CN114957857A - High-toughness BOPP film and manufacturing method thereof - Google Patents
High-toughness BOPP film and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of BOPP films and discloses a high-toughness BOPP film and a manufacturing method thereof, wherein the high-toughness BOPP film comprises the following raw materials in parts by weight: 100 portions of polypropylene, 60 portions to 80 portions of polystyrene, 15 portions to 25 portions of inorganic filler, 3 portions to 5 portions of nano titanium dioxide, 12 portions to 16 portions of metallocene ethylene-hexene copolymer, 17 portions to 27 portions of nano silicon dioxide, 1 portion to 3 portions of light stabilizer, 4 portions to 6 portions of toughener, 1 portion to 3 portions of hydroxyl of 1, 7-heptanediol, 8 portions to 12 portions of compatilizer, 2 portions to 4 portions of toluene, 3 portions to 9 portions of nucleating agent, 1 portion to 3 portions of silane coupling agent, 1 portion to 3 portions of dispersant, 2 portions to 4 portions of maleic anhydride, 0.8 portion to 1.2 portions of light stabilizer, 0.3 portion to 0.4 portion of flame retardant and 0.4 portion to 0.8 portion of antioxidant, the high-toughness BOPP film and the manufacturing method thereof utilize spheres to impact, grind and stir nano powder, and break the agglomeration of nano materials, the compatibility of the inorganic filler and the polyamic acid resin is improved, and the doping amount of the inorganic filler in the film is improved, so that the toughness and the strength of the film are further improved.
Description
Technical Field
The invention relates to the technical field of BOPP films, in particular to a high-toughness BOPP film and a manufacturing method thereof.
Background
BOPP films are biaxially oriented polypropylene films. BOPP films are produced by first passing a melt of high molecular polypropylene through a long and narrow head to form a sheet or thick film, then stretching the film in two perpendicular directions (longitudinal and transverse) simultaneously or stepwise at a certain temperature and a set speed in a special stretching machine, and subjecting the film to appropriate cooling or heat treatment or special processing (e.g. corona, coating, etc.). The BOPP film is colorless, odorless, tasteless and nontoxic, and has high tensile strength, impact strength, rigidity, toughness and good transparency.
Chinese patent CN03129378.6 provides a method for preparing reinforced and toughened polypropylene material, wherein a dynamic curing method is applied to a polypropylene/epoxy resin system, i.e. when the epoxy resin and polypropylene are melt blended, a curing reaction occurs, the polypropylene resin, a maleic anhydride grafted elastomer, the epoxy resin and a curing agent are sequentially added into an internal mixer, an open mill or a screw extruder at a certain blending temperature for mixing, the epoxy resin is cured in situ and dispersed into micron-sized particles under the action of high shear force, and the micron-sized particles are uniformly distributed in the polypropylene, so that the rigidity and modulus of the polypropylene are improved, and the elastomer in the system plays a role of increasing the volume on one hand and a role of toughening the polypropylene on the other hand.
The strength and toughness are two most important mechanical property indexes of the polypropylene film, and researches show that the rubber can effectively toughen but can cause great reduction of strength and rigidity, and the inorganic particles can effectively strengthen but can cause obvious reduction of impact toughness. This is because the inorganic particles are located at positions to be broken during the breaking process, resulting in a great decrease in the performance of the mechanical system. It can also be seen that the reinforcing effect is lost if the forces between the inorganic rigid particles and the polymer are so strong that no elastic transition zone can be formed between the inorganic rigid particles and the polymer.
Therefore, how to overcome the above-mentioned defects, obtain high-strength and high-toughness PP, and realize simultaneous toughening and reinforcement is a big problem troubling researchers, and is also an important development direction of materials.
Disclosure of Invention
Technical scheme
The invention provides the following technical scheme: a high-toughness BOPP film and a manufacturing method thereof comprise the following raw materials in parts by weight: 100 portions of polypropylene, 60 to 80 portions of polystyrene, 15 to 25 portions of inorganic filler, 3 to 5 portions of nano titanium dioxide, 12 to 16 portions of metallocene ethylene-hexene copolymer, 17 to 27 portions of nano silicon dioxide, 1 to 3 portions of light stabilizer, 4 to 6 portions of toughener, 1 to 3 portions of hydroxyl of 1, 7-heptanediol, 8 to 12 portions of compatilizer, 2 to 4 portions of toluene, 3 to 9 portions of nucleating agent, 1 to 3 portions of silane coupling agent, 1 to 3 portions of dispersant, 2 to 4 portions of maleic anhydride, 0.8 to 1.2 portions of light stabilizer, 0.3 to 0.4 portion of flame retardant and 0.4 to 0.8 portion of antioxidant.
Preferably, the dispersing agent is one or a mixture of polyethylene low molecular wax and stearate.
Preferably, the inorganic filler is at least one of alumina and silica, and is subjected to low-temperature plasma treatment for 20-40 min.
Preferably, the antioxidant is one of antioxidant 1010 and antioxidant PS 802.
Preferably, the toughening agent is carboxylated nitrile rubber, and the compatilizer is maleic anhydride grafted compatilizer
Preferably, the flame retardant is one or a mixture of more than two of tetrafluoro butyl sulfonate, organic hypophosphite, inorganic hypophosphite, organic phosphonate and organic silicon.
A high-toughness BOPP film and a manufacturing method thereof comprise the following steps:
s1, introducing nitrogen into a flask containing hydroxyl of 1, 7-heptanediol and the toughening agent to 0.8MPa at 200 ℃, reacting for 30-40min, adding toluene, stirring at the speed of 50r/min, and cooling to room temperature after 10min to obtain a new toughening agent;
s2, adding inorganic filler, nano-dioxide, nano-silica and maleic anhydride into a ball mill, and grinding for 1h at the rotating speed of 4500-;
s3, adding toughening agent, the material A and the rest material into a double-screw extruder, and performing melt extrusion at the temperature of 300-340 ℃ to obtain a material B;
and S4, adding the material B into an extruder, and performing extrusion forming to obtain the high-toughness BOPP film.
Preferably, the film thickness of the high-toughness BOPP film is controlled to be 80-100 mu m.
Advantageous effects
Compared with the prior art, the invention provides the high-toughness BOPP film and the manufacturing method thereof, and the high-toughness BOPP film has the following beneficial effects:
1. according to the high-toughness BOPP film and the manufacturing method thereof, the metallocene ethylene-hexene copolymer and the polyolefin elastomer are used for modifying polypropylene, so that the high toughness and high impact resistance of the film are improved, and the polypropylene is grafted by polar Maleic Anhydride (MAH) so that a proper polar branched chain is introduced into a macromolecular main chain, so that the compatibility of the film and a nanometer example is improved, and the toughness and the strength of the film are improved.
2. According to the high-toughness BOPP film and the manufacturing method thereof, the nano material is treated by low-temperature plasma to promote the surface of the nano material to further generate new active free radicals, the interaction between the nano particles and polypropylene is increased, the dispersion effect of the nano particles in the BOPP film is improved, the inorganic filler and the low-viscosity prepolymer are mixed by high-speed dispersion and ball milling, and in the ball milling process, the ball body is used for impacting, grinding and stirring nano powder, so that the agglomeration of the nano material is broken, the compatibility of the inorganic filler and polyamide acid resin is improved, the doping amount of the inorganic filler in the film is improved, and the toughness and the strength of the film are further improved.
3. The carboxyl of the toughening agent and the hydroxyl of the 1, 7-heptanediol are subjected to esterification reaction under the catalysis of a catalyst and then subjected to polycondensation reaction to finally prepare the novel toughening agent of the polymer, wherein the side chain of the novel toughening agent is provided with a plurality of ether bonds, the novel toughening agent can be well compatible with polypropylene resin, the softness of the film can be improved, and the novel toughening agent has good thermal stability, meanwhile, the prepared polymer is a benzene ring connected with an ester group, the ester group is connected with seven carbon atoms, wherein the benzene ring is conjugated with the ester group to form a rigid structure, the seven carbon atoms connected with the ester group are odd numbers, the seven carbon atoms and the benzene ring are not on the same plane according to the odd carbon effect, so that the polymer chains are arranged in a spiral shape, when external force is applied, the polymer molecular chains can be unfolded, but because the integral molecular configuration of the polymer is not changed, the original state can be recovered, so that the toughness of the plastic is improved, and finally, the polypropylene film with high toughness and good mechanical property and strength are obtained.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a high-toughness BOPP film and a manufacturing method thereof comprise the following raw materials in parts by weight: 100 parts of polypropylene, 60 parts of polystyrene, 15 parts of inorganic filler, 3 parts of nano titanium dioxide, 12 parts of metallocene ethylene-hexene copolymer, 17 parts of nano silicon dioxide, 1 part of light stabilizer, 4 parts of toughening agent, 1 part of hydroxyl of 1, 7-heptanediol, 8 parts of compatilizer, 2 parts of toluene, 3 parts of nucleating agent, 1 part of silane coupling agent, 1 part of dispersing agent, 2 parts of maleic anhydride, 0.8 part of light stabilizer, 0.3 part of flame retardant and 0.4 part of antioxidant.
Preferably, the dispersing agent is one or a mixture of polyethylene low molecular wax and stearate.
Preferably, the inorganic filler is at least one of alumina and silica, and is subjected to low-temperature plasma treatment for 20 min.
Preferably, the antioxidant is one of antioxidant 1010 and antioxidant PS 802.
Preferably, the toughening agent is carboxylated nitrile rubber, and the compatilizer is maleic anhydride grafted compatilizer
Preferably, the flame retardant is one or a mixture of more than two of tetrafluoro butyl sulfonate, organic hypophosphite, inorganic hypophosphite, organic phosphonate and organic silicon.
A high-toughness BOPP film and a manufacturing method thereof comprise the following steps:
s1, introducing nitrogen into a flask containing hydroxyl of 1, 7-heptanediol and the toughening agent to 0.8MPa at 200 ℃, reacting for 30min, adding toluene, stirring at the speed of 50r/min, and cooling to room temperature after 10min to obtain a new toughening agent;
s2, adding inorganic filler, nano-dioxide, nano-silica and maleic anhydride into a ball mill, and grinding for 1h at the rotating speed of 4500r/min to obtain a material A;
s3, adding the toughening agent, the material A and the rest material into a double-screw extruder, and performing melt extrusion at 300 ℃ to obtain a material B;
and S4, adding the material B into an extruder, and performing extrusion forming to obtain the high-toughness BOPP film.
Further, the film thickness of the high-toughness BOPP film is controlled to be 80 mu m
Example two:
a high-toughness BOPP film and a manufacturing method thereof comprise the following raw materials in parts by weight: 130 parts of polypropylene, 70 parts of polystyrene, 20 parts of inorganic filler, 4 parts of nano titanium dioxide, 14 parts of metallocene ethylene-hexene copolymer, 22 parts of nano silicon dioxide, 2 parts of light stabilizer, 5 parts of toughening agent, 2 parts of hydroxyl of 1, 7-heptanediol, 10 parts of compatilizer, 3 parts of toluene, 6 parts of nucleating agent, 2 parts of silane coupling agent, 2 parts of dispersing agent, 3 parts of maleic anhydride, 0.9 part of light stabilizer, 0.35 part of flame retardant and 0.6 part of antioxidant.
Preferably, the dispersing agent is one or a mixture of polyethylene low molecular wax and stearate.
Preferably, the inorganic filler is at least one of alumina and silica, and is subjected to low-temperature plasma treatment for 30 min.
Preferably, the antioxidant is one of antioxidant 1010 and antioxidant PS 802.
Preferably, the toughening agent is carboxylated nitrile rubber, and the compatilizer is maleic anhydride grafted compatilizer
Preferably, the flame retardant is one or a mixture of more than two of tetrafluoro butyl sulfonate, organic hypophosphite, inorganic hypophosphite, organic phosphonate and organic silicon.
A high-toughness BOPP film and a manufacturing method thereof comprise the following steps:
s1, introducing nitrogen into a flask containing hydroxyl of 1, 7-heptanediol and the toughening agent to 0.8MPa at 200 ℃, reacting for 35min, adding toluene, stirring at the speed of 50r/min, and cooling to room temperature after 10min to obtain a new toughening agent;
s2, adding inorganic filler, nano-dioxide, nano-silica and maleic anhydride into a ball mill, and grinding at a rotating speed of 4800r/min for 1h to obtain a material A;
s3, adding the toughening agent, the material A and the rest material into a double-screw extruder, and performing melt extrusion at 320 ℃ to obtain a material B;
and S4, adding the material B into an extruder, and performing extrusion forming to obtain the high-toughness BOPP film.
Further, the film thickness of the high-toughness BOPP film is controlled to be 90 mu m
Example three:
a high-toughness BOPP film and a manufacturing method thereof comprise the following raw materials in parts by weight: 160 parts of polypropylene, 80 parts of polystyrene, 25 parts of inorganic filler, 5 parts of nano titanium dioxide, 16 parts of metallocene ethylene-hexene copolymer, 27 parts of nano silicon dioxide, 3 parts of light stabilizer, 6 parts of toughening agent, 3 parts of hydroxyl of 1, 7-heptanediol, 12 parts of compatilizer, 4 parts of toluene, 9 parts of nucleating agent, 3 parts of silane coupling agent, 3 parts of dispersing agent, 4 parts of maleic anhydride, 1.2 parts of light stabilizer, 0.4 part of flame retardant and 0.8 part of antioxidant.
Preferably, the dispersing agent is one or a mixture of polyethylene low molecular wax and stearate.
Preferably, the inorganic filler is at least one of alumina and silica, and is subjected to low-temperature plasma treatment for 20-40 min.
Preferably, the antioxidant is one of antioxidant 1010 and antioxidant PS 802.
Preferably, the toughening agent is carboxylated nitrile rubber, and the compatilizer is maleic anhydride grafted compatilizer
Preferably, the flame retardant is one or a mixture of more than two of tetrafluoro butyl sulfonate, organic hypophosphite, inorganic hypophosphite, organic phosphonate and organic silicon.
A high-toughness BOPP film and a manufacturing method thereof comprise the following steps:
s1, introducing nitrogen into a flask containing hydroxyl of 1, 7-heptanediol and the toughening agent to 0.8MPa at 200 ℃, reacting for 40min, adding toluene, stirring at the speed of 50r/min, and cooling to room temperature after 10min to obtain a new toughening agent;
s2, adding inorganic filler, nano-dioxide, nano-silica and maleic anhydride into a ball mill, and grinding at a rotation speed of 5000r/min for 1h to obtain a material A;
s3, adding the toughening agent, the material A and the rest material into a double-screw extruder, and performing melt extrusion at 340 ℃ to obtain a material B;
and S4, adding the material B into an extruder, and performing extrusion forming to obtain the high-toughness BOPP film.
Further, the film thickness of the high-toughness BOPP film is controlled to be 100 mu m
And (4) judging the standard:
the invention has the beneficial effects that: 1. according to the high-toughness BOPP film and the manufacturing method thereof, the metallocene ethylene-hexene copolymer and the polyolefin elastomer are used for modifying polypropylene, so that the high toughness and high impact resistance of the film are improved, and the polypropylene is grafted by polar Maleic Anhydride (MAH) so that a proper polar branched chain is introduced into a macromolecular main chain, so that the compatibility of the film and a nanometer example is improved, and the toughness of the film is improved.
2. The high-toughness BOPP film and the manufacturing method thereof are characterized in that a nano material is treated by low-temperature plasma to promote the surface of the nano material to further generate new active free radicals, the interaction between nano particles and polypropylene is increased, the dispersion effect of the nano particles in the BOPP film is improved, inorganic filler and low-viscosity prepolymer are mixed by high-speed dispersion and ball milling, and in the ball milling process, a sphere is used for impacting, grinding and stirring nano powder to break the agglomeration of the nano material, improve the compatibility of the inorganic filler and polyamide acid resin, and improve the doping amount of the inorganic filler in the film, so that the toughness of the film is improved
3. The carboxyl of the toughening agent and the hydroxyl of the 1, 7-heptanediol are subjected to esterification reaction under the catalysis of a catalyst and then subjected to polycondensation reaction to finally prepare the novel toughening agent of the polymer, wherein the side chain of the novel toughening agent is provided with a plurality of ether bonds, the novel toughening agent can be well compatible with polypropylene resin, the softness of the film can be improved, and the novel toughening agent has good thermal stability, meanwhile, the prepared polymer is a benzene ring connected with an ester group, the ester group is connected with seven carbon atoms, wherein the benzene ring is conjugated with the ester group to form a rigid structure, the seven carbon atoms connected with the ester group are odd numbers, the seven carbon atoms and the benzene ring are not on the same plane according to the odd carbon effect, so that the polymer chains are arranged in a spiral shape, when external force is applied, the polymer molecular chains can be unfolded, but because the integral molecular configuration of the polymer is not changed, the original state can be recovered, so that the toughness of the plastic is improved, and the polypropylene film with high toughness and good mechanical property is finally obtained.
Experimental example: the high-toughness BOPP films prepared in the examples 1 to 3 and the common BOPP film are selected for detection
And (4) judging the standard: the mechanical properties of the obtained material were tested according to GB standard, and the flame retardant properties were tested according to UL-94 standard, with the test results shown in the following table
In summary, compared with the traditional BOPP film, the BOPP film manufactured by the high-toughness BOPP film and the manufacturing method thereof has better tensile strength and bending strength, exercise elongation at the bottom of intersection and better flame retardant property.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The high-toughness BOPP film is characterized by comprising the following raw materials in parts by weight: 100 portions of polypropylene, 60 to 80 portions of polystyrene, 15 to 25 portions of inorganic filler, 3 to 5 portions of nano titanium dioxide, 12 to 16 portions of metallocene ethylene-hexene copolymer, 17 to 27 portions of nano silicon dioxide, 1 to 3 portions of light stabilizer, 4 to 6 portions of toughener, 1 to 3 portions of hydroxyl of 1, 7-heptanediol, 8 to 12 portions of compatilizer, 2 to 4 portions of toluene, 3 to 9 portions of nucleating agent, 1 to 3 portions of silane coupling agent, 1 to 3 portions of dispersant, 2 to 4 portions of maleic anhydride, 0.8 to 1.2 portions of light stabilizer, 0.3 to 0.4 portion of flame retardant and 0.4 to 0.8 portion of antioxidant.
2. The high-toughness BOPP film and the manufacturing method thereof according to claim 1, wherein the dispersant is one or a mixture of polyethylene low-molecular wax and stearate.
3. The high-toughness BOPP film and the manufacturing method thereof according to claim 2, wherein the inorganic filler is at least one of alumina and silica, and is subjected to low-temperature plasma treatment for 20-40 min.
4. The high-toughness BOPP film and the manufacturing method thereof according to claim 3, wherein the antioxidant is one of antioxidant 1010 and antioxidant PS 802.
5. The high-toughness BOPP film and the manufacturing method thereof according to claim 4, wherein the toughening agent is carboxylated nitrile rubber, and the compatilizer is maleic anhydride grafted compatilizer.
6. The high-toughness BOPP film and the manufacturing method thereof according to claim 5, wherein the flame retardant is one or a mixture of two or more of tetrafluorobutyl sulfonate, organic hypophosphite, inorganic phosphonate and organic silicon.
7. The high toughness BOPP film and the manufacturing method thereof according to claim 6, wherein the method comprises the following steps:
s1, introducing nitrogen into a flask containing hydroxyl of 1, 7-heptanediol and the toughening agent to 0.8MPa at 200 ℃, reacting for 30-40min, adding toluene, stirring at the speed of 50r/min, and cooling to room temperature after 10min to obtain a new toughening agent;
s2, adding inorganic filler, nano-dioxide, nano-silica and maleic anhydride into a ball mill, and grinding for 1h at the rotating speed of 4500-;
s3, adding toughening agent, the material A and the rest material into a double-screw extruder, and performing melt extrusion at the temperature of 300-340 ℃ to obtain a material B;
and S4, adding the material B into an extruder, and carrying out extrusion forming to obtain the high-toughness BOPP film.
8. The high toughness BOPP film and the manufacturing method thereof according to claim 7, wherein the film thickness of the high toughness BOPP film is controlled to be 80-100 μm.
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| CN116253984A (en) * | 2022-09-09 | 2023-06-13 | 深圳市金露兴科技有限公司 | Sealing strip and production process thereof |
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