CN117343372B - Antibacterial plastic and preparation method thereof - Google Patents
Antibacterial plastic and preparation method thereof Download PDFInfo
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- CN117343372B CN117343372B CN202311403652.5A CN202311403652A CN117343372B CN 117343372 B CN117343372 B CN 117343372B CN 202311403652 A CN202311403652 A CN 202311403652A CN 117343372 B CN117343372 B CN 117343372B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 77
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- 239000004033 plastic Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920002472 Starch Polymers 0.000 claims abstract description 82
- 239000008107 starch Substances 0.000 claims abstract description 81
- 235000019698 starch Nutrition 0.000 claims abstract description 81
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229960003237 betaine Drugs 0.000 claims abstract description 43
- -1 sulfonyl betaine Chemical compound 0.000 claims abstract description 41
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 37
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 35
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 229920001661 Chitosan Polymers 0.000 claims abstract description 29
- 239000004475 Arginine Substances 0.000 claims abstract description 15
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 15
- 239000004626 polylactic acid Substances 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 101
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 10
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 8
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007987 MES buffer Substances 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 6
- ANRPYDCTHDLWGE-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;3-oxobutanoic acid Chemical compound CC(=O)CC(O)=O.CC(=C)C(=O)OCCO ANRPYDCTHDLWGE-UHFFFAOYSA-N 0.000 claims description 5
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 abstract description 3
- 238000005917 acylation reaction Methods 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 150000002081 enamines Chemical class 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000012745 toughening agent Substances 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OXIKLRTYAYRAOE-CMDGGOBGSA-N (e)-3-(1-benzyl-3-pyridin-3-ylpyrazol-4-yl)prop-2-enoic acid Chemical group N1=C(C=2C=NC=CC=2)C(/C=C/C(=O)O)=CN1CC1=CC=CC=C1 OXIKLRTYAYRAOE-CMDGGOBGSA-N 0.000 description 1
- XMCXTGRBAIZQCC-AATRIKPKSA-N (e)-3-[2-[n-acetyl-3-(trifluoromethyl)anilino]-1,3-thiazol-4-yl]prop-2-enoic acid Chemical group C=1C=CC(C(F)(F)F)=CC=1N(C(=O)C)C1=NC(\C=C\C(O)=O)=CS1 XMCXTGRBAIZQCC-AATRIKPKSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229940100445 wheat starch Drugs 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
-
- 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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Biochemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the field of plastics, in particular to an antibacterial plastic and a preparation method thereof, wherein starch and polylactic acid are selected as base material raw materials, and polyvinyl alcohol fiber is used as a toughening agent; gradually performing chemical modification on starch, amination firstly, and then performing long-chain quaternary ammonium salt modification; grafting arginine onto chitosan through acylation reaction, taking arginine chitosan as a membrane plate, taking isopropyl titanate as a titanium source, and generating nano titanium dioxide on the arginine chitosan in situ; an antibacterial coating capable of forming a self-repairing antibacterial surface is coated on the surface of a degradable substrate, and a reversible enamine covalent bond is generated by utilizing side chain acetoacetate, amino-rich quaternary ammonium salt starch and composite titanium dioxide in polyacrylate resin containing sulfonyl betaine through controlling the mass ratio of the antibacterial coating, so that the self-repairing surface with high strength and self-cleaning, antibacterial and self-repairing properties is obtained.
Description
Technical Field
The invention relates to the field of plastics, in particular to an antibacterial plastic and a preparation method thereof.
Background
The medical polymer materials consumed every year in the world are up to millions of tons, and most of the materials are polymer plastic products such as polyethylene, polypropylene, polyvinyl chloride, polystyrene and the like, and the materials can not be automatically degraded after being abandoned, so that the problems of environmental pollution, human health hazard and the like exist in the process of being abandoned after a large amount of use.
Along with popularization of the environmental protection concept, more and more people recognize that the difficult-to-degrade plastic has the problems of environmental pollution and the like, so that development of the degradable plastic has great significance for protecting the environment. Meanwhile, the plastic product used as medical consumable material not only needs to have better biodegradability, but also needs to have better mechanical property and antibacterial property so as to expand the application range; at present, a large amount of antibacterial agents including metals, salts thereof, organic antibacterial agents and the like are usually added to improve the antibacterial performance of plastics, but in practical application, microcracks, scratches and even damages are often caused by friction, collision and the like, so that the protection effect is weakened, more serious living space is provided for the propagation and propagation of microorganisms, and the long-acting performance of the antibacterial agents is obviously reduced.
Disclosure of Invention
The invention aims to provide an antibacterial plastic and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the antibacterial plastic comprises the following steps:
s1: mixing polylactic acid, long-chain quaternary ammonium salt starch, glycerol and polyvinyl alcohol fibers, extruding, cooling, granulating and injection molding to obtain a base material;
s2: preparing an antibacterial coating from long-chain quaternized starch, polyacrylate resin containing sulfonyl betaine, composite titanium dioxide and ethanol;
s3: and (3) coating the antibacterial coating on the surface of a substrate, and curing to obtain the antibacterial plastic.
Further, the temperature of each temperature zone during extrusion is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 100 ℃, and the rotating speed is 200-300r/min.
Further, the base material comprises the following components in parts by weight: 8-12 parts of polylactic acid, 23-33 parts of long-chain quaternized starch, 13-17 parts of glycerol and 0.5-1 part of polyvinyl alcohol fiber.
Further, the starch is one or more of corn starch, wheat starch and potato starch.
Further, the antibacterial coating comprises the following components in parts by weight: 1-5 parts of long-chain quaternized starch, 40-45 parts of polyacrylate resin containing sulfonyl betaine, 1-5 parts of composite titanium dioxide and 55-60 parts of ethanol.
Further, the ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine was 0.1.
Further, the preparation of the long-chain quaternized starch comprises the following steps:
(1) Mixing starch and anhydrous dimethyl sulfoxide, adding N, N-carbonyl diimidazole, stirring at 30-35deg.C for 1-2 hr, adding mixed solution of ethylenediamine and dimethyl sulfoxide under nitrogen protection, maintaining at 18-25deg.C for 22-24 hr, dialyzing, and lyophilizing at-80deg.C for 48 hr to obtain aminated starch;
(2) Mixing dimethylaminoethyl methacrylate, 1-bromodecane and ethanol, preserving heat at 70-75 ℃ for 9-10h, recrystallizing with ethanol, and freeze-drying to obtain long-chain quaternary ammonium salt;
(3) Mixing the aminated starch and deionized water, heating to 55-60 ℃, regulating the pH to 8-9, adding long-chain quaternary ammonium salt, preserving heat for 5-6h, dialyzing for 3d, and freeze-drying at-80 ℃ for 48h to obtain the long-chain quaternary ammonium salt starch.
Further, the mass ratio of the aminated starch to the long-chain quaternary ammonium salt is 1:1.
further, the preparation of the composite titanium dioxide comprises the following steps:
1) Mixing arginine and MES buffer solution, adding carbodiimide hydrochloride and N-hydroxysuccinimide, activating for 1-2h, adding mixed solution of chitosan and acetic acid solution, preserving heat at 30-35 ℃ for 44-48h, transferring into a dialysis bag with MWCO=3500, dialyzing in deionized water for 4d, and freeze-drying to obtain arginine chitosan;
2) Mixing arginized chitosan and deionized water, stirring for 20-30min, adding a mixed solution of isopropyl titanate, deionized water, acetic acid and absolute ethyl alcohol, ultrasonically stirring for 20-30min, preserving heat for 20-30min at 45-50 ℃, adding a sodium hydroxide solution, continuously stirring for 20-30min, centrifuging, centrifugally washing for 3-5 times with deionized water, and drying to obtain the composite titanium dioxide.
Further, the preparation of the polyacrylate resin containing the sulfonyl betaine comprises the following steps:
mixing dimethylaminoethyl methacrylate, 1, 3-propane sultone and 1, 2-dichloroethane, stirring at 18-25 ℃ for 30-60min, heating to 55-60 ℃ and preserving heat for 2-3h, cooling and filtering to obtain sulfonyl betaine methacrylate; mixing azodiisobutyronitrile, ethyl methacrylate, hexyl acrylate, acetoacetic acid ethylene glycol methacrylate, sulfonyl betaine methacrylate and ethanol under the protection of nitrogen, preserving heat for 1-2h at 70-75 ℃, adding into n-hexane, filtering, washing for 3-5 times with ethanol, and drying to obtain the polyacrylate resin containing the sulfonyl betaine.
The invention has the beneficial effects that:
the invention provides an antibacterial plastic and a preparation method thereof, and the antibacterial plastic is prepared from degradable raw materials and has the advantages of environmental protection, excellent mechanical property, good sealing performance and water resistance.
In order to endow the antibacterial plastic with higher water resistance and antibacterial property, the starch is modified, the starch is subjected to gradual chemical modification, amino groups are modified to starch branched chains, the compatibility of the starch, the polylactic acid and the polyethylene fiber is improved, the reactivity of amino groups is higher than that of hydroxyl groups, the subsequent long-chain quaternary ammonium salt modification is facilitated, the long-chain quaternary ammonium salt modification is performed on the aminated starch by using the dimethylaminoethyl methacrylate and the 1-bromodecane, the hydrophobic effect of the aminated starch is enhanced, a great amount of positive charges are carried on starch molecules, the quaternary ammonium salt starch with a cationic dendritic macromolecular structure is formed, and the cell membrane and the cell wall of bacteria can be destroyed by using strong cations on the surface, so that the bacterial killing capacity or the bacterial growth inhibiting capacity of the antibacterial plastic is improved.
According to the invention, titanium dioxide is added into the antibacterial coating to improve the antibacterial property and self-cleaning property of the antibacterial plastic, but the problem of dispersion uniformity exists, the titanium dioxide is modified, and through acylation reaction, carbodiimide hydrochloride/N-hydroxysuccinimide is used as an activating agent to graft arginine onto chitosan, so that argininated chitosan is prepared, chelation of argininated chitosan on titanium ions is utilized, argininated chitosan is used as a membrane plate, isopropyl titanate is used as a titanium source, and nano titanium dioxide is generated on the argininated chitosan in situ, so that the mechanical property, antibacterial property and barrier property of the antibacterial coating are effectively improved.
In order to ensure that the antibacterial plastic has self-repairing capability when suffering mechanical damage such as scratch and the like, so as to maintain the long-acting antibacterial capability, the surface of the degradable substrate is coated with a layer of antibacterial coating capable of forming the self-repairing antibacterial surface, and the side chain acetoacetate in the polyacrylate resin containing the sulfonyl betaine, the quaternary ammonium salt starch rich in amino and the composite titanium dioxide are utilized to jointly generate a reversible enamine covalent bond by controlling the mass ratio of the antibacterial coating, so that the high-strength, self-cleaning, antibacterial and self-repairing surface is obtained; the long-chain quaternary ammonium salt and the composite titanium dioxide in the sulfonyl betaine-containing polyacrylate resin and the quaternary ammonium salt starch have antibacterial effects, and the multi-active sites in the raw materials are utilized, so that the interfacial adhesion capability of each component in the antibacterial coating is greatly improved, the winding complexity of a molecular chain is increased, the precipitation of small molecules is avoided, and the crosslinking in the antibacterial coating achieves long-acting and safe antibacterial and sealing effects.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely in connection with the embodiments of the present invention, and it is apparent 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.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1: the preparation method of the antibacterial plastic comprises the following steps:
s1: mixing polylactic acid, long-chain quaternary ammonium salt starch, glycerol and polyvinyl alcohol fibers, extruding, cooling, granulating and injection molding to obtain a base material;
the preparation of the long-chain quaternized starch comprises the following steps:
(1) Mixing 1g of starch and 50mL of anhydrous dimethyl sulfoxide, adding 1g of N, N-carbonyl diimidazole, stirring at 30 ℃ for 2 hours, adding 1.54mL of mixed solution of ethylenediamine and 2.5mL of dimethyl sulfoxide under the protection of nitrogen, preserving heat at 18 ℃ for 24 hours, dialyzing for 2 days in a dialysis bag with the interception relative molecular mass of 5000, and lyophilizing at-80 ℃ for 48 hours to obtain aminated starch;
(2) 1.6g of dimethylaminoethyl methacrylate, 2.5g of 1-bromodecane and 3g of ethanol are mixed, the mixture is kept at 70 ℃ for 10 hours, recrystallized by ethanol and freeze-dried to obtain long-chain quaternary ammonium salt;
(3) Mixing 1g of aminated starch and 25mL of deionized water, heating to 55 ℃ to adjust the pH value to 9, adding 1g of long-chain quaternary ammonium salt, preserving heat for 5h, dialyzing for 3d in a dialysis bag with the interception relative molecular weight of 8000, and freeze-drying at-80 ℃ for 48h to obtain long-chain quaternized starch;
the base material comprises the following components in parts by mass: 8 parts of polylactic acid, 23 parts of long-chain quaternized starch, 13 parts of glycerol and 0.5 part of polyvinyl alcohol fiber;
the temperature of each temperature zone is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 100 ℃ and the rotating speed is 200r/min during extrusion;
s2: preparing an antibacterial coating from long-chain quaternized starch, polyacrylate resin containing sulfonyl betaine, composite titanium dioxide and ethanol;
the preparation of the composite titanium dioxide comprises the following steps:
1) 17.4mg of arginine and 50mL of MES buffer solution with pH=5 are mixed, 0.4mmol of carbodiimide hydrochloride and 0.4mmol of N-hydroxysuccinimide are added, the mixture is activated for 1h, 1g of chitosan and 100mL of acetic acid solution with mass fraction of 1% are added, the mixture is kept at 30 ℃ for 48h, transferred into a dialysis bag with MWCO=3500, dialyzed for 4d in deionized water, and freeze-dried, and arginine chitosan is obtained;
2) Mixing 0.1g of arginized chitosan and 10mL of deionized water, stirring for 20min, adding a mixed solution of 0.69g of isopropyl titanate, 10mL of deionized water, 30mL of acetic acid and 100mL of absolute ethyl alcohol, stirring for 20min by ultrasound, preserving heat for 30min at 45 ℃, adding 10mL of 0.2mol/L sodium hydroxide solution, stirring for 20min continuously, centrifuging, washing for 3 times by using deionized water in a centrifuging way, and drying to obtain composite titanium dioxide;
the preparation of the polyacrylate resin containing the sulfonyl betaine comprises the following steps:
1.57g of dimethylaminoethyl methacrylate, 1.57g of 1, 3-propane sultone and 10ml of 1, 2-dichloroethane are mixed, stirred for 60min at 18 ℃, heated to 55 ℃ and kept for 3h, cooled and filtered to obtain sulfonyl betaine methacrylate; mixing 0.3g of azodiisobutyronitrile, 2.8g of ethyl methacrylate, 5.2g of hexyl acrylate, 1g of acetoacetic acid ethylene glycol methacrylate, 2g of sulfonyl betaine methacrylate and 30mL of ethanol under the protection of nitrogen, preserving heat for 2 hours at 70 ℃, adding into 100mL of n-hexane, filtering, washing with ethanol for 3 times, and drying to obtain polyacrylate resin containing sulfonyl betaine;
the antibacterial coating comprises the following components in parts by weight: 3 parts of long-chain quaternized starch, 40 parts of polyacrylate resin containing sulfonyl betaine, 1 part of composite titanium dioxide and 55 parts of ethanol;
the ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine is 0.1;
s2: and (3) coating the antibacterial coating on the surface of a substrate, and curing to obtain the antibacterial plastic.
Example 2: the preparation method of the antibacterial plastic comprises the following steps:
s1: mixing polylactic acid, long-chain quaternary ammonium salt starch, glycerol and polyvinyl alcohol fibers, extruding, cooling, granulating and injection molding to obtain a base material;
the preparation of the long-chain quaternized starch comprises the following steps:
(1) Mixing 1g of starch and 50mL of anhydrous dimethyl sulfoxide, adding 1g of N, N-carbonyl diimidazole, stirring at 33 ℃ for 1.5h, adding a mixed solution of 1.54mL of ethylenediamine and 2.5mL of dimethyl sulfoxide under the protection of nitrogen, preserving heat at 20 ℃ for 23h, dialyzing for 2d in a dialysis bag with a cut-off relative molecular mass of 5000, and freeze-drying at-80 ℃ for 48h to obtain aminated starch;
(2) 1.6g of dimethylaminoethyl methacrylate, 2.5g of 1-bromodecane and 3g of ethanol are mixed, the mixture is kept at 72 ℃ for 9.5h, recrystallized by ethanol and freeze-dried to obtain long-chain quaternary ammonium salt;
(3) Mixing 1g of aminated starch and 25mL of deionized water, heating to 58 ℃ to adjust the pH to 8.5, adding 1g of long-chain quaternary ammonium salt, preserving heat for 5.5h, dialyzing for 3d in a dialysis bag with the relative molecular weight of 8000 interception, and freeze-drying at-80 ℃ for 48h to obtain long-chain quaternized starch;
the base material comprises the following components in parts by mass: 9 parts of polylactic acid, 25 parts of long-chain quaternized starch, 15 parts of glycerol and 0.8 part of polyvinyl alcohol fiber;
the temperature of each temperature zone is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 100 ℃ and the rotating speed is 240r/min during extrusion;
s2: preparing an antibacterial coating from long-chain quaternized starch, polyacrylate resin containing sulfonyl betaine, composite titanium dioxide and ethanol;
the preparation of the composite titanium dioxide comprises the following steps:
1) 17.4mg of arginine and 50mL of MES buffer solution with pH=5 are mixed, 0.4mmol of carbodiimide hydrochloride and 0.4mmol of N-hydroxysuccinimide are added, the mixture of 1g of chitosan and 100mL of acetic acid solution with mass fraction of 1% is activated for 1.5 hours, the mixture is kept at 33 ℃ for 46 hours, the mixture is transferred into a dialysis bag with MWCO=3500, dialysis is carried out for 4d in deionized water, and freeze drying is carried out, thus obtaining arginized chitosan;
2) Mixing 0.1g of arginized chitosan and 10mL of deionized water, stirring for 25min, adding a mixed solution of 0.69g of isopropyl titanate, 10mL of deionized water, 30mL of acetic acid and 100mL of absolute ethyl alcohol, stirring for 25min by ultrasound, preserving heat for 25min at 48 ℃, adding 10mL of 0.2mol/L sodium hydroxide solution, stirring for 25min continuously, centrifuging, washing for 4 times by using deionized water in a centrifuging way, and drying to obtain composite titanium dioxide;
the preparation of the polyacrylate resin containing the sulfonyl betaine comprises the following steps:
1.57g of dimethylaminoethyl methacrylate, 1.57g of 1, 3-propane sultone and 10ml of 1, 2-dichloroethane are mixed, stirred for 40min at 20 ℃, heated to 58 ℃ and kept for 2.5h, cooled and filtered to obtain sulfonyl betaine methacrylate; mixing 0.3g of azodiisobutyronitrile, 2.8g of ethyl methacrylate, 5.2g of hexyl acrylate, 1g of acetoacetic acid ethylene glycol methacrylate, 2g of sulfonyl betaine methacrylate and 30mL of ethanol under the protection of nitrogen, preserving heat for 1.5h at 72 ℃, adding into 100mL of n-hexane, filtering, washing with ethanol for 4 times, and drying to obtain polyacrylate resin containing sulfonyl betaine;
the antibacterial coating comprises the following components in parts by weight: 2.3 parts of long-chain quaternized starch, 43 parts of polyacrylate resin containing sulfonyl betaine, 2 parts of composite titanium dioxide and 56 parts of ethanol;
the ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine is 0.1;
s2: and (3) coating the antibacterial coating on the surface of a substrate, and curing to obtain the antibacterial plastic.
Example 3: the preparation method of the antibacterial plastic comprises the following steps:
s1: mixing polylactic acid, long-chain quaternary ammonium salt starch, glycerol and polyvinyl alcohol fibers, extruding, cooling, granulating and injection molding to obtain a base material;
the preparation of the long-chain quaternized starch comprises the following steps:
(1) Mixing 1g of starch and 50mL of anhydrous dimethyl sulfoxide, adding 1g of N, N-carbonyl diimidazole, stirring for 1h at 35 ℃, adding a mixed solution of 1.54mL of ethylenediamine and 2.5mL of dimethyl sulfoxide under the protection of nitrogen, preserving heat for 22h at 25 ℃, dialyzing for 2d in a dialysis bag with the interception relative molecular mass of 5000, and lyophilizing for 48h at-80 ℃ to obtain aminated starch;
(2) 1.6g of dimethylaminoethyl methacrylate, 2.5g of 1-bromodecane and 3g of ethanol are mixed, the mixture is kept at 75 ℃ for 9 hours, recrystallized by ethanol and freeze-dried to obtain long-chain quaternary ammonium salt;
(3) Mixing 1g of aminated starch and 25mL of deionized water, heating to 60 ℃ to adjust the pH value to 8, adding 1g of long-chain quaternary ammonium salt, preserving heat for 6 hours, dialyzing for 3 days in a dialysis bag with the interception relative molecular weight of 8000, and freeze-drying for 48 hours at-80 ℃ to obtain long-chain quaternized starch;
the base material comprises the following components in parts by mass: 12 parts of polylactic acid, 33 parts of long-chain quaternized starch, 17 parts of glycerol and 1 part of polyvinyl alcohol fiber;
the temperature of each temperature zone is 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 100 ℃ and the rotating speed is 300r/min during extrusion;
s2: preparing an antibacterial coating from long-chain quaternized starch, polyacrylate resin containing sulfonyl betaine, composite titanium dioxide and ethanol;
the preparation of the composite titanium dioxide comprises the following steps:
1) 17.4mg of arginine and 50mL of MES buffer solution with pH=5 are mixed, 0.4mmol of carbodiimide hydrochloride and 0.4mmol of N-hydroxysuccinimide are added, the mixture is activated for 2 hours, 1g of chitosan and 100mL of acetic acid solution with mass fraction of 1% are added, the mixture is kept at 35 ℃ for 44 hours, transferred into a dialysis bag with MWCO=3500, dialyzed for 4 days in deionized water, and freeze-dried, and arginine chitosan is obtained;
2) Mixing 0.1g of arginized chitosan and 10mL of deionized water, stirring for 30min, adding a mixed solution of 0.69g of isopropyl titanate, 10mL of deionized water, 30mL of acetic acid and 100mL of absolute ethyl alcohol, carrying out ultrasonic stirring for 30min, preserving heat at 50 ℃ for 20min, adding 10mL of 0.2mol/L sodium hydroxide solution, continuing stirring for 30min, centrifuging, centrifugally washing for 5 times by using deionized water, and drying to obtain composite titanium dioxide;
the preparation of the polyacrylate resin containing the sulfonyl betaine comprises the following steps:
1.57g of dimethylaminoethyl methacrylate, 1.57g of 1, 3-propane sultone and 10ml of 1, 2-dichloroethane are mixed, stirred for 30min at 25 ℃, heated to 60 ℃ and kept for 2h, cooled and filtered to obtain sulfonyl betaine methacrylate; mixing 0.3g of azodiisobutyronitrile, 2.8g of ethyl methacrylate, 5.2g of hexyl acrylate, 1g of acetoacetic acid ethylene glycol methacrylate, 2g of sulfonyl betaine methacrylate and 30mL of ethanol under the protection of nitrogen, preserving heat for 1h at 75 ℃, adding into 100mL of n-hexane, filtering, washing with ethanol for 5 times, and drying to obtain polyacrylate resin containing sulfonyl betaine;
the antibacterial coating comprises the following components in parts by weight: 1 part of long-chain quaternized starch, 45 parts of polyacrylate resin containing sulfonyl betaine, 3.5 parts of composite titanium dioxide and 60 parts of ethanol;
the ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine is 0.1;
s2: and (3) coating the antibacterial coating on the surface of a substrate, and curing to obtain the antibacterial plastic.
Comparative example 1: using example 3 as a control, 2, 3-epoxypropyltrimethylammonium chloride was used in place of the long-chain quaternary ammonium salt, with the other procedures being normal.
Comparative example 2: using example 3 as a control, the long chain quaternized starch was replaced with starch and the other procedures were normal.
Comparative example 3: with example 3 as a control group, the mass ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine is 0.08, namely 1 part of the long-chain quaternized starch, 45 parts of the polyacrylate resin containing the sulfonyl betaine, 2.6 parts of the composite titanium dioxide, 60 parts of ethanol, and other processes are normal.
Comparative example 4: using example 3 as a control, the polyacrylate resin containing the sulfonyl betaine was replaced with a polyacrylate resin (P477951: A Ding Shiji), and the other steps were normal.
Comparative example 5: using example 3 as a control, the composite titanium dioxide was replaced with titanium dioxide (T299267: A Ding Shiji) and the other procedures were normal.
The thickness of the base material in the above examples and comparative examples was 400. Mu.m, and the thickness of the antibacterial layer formed by the antibacterial paint was 100. Mu.m.
The sources of the raw materials are as follows:
polylactic acid 26023-30-3: hubei fact cis biotechnology limited; glycerol 56-81-5: nantong Runfeng petrochemical Co., ltd; polyvinyl alcohol fibers (linear density 2.0dtex, breaking strength 10.5cN/dtex, elongation at break 7%, length 4 mm): chinese petrochemical Chuan vitamin chemical company; 1-bromodecane (98%): nanjing chemical Agents Co Ltd; corn starch S116030, dimethyl sulfoxide D103276, N-carbonyldiimidazole C109315, ethylenediamine E112132, dimethylaminoethyl methacrylate D111129, arginine A108220, MES buffer M301886, carbodiimide hydrochloride E106172, N-hydroxysuccinimide H109330, chitosan C434552, isopropyl titanate T105735, 1, 3-propane sultone P105652, 1, 2-dichloroethane D116247, azobisisobutyronitrile A434183, ethyl methacrylate E103002, hexyl acrylate H156906, ethylene acetoacetate methacrylate A107223: ala Ding Shiji; ethanol, acetic acid, sodium hydroxide, n-hexane, analytically pure: national drug group reagent.
Performance test:
tensile strength: testing by adopting an electronic universal tester, cutting into strips with the length of 100mm and the width of 80mm, and testing at the stretching rate of 5mm/min; antibacterial durability: reference ISO22196:2007, using ATCC 6538 staphylococcus aureus as strain, using plate count method, and performing 50 times of standard water washing; self-repairability: drawing cross cracks with the width of 40 mu m and the length of 100 mu m on the antibacterial plastic, preserving heat for 24 hours at the temperature of 60 ℃, measuring the tensile strength, and using the change rate to characterize the self-repairing property; hydrophobicity: water contact angle test was performed with 2 μl water drops; the results are shown in Table 1;
TABLE 1
In the invention, starch and polylactic acid with excellent biocompatibility, biodegradability, thermoplastic processability and other advantages are selected as raw materials, polyvinyl alcohol is used as a toughening agent to achieve a toughening effect, and in order to endow antibacterial plastics with higher water resistance and antibacterial property, the starch is modified, and the starch is subjected to gradual chemical modification, so that amino groups are modified to starch branched chains, the compatibility of the starch with polylactic acid and polyethylene fibers is improved, the reactivity of amino groups is stronger than that of hydroxyl groups, the subsequent long-chain quaternary ammonium salt modification is facilitated, the dimethyl amino ethyl methacrylate and 1-bromodecane are used for synthesizing the long-chain quaternary ammonium salt, the long-chain quaternary ammonium salt modification is carried out on the aminated starch, the hydrophobic effect of the aminated starch is enhanced, and meanwhile, the starch molecules are provided with a large amount of positive charges to form cationic dendritic macromolecular structure quaternary ammonium salt starch, and the strong cations on the surfaces can destroy cell membranes and cell walls of bacteria, so that the bacterial killing capacity or bacterial growth inhibiting capacity of the antibacterial plastics is improved.
In order to ensure that the antibacterial plastic has self-repairing capability when suffering mechanical damage such as scratch and the like and further maintains the long-acting antibacterial capability, the surface of the degradable substrate is coated with a layer of antibacterial coating capable of forming a self-repairing antibacterial surface, and the side chain acetoacetate in the polyacrylate resin containing the sulfonyl betaine, the quaternary ammonium salt starch rich in amino and the composite titanium dioxide are utilized to jointly generate a reversible enamine covalent bond by controlling the mass ratio of the antibacterial coating, so that the high-strength, self-cleaning, antibacterial and self-repairing surface is obtained; the long-chain quaternary ammonium salt and the composite titanium dioxide in the sulfonyl betaine-containing polyacrylate resin and the quaternary ammonium salt starch have antibacterial effects, and the multi-active sites in the raw materials are utilized, so that the interfacial adhesion capability of each component in the antibacterial coating is greatly improved, the winding complexity of a molecular chain is increased, the precipitation of small molecules is avoided, and the crosslinking in the antibacterial coating achieves long-acting and safe antibacterial and sealing effects.
In the invention, titanium dioxide is modified, and arginine is grafted onto chitosan by using carbodiimide hydrochloride/N-hydroxysuccinimide as an activating agent through acylation reaction to prepare argininated chitosan, and the argininated chitosan is used for chelating titanium ions, and the argininated chitosan is used as a membrane plate, and isopropyl titanate is used as a titanium source, so that nano titanium dioxide is generated on the argininated chitosan in situ, and the mechanical property, the antibacterial property and the barrier property of the antibacterial coating are effectively improved.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (3)
1. The preparation method of the antibacterial plastic is characterized by comprising the following steps of:
s1: mixing polylactic acid, long-chain quaternary ammonium salt starch, glycerol and polyvinyl alcohol fibers, extruding, cooling, granulating and injection molding to obtain a base material;
s2: preparing an antibacterial coating from long-chain quaternized starch, polyacrylate resin containing sulfonyl betaine, composite titanium dioxide and ethanol;
s3: coating the antibacterial coating on the surface of a substrate, and curing to obtain antibacterial plastic;
the base material comprises the following components in parts by mass: 8-12 parts of polylactic acid, 23-33 parts of long-chain quaternized starch, 13-17 parts of glycerol and 0.5-1 part of polyvinyl alcohol fiber;
the antibacterial coating comprises the following components in parts by weight: 1-5 parts of long-chain quaternized starch, 40-45 parts of polyacrylate resin containing sulfonyl betaine, 1-5 parts of composite titanium dioxide and 55-60 parts of ethanol;
the ratio of the sum of the mass of the long-chain quaternized starch and the mass of the composite titanium dioxide to the mass of the polyacrylate resin containing the sulfonyl betaine is 0.1;
the preparation of the long-chain quaternized starch comprises the following steps:
(1) Mixing starch and anhydrous dimethyl sulfoxide, adding N, N-carbonyl diimidazole, stirring at 30-35deg.C for 1-2 hr, adding mixed solution of ethylenediamine and dimethyl sulfoxide under nitrogen protection, maintaining at 18-25deg.C for 22-24 hr, dialyzing, and lyophilizing at-80deg.C for 48 hr to obtain aminated starch;
(2) Mixing dimethylaminoethyl methacrylate, 1-bromodecane and ethanol, preserving heat at 70-75 ℃ for 9-10h, recrystallizing with ethanol, and freeze-drying to obtain long-chain quaternary ammonium salt;
(3) Mixing the aminated starch and deionized water, heating to 55-60 ℃ to adjust the pH to 8-9, adding long-chain quaternary ammonium salt, preserving heat for 5-6h, dialyzing for 3d, and freeze-drying at-80 ℃ for 48h to obtain the long-chain quaternary ammonium salt starch;
the mass ratio of the aminated starch to the long-chain quaternary ammonium salt is 1:1, a step of;
the preparation of the composite titanium dioxide comprises the following steps:
1) Mixing arginine and MES buffer solution, adding carbodiimide hydrochloride and N-hydroxysuccinimide, activating for 1-2h, adding mixed solution of chitosan and acetic acid solution, preserving heat at 30-35 ℃ for 44-48h, transferring into a dialysis bag with MWCO=3500, dialyzing in deionized water for 4d, and freeze-drying to obtain arginine chitosan;
2) Mixing arginized chitosan and deionized water, stirring for 20-30min, adding a mixed solution of isopropyl titanate, deionized water, acetic acid and absolute ethyl alcohol, ultrasonically stirring for 20-30min, preserving heat for 20-30min at 45-50 ℃, adding a sodium hydroxide solution, continuously stirring for 20-30min, centrifuging, centrifugally washing for 3-5 times with deionized water, and drying to obtain composite titanium dioxide;
the preparation of the polyacrylate resin containing the sulfonyl betaine comprises the following steps:
mixing dimethylaminoethyl methacrylate, 1, 3-propane sultone and 1, 2-dichloroethane, stirring at 18-25 ℃ for 30-60min, heating to 55-60 ℃ and preserving heat for 2-3h, cooling and filtering to obtain sulfonyl betaine methacrylate; mixing azodiisobutyronitrile, ethyl methacrylate, hexyl acrylate, acetoacetic acid ethylene glycol methacrylate, sulfonyl betaine methacrylate and ethanol under the protection of nitrogen, preserving heat for 1-2h at 70-75 ℃, adding into n-hexane, filtering, washing for 3-5 times with ethanol, and drying to obtain the polyacrylate resin containing the sulfonyl betaine.
2. The method for preparing an antibacterial plastic according to claim 1, wherein the temperature of each temperature zone is 90 ℃, 100 ℃, 110 ℃, 120 ℃, 100 ℃ and the rotation speed is 200-300r/min during extrusion.
3. An antibacterial plastic, characterized in that it is prepared by the preparation method according to any one of claims 1-2.
Priority Applications (1)
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