CN114957846A - Fresh-keeping breathing film with double anti-fog performance and preparation method thereof - Google Patents
Fresh-keeping breathing film with double anti-fog performance and preparation method thereof Download PDFInfo
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- CN114957846A CN114957846A CN202210605621.7A CN202210605621A CN114957846A CN 114957846 A CN114957846 A CN 114957846A CN 202210605621 A CN202210605621 A CN 202210605621A CN 114957846 A CN114957846 A CN 114957846A
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- 230000029058 respiratory gaseous exchange Effects 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 76
- JUUBCHWRXWPFFH-UHFFFAOYSA-N Hydroxytyrosol Chemical compound OCCC1=CC=C(O)C(O)=C1 JUUBCHWRXWPFFH-UHFFFAOYSA-N 0.000 claims abstract description 62
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 50
- 239000000661 sodium alginate Substances 0.000 claims abstract description 50
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 50
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims abstract description 47
- 235000011071 sorbitan monopalmitate Nutrition 0.000 claims abstract description 47
- 239000001570 sorbitan monopalmitate Substances 0.000 claims abstract description 47
- 229940031953 sorbitan monopalmitate Drugs 0.000 claims abstract description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 45
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 41
- 229940095066 hydroxytyrosol Drugs 0.000 claims abstract description 31
- 235000003248 hydroxytyrosol Nutrition 0.000 claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 239000002216 antistatic agent Substances 0.000 claims abstract description 23
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 23
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 19
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 19
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 19
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 238000004080 punching Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 229920001661 Chitosan Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 10
- 238000000071 blow moulding Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 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
- 230000000694 effects Effects 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 235000012055 fruits and vegetables Nutrition 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000241 respiratory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004099 anaerobic respiration Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
- B23K26/382—Removing material by boring or cutting by boring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/40—Removing material taking account of the properties of the material involved
- B23K26/402—Removing material taking account of the properties of the material involved involving non-metallic material, e.g. isolators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- 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
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Abstract
The invention discloses a fresh-keeping breathing film with double anti-fog performance and a preparation method thereof. The fresh-keeping breathing film with double anti-fog performance is prepared by adopting low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, an antioxidant, an antistatic agent and modified porous silicon dioxide grafted with sorbitan monopalmitate and punching holes on the breathing film by using a carbon dioxide laser and the preparation method thereof. The modified porous silica grafted with the sorbitan monopalmitate is added with sodium alginate grafted with hydroxytyrosol and loaded on the porous silica nanoparticles, so that the antibacterial property and the antifogging property of the fresh-keeping breathing film are improved.
Description
Technical Field
The invention relates to the technical field of fresh-keeping breathing films, in particular to a fresh-keeping breathing film with double anti-fog performance and a preparation method thereof.
Background
The polyethylene plastic wrap is widely applied to the field of fruit and vegetable preservation. The polyethylene preservative film has the functions of ventilation and moisture preservation, reduces the loss of water of fruits and vegetables, keeps the appearance of products, and simultaneously protects the fruits and vegetables from being polluted. However, the traditional preservative film can not make different preservation processes according to different types of fruits and vegetables and can achieve the cold and hot anti-fog effects. The antifogging property of the preservative film is poor, the transparency of the film is influenced, and the propagation and growth of microorganisms are accelerated due to water drop aggregation, so that bacteria are bred, and the rot of fruits and vegetables is caused.
In order to solve the problems, the application provides a fresh-keeping breathing film with double anti-fog performance and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a fresh-keeping breathing film with double anti-fog performance and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a fresh-keeping breathing film with double anti-fog performance comprises the following components: according to weight, 15-25 parts of low-density polyethylene, 20-50 parts of linear low-density polyethylene, 20-50 parts of high-density polyethylene, 0.2-0.8 part of slipping agent, 1-15 parts of antioxidant, 1-5 parts of antistatic agent and 0.5-15 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Preferably, the fresh-keeping breathing film comprises the following components: according to weight, 18-22 parts of low density polyethylene, 35-45 parts of linear low density polyethylene, 35-45 parts of high density polyethylene, 0.4-0.6 part of slipping agent, 2-15 parts of antioxidant, 1-3 parts of antistatic agent and 5-15 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Preferably, the antioxidant is an antioxidant 1010; the slipping agent is one or more of calcium stearate and oleamide; the antistatic agent is an antistatic agent SWJU-1.
Preferably, the main components of the modified porous silica grafted with the sorbitan monopalmitate are sodium alginate grafted with hydroxytyrosol, a chitosan solution, porous silica nanoparticles and sorbitan monopalmitate.
A preparation method of a fresh-keeping breathing film with double anti-fog performance comprises the following steps:
the method comprises the following steps: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, an antioxidant, an antistatic agent and modified porous silicon dioxide grafted with sorbitan monopalmitate, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane;
step two: and punching a hole on the breathing film by using a carbon dioxide laser, and placing the product at a positive focus to obtain the fresh-keeping breathing film with double anti-fog properties.
Preferably, the preparation method of the modified porous silica grafted with sorbitan monopalmitate comprises the following steps: the method comprises the following steps:
s1: adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 5-6h to obtain a sodium alginate composite solution;
s2: taking the porous silicon dioxide nano particle and sodium alginate composite solution, stirring for 24-28h, centrifuging, washing, and freeze-drying to obtain modified porous silicon dioxide;
s3: heating and melting sorbitan monopalmitate at 70-80 ℃, adding modified porous silica and azodiisobutyronitrile, reacting for 7-8h under the protection of nitrogen, washing, and drying to obtain the modified porous silica grafted with sorbitan monopalmitate.
Preferably, in S1, the preparation method of the sodium alginate grafted with hydroxytyrosol comprises the following steps: taking sodium alginate and acetic acid, stirring uniformly, adding hydroxytyrosol, stirring at 85-90 deg.C for 11-13h, and standing to obtain sodium alginate grafted with hydroxytyrosol.
Preferably, in S2, the preparation method of the porous silica nanoparticles comprises: tetraethyl orthosilicate and cyclohexane are taken and uniformly stirred to obtain tetraethyl orthosilicate solution; taking water, cetyl trimethyl ammonium chloride solution and triethanolamine, and stirring at 55-65 deg.C for 40-70 min; adding tetraethyl orthosilicate solution, continuing to react for 10-11h at the temperature of 55-65 ℃ for 1-2h, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Preferably, in the second step, the carbon dioxide laser is a pulse laser, the pulse energy of the laser is 0.8-1J, the number of pulses is 3/s, the pulse width is 1-1.1ms, and the repetition frequency is 30-40 Hz.
Compared with the prior art, the invention has the following beneficial effects:
(1) the sodium alginate has the advantages of biodegradability and good biocompatibility, the structure of the sodium alginate contains C-2, C-3 hydroxyl and C-6 carboxyl reaction active sites, wherein the hydroxyl is a hydrophilic group and is added into the fresh-keeping breathing film, so that the hydrophilicity of the fresh-keeping breathing film is greatly enhanced, water drops easily slide off and cannot stay on the surface of the breathing film, and a good anti-fogging effect is achieved.
The hydroxytyrosol is a natural polyphenol compound and has a strong antibacterial effect, and hydroxyl groups on the hydroxytyrosol can be subjected to esterification reaction with carboxyl groups on sodium alginate and combined together, so that the antibacterial performance of the preservative breathing film is endowed.
(2) The porous silica nano particles are added, so that the specific surface area is enlarged, and more sodium alginate grafted with hydroxytyrosol and more sorbitan monopalmitate can be grafted; meanwhile, chitosan is added, so that the antibacterial property and the hydrophilicity of the fresh-keeping breathing film are enhanced.
(4) The sorbitan monopalmitate contains three hydroxyl groups and one carbonyl group; has strong hydrophilicity, and is a substance with antifogging effect. The modified porous silica grafted with the sorbitan monopalmitate is bonded to polyethylene, so that migration of the sorbitan monopalmitate is inhibited, precipitation of the sorbitan monopalmitate is delayed, and the anti-fog effect of the fresh-keeping breathing film is prolonged.
(5) The carbon dioxide laser is used for punching holes on the breathing membrane, the product is placed at the positive focus, and when the focal distance is located at the positive focus, the light spot is minimum, so that the punched holes are minimum. By utilizing the laser drilling technology, air holes which cannot be identified by naked eyes are formed on the film, and the minimum aperture can be more than or equal to 30 mu m. Different fresh-keeping processes can be made according to different types of fruits and vegetables, and cold and hot antifogging effects are achieved. The gas permeability of film can effectively be improved to tiny bleeder vent, can strengthen the inside and outside gas exchange of bag, keep the concentration of certain proportion oxygen and carbon dioxide, prevent that oxygen from being low excessively leading to fruit vegetables anaerobic respiration, produce volatile substance accumulation such as a large amount of ethanol and acetaldehyde and influence product quality, and can also reduce the humidity in the bag, reduce volatile metabolite's accumulation, there are higher gas permeability and high vapor, but can not see through liquid water, prevented that carbon dioxide from excessively playing good effect, simultaneously to carbon dioxide, oxygen carries out two-way regulating power, can slow down fruit vegetables respiratory intensity, it is ageing to delay fruit vegetables, thereby it runs off to reduce the water powder and reaches the effect of extension shelf life.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: preparing a sodium alginate composite solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring at 57 ℃ for 35min to obtain a chitosan solution; taking 3g of sodium alginate and 100mL of acetic acid, uniformly stirring, adding 7.5g of hydroxytyrosol, stirring for 12h at 87 ℃, and standing to obtain the sodium alginate grafted with hydroxytyrosol; adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 5.5h to obtain a sodium alginate composite solution.
Step two: preparing porous silica nanoparticles: taking 5g of tetraethyl orthosilicate and 20mL of cyclohexane, and uniformly stirring to obtain a tetraethyl orthosilicate solution; taking 40mL of water, 25mL of hexadecyltrimethylammonium chloride solution and 0.2g of triethanolamine, and stirring at 60 ℃ for 55 min; adding tetraethyl orthosilicate solution, continuing to react for 10.5h at the temperature of 60 ℃, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Step three: preparation of modified porous silica: and (3) taking 5g of porous silicon dioxide nano particles and 40mL of sodium alginate composite solution, stirring for 26h, centrifuging, washing, and freeze-drying to obtain the modified porous silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate to melt at 70-80 ℃, adding 3g of modified porous silica and 0.3g of azobisisobutyronitrile, reacting for 7.5h under the protection of nitrogen, washing, and drying to obtain the modified porous silica grafted with sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified porous silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, the low-density polyethylene comprises 20 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 40 parts of high-density polyethylene, 0.5 part of slipping agent, 10 parts of antioxidant, 2 parts of antistatic agent and 10 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Example 2
The method comprises the following steps: preparing a sodium alginate composite solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring for 30min at 55 ℃ to obtain a chitosan solution; taking 3g of sodium alginate and 100mL of acetic acid, uniformly stirring, adding 7.5g of hydroxytyrosol, stirring for 11 hours at 85 ℃, and standing to obtain the sodium alginate grafted with hydroxytyrosol; adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 5 hours to obtain a sodium alginate composite solution.
Step two: preparing porous silica nanoparticles: taking 5g of tetraethyl orthosilicate and 20mL of cyclohexane, and uniformly stirring to obtain a tetraethyl orthosilicate solution; taking 40mL of water, 25mL of hexadecyltrimethylammonium chloride solution and 0.2g of triethanolamine, and stirring at 55 ℃ for 40 min; adding tetraethyl orthosilicate solution, continuing to react for 10h at the temperature of 55 ℃ for 1h, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Step three: preparation of modified porous silica: and (3) taking 5g of porous silicon dioxide nano particles and 40mL of sodium alginate composite solution, stirring for 24h, centrifuging, washing, and freeze-drying to obtain the modified porous silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate at 70 ℃ for melting, adding 3g of modified porous silica and 0.3g of azobisisobutyronitrile, reacting for 7 hours under the protection of nitrogen, washing and drying to obtain the modified porous silica grafted with sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified porous silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, 18 parts of low-density polyethylene, 35 parts of linear low-density polyethylene, 35 parts of high-density polyethylene, 0.4 part of slipping agent, 2 parts of antioxidant, 1 part of antistatic agent and 5 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Example 3
The method comprises the following steps: preparing a sodium alginate composite solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring for 40min at 60 ℃ to obtain a chitosan solution; taking 3g of sodium alginate and 100mL of acetic acid, uniformly stirring, adding 7.5g of hydroxytyrosol, stirring for 13h at 90 ℃, and standing to obtain the sodium alginate grafted with hydroxytyrosol; adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 6 hours to obtain a sodium alginate composite solution.
Step two: preparing porous silica nanoparticles: taking 5g of tetraethyl orthosilicate and 20mL of cyclohexane, and uniformly stirring to obtain a tetraethyl orthosilicate solution; taking 40mL of water, 25mL of hexadecyltrimethylammonium chloride solution and 0.2g of triethanolamine, and stirring at 65 ℃ for 70 min; adding tetraethyl orthosilicate solution, continuing to react for 11h at 65 ℃ for 2h, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Step three: preparation of modified porous silica: and (3) taking 5g of porous silicon dioxide nano particles and 40mL of sodium alginate composite solution, stirring for 28h, centrifuging, washing, and freeze-drying to obtain the modified porous silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate to melt at 80 ℃, adding 3g of modified porous silica and 0.3g of azobisisobutyronitrile, reacting for 8 hours under the protection of nitrogen, washing and drying to obtain the modified porous silica grafted with the sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified porous silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, 22 parts of low-density polyethylene, 45 parts of linear low-density polyethylene, 45 parts of high-density polyethylene, 0.4-0.6 part of slipping agent, 15 parts of antioxidant, 3 parts of antistatic agent and 15 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Example 4: the procedure of example 1 was repeated except that hydroxytyrosol was not added.
The method comprises the following steps: preparing a sodium alginate composite solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring for 35min at 57 ℃ to obtain a chitosan solution; and 3g of sodium alginate and 100mL of acetic acid are taken, stirred uniformly, added with the chitosan solution and stirred for 5.5 hours to obtain the sodium alginate composite solution.
Step two: preparing porous silica nanoparticles: 5g of tetraethyl orthosilicate and 20mL of cyclohexane are uniformly stirred to obtain a tetraethyl orthosilicate solution; taking 40mL of water, 25mL of hexadecyltrimethylammonium chloride solution and 0.2g of triethanolamine, and stirring at 60 ℃ for 55 min; adding tetraethyl orthosilicate solution, continuing to react for 10.5h at 60 ℃, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Step three: preparation of modified porous silica: and (3) taking 5g of porous silicon dioxide nano particles and 40mL of sodium alginate composite solution, stirring for 26h, centrifuging, washing, and freeze-drying to obtain the modified porous silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate to melt at 70-80 ℃, adding 3g of modified porous silica and 0.3g of azobisisobutyronitrile, reacting for 7.5h under the protection of nitrogen, washing, and drying to obtain the modified porous silica grafted with sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified porous silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, the low-density polyethylene comprises 20 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 40 parts of high-density polyethylene, 0.5 part of slipping agent, 10 parts of antioxidant, 2 parts of antistatic agent and 10 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Example 5: the same procedure as in example 1 was repeated except that sodium alginate grafted with hydroxytyrosol was not added.
The method comprises the following steps: preparation of chitosan solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring for 35min at 57 ℃ to obtain a chitosan solution.
Step two: preparing porous silica nanoparticles: taking 5g of tetraethyl orthosilicate and 20mL of cyclohexane, and uniformly stirring to obtain a tetraethyl orthosilicate solution; taking 40mL of water, 25mL of hexadecyltrimethylammonium chloride solution and 0.2g of triethanolamine, and stirring at 60 ℃ for 55 min; adding tetraethyl orthosilicate solution, continuing to react for 10.5h at the temperature of 60 ℃, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
Step three: preparation of modified porous silica: and taking 5g of porous silicon dioxide nano particles and chitosan solution, stirring for 26 hours, centrifuging, washing, and freeze-drying to obtain the modified porous silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate to melt at 70-80 ℃, adding 3g of modified porous silica and 0.3g of azobisisobutyronitrile, reacting for 7.5h under the protection of nitrogen, washing, and drying to obtain the modified porous silica grafted with sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified porous silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, the low-density polyethylene comprises 20 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 40 parts of high-density polyethylene, 0.5 part of slipping agent, 10 parts of antioxidant, 2 parts of antistatic agent and 10 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
Example 6: the porous silica nanoparticles were not added, and the rest was the same as in example 1.
The method comprises the following steps: preparing a sodium alginate composite solution: taking 2g of chitosan and 100mL of acetic acid solution, and stirring at 57 ℃ for 35min to obtain a chitosan solution; taking 3g of sodium alginate and 100mL of acetic acid, uniformly stirring, adding 7.5g of hydroxytyrosol, stirring for 12h at 87 ℃, and standing to obtain the sodium alginate grafted with hydroxytyrosol; adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 5.5h to obtain a sodium alginate composite solution.
Step two: preparing nano silicon dioxide: stirring 1.2gKH570, 15mL of absolute ethyl alcohol and 3mL of acetic acid for 50-70min to obtain KH570 solution; taking 5g of nano silicon dioxide, 100mL of deionized water and 300mL of absolute ethyl alcohol, carrying out ultrasonic dispersion for 2-3h, adding KH570 solution, stirring for 3-5h at 70-80 ℃, centrifuging, and drying to obtain the nano silicon dioxide.
Step three: preparation of modified silica: and taking 5g of nano silicon dioxide and 40mL of sodium alginate composite solution, stirring for 26h, centrifuging, washing, and freeze-drying to obtain the modified silicon dioxide.
Step four: heating 20g of sorbitan monopalmitate to melt at 70-80 ℃, adding 3g of modified silicon dioxide and 0.3g of azobisisobutyronitrile, reacting for 7.5h under the protection of nitrogen, washing, and drying to obtain the modified silicon dioxide grafted with sorbitan monopalmitate.
Step five: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, modified silicon dioxide grafted with sorbitan monopalmitate, an antioxidant 1010 and an antistatic agent, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane; the carbon dioxide laser is utilized to punch holes on the breathing film, so that the fresh-keeping breathing film with double anti-fog performance is obtained.
The fresh-keeping breathing film comprises the following components: according to the weight, the low-density polyethylene comprises 20 parts of low-density polyethylene, 40 parts of linear low-density polyethylene, 40 parts of high-density polyethylene, 0.5 part of slipping agent, 10 parts of antioxidant, 2 parts of antistatic agent and 10 parts of modified silicon dioxide grafted with sorbitan monopalmitate.
Experiment of
The fresh keeping breathing films prepared in examples 1 to 6 were subjected to performance tests. Taking a beaker filled with 350mL of pure water at the ambient temperature of-5 ℃, cutting the fresh-keeping breathing film into square pieces of 15cm multiplied by 15cm, sealing the beaker by the fresh-keeping breathing film, placing the beaker in a constant-temperature water bath kettle at the temperature of 20 ℃, inclining the beaker at 20 degrees, observing the fogging condition of the surface of the fresh-keeping breathing film within 20min, and testing the antifogging performance of the film. The concentration of the adopted bacterial liquid is 5 multiplied by 10 8 Of Cfu/mlAnd (2) cutting the preservative breathing film into 7mm round pieces, uniformly coating 50 mu of bacterial suspension on a culture medium, placing the cut preservative breathing film on the culture medium, culturing for 20 hours at 38 ℃, measuring the size of a bacteriostatic zone, and testing the antibacterial performance of the preservative breathing film. The data obtained are shown in the following table:
and (4) conclusion: as can be seen from the data in the table, the antibacterial performance is reduced to some extent when no hydroxytyrosol is added in example 4, and the antibacterial and antifogging performances are reduced when no sodium alginate grafted with hydroxytyrosol is added in example 5; example 6 the addition of porous silica nanoparticles is omitted, the specific surface area is reduced, and the loaded sodium alginate and chitosan grafted with hydroxytyrosol are reduced, which affects the antifogging and antibacterial properties of the fresh-keeping respiratory membrane.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The utility model provides a plastic wrap with two antifog properties which characterized in that: the fresh-keeping breathing film comprises the following components: according to weight, 15-25 parts of low-density polyethylene, 20-50 parts of linear low-density polyethylene, 20-50 parts of high-density polyethylene, 0.2-0.8 part of slipping agent, 1-15 parts of antioxidant, 1-5 parts of antistatic agent and 0.5-15 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
2. The fresh-keeping breathing film with double anti-fog performance as claimed in claim 1, wherein: the fresh-keeping breathing film comprises the following components: according to weight, 18-22 parts of low-density polyethylene, 35-45 parts of linear low-density polyethylene, 35-45 parts of high-density polyethylene, 0.4-0.6 part of slipping agent, 2-15 parts of antioxidant, 1-3 parts of antistatic agent and 5-15 parts of modified porous silicon dioxide grafted with sorbitan monopalmitate.
3. The fresh-keeping breathing film with double anti-fog performance as claimed in claim 1, wherein: the antioxidant is 1010; the slipping agent is one or more of calcium stearate and oleamide; the antistatic agent is an antistatic agent SWJU-1.
4. The fresh-keeping breathing film with double anti-fog performance as claimed in claim 1, wherein: the modified porous silica grafted with the sorbitan monopalmitate mainly comprises sodium alginate grafted with hydroxytyrosol, a chitosan solution, porous silica nanoparticles and sorbitan monopalmitate.
5. A preparation method of a fresh-keeping breathing film with double anti-fog performance is characterized in that: the method comprises the following steps:
the method comprises the following steps: taking low-density polyethylene, linear low-density polyethylene, high-density polyethylene, a slipping agent, an antioxidant, an antistatic agent and modified porous silicon dioxide grafted with sorbitan monopalmitate, uniformly mixing, plasticizing, extruding, blow molding, cooling, drawing and rolling to prepare the breathing membrane;
step two: and punching a hole on the breathing film by using a carbon dioxide laser, and placing the product at a positive focus to obtain the fresh-keeping breathing film with double anti-fog properties.
6. The method for preparing the fresh-keeping breathing film with double anti-fog performance as claimed in claim 5, wherein the method comprises the following steps: the preparation method of the modified porous silicon dioxide of the grafted sorbitan monopalmitate comprises the following steps: the method comprises the following steps:
s1: adding a chitosan solution into the sodium alginate grafted with hydroxytyrosol, and stirring for 5-6h to obtain a sodium alginate composite solution;
s2: taking the porous silicon dioxide nano particle and sodium alginate composite solution, stirring for 24-28h, centrifuging, washing, and freeze-drying to obtain modified porous silicon dioxide;
s3: heating and melting sorbitan monopalmitate at 70-80 ℃, adding modified porous silicon dioxide and azobisisobutyronitrile, reacting for 7-8h under the protection of nitrogen, washing, and drying to obtain the modified porous silicon dioxide grafted with sorbitan monopalmitate.
7. The method for preparing the fresh-keeping breathing film with double anti-fog performance as claimed in claim 6, wherein the method comprises the following steps: in S1, the preparation method of the sodium alginate grafted with hydroxytyrosol comprises the following steps: taking sodium alginate and acetic acid, stirring uniformly, adding hydroxytyrosol, stirring at 85-90 deg.C for 11-13h, and standing to obtain sodium alginate grafted with hydroxytyrosol.
8. The method for preparing the fresh-keeping breathing film with double anti-fog performance as claimed in claim 6, wherein the method comprises the following steps: in S2, the preparation method of the porous silica nanoparticles comprises: tetraethyl orthosilicate and cyclohexane are taken and uniformly stirred to obtain tetraethyl orthosilicate solution; taking water, cetyl trimethyl ammonium chloride solution and triethanolamine, and stirring at 55-65 deg.C for 40-70 min; adding tetraethyl orthosilicate solution, continuing to react for 10-11h at the temperature of 55-65 ℃ for 1-2h, taking a water phase, centrifuging, extracting, washing and drying in vacuum to obtain the porous silicon dioxide nano particles.
9. The method for preparing the fresh-keeping breathing film with double anti-fog performance as claimed in claim 5, wherein the method comprises the following steps: in the second step, the carbon dioxide laser is a pulse laser; the pulse energy of the laser is 0.8-1J, the number of pulses is 3/s, the pulse width is 1-1.1ms, and the repetition frequency is 30-40 Hz.
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