CN116535760A - Aluminum-free composite material for pesticide packaging and preparation method thereof - Google Patents
Aluminum-free composite material for pesticide packaging and preparation method thereof Download PDFInfo
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- CN116535760A CN116535760A CN202310427837.3A CN202310427837A CN116535760A CN 116535760 A CN116535760 A CN 116535760A CN 202310427837 A CN202310427837 A CN 202310427837A CN 116535760 A CN116535760 A CN 116535760A
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- composite material
- aluminum
- modified
- polysiloxane
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- 239000000575 pesticide Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 37
- 229920000728 polyester Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 21
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 13
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- -1 polysiloxane Polymers 0.000 claims description 60
- 229920001296 polysiloxane Polymers 0.000 claims description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 48
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 150000002334 glycols Chemical class 0.000 claims description 17
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012964 benzotriazole Substances 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses an aluminum-free composite material for pesticide packaging and a preparation method thereof, wherein when modified polyester and PE particles are dissolved and blended, under the action of dibenzoyl peroxide, double bonds on side chains of the modified polyester are grafted with PE particle molecular chains, then modified filler is added, after ultraviolet irradiation treatment, unreacted double bonds are grafted with sulfhydryl groups on the modified filler, and then a substrate is soaked in a copper sulfate pentahydrate aqueous solution, so that benzotriazole groups in the molecular chains are coordinated with copper ions, and meanwhile, the modified polyester has a hyperbranched structure, so that the molecular density after crosslinking can be enhanced, further, the barrier property of the composite material is improved, meanwhile, silicon dioxide and metallic copper oxides on the surface of the composite material can well prevent pesticide corrosion, further, pesticides can not be separated out from packages, and meanwhile, the composite material has high mechanical property, and the problem of package breakage in the transportation process of pesticides is effectively avoided.
Description
Technical Field
The invention relates to the technical field of packaging material preparation, in particular to an aluminum-free composite material for pesticide packaging and a preparation method thereof.
Background
Besides the requirements for the common packaging materials, the packaging materials for pesticides have special requirements, such as ensuring that the pesticides are not damaged in normal storage and transportation and meeting the requirements of corresponding packaging material standards due to the toxic hazard of packaged objects. The outer packing material of the pesticide should be firm and durable to ensure that the contents are not destroyed. The inner packing material of the pesticide should be firm and durable, and the inner packing material does not have any physical and chemical action with the pesticide to damage products, does not swell, does not leak, and does not influence the quality of the products. The earliest classical liquid pesticide flexible packaging bag is composed of polyester, aluminum foil, nylon and polyolefin films, and the traditional aluminum foil packaging bag has the problem that an aluminum plating layer is transferred and separated in the aluminum plating process, so that the problem is avoided, and the traditional aluminum foil packaging bag is replaced by a high-barrier material.
Disclosure of Invention
The invention aims to provide an aluminum-free composite material for pesticide packaging and a preparation method thereof, which solve the problems of poor barrier property and low mechanical strength of the aluminum-free composite material for packaging at the present stage.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the aluminum-free composite material for pesticide packaging specifically comprises the following steps:
mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide, keeping the temperature at 30-40 ℃ for 5-7h, heating to 95-100 ℃ for reaction for 2-3h, adding modified filler, uniformly mixing, radiating Ultraviolet (UV) for 10-15s, filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution for 10-12h, taking out, and drying to obtain the aluminum-free composite material for pesticide packaging.
Further, the mass ratio of the PE particles to the modified polyester is 10:0.8-1, the dosage of dibenzoyl peroxide is 0.5-1.0% of the sum of the PE particles and the modified polyester, and the concentration of the aqueous solution of the copper sulfate pentahydrate is 0.1M.
Further, the modified polyester is prepared by the following steps:
step A1: mixing benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide, introducing nitrogen for protection, carrying out reflux reaction for 5-7h at the rotation speed of 120-150r/min and the temperature of 80-85 ℃ to obtain an intermediate 1, uniformly mixing 1, 3-diamino-2-propanol, acrylic acid, p-toluenesulfonic acid and toluene, and carrying out reaction for 6-8h at the rotation speed of 150-200r/min and the temperature of 110-120 ℃ to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 1, the intermediate 2 and DMF, reacting for 3-5 hours under the conditions of 200-300r/min of rotating speed and alkaline pH to obtain an intermediate 3, adding Y-aminopropyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 20-30 minutes under the conditions of 150-200r/min of rotating speed, adding tetrahydrofuran and concentrated sulfuric acid, preserving heat for 5-10 minutes under the conditions of 60-70 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 3-5 hours to obtain hydrogen-terminated polysiloxane;
step A3: uniformly mixing hydrogen-terminated polysiloxane, an intermediate 3 and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 150-200r/min and the temperature of 50-60 ℃, heating to 70-80 ℃, reacting for 3-4 hours to obtain a diol polysiloxane, mixing the diol polysiloxane, maleic anhydride and diethyl ether, stirring for 3-5 hours at the rotating speed of 200-300r/min, removing diethyl ether, adding manganese acetate, triethylamine and anhydride, and reacting for 2-3 hours at the temperature of 50-60 ℃ to obtain the modified diol polysiloxane;
step A4: mixing modified glycol polysiloxane, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen to remove air, reacting for 2-4 hours at 225-240 ℃ and 0.3-0.5MPa, and reacting for 8-10 hours at 280-285 ℃ and 50-60Pa to obtain the modified polyester.
Further, the molar ratio of benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide in the step A1 is 2:3:3:0.2, the molar ratio of 1, 3-diamino-2-propanol and acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 3-5% of the sum of the mass of 1, 3-diamino-2-propanol and acrylic acid.
Further, the molar ratio of the intermediate 1 to the intermediate 2 in the step A2 is 2:1, the mass ratio of the Y-aminopropyl methyldiethoxysilane, the dimethyldichlorosilane, the deionized water and the 1, 3-tetramethyl disiloxane is 1mmol:5 mL 2mmol, and the mass ratio of the concentrated sulfuric acid is 5-8% and the mass ratio of the Y-aminopropyl methyldiethoxysilane, the dimethyldichlorosilane and the 1, 3-tetramethyl disiloxane is 1 mmol.
Further, the molar ratio of the hydrogen-terminated polysiloxane to the intermediate 3 in the step A3 is 1:2, and the concentration of chloroplatinic acid in the mixture of the hydrogen-terminated polysiloxane and the intermediate 3 dissolved in the mixture is 10-15ppm, and the dosage ratio of the glycol polysiloxane, the maleic anhydride, the manganese acetate, the triethylamine and the anhydride is 0.1mol:0.2mol:0.11g:7mL 60mL.
Further, the mole ratio of the modified glycol polysiloxane to the terephthalic acid to the glycol in the step A4 is 0.8:1.4:0.5, and the amount of the antimony trioxide is 0.025-0.03 percent of the mass sum of the modified glycol polysiloxane, the terephthalic acid and the glycol.
Further, the modified filler is prepared by the following steps:
uniformly mixing graphene oxide, deionized water and ethanol, stirring for 1-1.5 hours at the rotation speed of 600-800r/min and the temperature of 40-50 ℃, adding ammonia water and tetraethoxysilane, continuously stirring for 10-15 hours, centrifugally removing supernatant, washing a substrate with ammonia water and drying to obtain a pretreated filler, dispersing the pretreated filler in deionized water, adding KH580, stirring for 1-1.5 hours at the rotation speed of 200-300r/min and the temperature of 60-65 ℃, filtering to remove filtrate, and drying a filter cake to obtain the modified filler.
Further, the dosage ratio of graphene oxide, deionized water, ethanol, ammonia water and tetraethoxysilane is 0.04g:3mL:80mL:4mL:1mL, and KH580 is 3-5% of the mass of the pretreated filler.
The invention has the beneficial effects that: the aluminum-free composite material for pesticide packaging prepared by the invention is prepared by mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide for reaction, adding a modified filler for uniform mixing, carrying out ultraviolet UV irradiation, filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution, taking out and drying after soaking treatment, wherein the modified polyester is prepared by taking benzotriazole and epichlorohydrin as raw materials, enabling NH and epoxy chlorine atom sites on the benzotriazole to react to prepare an intermediate 1, carrying out esterification reaction on 1, 3-diamino-2-propanol and acrylic acid to prepare an intermediate 2, enabling the intermediate 1 to react with the intermediate 2 under alkaline conditions, enabling epoxy groups on the intermediate 1 to react with amino groups on the intermediate 2 to prepare an intermediate 3, hydrolyzing Y-aminopropyl methyl diethoxy silane and dimethyl dichloro silane, and polymerizing with 1, 3-tetramethyl disiloxane, forming hydrogen-terminated polysiloxane, reacting Si-H bond on the hydrogen-terminated polysiloxane with double bond on the intermediate 3 under the action of chloroplatinic acid to obtain glycol polysiloxane, reacting the glycol polysiloxane with maleic anhydride to react maleic anhydride with amino on the glycol polysiloxane to obtain modified glycol polysiloxane, esterifying and polymerizing the modified glycol polysiloxane, terephthalic acid and ethylene glycol to obtain modified polyester, treating the modified filler with graphene oxide as raw material with tetraethoxysilane to coat the surface of the graphene oxide with nano silicon dioxide, treating with KH580 to graft mercapto on the surface, dissolving and blending the modified polyester and PE particles, treating under the action of dibenzoyl peroxide to graft double bond on the side chain of the modified polyester with PE particle molecular chain, then adding modified filler, after irradiation treatment by ultraviolet rays UV, grafting unreacted double bonds with mercapto groups on the modified filler, soaking a substrate in a pentahydrate copper sulfate aqueous solution to coordinate benzotriazole groups in a molecular chain with copper ions, and meanwhile, the modified polyester is of a hyperbranched structure to enhance the molecular density after crosslinking, so that the barrier property of the composite material is improved, and meanwhile, silicon dioxide and metallic copper oxide on the surface of the material can well prevent pesticide corrosion, so that pesticides are prevented from being separated out from packages, and meanwhile, the composite material is high in mechanical property, and the problem of package breakage in the transportation process of pesticides is effectively avoided.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the aluminum-free composite material for pesticide packaging specifically comprises the following steps:
mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide, preserving heat at 30 ℃ for 5 hours, heating to 95 ℃, reacting for 2 hours, adding modified filler, uniformly mixing, radiating ultraviolet light (UV) for 10 seconds, filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution for 10 hours, taking out, and drying to obtain the aluminum-free composite material for pesticide packaging.
The mass ratio of the PE particles to the modified polyester is 10:0.8, the dosage of dibenzoyl peroxide is 0.5% of the sum of the PE particles and the modified polyester, and the concentration of the aqueous solution of the copper sulfate pentahydrate is 0.1M.
The modified polyester is prepared by the following steps:
step A1: mixing benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide, introducing nitrogen for protection, carrying out reflux reaction for 5 hours at the rotation speed of 120r/min and the temperature of 80 ℃ to obtain an intermediate 1, uniformly mixing 1, 3-diamino-2-propanol, acrylic acid, p-toluenesulfonic acid and toluene, and carrying out reaction for 6 hours at the rotation speed of 150r/min and the temperature of 110 ℃ to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 1, the intermediate 2 and DMF, reacting for 3 hours under the conditions of 200r/min of rotating speed and alkaline pH to obtain an intermediate 3, adding Y-aminopropyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 20 minutes under the conditions of 150r/min of rotating speed, adding tetrahydrofuran and concentrated sulfuric acid, preserving heat for 5 minutes under the conditions of 60 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 3 hours to obtain hydrogen-terminated polysiloxane;
step A3: uniformly mixing hydrogen-terminated polysiloxane, an intermediate 3 and DMF (dimethyl formamide), stirring at a rotating speed of 150r/min and a temperature of 50 ℃, adding chloroplatinic acid, heating to 70 ℃, reacting for 3 hours to obtain a diol polysiloxane, mixing the diol polysiloxane, maleic anhydride and diethyl ether, stirring at a rotating speed of 200r/min for 3 hours, removing diethyl ether, adding manganese acetate, triethylamine and anhydride, and reacting at a temperature of 50 ℃ for 2 hours to obtain the modified diol polysiloxane;
step A4: mixing modified glycol polysiloxane, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen to remove air, reacting for 2 hours at 225 ℃ and 0.3MPa, and reacting for 8 hours at 280 ℃ and 50Pa to obtain the modified polyester.
The molar ratio of the benzotriazole, the potassium hydroxide, the epichlorohydrin and the tetrabutylammonium bromide in the step A1 is 2:3:3:0.2, the molar ratio of the 1, 3-diamino-2-propanol and the acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 3 percent of the sum of the mass of the 1, 3-diamino-2-propanol and the acrylic acid.
The molar ratio of the intermediate 1 to the intermediate 2 in the step A2 is 2:1, the mass ratio of the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the deionized water to the 1, 3-tetramethyl disiloxane is 1mmol to 5mL to 2mmol, and the mass ratio of the concentrated sulfuric acid to the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the 1, 3-tetramethyl disiloxane is 5%.
The mol ratio of the hydrogen-terminated polysiloxane to the intermediate 3 in the step A3 is 1:2, and the concentration of chloroplatinic acid in the mixture of the hydrogen-terminated polysiloxane and the intermediate 3 dissolved in the mixture is 10-15ppm, and the dosage ratio of the glycol polysiloxane, the maleic anhydride, the manganese acetate, the triethylamine and the anhydride is 0.1mol:0.2mol:0.11g:7mL 60mL.
The molar ratio of the modified glycol polysiloxane to the terephthalic acid to the glycol in the step A4 is 0.8:1.4:0.5, and the amount of the antimony trioxide is 0.025 percent of the mass sum of the modified glycol polysiloxane, the terephthalic acid and the glycol.
The modified filler is prepared by the following steps:
uniformly mixing graphene oxide, deionized water and ethanol, stirring for 1h at the rotation speed of 600r/min and the temperature of 40 ℃, adding ammonia water and tetraethoxysilane, continuously stirring for 10h, centrifuging to remove supernatant, washing a substrate with ammonia water, drying to obtain a pretreated filler, dispersing the pretreated filler in deionized water, adding KH580, stirring for 1h at the rotation speed of 200r/min and the temperature of 60 ℃, filtering to remove filtrate, and drying a filter cake to obtain the modified filler.
The dosage ratio of graphene oxide, deionized water, ethanol, ammonia water and tetraethoxysilane is 0.04g:3mL:80mL:4mL:1mL, and KH580 is 3% of the mass of the pretreated filler.
Example 2
The preparation method of the aluminum-free composite material for pesticide packaging specifically comprises the following steps:
mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide, preserving heat at 35 ℃ for 6 hours, heating to 98 ℃, reacting for 2.5 hours, adding modified filler, uniformly mixing, radiating ultraviolet light (UV) for 13 seconds, filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution, soaking for 11 hours, taking out, and drying to obtain the aluminum-free composite material for pesticide packaging.
The mass ratio of the PE particles to the modified polyester is 10:0.9, the dosage of dibenzoyl peroxide is 0.8% of the sum of the PE particles and the modified polyester, and the concentration of the aqueous solution of the copper sulfate pentahydrate is 0.1M.
The modified polyester is prepared by the following steps:
step A1: mixing benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide, introducing nitrogen for protection, carrying out reflux reaction for 6 hours at the rotation speed of 120r/min and the temperature of 83 ℃ to obtain an intermediate 1, uniformly mixing 1, 3-diamino-2-propanol, acrylic acid, p-toluenesulfonic acid and toluene, and carrying out reaction for 7 hours at the rotation speed of 150r/min and the temperature of 115 ℃ to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 1, the intermediate 2 and DMF, reacting for 4 hours under the conditions of 200r/min of rotating speed and alkaline pH to obtain an intermediate 3, adding Y-aminopropyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 25 minutes under the conditions of 200r/min of rotating speed, adding tetrahydrofuran and concentrated sulfuric acid, preserving heat for 8 minutes under the conditions of 65 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 4 hours to obtain hydrogen-terminated polysiloxane;
step A3: uniformly mixing hydrogen-terminated polysiloxane, an intermediate 3 and DMF (dimethyl formamide), stirring at a rotating speed of 150r/min and a temperature of 55 ℃, adding chloroplatinic acid, heating to 78 ℃, reacting for 3.5 hours to obtain a diol polysiloxane, mixing the diol polysiloxane, maleic anhydride and diethyl ether, stirring at a rotating speed of 200r/min for 4 hours, removing diethyl ether, adding manganese acetate, triethylamine and anhydride, and reacting at a temperature of 55 ℃ for 2.5 hours to obtain the modified diol polysiloxane;
step A4: mixing modified glycol polysiloxane, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen to remove air, reacting for 3 hours at 230 ℃ and 0.4MPa, and reacting for 9 hours at 285 ℃ and 55Pa to obtain the modified polyester.
The molar ratio of benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide in the step A1 is 2:3:3:0.2, the molar ratio of 1, 3-diamino-2-propanol and acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 4% of the sum of the mass of 1, 3-diamino-2-propanol and acrylic acid.
The molar ratio of the intermediate 1 to the intermediate 2 in the step A2 is 2:1, the mass ratio of the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the deionized water to the 1, 3-tetramethyl disiloxane is 1mmol to 5mL to 2mmol, and the mass ratio of the concentrated sulfuric acid to the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the 1, 3-tetramethyl disiloxane is 6%.
The molar ratio of the hydrogen-terminated polysiloxane to the intermediate 3 in the step A3 is 1:2, and the concentration of chloroplatinic acid in the mixed solution of the hydrogen-terminated polysiloxane and the intermediate 3 is 13ppm, and the dosage ratio of the dihydroxypolysiloxane, the maleic anhydride, the manganese acetate, the triethylamine and the anhydride is 0.1mol:0.2mol:0.11g:7mL:60mL.
The molar ratio of the modified glycol polysiloxane to the terephthalic acid to the glycol in the step A4 is 0.8:1.4:0.5, and the amount of the antimony trioxide is 0.03 percent of the sum of the mass of the modified glycol polysiloxane, the mass of the terephthalic acid and the mass of the glycol.
The modified filler is prepared by the following steps:
uniformly mixing graphene oxide, deionized water and ethanol, stirring for 1.3 hours at the rotation speed of 600r/min and the temperature of 45 ℃, adding ammonia water and tetraethoxysilane, continuously stirring for 13 hours, centrifuging to remove supernatant, washing a substrate with ammonia water, drying to obtain a pretreatment filler, dispersing the pretreatment filler in deionized water, adding KH580, stirring for 1.5 hours at the rotation speed of 200r/min and the temperature of 65 ℃, filtering to remove filtrate, and drying a filter cake to obtain the modified filler.
The dosage ratio of graphene oxide, deionized water, ethanol, ammonia water and tetraethoxysilane is 0.04g:3mL:80mL:4mL:1mL, and KH580 is 4% of the mass of the pretreated filler.
Example 3
The preparation method of the aluminum-free composite material for pesticide packaging specifically comprises the following steps:
mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide, preserving heat at 40 ℃ for 7 hours, heating to 100 ℃, reacting for 3 hours, adding modified filler, uniformly mixing, radiating ultraviolet light (UV) for 15 seconds, filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution for 12 hours, taking out, and drying to obtain the aluminum-free composite material for pesticide packaging.
The mass ratio of the PE particles to the modified polyester is 10:1, the dosage of dibenzoyl peroxide is 1.0% of the sum of the PE particles and the modified polyester, and the concentration of the aqueous solution of the copper sulfate pentahydrate is 0.1M.
The modified polyester is prepared by the following steps:
step A1: mixing benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide, introducing nitrogen for protection, carrying out reflux reaction for 7 hours at the rotation speed of 150r/min and the temperature of 85 ℃ to obtain an intermediate 1, uniformly mixing 1, 3-diamino-2-propanol, acrylic acid, p-toluenesulfonic acid and toluene, and carrying out reaction for 8 hours at the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 1, the intermediate 2 and DMF, reacting for 5 hours under the conditions of 300r/min of rotating speed and alkaline pH to obtain an intermediate 3, adding Y-aminopropyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring for 30 minutes under the conditions of 200r/min of rotating speed, adding tetrahydrofuran and concentrated sulfuric acid, preserving heat for 10 minutes under the conditions of 70 ℃, adding 1, 3-tetramethyl disiloxane, and reacting for 5 hours to obtain hydrogen-terminated polysiloxane;
step A3: uniformly mixing hydrogen-terminated polysiloxane, an intermediate 3 and DMF (dimethyl formamide), stirring at a rotating speed of 200r/min and a temperature of 60 ℃, adding chloroplatinic acid, heating to 80 ℃, reacting for 4 hours to obtain a diol polysiloxane, mixing the diol polysiloxane, maleic anhydride and diethyl ether, stirring at a rotating speed of 300r/min for 5 hours, removing diethyl ether, adding manganese acetate, triethylamine and anhydride, and reacting at a temperature of 60 ℃ for 3 hours to obtain the modified diol polysiloxane;
step A4: mixing modified glycol polysiloxane, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen to remove air, reacting for 4 hours at the temperature of 240 ℃ and the pressure of 0.5MPa, and reacting for 10 hours at the temperature of 285 ℃ and the pressure of 60Pa to obtain the modified polyester.
The molar ratio of the benzotriazole, the potassium hydroxide, the epichlorohydrin and the tetrabutylammonium bromide in the step A1 is 2:3:3:0.2, the molar ratio of the 1, 3-diamino-2-propanol and the acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 5 percent of the sum of the mass of the 1, 3-diamino-2-propanol and the acrylic acid.
The molar ratio of the intermediate 1 to the intermediate 2 in the step A2 is 2:1, the mass ratio of the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the deionized water to the 1, 3-tetramethyl disiloxane is 1mmol to 5mL to 2mmol, and the mass ratio of the concentrated sulfuric acid to the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the 1, 3-tetramethyl disiloxane is 8%.
The molar ratio of the hydrogen-terminated polysiloxane to the intermediate 3 in the step A3 is 1:2, and the concentration of chloroplatinic acid in the mixture of the hydrogen-terminated polysiloxane and the intermediate 3 is 15ppm, and the dosage ratio of the dihydroxypolysiloxane, the maleic anhydride, the manganese acetate, the triethylamine and the anhydride is 0.1mol:0.2mol:0.11g:7mL:60mL.
The molar ratio of the modified glycol polysiloxane to the terephthalic acid to the glycol in the step A4 is 0.8:1.4:0.5, and the amount of the antimony trioxide is 0.03 percent of the sum of the mass of the modified glycol polysiloxane, the mass of the terephthalic acid and the mass of the glycol.
The modified filler is prepared by the following steps:
uniformly mixing graphene oxide, deionized water and ethanol, stirring for 1.5 hours at the speed of 800r/min and the temperature of 50 ℃, adding ammonia water and tetraethoxysilane, continuously stirring for 15 hours, centrifuging to remove supernatant, washing a substrate with ammonia water, drying to obtain a pretreated filler, dispersing the pretreated filler in deionized water, adding KH580, stirring for 1.5 hours at the speed of 300r/min and the temperature of 65 ℃, filtering to remove filtrate, and drying a filter cake to obtain the modified filler.
The dosage ratio of graphene oxide, deionized water, ethanol, ammonia water and tetraethoxysilane is 0.04g:3mL:80mL:4mL:1mL, and KH580 is 5% of the mass of the pretreated filler.
Comparative example 1
This comparative example uses propenol instead of intermediate 3 as compared with example 1, without soaking in an anhydrous aqueous sulfuric acid solution, and the rest of the steps are the same.
Comparative example 2
This comparative example was not added with modified filler as compared with example 1, and the rest of the procedure was the same.
PE particles were linear low density polyethylene 218W, the composites prepared in examples 1-3 and comparative examples 1-2 were tested for tensile strength according to GB/T13022-1991, tensile speed 50mm/min, moisture permeability according to GB/T1037-2021, test temperature 38℃and relative humidity difference 90%, oxygen permeability according to GB/T1038-2000, test temperature 23℃and relative humidity difference 50%, and the test results were as follows.
The table shows that the invention has good mechanical strength and barrier effect.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. A preparation method of an aluminum-free composite material for pesticide packaging is characterized by comprising the following steps: the method specifically comprises the following steps:
mixing PE particles, modified polyester, dimethylbenzene and dibenzoyl peroxide for reaction, adding modified filler, uniformly mixing, radiating by Ultraviolet (UV), filtering to remove filtrate, soaking a substrate in a copper sulfate pentahydrate aqueous solution, taking out and drying after soaking treatment, and thus obtaining the aluminum-free composite material for pesticide packaging.
2. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 1, wherein the method comprises the following steps: the mass ratio of the PE particles to the modified polyester is 10:0.8-1, the dosage of dibenzoyl peroxide is 0.5-1.0% of the sum of the PE particles and the modified polyester, and the concentration of the aqueous solution of the copper sulfate pentahydrate is 0.1M.
3. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 1, wherein the method comprises the following steps: the modified polyester is prepared by the following steps:
step A1: mixing and refluxing benzotriazole, potassium hydroxide, epichlorohydrin and tetrabutylammonium bromide to react to prepare an intermediate 1, and mixing and reacting 1, 3-diamino-2-propanol, acrylic acid, p-toluenesulfonic acid and toluene to prepare an intermediate 2;
step A2: mixing intermediate 1, intermediate 2 and DMF for reaction to obtain intermediate 3, adding Y-aminopropyl methyl diethoxy silane and dimethyl dichlorosilane into deionized water, stirring, adding tetrahydrofuran and concentrated sulfuric acid, performing heat preservation treatment, adding 1, 3-tetramethyl disiloxane, and reacting to obtain hydrogen-terminated polysiloxane;
step A3: mixing and stirring hydrogen-terminated polysiloxane, an intermediate 3 and DMF, adding chloroplatinic acid, heating for reaction to obtain a diol polysiloxane, mixing and stirring the diol polysiloxane, maleic anhydride and diethyl ether, removing diethyl ether, adding manganese acetate, triethylamine and anhydride, and reacting to obtain a modified diol polysiloxane;
step A4: mixing modified glycol polysiloxane, terephthalic acid, ethylene glycol and antimony trioxide, introducing nitrogen to remove air, reacting, and heating to react to obtain the modified polyester.
4. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 3, wherein the method comprises the following steps: the molar ratio of the benzotriazole, the potassium hydroxide, the epichlorohydrin and the tetrabutylammonium bromide in the step A1 is 2:3:3:0.2, the molar ratio of the 1, 3-diamino-2-propanol and the acrylic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 3-5% of the sum of the mass of the 1, 3-diamino-2-propanol and the acrylic acid.
5. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 3, wherein the method comprises the following steps: the molar ratio of the intermediate 1 to the intermediate 2 in the step A2 is 2:1, the mass ratio of the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the deionized water to the 1, 3-tetramethyl disiloxane is 1mmol to 5mL to 2mmol, and the mass ratio of the concentrated sulfuric acid to the Y-aminopropyl methyl diethoxy silane to the dimethyl dichloro silane to the 1, 3-tetramethyl disiloxane is 5-8%.
6. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 3, wherein the method comprises the following steps: the mol ratio of the hydrogen-terminated polysiloxane to the intermediate 3 in the step A3 is 1:2, and the concentration of chloroplatinic acid in the mixture of the hydrogen-terminated polysiloxane and the intermediate 3 dissolved in the mixture is 10-15ppm, and the dosage ratio of the glycol polysiloxane, the maleic anhydride, the manganese acetate, the triethylamine and the anhydride is 0.1mol:0.2mol:0.11g:7mL 60mL.
7. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 3, wherein the method comprises the following steps: the mole ratio of the modified glycol polysiloxane to the terephthalic acid to the glycol in the step A4 is 0.8:1.4:0.5, and the amount of the antimony trioxide is 0.025-0.03 percent of the mass sum of the modified glycol polysiloxane, the terephthalic acid and the glycol.
8. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 1, wherein the method comprises the following steps: the modified filler is prepared by the following steps:
mixing graphene oxide, deionized water and ethanol, stirring, adding ammonia water and tetraethoxysilane, continuously stirring for 10-15h, centrifuging to remove supernatant, washing a substrate with ammonia water, drying to obtain a pretreated filler, dispersing the pretreated filler in deionized water, adding KH580, stirring, filtering to remove filtrate, and drying a filter cake to obtain the modified filler.
9. The method for preparing the aluminum-free composite material for pesticide packaging according to claim 8, wherein the method comprises the following steps: the dosage ratio of graphene oxide, deionized water, ethanol, ammonia water and tetraethoxysilane is 0.04g:3mL:80mL:4mL:1mL, and KH580 is 3-5% of the mass of the pretreated filler.
10. An aluminum-free composite material for pesticide packaging, which is characterized in that: the preparation method according to any one of claims 1 to 9.
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