorganic filler into the bio-based polyamide, and then the bio-based polyamide biaxially oriented film is obtained by biaxial orientation. The adopted matrix material is bio-based polyamide, the bio-based polyamide biaxially oriented film has biodegradability and good environmental protection, and compared with the existing polyamide film, the bio-based polyamide biaxially oriented film provided by the invention has excellent physical and mechanical properties, high barrier property and lower water absorption; in addition, the invention can achieve the purpose of regulating and controlling the barrier property and the mechanical property of the film by controlling the content of the inorganic filler and the stretching parameters, obtain the bio-based polyamide biaxial stretching films with different properties, and widen the application range of the film.
Description
Technical Field
The invention relates to the technical field of film materials, in particular to a bio-based polyamide biaxially oriented film and a preparation method thereof.
Background
At present, the industry mainly uses petroleum-based PA6 (polyamide-6) to prepare polyamide biaxial stretching film, and with the gradual decrease of petroleum resources and the increasing load of petroleum-based monomer synthesis to environment and ecology, it is very important to find alternatives of petroleum-based products. In recent years, with the increasing public awareness of environmental protection and sustainable development and attention on novel polymer materials, bio-based polymers derived from renewable resources have become a research hotspot in recent years. Compared with the traditional petroleum-based products, the processing technology of the bio-based polyamide is more environment-friendly, and the bio-based material is undoubtedly the best substitute. The bio-based polyamide PA510 is a novel full bio-based synthetic material independently developed in China, and is formed by polymerizing bio-based pentanediamine and bio-based dodecanedioic acid. And the mechanical property index of the material can meet the use requirement, and the material is expected to replace the traditional PA6 and PA66 in the future. The production process of the PA510 monomer greatly reduces the carbon emission, and the raw materials are all renewable resources, so the environmental benefit is considerable.
The biaxially oriented polyamide film (BOPA) has the characteristics of high strength, good barrier property, strong light transmission, excellent dimensional stability, heat resistance, cold resistance, oil resistance, organic solvent resistance and the like, and is widely applied to the fields of light industry, agricultural energy, resource environment and the like. However, the conventional BOPA film has poor water absorption stability, the tensile strength and the bending strength of the film are reduced rapidly after water absorption, the oxygen barrier property of the film can be reduced obviously, and the application aspect has certain limitation. The presence of bio-based polyamides may compensate for these deficiencies of conventional BOPA films. In many fields of application, the comprehensive performance of the bio-based polyamide is more excellent. However, the existing method for preparing the biaxially oriented film by using the bio-based polyamide still has the problems that the barrier property needs to be improved, the mechanical property and the barrier property are difficult to regulate and control, and different packaging requirements cannot be met.
Disclosure of Invention
In view of the above, the invention provides a bio-based polyamide biaxially oriented film and a preparation method thereof. The bio-based polyamide biaxially oriented film provided by the invention has good mechanical property and barrier property, can regulate and control the mechanical property and barrier property of the film according to the packaging requirement, and has wide application range.
In order to achieve the above object, the present invention provides the following technical solutions:
the bio-based polyamide biaxially oriented film is prepared by biaxially orienting a bio-based polyamide film, wherein the preparation raw materials of the bio-based polyamide film comprise the following components in percentage by mass: 91-99 percent of bio-based polyamide, 0.5-8 percent of inorganic filler, 0.05-0.5 percent of nucleating agent and 0.1-0.5 percent of antioxidant.
Preferably, the bio-based polyamide comprises at least one of polyamide 510, polyamide 512 and polyamide 514.
Preferably, the inorganic filler includes at least one of layered silica, montmorillonite and mica powder.
Preferably, the nucleating agent comprises at least one of licoont NAV101, licoont NAV102, and licoont NAV 103.
Preferably, the antioxidant comprises at least one of GSNOX-168, THP-24 and RIANOX-1098.
The invention also provides a preparation method of the bio-based polyamide biaxially oriented film, which comprises the following steps:
mixing the bio-based polyamide, the inorganic filler, the nucleating agent and the antioxidant, and then extruding by a double screw to obtain granules;
carrying out melt tape casting on the granules to form a film so as to obtain a bio-based polyamide film;
and (3) performing biaxial tension on the bio-based polyamide film to obtain the bio-based polyamide biaxial tension film.
Preferably, the parameters of the twin-screw extrusion include: the temperature of the die head is 160-220 ℃, the processing temperature is 225-270 ℃, and the rotating speed of the screw is 10-30 r/min.
Preferably, the melt casting film forming is performed in a casting machine, and the parameters of the melt casting film forming comprise: the processing temperature is 225-275 ℃, the rotating speed of the casting roll is 1-1.5 m/min, the rotating speed of the traction roll is 1.2-1.6 m/min, the synchronous coefficient of the traction roll is 1-1.5, the tension of the wind-up roll is 2.5-3.5 Kg, the synchronous coefficient of the wind-up roll is 0.2-0.5, and the temperature of the cooling roll is 20-50 ℃.
Preferably, the thickness of the bio-based polyamide film is 110-130 μm.
Preferably, the biaxial stretching is asynchronous biaxial stretching or synchronous biaxial stretching; the parameters of the asynchronous biaxial stretching or the synchronous biaxial stretching independently comprise: preheating at 100-140 ℃, stretching at 100-170 ℃, heat setting at 130-160 ℃ and stretching at 50-348 mm/s; when the stretching is asynchronous biaxial stretching, the stretching times in the transverse direction or the longitudinal direction are independently 1-3.6 times; when the biaxial stretching is synchronous biaxial stretching, the stretching ratio is 1.2 × 1.2 to 3.6 × 3.6.
The invention provides a bio-based polyamide biaxially oriented film, which is prepared by biaxially orienting a bio-based polyamide film, wherein the preparation raw material of the bio-based polyamide film comprises the following components in percentage by mass: 91-99 percent of bio-based polyamide, 0.5-8 percent of inorganic filler, 0.05-0.5 percent of nucleating agent and 0.1-0.5 percent of antioxidant. The matrix material adopted by the invention is bio-based polyamide, has biodegradation performance, and can effectively reduce the consumption of petrochemical resources and the pollution to the environment compared with the traditional polyamide raw material; according to the invention, the barrier property of the film can be effectively improved by adding the inorganic filler, the content and the dispersion form of the inorganic filler can influence the crystal structure of the bio-based polyamide biaxial stretching film, the crystal structure is related to the macroscopic mechanical property and the barrier property of the film, and the purpose of regulating and controlling the barrier property and the mechanical property of the film can be achieved by controlling the content of the inorganic filler. Compared with the existing polyamide film, the bio-based polyamide biaxially oriented film provided by the invention has excellent physical and mechanical properties, high barrier property and low water absorption (the water absorption is only 0.25%, which is 1/7 of PA 6), and can be used in the field of vegetable and fruit packaging.
The invention also provides a preparation method of the bio-based polyamide biaxially oriented film. According to the invention, inorganic filler is dispersed in the bio-based polyamide through screw extrusion, and then the bio-based polyamide biaxial tension is prepared through melt tape casting film formation and biaxial tension. Furthermore, the stretching temperature, the stretching rate and the stretching multiple are controlled within a specific range, so that the prepared bio-based polyamide biaxially oriented film has the advantages of good crease form fixity, excellent comprehensive mechanical property, barrier property and the like; and the stretching parameters affect the crystal morphology and crystal orientation in the biaxially oriented film. According to the invention, by regulating and controlling the biaxial stretching parameters, the influence rule of the microstructure of the film on the performance and quality of the film can be revealed, and then the barrier property and the mechanical property of the film can be regulated and controlled according to the packaging requirements, so that the bio-based polyamide biaxial stretching films with different properties can be obtained, and the application range of the film is widened.
Drawings
FIG. 1 is a schematic view of a biaxial stretching process in the present invention;
FIG. 2 is a scanning electron micrograph of the layered silica and S1, S2, S3, S4;
FIG. 3 is an XRD pattern of S0, S1, S2, S3, S4;
FIG. 4 shows WAXD patterns from P0 to P7.
Detailed Description
The invention provides a bio-based polyamide biaxially oriented film, which is prepared by biaxially orienting a bio-based polyamide film, wherein the preparation raw material of the bio-based polyamide film comprises the following components in percentage by mass: 91-99 percent of bio-based polyamide, 0.5-8 percent of inorganic filler, 0.05-0.5 percent of nucleating agent and 0.1-0.5 percent of antioxidant.
Unless otherwise specified, the raw materials for preparing the bio-based polyamide film according to the present invention are commercially available.
The preparation raw material of the bio-based polyamide film comprises 91-99% of bio-based polyamide, preferably 93-98%, and more preferably 95-97% by mass. In the invention, the bio-based polyamide preferably comprises at least one of polyamide 510, polyamide 512 and polyamide 514, more preferably polyamide 510, and the relative viscosity of the polyamide 510 is preferably 2.8-3.3, more preferably 2.9-3.2; the relative viscosity of the polyamide 510 is measured specifically by using a RH7-I type melt index apparatus at 230 ℃; specifically, the polyamide 510 is polymerized by bio-based pentamethylene diamine and dodecanedioic acid produced by a biological manufacturing method, and the polyamide 512 is polymerized by bio-based pentamethylene diamine and dodecanedioic acid produced by a biological manufacturing method; the polyamide 514 is polymerized by bio-based pentamethylene diamine and tetradecanedioic acid produced by a biological manufacturing method; in the embodiment of the present invention, the above-mentioned bio-based polyamide may be used as it is.
The preparation raw material of the bio-based polyamide film comprises, by mass, 0.5% -8% of an inorganic filler, preferably 0.5-3%, and more preferably 1-2.5%. In the invention, the inorganic filler preferably comprises at least one of layered silica, montmorillonite and mica powder, more preferably layered silica, and the layered silica has excellent characteristics of wear resistance, high temperature resistance, oxidation resistance, low expansion coefficient, chemical corrosion resistance and the like, is an ideal barrier filler in the industrial field, and can remarkably improve the barrier property of a base material. The content and the dispersion form of the inorganic filler can influence the crystal structure of the bio-based polyamide biaxially oriented film, the crystal structure is related to the macroscopic mechanical property and the barrier property of the film, and the purpose of regulating and controlling the barrier property and the mechanical property of the film can be achieved by controlling the content of the inorganic filler. In the specific embodiment of the invention, in the above range, the larger the addition amount of the inorganic filler, the more stable the content of the gamma crystal form in the film, the higher the mechanical strength of the film, and the better the barrier property.
The preparation raw material of the bio-based polyamide film comprises 0.05-0.5% of nucleating agent by mass percentage, and preferably 0.1-0.4%. In the present invention, the nucleating agent includes at least one of Licomont NAV101, Licomont NAV102, and Licomont NAV 103.
The raw materials for preparing the bio-based polyamide film comprise 0.1-0.5% of antioxidant, preferably 0.2-0.3% by mass. In the present invention, the antioxidant preferably comprises at least one of GSNOX-168, THP-24 and RIANOX-1098.
In the invention, the thickness of the biobased polyamide biaxially oriented film is preferably 7-25 μm, the tensile strength is preferably 135.27-305.16 MPa, the elongation at break is preferably 90.11-291.89%, and the oxygen transmission rate is preferably 4.98-65.23 cc/m2·day·atm。
The bio-based polyamide biaxially oriented film is prepared by biaxially stretching a bio-based polyamide film, and stretching parameters in the biaxially oriented process can influence the crystal form and orientation of the film, thereby influencing the performance and quality of the film. The invention can effectively regulate and control the mechanical property and the barrier property of the film by controlling the stretching parameters and the content of the inorganic filler, and the specific stretching parameters and the influence of the stretching parameters on the film property are specifically explained in the preparation method part.
The invention also provides a preparation method of the bio-based polyamide biaxially oriented film, which comprises the following steps:
mixing the bio-based polyamide, the inorganic filler, the nucleating agent and the antioxidant, and then extruding by a double screw to obtain granules;
carrying out melt tape casting on the granules to form a film so as to obtain a bio-based polyamide film;
and (3) performing biaxial tension on the bio-based polyamide film to obtain the bio-based polyamide biaxial tension film.
The invention mixes the bio-based polyamide, the inorganic filler, the nucleating agent and the antioxidant and then carries out double-screw extrusion to obtain the granules. In the present invention, the mixing is preferably carried out in a high-speed mixer, and the mixing conditions in the present invention are not particularly limited, and the respective raw materials may be mixed uniformly.
In the present invention, the parameters of the twin-screw extrusion include: the temperature of the die head is 160-220 ℃, preferably 180-200 ℃, the processing temperature is 225-270 ℃, preferably 230-250 ℃, and the rotating speed of the screw is 10-30 r/min, preferably 15-25 r/min. In the process of double-screw extrusion, the mixture is melted, plasticized and co-extruded in a double-screw extruder, so that the inorganic filler is uniformly dispersed in the bio-based polyamide, and finally, the mixture is cooled and granulated to form granules.
After obtaining the granules, the invention carries out melt tape casting on the granules to form a film, thus obtaining the bio-based polyamide film. The granules are preferably dried and dewatered and then subjected to melt casting to form a film, and the drying and dewatering are not particularly required in the invention and can be carried out according to a method well known by a person skilled in the art. In the present invention, the melt-casting film formation is preferably performed in a casting machine, and the parameters of the melt-casting film formation include: the processing temperature is preferably 225-275 ℃, the further preferred is 230-260 ℃, the rotating speed of the casting roll is preferably 1-1.5 m/min, the further preferred is 1.2-1.3 m/min, the rotating speed of the drawing roll is preferably 1.2-1.6 m/min, the further preferred is 1.3-1.5 m/min, the synchronous coefficient of the drawing roll is preferably 1-1.5, the further preferred is 1.2-1.3, the tension of the winding roll is preferably 2.5-3.5 Kg, the further preferred is 2.8-3.2 Kg, the synchronous coefficient of the winding roll is preferably 0.2-0.5, the further preferred is 0.3-0.4, and the temperature of the cooling roll is preferably 20-50 ℃, and the further preferred is 30-40 ℃. In the casting film forming process, the granules form a melt film at the processing temperature, the melt film is cooled on the surface of a cooling roller to form a film, and then traction and rolling are carried out to obtain a casting sheet, wherein the casting sheet is the bio-based polyamide film.
After the bio-based polyamide film is obtained, the bio-based polyamide film is subjected to biaxial tension to obtain the bio-based polyamide biaxial tension film. In the present invention, the biaxial stretching is preferably asynchronous biaxial stretching or synchronous biaxial stretching, and a schematic diagram of the stretching process is shown in fig. 1, in which MD means a machine direction and TD means a transverse direction.
In the invention, the asynchronous biaxial stretching is preferably carried out in a stretching device, the stretching device comprises a preheating zone, a stretching zone and a heat setting zone, the bio-based polyamide film is clamped by chain clamps in the stretching device to move, the bio-based polyamide film is softened in the preheating zone and then enters the stretching zone to sequentially carry out transverse (longitudinal) direction stretching and longitudinal (transverse) direction stretching, namely, the transverse direction stretching and the longitudinal direction stretching are carried out in two steps, the bio-based polyamide film enters the heat setting zone to carry out heat setting after stretching, the internal stress of the biaxially stretched film is eliminated through heat setting, the crystallinity of the film is increased, and the dimensional stability of the film is increased.
In the invention, the synchronous biaxial stretching is preferably carried out in a stretching device, the device comprises a preheating zone, a stretching zone and a heat setting zone, the bio-based polyamide film is clamped by chain clamps in the stretching device to move, the bio-based polyamide film is softened in the preheating zone and then enters the stretching zone to simultaneously carry out synchronous stretching in the transverse direction and the longitudinal direction, the stretching ratios in the two directions are consistent, and the bio-based polyamide film enters the heat setting zone to be subjected to heat setting after being stretched.
In the invention, the bio-based polyamide biaxially oriented film obtained by synchronous biaxial stretching has better uniformity, and the bio-based polyamide biaxially oriented film obtained by asynchronous biaxial stretching has better heat shrinkage.
In the present invention, the parameters of the synchronous biaxial stretching and the asynchronous biaxial stretching independently include: the preheating temperature is preferably 100-140 ℃, the further preferred temperature is 110-130 ℃, the stretching temperature is preferably 100-170 ℃, the further preferred temperature is 120-150 ℃, the heat setting temperature is preferably 130-160 ℃, the further preferred temperature is 140-150 ℃, the stretching speed is preferably 50-348 mm/s, and the further preferred speed is 100-320 mm/s; when the stretching is asynchronous biaxial stretching, the stretching times in the transverse direction or the longitudinal direction are independently preferably 1-3.6 times; when the biaxial stretching is synchronous biaxial stretching, the stretching multiple is preferably 1.2 multiplied by 1.2 to 3.6 multiplied by 3.6; in the present invention, the total stretching ratio in the transverse direction and the longitudinal direction is preferably 2 to 8 times, in consideration of the strength, thickness, and the like of the biaxially oriented film.
In the invention, the stretching parameters (stretching temperature, stretching speed and stretching ratio) can influence the crystal form and crystal orientation in the biaxially oriented film, and the invention can reveal the influence rule of the microstructure of the film on the film performance and quality by regulating and controlling the biaxially oriented parameters, and further regulate and control the barrier property and mechanical property of the film according to the packaging requirement, so as to obtain the biobased polyamide biaxially oriented film with different properties and widen the application range of the film. Specifically, when the stretching temperature is lower than 110 ℃, the higher the biaxial stretching temperature is, the higher the gamma crystal form content in the obtained film is, the higher the mechanical strength of the film is, and the better the barrier property is; the larger the biaxial stretching rate is, the more imperfect crystal structures are in the obtained film, the lower the mechanical strength of the film is, the poorer the barrier property is, the larger the biaxial stretching multiple is, the better the isotropy of the obtained film is, and the better the mechanical strength and the barrier property of the film are.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Preparing raw materials: 98.65 percent of bio-based polyamide 510, 0.2 percent of nucleating agent NAV101, 1 percent of layered silicon dioxide and 0.15 percent of antioxidant RINOX-1098.
The preparation method comprises the following steps:
(1) mixing the bio-based polyamide 510, the layered silicon dioxide, the nucleating agent NAV101 and the antioxidant RINOX-1098 in proportion, and uniformly mixing by a high-speed mixer; carrying out double-screw extrusion on the mixture to obtain granules, wherein the parameters of the double-screw extrusion are as follows: the die head temperature is 190 ℃, the processing temperature is 225 ℃, and the screw rotating speed is 20 r/min.
(2) Drying the granules, dewatering, adding the granules into a casting machine for casting and film forming, wherein the processing temperature is 260 ℃, the rotating speed of a casting roller is 1.3m/min, the speed of a traction roller is 1.2m/min, and the synchronous coefficient of the traction roller is 1.2; the tension of the wind-up roll is 3Kg, and the synchronous coefficient of the wind-up roll is 0.4; the cooling roll temperature was 35 ℃ to obtain a cast sheet (i.e., a bio-based polyamide film) having a thickness of 120 μm, and the obtained cast sheet was designated as S1.
(3) Synchronously and bidirectionally stretching the casting sheet, wherein the preheating temperature is 90 ℃, the stretching temperature is 110 ℃, the heat setting temperature is 155 ℃, the stretching speed is 150mm/min, and the stretching multiple is 3.6 multiplied by 3.6; obtaining the bio-based polyamide biaxial tension film.
Example 2
Preparing raw materials: 96.65 percent of bio-based polyamide 510, 0.2 percent of nucleating agent NAV101, 3 percent of layered silicon dioxide and 0.15 percent of antioxidant RINOX-1098.
The procedure was the same as in example 1 to obtain a biobased polyamide biaxially oriented film, and the cast sheet obtained by casting was designated as S2.
Example 3
Preparing raw materials: 94.65 percent of bio-based polyamide 510, 0.2 percent of nucleating agent NAV101, 5 percent of layered silicon dioxide and 0.15 percent of antioxidant RINOX-1098.
The procedure was the same as in example 1 to obtain a biobased polyamide biaxially oriented film, and the cast sheet obtained by casting was designated as S3.
Example 4
Preparing raw materials: 92.65 percent of bio-based polyamide 510, 0.2 percent of nucleating agent NAV101, 7 percent of layered silicon dioxide and 0.15 percent of antioxidant RINOX-1098.
The procedure was the same as in example 1 to obtain a biobased polyamide biaxially oriented film, and the cast sheet obtained by casting was designated as S4.
Example 5
The raw materials were prepared in the same manner as in example 2, and the test was divided into 7 groups according to the stretching parameters, and the obtained biaxially oriented films were designated as P1, P2, P3, P4, P5, P6 and P7, respectively.
The stretching parameters were as follows:
p1: the stretching temperature is 110 ℃, the stretching speed is 150mm/min, and the stretching multiplying power is 1.0 multiplied by 3.6;
p2: the stretching temperature is 110 ℃, the stretching speed is 150mm/min, and the stretching multiplying power is 2.2 multiplied by 2.2;
p3: the biobased polyamide biaxially oriented film prepared in example 2 was designated as P3, the stretching temperature was 110 ℃, the stretching rate was 150mm/min, and the stretching ratio was 3.6 × 3.6;
p4: the stretching temperature is 110 ℃, the stretching speed is 50mm/min, and the stretching multiplying power is 3.6 multiplied by 3.6;
p5: the stretching temperature is 110 ℃, the stretching speed is 348mm/min, and the stretching multiplying power is 3.6 multiplied by 3.6;
p6: the stretching temperature is 80 ℃, the stretching speed is 150mm/min, and the stretching multiplying power is 3.6 multiplied by 3.6;
p7: the stretching temperature was 140 ℃, the stretching rate was 150mm/min, and the stretching magnification was 3.6 × 3.6.
The parameters of the other preparation steps were the same as in example 2.
Comparative example 1
The starting material was only polyamide 510, the procedure and operating parameters were the same as in example 1, giving a biaxially oriented film of pure polyamide 510, designated P0, and cast sheet designated S0.
And (3) performance testing:
FIG. 2 is a scanning electron micrograph of the layered silica and S1, S2, S3, S4; as can be seen from fig. 2, the dispersion state of the layered silica in the bio-based polyamide matrix is different depending on the amount of the layered silica added.
Fig. 3 is an XRD pattern of S0, S1, S2, S3, S4. As can be seen from fig. 3, different addition amounts of the layered silica may affect the crystal form of the bio-based polyamide matrix, and when the addition amount of the lamellar silica is less than 3%, the addition of the silica mainly increases the content of the γ (100) crystal form at 20.90 ° 2 θ in PA 510; continuing to increase the amount of addition of the plate-like silica, not only the contents of γ (004), γ (008), and γ (100) crystal forms of PA510 at 2 θ ═ 8.84 °, 17.74 °, and 20.90 °, but also α (100/020) -like and α (112) -like crystal forms of PA510 at 2 θ ═ 12.32 °, and 26.68 ° were increased. And the intensity of each crystal form diffraction peak in the PA510 is gradually enhanced along with the increase of the content of the flaky silica.
FIG. 4 is a WAXD graph of P0-P7, it can be seen from FIG. 4 that the crystal structure and crystal orientation of the bio-based polyamide biaxially oriented film are different according to the stretching parameters, specifically, in the uniaxially stretched film (P1), the equatorial direction mainly has gamma (100) crystal form and α (110) crystal form, and the interplanar spacings thereof are respectively
And
the meridian direction mainly has gamma (002), gamma (004) and gamma (006) crystal forms, and the interplanar spacing thereof is respectively
And
however, the biaxially oriented film prepared by changing the stretching temperature, the stretching rate and the stretching ratio has only a single diffraction ring and no obvious orientation in a WAXD diagram, which shows that the biaxially oriented film prepared under different stretching parameters has better uniformity.
The mechanical properties and barrier properties of P1-P7 were tested, and the results are shown in Table 1;
TABLE 1 Performance data for biobased polyamide biaxially oriented polyamide films P1-P7
According to the data in table 1, it can be seen that the difference of the stretching parameters causes the difference of the crystal structure and the crystal orientation presented by the bio-based polyamide biaxially oriented film, the mechanical properties and the barrier properties of the obtained biaxially oriented film are different, specifically, the change of the stretching ratio shows that the comparison of P1, P2 and P3 shows that the tensile strength of the uniaxially stretched film (P1) in the stretching direction can be significantly increased, but the PA510 biaxially oriented film has lower elongation at break and higher barrier properties in the stretching direction due to the molecular chain, the crystal orientation and the orientation of the sheet-like silica in the stretching direction, and in the biaxially oriented films (P2 and P3), the isotropy of the film is enhanced, the barrier properties and the tensile strength of the biaxially oriented film are gradually enhanced, and the elongation at break is gradually reduced along with the increase of the stretching ratio; the stretching speed (P4, P3 and P5) of the film is changed, and the mechanical strength and the barrier property of the biaxial stretching film are gradually reduced along with the increase of the stretching speed; changing the stretching temperature (P6, P3 and P7) of the biaxially oriented film can find that 110 ℃ is the optimal temperature for biaxial stretching, the stretching temperature is too high or too low, and the prepared biaxially oriented film has lower mechanical property and barrier property. In practical application, the mechanical property and the barrier property of the biaxially oriented film can be regulated and controlled by controlling the stretching parameters so as to meet different packaging requirements.
The mechanical properties and barrier properties of the biaxially oriented films prepared in examples 1 to 4 and comparative example 1 were tested, and the results are shown in table 2;
table 2 mechanical properties and barrier properties test data of biaxially oriented films prepared in examples 1 to 4 and comparative example 1
As can be seen from Table 2, when the addition amount of the flaky silicon dioxide is not more than 3%, the mechanical strength and the barrier property of the film can be remarkably improved; when the addition amount of the platy silica is continuously increased, the mechanical strength of the platy silica is gradually reduced due to the agglomeration effect of the silica in the PA510 and is even lower than that of a pure PA510 film, but the barrier property of the film is still slightly higher than that of the pure PA510 film due to the barrier effect of the platy silica on oxygen.
Further, the water absorption of the biaxially oriented film obtained in example 2 was measured, and it was found that the water absorption of the film was only 0.25%, which was 1/7 of PA 6.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The bio-based polyamide biaxially oriented film is characterized by being prepared by biaxially stretching a bio-based polyamide film, wherein the raw materials for preparing the bio-based polyamide film comprise the following components in percentage by mass: 91-99 percent of bio-based polyamide, 0.5-8 percent of inorganic filler, 0.05-0.5 percent of nucleating agent and 0.1-0.5 percent of antioxidant.
2. The bio-based polyamide biaxially oriented film of claim 1, wherein the bio-based polyamide comprises at least one of polyamide 510, polyamide 512 and polyamide 514.
3. The bio-based polyamide biaxially oriented film according to claim 1, wherein the inorganic filler comprises at least one of layered silica, montmorillonite and mica powder.
4. The biobased polyamide biaxially oriented film of claim 1, wherein the nucleating agent comprises at least one of LicomontNAV101, LicomontNAV102, and LicomontNAV 103.
5. The biobased polyamide biaxially oriented film of claim 1, wherein the antioxidant comprises at least one of GSNOX-168, THP-24 and RIANOX-1098.
6. The method for preparing a biobased polyamide biaxially oriented film according to any one of claims 1 to 5, comprising the steps of:
mixing the bio-based polyamide, the inorganic filler, the nucleating agent and the antioxidant, and then extruding by a double screw to obtain granules;
carrying out melt tape casting on the granules to form a film so as to obtain a bio-based polyamide film;
and (3) performing biaxial tension on the bio-based polyamide film to obtain the bio-based polyamide biaxial tension film.
7. The method of claim 6, wherein the parameters of the twin-screw extrusion comprise: the temperature of the die head is 160-220 ℃, the processing temperature is 225-270 ℃, and the rotating speed of the screw is 10-30 r/min.
8. The production method according to claim 6, wherein the melt-cast film formation is performed in a casting machine, and the parameters of the melt-cast film formation include: the processing temperature is 225-275 ℃, the rotating speed of the casting roll is 1-1.5 m/min, the rotating speed of the traction roll is 1.2-1.6 m/min, the synchronous coefficient of the traction roll is 1-1.5, the tension of the wind-up roll is 2.5-3.5 Kg, the synchronous coefficient of the wind-up roll is 0.2-0.5, and the temperature of the cooling roll is 20-50 ℃.
9. The method according to claim 6, wherein the thickness of the bio-based polyamide film is 110 to 130 μm.
10. The production method according to claim 6, wherein the biaxial stretching is asynchronous biaxial stretching or synchronous biaxial stretching; the parameters of the asynchronous biaxial stretching or the synchronous biaxial stretching independently comprise: preheating at 100-140 ℃, stretching at 100-170 ℃, heat setting at 130-160 ℃ and stretching at 50-348 mm/s; when the stretching is asynchronous biaxial stretching, the stretching times in the transverse direction or the longitudinal direction are independently 1-3.6 times; when the biaxial stretching is synchronous biaxial stretching, the stretching ratio is 1.2 × 1.2 to 3.6 × 3.6.
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