CN117487217A - High-strength heat-resistant PETG battery label film and preparation method thereof - Google Patents
High-strength heat-resistant PETG battery label film and preparation method thereof Download PDFInfo
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- CN117487217A CN117487217A CN202311470926.2A CN202311470926A CN117487217A CN 117487217 A CN117487217 A CN 117487217A CN 202311470926 A CN202311470926 A CN 202311470926A CN 117487217 A CN117487217 A CN 117487217A
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- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 29
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005266 casting Methods 0.000 claims abstract description 14
- DWKPPFQULDPWHX-UHFFFAOYSA-N methyl 2-aminopropanoate Chemical compound COC(=O)C(C)N DWKPPFQULDPWHX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 33
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 125000003158 alcohol group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 7
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 229940119177 germanium dioxide Drugs 0.000 claims description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000009966 trimming Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000000052 comparative effect Effects 0.000 description 22
- 230000001105 regulatory effect Effects 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007718 adhesive strength test Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a high-strength heat-resistant PETG battery label film and a preparation method thereof, and relates to the technical field of PETG films. The high-strength heat-resistant PETG battery label film is prepared by adding a chain extender and a cross-linking agent into PETG, then melting and extruding, casting and stretching into a film; the chain extender is prepared by reacting 2-aminobenzothiazole, dialdehydylbenzene and triphenyl phosphite, the dialdehydylbenzene is prepared by reacting 2, 5-dimethyl-1, 4-dibromobenzene and N, N-dimethylformamide, the cross-linking agent is prepared by reacting 1,3, 5-tribenzyl alcohol-s-triazine and methyl aminopropionate, and the cross-linking agent is tightly entangled with PETG while reacting with PETG end groups, so that the heat resistance of the PETG battery label film is enhanced, and the tensile strength of the PETG battery label film is improved.
Description
Technical Field
The invention relates to the technical field of PETG (polyethylene terephthalate glycol) films, in particular to a high-strength heat-resistant PETG battery label film and a preparation method thereof.
Background
Compared with PET, the PETG has greatly improved performance and processing performance, and the product has high transparency, excellent shock resistance, good heat stability and toughness, and even maintains the due toughness at low temperature.
When the PETG film is used for a battery label, the PETG film is often required to have higher strength, enough heat resistance and enough viscosity to meet the long-time temperature rise when the battery is used, and the falling off and damage of the PETG battery label film are prevented. Therefore, the invention researches and prepares the high-strength heat-resistant PETG battery label film with high strength, heat resistance and excellent viscosity.
Disclosure of Invention
The invention aims to provide a high-strength heat-resistant PETG battery label film and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a high-strength heat-resistant PETG battery label film is prepared by adding a chain extender and a cross-linking agent into PETG, then melting and extruding, casting a sheet and stretching to form a film.
Preferably, the chain extender is prepared by reacting 2-aminobenzothiazole, dialdehyde benzene and triphenyl phosphite.
Preferably, the dialkybenzene is prepared by reacting 2, 5-dimethyl-1, 4-dibromobenzene with N, N-dimethylformamide.
Preferably, the cross-linking agent is prepared by reacting 1,3, 5-tribenzyl alcohol group sym-triazine with methyl amino propionate.
Preferably, the preparation method of the high-strength heat-resistant PETG battery label film comprises the following specific steps:
(1) Mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 8-9:7, stirring and dissolving, adding dialdehyde with the mass of 0.3-0.6 times of 2-aminobenzothiazole, heating an oil bath to 50-60 ℃, stirring and reacting for 2-3 hours at 200-400 rpm, adding triphenyl phosphite with the mass of 1.85-1.95 times of 2-aminobenzothiazole, dripping benzaldehyde with the mass of 0.6-0.8 times of 2-aminobenzothiazole at the rate of 1-3 mL/min, continuing to react for 2-4 hours, cooling to room temperature and decompressing to prepare the chain extender;
(2) Under the nitrogen atmosphere, trimethylolpropane, 1,3, 5-tribenzyl alcohol group s-triazine and p-toluenesulfonic acid are mixed according to the mass ratio of 1-3:9:0.06, the temperature is raised to 120-130 ℃ under an oil bath, the heat preservation reaction is carried out for 2-4 hours, after the methanol is removed by vacuum pumping, methyl aminopropionate with the mass of 1.1-1.3 times of that of the 1,3, 5-tribenzyl alcohol group s-triazine is added, the reaction is continued for 2-3 hours, the temperature is reduced to 62-65 ℃, mercaptoacetic acid with the mass of 2-3 times of that of the 1,3, 5-tribenzyl alcohol group s-triazine and azodiisobutyronitrile with the mass of 0.02-0.08 times of that of the 1,3, 5-tribenzyl alcohol group s-triazine are added, and the reaction is continued for 6-8 hours, so as to prepare the cross-linking agent;
(3) Mixing terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony and germanium dioxide into a reaction kettle under the nitrogen atmosphere, regulating the pressure to 0.22-0.24 MPa, regulating the temperature to 220-240 ℃, reacting for 2-4 hours, adding tetrabutyl titanate, pre-condensing for 30-40 minutes, heating to 275-278 ℃, continuing to react for 4-6 hours, discharging and granulating to obtain PETG master batch;
(4) And mixing PETG master batches, a chain extender and a cross-linking agent according to the mass ratio of 80-90:2-4:1-3, carrying out melt extrusion, cooling and forming through a casting roll to form a casting sheet, and finally carrying out stretching, trimming and rolling to obtain the high-strength heat-resistant PETG battery label film.
Preferably, in the step (1): the preparation method of dialdehyde benzene comprises the following steps: 2, 5-dimethyl-1, 4-dibromobenzene, tetramethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 5:0.15-0.17:100 in a nitrogen atmosphere, placed in a dry ice ethanol bath, the temperature is controlled to be minus 75-minus 80 ℃, a normal hexane solution of 3-5% of tert-butyllithium with the mass ratio of 6-8 times of the mass of 2, 5-dimethyl-1, 4-dibromobenzene is dropwise added at the rate of 1-3 mL/min, stirred at 50-100 rpm for reaction for 20-40 min, N-dimethylformamide with the mass ratio of 0.75-0.85 times of the 2, 5-dimethyl-1, 4-dibromobenzene is added, the mixture is transferred to room temperature, the mixture is continuously stirred for reaction for 50-80 min, the mixture is transferred to an ice bath, then saturated ammonium chloride solution with the mass ratio of 6-8 times of 2, 5-dimethyl-1, 4-dibromobenzene is added, the mixture is extracted by ethyl acetate, washed by saturated sodium chloride, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure, and silica gel column chromatography is performed to obtain dialdehyde benzene.
Preferably, in the step (2): the preparation method of the 1,3, 5-tribenzyl alcohol group s-triazine comprises the following steps: mixing formaldehyde solution with the mass fraction of 20-30% with o-aminobenzyl alcohol according to the volume ratio of 4-6:1 in nitrogen atmosphere, stirring and dissolving, stirring and reacting for 2-4 hours at 100-200 rpm, standing and layering, performing rotary evaporation, and separating by column chromatography to obtain the 1,3, 5-tribenzyl alcohol group sym-triazine.
Preferably, in the step (2): the preparation method of the methyl aminopropionate comprises the following steps: under the nitrogen atmosphere, mixing diallyl amine, methyl acrylate and methanol according to the mass ratio of 1-1.2:1:100, heating to 30-35 ℃ after uniformly stirring, continuously reacting for 4-6 h, and vacuumizing to remove the methanol to obtain the methyl amino propionate.
Preferably, in the step (3): the mass ratio of terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony, germanium dioxide and tetrabutyl titanate is 1:1.4-1.6:0.6-0.8:0.4:0.3:0.02-0.05.
Preferably, in the step (4): the temperature of the melt extrusion is 260-280 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the high-strength heat-resistant PETG battery label film prepared by the invention is prepared by adding a chain extender and a cross-linking agent into PETG, then melting and extruding, casting and stretching into a film;
the chain extender is prepared by reacting 2-aminobenzothiazole, dialdehyde benzene and triphenyl phosphite, dialdehyde benzene is prepared by reacting 2, 5-dimethyl-1, 4-dibromobenzene and N, N-dimethylformamide, two aldehyde groups are introduced at the para position of a benzene ring to react with 2-aminobenzothiazole in a dehydration way, symmetrical benzothiazole heterocyclic structures are introduced at the para position of the benzene ring, and then the benzene ring reacts with triphenyl phosphite and water to react to form diphenyl phosphite, so that the chain extender with long chain and symmetrical structure is prepared, after the chain extender is mixed with PETG, the entanglement of molecular chains is increased, and the balance torque can be increased, thereby improving the bonding strength of PETG battery label film;
the cross-linking agent is prepared by reacting 1,3, 5-tribenzyl alcohol group sym-triazine with methyl amino propionate; methyl amino propionate with double bond and amino is introduced to 1,3, 5-tribenzyl alcohol group sym-triazine with triazine structure to form cross-linking agent with hyperbranched structure of triazine ring, and the cross-linking agent is added into a system of PETG and chain extender to react with PETG end groups to form three-dimensional cross-linked network structure, and the chain extender is tightly entangled with PETG to increase cross-linking density, thereby enhancing heat resistance of PETG battery label film and improving tensile strength of PETG battery label film.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the respective index test methods of the high-strength heat-resistant PETG battery label films prepared in the examples and comparative examples as follows:
tensile strength: the high strength heat resistant PETG battery label films prepared in examples and comparative examples were subjected to tensile strength test with reference to GB/T1040.3.
Adhesive strength: the high-strength heat-resistant PETG battery label films prepared in examples and comparative examples were adhered to the same battery surface, and the adhesive strength was measured with an adhesive strength tester.
Heat resistance: the high-strength heat-resistant PETG battery label films prepared in examples and comparative examples were subjected to adhesive strength test again after being left at 80 ℃ for 24 hours.
Example 1
(1) Mixing 2, 5-dimethyl-1, 4-dibromobenzene, tetramethyl ethylenediamine and tetrahydrofuran according to a mass ratio of 5:0.15:100 in a nitrogen atmosphere, placing the mixture in a dry ice ethanol bath, controlling the temperature to be minus 75 ℃, dropwise adding an N-hexane solution of tert-butyllithium with the mass fraction of 3% which is 6 times that of 2, 5-dimethyl-1, 4-dibromobenzene at a rate of 1mL/min, stirring at 50rpm for reacting for 20min, adding N, N-dimethylformamide with the mass of 0.75 times that of 2, 5-dimethyl-1, 4-dibromobenzene, transferring to room temperature, continuing stirring for reacting for 50min, transferring to an ice bath, adding a saturated ammonium chloride solution with the mass of 6 times that of 2, 5-dimethyl-1, 4-dibromobenzene, extracting with ethyl acetate, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, filtering, decompressing and concentrating, and performing silica gel column chromatography to obtain dialdehyde benzene; mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 8:7, stirring and dissolving, adding dialdehyde benzene with the mass of 0.3 times of the 2-aminobenzothiazole, heating to 50 ℃ in an oil bath, stirring and reacting for 2 hours at 200rpm, adding triphenyl phosphite with the mass of 1.85 times of the 2-aminobenzothiazole, dripping benzaldehyde with the mass of 0.6 times of the 2-aminobenzothiazole at the rate of 1mL/min, continuing to react for 2 hours, cooling to room temperature and decompressing to obtain the chain extender;
(2) Mixing formaldehyde solution with the mass fraction of 20% with o-aminobenzyl alcohol according to the volume ratio of 4:1 in nitrogen atmosphere, stirring and dissolving, stirring and reacting for 2 hours at 100rpm, standing and layering, performing rotary evaporation, and separating by column chromatography to obtain 1,3, 5-tribenzyl alcohol group sym-triazine; under the nitrogen atmosphere, mixing diallyl amine, methyl acrylate and methanol according to the mass ratio of 1:1:100, uniformly stirring, heating to 30 ℃, continuously reacting for 4 hours, and vacuumizing to remove the methanol to obtain methyl amino propionate; under the nitrogen atmosphere, mixing trimethylolpropane, 1,3, 5-tribenzyl alcohol-based s-triazine and p-toluenesulfonic acid according to the mass ratio of 1:9:0.06, heating to 120 ℃ in an oil bath, preserving heat for 2 hours, vacuumizing to remove methanol, adding methyl aminopropionate with the mass 1.1 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine, continuously reacting for 2 hours, cooling to 62 ℃, adding thioglycollic acid with the mass 2 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine and azodiisobutyronitrile with the mass 0.02 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine, and continuously reacting for 6 hours to obtain a cross-linking agent;
(3) Mixing terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony and germanium dioxide in a reaction kettle under the nitrogen atmosphere, regulating the pressure to 0.22MPa, regulating the temperature to 220 ℃, adding tetrabutyl titanate after reacting for 2 hours, pre-condensing for 30 minutes, heating to 275 ℃ and continuously reacting for 4 hours, discharging and granulating to obtain PETG master batch;
(4) And mixing PETG master batches, a chain extender and a cross-linking agent according to a mass ratio of 80:2:1, carrying out melt extrusion at 260 ℃, cooling and forming through a casting roll to form a casting sheet, and finally stretching, trimming and rolling to obtain the high-strength heat-resistant PETG battery label film.
Example 2
(1) Mixing 2, 5-dimethyl-1, 4-dibromobenzene, tetramethyl ethylenediamine and tetrahydrofuran according to a mass ratio of 5:0.16:100 in a nitrogen atmosphere, placing the mixture in a dry ice ethanol bath, controlling the temperature to be minus 78 ℃, dropwise adding an N-hexane solution of tert-butyllithium with the mass fraction of 4% which is 7 times that of 2, 5-dimethyl-1, 4-dibromobenzene at a rate of 2mL/min, stirring at 70rpm for reaction for 30min, adding N, N-dimethylformamide with the mass of 0.8 times that of 2, 5-dimethyl-1, 4-dibromobenzene, transferring to room temperature, continuing stirring for reaction for 60min, transferring to an ice bath, adding a saturated ammonium chloride solution with the mass of 7 times that of 2, 5-dimethyl-1, 4-dibromobenzene, extracting with ethyl acetate, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, filtering, decompressing and concentrating, and performing silica gel column chromatography to obtain dialdehyde benzene; mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 8.5:7, stirring and dissolving, adding dialdehyde benzene with the mass of 0.45 times of the 2-aminobenzothiazole, heating to 55 ℃ in an oil bath, stirring and reacting for 2.5 hours at 300rpm, adding triphenyl phosphite with the mass of 1.9 times of the 2-aminobenzothiazole, dripping benzaldehyde with the mass of 0.7 times of the 2-aminobenzothiazole at the rate of 2mL/min, continuing to react for 3 hours, cooling to room temperature and decompressing to obtain the chain extender;
(2) Mixing formaldehyde solution with the mass fraction of 25% with o-aminobenzyl alcohol according to the volume ratio of 5:1 in a nitrogen atmosphere, stirring and dissolving, stirring and reacting for 3 hours at 150rpm, standing and layering, performing rotary evaporation, and separating by column chromatography to obtain 1,3, 5-tribenzyl alcohol group sym-triazine; under the nitrogen atmosphere, mixing diallyl amine, methyl acrylate and methanol according to the mass ratio of 1.1:1:100, uniformly stirring, heating to 32 ℃, continuously reacting for 5 hours, and vacuumizing to remove the methanol to obtain methyl amino propionate; under the nitrogen atmosphere, mixing trimethylolpropane, 1,3, 5-dibenzyl alcohol-based s-triazine and p-toluenesulfonic acid according to the mass ratio of 2:9:0.06, heating to 125 ℃ in an oil bath, preserving heat for 3 hours, vacuumizing to remove methanol, adding methyl aminopropionate with the mass of 1.2 times that of the 1,3, 5-dibenzyl alcohol-based s-triazine, continuously reacting for 2.5 hours, cooling to 64 ℃, adding thioglycollic acid with the mass of 2.5 times that of the 1,3, 5-dibenzyl alcohol-based s-triazine and azodiisobutyronitrile with the mass of 0.06 times that of the 1,3, 5-dibenzyl alcohol-based s-triazine, and continuously reacting for 9 hours to obtain a cross-linking agent;
(3) Mixing terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony and germanium dioxide in a reaction kettle under the nitrogen atmosphere, regulating the pressure to 0.23MPa, regulating the temperature to 230 ℃, adding tetrabutyl titanate after reacting for 3 hours, pre-condensing for 35 minutes, heating to 276 ℃, continuously reacting for 5 hours, discharging and granulating to obtain PETG master batch;
(4) And mixing PETG master batches, a chain extender and a cross-linking agent according to a mass ratio of 85:3:2, carrying out melt extrusion at 270 ℃, cooling and forming through a casting roll to form a casting sheet, and finally stretching, trimming and rolling to obtain the high-strength heat-resistant PETG battery label film.
Example 3
(1) Mixing 2, 5-dimethyl-1, 4-dibromobenzene, tetramethyl ethylenediamine and tetrahydrofuran according to a mass ratio of 5:0.17:100 in a nitrogen atmosphere, placing the mixture in a dry ice ethanol bath, controlling the temperature to be-80 ℃, dropwise adding an N-hexane solution of tert-butyllithium with the mass fraction of 5% which is 8 times that of 2, 5-dimethyl-1, 4-dibromobenzene at a rate of 3mL/min, stirring at 100rpm for reaction for 40min, adding N, N-dimethylformamide with the mass of 0.85 times that of 2, 5-dimethyl-1, 4-dibromobenzene, transferring to room temperature, continuing stirring for reaction for 80min, transferring to an ice bath, adding a saturated ammonium chloride solution with the mass of 8 times that of 2, 5-dimethyl-1, 4-dibromobenzene, extracting with ethyl acetate, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, filtering, decompressing and concentrating, and performing silica gel column chromatography to obtain dialdehyde benzene; mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 9:7, stirring and dissolving, adding dialdehyde benzene with the mass of 0.6 times of the 2-aminobenzothiazole, heating to 60 ℃ in an oil bath, stirring and reacting for 3 hours at 400rpm, adding triphenyl phosphite with the mass of 1.95 times of the 2-aminobenzothiazole, dripping benzaldehyde with the mass of 0.8 times of the 2-aminobenzothiazole at the rate of 3mL/min, continuing to react for 4 hours, cooling to room temperature and decompressing to obtain the chain extender;
(2) Mixing formaldehyde solution with the mass fraction of 30% with o-aminobenzyl alcohol according to the volume ratio of 6:1 in nitrogen atmosphere, stirring and dissolving, stirring and reacting for 4 hours at 200rpm, standing and layering, performing rotary evaporation, and separating by column chromatography to obtain 1,3, 5-tribenzyl alcohol group sym-triazine; under the nitrogen atmosphere, mixing diallyl amine, methyl acrylate and methanol according to the mass ratio of 1.2:1:100, uniformly stirring, heating to 35 ℃, continuously reacting for 6 hours, and vacuumizing to remove the methanol to obtain methyl amino propionate; under the nitrogen atmosphere, mixing trimethylolpropane, 1,3, 5-tribenzyl alcohol-based s-triazine and p-toluenesulfonic acid according to the mass ratio of 3:9:0.06, heating to 130 ℃ in an oil bath, preserving heat for 4 hours, vacuumizing to remove methanol, adding methyl aminopropionate with the mass 1.3 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine, continuously reacting for 3 hours, cooling to 65 ℃, adding thioglycollic acid with the mass 3 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine and azodiisobutyronitrile with the mass 0.08 times of that of the 1,3, 5-tribenzyl alcohol-based s-triazine, and continuously reacting for 8 hours to obtain a cross-linking agent;
(3) Mixing terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony and germanium dioxide in a reaction kettle under the nitrogen atmosphere, regulating the pressure to 0.24MPa, regulating the temperature to 240 ℃, adding tetrabutyl titanate after reacting for 4 hours, pre-condensing for 40 minutes, heating to 278 ℃, continuously reacting for 6 hours, discharging and granulating to obtain PETG master batch;
(4) And mixing PETG master batches, a chain extender and a cross-linking agent according to a mass ratio of 90:4:3, carrying out melt extrusion at 280 ℃, cooling and forming through a casting roll to form a casting sheet, and finally stretching, trimming and rolling to obtain the high-strength heat-resistant PETG battery label film.
Comparative example 1
Comparative example 1 has the same composition as example 2. The method for preparing the high-strength heat-resistant PETG battery label film is different from example 2 in that step (1) is modified as follows: mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 8.5:7, stirring and dissolving, heating an oil bath to 55 ℃, stirring and reacting for 2.5 hours at 300rpm, adding triphenyl phosphite with the mass 1.9 times of that of the 2-aminobenzothiazole, dripping benzaldehyde with the mass 0.7 times of that of the 2-aminobenzothiazole at the rate of 2mL/min, continuing to react for 3 hours, cooling to room temperature and decompressing to obtain the chain extender.
Comparative example 2
Comparative example 2 has the same composition as example 2. The preparation method of the high-strength heat-resistant PETG battery label film is different from that of the embodiment 2 in that the chain extender is only triphenyl phosphite.
Comparative example 3
Comparative example 3 has the same composition as example 2. The preparation method of the high-strength heat-resistant PETG battery label film is different from example 2 only in that the crosslinking agent is methyl amino propionate only.
Comparative example 4
Comparative example 4 has the same composition as example 2. The preparation method of the high-strength heat-resistant PETG battery label film is different from that of the example 2 in that the cross-linking agent is only 1,3, 5-tribenzyl alcohol group s-triazine.
Comparative example 5
Comparative example 5 has the same composition as example 2. The method of preparing the high strength heat resistant PETG battery label film differs from example 2 in that the high strength heat resistant PETG battery label film further comprises PETG master batch and a chain extender.
Comparative example 6
Comparative example 6 has the same composition as example 2. The method for preparing the high-strength heat-resistant PETG battery label film is different from example 2 in that the high-strength heat-resistant PETG battery label film further comprises PETG master batch and a crosslinking agent.
Effect example
The following table 1 gives the results of performance analysis of the high strength heat-resistant PETG battery label films prepared using examples 1 to 3 of the present invention and comparative examples 1 to 6:
TABLE 1
As is apparent from comparison of experimental data of examples in table 1 with comparative examples, the high-strength heat-resistant PETG battery label films prepared using examples 1, 2, 3 were superior in weather resistance, deformation resistance, and adhesive strength.
From the comparison of experimental data of example 1, example 2, example 3 and comparative example 1, comparative example 2 and comparative example 6, it can be found that dialdehyde benzene prepared by reacting 2, 5-dimethyl-1, 4-dibromobenzene with N, N-dimethylformamide, chain extender prepared by reacting 2-aminobenzothiazole with triphenyl phosphite, two aldehyde groups introduced at para position of benzene ring, dehydration reaction with 2-aminobenzothiazole, symmetrical benzothiazole heterocyclic structure introduced at para position of benzene ring, diphenyl phosphite reacted with triphenyl phosphite to form diphenyl phosphite, chain extender with long chain and symmetrical structure is prepared, after mixing with PETG, molecular chain entanglement is increased, balance torque can be increased, and viscosity of PETG battery label film is improved.
From comparison of experimental data of examples 1, 2, 3 and 3, and comparative examples 4 and 5, it can be found that the cross-linking agent prepared by reacting 1,3, 5-tribenzyl alcohol group s-triazine with methyl amino propionate introduces methyl amino propionate having double bond and amino group on the 1,3, 5-tribenzyl alcohol group s-triazine having triazine structure, forms cross-linking agent with hyperbranched structure of triazine ring, adds into the system of PETG and chain extender, reacts with PETG end group, forms three-dimensional cross-linked network structure, and tightly entangles the chain extender with PETG to increase cross-linking density, thereby enhancing heat resistance of PETG battery label film and improving tensile strength of PETG battery label film.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The high-strength heat-resistant PETG battery label film is characterized in that the high-strength heat-resistant PETG battery label film is prepared by adding a chain extender and a cross-linking agent into PETG, then melting and extruding, casting and then stretching into a film.
2. The high strength heat resistant PETG battery label film of claim 1, wherein the chain extender is 2-aminobenzothiazole, dialdehyde benzene and triphenyl phosphite.
3. The high strength heat resistant PETG battery label film of claim 2, wherein said dialdehyde benzene is prepared by reacting 2, 5-dimethyl-1, 4-dibromobenzene with N, N-dimethylformamide.
4. The high strength heat resistant PETG battery label film of claim 1, wherein the cross-linking agent is 1,3,5, -tribenzyl alcohol s-triazine reacted with methyl amino propionate.
5. The preparation method of the high-strength heat-resistant PETG battery label film is characterized by comprising the following specific steps of:
(1) Mixing 2-aminobenzothiazole and glacial acetic acid according to the mass ratio of 8-9:7, stirring and dissolving, adding dialdehyde with the mass of 0.3-0.6 times of 2-aminobenzothiazole, heating an oil bath to 50-60 ℃, stirring and reacting for 2-3 hours at 200-400 rpm, adding triphenyl phosphite with the mass of 1.85-1.95 times of 2-aminobenzothiazole, dripping benzaldehyde with the mass of 0.6-0.8 times of 2-aminobenzothiazole at the rate of 1-3 mL/min, continuing to react for 2-4 hours, cooling to room temperature and decompressing to obtain the chain extender;
(2) Under the nitrogen atmosphere, mixing trimethylolpropane, 1,3, 5-tribenzyl alcohol-based s-triazine and p-toluenesulfonic acid according to the mass ratio of 1-3:9:0.06, heating to 120-130 ℃ in an oil bath, preserving heat for 2-4 h, vacuumizing to remove methanol, adding methyl aminopropionate with the mass of 1.1-1.3 times that of 1,3, 5-tribenzyl alcohol-based s-triazine, continuously reacting for 2-3 h, cooling to 62-65 ℃, adding mercaptoacetic acid with the mass of 2-3 times that of 1,3, 5-tribenzyl alcohol-based s-triazine and azodiisobutyronitrile with the mass of 0.02-0.08 times that of 1,3, 5-tribenzyl alcohol-based s-triazine, and continuously reacting for 6-8 h to obtain a cross-linking agent;
(3) Mixing terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony and germanium dioxide into a reaction kettle in a nitrogen atmosphere, adjusting the pressure to 0.22-0.24 MPa, adjusting the temperature to 220-240 ℃, reacting for 2-4 hours, adding tetrabutyl titanate, pre-condensing for 30-40 minutes, heating to 275-278 ℃, continuously reacting for 4-6 hours, discharging and granulating to obtain PETG master batch;
(4) And mixing PETG master batches, a chain extender and a cross-linking agent according to a mass ratio of 80-90:2-4:1-3, carrying out melt extrusion, cooling and forming through a casting roll to form a casting, and finally stretching, trimming and rolling to obtain the high-strength heat-resistant PETG battery label film.
6. The method for producing a high-strength heat-resistant PETG battery label film according to claim 5, wherein in the above step (1): the preparation method of dialdehyde benzene comprises the following steps: 2, 5-dimethyl-1, 4-dibromobenzene, tetramethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 5:0.15-0.17:100 in a nitrogen atmosphere, placed in a dry ice ethanol bath, the temperature is controlled to be minus 75-80 ℃, a normal hexane solution of 3-5% of tert-butyllithium with the mass ratio of 6-8 times of that of 2, 5-dimethyl-1, 4-dibromobenzene is dropwise added at the rate of 1-3 mL/min, stirred at 50-100 rpm for reaction for 20-40 min, N-dimethylformamide with the mass ratio of 0.75-0.85 times of that of 2, 5-dimethyl-1, 4-dibromobenzene is added, the mixture is transferred to room temperature, the mixture is continuously stirred for reaction for 50-80 min, the mixture is transferred to an ice bath, then saturated ammonium chloride solution with the mass ratio of 6-8 times of 2, 5-dimethyl-1, 4-dibromobenzene is added, the mixture is extracted by ethyl acetate, washed by saturated sodium chloride, dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure, and silica gel column chromatography is performed to obtain dialdehyde benzene.
7. The method for producing a high-strength heat-resistant PETG battery label film according to claim 5, wherein in the above step (2): the preparation method of the 1,3, 5-tribenzyl alcohol group s-triazine comprises the following steps: mixing formaldehyde solution with the mass fraction of 20-30% with o-aminobenzyl alcohol according to the volume ratio of 4-6:1 in a nitrogen atmosphere, stirring and dissolving, stirring and reacting for 2-4 hours at 100-200 rpm, standing and layering, performing rotary evaporation, and separating by column chromatography to obtain the 1,3, 5-tribenzyl alcohol-based sym-triazine.
8. The method for producing a high-strength heat-resistant PETG battery label film according to claim 5, wherein in the above step (2): the preparation method of the methyl aminopropionate comprises the following steps: under the nitrogen atmosphere, mixing diallyl amine, methyl acrylate and methanol according to the mass ratio of 1-1.2:1:100, heating to 30-35 ℃ after uniformly stirring, continuously reacting for 4-6 h, and vacuumizing to remove the methanol to obtain the methyl amino propionate.
9. The method for producing a high-strength heat-resistant PETG battery label film according to claim 5, wherein in the above step (3): the mass ratio of terephthalic acid, ethylene glycol, 1, 4-cyclohexanedimethanol, ethylene glycol antimony, germanium dioxide and tetrabutyl titanate is 1:1.4-1.6:0.6-0.8:0.4:0.3:0.02-0.05.
10. The method for producing a high-strength heat-resistant PETG battery label film according to claim 5, wherein in the above step (4): the temperature of the melt extrusion is 260-280 ℃.
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