CN116714335A - Antistatic PE film suitable for powder product packaging and preparation method thereof - Google Patents
Antistatic PE film suitable for powder product packaging and preparation method thereof Download PDFInfo
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- CN116714335A CN116714335A CN202311004810.XA CN202311004810A CN116714335A CN 116714335 A CN116714335 A CN 116714335A CN 202311004810 A CN202311004810 A CN 202311004810A CN 116714335 A CN116714335 A CN 116714335A
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- 239000000843 powder Substances 0.000 title claims abstract description 39
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 113
- 229920000573 polyethylene Polymers 0.000 claims abstract description 101
- -1 polyethylene Polymers 0.000 claims abstract description 88
- 239000010410 layer Substances 0.000 claims description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 239000002041 carbon nanotube Substances 0.000 claims description 52
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 51
- 239000012793 heat-sealing layer Substances 0.000 claims description 40
- 239000012792 core layer Substances 0.000 claims description 39
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 29
- 239000002216 antistatic agent Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 21
- 238000010096 film blowing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 8
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 2
- RNHWYOLIEJIAMV-UHFFFAOYSA-N 1-chlorotetradecane Chemical compound CCCCCCCCCCCCCCCl RNHWYOLIEJIAMV-UHFFFAOYSA-N 0.000 claims description 2
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 19
- 238000007664 blowing Methods 0.000 description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012785 packaging film Substances 0.000 description 6
- 229920006280 packaging film Polymers 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of polyethylene films, and particularly discloses an antistatic PE film suitable for powder product packaging and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of polyethylene films, in particular to an antistatic PE film suitable for powder product packaging and a preparation method thereof.
Background
Polyethylene (PE) has rich resources, low price, excellent mechanical property and stability, and has wide application in the fields of packaging, films, wires and cables, and the like. In particular, in the packaging field, polyethylene has very high cost performance due to comprehensive reasons such as price, performance and the like, and the dosage of the polyethylene occupies the first time of a general plastic packaging material. The nonpolar and inert characteristics of polyethylene make the compatibility with other materials worse, and the molecule chain formed by covalent bonds is neither ionized nor hard to transfer free electrons, is easy to accumulate static electricity and is difficult to eliminate. The static electricity generated in the processing process of the polyethylene material brings a plurality of inconveniences to the processing of the packaging film, particularly when the polyethylene material is used as the packaging film of powder products, electric charges are generated by friction between the powder products and the polyethylene packaging film, the packaging film and powder are adhered, meanwhile, the self weight of the powder products is light, the particles are fine, when the polyethylene film is used as the packaging film for high-speed automatic packaging, the sealing is not tight due to the electrostatic attraction effect, the problems of air leakage, powder leakage and the like are caused, and the packaging film and materials are wasted.
Chinese patent CN103042796B discloses an antistatic polyethylene film and a method for preparing the same, which is produced by blowing film through co-extrusion process from an antistatic layer, an intermediate layer and a corona layer, wherein the antistatic layer is made of low density polyethylene, linear low density polyethylene and nano-scale SiO 2 The intermediate layer is low-density polyethylene, and the corona layer is a mixture of low-density polyethylene and linear low-density polyethylene. The novel antistatic polyethylene film is prepared by grafting the nanoscale silica in the polyolefin, the specific surface area of the surface of the film and the overall antistatic performance are improved, but the antistatic polyethylene film obtained by only adding the nanoscale silica has poor antistatic performance and poor dispersibility, and has a certain influence on the mechanical properties of the film.
Therefore, it is important to develop a polyethylene film having excellent mechanical properties and excellent antistatic properties.
Disclosure of Invention
In order to solve the technical problems, the invention provides an antistatic PE film suitable for packaging powder products and a preparation method thereof, and solves the problem that the PE film is easy to generate static electricity when packaging powder products.
In order to achieve the aim, the invention discloses an antistatic PE film suitable for packaging powder products, which consists of a three-layer coextrusion composite structure, wherein an antistatic electric heat sealing layer, a core layer and a corona layer are sequentially arranged from inside to outside; the interlayer thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40 percent to 30 percent; the antistatic electric heat seal layer comprises the following raw materials in parts by mass: 45-65 parts of high-pressure polyethylene, 24-35 parts of linear polyethylene, 12-20 parts of metallocene polyethylene, 2-3 parts of opening agent, 3-7 parts of carbon nano tube grafted antistatic agent and 0.1-0.3 part of antioxidant; the core layer comprises the following raw materials in parts by weight: 32-45 parts of linear polyethylene, 15-25 parts of metallocene polyethylene and 1-2 parts of coupling agent; the corona layer comprises the following raw materials in parts by mass: 55-68 parts of high-pressure polyethylene, 30-40 parts of linear polyethylene and 0.5-1 part of thickener.
Preferably, the opening agent comprises oleamide.
Preferably, the antioxidant comprises one of a phenolic antioxidant and a phosphite antioxidant.
Further, the phenolic antioxidant is antioxidant 1010.
Preferably, the coupling agent comprises one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
Further, the silane coupling agent includes a vinyl silane coupling agent.
Preferably, the thickener comprises methyl hydroxyethyl cellulose.
Preferably, the carbon nano tube grafted antistatic agent is prepared by the following steps:
uniformly stirring and mixing absolute ethyl alcohol, carbon nano tubes and gamma-methacryloxypropyl trimethoxy silane, heating for reaction, cooling, filtering, washing filter residues by using ethanol, and vacuum drying at 60 ℃ for 8 hours to obtain alkenyl modified carbon nano tubes;
step (2) dispersing alkenyl modified carbon nano tubes into deionized water by ultrasonic, after dispersing uniformly, adding dimethylaminoethyl methacrylate, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding an initiator to react, after the reaction is finished, carrying out suction filtration, washing by using absolute ethyl alcohol, and drying at 70 ℃ for 12 hours to obtain the carbon nano tube grafted dimethylaminoethyl methacrylate;
and (3) ultrasonically dispersing the carbon nano tube grafted polymethyl amino ethyl acrylate into isopropanol, uniformly mixing, adding long-chain chloralkane, reacting, performing rotary evaporation and recrystallization after the reaction is finished, and performing vacuum drying at 55 ℃ for 6 hours to obtain the carbon nano tube grafted antistatic agent.
Preferably, in the step (1), the raw materials in parts by weight are as follows: 3200-4000 parts of absolute ethyl alcohol, 100 parts of carbon nano tubes and 75-105 parts of gamma-methacryloxypropyl trimethoxy silane.
Preferably, the temperature of the reaction in the step (1) is 60-70 ℃ and the reaction time is 10-15h.
Preferably, in the step (2), the raw materials in parts by weight are as follows: 2400-3000 parts of deionized water, 25-40 parts of alkenyl modified carbon nano tubes, 100 parts of dimethylaminoethyl methacrylate and 2-5 parts of initiator.
Preferably, the temperature of the reaction in the step (2) is 55-60 ℃ and the reaction time is 4-6h.
Preferably, the initiator in the step (2) comprises one of benzoyl peroxide and ammonium persulfate.
Preferably, in the step (3), the raw materials in parts by weight are as follows: 100 parts of carbon nano tube grafted polymethyl methacrylate, 6200-8000 parts of isopropanol and 210-300 parts of long-chain chlorinated alkane.
Preferably, the long-chain chlorinated alkane in the step (3) comprises one of chlorododecane, chlorotetradecane and chlorohexadecane.
Preferably, the temperature of the reaction in the step (3) is 60-70 ℃ and the reaction time is 4-6h.
Preferably, the preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, uniformly mixing in a mixer, and then drying;
and secondly, heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder, extruding through three layers of co-extrusion blown films to obtain a film finished product, and carrying out traction, edge cutting and curling on the film finished product after cooling and forming to obtain the antistatic PE film suitable for packaging of powder products.
Preferably, in the second step, the melting temperature of the antistatic heat sealing layer is 125-135 ℃, the melting temperature of the core layer is 145-155 ℃, and the melting temperature of the corona layer is 135-145 ℃.
Preferably, the extrusion temperature of the three-layer co-extrusion blown film in the second step is 170-190 ℃, the blowing ratio in the film blowing process is 2-2.4, and the traction ratio is 4.5-5.5.
The invention uses high-pressure polyethylene, linear polyethylene, metallocene polyethylene, opening agent, carbon nanotube antistatic agent and antioxidant as raw materials of antistatic heat sealing layer, uses linear polyethylene, metallocene polyethylene and coupling agent as raw materials of core layer, uses high-pressure polyethylene, linear polyethylene and thickening agent as raw materials of corona layer, and uses three-layer co-extrusion blowing film to make antistatic heat sealing layer, core layer and corona layer into antistatic PE film suitable for packaging powder products.
Compared with the prior art, the invention has the beneficial effects that: the high-pressure polyethylene used in the antistatic layer is soft in material, good in processability, good in surface glossiness and good in low temperature resistance of the linear polyethylene, the compatibility among the high-pressure polyethylene, the linear polyethylene, the opening agent, the carbon nanotube grafted antistatic agent and the antioxidant can be improved by the aid of the added metallocene polyethylene, the added opening agent is used as a lubricant and an anti-blocking agent of the polyethylene, the dispersibility among raw materials is improved, and the prepared carbon nanotube grafted antistatic agent has excellent antistatic property and mechanical property and is uniformly dispersed in the antistatic layer, so that the comprehensive performance of a matrix is improved. The coupling agent is added in the mixing process of the linear polyethylene and the metallocene polyethylene, so that the acting force among the antistatic layer, the core layer and the corona layer is effectively improved, the thickening agent is added in the corona layer, the film forming property of the film is effectively improved, the flow is stable, the quality of the film surface is improved, and the damage in the use process is prevented. The PE film obtained after three-layer coextrusion can improve the overall mechanical property and the impact resistance of the film material.
According to the invention, the carbon nanotube grafted antistatic agent is prepared, the carbon nanotube has excellent conductivity, mechanical property, extensibility and high transmittance, the carbon nanotube is added into the PE film, higher transmittance can still be kept, carbon-carbon double bonds are introduced into the surface of the carbon nanotube, the introduced carbon-carbon double bonds and dimethylaminoethyl methacrylate are polymerized under the action of an initiator to obtain the carbon nanotube grafted dimethylaminoethyl methacrylate, the dimethylaminoethyl methacrylate can also effectively improve the antistatic property of a matrix, and the long-chain chlorinated alkane is subjected to quaternization reaction to obtain the carbon nanotube grafted antistatic agent, so that agglomeration of the carbon nanotube is effectively avoided, a conductive network passage is formed, the resistivity of an antistatic layer is effectively reduced, the excellent antistatic capability is endowed to the antistatic layer, hydrophilic units such as nitrogen, imine and the like on the surface of a quaternary ammonium salt introduced on the surface of the carbon nanotube can absorb moisture in the atmosphere, a layer of conductive network structure, namely a conductive film is formed on the surface of the material, the antistatic film is effectively prevented from being generated and accumulated, the antistatic capability of the matrix is further improved, the introduced diethylaminoethyl methacrylate and the polyethylene has the poor mechanical property, and the compatibility of the carbon nanotube is just improved, and the compatibility is also improved.
Drawings
FIG. 1 is a flow chart of the preparation of an antistatic PE film according to the invention.
FIG. 2 is a diagram showing a reaction mechanism for synthesizing an alkenyl-modified carbon nanotube in the present invention.
FIG. 3 is a drawing showing tensile strength test of samples 1 to 6 corresponding to examples 1 to 4 and comparative examples 1 to 2 in the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 45 parts of high-pressure polyethylene, 24 parts of linear polyethylene, 12 parts of metallocene polyethylene, 2 parts of opening agent oleamide, 3 parts of carbon nano tube grafted antistatic agent and 0.1 part of antioxidant 1010; the core layer comprises 32 parts of linear polyethylene, 15 parts of metallocene polyethylene and 1 part of coupling agent vinyl triethoxysilane; the corona layer comprises 55 parts of high-pressure polyethylene, 30 parts of linear polyethylene and 0.5 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder respectively, wherein the melting temperature of the antistatic heat sealing layer is 125 ℃, the melting temperature of the core layer is 145 ℃, the melting temperature of the corona layer is 135 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 170 ℃, the blowing ratio in the film blowing process is 2, and the traction ratio is 4.5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30%, and the antistatic PE film suitable for packaging of powder products is obtained.
Wherein the carbon nano tube grafted antistatic agent is prepared by the following steps:
the preparation method comprises the following steps of (1) uniformly stirring and mixing 3200 parts by mass of absolute ethyl alcohol, 100 parts by mass of carbon nano tubes and 75 parts by mass of gamma-methacryloxypropyl trimethoxy silane, heating and reacting at 60 ℃ for 15 hours, cooling, carrying out suction filtration, washing filter residues by using the ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 8 hours to obtain alkenyl modified carbon nano tubes;
ultrasonically dispersing 25 parts by mass of alkenyl modified carbon nano tubes into 2400 parts of deionized water, adding 100 parts of dimethylaminoethyl methacrylate after uniformly dispersing, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding 2 parts of initiator benzoyl peroxide, reacting at 55 ℃ for 6 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 70 ℃ for 12 hours to obtain the carbon nano tube grafted dimethylaminoethyl polymethacrylate;
and (3) ultrasonically dispersing 100 parts by mass of carbon nano tube grafted polymethyl methacrylate into 6200 parts of isopropanol, uniformly mixing, adding 210 parts of chlorohexadecane, reacting at 60 ℃ for 6 hours, performing rotary evaporation, recrystallizing, and performing vacuum drying at 55 ℃ for 6 hours to obtain the carbon nano tube grafted antistatic agent.
Example 2
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 55 parts of high-pressure polyethylene, 30 parts of linear polyethylene, 16 parts of metallocene polyethylene, 2.5 parts of opening agent oleamide, 4 parts of carbon nano tube grafted antistatic agent and 0.2 part of antioxidant 1010; 38 parts of linear polyethylene, 20 parts of metallocene polyethylene and 1.5 parts of coupling agent vinyl triethoxysilane; the corona layer comprises 60 parts of high-pressure polyethylene, 35 parts of linear polyethylene and 0.8 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder respectively, wherein the melting temperature of the antistatic heat sealing layer is 130 ℃, the melting temperature of the core layer is 150 ℃, the melting temperature of the corona layer is 140 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 180 ℃, the blowing ratio in the film blowing process is 2.2, and the traction ratio is 5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30%, and the antistatic PE film suitable for packaging of powder products is obtained.
Wherein the carbon nano tube grafted antistatic agent is prepared by the following steps:
uniformly stirring and mixing 3600 parts of absolute ethyl alcohol, 100 parts of carbon nano tubes and 90 parts of gamma-methacryloxypropyl trimethoxy silane, heating to react at 65 ℃ for 12 hours, cooling, carrying out suction filtration, washing filter residues by using ethanol, and carrying out vacuum drying at 60 ℃ for 8 hours to obtain alkenyl modified carbon nano tubes;
ultrasonically dispersing 32 parts by mass of alkenyl modified carbon nano tubes into 2700 parts of deionized water, adding 100 parts of dimethylaminoethyl methacrylate after uniform dispersion, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding 3 parts of initiator benzoyl peroxide, reacting at 58 ℃ for 5 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 70 ℃ for 12 hours to obtain the carbon nano tube grafted dimethylaminoethyl polymethacrylate;
and (3) ultrasonically dispersing 100 parts by mass of carbon nano tube grafted polymethyl methacrylate into 7200 parts by mass of isopropanol, uniformly mixing, adding 260 parts of chlorohexadecane, reacting for 5 hours at 65 ℃, performing rotary evaporation, recrystallizing, and drying in vacuum at 55 ℃ for 6 hours to obtain the carbon nano tube grafted antistatic agent.
Example 3
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 55 parts of high-pressure polyethylene, 30 parts of linear polyethylene, 16 parts of metallocene polyethylene, 2.5 parts of opening agent oleamide, 6 parts of carbon nanotube grafted antistatic agent and 0.2 part of antioxidant 1010; 38 parts of linear polyethylene, 20 parts of metallocene polyethylene and 1.5 parts of coupling agent vinyl triethoxysilane; the corona layer comprises 60 parts of high-pressure polyethylene, 35 parts of linear polyethylene and 0.8 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder respectively, wherein the melting temperature of the antistatic heat sealing layer is 130 ℃, the melting temperature of the core layer is 150 ℃, the melting temperature of the corona layer is 140 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 180 ℃, the blowing ratio in the film blowing process is 2.2, and the traction ratio is 5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30%, and the antistatic PE film suitable for packaging of powder products is obtained.
Wherein, the preparation method of the carbon nanotube grafted antistatic agent is the same as that of example 2.
Example 4
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 65 parts of high-pressure polyethylene, 35 parts of linear polyethylene, 20 parts of metallocene polyethylene, 3 parts of opening agent oleamide, 7 parts of carbon nano tube grafted antistatic agent and 0.3 part of antioxidant 1010; 45 parts of linear polyethylene, 25 parts of metallocene polyethylene and 2 parts of coupling agent vinyl triethoxysilane; the corona layer comprises 68 parts of high-pressure polyethylene, 40 parts of linear polyethylene and 1 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
and secondly, heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder, wherein the melting temperature of the antistatic heat sealing layer is 135 ℃, the melting temperature of the core layer is 155 ℃, the melting temperature of the corona layer is 145 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 190 ℃, the blowing ratio in the film blowing process is 2.4, and the traction ratio is 5.5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30% and 30%, so that the antistatic PE film suitable for packaging of powder products is obtained.
Wherein the carbon nano tube grafted antistatic agent is prepared by the following steps:
uniformly stirring and mixing 4000 parts of absolute ethyl alcohol, 100 parts of carbon nano tubes and 105 parts of gamma-methacryloxypropyl trimethoxy silane, heating to react at 70 ℃ for 10 hours, cooling after the reaction is finished, carrying out suction filtration, washing filter residues by using ethanol, and carrying out vacuum drying at 60 ℃ for 8 hours to obtain alkenyl modified carbon nano tubes;
ultrasonically dispersing 40 parts by mass of alkenyl modified carbon nano tubes into 3000 parts of deionized water, adding 100 parts of dimethylaminoethyl methacrylate after uniformly dispersing, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding 5 parts of initiator benzoyl peroxide, reacting at 60 ℃ for 4 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 70 ℃ for 12 hours to obtain the carbon nano tube grafted dimethylaminoethyl polymethacrylate;
and (3) ultrasonically dispersing 100 parts by mass of carbon nano tube grafted polymethyl methacrylate into 8000 parts of isopropanol, uniformly mixing, adding 300 parts of chlorohexadecane, reacting for 4 hours at 70 ℃, performing rotary evaporation, recrystallizing, and vacuum drying for 6 hours at 55 ℃ to obtain the carbon nano tube grafted antistatic agent.
Comparative example 1
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 55 parts of high-pressure polyethylene, 30 parts of linear polyethylene, 16 parts of metallocene polyethylene, 2.5 parts of opening agent oleamide, 6 parts of alkenyl modified carbon nano tube and 0.2 part of antioxidant 1010; 38 parts of linear polyethylene, 20 parts of metallocene polyethylene and 1.5 parts of coupling agent vinyl triethoxysilane; the corona layer comprises 60 parts of high-pressure polyethylene, 35 parts of linear polyethylene and 0.8 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder respectively, wherein the melting temperature of the antistatic heat sealing layer is 130 ℃, the melting temperature of the core layer is 150 ℃, the melting temperature of the corona layer is 140 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 180 ℃, the blowing ratio in the film blowing process is 2.2, and the traction ratio is 5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30%, and the antistatic PE film suitable for packaging of powder products is obtained.
Wherein, the alkenyl modified carbon nano tube is prepared by the following steps: and (3) uniformly stirring and mixing 3600 parts of absolute ethyl alcohol, 100 parts of carbon nano tubes and 90 parts of gamma-methacryloxypropyl trimethoxy silane, heating to react at 65 ℃ for 12 hours, cooling, filtering, washing filter residues by using ethanol, and vacuum drying at 60 ℃ for 8 hours to obtain the alkenyl modified carbon nano tubes.
Comparative example 2
The preparation method of the antistatic PE film suitable for powder product packaging comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, wherein the antistatic heat sealing layer comprises 55 parts of high-pressure polyethylene, 30 parts of linear polyethylene, 16 parts of metallocene polyethylene, 2.5 parts of opening agent oleamide, 6 parts of antistatic agent and 0.2 part of antioxidant 1010; 38 parts of linear polyethylene, 20 parts of metallocene polyethylene and 1.5 parts of coupling agent vinyl triethoxysilane; the corona layer comprises 60 parts of high-pressure polyethylene, 35 parts of linear polyethylene and 0.8 part of thickener methyl hydroxyethyl cellulose, and after weighing, the components are uniformly mixed in a mixer, and then drying treatment is carried out;
heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder respectively, wherein the melting temperature of the antistatic heat sealing layer is 130 ℃, the melting temperature of the core layer is 150 ℃, the melting temperature of the corona layer is 140 ℃, and preparing a film finished product through three-layer coextrusion film blowing extrusion, wherein the film finished product after cooling and forming is subjected to traction, edge cutting and curling, the three-layer coextrusion film blowing extrusion temperature is 180 ℃, the blowing ratio in the film blowing process is 2.2, and the traction ratio is 5, wherein the thickness ratio of the antistatic heat sealing layer, the core layer and the corona layer is 40%, 30%, and the antistatic PE film suitable for packaging of powder products is obtained.
Wherein the antistatic agent is prepared by the following steps:
neutralizing 2700 parts of deionized water with 100 parts of dimethylaminoethyl methacrylate, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding 3 parts of initiator benzoyl peroxide, reacting for 5 hours at 58 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the dimethylaminoethyl methacrylate;
and (2) ultrasonically dispersing 100 parts by mass of polymethyl methacrylate into 7200 parts by mass of isopropanol, uniformly mixing, adding 260 parts by mass of chlorohexadecane, reacting for 5 hours at 65 ℃, performing rotary evaporation, recrystallizing, and drying in vacuum at 55 ℃ for 6 hours to obtain the antistatic agent.
The high pressure polyethylene used in the above examples and comparative examples was linear Low Density Polyethylene (LDPE) available from TONGGUN, inc. under the designation 2426H; the linear polyethylene is Linear Low Density Polyethylene (LLDPE) purchased from Shanghai GanGanGanGanGanGanGanCo, inc., product number: px-21; metallocene polyethylene was purchased from Dongguan Ming Yuan Plastic Co., ltd., brand: ceramic, trade name NG5401B; carbon Nanotubes (CNTs) were purchased from Beijing, kyodo island gold technology Co., ltd, model number CNT204; other reagents are commercially available.
The antistatic PE films prepared in examples 1-4 and comparative examples 1-2 were used as samples for performance testing, the samples in examples 1-4 and comparative examples 1-2 were subjected to thickness measurement using the test standard of GB/T6672-2001 mechanical measurement for Plastic film and sheet thickness measurement, and 45 μm samples were selected and recorded as samples 1-6, respectively, for the related tests, as follows:
(1) Antistatic performance test: the antistatic performance of samples 1 to 6 is tested according to the test standard of GB/T1410-2006 solid insulation material volume resistivity and surface resistivity test method;
(2) Heat seal strength test: the heat sealing strength of samples 1 to 6 is tested by adopting the test standard of QB/T2358-98 heat sealing strength test method of plastic film packaging bag; each set of samples was tested three times and the specific test results are shown in table 1:
as can be seen from the test results in Table 1, the PE films corresponding to samples 1-4 have excellent antistatic performance, so that the problem of reduced heat sealing strength caused by the problem of electrostatic adsorption of powder products during sealing is effectively solved, and the obtained PE films have higher heat sealing strength. Wherein sample 3 corresponds to a surface resistance of 8.58×10 10 Ω/m 2 The heat sealing strength of the PE film corresponding to the sample 2 reaches 9.9N/15mm, the alkenyl modified carbon nano tube is added into the PE film corresponding to the sample 5, the subsequent modification is not performed, the antistatic agent is introduced, the surface resistance is improved to some extent, the heat sealing strength is poor, the carbon nano tube is not added into the PE film corresponding to the sample 6, the antistatic agent is added, the surface resistance is also improved to some extent, the heat sealing strength is poor, and the surface resistance corresponding to the sample 5 is 6.97X10 11 Ω/m 2 The heat seal strength was 7.9N/15mm, and the surface resistance corresponding to sample 6 was 6.30X10 11 Ω/m 2 The heat seal strength is 8.1N/15mm;
(3) Mechanical property test: determination of Plastic tensile Properties using GB/T1040.3-2006 section 3: the mechanical property test is carried out on the samples 1 to 6 according to the test standard of the test conditions of the films and the sheets; each set of samples was tested three times and the specific test results are shown in table 2:
as can be seen from the test results of Table 2, the PE films corresponding to samples 1 to 4 have excellent mechanical tensile properties, and the PE film corresponding to sample 4 has a transverse tensile property of 96.4MPa and a longitudinal tensile property of 59.3MPa. The carbon nano tube is modified in the sample 5 to obtain the alkenyl modified carbon nano tube which can be uniformly dispersed in a matrix, and the antistatic agent is not introduced into the surface, so that the mechanical property is improved, the carbon nano tube is not added in the sample 6, the tensile property is greatly reduced, the corresponding transverse tensile property in the sample 6 is 82.5MPa, and the longitudinal tensile property is 48.9MPa;
(4) Impact resistance test: the GB/T9639.1-2008 free dart method part 1 of the impact resistance test method of plastic films and sheets is adopted: the impact performance of the samples 1-6 is tested according to the test standard of the step method; each set of samples was tested three times and the specific test results are shown in table 3:
as can be seen from the test results of Table 3, the PE films corresponding to samples 1 to 4 have excellent impact resistance, the impact breakage quality corresponding to sample 3 is 713.4g, the alkyl long chain is not introduced into sample 5, the impact resistance is reduced, the carbon nano tube is not added into sample 6, and the impact resistance is also reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. An antistatic PE film suitable for powder product packaging, which is characterized in that: consists of a three-layer coextrusion composite structure, and comprises an antistatic electric heating sealing layer, a core layer and a corona layer from inside to outside in sequence; the antistatic electric heat seal layer comprises the following raw materials in parts by mass: 45-65 parts of high-pressure polyethylene, 24-35 parts of linear polyethylene, 12-20 parts of metallocene polyethylene, 2-3 parts of opening agent, 3-7 parts of carbon nano tube grafted antistatic agent and 0.1-0.3 part of antioxidant; the core layer comprises the following raw materials in parts by weight: 32-45 parts of linear polyethylene, 15-25 parts of metallocene polyethylene and 1-2 parts of coupling agent; the corona layer comprises the following raw materials in parts by mass: 55-68 parts of high-pressure polyethylene, 30-40 parts of linear polyethylene and 0.5-1 part of thickener.
2. An antistatic PE film suitable for packaging of powder products according to claim 1 characterized in that: the opening agent comprises oleamide.
3. An antistatic PE film suitable for packaging of powder products according to claim 1 characterized in that: the antioxidant comprises one of a phenolic antioxidant and a phosphite antioxidant.
4. An antistatic PE film suitable for packaging of powder products according to claim 1 characterized in that: the coupling agent comprises one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
5. An antistatic PE film suitable for packaging of powder products according to claim 1 characterized in that: the thickener comprises methyl hydroxyethyl cellulose.
6. An antistatic PE film suitable for packaging of powder products according to claim 1 characterized in that: the carbon nano tube grafted antistatic agent is prepared by the following steps:
uniformly stirring and mixing absolute ethyl alcohol, a carbon nano tube and gamma-methacryloxypropyl trimethoxy silane, heating for reaction, cooling, filtering, washing and drying after the reaction is finished to obtain an alkenyl modified carbon nano tube;
step (2) dispersing alkenyl modified carbon nano tubes into deionized water by ultrasonic, adding dimethylaminoethyl methacrylate after uniform dispersion, stirring and mixing, adding sodium hydroxide to adjust the pH to 5, adding an initiator, reacting, filtering, washing and drying after the reaction is finished to obtain the carbon nano tube grafted dimethylaminoethyl polymethacrylate;
and (3) ultrasonically dispersing the carbon nano tube grafted polymethyl amino ethyl acrylate into isopropanol, uniformly mixing, adding long-chain chloralkane, reacting, performing rotary evaporation, recrystallizing and vacuum drying to obtain the carbon nano tube grafted antistatic agent.
7. An antistatic PE film suitable for packaging of powder products according to claim 6 characterized in that: the long-chain chloralkane in the step (3) comprises one of chlorododecane, chlorotetradecane and chlorohexadecane.
8. A method for preparing an antistatic PE film suitable for packaging of powder products according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
weighing the raw materials of the antistatic heat sealing layer, the core layer and the corona layer according to the mass parts, uniformly mixing in a mixer, and then drying;
and secondly, heating and melting raw materials of the antistatic heat sealing layer, the core layer and the corona layer through an extruder, extruding through three layers of co-extrusion blown films to obtain a film finished product, and carrying out traction, edge cutting and curling on the film finished product after cooling and forming to obtain the antistatic PE film suitable for packaging of powder products.
9. The method for preparing the antistatic PE film suitable for packaging powder products according to claim 8, wherein the method comprises the following steps: the melting temperature of the antistatic heat sealing layer is 125-135 ℃, the melting temperature of the core layer is 145-155 ℃, and the melting temperature of the corona layer is 135-145 ℃.
10. The method for preparing the antistatic PE film suitable for packaging powder products according to claim 8, wherein the method comprises the following steps: the extrusion temperature of the three-layer co-extrusion film blowing is 170-190 ℃, and the inflation ratio in the film blowing process is 2-2.4; the traction ratio is 4.5-5.5.
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