CN119409885A - Dicyclopentadiene hydrogenated petroleum resin, BOPP film and preparation method thereof - Google Patents
Dicyclopentadiene hydrogenated petroleum resin, BOPP film and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种双环戊二烯氢化石油树脂、BOPP薄膜及其制备方法，属于高分子材料技术领域。该双环戊二烯氢化石油树脂的制备包括：将双环戊二烯和全氟聚醚单体溶解于有机溶剂后发生热聚合反应，得到石油树脂；将石油树脂在催化剂存在的条件下与氢气发生加氢反应，得到双环戊二烯氢化石油树脂。通过在氢化石油树脂中引入全氟官能团，能够提高氢化石油树脂与聚丙烯树脂的相容性，提高加工利用性能；同时全氟官能团具有低表面自由能特性，可提高膜制品的疏水和抗粘附效果，均匀分散后的氢化石油树脂还能够提高共混物种玻璃态晶相区域，进而提高膜制品的阻氧和阻水性能。含上述双环戊二烯氢化石油树脂的BOPP薄膜可兼具较佳的阻氧和阻水性能。The invention discloses a dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof, and belongs to the technical field of polymer materials. The preparation of the dicyclopentadiene hydrogenated petroleum resin comprises: dissolving dicyclopentadiene and perfluoropolyether monomers in an organic solvent and then subjecting the monomers to a thermal polymerization reaction to obtain a petroleum resin; subjecting the petroleum resin to a hydrogenation reaction with hydrogen in the presence of a catalyst to obtain the dicyclopentadiene hydrogenated petroleum resin. By introducing a perfluoro functional group into the hydrogenated petroleum resin, the compatibility of the hydrogenated petroleum resin with the polypropylene resin can be improved, and the processing and utilization performance can be improved; at the same time, the perfluoro functional group has the characteristics of low surface free energy, which can improve the hydrophobic and anti-adhesion effects of the film product, and the uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystal phase region of the blended species, thereby improving the oxygen and water barrier properties of the film product. The BOPP film containing the above-mentioned dicyclopentadiene hydrogenated petroleum resin can have both good oxygen and water barrier properties.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof.
Background
Biaxially oriented polypropylene film (Biaxially Oriented Polypropylene, BOPP for short) is a plastic film made by a special process. BOPP film has taken an important place in the packaging material market by virtue of the advantages of light weight, innocuity, odorlessness, moisture resistance, high mechanical strength, good dimensional stability, good printing performance, good transparency and the like. The BOPP film is produced through the processes of compounding material, smelting, plasticizing extrusion, filtering, longitudinal stretching, transverse stretching, corona treatment, rolling, ageing treatment, cutting, etc. The BOPP film has high transparency, good luster, good barrier property, high impact strength and strong low temperature resistance, and is an ideal choice for packaging foods, candies, cigarettes, tea, fruit juice, milk, textiles and the like.
Although BOPP films have good general properties, in some applications, the barrier properties (i.e., the barrier properties of the film to gases, water vapor, light, etc.) need to be further improved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide dicyclopentadiene hydrogenated petroleum resin, a BOPP film and a preparation method thereof, so as to solve or improve the technical problems.
The invention can be realized as follows:
In a first aspect, the invention provides a method for preparing dicyclopentadiene hydrogenated petroleum resin, comprising the steps of dissolving dicyclopentadiene and perfluoropolyether monomers in an organic solvent and performing thermal polymerization reaction to obtain petroleum resin;
The petroleum resin is subjected to hydrogenation reaction with hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.
In alternative embodiments, the perfluoropolyether monomers include perfluoropolyether acrylates or perfluoropolyether styrenes;
and/or the organic solvent comprises at least one of cyclohexane, benzene, toluene, and xylene.
In an alternative embodiment, the mass ratio of dicyclopentadiene to organic solvent is from 1:1.5 to 1:3 and the mass ratio of perfluoropolyether monomer to dicyclopentadiene is from 1:5 to 1:15.
In an alternative embodiment, the temperature of the thermal polymerization reaction is 220 ℃ to 280 ℃, the pressure of the thermal polymerization reaction is 0.8MPa to 2.0MPa, and the time of the thermal polymerization reaction is 150min to 300min.
In an alternative embodiment, the catalyst is a nickel-based catalyst.
In an alternative embodiment, the molar ratio of petroleum resin to hydrogen is 1:2 to 1:4, and the catalyst is used in an amount of 0.5wt% to 2.0wt% of petroleum resin.
In an alternative embodiment, the hydrogenation reaction time is 180-300 min, the hydrogenation reaction pressure is 4.0-8.0 MPa, and the hydrogenation reaction temperature is 180-240 ℃.
In a second aspect, the present invention provides a dicyclopentadiene hydrogenated petroleum resin prepared by the method of any of the preceding embodiments.
In a third aspect, the present invention provides a BOPP film with high barrier properties, wherein the BOPP film is prepared from the dicyclopentadiene hydrogenated petroleum resin according to the foregoing embodiment.
In a fourth aspect, the present invention provides a method for preparing a BOPP film with high barrier properties according to the previous embodiment, comprising the steps of preparing dicyclopentadiene hydrogenated petroleum resin and homo-polypropylene into a master batch, mixing the master batch and homo-polypropylene, and then extruding, casting, biaxially stretching and post-treating.
The beneficial effects of the invention include:
The perfluorinated functional group is introduced into the hydrogenated petroleum resin, so that the compatibility of the hydrogenated petroleum resin and the polypropylene resin can be improved, the processing and utilization performance can be improved, meanwhile, the perfluorinated functional group has low surface free energy characteristics, the hydrophobic and anti-adhesion effects of the film product can be improved, the uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystalline phase area of the blend species, and further the oxygen and water resistance performance of the film product can be improved. The BOPP film containing the dicyclopentadiene hydrogenated petroleum resin has better oxygen and water resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The dicyclopentadiene hydrogenated petroleum resin and BOPP film provided by the invention and the preparation method thereof are specifically described below.
The invention provides a preparation method of dicyclopentadiene hydrogenated petroleum resin, which comprises the following steps of dissolving dicyclopentadiene (DCPD) and perfluoropolyether monomer in an organic solvent for thermal polymerization reaction to obtain petroleum resin;
The petroleum resin is subjected to hydrogenation reaction with hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.
The invention creatively introduces the perfluorinated functional group into the hydrogenated petroleum resin, can improve the compatibility of the hydrogenated petroleum resin and the polypropylene resin and the processing and utilization performance, and simultaneously has the characteristic of low surface free energy, can improve the hydrophobic and anti-adhesion effects of the film product, and can improve the glassy crystalline phase area of the blend species after being uniformly dispersed, thereby being beneficial to improving the oxygen and water resistance of the film product. The traditional hydrogenated petroleum resin has poor compatibility with polypropylene, so that the addition amount of the hydrogenated petroleum resin in the polypropylene is limited, and the barrier property of a corresponding film product is poor.
In some alternative embodiments, the perfluoropolyether monomer may comprise a perfluoropolyether acrylate or a perfluoropolyether styrenic. In some more typical embodiments, the perfluoropolyether monomer is a perfluoropolyether styrenic.
The structural formula of the perfluoropolyether acrylate is as follows:;
the structural formula of the perfluoropolyether styrenes is as follows: ;
Wherein rf=cf 3CF2CF2O[CF(CF3)CF2O]nCF(CF3), n=2 to 4.
In some alternative embodiments, the organic solvent may illustratively include at least one of cyclohexane, benzene, toluene, and xylene. In some more typical embodiments, toluene is used as the organic solvent.
In some alternative embodiments, the mass ratio of dicyclopentadiene to organic solvent may be 1:1.5 to 1:3, such as 1:1.5, 1:2, 1:2.5, or 1:3, etc., as well as other values in the range of 1:1.5 to 1:3. In some more typical embodiments, the mass ratio of dicyclopentadiene to organic solvent is 1:2.
The mass ratio of perfluoropolyether monomer to dicyclopentadiene may be 1:5 to 1:15, such as 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15, etc., but may also be other values in the range of 1:5 to 1:15. In some more typical embodiments, the mass ratio of perfluoropolyether monomer to dicyclopentadiene is 1:10.
If the mass ratio of the perfluoropolyether monomer to the dicyclopentadiene is smaller than 1:5 (such as 1:2), the synthesis of the petroleum resin structure is not facilitated, and if the mass ratio of the perfluoropolyether monomer to the dicyclopentadiene is larger than 1:15 (such as 1:18), the ratio of the perfluoro group is too small, and the effect on improving the hydrophobicity and the anti-adhesion performance of the film product is not obvious.
In some alternative embodiments, the temperature of the thermal polymerization reaction may be 220 ℃ to 280 ℃, such as 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, etc., and may be other values within the range of 220 ℃ to 280 ℃. In some more typical embodiments, the temperature of the thermal polymerization reaction is 240 ℃ to 260 ℃.
If the temperature of the thermal polymerization reaction is lower than 220 ℃, the formation of a polymerization product with a target molecular weight is not facilitated, and if the temperature of the thermal polymerization reaction is lower than 280 ℃, the color of the petroleum resin product is deepened, and the appearance of a film after processing is affected.
In some alternative embodiments, the pressure of the thermal polymerization reaction may be 0.8MPa to 2.0MPa, such as 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, or 2.0MPa, and may be other values within the range of 0.8MPa to 2.0MPa. In some more typical embodiments, the pressure of the thermal polymerization reaction is 1.0MPa to 2.0MPa.
In some alternative embodiments, the thermal polymerization reaction time may be 150min to 300min, such as 150min, 180min, 200min, 220min, 250min, 280min, or 300min, or may be other values within the range of 150min to 300 min. In some more typical embodiments, the thermal polymerization reaction time is 180min to 240min.
In some alternative embodiments, the catalyst is a nickel-based catalyst. Illustratively, the average pore diameter of the nickel-based catalyst used in the present invention may be 5nm to 30nm (e.g., 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, etc.), and the nickel content may be 40wt% to 85wt% (e.g., 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, etc.).
In some alternative embodiments, the molar ratio of petroleum resin to hydrogen may be 1:2 to 1:4, such as 1:2, 1:2.5, 1:3, 1:3.5, or 1:4, etc., as well as other values in the range of 1:2 to 1:4. In some more typical embodiments, the molar ratio of petroleum resin to hydrogen is 1:3.
In some alternative embodiments, the catalyst may be used in an amount of 0.5wt% to 2.0wt% of the petroleum resin, such as 0.5wt%, 1.0wt%, 1.5wt% or 2.0wt%, etc., or may be other values in the range of 0.5wt% to 2.0 wt%. In some more typical embodiments, the catalyst is present in an amount of 1.5wt% of the petroleum resin.
In some alternative embodiments, the hydrogenation reaction time may be 180min to 300min, such as 180min, 200min, 220min, 250min, 280min or 300min, or may be other values within the range of 180min to 300min. In some more typical embodiments, the hydrogenation reaction time is 240min to 300min.
In some alternative embodiments, the hydrogenation reaction pressure may be 4.0MPa to 8.0MPa, such as 4.0MPa, 4.5MPa, 5.0MPa, 5.5MPa, 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, or 8.0MPa, and the like, and may also be other values in the range of 4.0MPa to 8.0MPa. In some more typical embodiments, the hydrogenation reaction is carried out at a pressure of 6.0MPa to 8.0MPa.
In some alternative embodiments, the temperature of the hydrogenation reaction may be 180 ℃ to 240 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃,200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, or the like, as well as other values within the range of 180 ℃ to 240 ℃. In some more typical embodiments, the hydrogenation reaction temperature is 210 ℃ to 240 ℃.
Correspondingly, the invention also provides dicyclopentadiene hydrogenated petroleum resin which is prepared by the preparation method.
The dicyclopentadiene hydrogenated petroleum resin has good compatibility with polypropylene, so that the dicyclopentadiene hydrogenated petroleum resin and the polypropylene have better blending processability. The dicyclopentadiene hydrogenated petroleum resin is suitable for preparing biaxially oriented polypropylene films (BOPP films), and can enable the biaxially oriented polypropylene films to have higher barrier properties.
In addition, the invention also provides a BOPP film with high barrier property, the BOPP film is prepared from the dicyclopentadiene hydrogenated petroleum resin, and the BOPP film has good water vapor and oxygen barrier property.
Correspondingly, the invention also provides a preparation method of the BOPP film with high barrier property, which comprises the following steps of preparing dicyclopentadiene hydrogenated petroleum resin and homo-polypropylene into master batch, mixing the master batch and the homo-polypropylene, and then extruding, casting, biaxially stretching and post-processing.
It should be noted that, the specific preparation conditions of the BOPP film are not developed in the present invention, and the related content may refer to the prior art, and is not described and limited in detail herein.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides dicyclopentadiene hydrogenated petroleum resin, and the preparation method comprises the following steps:
s1, dissolving dicyclopentadiene (DCPD) and a perfluoropolyether monomer in an organic solvent to perform thermal polymerization reaction to obtain petroleum resin;
Wherein the organic solvent is toluene, the perfluoropolyether monomer adopts a styrene monomer, and the structural formula of the perfluoropolyether monomer is as follows: ,Rf=CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3),n=2.DCPD The mass ratio of the perfluoropolyether monomer to toluene is 1:1.5, the mass ratio of the perfluoropolyether monomer to DCPD is 1:10, the temperature of the thermal polymerization reaction is 240 ℃, the pressure of the thermal polymerization reaction is 1.0MPa, and the time of the thermal polymerization reaction is 210min.
And S2, carrying out hydrogenation reaction on the petroleum resin and hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.
Wherein the catalyst is nickel catalyst, and specifically, the average pore diameter of the catalyst is 10nm, and the nickel content is 65wt%. The molar ratio of petroleum resin to hydrogen is 1:3, the catalyst is 1.5wt% of petroleum resin, the hydrogenation reaction time is 300min, the hydrogenation reaction pressure is 6.0MPa, and the hydrogenation reaction temperature is 240 ℃.
Examples 2 to 7
Examples 2 to 7 are the same as the reaction materials used in example 1, and the process conditions for steps S1 and S2 in each example are shown in tables 1 and 2.
TABLE 1 summary of reaction conditions for step S1
TABLE 2 summary of reaction conditions for step S2
Example 8
The difference between the embodiment and the embodiment 1 is that the perfluoropolyether monomer is a perfluoropolyether styrene monomer, and the structural formula of the perfluoropolyether monomer is as follows: Rf=cf 3CF2CF2O[CF(CF3)CF2O]nCF(CF3), n=3, and the organic solvent is cyclohexane.
Example 9
The difference between the embodiment and the embodiment 1 is that the perfluoropolyether monomer is a perfluoropolyether acrylic monomer, and the structural formula of the perfluoropolyether monomer is as follows:,Rf=CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3),n=2。
Comparative example 1
The comparative example provides a dicyclopentadiene hydrogenated petroleum resin, which is prepared as follows:
Dissolving dicyclopentadiene and toluene according to a mass ratio of 1:2, reacting for 180min at 250 ℃ and 1.0MPa to obtain dicyclopentadiene petroleum resin, mixing the dicyclopentadiene petroleum resin and hydrogen according to a mass ratio of 1:3, and reacting for 300min at 240 ℃ and 6.0MPa under the action of a catalyst with the weight ratio of 1.5% to obtain dicyclopentadiene hydrogenated petroleum resin.
Comparative example 2
The difference between this comparative example and example 1 is that in S1 the mass ratio of perfluoropolyether monomer to dicyclopentadiene is 1:18.
Comparative example 3
This comparative example differs from example 1 in that methacrylic acid was used instead of the perfluoropolyether monomer.
Test examples
① . The hydrogenated dicyclopentadiene petroleum resin prepared in comparative example 1 and the homo-polypropylene, and the hydrogenated dicyclopentadiene petroleum resin prepared in example 1 and the homo-polypropylene were mixed in different proportions, and then formed into a film using a flat vulcanizing machine (temperature: 200 ℃ C., pressure: 2.0 MPa), and then the film was observed under a scanning electron microscope, and the results thereof are shown in Table 3.
TABLE 3 section results
As can be seen from Table 3, the perfluoropolyether-grafted dicyclopentadiene hydrogenated petroleum resin has better compatibility with homo-polypropylene than dicyclopentadiene hydrogenated petroleum resin not subjected to perfluoro group modification, and specifically, at least when the amount of dicyclopentadiene hydrogenated petroleum resin reaches 20wt%, the dicyclopentadiene hydrogenated petroleum resin and homo-polypropylene are mixed and pressed without phase separation.
② . The dicyclopentadiene hydrogenated petroleum resins obtained in examples 1 to 9 and comparative examples 1 to 3 were respectively prepared into BOPP films in the following manner:
Mixing dicyclopentadiene hydrogenated petroleum resin and homo-polypropylene obtained in each example according to the mass ratio of 1:1, extruding and granulating to form master batch, mixing the master batch and the homo-polypropylene according to the mass ratio of 1:4, extruding at 230-250 ℃, and casting by using a cold roller. After the casting sheet is finished, preheating the film to 120 ℃, longitudinally stretching for 5 times, preheating to 180 ℃ and transversely stretching for 8 times to obtain the BOPP film.
Meanwhile, a control group is arranged, wherein the control group is to directly extrude and granulate the homo-polypropylene to form a master batch, and then the BOPP film without hydrogenated petroleum resin is obtained through the steps.
The BOPP films prepared in each example and comparative example and control group were subjected to performance test, wherein Young's modulus was measured by a dynamic mechanical analyzer, haze was measured by a haze meter, and measured by GB/T2410-2008 method, gas permeability was tested, namely, water vapor permeability was measured on PERMATRAN-w3/61 type moisture permeability meter, and measured by GB/T26153-2010 method, and oxygen permeability was measured by 8001 type oxygen permeability meter, and measured according to GB/T19789-2005 method.
The test results are shown in Table 4.
TABLE 4 Performance test results
As can be seen from Table 4, the BOPP film with the dicyclopentadiene hydrogenated petroleum resin has improved Young's modulus and gas permeability compared with the BOPP film without the dicyclopentadiene hydrogenated petroleum resin (control group), because the hydrogenated petroleum resin has a higher glass transition temperature, and can improve the rigidity of the rubbery amorphous phase of polypropylene and reduce the gas permeability.
Compared with comparative example 1, examples 1 to 9, after the dicyclopentadiene hydrogenated petroleum resin was subjected to perfluoro group grafting, the perfluoro group had extremely low surface energy, and thus the gas permeability of the BOPP film could be further reduced.
Even if the dicyclopentadiene hydrogenated petroleum resin is subjected to perfluoro group grafting, the oxygen and water blocking properties of the BOPP film are effectively improved by the improper setting of the preparation conditions, as compared with comparative example 2, by example 1.
By comparison with comparative example 3, example 1 has far less effect of improving oxygen and water blocking properties of BOPP film than that obtained by the perfluoro group grafting specifically employed in the present application even if other monomer types are employed which can also improve the compatibility of hydrogenated petroleum resin with polypropylene resin.
In conclusion, the invention creatively introduces the perfluoro functional group into the hydrogenated petroleum resin, can improve the compatibility of the hydrogenated petroleum resin and the polypropylene resin and improve the processing and utilization performance, and meanwhile, the perfluoro functional group has low surface free energy characteristic, can improve the hydrophobic and anti-adhesion effects of the film product, and the uniformly dispersed hydrogenated petroleum resin can also improve the glassy crystalline phase area of the blend species, thereby being beneficial to improving the oxygen and water resistance of the film product.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of dicyclopentadiene hydrogenated petroleum resin is characterized by comprising the following steps of dissolving dicyclopentadiene and perfluoropolyether monomers in an organic solvent and performing thermal polymerization reaction to obtain petroleum resin;
And (3) carrying out hydrogenation reaction on the petroleum resin and hydrogen in the presence of a catalyst to obtain dicyclopentadiene hydrogenated petroleum resin.
2. The method of claim 1, wherein the perfluoropolyether monomer comprises a perfluoropolyether acrylate or a perfluoropolyether styrene;
and/or the organic solvent comprises at least one of cyclohexane, benzene, toluene and xylene.
3. The preparation method according to claim 1, wherein the mass ratio of the dicyclopentadiene to the organic solvent is 1:1.5 to 1:3, and the mass ratio of the perfluoropolyether monomer to the dicyclopentadiene is 1:5 to 1:15.
4. The method according to any one of claims 1 to 3, wherein the temperature of the thermal polymerization reaction is 220 ℃ to 280 ℃, the pressure of the thermal polymerization reaction is 0.8mpa to 2.0mpa, and the time of the thermal polymerization reaction is 150min to 300min.
5. The method according to claim 1, wherein the catalyst is a nickel-based catalyst.
6. The method of claim 1, wherein the molar ratio of the petroleum resin to the hydrogen is 1:2 to 1:4, and the catalyst is used in an amount of 0.5wt% to 2.0wt% of the petroleum resin.
7. The preparation method according to claim 5 or 6, wherein the hydrogenation reaction time is 180-300 min, the hydrogenation reaction pressure is 4.0-8.0 mpa, and the hydrogenation reaction temperature is 180-240 ℃.
8. The dicyclopentadiene hydrogenated petroleum resin is characterized by being prepared by the preparation method according to any one of claims 1 to 7.
9. A BOPP film with high barrier properties, wherein the BOPP film is prepared from the dicyclopentadiene hydrogenated petroleum resin according to claim 8.
10. A process for preparing a BOPP film having high barrier properties as described in claim 9, comprising the steps of preparing a master batch from said dicyclopentadiene hydrogenated petroleum resin and said homo-polypropylene, mixing said master batch with said homo-polypropylene, and then extruding, casting, biaxially stretching and post-treating.
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| CN110078847A (en) * | 2019-04-28 | 2019-08-02 | 恒河材料科技股份有限公司 | A kind of preparation method of high softening-point hydrogenated petroleum resin |
| US20230374181A1 (en) * | 2021-09-17 | 2023-11-23 | Henghe Materials & Science Technology Co., Ltd. | Preparation method of bopp film stiffening agent |
| CN116217916A (en) * | 2023-02-07 | 2023-06-06 | 湖南天氟新材料有限公司 | Y-type perfluoropolyether modified acrylic ester, antifouling paint, preparation method and application |
| CN117757002A (en) * | 2023-12-13 | 2024-03-26 | 恒河材料科技股份有限公司 | Modified resin and preparation method thereof, stiffening master batch, BOPP film and preparation method thereof |
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