CN115384153A - Composite film capable of being repeatedly heat-sealed and preparation method thereof - Google Patents
Composite film capable of being repeatedly heat-sealed and preparation method thereof Download PDFInfo
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- CN115384153A CN115384153A CN202210871538.4A CN202210871538A CN115384153A CN 115384153 A CN115384153 A CN 115384153A CN 202210871538 A CN202210871538 A CN 202210871538A CN 115384153 A CN115384153 A CN 115384153A
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 48
- -1 polyethylene Polymers 0.000 claims abstract description 44
- 229920000573 polyethylene Polymers 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002799 BoPET Polymers 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 14
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 66
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 34
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 32
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011246 composite particle Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 11
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229940078494 nickel acetate Drugs 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000071 blow moulding Methods 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 2
- 239000012793 heat-sealing layer Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a composite film capable of being repeatedly heat-sealed and a preparation method thereof, wherein the heat-sealed composite film is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressing film, the PET film and the aluminum foil are firstly subjected to hot pressing, and then are subjected to bonding and hot pressing with the modified polyethylene film, a heat-sealing layer of the heat-sealed composite film is the modified polyethylene film, so that the heat-sealing film can be repeatedly heat-sealed, meanwhile, the heat-sealing film can effectively isolate water vapor, the heat-sealing film has good isolation effect due to oxygen isolation, meanwhile, the modified polyethylene film contains polar groups, so that the polyethylene film can be well bonded with an adhesive, the film opening phenomenon of the heat-sealed composite film can not occur after long-time use or in a special environment, and the heat-sealing effect is improved.
Description
Technical Field
The invention relates to the technical field of composite film preparation, in particular to a composite film capable of being repeatedly heat-sealed and a preparation method thereof.
Background
In recent years, with the rapid development of the packaging industry, the requirements of consumers on the packaging of various products are higher and higher, and the delustering PE film is one of the products which is developed more rapidly. The extinction PE film has a good visual presentation effect, can improve the product packaging grade, has the characteristic of low price compared with common extinction film materials such as PP, PET, NY and the like, is favored by more and more packagers, has the characteristics of rich raw material resources, moderate price, stable and reliable production process, excellent product comprehensive performance and the like, gradually expands the application range of the PE film, and particularly in the fields of packaging and protective films, the consumption of the PE film is always the first of general packaging materials because the PE film is superior to other materials in cost performance. Traditional PE membrane is after making PE membrane composite bag, after filling the product, and the heat-seal seals, and the preservation that can be fine keeps the product quality, and PE membrane has fine dampproofing effect, but the gas permeability is high for the separation effect is lower, simultaneously because do not contain polar group in the molecular chain, makes self adhesive effect poor.
Disclosure of Invention
The invention aims to provide a composite film capable of being repeatedly heat-sealed and a preparation method thereof, and solves the problems that a PE heat-sealing film at the present stage is poor in gas barrier property, general in barrier effect and not easy to bond.
The purpose of the invention can be realized by the following technical scheme:
a composite film capable of being repeatedly heat-sealed is prepared from modified polyethylene film, PET film and aluminum foil through laminating.
Further, the modified polyethylene film is prepared by the following steps:
step A1: dissolving maleic anhydride in acetone, stirring and adding 2-amino-1,3-propylene glycol acetone solution under the conditions that the rotation speed is 150-200r/min and the temperature is 5-10 ℃, stirring for 10-15min, heating to the temperature of 60-70 ℃, performing reflux treatment for 30-40min, adding triethylamine, acetic anhydride and nickel acetate, continuing refluxing for 2-3h, adding reactants into ice water, filtering to remove filtrate, drying a filter cake to prepare an intermediate 1, adding linear low-density polyethylene particles, the intermediate 1 and benzoyl peroxide into a double-screw extruder, and performing extrusion granulation under the conditions that the screw rotation speed is 60-120r/min and the temperature is 160-170 ℃ to prepare modified particles;
the reaction process is as follows:
step A2: dispersing graphene oxide in deionized water, adding thionyl chloride, stirring and refluxing for 7-9h at the rotation speed of 200-300r/min and the temperature of 110-120 ℃, then removing thionyl chloride and deionized water by reduced pressure distillation, dispersing a substrate in deionized water again, adding diethanolamine and triethylamine, stirring for 5-8h at the rotation speed of 500-800r/min and the temperature of 70-80 ℃, centrifuging to remove a supernatant, and drying the substrate to obtain modified graphene;
step A3: uniformly mixing aluminum nitrate, magnesium nitrate, methanol and ethylene glycol to prepare dropping liquid, uniformly mixing sodium dodecyl sulfate, methanol and ethylene glycol, stirring and adding the dropping liquid under the conditions that the rotating speed is 200-300r/min and the temperature is 20-25 ℃, maintaining the pH value of reaction liquid to be 9, heating to 155-165 ℃, carrying out reflux treatment for 15-20h, filtering to remove filtrate, washing a substrate to be neutral and drying, dispersing the substrate in n-butyl alcohol, carrying out reflux treatment for 20-30h under the condition that the temperature is 120-130 ℃, adding modified graphene, carrying out ultrasonic treatment for 5-7h under the condition that the frequency is 40-50kHz, filtering to remove filtrate, and drying the substrate to prepare composite particles;
step A4: dissolving the modified particles in p-xylene, adding PTMG-1000 and composite particles, stirring and dropwise adding toluene-2,3-diisocyanate under the conditions that the rotation speed is 120-150r/min and the temperature is 60-70 ℃, reacting for 20-30min, heating to 80-90 ℃, reacting for 2-3h, cooling to 40-50 ℃, adding triethylamine, continuously stirring for 20-30min, uniformly mixing the reaction liquid and deionized water, filtering to remove filtrate, drying a substrate, adding the substrate into a blow molding machine, and blow molding to form a film to obtain the modified polyethylene film.
Further, the dosage ratio of the maleic anhydride, the 2-amino-1,3-propylene glycol, the triethylamine, the acetic anhydride and the nickel acetate in the step A1 is 0.05mol.
Further, the dosage ratio of the graphene oxide, thionyl chloride and diethanolamine in the step A2 is 1g.
Further, the dosage ratio of the aluminum nitrate, the magnesium nitrate, the methanol and the ethylene glycol in the step A3 is 0.03mol, 10ml, the dosage ratio of the sodium dodecyl sulfate, the methanol, the ethylene glycol and the dropwise added liquid is 7g 404040ml, and the dosage mass ratio of the substrate to the modified graphene is 5:3.
Further, the dosage mass ratio of the modified particles, PTMG-1000, the composite particles and toluene-2,3-diisocyanate in the step A4 is 5.8.
A preparation method of a composite film capable of being repeatedly heat-sealed specifically comprises the following steps:
step S1: attaching the PET film and the aluminum foil, and performing hot-pressing treatment for 10-15min at the temperature of 250-300 ℃ and the pressure of 10-12MPa to obtain a modified film;
step S2: coating an adhesive on the PET surface of the modified film and the modified polyethylene film at the coating speed of 20-33m/min, carrying out hot pressing on the coated surfaces of the modified film and the modified polyethylene film at the temperature of 75-85 ℃ and the pressure of 0.5-0.8MPa to form a film, and thus obtaining the composite film.
Furthermore, the adhesive is DORUSMD3931 water-based adhesive, and the coating thickness of the adhesive is 30-40 μm.
The invention has the beneficial effects that: the invention relates to a composite film capable of being repeatedly heat sealed, which is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressed film, wherein the PET film and the aluminum foil are firstly hot pressed, then the composite film is prepared by bonding and hot pressing with the modified polyethylene film, the modified polyethylene film takes maleic anhydride as a raw material to react with 2-amino-1,3-propylene glycol, so that maleic anhydride molecules are subjected to ring opening to form carboxyl, one carboxyl is reacted with amino on the 2-amino-1,3-propylene glycol, then under the action of triethylamine, acetic anhydride and nickel acetate, dehydration condensation is carried out to prepare an intermediate 1, the intermediate 1 and linear low-density polyethylene particles are subjected to melt grafting, under the action of benzoyl peroxide, a linear low-density polyethylene molecular chain generates a free radical, the free radical reacts with the intermediate 1 to form a new free radical, then combining with a linear low-density polyethylene molecular chain to capture hydrogen atoms on the molecular chain, further grafting an intermediate 1 on the linear low-density polyethylene molecular chain to prepare modified particles, treating graphene oxide with thionyl chloride to convert partial carboxyl on the surface of the graphene oxide into acyl chloride, further reacting with ethylene glycol amine and primary amine under the action of triethylamine to graft a large amount of alcoholic hydroxyl on the surface of the graphene to prepare modified graphene, preparing hydrotalcite-like compound by using aluminum nitrate and magnesium nitrate through a hydrothermal method, dissolving the hydrotalcite-like compound in n-butyl alcohol, then carrying out ultrasonic treatment on the hydrotalcite-like compound and the modified graphene to disperse the hydrotalcite-like compound on the surface of the graphene to prepare composite particles, and reacting the alcoholic hydroxyl with isocyanate under the action of toluene-3763 zft 3763-diisocyanate, form the polymerization with the composite particle surface on the modified particle molecular chain, blow the membrane again, make modified polyethylene membrane, heat-seal complex film heat-seal layer is modified polyethylene film, make this heat-seal membrane heat-seal repeatedly, this heat-seal membrane can effectual steam insulation simultaneously, separate oxygen and make the fine separation effect that heat-seal membrane has, contain polar group in the modified polyethylene membrane simultaneously, make the polyethylene membrane can be sticky with the fine gluing of adhesive, use for a long time or under special environment, the phenomenon of opening the membrane of heat-seal complex film can not appear, the heat-seal effect has been promoted.
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
A composite film capable of being repeatedly heat-sealed is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressed film;
the composite membrane is prepared by the following steps:
step S1: attaching a PET film and an aluminum foil, and carrying out hot-pressing treatment for 10min under the conditions that the temperature is 250 ℃ and the pressure is 10MPa to obtain a modified film;
step S2: coating a DORUSMD3931 aqueous binder on the PET surface of the modified film and the modified polyethylene film at the coating speed of 20m/min, wherein the coating thickness of the binder is 30 mu m, bonding the adhesive surfaces of the modified film and the modified polyethylene film, and performing hot pressing to form a film under the conditions that the temperature is 75 ℃ and the pressure is 0.5MPa to obtain the composite film.
The modified polyethylene film is prepared by the following steps:
step A1: dissolving maleic anhydride in acetone, stirring and adding 2-amino-1,3-propylene glycol acetone solution under the conditions that the rotation speed is 150r/min and the temperature is 5 ℃, stirring for 10min, heating to the temperature of 60 ℃, performing reflux treatment for 30min, adding triethylamine, acetic anhydride and nickel acetate, continuously refluxing for 2h, adding reactants into ice water, filtering to remove filtrate, drying a filter cake to obtain an intermediate 1, adding linear low-density polyethylene particles, the intermediate 1 and benzoyl peroxide into a double-screw extruder, and performing extrusion granulation under the conditions that the screw rotation speed is 60r/min and the temperature is 160 ℃ to obtain modified particles;
step A2: dispersing graphene oxide in deionized water, adding thionyl chloride, stirring and refluxing for 7 hours at the rotation speed of 200r/min and the temperature of 110 ℃, distilling under reduced pressure to remove thionyl chloride and deionized water, dispersing a substrate in deionized water again, adding diethanolamine and triethylamine, stirring for 5 hours at the rotation speed of 500r/min and the temperature of 70 ℃, centrifuging to remove a supernatant, and drying the substrate to obtain modified graphene;
step A3: uniformly mixing aluminum nitrate, magnesium nitrate, methanol and ethylene glycol to prepare a dropping liquid, uniformly mixing sodium dodecyl sulfate, methanol and ethylene glycol, stirring and adding the dropping liquid under the conditions of a rotation speed of 200r/min and a temperature of 20 ℃, maintaining the pH value of a reaction solution to be 9, heating to a temperature of 155 ℃, refluxing for 15 hours, filtering to remove filtrate, washing a substrate to be neutral, drying, dispersing in n-butyl alcohol, refluxing for 20 hours at a temperature of 120 ℃, adding modified graphene, performing ultrasonic treatment for 5 hours under the condition of a frequency of 40kHz, filtering to remove filtrate, and drying the substrate to prepare composite particles;
step A4: dissolving the modified particles in paraxylene, adding PTMG-1000 and composite particles, stirring and dropwise adding toluene-2,3-diisocyanate under the conditions of a rotation speed of 120r/min and a temperature of 60 ℃, reacting for 20min, heating to 80 ℃, reacting for 2h, cooling to 40 ℃, adding triethylamine, continuously stirring for 20min, uniformly mixing the reaction liquid with deionized water, filtering to remove filtrate, drying a substrate, adding the substrate into a blow molding machine, and blow molding to form a film to obtain the modified polyethylene film.
The dosage ratio of the maleic anhydride, the 2-amino-1,3-propylene glycol, the triethylamine, the acetic anhydride and the nickel acetate in the step A1 is 0.05mol.
The use amount ratio of the graphene oxide, the thionyl chloride and the diethanolamine in the step A2 is 1g.
The dosage ratio of the aluminum nitrate, the magnesium nitrate, the methanol and the ethylene glycol in the step A3 is 0.03mol.
The dosage mass ratio of the modified particles, the PTMG-1000, the composite particles and the toluene-2,3-diisocyanate in the step A4 is 5.8.
Example 2
A composite film capable of being repeatedly heat-sealed is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressed film;
the composite membrane is prepared by the following steps:
step S1: attaching the PET film and the aluminum foil, and carrying out hot-pressing treatment for 10min at the temperature of 280 ℃ and the pressure of 11MPa to obtain a modified film;
step S2: coating a DORUSMD3931 aqueous binder on the PET surface of the modified film and the modified polyethylene film at the coating speed of 33m/min, wherein the coating thickness of the binder is 35 mu m, bonding the adhesive surfaces of the modified film and the modified polyethylene film, and performing hot pressing to form a film under the conditions that the temperature is 80 ℃ and the pressure is 0.7MPa to obtain the composite film.
The modified polyethylene film is prepared by the following steps:
step A1: dissolving maleic anhydride in acetone, stirring and adding 2-amino-1,3-propylene glycol acetone solution under the conditions that the rotation speed is 180r/min and the temperature is 8 ℃, stirring for 13min, heating to 65 ℃, performing reflux treatment for 35min, adding triethylamine, acetic anhydride and nickel acetate, continuously refluxing for 2.5h, adding reactants into ice water, filtering to remove filtrate, drying a filter cake to prepare an intermediate 1, adding linear low-density polyethylene particles, the intermediate 1 and benzoyl peroxide into a double-screw extruder, and extruding and granulating under the conditions that the screw rotation speed is 60r/min and the temperature is 165 ℃ to prepare modified particles;
step A2: dispersing graphene oxide in deionized water, adding thionyl chloride, stirring and refluxing for 8 hours at the rotation speed of 300r/min and the temperature of 115 ℃, distilling under reduced pressure to remove thionyl chloride and deionized water, dispersing a substrate in deionized water again, adding diethanolamine and triethylamine, stirring for 6 hours at the rotation speed of 500r/min and the temperature of 75 ℃, centrifuging to remove a supernatant, and drying the substrate to obtain modified graphene;
step A3: uniformly mixing aluminum nitrate, magnesium nitrate, methanol and ethylene glycol to prepare dropping liquid, uniformly mixing sodium dodecyl sulfate, methanol and ethylene glycol, stirring and adding the dropping liquid under the conditions that the rotating speed is 300r/min and the temperature is 23 ℃, maintaining the pH value of a reaction solution to be 9, heating to 160 ℃, carrying out reflux treatment for 18 hours, filtering to remove filtrate, washing a substrate to be neutral, drying, dispersing in n-butyl alcohol, carrying out reflux treatment for 25 hours under the condition that the temperature is 125 ℃, adding modified graphene, carrying out ultrasonic treatment for 6 hours under the condition that the frequency is 45kHz, filtering to remove filtrate, and drying the substrate to prepare composite particles;
step A4: dissolving the modified particles in paraxylene, adding PTMG-1000 and composite particles, stirring and dropwise adding toluene-2,3-diisocyanate under the conditions of a rotation speed of 150r/min and a temperature of 65 ℃, reacting for 25min, heating to 85 ℃, reacting for 2.5h, cooling to 45 ℃, adding triethylamine, continuing stirring for 25min, uniformly mixing the reaction liquid with deionized water, filtering to remove filtrate, drying a substrate, adding the substrate into a blow molding machine, and blow molding to form a film to obtain the modified polyethylene film.
The weight ratio of the maleic anhydride, 2-amino-1,3-propylene glycol, triethylamine, acetic anhydride and nickel acetate in the step A1 is 0.05mol.
The dosage ratio of the graphene oxide, the thionyl chloride and the diethanolamine in the step A2 is 1g.
The dosage ratio of the aluminum nitrate, the magnesium nitrate, the methanol and the ethylene glycol in the step A3 is 0.03mol.
The dosage mass ratio of the modified particles, the PTMG-1000, the composite particles and the toluene-2,3-diisocyanate in the step A4 is 5.8.
Example 3
A composite film capable of being repeatedly heat-sealed is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressing film;
the composite membrane is prepared by the following steps:
step S1: attaching the PET film and the aluminum foil, and carrying out hot-pressing treatment for 15min under the conditions that the temperature is 300 ℃ and the pressure is 12MPa to obtain a modified film;
step S2: coating a DORUSMD3931 aqueous binder on the PET surface of the modified film and the modified polyethylene film at the coating speed of 33m/min, wherein the coating thickness of the binder is 40 mu m, bonding the adhesive surfaces of the modified film and the modified polyethylene film, and performing hot pressing to form a film under the conditions that the temperature is 85 ℃ and the pressure is 0.8MPa to obtain the composite film.
The modified polyethylene film is prepared by the following steps:
step A1: dissolving maleic anhydride in acetone, stirring and adding 2-amino-1,3-propylene glycol acetone solution under the conditions that the rotation speed is 200r/min and the temperature is 10 ℃, stirring for 15min, heating to the temperature of 70 ℃, performing reflux treatment for 40min, adding triethylamine, acetic anhydride and nickel acetate, continuously refluxing for 3h, adding reactants into ice water, filtering to remove filtrate, drying a filter cake to obtain an intermediate 1, adding linear low-density polyethylene particles, the intermediate 1 and benzoyl peroxide into a double-screw extruder, and performing extrusion granulation under the conditions that the screw rotation speed is 60-120r/min and the temperature is 170 ℃ to obtain modified particles;
step A2: dispersing graphene oxide in deionized water, adding thionyl chloride, stirring and refluxing for 9 hours at the rotation speed of 300r/min and the temperature of 120 ℃, distilling under reduced pressure to remove thionyl chloride and deionized water, dispersing a substrate in deionized water again, adding diethanolamine and triethylamine, stirring for 8 hours at the rotation speed of 800r/min and the temperature of 80 ℃, centrifuging to remove supernatant, and drying the substrate to obtain modified graphene;
step A3: uniformly mixing aluminum nitrate, magnesium nitrate, methanol and ethylene glycol to prepare dropping liquid, uniformly mixing sodium dodecyl sulfate, methanol and ethylene glycol, stirring and adding the dropping liquid under the conditions of a rotating speed of 300r/min and a temperature of 25 ℃, maintaining the pH value of a reaction solution to be 9, heating to a temperature of 165 ℃, refluxing for 20 hours, filtering to remove filtrate, washing a substrate to be neutral, drying, dispersing in n-butyl alcohol, refluxing for 30 hours under the condition of a temperature of 130 ℃, adding modified graphene, performing ultrasonic treatment for 7 hours under the condition of a frequency of 50kHz, filtering to remove filtrate, and drying the substrate to prepare composite particles;
step A4: dissolving the modified particles in paraxylene, adding PTMG-1000 and composite particles, stirring and dropwise adding toluene-2,3-diisocyanate under the conditions of a rotation speed of 150r/min and a temperature of 70 ℃, reacting for 30min, heating to 90 ℃, reacting for 3h, cooling to 50 ℃, adding triethylamine, continuously stirring for 30min, uniformly mixing the reaction liquid with deionized water, filtering to remove filtrate, drying a substrate, adding the substrate into a blow molding machine, and blow molding to form a film to obtain the modified polyethylene film.
The dosage ratio of the maleic anhydride, the 2-amino-1,3-propylene glycol, the triethylamine, the acetic anhydride and the nickel acetate in the step A1 is 0.05mol.
The dosage ratio of the graphene oxide, the thionyl chloride and the diethanolamine in the step A2 is 1g.
The dosage ratio of the aluminum nitrate, the magnesium nitrate, the methanol and the ethylene glycol in the step A3 is 0.03mol.
The dosage mass ratio of the modified particles, the PTMG-1000, the composite particles and the toluene-2,3-diisocyanate in the step A4 is 5.8.
Comparative example 1
This comparative example uses a linear low density polyethylene film in place of the modified polyethylene film, and the same procedure was followed.
Comparative example 2
The comparative example is a repeatedly heat-sealing film disclosed in Chinese patent CN 108189506A.
Comparative example 3
The comparative example is a repeatedly heat-sealing film disclosed in Chinese patent CN 108504024A.
The heat-sealable films obtained in examples 1 to 3 and comparative examples 1 to 3 were tested by a gas barrier tester based on a differential pressure method, and the water vapor permeability was measured in units of g.mm/24 h.m 3 mPa, oxygen transmission in cm 3 ·mm/24h·m 3 mPa, and soaking the composite membrane in water for 48h,96h,144h, and observing whether the composite membrane is in a state of being immersedThe film opening phenomenon occurred, and the results are shown in the following table;
from the above table, it is understood that the composite heat-sealable films obtained in examples 1 to 3 had a water vapor permeability of 1.91 to 1.95 g.mm/24 h.m 3 mPa, oxygen transmission rate of 0.82-0.85cm 3 ·mm/24h·m 3 mPa, soaking in water for 144h without membrane opening, which shows that the invention has good barrier effect and solves the problem of poor adhesion effect of polyethylene material.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A composite film capable of being repeatedly heat sealed is characterized in that: is prepared by compounding a modified polyethylene film, a PET film and an aluminum foil pressed film;
the modified polyethylene film is prepared by the following steps:
step A1: dissolving maleic anhydride in acetone, stirring, adding a 2-amino-1,3-propylene glycol acetone solution, stirring, heating for reflux treatment, adding triethylamine, acetic anhydride and nickel acetate, continuously refluxing, adding reactants into ice water, filtering to remove filtrate, drying a filter cake to obtain an intermediate 1, adding linear low-density polyethylene particles, the intermediate 1 and benzoyl peroxide into a double-screw extruder, and carrying out extrusion granulation to obtain modified particles;
step A2: dispersing graphene oxide in deionized water, adding thionyl chloride, stirring and refluxing, carrying out reduced pressure distillation to remove thionyl chloride and deionized water, dispersing a substrate in deionized water again, adding diethanolamine and triethylamine, stirring, centrifuging to remove supernatant, and drying the substrate to obtain modified graphene;
step A3: uniformly mixing aluminum nitrate, magnesium nitrate, methanol and ethylene glycol to prepare dropping liquid, uniformly mixing sodium dodecyl sulfate, methanol and ethylene glycol, adding the dropping liquid, maintaining the pH value of the reaction liquid, heating for reflux treatment, filtering to remove filtrate, washing a substrate to be neutral, drying, dispersing in n-butyl alcohol, carrying out reflux treatment, adding modified graphene, carrying out ultrasonic treatment, filtering to remove the filtrate, drying the substrate, and preparing composite particles;
step A4: dissolving the modified particles in paraxylene, adding PTMG-1000 and composite particles, stirring and dropwise adding toluene-2,3-diisocyanate, reacting, heating to continue reacting, cooling and adding triethylamine, continuing stirring, uniformly mixing the reaction liquid and deionized water, filtering to remove filtrate, drying the substrate, adding the substrate into a blow molding machine, and blow molding to form a film to obtain the modified polyethylene film.
2. A heat-sealable composite film according to claim 1 wherein: the dosage ratio of the maleic anhydride, the 2-amino-1,3-propylene glycol, the triethylamine, the acetic anhydride and the nickel acetate in the step A1 is 0.05mol.
3. A heat-resealable composite film according to claim 1, wherein: the dosage ratio of the graphene oxide, the thionyl chloride and the diethanolamine in the step A2 is 1g.
4. A heat-resealable composite film according to claim 1, wherein: the dosage ratio of the aluminum nitrate, the magnesium nitrate, the methanol and the ethylene glycol in the step A3 is 0.03mol.
5. A heat-resealable composite film according to claim 1, wherein: the dosage mass ratio of the modified particles, the PTMG-1000, the composite particles and the toluene-2,3-diisocyanate in the step A4 is 5.8.
6. A method of preparing a heat-resealable composite film according to claim 1, wherein: the method specifically comprises the following steps:
step S1: attaching the PET film and the aluminum foil, and performing hot-pressing treatment for 10-15min at the temperature of 250-300 ℃ and the pressure of 10-12MPa to obtain a modified film;
step S2: coating an adhesive on the PET surface of the modified film and the modified polyethylene film at the coating speed of 20-33m/min, carrying out hot pressing on the coated surfaces of the modified film and the modified polyethylene film at the temperature of 75-85 ℃ and the pressure of 0.5-0.8MPa to form a film, and thus obtaining the composite film.
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Denomination of invention: A composite film that can be repeatedly heat sealed and its preparation method Effective date of registration: 20231116 Granted publication date: 20230516 Pledgee: Zhejiang Hecheng Rural Commercial Bank Co.,Ltd. Pledgor: ZHEJIANG BAOLU PACKAGING TECHNOLOGY CO.,LTD. Registration number: Y2023330002674 |