CN115991033A - High-adhesion high-impact polypropylene composite film and preparation method and application thereof - Google Patents
High-adhesion high-impact polypropylene composite film and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of films, and relates to a high-adhesion high-impact polypropylene composite film, and a preparation method and application thereof. The polypropylene composite film comprises at least one film layer A formed by a polypropylene composition A and at least one film layer B formed by a polypropylene composition B; wherein the polypropylene composition a comprises polypropylene a and optionally a polyolefin elastomer b; the polypropylene composition B comprises atactic polypropylene x, polyolefin elastomer y, propylene impact copolymer z and polar monomer modified polypropylene k. The composite film of the invention has good impact resistance, tensile property and adhesion, and has good heat seal strength at lower heat seal temperature.
Description
Technical Field
The invention belongs to the field of films, and particularly relates to a high-adhesion high-impact polypropylene composite film, and a preparation method and application thereof.
Background
Polypropylene films are typically produced by casting, biaxially oriented drawing, and the like, but polypropylene films produced from homopolymerized polypropylene materials typically have lower impact strength. Polypropylene films are commonly used in packaging applications where higher impact properties are required. And some polypropylene films need to be used after being bonded with other materials, such as aluminum plastic films, so good bonding of the films with other materials is also desirable. The existing polypropylene film is difficult to have better impact resistance and adhesion.
To improve the impact properties and toughness of the film, a block impact polypropylene may be used to make the film, or a polyolefin elastomer may be added to the polypropylene. The impact performance of the polypropylene film can be improved by preparing the film through a multilayer coextrusion method, for example, a three-layer coextrusion method is adopted in CN101913279A to prepare the composite film, the middle layer of the film is elastomer and PP which are blended according to the proportion of 1:10-1:3, and the elastomer provides good impact performance, but the method has the problem that the elastomer is difficult to disperse uniformly under the condition of high elastomer content, and the addition amount of the elastomer has certain limit, because the problem of phase separation occurs when the addition amount is up to a certain level, the further improvement of the impact performance is limited.
Therefore, there is a need to develop a polypropylene film having both good impact properties and good adhesion.
Disclosure of Invention
The invention aims to solve the problem that the existing polypropylene film is difficult to have better impact resistance and adhesiveness at the same time, and provides a high-adhesiveness high-impact polypropylene composite film and a preparation method thereof.
A first aspect of the present invention provides a high adhesion high impact polypropylene composite film comprising at least one film layer a formed from a polypropylene composition a and at least one film layer B formed from a polypropylene composition B; wherein the polypropylene composition a comprises polypropylene a and optionally a polyolefin elastomer b; the polypropylene composition B comprises atactic polypropylene x, polyolefin elastomer y, propylene impact copolymer z and polar monomer modified polypropylene k.
The second aspect of the present invention provides a method for preparing the above-mentioned high-adhesion high-impact polypropylene composite film, comprising: the raw material composition for forming each layer is extrusion-cast after an optional granulating process to form the composite film.
A third aspect of the present invention provides the use of the above-described high adhesion high impact polypropylene composite film in the field of packaging materials.
The composite film of the invention has good impact resistance, tensile property and adhesion, and has good heat seal strength at lower heat seal temperature. The tensile strength of the film in the Machine Direction (MD) is more than or equal to 40MPa, and the tensile strength of the film in the Machine Direction (MD) is more than or equal to 52MPa; the surface energy is more than or equal to 33mN/m, preferably more than or equal to 34.5mN/m; the impact strength of the pendulum bob is more than or equal to 0.55J, preferably the impact strength of the pendulum bob is more than or equal to 0.9J; the heat seal strength at 150 ℃ is more than or equal to 12N/15mm, and the heat seal strength at 150 ℃ is more than or equal to 17N/15mm.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a high-adhesion high-impact polypropylene composite film, which comprises at least one film layer A formed by a polypropylene composition A and at least one film layer B formed by a polypropylene composition B; wherein the polypropylene composition a comprises polypropylene a and optionally a polyolefin elastomer b; the polypropylene composition B comprises atactic polypropylene x, polyolefin elastomer y, propylene impact copolymer z and polar monomer modified polypropylene k.
According to some embodiments of the invention, a rubber phase is present in the composite film, the rubber phase having an average width of 20 to 200nm and an average aspect ratio of 5 to 20. The rubber phase was observed by atomic force microscopy and was in the form of a bar. The meaning of aspect ratio is well known to those skilled in the art, and for the bar particle test, the aspect ratio is the same concept as aspect ratio, namely: the ratio of the longest diameter passing through the interior of the particle to the longest diameter perpendicular thereto corresponds to the length of the particle, and the width of the particle.
According to some embodiments of the invention, the polypropylene composite film has at least one of the following features: the tensile strength in the Machine Direction (MD) is more than or equal to 40MPa, and the tensile strength in the Machine Direction (MD) is more than or equal to 52MPa; the surface energy is more than or equal to 33mN/m, preferably more than or equal to 34.5mN/m; the impact strength of the pendulum bob is more than or equal to 0.55J, preferably the impact strength of the pendulum bob is more than or equal to 0.9J; the heat seal strength at 150 ℃ is more than or equal to 12N/15mm, and the heat seal strength at 150 ℃ is more than or equal to 17N/15mm.
According to some embodiments of the invention, the polypropylene a may be selected from homo-polypropylene and/or propylene impact copolymers.
Preferably, the melt mass flow rate of the homo-polypropylene a at 230 ℃ under a load of 2.16kg is 2-15g/10min, the isotacticity is more than 97%, and the molecular weight distribution Mw/Mn is 4.5-7.0. Homo-polypropylene meeting the above characteristics is commercially available. Such as the homopolypropylene with the Qingdao brand of PPH-FA03 and the homopolypropylene with the Shanghai brand of FC 801. Or may be prepared by methods conventional in the art.
According to the present invention, the propylene impact copolymer is preferably a propylene impact copolymer containing ethylene units, the propylene impact copolymer comprising an elastic portion which is a copolymerized portion containing ethylene units, preferably selected from the group consisting of an ethylene-propylene copolymerized portion and an ethylene-butene copolymerized portion.
Preferably, the propylene impact copolymer comprises a propylene homo-polymer portion and the ethylene unit containing co-polymer portion. The propylene homo-portion may comprise an isotactic polymeric structure.
The content of the copolymerized portion containing ethylene units in the propylene impact copolymer z is preferably 3 to 15% by weight based on the total weight of the propylene impact copolymer z by 13 C NMR measurement.
The ethylene content of the propylene impact copolymer z is preferably from 1 to 12wt%, based on the total weight of the propylene impact copolymer z.
The melt mass flow rate of the propylene impact copolymer z at 230℃under a load of 2.16kg is preferably from 1 to 10g/10min.
The propylene impact copolymer may have a block structure or comprise a propylene block copolymer.
The polypropylene a optional propylene impact copolymer may be the same or different from the propylene impact copolymer z, preferably meeting the above conditions.
Propylene impact copolymers meeting the above characteristics are commercially available. Such as propylene impact copolymer with the trade name EP200K, propylene impact copolymer with the trade name M180R, and propylene impact copolymer with the trade name PPB-M02D. Or may be prepared by methods conventional in the art.
According to some embodiments of the invention, the polyolefin elastomer b is an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
According to some embodiments of the invention, the polyolefin elastomer y is an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
Polyolefin elastomers meeting the above characteristics are commercially available. For example, the polyolefin elastomer of Exxon brand 6102, the polyolefin elastomer of Santa Clay brand DF640, and the polyolefin elastomer of ExACT 3139. Or may be prepared by methods conventional in the art.
According to some embodiments of the present invention, the random polypropylene x is a copolymer of propylene and ethylene and/or butene, that is, at least one of a copolymer of propylene and ethylene, a copolymer of propylene and butene, and a copolymer of propylene and ethylene and butene, preferably at least one selected from an ethylene-propylene-butene ternary random copolymer, a propylene-ethylene binary random copolymer, and a propylene-butene binary random copolymer.
The melt mass flow rate of the atactic polypropylene x at 230℃under a load of 2.16kg is preferably 2-10g/10min.
Random polypropylene meeting the above characteristics is commercially available. Such as atactic polypropylene with the brand of F5006, atactic polypropylene with the brand of F500EPS, and atactic polypropylene with the brand of F800 EPS. Or may be prepared by methods conventional in the art.
Polypropylene belongs to a nonpolar material, has low surface energy and poor interfacial adhesion with other materials. The introduction of polar groups can improve the adhesive properties, such as hydroxyl (-OH), cyano (-CN), maleic anhydride (-MAH), etc.
According to some embodiments of the invention, the polar monomer in the polar monomer modified polypropylene k is selected from at least one of a hydroxyl-containing comonomer, a cyano-containing comonomer, and an anhydride monomer; the hydroxyl-containing comonomer is preferably a hydroxy acid and/or vinyl alcohol; the cyano-containing comonomer is preferably cyanoacrylate; the anhydride monomer is preferably maleic anhydride and/or itaconic anhydride, more preferably maleic anhydride. The maleic anhydride grafted polypropylene (PP-g-MAH) has both polar groups and olefin nonpolar chain segments, has the basic physical properties of original polypropylene, such as high crystallinity, high strength, high impact resistance and the like, and improves the adhesive force with other materials.
The polar monomer-modified polypropylene of the present invention is commercially available, for example, maleic anhydride-modified polypropylene having a brand of QF551A by Mitsui, maleic anhydride-modified polypropylene having a brand of CMG9801 by Jia Yi, and maleic anhydride-modified polypropylene having a brand of PO1015 by Ekksen. Or may be prepared by methods conventional in the art.
According to some embodiments of the invention, the polypropylene composition a comprises 50 to 100wt% of polypropylene a and 0 to 50wt% of polyolefin elastomer b, based on the total weight of the polypropylene composition a.
According to a preferred embodiment of the present invention, the polypropylene composition A comprises 75 to 95 wt.% polypropylene a and 5 to 25 wt.% polyolefin elastomer b, based on the total weight of the polypropylene composition A.
The elastomer or propylene impact copolymer in the composition contains a rubber phase, so that good impact performance is provided for the film, and meanwhile, as the homo-polymer phase part macromolecular chain segments of the homo-polymer polypropylene and the propylene impact copolymer are relatively regular, crystallization and orientation occur in the film preparation process, so that good mechanical performance is provided for the film. According to the composition provided by the invention, the rubber phase in the composition can absorb impact energy well, so that the requirement of impact performance is met, and the film has good impact performance. Meanwhile, as the macromolecular chain segments of the homo-polymer phase are more regular, crystallization occurs in the film preparation process, so that the film also has better tensile property.
According to some embodiments of the present invention, the polypropylene composition B comprises 30 to 90wt% of the random polypropylene x, 5 to 40wt% of the polyolefin elastomer y, 2.5 to 20wt% of the propylene impact copolymer z, and 2.5 to 20wt% of the polar monomer modified polypropylene k, based on the total weight of the polypropylene composition B.
According to a preferred embodiment of the present invention, the polypropylene composition B comprises 60 to 85wt% of the random polypropylene x, 5 to 20wt% of the polyolefin elastomer y, 5 to 10wt% of the propylene impact copolymer z and 5 to 10wt% of the polar monomer modified polypropylene k, based on the total weight of the polypropylene composition B.
The polar monomer modified polypropylene k in the composition B provides good adhesive property for the film, and has the basic physical properties of original polypropylene and improved adhesive force with other materials due to the polar group introduced into the polar monomer modified polypropylene. According to the composition B provided by the invention, not only can the impact resistance and heat sealing strength of the film be ensured, but also the adhesion degree of the film and other materials can be improved.
According to some embodiments of the invention, the ratio of Wb to Wy is 10:1-1:6, calculated as wt. parts Wb of the polyolefin elastomer B to 100 wt. parts of the polypropylene composition B, calculated as wt. parts Wb of the polyolefin elastomer B to 100 wt. parts of the polypropylene composition B, for example, may be 9.5:1, 9:1, 8.5:1, 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5 and any value therebetween.
According to a preferred embodiment of the invention, the ratio of Wb to Wy is 4:1 to 1:4.
As a result of the study of the present inventors, when a double-layer or multi-layer film is co-extruded, the impact properties of the film can be further improved and the extrusion process can be more stable at the same time when the ratio of Wb to Wy is within the range of the present invention.
According to some embodiments of the invention, the melt mass flow rate of the polypropylene composition A is 2-10g/10min, preferably 3-8g/10min, at 230℃under a load of 2.16 kg.
According to some embodiments of the invention, the melt mass flow rate of the polypropylene composition B is 3-10g/10min, preferably 4-8g/10min, at 230℃under a load of 2.16 kg.
When the melt mass flow rates of the polypropylene composition A and the polypropylene composition B are within the above ranges, the film preparation process can be made more stable, thereby ensuring that the film has better uniformity and mechanical properties.
The composite film can be of a double-layer structure, can also be of a three-layer or more than three-layer film structure, and other layers can be the same as the film layer A or the film layer B in composition, can also be different from the film layer A or the film layer B in composition, and can also be formed by mixing a polypropylene composition A and a polypropylene composition B. When the polypropylene composite film has a structure with more than three layers, the film layer B is preferably used as a surface layer, such as a three-layer film comprising a film layer A, a film layer B and a film layer C, wherein the layer B and the layer C can be respectively positioned at two sides of the layer A.
According to some embodiments of the invention, the ratio of the sum of the thicknesses of the other film layers to the thickness of the film layer a is 1:4-2:1, for example, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.5, 1:1, 1.5:1 and any value therebetween.
According to a preferred embodiment of the present invention, in the polypropylene composite film, the ratio of the sum of the thicknesses of the other film layers to the thickness of the film layer A is 1:2 to 1:1. At this ratio, the composite film has good mechanical properties.
In the present invention, in order to improve the performance of the composite film during processing, it is preferable that the composite film further contains an antioxidant and/or a lubricant.
In the present invention, the antioxidant may be various antioxidants commonly used in the art, and is not particularly limited. For example, antioxidant 1076, antioxidant 1010, antioxidant 168, and thioester antioxidants (such as DLTP and DSTP) can be used. The antioxidant may be contained in an amount of 0.1 to 0.8 parts by weight, preferably 0.2 to 0.4 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition A or the polypropylene composition B.
In the present invention, the lubricant is preferably a PEG-based lubricant and/or a mono Gan Zhilei lubricant. The lubricant is contained in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition A or the polypropylene composition B.
In accordance with the present invention, the composite film preferably further comprises a film forming aid in order to enhance other properties of the composite film (e.g., stability, antistatic properties, etc.). The film forming aid may be at least one selected from the group consisting of an anti-halogen agent, a light stabilizer, a heat stabilizer, a colorant, a filler, a slip agent, an anti-sticking agent (anti-blocking agent), and an antistatic agent. The specific kind of the film forming aid may be selected conventionally in the art, and the present invention is not particularly limited thereto.
In the present invention, the content of the film forming aid may be 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
The invention also provides a preparation method of the polypropylene composite film, which comprises the following steps: the raw material composition for forming each layer is extrusion-cast after an optional granulating process to form the composite film.
In the preparation method of the present invention, the process of granulating the pellets may generally include: and uniformly mixing the components of the polypropylene composition, an optional antioxidant, a lubricant and a film forming auxiliary agent in a high-speed stirrer, adding the uniformly mixed materials into a double-screw extruder, performing melt mixing, uniformly extruding, granulating and drying to obtain granules. Wherein, the processing temperature of the double-screw extruder can be controlled to be 170-230 ℃.
According to some embodiments of the invention, the pellets may be processed using extrusion casting. The process of the extrusion casting method can comprise the steps of respectively conveying the granules of different compositions into a plurality of extruders, enabling the granules to flow out through coextrusion compounding of die openings of the extruders, sequentially passing through a casting roller, a traction roller, cutting edges and rolling, and thus obtaining the composite film. Wherein the temperature of the extrusion casting may be controlled to 170-230 ℃ and the temperature of the casting roll may be 10-50 ℃. The specific process of preparing the film by the extrusion casting method is a common choice in the field, and will not be described herein.
The resulting composite film may be stretched in a subsequent process, such as biaxially stretching, to advantageously further improve the mechanical properties of the composite film.
According to one embodiment of the present invention, the polypropylene composite film is produced by extrusion casting and optionally stretching the polypropylene composition a and the polypropylene composition B after pelletization.
The polypropylene composite film of the present invention can be used in the field of packaging materials, such as high-end packaging fields with high requirements on film impact resistance, including but not limited to battery packaging materials, electronic product packaging and food (high-end food) packaging.
Specific embodiments of the present invention will be described in detail below by way of examples. It should be understood that the examples described below are illustrative and explanatory only and are not restrictive of the invention.
In the following examples and comparative examples:
the film casting apparatus was purchased from Labtech, sweden under the model LCR400.
The polypropylene composition and film properties were tested according to the following methods, the film test results are shown in table 1:
(1) Melt Mass Flow Rate (MFR): the measurement was carried out according to the method specified in GB/T3682-2000, wherein the test temperature was 230℃and the load was 2.16kg.
(2) Film tensile strength: the measurement was carried out according to the method specified in GB/T1040.3-2006.
(3) Film pendulum impact strength: the measurement was performed according to the method specified in GB/T8809-2015.
(4) Film haze: the measurement was carried out according to the method specified in GB/T2410-2008.
(5) Film heat seal strength: the measurement was performed according to the method specified in QB/T2358. When the sample is prepared, the heat sealing temperature is 150 ℃, the heat sealing pressure is 0.2MPa, and the heat sealing time is 3s.
(6) Film surface energy: the measurement was carried out according to the method specified in GB/T14216-2008.
(7) Method for measuring average width and average length-diameter ratio of film rubber phase: the cross section of the film sample was scanned and observed using a model Dimension FastScan Icon atomic force microscope from Bruker, usa, using a quantitative nanomechanical scanning mode, and the width of the rubber phase was measured and counted to obtain an average width (based on 200 sample points). The aspect ratio of the rubber phase is the ratio of the dimension in the length direction to the dimension in the width direction, and the average aspect ratio (based on 200 sample points) is obtained through measurement, calculation and statistics.
(8) Degree of isotacticity: by passing through 13 C NMR measurement, nuclear magnetic carbon Spectrometry of propylene Polymer at 400MHz was measured by Nuclear magnetic resonance spectrometer (NMR) of model AVANCE III of Bruker, switzerland 13 C-NMR), wherein the solvent was deuterated o-dichlorobenzene and the sample concentration was 250mg sample/2.5 mL solvent. To prevent oxidative degradation of the sample during dissolution and data collection, 2mg of 2, 6-di-tert-butyl-4-methylphenol antioxidant (BHT for short) was added to the sample. Dissolving the sample at 140 ℃ and collecting 13 C-NMR, test temperature 125 ℃, probe gauge 10 mm, 90 pulse, sampling time AQ 5 seconds, delay time D1 seconds, number of scans 6000. Isotatic with two sets of units [ mm]The content of (2) is taken as isotacticity.
(9) Molecular weight distribution (Mw/Mn): the gel permeation chromatograph was used in combination with an IR5 type infrared detector, and the gel permeation chromatograph was used as a model PL-GPC 220 by UK Polymer Laboratories, wherein the gel permeation chromatograph comprises 3 columns of Plgel 10 μm MIXED-B connected in series, the solvent and mobile phase were 1,2, 4-trichlorobenzene (containing 0.3g/1000mL of antioxidant 2, 6-di-tert-butyl-p-cresol), the column temperature was 150℃and the flow rate was 1.0mL/min, and the well-suited calibration was performed using EasiCal PS-1 narrow distribution polystyrene standard produced by PL.
Example 1
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
component (A)a is homo-polypropylene with the brand name of PPH-FA03, which is purchased from Qingdao refining, the mass flow rate of the melt is 3.1g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.7; component b was a polyolefin elastomer having a trade designation 6102, available from Exxon and was an ethylene-propylene copolymer having an ethylene structural unit content of 16% by weight. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wa of the component a is 80 weight parts, and the weight part Wb of the component b is 20 weight parts. Adding lubricant (PEG lubricant manufactured by Swiss Corp., molecular weight 10000, and the addition amount of lubricant is 0.1 weight part based on 100 weight parts of the sum of the weight of the component a and the weight of the component b), adding the mixture into a high-speed stirrer, mixing uniformly, and adding the mixed material into W&In a feeder of a double-screw extruder manufactured by P company, materials enter a double screw through the feeder, the temperature of the screw is kept between 160 ℃ and 230 ℃ in the processing process, and the materials are evenly mixed by melting the screw, extruded, granulated and dried to obtain polypropylene composition A granules, and the melt mass flow rate MFR of the polypropylene composition A granules is detected A ＝3.5g/10min。
(2) Preparation of polypropylene composition B:
the component x is random polypropylene with the brand number of F5006, is purchased from the petrifaction of Yanshan and is an ethylene-propylene-butene terpolymer, and the melt mass flow rate is 5.2g/10min; the component y is a polyolefin elastomer with the trade name 6102, which is purchased from the Ekken company and is an ethylene-propylene copolymer, and the content of ethylene structural units is 16wt%; the component z is propylene impact copolymer with the brand of EP200K, which is purchased from the medium sand petrochemical industry, the ethylene content is 8wt%, the ethylene-propylene copolymerization part content is 13wt%, and the melt mass flow rate is 3.2g/10min; the component k is maleic anhydride modified polypropylene with the brand of QF551A and is purchased from Mitsui company. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wx of the component x is 85 weight parts, the weight part Wy of the component y is 5 weight parts, the weight part Wz of the component z is 5 weight parts, and the weight part Wk of the component k is 5 weight parts. Wb: wy is 4:1. Other steps are the same as the step (1), and finally the polypropylene composition B granules are obtained, and the melt mass flow rate M of the polypropylene composition B granules is detectedFR B ＝4.9g/10min。
(3) Preparation of a composite film:
drying the polypropylene composition A and the polypropylene composition B pellets obtained in the step (1) and the step (2), and then adding the polypropylene composition A into a core layer extruder of a multilayer extrusion casting machine, and adding the polypropylene composition B into an upper surface layer extruder of the multilayer extrusion casting machine, wherein an inorganic anti-sticking agent (silicon dioxide, the same applies below) is added into the upper surface layer extruder, and the weight ratio of the anti-sticking agent to the polypropylene composition pellets is 0.2:100. In the casting process, the casting chill roll temperature was set to 30 ℃, and wound up to produce a composite film consisting of an upper skin layer (film layer B) and a core layer (film layer a). The film thickness was 50 μm, with a thickness ratio of film layer B to film layer A of 1:2.
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 70nm and an average aspect ratio of 10.5.
Example 2
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
component a is propylene impact copolymer with the brand of M180R, which is purchased from Shanghai petrochemical industry, the ethylene content is 11wt%, the ethylene-propylene copolymerization part content is 15wt%, and the melt mass flow rate is 2.0g/10min; component b is a polyolefin elastomer, commercially available from Sanjing, as an ethylene-1-butene copolymer, having a butene structural unit content of 32% by weight, having a brand DF 640. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wa of the component a is 95 weight parts, and the weight part Wb of the component b is 5 weight parts. Adding lubricant (PEG lubricant manufactured by Swiss Corp., molecular weight 10000, and the addition amount of lubricant is 0.1 weight part based on 100 weight parts of the sum of the weight of the component a and the weight of the component b), adding the mixture into a high-speed stirrer, mixing uniformly, and adding the mixed material into W&In a feeder of a double-screw extruder manufactured by a company P, materials enter the double screws through the feeder, and are added The temperature of the screw is kept between 160 ℃ and 230 ℃ in the process, and the polypropylene composition A granules are obtained by the melt mixing, extrusion, granulation and drying of the screw, and the melt mass flow rate MFR is detected A ＝3.1g/10min。
(2) Preparation of polypropylene composition B:
the component x is random polypropylene with the brand of F500EPS, is purchased from Shanghai petrochemical industry, is an ethylene-propylene-butene terpolymer, and has a melt mass flow rate of 5.3g/10min; the component y is a polyolefin elastomer with the brand DF640, which is purchased from Sanjing corporation and is an ethylene-1-butene copolymer, and the butene structural unit content is 32 weight percent; the component z is propylene impact copolymer with the brand of M180R, which is purchased from Shanghai petrochemical industry, the ethylene content is 11wt%, the ethylene-propylene copolymerization part content is 15wt%, and the melt mass flow rate is 2.0g/10min; the component k is maleic anhydride modified polypropylene with the brand of CMG9801, and is purchased from Jiayi corporation. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wx of the component x is 60 weight parts, the weight part Wy of the component y is 20 weight parts, the weight part Wz of the component z is 10 weight parts, and the weight part Wk of the component k is 10 weight parts. Wb: wy is 1:4. Other steps are the same as in step (1), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝4.8g/10min。
(3) Preparation of a composite film:
drying the polypropylene composition A and the polypropylene composition B pellets obtained in the step (1) and the step (2), adding the polypropylene composition A into a core layer extruder of a multilayer extrusion casting machine, and adding the polypropylene composition B into an upper surface layer extruder and a lower surface layer extruder of the multilayer extrusion casting machine, wherein inorganic anti-sticking agents (silicon dioxide, the same applies below) are added into the upper surface layer extruder and the lower surface layer extruder, and the weight ratio of the anti-sticking agents to the polypropylene composition pellets is 0.2:100. In the casting process, the casting chill roll temperature was set to 30 ℃ and wound up to produce a composite film consisting of upper and lower skin layers (film layer B) and a core layer (film layer a). The film thickness was 50 μm, wherein the ratio of the sum of the upper and lower skin layers thickness to the core layer thickness was 1:1.
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 138nm and an average aspect ratio of 6.5.
Example 3
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
component a is homo-polypropylene with the brand of FC801, which is purchased from Shanghai petrochemical industry, the melt mass flow rate is 7.8g/10min, the isotacticity is 98%, and the molecular weight distribution Mw/Mn is 4.8; component b was a polyolefin elastomer having the trade designation EXACT3139, available from Exxon and was an ethylene-1-octene copolymer having an octene structural unit content of 14wt%. The components prepared above were weighed and mixed in a ratio in which the weight part Wa of component a was 85 parts by weight and the weight part Wb of component b was 15 parts by weight. Adding lubricant (PEG lubricant manufactured by Swiss Corp., molecular weight 10000, and the addition amount of lubricant is 0.1 weight part based on 100 weight parts of the sum of the weight of the component a and the weight of the component b), adding the mixture into a high-speed stirrer, mixing uniformly, and adding the mixed material into W &In a feeder of a double-screw extruder manufactured by P company, materials enter a double screw through the feeder, the temperature of the screw is kept between 160 ℃ and 230 ℃ in the processing process, and the materials are evenly mixed by melting the screw, extruded, granulated and dried to obtain polypropylene composition A granules, and the melt mass flow rate MFR of the polypropylene composition A granules is detected A ＝7.9g/10min。
(2) Preparation of polypropylene composition B:
the component x is random polypropylene with the brand of F800EPS, is purchased from Shanghai petrochemical industry, is an ethylene-propylene-butene terpolymer, and has a melt mass flow rate of 8.2g/10min; the component y is a polyolefin elastomer with the brand of EXACT3139, which is purchased from the Ekken company and is an ethylene-1-octene copolymer, and the content of octene structural units is 14wt%; the component z is propylene impact copolymer with the brand name of PPB-M02D, which is purchased from the luxuriant petrochemical industry, the ethylene content is 8wt%, the ethylene-propylene copolymerization part content is 10wt%, and the melt mass flow rate is 1.5g/10min;component k is a maleic anhydride modified polypropylene, commercially available from Exxon under the trade designation PO 1015. The components prepared above are weighed and mixed according to the proportion, wherein the weight part Wx of the component x is 85 weight parts, the weight part Wy of the component y is 5 weight parts, the weight part Wz of the component z is 5 weight parts, and the weight part Wk of the component k is 5 weight parts. Wb: wy is 3:1. Other steps are the same as in step (1), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝7.5g/10min。
(3) Preparation of a composite film:
the preparation procedure is the same as in step (3) of example 1.
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 75nm and an average aspect ratio of 13.6.
Example 4
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 95 parts by weight of Wa and the component b was 5 parts by weight of Wb. Wb: wy is 1:1. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.2g/10min。
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 126nm and an average aspect ratio of 7.1.
Example 5
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 90 parts by weight of Wa and the component b was 10 parts by weight of Wb. Wb: wy is 2:1. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.3g/10min。
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 52nm and an average aspect ratio of 11.4.
Example 6
A polypropylene composite film was prepared as in example 1. In polypropylene, differentlyIn the preparation of the composition A, the part by weight Wa of the component a was 75 parts by weight, and the part by weight Wb of the component b was 25 parts by weight. Wb: wy is 5:1. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.1g/10min。
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 62nm and an average aspect ratio of 13.5.
Example 7
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the procedure is as in example 1. Except that the part by weight Wa of the component a was 70 parts by weight and the part by weight Wb of the component b was 30 parts by weight. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of which was measured A ＝3.2g/10min。
(2) Preparation of polypropylene composition B:
the procedure is as in example 1. The difference is that the weight part Wx of the component x is 90 parts by weight, the weight part Wy of the component y is 5 parts by weight, the weight part Wz of the component z is 2.5 parts by weight, and the weight part Wk of the component k is 2.5 parts by weight. Wb: wy is 6:1. Other steps are the same as in step (1), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝8.3g/10min。
(3) Preparation of a composite film:
the procedure is as in example 1. The difference is that the film thickness is 50 μm, wherein the thickness ratio of film layer B and film layer A is 1:3.
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 89nm and an average aspect ratio of 11.3.
Example 8
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the procedure is as in example 3. The difference is that the weight part Wa of the component a is 75 weight percentThe weight portion Wb of the component b is 25 weight portions. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of which was measured A ＝9.3g/10min。
(2) Preparation of polypropylene composition B:
the procedure is as in example 3. The difference is that the part by weight Wx of the component x is 85 parts by weight, the part by weight Wy of the component y is 10 parts by weight, the part by weight Wz of the component z is 3 parts by weight, and the part by weight Wk of the component k is 2 parts by weight. Wb: wy is 5:2. Finally, pellets of the polypropylene composition B were obtained, the melt mass flow rate MFR of which was examined B ＝8.9g/10min。
(3) Preparation of a composite film:
the procedure is as in example 2. The difference is that the film thickness is 50 μm, wherein the ratio of the sum of the upper and lower skin layer thicknesses to the core layer thickness is 2:1.
Example 9
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the procedure is as in example 3. Except that the part by weight Wa of the component a was 100 parts by weight. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of which was measured A ＝7.8g/10min。
(2) Preparation of polypropylene composition B:
the procedure is as in example 3. The difference is that the part by weight Wx of the component x is 50 parts by weight, the part by weight Wy of the component y is 20 parts by weight, the part by weight Wz of the component z is 20 parts by weight, and the part by weight Wz of the component k is 10 parts by weight. Finally, pellets of the polypropylene composition B were obtained, the melt mass flow rate MFR of which was examined B ＝7.1g/10min。
(3) Preparation of a composite film:
the procedure is as in example 3. The difference is that the film thickness is 50 μm, with a ratio of upper skin layer thickness to core layer thickness of 1:4.
Example 10
This example is used to illustrate the preparation of the polypropylene composite film provided by the present invention.
(1) Preparation of polypropylene composition A:
the procedure is as in example 1. Except that the part by weight Wa of the component a was 100 parts by weight. To obtain pellets of the polypropylene composition A, the melt mass flow rate MFR of which was measured A ＝3.1g/10min。
(2) Preparation of polypropylene composition B:
The procedure is as in example 1. The difference is that the part by weight Wx of the component x is 50 parts by weight, the part by weight Wy of the component y is 20 parts by weight, the part by weight Wz of the component z is 20 parts by weight, and the part by weight Wk of the component k is 10 parts by weight. Other steps are the same as in step (1), and pellets of the polypropylene composition B are finally obtained, which are examined for melt mass flow rate MFR B ＝3.8g/10min。
(3) Preparation of a composite film:
the procedure is as in example 1. The difference is that the film thickness is 50 μm, wherein the thickness ratio of film layer B and film layer A is 1:3.
Example 11
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 100 parts by weight of Wa.
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 138nm and an average aspect ratio of 7.6.
Example 12
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 50 parts by weight of Wa and the component b was 50 parts by weight of Wb. Wb: wy is 10:1. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.5g/10min。
Example 13
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition B, the component x was 40 parts by weight, the component y was 30 parts by weight, the component z was 15 parts by weight, and the component k was 15 parts by weightParts by weight. Wb: wy is 2:3. To obtain pellets of the polypropylene composition B, the melt mass flow rate MFR of which was measured B ＝5.1g/10min。
Example 14
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition B, the component x was 50 parts by weight, the component y was 40 parts by weight, the component z was 5 parts by weight, and the component k was 5 parts by weight. Wb: wy is 1:2. To obtain pellets of the polypropylene composition B, the melt mass flow rate MFR of which was measured B ＝5.2g/10min。
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 186nm and an average aspect ratio of 5.5.
Example 15
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition B, the component x was 50 parts by weight, the component y was 10 parts by weight, the component z was 20 parts by weight, and the component k was 20 parts by weight. Wb: wy is 2:1. To obtain pellets of the polypropylene composition B, the melt mass flow rate MFR of which was measured B ＝5.6g/10min。
The composite film was observed under an atomic force microscope to see a rubber phase having an average width of 95nm and an average aspect ratio of 13.8.
Example 16
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 99 parts by weight of Wa and the component b was 1 part by weight of Wb. Wb: wy is 1:5. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.2g/10min。
Example 17
A polypropylene composite film was prepared as in example 1. In the preparation of the polypropylene composition A, the component a was 97.5 parts by weight of Wa and the component b wasThe number Wb is 2.5 parts by weight. Wb: wy is 1:2. Finally, pellets of the polypropylene composition A were obtained, the melt mass flow rate MFR of which was examined A ＝3.1g/10min。
Comparative example 1
A polypropylene composite film was prepared as in example 1. Except that the polypropylene composition A alone was extrusion-cast as a monolayer film having a film thickness of 50. Mu.m.
Comparative example 2
A polypropylene composite film was prepared as in example 2. Except that the polypropylene composition B alone was extrusion cast as a monolayer film having a film thickness of 50. Mu.m.
Comparative example 3
A polypropylene composite film was prepared as in example 1. The polypropylene composition B, however, only contains component x.
Comparative example 4
A polypropylene composite film was prepared as in example 1. The polypropylene composition B was different in that it contained only the component x and the component y, wherein the component x was 85 parts by weight of Wx and the component y was 15 parts by weight of Wy.
Comparative example 5
A polypropylene composite film was prepared as in example 2. The polypropylene composition B, however, contained only the component x and the component z, wherein the component x has a weight part Wx of 70 parts by weight and the component z has a weight part Wz of 30 parts by weight.
Comparative example 6
A polypropylene composite film was prepared as in example 2. The polypropylene composition B, however, contains only the component x and the component k, wherein the component x has a weight part Wx of 70 parts by weight and the component k has a weight part Wk of 30 parts by weight.
TABLE 1
As can be seen from the results of the examples in Table 1, the polypropylene composite film provided by the present invention has both good impact resistance and higher surface energy, and also has good heat seal strength. The film of the invention has a Machine Direction (MD) tensile strength of not less than 40MPa, a pendulum impact strength of not less than 0.55J, a surface energy of not less than 33mN/m, and a heat seal strength at 150 ℃ of not less than 12N/15mm. As can be seen from the preferred examples, the tensile strength in the Machine Direction (MD) of the film is not less than 52MPa, the pendulum impact strength is not less than 1.5J, the surface energy is not less than 34.5mN/m, and the heat seal strength at 150 ℃ is not less than 17N/15mm. As can be seen from the comparative examples, it is difficult to achieve a balance of various properties by using only a single film or a film having a uniform thickness due to the change in the composition ratio of the film layers, and the film surface is unstable during extrusion casting.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (18)
1. A high-adhesion high-impact polypropylene composite film, which is characterized in that the polypropylene composite film comprises at least one film layer A formed by a polypropylene composition A and at least one film layer B formed by a polypropylene composition B; wherein the polypropylene composition a comprises polypropylene a and optionally a polyolefin elastomer b; the polypropylene composition B comprises atactic polypropylene x, polyolefin elastomer y, propylene impact copolymer z and polar monomer modified polypropylene k.
2. The high adhesion high impact polypropylene composite film according to claim 1, wherein a rubber phase is present in the polypropylene composite film, the rubber phase having an average width of 20 to 200nm and an average aspect ratio of 5 to 20.
3. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 2, wherein the polypropylene composite film has at least one of the following characteristics: the longitudinal tensile strength is more than or equal to 40MPa, preferably more than or equal to 52MPa; the surface energy is more than or equal to 33mN/m, preferably more than or equal to 34.5mN/m; the impact strength of the pendulum bob is more than or equal to 0.55J, preferably the impact strength of the pendulum bob is more than or equal to 0.9J; the heat seal strength at 150 ℃ is more than or equal to 12N/15mm, and the heat seal strength at 150 ℃ is more than or equal to 17N/15mm.
4. A high adhesion high impact polypropylene composite film according to any one of claims 1 to 3, wherein the melt mass flow rate of the polypropylene composition a is 2-10g/10min, preferably 3-8g/10min, at 230 ℃ under a load of 2.16 kg; and/or
The melt mass flow rate of the polypropylene composition B is 3-10g/10min, preferably 4-8g/10min, at 230℃under a load of 2.16 kg.
5. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 4, wherein the polypropylene a is selected from homo-polypropylene and/or propylene impact copolymers;
Preferably, the melt mass flow rate of the homo-polypropylene under the load of 2.16kg at 230 ℃ is 2-15g/10min, the isotacticity is more than 97%, and the molecular weight distribution Mw/Mn is 4.5-7.0;
preferably, the propylene impact copolymer is a propylene impact copolymer containing ethylene units; the ethylene content of the propylene impact copolymer is 1 to 12wt% based on the total weight of the propylene impact copolymer; and/or the content of the copolymerization part containing ethylene units in the propylene impact copolymer is 3-15wt%; and/or the propylene impact copolymer has a melt mass flow rate of 1-10g/10min at 230 ℃, under a 2.16kg load.
6. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 5, wherein the propylene impact copolymer z is a propylene impact copolymer containing ethylene units; the ethylene content of the propylene impact copolymer z is 1 to 12wt% based on the total weight of the propylene impact copolymer z; and/or the number of the groups of groups,
the content of the copolymerization part containing ethylene units in the propylene impact copolymer z is 3-15wt%; and/or the number of the groups of groups,
the propylene impact copolymer z has a melt mass flow rate of 1-10g/10min at 230 ℃ under a 2.16kg load.
7. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 6 wherein the polyolefin elastomer b and the polyolefin elastomer y are each independently an elastomeric copolymer of ethylene and an alpha olefin, wherein the alpha olefin is preferably C 3 -C 12 More preferably at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
8. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 7, wherein the random polypropylene x is a copolymer of propylene with ethylene and/or butene, preferably at least one selected from the group consisting of ethylene-propylene-butene ternary random copolymer, propylene-ethylene binary random copolymer, propylene-butene binary random copolymer; and/or the melt mass flow rate of the atactic polypropylene x at 230 ℃ under a load of 2.16kg is 2-10g/10min.
9. The high-adhesion high-impact polypropylene composite film according to any one of claims 1 to 8, wherein the polar monomer in the polar monomer-modified polypropylene k is at least one selected from the group consisting of a hydroxyl-containing comonomer, a cyano-containing comonomer, and an acid anhydride monomer; the hydroxyl-containing comonomer is preferably a hydroxy acid and/or vinyl alcohol; the cyano-containing comonomer is preferably cyanoacrylate; the anhydride monomer is preferably maleic anhydride and/or itaconic anhydride.
10. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 9, wherein the polypropylene composition a comprises 50 to 100wt% of polypropylene a and 0 to 50wt% of polyolefin elastomer b based on the total weight of the polypropylene composition a; preferably, the polypropylene composition A comprises 75 to 95wt% of polypropylene a and 5 to 25wt% of polyolefin elastomer b.
11. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 10, wherein the polypropylene composition B comprises 30 to 90wt% of the random polypropylene x, 5 to 40wt% of the polyolefin elastomer y, 2.5 to 20wt% of the propylene impact copolymer z and 2.5 to 20wt% of the polar monomer modified polypropylene k, based on the total weight of the polypropylene composition B; preferably, the polypropylene composition B comprises 60 to 85wt% of random polypropylene x, 5 to 20wt% of polyolefin elastomer y, 5 to 10wt% of propylene impact copolymer z and 5 to 10wt% of polar monomer modified polypropylene k.
12. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 11, wherein the weight fraction of the polyolefin elastomer B is Wb based on 100 parts by weight of the total polypropylene composition a, the weight fraction of the polyolefin elastomer y is Wy based on 100 parts by weight of the total polypropylene composition B, and the ratio of Wb to Wy is 10:1 to 1:6, preferably 4:1 to 1:4.
13. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 12, wherein the ratio of the sum of the other film layer thicknesses to the film layer a thickness in the polypropylene composite film is 1:4 to 2:1, preferably 1:2 to 1:1.
14. The high-adhesion high-impact polypropylene composite film according to any one of claims 1 to 13, wherein when the polypropylene composite film has a three-layer structure or more, the film layer B is a skin layer.
15. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 14 wherein the polypropylene composition a and/or the polypropylene composition B further comprises an antioxidant and/or a lubricant;
preferably, the antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, antioxidant 168 and a thioester antioxidant;
preferably, the antioxidant is contained in an amount of 0.1 to 0.8 parts by weight, preferably 0.2 to 0.4 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B;
preferably, the lubricant is a PEG-based lubricant and/or a mono Gan Zhilei lubricant;
preferably, the lubricant is contained in an amount of 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
16. The high adhesion high impact polypropylene composite film according to any one of claims 1 to 15, wherein the polypropylene composition a and/or the polypropylene composition B further comprises a film forming aid, preferably at least one selected from the group consisting of halogen-resistant agents, light stabilizers, heat stabilizers, colorants, fillers, slip agents, anti-tackifiers and antistatic agents; more preferably, the content of the film forming aid is 0.01 to 0.5 parts by weight, preferably 0.05 to 0.3 parts by weight, based on 100 parts by weight of the total amount of the polypropylene composition a or the polypropylene composition B.
17. The method for producing a high-adhesion high-impact polypropylene composite film according to any one of claims 1 to 16, comprising: extruding and casting the raw material composition for forming each layer after an optional granulating process to form the composite film; optionally, the method further comprises stretching, preferably biaxially stretching, the resulting composite film.
18. Use of the high adhesion high impact polypropylene composite film according to any one of claims 1 to 16 in the field of packaging materials; the package is preferably a battery package, an electronic product package or a food package.
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