CN117700955A - Antibacterial PET film material and preparation method thereof - Google Patents
Antibacterial PET film material and preparation method thereof Download PDFInfo
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- CN117700955A CN117700955A CN202410169317.1A CN202410169317A CN117700955A CN 117700955 A CN117700955 A CN 117700955A CN 202410169317 A CN202410169317 A CN 202410169317A CN 117700955 A CN117700955 A CN 117700955A
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- isophthalate
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 229920002799 BoPET Polymers 0.000 title claims abstract description 42
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 59
- 239000005011 phenolic resin Substances 0.000 claims abstract description 32
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 31
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 30
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 26
- 125000001302 tertiary amino group Chemical group 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 16
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- AUESJGZPPPVYJZ-UHFFFAOYSA-N 2-(chloromethyl)phenol Chemical compound OC1=CC=CC=C1CCl AUESJGZPPPVYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 19
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VKRJVJZWDJDJBX-UHFFFAOYSA-N 1-chloro-4-(chloromethoxy)butane Chemical compound ClCCCCOCCl VKRJVJZWDJDJBX-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
The invention relates to the technical field of PET (polyethylene terephthalate) polyester and discloses an antibacterial PET film material and a preparation method thereof. And (3) blending with polyethylene terephthalate, casting to form a film, and obtaining the antibacterial PET film material. The quaternary ammonium salt groups between the phenolic resin and the polyester are uniformly distributed in the PET film, so that the antibacterial property, the thermal decomposition temperature and the barrier property of the film material are obviously improved.
Description
Technical Field
The invention relates to the technical field of PET (polyethylene terephthalate) polyesters, in particular to an antibacterial PET film material and a preparation method thereof.
Background
The antibacterial film material is required to have the performances of no toxicity, environmental protection, good antibacterial broad spectrum and the like, and has important application in the aspects of medical supplies, food packaging and the like. Antibacterial agents such as halamines, polypeptides, quaternary ammonium salts and the like are usually added to the membrane material; compared with a small molecular antibacterial agent, the compatibility of the macromolecular antibacterial agent and a material matrix is better; has no great influence on the service performance of the material. Polyethylene terephthalate PET film material is widely applied in the fields of electronic appliances, medical supplies, packaging materials and the like. The traditional PET and the film material thereof have no antibacterial property, which prevents the practical application of the PET and the film material thereof. The phenolic resin has good chemical stability, high temperature resistance and mechanical strength, can be used as a modified material, and has good application in high polymer materials such as polyester, epoxy resin and the like. The invention aims to improve the heat resistance, the barrier property and the antibacterial property of PET and film materials thereof by utilizing functional quaternary ammonium salt phenolic resin-polyester master batches.
Disclosure of Invention
The invention solves the technical problems that: provides an antibacterial PET film material, solves the problems that the PET film material has poor heat resistance and no antibacterial property.
The technical scheme of the invention is as follows:
an antibacterial PET film material comprises the following components: 100 parts by weight of polyethylene terephthalate, 5-20 parts by weight of quaternary ammonium salt phenolic resin-polyester master batch and 0.4-0.8 part by weight of antioxidant.
The quaternary ammonium salt phenolic resin-polyester master batch is prepared according to the following method:
(1) Adding dimethyl terephthalate, 5- (tertiary amino) dimethyl isophthalate, ethylene glycol and manganese acetate into a reaction kettle, introducing nitrogen, uniformly mixing, heating to 170-180 ℃, reacting for 30-60min, heating to 220-235 ℃, reacting for 2-4h, finally adding ethylene glycol antimony, heating to 265-275 ℃, reacting for 3-4h, and pressurizing and discharging with nitrogen to obtain tertiary amino polyester.
(2) Adding tertiary amine polyester and chloromethyl phenolic resin into a double screw extruder, and blending and extruding to obtain quaternary ammonium salt phenolic resin-polyester master batch.
Further, the ratio of dimethyl terephthalate, dimethyl 5- (tertiary amino) isophthalate, and ethylene glycol in (1) is (0.7-0.95) mol, (0.05-0.3) mol and (1.8-2.3) mol.
Further, the mass ratio of the tertiary amine polyester to the chloromethyl phenol resin in (2) is 1g (0.1-0.5 g).
Further, the temperature of each section of the twin-screw extruder in the step (2) is 240-260 ℃, and the screw rotating speed is 30-60r/min.
Further, dimethyl 5- (tertiary amino) isophthalate was prepared as follows:
(3) Adding thionyl chloride and 5,5- (hydroxymethyl) dimethyl isophthalate into a reaction bottle, reacting for 2-4 hours at 60-70 ℃, concentrating to remove thionyl chloride, and recrystallizing the product in ethyl acetate to obtain 5,5- (chloromethyl) dimethyl isophthalate; the structure is that。
(4) Adding ethanol, 5- (chloromethyl) dimethyl isophthalate, dimethylamine and catalyst sodium carbonate into a reaction bottle, stirring for reaction, concentrating a solvent, washing with water, and recrystallizing the product in ethyl acetate to obtain 5- (tertiary amino) dimethyl isophthalate; the structure is that。
Further, the ratio of 5,5- (chloromethyl) isophthalate to dimethylamine to sodium carbonate in (4) was 1mol (2.5-3.2) mol (2-3) mol.
Further, the reaction in (4) is carried out at 40-60℃for 2-5 hours.
Further, the preparation method of the antibacterial PET film material is characterized in that 100 parts by weight of polyethylene terephthalate, 5-20 parts by weight of quaternary ammonium salt phenolic resin-polyester master batch and 0.4-0.8 part by weight of antioxidant are added into a double-screw extruder for extrusion, the temperature of each section is 250-275 ℃, and the screw rotating speed is 30-50r/min; then extruding and casting the film in an extrusion casting machine at 270-280 ℃ to obtain the antibacterial PET film material.
The invention has the technical effects that: the method comprises the steps of chlorinating 5,5- (hydroxymethyl) isophthalate, then reacting with dimethylamine to obtain 5- (tertiary amino) isophthalate, and finally carrying out transesterification polycondensation reaction with dimethyl terephthalate and ethylene glycol to obtain tertiary amino polyester, so that tertiary amine groups are introduced into the side chains of the polyester.
According to the invention, tertiary amine polyester and chloromethyl phenolic resin are blended and extruded, and in the extrusion process, the tertiary amine group of PET polyester and chloromethyl of phenolic resin generate a quaternary ammonium salt structure, so that the phenolic resin and polyester are bonded through chemical bonds, the compatibility between the phenolic resin and polyester is improved, and the quaternary ammonium salt phenolic resin-polyester functional master batch with uniform disperse phase is formed.
The invention blends functional quaternary ammonium salt phenolic resin-polyester master batch and polyethylene glycol terephthalate and tape-casts the blend to form a film, thus obtaining the antibacterial PET film material. The quaternary ammonium salt groups between the phenolic resin and the polyester are uniformly distributed in the PET film, so that the antibacterial performance of the film material is remarkably improved; meanwhile, the phenolic resin has strong heat resistance, good compatibility with PET matrix and excellent dispersibility, and can improve the thermal decomposition temperature and heat resistance of the PET film, reduce the water vapor permeability of the PET film and facilitate the improvement of the barrier property of the film material.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
10g of phenolic resin is dissolved in an acetone solvent, 5.8g of zinc chloride and 44g of 1, 4-dichloro methoxybutane are slowly added, the temperature is raised to 58 ℃ for reaction for 6 hours, water is added for standing to form a precipitate, the precipitate is filtered, ethanol and water are washed, and the chloromethyl phenolic resin is obtained after drying.
Example 1
To the reaction flask were added 8mL of thionyl chloride and 50mmol of dimethyl 5,5- (hydroxymethyl) isophthalate, and the mixture was reacted at 65℃for 4 hours, concentrated to remove thionyl chloride, and the product was recrystallized from ethyl acetate to give dimethyl 5,5- (chloromethyl) isophthalate.
To the reaction flask were added ethanol, 50mmol of dimethyl 5,5- (chloromethyl) isophthalate, 125mmol of dimethylamine, 150mmol of sodium carbonate as catalyst, stirred at 40℃for 2 hours, concentrated solvent, washed with water, and the product was recrystallized in ethyl acetate to give dimethyl 5- (tertiary amino) isophthalate. The reaction route is as follows:
95mmol of dimethyl terephthalate, 5mmol of 5- (tertiary amino) dimethyl isophthalate, 180mmol of ethylene glycol and 0.03mmol of manganese acetate are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 180 ℃ after uniform mixing, the reaction is carried out for 60min, then the temperature is raised to 230 ℃ for 3h, finally 0.028mmol of ethylene glycol antimony is added, the temperature is raised to 265 ℃, the reaction is carried out for 4h, and the tertiary amino polyester is obtained after nitrogen pressurization and discharge.
50g tertiary amine polyester and 5g chloromethyl phenolic resin are added into a double screw extruder for blending extrusion, the temperature of each section is 240 ℃, 250 ℃, 260 ℃, 255 ℃ and the screw speed is 60r/min, and the quaternary ammonium salt phenolic resin-polyester master batch is obtained.
1000g of polyethylene terephthalate, 50g of quaternary ammonium salt phenolic resin-polyester master batch and 6g of antioxidant; extruding in a twin-screw extruder at a temperature of 250deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 40r/min; then extruding and casting the film in an extrusion casting machine at the extrusion temperature of 270 ℃ to obtain the antibacterial PET film material.
Example 2
To the reaction flask, 10mL of thionyl chloride and 50mmol of dimethyl 5,5- (hydroxymethyl) isophthalate were added, the mixture was reacted at 70℃for 2 hours, the thionyl chloride was concentrated and removed, and the product was recrystallized from ethyl acetate to give dimethyl 5,5- (chloromethyl) isophthalate.
To the reaction flask were added ethanol, 50mmol of dimethyl 5,5- (chloromethyl) isophthalate, 160mmol of dimethylamine, 150mmol of sodium carbonate as a catalyst, and the mixture was stirred at 40℃for 3 hours to react, the solvent was concentrated, washed with water, and the product was recrystallized from ethyl acetate to obtain dimethyl 5- (tertiary amino) isophthalate.
85mmol of dimethyl terephthalate, 15mmol of 5- (tertiary amino) dimethyl isophthalate, 200mmol of ethylene glycol and 0.04mmol of manganese acetate are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 180 ℃ after uniform mixing, the reaction is carried out for 30min, then the temperature is raised to 220 ℃ for 4h, finally 0.028mmol of ethylene glycol antimony is added, the temperature is raised to 265 ℃, the reaction is carried out for 3h, and the tertiary amino polyester is obtained after nitrogen pressurization and discharge.
50g tertiary amine polyester and 15g chloromethyl phenolic resin are added into a double screw extruder for blending extrusion, the temperature of each section is 240 ℃, 250 ℃, 260 ℃, 255 ℃ and the screw speed is 30r/min, and the quaternary ammonium salt phenolic resin-polyester master batch is obtained.
1000g of polyethylene terephthalate, 120g of quaternary ammonium salt phenolic resin-polyester master batch and 8g of antioxidant; extruding in a twin-screw extruder at a temperature of 250 deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 50r/min; then extruding and casting the film in an extrusion casting machine at the extrusion temperature of 270 ℃ to obtain the antibacterial PET film material.
Example 3
To the reaction flask, 10mL of thionyl chloride and 50mmol of dimethyl 5,5- (hydroxymethyl) isophthalate were added, the mixture was reacted at 60℃for 4 hours, the thionyl chloride was concentrated and removed, and the product was recrystallized from ethyl acetate to give dimethyl 5,5- (chloromethyl) isophthalate.
To the reaction flask were added ethanol, 50mmol of 5,5- (chloromethyl) isophthalate dimethyl ester, 160mmol of dimethylamine, 100mmol of catalyst sodium carbonate, stirred at 60℃for reaction for 5 hours, concentrated solvent, washed with water, and the product was recrystallized in ethyl acetate to obtain 5- (tertiary amino) isophthalate dimethyl ester.
70mmol of dimethyl terephthalate, 30mmol of 5- (tertiary amino) dimethyl isophthalate, 230mmol of ethylene glycol and 0.04mmol of manganese acetate are added into a reaction kettle, nitrogen is introduced, the temperature is raised to 170 ℃ after uniform mixing, the reaction is carried out for 60min, then the temperature is raised to 235 ℃ for 2h, finally 0.038mmol of ethylene glycol antimony is added, the temperature is raised to 275 ℃, the reaction is carried out for 3h, and the tertiary amino polyester is obtained after nitrogen pressurization and discharge.
50g tertiary amine polyester and 25g chloromethyl phenolic resin are added into a double screw extruder for blending extrusion, the temperature of each section is 240 ℃, 250 ℃, 260 ℃, 255 ℃ and the screw speed is 30r/min, and the quaternary ammonium salt phenolic resin-polyester master batch is obtained.
1000g of polyethylene terephthalate, 200g of quaternary ammonium salt phenolic resin-polyester master batch and 4g of antioxidant; extruding in a twin-screw extruder at a temperature of 250 deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 30r/min; then extruding and casting the film in an extrusion casting machine at the extrusion temperature of 280 ℃ to obtain the antibacterial PET film material.
Comparative example 1 and example 1 differ in that in the preparation of the phenolic resin-polyester master batch, a phenolic resin was used instead of chloromethyl phenolic resin.
50g tertiary amine polyester and 5g phenolic resin are added into a double screw extruder for blending extrusion, the temperature of each section is 240 ℃, 250 ℃, 260 ℃, 255 ℃ and the screw speed is 60r/min, and the phenolic resin-polyester master batch is obtained.
1000g of polyethylene terephthalate, 50g of phenolic resin-polyester master batch and 6g of antioxidant; extruding in a twin-screw extruder at a temperature of 250deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 40r/min; and then extruding and casting the PET film material in an extruding and casting machine to form a film, wherein the extruding temperature is 270 ℃.
Comparative example 2 and example 1 differ in that polyethylene terephthalate was used in place of the tertiary amine polyester in the preparation of the phenolic resin-polyester master batch.
50g of polyethylene terephthalate and 5g of chloromethyl phenolic resin are added into a double-screw extruder, and are mixed and extruded, wherein the temperature of each section is 240 ℃, 250 ℃, 260 ℃, 255 ℃ and the screw speed is 60r/min, so as to obtain phenolic resin-polyester master batch.
1000g of polyethylene terephthalate, 50g of phenolic resin-polyester master batch and 6g of antioxidant; extruding in a twin-screw extruder at a temperature of 250deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 40r/min; and then extruding and casting the PET film material in an extruding and casting machine to form a film, wherein the extruding temperature is 270 ℃.
Comparative example 3 and example 1 differ in that no quaternary ammonium salt phenolic resin-polyester master batch was added.
1000g of polyethylene terephthalate and 6g of antioxidant; extruding in a twin-screw extruder at a temperature of 250deg.C, 260 deg.C, 275 deg.C, 270 deg.C and screw rotation speed of 40r/min; and then extruding and casting the PET film material in an extruding and casting machine to form a film, wherein the extruding temperature is 270 ℃.
Antibacterial performance test of PET film material:
the PET film material is cleaned, dried, cut into a diaphragm with the radius of 30mm, and irradiated under an ultraviolet lamp for sterilization.
Activating 24. 24h strain on plate agar medium, adding 2 rings into culture solution, and diluting to 1.0X10 6 CFU/mL of bacterial suspension. Transferring 0.2mL of bacterial suspension, dripping the bacterial suspension on a PET film material, covering a sterilized polyethylene film on a sample, culturing the sample at 37 ℃ for 24 hours in an incubator, washing the sample with eluent, fully shaking and shaking the eluted bacteria uniformly, inoculating the bacteria into a nutrient agar culture medium, culturing the bacteria at 37 ℃ for 24 hours, and then counting viable bacteria.
Antibacterial ratio a= (B-C)/bx 100%; b is the average recovery bacteria number of the control group; a is the average number of recovered bacteria in the practical group.
The PET film materials of examples 1 to 3, and comparative examples 1 to 2 were experimental groups. The PET film material of comparative example 3 served as a control group.
Thermogravimetric analysis test of PET film material: the temperature rising rate of the TG thermogravimetric analyzer is 10 ℃/min under nitrogen atmosphere, the test temperature is 20-700 ℃, and the sample size is 20mm multiplied by 2mm.
Water vapor transmission rate test: the water vapor transmittance tester tests the temperature of 40 ℃ and the relative humidity of 90 percent, and the test method is according to GB/T21529-2008 standard.
| Onset decomposition temperature T 5% （℃） | Water vapor transmission rate (g/cm) 2 ·h） | |
| Example 1 | 382.2 | 0.121 |
| Example 2 | 389.1 | 0.117 |
| Example 3 | 390.2 | 0.126 |
| Comparative example 1 | 377.1 | 0.149 |
| Comparative example 2 | 377.6 | 0.153 |
| Comparative example 3 | 374.0 | 0.123 |
In the embodiment 1-3, tertiary amine group of PET polyester and chloromethyl phenolic resin are blended and extruded, and in the extrusion process, the tertiary amine group of PET polyester and chloromethyl of the phenolic resin generate quaternary ammonium salt structure, so that the phenolic resin and the polyester are bonded through chemical bonds, the compatibility between the phenolic resin and the polyester is improved, and the functional master batch of the quaternary ammonium salt phenolic resin-polyester with uniform disperse phase is formed; and then blending and casting the functional master batch and polyethylene terephthalate to form a film, thus obtaining the antibacterial PET film material. The quaternary ammonium salt groups between the phenolic resin and the polyester are uniformly distributed in the PET film, so that the antibacterial performance of the film material is remarkably improved; meanwhile, the phenolic resin has strong heat resistance, good compatibility with PET matrix and excellent dispersibility, and can improve the thermal decomposition temperature and heat resistance of the PET film, reduce the water vapor permeability of the PET film and facilitate the improvement of the barrier property of the film material.
Comparative example 1 when preparing a phenolic resin-polyester master batch, a phenolic resin was used instead of chloromethyl phenolic resin; comparative example 2 polyethylene terephthalate was used instead of the tertiary amine polyester. Neither phenolic resin forms quaternary ammonium salt antibacterial groups with the polyester; the PET film material does not have antibacterial property.
And the phenolic resin and the polyester are not chemically bonded, so that the phenolic resin and the PET matrix are poor in compatibility and poor in dispersibility, phase separation exists between the phenolic resin and the PET matrix, phase separation micropores are formed in the film material matrix, the water vapor permeability is increased, and the barrier property of the film material is reduced.
The foregoing detailed description has been provided for the purposes of illustration in connection with specific embodiments and exemplary examples, but such description is not to be construed as limiting the application. Those skilled in the art will appreciate that various equivalent substitutions, modifications and improvements may be made to the technical solution of the present application and its embodiments without departing from the spirit and scope of the present application, and these all fall within the scope of the present application. The scope of the application is defined by the appended claims.
Claims (8)
1. An antibacterial PET film material is characterized by comprising the following components: 100 parts by weight of polyethylene terephthalate, 5-20 parts by weight of quaternary ammonium salt phenolic resin-polyester master batch and 0.4-0.8 part by weight of antioxidant;
the quaternary ammonium salt phenolic resin-polyester master batch is prepared according to the following method:
(1) Adding dimethyl terephthalate, 5- (tertiary amino) dimethyl isophthalate, ethylene glycol and manganese acetate into a reaction kettle, introducing nitrogen, uniformly mixing, heating to 170-180 ℃, reacting for 30-60min, heating to 220-235 ℃, reacting for 2-4h, finally adding ethylene glycol antimony, heating to 265-275 ℃, reacting for 3-4h, and pressurizing and discharging with nitrogen to obtain tertiary amino polyester;
(2) Adding tertiary amine polyester and chloromethyl phenolic resin into a double screw extruder, and blending and extruding to obtain quaternary ammonium salt phenolic resin-polyester master batch.
2. The antibacterial PET film material according to claim 1, wherein the ratio of dimethyl terephthalate to dimethyl 5- (tertiary amino) isophthalate to ethylene glycol in (1) is (0.7-0.95) mol (0.05-0.3) mol (1.8-2.3).
3. The antibacterial PET film material according to claim 1, wherein the mass ratio of the tertiary amine-based polyester to the chloromethyl phenol resin in (2) is 1g (0.1 to 0.5 g).
4. The antibacterial PET film material according to claim 1, wherein the temperature of each section of the twin-screw extruder in (2) is 240-260 ℃ and the screw rotation speed is 30-60r/min.
5. The antibacterial PET film material according to claim 1, wherein the dimethyl 5- (tertiary amino) isophthalate is prepared as follows:
(3) Adding thionyl chloride and 5,5- (hydroxymethyl) isophthalate into a reaction bottle, reacting for 2-4 hours at 60-70 ℃, concentrating, and recrystallizing to obtain 5,5- (chloromethyl) isophthalate;
(4) Ethanol, 5- (chloromethyl) dimethyl isophthalate, dimethylamine and catalyst sodium carbonate are added into a reaction bottle, stirred for reaction, concentrated, washed and recrystallized to obtain the 5- (tertiary amino) dimethyl isophthalate.
6. The antibacterial PET film material according to claim 5, wherein the ratio of 5,5- (chloromethyl) isophthalate to dimethylamine to sodium carbonate in (4) is 1mol (2.5 to 3.2 mol) and (2 to 3 mol).
7. The antibacterial PET film material according to claim 5, wherein the reaction in (4) is carried out at 40 to 60 ℃ for 2 to 5 hours.
8. A method for preparing the antibacterial PET film material according to any one of claims 1 to 7, wherein 100 parts by weight of polyethylene terephthalate, 5 to 20 parts by weight of quaternary ammonium salt phenolic resin-polyester master batch and 0.4 to 0.8 part by weight of antioxidant are added into a double screw extruder for extrusion, and each section is at a temperature of 250 to 275 ℃ and a screw speed of 30 to 50r/min; then extruding and casting the film in an extrusion casting machine at 270-280 ℃ to obtain the antibacterial PET film material.
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| JP2011074338A (en) * | 2009-10-02 | 2011-04-14 | Ube Industries Ltd | Phenol resin, epoxy resin, and epoxy resin cured product |
| US20120251607A1 (en) * | 2011-03-31 | 2012-10-04 | Coady Daniel J | Antimicrobial compositions, methods of preparation thereof, and uses thereof |
| CN102796214A (en) * | 2012-06-08 | 2012-11-28 | 上海师范大学 | Bactericidal polymer containing quaternary ammonium salt and halogen amine or halogen amine precursor functional group and preparation method and application thereof |
| CN103232587A (en) * | 2013-04-19 | 2013-08-07 | 淮海工学院 | Antibacterial polyurethane and preparation method thereof |
| CN103265686A (en) * | 2013-04-19 | 2013-08-28 | 淮海工学院 | Antibacterial polyether type polyurethane and preparation method thereof |
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| CN113248781A (en) * | 2021-05-24 | 2021-08-13 | 井冈山大学 | Green recycling method for non-metal materials in circuit board waste |
| JP2022175589A (en) * | 2021-05-14 | 2022-11-25 | 住友ベークライト株式会社 | Phenolic resin composition |
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| JP2011074338A (en) * | 2009-10-02 | 2011-04-14 | Ube Industries Ltd | Phenol resin, epoxy resin, and epoxy resin cured product |
| US20120251607A1 (en) * | 2011-03-31 | 2012-10-04 | Coady Daniel J | Antimicrobial compositions, methods of preparation thereof, and uses thereof |
| CN102796214A (en) * | 2012-06-08 | 2012-11-28 | 上海师范大学 | Bactericidal polymer containing quaternary ammonium salt and halogen amine or halogen amine precursor functional group and preparation method and application thereof |
| CN103232587A (en) * | 2013-04-19 | 2013-08-07 | 淮海工学院 | Antibacterial polyurethane and preparation method thereof |
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| CN113248781A (en) * | 2021-05-24 | 2021-08-13 | 井冈山大学 | Green recycling method for non-metal materials in circuit board waste |
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