CN118146608A - Modified PET (polyethylene terephthalate) base film with high puncture resistance and preparation method thereof - Google Patents
Modified PET (polyethylene terephthalate) base film with high puncture resistance and preparation method thereof Download PDFInfo
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- CN118146608A CN118146608A CN202410412197.3A CN202410412197A CN118146608A CN 118146608 A CN118146608 A CN 118146608A CN 202410412197 A CN202410412197 A CN 202410412197A CN 118146608 A CN118146608 A CN 118146608A
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 29
- -1 polyethylene terephthalate Polymers 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001125 extrusion Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 14
- 239000004417 polycarbonate Substances 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 229920002799 BoPET Polymers 0.000 claims description 63
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 25
- 230000005855 radiation Effects 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- 239000002131 composite material Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The scheme relates to a modified PET (polyethylene terephthalate) base film with high puncture resistance and a preparation method thereof, wherein a silane coupling agent is used for modifying the surface of graphene to obtain modified rGO, the modified rGO is grafted on the surface of the PET by an irradiation method, and the modified rGO is mixed with polycarbonate after grafting is finished, and then extrusion granulation, cast sheet forming, biaxial stretching and heat treatment are sequentially carried out, and the modified rGO is obtained through traction and rolling. According to the application, the conductive substance is polymerized and grafted on the PET surface, and the bonding is more stable through the connection of chemical bonds, so that the uniformity and consistency of the conductive property of the material are more excellent; the graft polymerization can also improve the mechanical strength of the material, improve the dielectric strength and have good breakdown resistance; when the metal layer is plated on the corona, the surface of the base film has conductivity, so that the binding force between the metal layer and the base film is effectively improved, and the problem of battery safety caused by possible falling of the metal layer is avoided.
Description
Technical Field
The invention relates to the technical field of organic polymer films, in particular to a modified PET (polyethylene terephthalate) base film with high puncture resistance and a preparation method thereof.
Background
The composite current collector is a novel material with a sandwich structure of a metal layer, an organic thin film layer and a metal layer formed by depositing the metal layer on the surface of an ultrathin organic high polymer film, and can be applied to a new energy lithium battery instead of the traditional negative metal current collector. The composite current collector has several advantages, the biggest advantage is that the consumption of metal materials is reduced, and the metal materials are replaced by partial cheap organic films, so that great potential for cost reduction exists; secondly, due to the use of organic materials in the composite current collector, the weight of the battery is reduced, the thickness of the battery is reduced, and the active materials are increased, so that the energy density of the battery is effectively increased by 5% -10%; in addition, the composite current collector can absorb expansion-contraction stress generated by the pole piece, maintain the long-term integrity of the pole piece interface, and improve the cycle life of the battery by 5%. The application of the composite current collector material can obviously reduce the occurrence probability of combustion caused by short circuit of the battery, and can effectively solve the problem of safety of the battery.
The main technical route of the composite current collector comprises a one-step method, a two-step method and a three-step method. The one-step method comprises the following steps: namely, chemical plating; the two-step method comprises the following steps: namely magnetron sputtering-water electroplating; the three-step method comprises the following steps: namely magnetron sputtering, evaporation plating and water electroplating. The vacuum magnetron sputtering technology is the core of the composite copper foil manufacturing process, has higher requirements on equipment and is a key for influencing the yield and the performance of products. The problems of foil perforation, poor copper film binding force, low production line efficiency and the like easily occur in the magnetron sputtering process. The base film used for the composite current collector is PP (polypropylene), PET (polyethylene terephthalate), PI (polyimide). The PET film is superior in temperature performance and mechanical stretching performance, while the PP film is thinner in material, has higher chemical stability and is beneficial to the improvement of battery energy density, so PP and PET are the most used base film materials at present.
PET is generally prepared by the transesterification of dimethyl terephthalate and ethylene glycol, belongs to crystalline saturated polyester, has excellent physical and mechanical properties in a wider temperature range, and has the advantages of fatigue resistance, friction resistance and the like. However, at the same time, the PET film is a polar polymer and has excellent electrical insulation properties. The conventional magnetron sputtering technology has low ion density and can not effectively activate the surface of the insulated PET film, so that the bonding force between the metal layer and the PET film is poor. The prior art CN116504992A prepares a conductive substrate, and effectively improves the binding force between the metal layer and the film layer. However, the direct addition of conductive particles to PET may result in non-uniform conductivity of the film, and may also result in perforation of the PET film during corona, which increases the safety risk of the battery.
Disclosure of Invention
Aiming at the defects in the prior art, the modification method of the PET film is provided, the PET film has higher puncture resistance, and meanwhile, the PET film has good bonding force between conductivity and a metal layer.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of a modified PET base film with high puncture resistance comprises the following steps:
s1, modifying the surface of graphene by using a silane coupling agent to obtain modified rGO;
s2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
s4, mixing the dried modified grafted PET film and polycarbonate, sequentially carrying out extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
Further, the preparation process of the modified rGO is as follows:
Taking graphene oxide rGO, ultrasonically dispersing the graphene oxide rGO in tetrahydrofuran, dissolving a silane coupling agent KH570 in absolute ethyl alcohol, then adding the solution into rGO dispersion liquid, continuing to ultrasonically stir the solution uniformly, heating the solution to 50 ℃ in an inert gas atmosphere, adding triethylamine, stirring the solution overnight, continuously heating the solution to 70 ℃ to reflux the solution for 2 hours, cooling the solution, centrifuging the solution, sequentially using absolute ethyl alcohol and water to clean the solution, and drying the solution to obtain modified rGO.
Further, the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 1-3:9-7; the mass ratio of the sum of the two to the PET film is 0.1-0.4:1.
Further, in the step S3, the irradiation source is a cobalt source, and the irradiation dose is 25kGy.
Further, the mass ratio of the modified grafted PET film to the polycarbonate is 100:2-10.
Further, in the step S4, the extrusion temperature is set to be 270-290 ℃, and the cooling temperature of the cast sheet is set to be 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
The invention further provides a modified PET base film with high puncture resistance, which is prepared by the preparation method.
Compared with the prior art, the application has the beneficial effects that: compared with the traditional mode of melt blending conductive particles and PET in a physical mode, the conductive material is polymerized and grafted on the surface of PET, and the conductive material is more firmly combined through the connection of chemical bonds, so that the uniformity and consistency of the conductive performance of the material are more excellent; the modified graphene and the p-styrenesulfonic acid are used as comonomers to be grafted and polymerized on the surface of the PET film, so that the mechanical strength of the material can be improved, and the modified PET film and the polycarbonate with good compatibility are mixed, extruded, granulated and cast into a sheet, so that a high-quality film material is obtained, the dielectric strength is improved, and the breakdown resistance is good; when the metal layer is plated on the corona, the surface of the base film has conductivity, so that the binding force between the metal layer and the base film is effectively improved, and the problem of battery safety caused by possible falling of the metal layer is avoided; the film has high strength and good conductivity, and avoids breakdown phenomenon caused by uneven current in the high-voltage and electron transmission process.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Examples: a preparation method of a modified PET base film with high puncture resistance comprises the following steps:
S1, preparing graphene oxide rGO by using a modified Hummers method, then dispersing the graphene oxide rGO in 100ml of tetrahydrofuran by using ultrasonic waves, dissolving 10 times of silane coupling agent KH570 in absolute ethyl alcohol, adding the solution into rGO dispersion, continuing to stir the solution uniformly by using ultrasonic waves, heating to 50 ℃ under an inert gas atmosphere, adding catalytic amount of triethylamine, stirring the solution overnight, continuing to heat the solution to 70 ℃ for refluxing for 2 hours, cooling the solution, centrifuging the solution, sequentially using absolute ethyl alcohol and water for cleaning, and drying the solution to obtain the modified rGO.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 1-3:9-7.
S3, cutting a PET film (the thickness is 25 mu m, the PET film is purchased from Shanghai Pont Kaiki Co., ltd.) into small squares (because the film material in the form of a sheet has larger contact area than resin particles and a polymerization monomer, the PET film is selected to be cut into pieces for reaction, the control variable can be calculated by cutting into uniform small squares in the small test stage, the control variable is cut into pieces in actual production), soaking the PET film in acetone for 1-2 hours, taking out and drying the PET film, then placing the PET film in a mixed solution in the step S2, introducing nitrogen to replace air in a system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; and (5) taking out the film after the irradiation is finished, extracting, and finally washing and drying the film to obtain the modified grafted PET film.
Graphene has excellent conductivity and lighter weight, graphene oxide prepared by a modified Hummers method is introduced with rich carboxyl, hydroxyl and epoxy functional groups on the surface of the graphene oxide, and GO is polymerizable after being treated by a silane coupling agent with double bonds. At present, gamma-rays are adopted to irradiate a PET film to carry out free radical polymerization on the surface of the PET film, the modified rGO is grafted and polymerized to the PET surface by the method, but rGO homopolymerization is difficult to carry out, so that the method tries to copolymerize a vinyl monomer and the modified rGO, and after multiple experiments, the method finds that the grafting rate of the modified rGO on the PET surface can be improved by the p-styrenesulfonic acid, and meanwhile, certain conductivity can be given to the material due to the resonance effect and the strong electron-withdrawing effect of the sulfonic acid group, and on the other hand, the benzene ring structure can improve the rigidity of the material, the mechanical property of the material and the breakdown preventing capability of the material.
S4, mixing the dried modified grafted PET film and polycarbonate according to the mass ratio of 100:2-10, sequentially carrying out extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film. The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
The polycarbonate selected in the application has better compatibility with PET, and the polycarbonate has the function of further enhancing the quality strength of the finally prepared PET film.
Example 1:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 2:8;
s3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, wherein the mass ratio of the sum of the modified rGO and the p-styrenesulfonic acid in the mixed solution to the PET film is 0.1:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
s4, mixing the dried modified grafted PET film and polycarbonate according to the mass ratio of 100:4, sequentially performing extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Example 2:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 2:8;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, wherein the mass ratio of the sum of the modified rGO and the p-styrenesulfonic acid in the mixed solution to the PET film is 0.2:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
S4, mixing the dried modified grafted PET film and polycarbonate according to the mass ratio of 100:6, sequentially performing extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Example 3:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 2:8;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, wherein the mass ratio of the sum of the modified rGO and the p-styrenesulfonic acid in the mixed solution to the PET film is 0.4:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
S4, mixing the dried modified grafted PET film and polycarbonate according to the mass ratio of 100:6, sequentially performing extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Example 4:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 3:7;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, wherein the mass ratio of the sum of the modified rGO and the p-styrenesulfonic acid in the mixed solution to the PET film is 0.4:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
S4, mixing the dried modified grafted PET film and polycarbonate according to the mass ratio of 100:8, sequentially performing extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Comparative example 1:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane;
s3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the dispersion liquid in the step S2, wherein the mass ratio of the modified rGO in the mixed liquid to the PET film is 0.4:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; and taking out the film after the irradiation is finished, observing turbidity in the system, and finding that the modified rGO cannot be successfully grafted to the PET surface after centrifugation.
And S4, sequentially carrying out extrusion granulation, cast sheet forming, biaxial stretching and heat treatment on the dried modified grafted PET film, and carrying out traction rolling to obtain the PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Comparative example 2:
s1, preparing the modified rGO according to the preparation process.
S2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution; the mass ratio of the modified rGO to the p-styrenesulfonic acid in the mixed solution is 2:8;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, wherein the mass ratio of the sum of the modified rGO and the p-styrenesulfonic acid in the mixed solution to the PET film is 0.2:1, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation (cobalt source, radiation dose is 25 kGy) under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
And S4, sequentially carrying out extrusion granulation, cast sheet forming, biaxial stretching and heat treatment on the dried modified grafted PET film, and carrying out traction rolling to obtain the PET film.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
Comparative example 3:
the modified rGO is prepared according to the preparation process;
Mixing the dried PET resin, the modified rGO, the p-styrenesulfonic acid and the polycarbonate according to the mass ratio of 100:2:8:2:4, sequentially carrying out extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the PET resin.
The extrusion temperature is set at 270-290 ℃, and the cooling temperature of the cast sheet is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
The PET composite films produced in examples 1 to 4 and comparative examples 1 to 3 were subjected to the relevant performance test.
The tensile strength and the elongation at break are tested on a universal tensile tester, the conductivity is tested by a four-probe tester, and the breakdown strength is tested by a breakdown voltage tester; the relevant test results are recorded in table 1.
TABLE 1
As can be seen from table 1, the composite film prepared by the chemical bonding method of the present application has higher electrical conductivity and breakdown strength than the final composite film prepared by directly mixing the modified graphene oxide with PET by physical mixing and extruding and granulating.
Copper plating treatment is carried out on the surface of the film by the mode of magnetron sputtering and water electroplating on the composite film, a sandwich composite current collector copper foil material of copper layer, composite film layer and copper layer is obtained, and relevant performance tests of current collector sheet resistance and adhesion force between the metal layer and the film are carried out, and the results are recorded in table 2.
TABLE 2
As shown in the table, the application can not only improve the conductivity of the material, but also improve the adhesive force between the metal layer and the composite film layer by grafting polymerization modification rGO and p-styrenesulfonic acid on the PET surface, and the composite film can be used as a current collector base film.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. The preparation method of the modified PET base film with high puncture resistance is characterized by comprising the following steps of:
s1, modifying the surface of graphene by using a silane coupling agent to obtain modified rGO;
s2, pre-dispersing the modified rGO in dichloromethane, and adding p-styrenesulfonic acid to obtain a mixed solution;
S3, cutting the PET film into small squares, soaking in acetone for 1-2 hours, taking out and drying, then placing in the mixed solution in the step S2, introducing nitrogen to replace air in the system, and then placing the mixed system in a radiation field for radiation under the nitrogen atmosphere; taking out the film after irradiation is finished, extracting, and finally washing and drying the film to obtain a modified grafted PET film;
s4, mixing the dried modified grafted PET film and polycarbonate, sequentially carrying out extrusion granulation, cast sheet molding, biaxial stretching and heat treatment, and carrying out traction rolling to obtain the modified grafted PET film.
2. The method for preparing a modified PET base film with high puncture resistance according to claim 1, wherein the preparation process of the modified rGO is as follows:
Taking graphene oxide rGO, ultrasonically dispersing the graphene oxide rGO in tetrahydrofuran, dissolving a silane coupling agent KH570 in absolute ethyl alcohol, then adding the solution into rGO dispersion liquid, continuing to ultrasonically stir the solution uniformly, heating the solution to 50 ℃ in an inert gas atmosphere, adding triethylamine, stirring the solution overnight, continuously heating the solution to 70 ℃ to reflux the solution for 2 hours, cooling the solution, centrifuging the solution, sequentially using absolute ethyl alcohol and water to clean the solution, and drying the solution to obtain modified rGO.
3. The method for producing a modified PET base film with high puncture resistance according to claim 1, wherein the mass ratio of modified rGO to p-styrenesulfonic acid in the mixed solution is 1-3:9-7; the mass ratio of the sum of the two to the PET film is 0.1-0.4:1.
4. The method for producing a modified PET base film having high puncture resistance according to claim 1, wherein in the step S3, the irradiation source is a cobalt source and the irradiation dose is 25kGy.
5. The method for producing a modified PET base film having high puncture resistance according to claim 1, wherein the mass ratio of the modified graft PET film to the polycarbonate is 100:2-10.
6. The method for producing a modified PET base film having high puncture resistance according to claim 1, wherein in S4, the extrusion temperature is set at 270 to 290 ℃ and the cast sheet cooling temperature is set at 15 ℃; the biaxial stretching condition is that the material is firstly stretched in the longitudinal direction by 4 times at 90-120 ℃ and then cooled to 50 ℃, and then stretched in the transverse direction by 3 times at 110-120 ℃.
7. A modified PET base film having high puncture resistance produced by the production method according to any one of claims 1 to 6.
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