CN117024902B - Preparation method of ABS plastic containing quaternary ammonium salt polymer antibacterial agent - Google Patents
Preparation method of ABS plastic containing quaternary ammonium salt polymer antibacterial agent Download PDFInfo
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- CN117024902B CN117024902B CN202311012705.0A CN202311012705A CN117024902B CN 117024902 B CN117024902 B CN 117024902B CN 202311012705 A CN202311012705 A CN 202311012705A CN 117024902 B CN117024902 B CN 117024902B
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- ammonium salt
- quaternary ammonium
- antibacterial agent
- polylactic acid
- abs plastic
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 69
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 58
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 52
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 66
- 239000004626 polylactic acid Substances 0.000 claims abstract description 64
- -1 bis-azido phenyl Chemical group 0.000 claims abstract description 37
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 10
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 10
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 50
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 32
- 238000001746 injection moulding Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FCMCDVRJVMDKAQ-UHFFFAOYSA-N 1-chloro-n,n-dimethylpropan-1-amine;hydrochloride Chemical compound Cl.CCC(Cl)N(C)C FCMCDVRJVMDKAQ-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- MSUCLKFPHDRRGG-UHFFFAOYSA-N 1-chloro-n,n-dimethylpropan-1-amine Chemical compound CCC(Cl)N(C)C MSUCLKFPHDRRGG-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UFBHSXXPAZMVSI-UHFFFAOYSA-N but-2-ynoyl chloride Chemical compound CC#CC(Cl)=O UFBHSXXPAZMVSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 125000006285 dibromobenzyl group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 24
- 241000222122 Candida albicans Species 0.000 abstract description 7
- 229940095731 candida albicans Drugs 0.000 abstract description 7
- 241000588724 Escherichia coli Species 0.000 abstract description 6
- 238000012650 click reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
- C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
- C07C247/04—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
Abstract
The invention relates to the technical field of ABS plastic and discloses a preparation method of ABS plastic containing a quaternary ammonium salt polymer antibacterial agent, wherein in a catalysis system of cuprous bromide and pentamethyl diethylenetriamine, a click reaction is carried out on the ternary alkynyl polylactic acid and a bis-azido group of a bis-azido phenyl bis-quaternary ammonium salt compound to form the polylactic acid quaternary ammonium salt polymer antibacterial agent with a hyperbranched structure, the polylactic acid quaternary ammonium salt polymer antibacterial agent has better heat resistance and temperature, can be melt blended with ABS and injection molded, contains a hyperbranched three-dimensional structure, forms a crosslinking site in the ABS plastic, obviously improves the tensile property and the shock resistance of the ABS plastic, and meanwhile has an antibacterial quaternary ammonium salt structure, and the antibacterial property of the ABS plastic to escherichia coli and candida albicans is obviously improved.
Description
Technical Field
The invention relates to the technical field of ABS plastic, in particular to a preparation method of ABS plastic containing quaternary ammonium salt polymer antibacterial agent.
Background
ABS plastic is a terpolymer of acrylonitrile, butadiene and styrene, has the advantages of toughness, hardness, good comprehensive performance and the like, and has wide application in the fields of machinery manufacture, textile industry, transportation and the like, but the traditional ABS has no antibacterial performance, and limits the practical application of ABS materials.
The antibacterial material is widely applied to the aspects of medical treatment and health, food and drug safety, biological tissue engineering and the like, and the antibacterial agent is usually added into the material, and the traditional antibacterial agent mainly comprises an inorganic antibacterial agent and an organic antibacterial agent, wherein the organic antibacterial agent such as quaternary ammonium salt, quaternary phosphonium salt, acylaniline and the like has the advantages of good antibacterial broad spectrum, no toxicity, safety and the like, and is widely applied to high polymer materials.
Compared with organic micromolecular antibacterial agents, the high-molecular antibacterial agents have the advantages of good stability, high heat resistance, difficult migration of the antibacterial agents and the like, as in paper (research on synthesis of methacrylate polymer antibacterial agents containing quaternary phosphonium salt structures and application of the methacrylate polymer antibacterial agents in antibacterial ABS plastics), novel methacrylate oxyalkyl triphenyl phosphonium bromide antibacterial monomers with alkyl side chains and methacrylate polymer antibacterial agents containing quaternary phosphonium salt structures are synthesized, and are melt blended with ABS plastics through a double-screw extruder to prepare antibacterial master batches, so that the antibacterial ABS plastics with high-efficiency and durable antibacterial performance are prepared, but the mechanical properties of the antibacterial ABS plastics are poor. The invention provides a hyperbranched polylactic acid based quaternary ammonium salt polymer antibacterial agent and ABS plastic, which solve the problem of poor antibacterial property and mechanical strength of the ABS plastic
Disclosure of Invention
(one) solving the technical problems
The invention provides a preparation method of ABS plastic containing quaternary ammonium salt polymer antibacterial agent, which solves the problem of poor antibacterial property and mechanical strength of ABS plastic.
(II) technical scheme
In order to solve the technical problems, the invention improves the following technical scheme: the preparation method of the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent comprises the following steps:
s1, adding a tri-alkynyl polylactic acid, a bis-azidophenyl bis-quaternary ammonium salt compound and an N, N-dimethylformamide solvent into a reaction bottle, adding cuprous bromide and pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen, circularly treating, heating to 55-70 ℃, reacting for 6-12h, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, carrying out suction filtration, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent.
S2, melting and blending the ABS resin, the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and the antioxidant in a double-screw extruder, extruding and granulating, and performing injection molding by an injection molding machine to obtain the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent.
Further, the mass of the bis-azidophenylbis-quaternary ammonium salt compound in the S1 is 3-8% of that of the trialkynyl polylactic acid. The mass of cuprous bromide is 0.2-0.6% of the mass of the trialkynyl polylactic acid, and the mass of the pentamethyldiethylenetriamine is 0.25-0.7% of the mass of the trialkynyl polylactic acid.
Further, the mass of the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent in S2 is 2-20% of that of the ABS resin.
Further, the preparation method of the trialkynyl polylactic acid in the S1 comprises the following steps: dissolving diethanolamine modified polylactic acid into a reaction solvent, then adding butynyl acyl chloride and a catalyst pyridine, stirring at room temperature for reaction for 4-12h, removing the solvent by rotary evaporation, and washing with ethanol to obtain trialkynyl polylactic acid; the preparation reaction formula is as follows:
further, the mass of butynoyl chloride is 4-7% of that of diethanolamine modified polylactic acid, and the mass of pyridine catalyst is 5-9% of that of diethanolamine modified polylactic acid.
Further, the reaction solvent comprises one of dichloromethane, chloroform, toluene or tetrahydrofuran.
Further, the preparation method of the bis-azidophenyl bis-quaternary ammonium salt compound comprises the following steps:
(1) Dissolving sodium azide and N, N-dimethylamino chloropropane hydrochloride into a sodium carbonate aqueous solution, heating to 50-70 ℃ for reaction for 6-18h, adding ethyl acetate after the reaction, drying an upper solution for dewatering after extraction and separation, and removing an ethyl acetate solvent by rotary evaporation to obtain the N, N-dimethylamino chloropropane intermediate.
(2) Dissolving the N, N-dimethylamino azidopropane intermediate and p-dibromobenzyl into acetonitrile solvent, heating to 75-90 ℃ for reaction for 24-48h, performing rotary evaporation on the acetonitrile solvent after the reaction, washing a crude product with diethyl ether, and performing recrystallization and purification in ethanol to obtain the bisazidophenyl bisquaternary ammonium salt compound. The preparation reaction formula is as follows:
further, the mass fraction of the sodium carbonate aqueous solution in (1) is 2-5%.
Further, the mass of the sodium azide is 40-55% of that of the N, N-dimethylamino chloropropane hydrochloride.
Further, the mass of the N, N-dimethylamino azidopropane intermediate is 90-140% of that of the dibromobenzyl.
(III) beneficial technical effects
1. The invention uses sodium azide N, N-dimethylamino chloropropane hydrochloride to carry out substitution reaction in a sodium carbonate system to obtain an N, N-dimethylamino chloropropane intermediate, and then carries out quaternization reaction with p-dibromobenzyl to obtain the novel bis-azido phenyl bis-quaternary ammonium salt compound.
2. The preparation method comprises the steps of reacting the imino group and the hydroxyl-terminated group of butynoyl chloride and diethanolamine modified polylactic acid to obtain trialkynyl polylactic acid, and then in a catalytic system of cuprous bromide and pentamethyldiethylenetriamine, enabling the trialkynyl structure of the polylactic acid to perform click reaction with the bis-azido group of the bis-azidophenyl bis-quaternary ammonium salt compound, so that the polylactic acid based quaternary ammonium salt polymer antibacterial agent with a hyperbranched structure is formed.
3. Compared with the quaternary ammonium salt organic micromolecule antibacterial agent, the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent has better heat resistance and temperature property, can be melt blended with ABS and injection molded, contains hyperbranched three-dimensional structures, forms crosslinking sites in ABS plastic, obviously improves the tensile property and the shock resistance of the ABS plastic, has an antibacterial quaternary ammonium salt structure, and obviously improves the antibacterial property of the ABS plastic to escherichia coli and candida albicans.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The preparation method of the diethanolamine modified polylactic acid comprises the following steps: pre-polymerizing diethanolamine and D, L-lactic acid in the molar ratio of 1 to 200 and stannous oxide catalyst in 0.7 wt% of the total amount of the reactants for 8 hr, melt-polycondensing at 160 deg.c for 8 hr, cooling to obtain coarse product, dissolving in chloroform, adding methanol and deionized water to separate out precipitate, suction filtering and drying to obtain modified diethanolamine polylactic acid with structureIs of the type
Example 1
(1) 2.2g of sodium azide and 4g of N, N-dimethylamino chloropropane hydrochloride are dissolved in a 5% sodium carbonate aqueous solution with the mass fraction of 80mL, the mixture is heated to 50 ℃ for reaction for 12 hours, ethyl acetate is added after the reaction, the upper solution is dried for water removal after extraction and separation, and the ethyl acetate solvent is removed by rotary evaporation, so that the N, N-dimethylamino azidopropane intermediate is obtained.
(2) 3.8g of N, N-dimethylamino azidopropane intermediate and 3g of p-dibromobenzyl are dissolved in acetonitrile solvent, heated to 80 ℃ for reaction for 36h, the acetonitrile solvent is distilled off after the reaction, and the crude product is washed by diethyl ether and then recrystallized and purified in ethanol to obtain the bisazidophenylbis-quaternary ammonium salt compound.
(3) 20g of diethanolamine modified polylactic acid is dissolved in 400mL of toluene solvent, then 1.4g of butynyl acyl chloride and 1.8g of catalyst pyridine are added, the mixture is stirred at room temperature for reaction for 4 hours, the solvent is removed by rotary evaporation, and the mixture is washed by ethanol, so that the trialkynyl polylactic acid is obtained.
(4) Adding 20g of trialkynyl polylactic acid, 0.6g of bis-azidophenyl bis-quaternary ammonium salt compound and 200mL of N, N-dimethylformamide solvent into a reaction bottle, adding 40mg of cuprous bromide and 50mg of pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen for cyclic treatment, heating to 55 ℃, reacting for 10 hours, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, filtering, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid quaternary ammonium salt polymer antibacterial agent.
(5) 200g of ABS resin, 4g of hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and 0.5g of antioxidant 1076 are melted and blended in a double screw extruder, the melting temperature is 190 ℃, and the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent is obtained through extrusion granulation and injection molding by an injection molding machine, wherein the injection molding temperature is 200 ℃.
Example 2
(1) 2g of sodium azide and 4g of N, N-dimethylamino chloropropane hydrochloride are dissolved in a 5% sodium carbonate aqueous solution with the mass fraction of 80mL, the mixture is heated to 50 ℃ for reaction for 12 hours, ethyl acetate is added after the reaction, the upper solution is dried for dewatering after extraction and separation, and the ethyl acetate solvent is removed by rotary evaporation, so that the N, N-dimethylamino chloropropane intermediate is obtained.
(2) 2.7g of N, N-dimethylamino azidopropane intermediate and 3g of p-dibromobenzyl are dissolved in acetonitrile solvent, heated to 75 ℃ for reaction for 48 hours, the acetonitrile solvent is distilled off after the reaction, and the crude product is washed by diethyl ether and then recrystallized and purified in ethanol to obtain the bisazidophenylbis-quaternary ammonium salt compound.
(3) Dissolving 20g of diethanolamine modified polylactic acid into 400mL of tetrahydrofuran solvent, then adding 1g of butynyl chloride and 1.5g of catalyst pyridine, stirring at room temperature for reaction for 8h, removing the solvent by rotary evaporation, and washing with ethanol to obtain the trialkynyl polylactic acid.
(4) Adding 20g of trialkynyl polylactic acid, 1.2g of bis-azidophenyl bis-quaternary ammonium salt compound and 500mL of N, N-dimethylformamide solvent into a reaction bottle, adding 90mg of cuprous bromide and 120mg of pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen for cyclic treatment, heating to 70 ℃, reacting for 12 hours, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, filtering, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid quaternary ammonium salt polymer antibacterial agent.
(5) 200g of ABS resin, 15g of hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and 0.3g of antioxidant 1076 are melted and blended in a double screw extruder, the melting temperature is 190 ℃, and the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent is obtained through extrusion granulation and injection molding by an injection molding machine, wherein the injection molding temperature is 200 ℃.
Example 3
(1) 2g of sodium azide and 4g of N, N-dimethylamino chloropropane hydrochloride are dissolved in 5% sodium carbonate aqueous solution with the mass fraction of 50mL, the mixture is heated to 70 ℃ for reaction for 6 hours, ethyl acetate is added after the reaction, the upper solution is dried for dewatering after extraction and separation, and the ethyl acetate solvent is removed by rotary evaporation, so that the N, N-dimethylamino chloropropane intermediate is obtained.
(2) 4.2g of N, N-dimethylamino azidopropane intermediate and 3g of p-dibromobenzyl are dissolved in acetonitrile solvent, heated to 90 ℃ for reaction for 36h, the acetonitrile solvent is distilled off after the reaction, and the crude product is washed by diethyl ether and then recrystallized and purified in ethanol to obtain the bisazidophenylbis-quaternary ammonium salt compound.
(3) Dissolving 20g of diethanolamine modified polylactic acid into 500mL of chloroform solvent, then adding 1.4g of butynyl chloride and 1.8g of pyridine catalyst, stirring at room temperature for reaction for 12h, removing the solvent by rotary evaporation, and washing with ethanol to obtain the trialkynyl polylactic acid.
(4) Adding 20g of trialkynyl polylactic acid, 1.6g of bis-azidophenyl bis-quaternary ammonium salt compound and 500mL of N, N-dimethylformamide solvent into a reaction bottle, adding 120mg of cuprous bromide and 140mg of pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen for cyclic treatment, heating to 60 ℃, reacting for 12 hours, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, filtering, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid quaternary ammonium salt polymer antibacterial agent.
(5) 200g of ABS resin, 30g of hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and 1g of antioxidant 1076 are melted and blended in a double-screw extruder, the melting temperature is 190 ℃, the extrusion granulation and the injection molding of an injection molding machine are carried out, the injection molding temperature is 200 ℃, and the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent is obtained.
Example 4
(1) 1.6g of sodium azide and 4g of N, N-dimethylamino chloropropane hydrochloride are dissolved in 5% sodium carbonate aqueous solution with the mass fraction of 40mL, the mixture is heated to 50 ℃ for reaction for 18 hours, ethyl acetate is added after the reaction, the upper solution is dried for water removal after extraction and separation, and the ethyl acetate solvent is removed by rotary evaporation, so that the N, N-dimethylamino azidopropane intermediate is obtained.
(2) 2g of N, N-dimethylamino azidopropane intermediate and 3g of p-dibromobenzyl are dissolved in acetonitrile solvent, heated to 80 ℃ for reaction for 48 hours, the acetonitrile solvent is distilled off after the reaction, and the crude product is washed by diethyl ether and then recrystallized and purified in ethanol to obtain the bisazidophenyl bisquaternary ammonium salt compound.
(3) Dissolving 20g of diethanolamine modified polylactic acid into 200mL of dichloromethane solvent, then adding 0.8g of butynyl acyl chloride and 1g of catalyst pyridine, stirring at room temperature for reaction for 4 hours, removing the solvent by rotary evaporation, and washing with ethanol to obtain the trialkynyl polylactic acid.
(4) Adding 20g of trialkynyl polylactic acid, 1.2g of bis-azidophenyl bis-quaternary ammonium salt compound and 500mL of N, N-dimethylformamide solvent into a reaction bottle, adding 90mg of cuprous bromide and 100mg of pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen for cyclic treatment, heating to 70 ℃, reacting for 6 hours, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, filtering, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid quaternary ammonium salt polymer antibacterial agent.
(5) 200g of ABS resin, 40g of hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and 0.3g of antioxidant 1076 are melted and blended in a double screw extruder, the melting temperature is 190 ℃, and the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent is obtained through extrusion granulation and injection molding by an injection molding machine, wherein the injection molding temperature is 200 ℃.
Comparative example 1
(1) 200g of ABS resin, 4g of the bis-azidophenylbis-quaternary ammonium salt compound prepared in example 1 and 0.5g of antioxidant 1076 are melt-blended in a twin-screw extruder, the melt temperature is 190 ℃, and the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent is obtained through extrusion granulation and injection molding by an injection molding machine, and the injection molding temperature is 200 ℃.
Comparative example 2
(1) 200g of ABS resin, 4g of the trialkynyl polylactic acid prepared in the example 1 and 0.5g of the antioxidant 1076 are melted and blended in a double screw extruder, the melting temperature is 190 ℃, the extrusion granulation is carried out, the injection molding is carried out by an injection molding machine, the injection molding temperature is 200 ℃, and the ABS plastic containing the polylactic acid polymer is obtained.
Comparative example 3
(1) 200g of ABS resin, 0.2g of the bisazidophenylbis-quaternary ammonium salt compound prepared in example 1, 3.8g of trialkynyl polylactic acid and 0.5g of antioxidant 1076 are melt-blended in a double-screw extruder, the melt temperature is 190 ℃, extrusion granulation and injection molding are carried out by an injection molding machine, and the injection molding temperature is 200 ℃, so that the ABS plastic containing polylactic acid polymer is obtained.
The antibacterial properties of ABS plastic were tested using the shake flask method.
E.coli antibacterial test: ABS plastic was cut into a wafer specimen having a radius of 0.5cm, and then concentrated to 10 7 The CFU/mL of the E.coli suspension was added to the phosphate buffer solution, and the disc sample was added, and the mixture was shaken at room temperature for 3 hours to obtain 2mL of the solution as the experimental group solution. The E.coli bacterial suspension was added to phosphate buffer solution, and after shaking well, 2mL of the solution was taken as a blank solution. E.coli experimental group solution and blank group solution are inoculated in a plate by an agar pouring method, and are cultured for 24 hours at 37 ℃, the experiment is repeated for 3 times, and viable bacteria are cultured and counted after the culture, and the average value is obtained.
Candida albicans antibacterial test: ABS plastic was cut into a wafer specimen having a radius of 0.5cm, and then concentrated to 10 6 CFU/mL candida albicans was added to the phosphate buffer solution, and the disc sample was added, and the mixture was shaken at room temperature for 2 hours, and then 2mL of the solution was taken as an experimental group solution. Candida albicans suspension was added to phosphate buffer solution, and after shaking uniformly, 2mL of solution was taken as blank group solution. The candida albicans experimental group solution and the blank group solution are inoculated in a plate by an agar pouring method, are cultured for 24 hours at 37 ℃, the experiment is repeated for 3 times, and viable bacteria are cultured and counted after the culture, and the average value is obtained.
Antibacterial ratio = (number of colonies in blank group-number of colonies in experimental group)/number of colonies in blank group×100%
The tensile property of the ABS plastic is tested by a tensile testing machine according to GB/T1040-2018 standard, and the tensile loading rate is 5mm/min. The unnotched impact strength was tested by a simple beam impact strength tester according to the GB/T1043-2018 standard.
TABLE 1 mechanical and antibacterial Properties test of ABS Plastic
The ABS in examples 1-4 is added with hyperbranched polylactic acid based quaternary ammonium salt polymer antibacterial agent, the hyperbranched polylactic acid structure contained in the polymer has obvious improvement effect on the tensile property and impact resistance of ABS plastic, the tensile strength reaches 44.8-58.2MPa, the elongation at break reaches 16.8-22.2%, and the impact resistance reaches 25.9-35.0kJ/m 2 However, in example 4, the mechanical properties of ABS are affected and the tensile properties and impact resistance are lowered due to the excessive amount of the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent. The comparative example 2 and the comparative example 3 are both added with the tri-alkynyl polylactic acid, have no hyperbranched structure, have little enhancement effect on the mechanical properties of ABS plastic, and the comparative example 1 is not added with the polylactic acid, so that the mechanical properties are the worst.
The ABS in examples 1-4 is added with hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent, the double quaternary ammonium salt structure contained in the polymer has stronger antibacterial performance to colibacillus and candida albicans as the dosage of the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent is increased, and the antibacterial rate reaches 99.99%; the ABS plastics of comparative example 1 and comparative example 3 both incorporate the bis-azidophenylbis-quaternary ammonium salt compound and also have excellent antibacterial properties. The ABS of comparative example 2 does not contain a quaternary ammonium salt structure and thus does not have antibacterial properties.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. A preparation method of ABS plastic containing quaternary ammonium salt polymer antibacterial agent is characterized in that: the preparation method of the ABS plastic comprises the following steps:
s1, adding a tri-alkynyl polylactic acid, a bis-azidophenyl bis-quaternary ammonium salt compound and an N, N-dimethylformamide solvent into a reaction bottle, adding cuprous bromide and pentamethyldiethylenetriamine, vacuumizing the reaction bottle, freezing, introducing nitrogen for cyclic treatment, heating to 55-70 ℃, reacting for 6-12 hours, cooling after the reaction, adding methanol until a large amount of precipitate is separated out, carrying out suction filtration, and washing with deionized water and ethanol in sequence to obtain the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent;
s2, melting and blending the ABS resin, the hyperbranched polylactic acid-based quaternary ammonium salt polymer antibacterial agent and the antioxidant in a double-screw extruder, extruding and granulating, and performing injection molding by an injection molding machine to obtain the ABS plastic containing the quaternary ammonium salt polymer antibacterial agent.
2. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 1, wherein: the mass of the bis-azidophenylbis-quaternary ammonium salt compound in the S1 is 3-8% of the tricynyl polylactic acid, the mass of the cuprous bromide is 0.2-0.6% of the tricynyl polylactic acid, and the mass of the pentamethyldiethylenetriamine is 0.25-0.7% of the tricynyl polylactic acid.
3. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 1, wherein: the mass of the hyperbranched polylactic acid based quaternary ammonium salt polymer antibacterial agent in the S2 is 2-20% of that of the ABS resin.
4. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 1, wherein: the preparation method of the trialkynyl polylactic acid in the S1 comprises the following steps: dissolving diethanolamine modified polylactic acid into a reaction solvent, then adding butynoyl chloride and a catalyst pyridine, stirring at room temperature for reaction for 4-12h, removing the solvent by rotary evaporation, and washing with ethanol to obtain the trialkynyl polylactic acid.
5. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 4, wherein: the butynoyl chloride accounts for 4-7% of the weight of the diethanolamine modified polylactic acid, and the pyridine catalyst accounts for 5-9% of the weight of the diethanolamine modified polylactic acid.
6. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 4, wherein: the reaction solvent comprises one of dichloromethane, chloroform, toluene or tetrahydrofuran.
7. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 1, wherein: the preparation method of the bis-azidophenyl bis-quaternary ammonium salt compound comprises the following steps:
(1) Dissolving sodium azide and N, N-dimethylamino chloropropane hydrochloride into a sodium carbonate aqueous solution, heating to 50-70 ℃ for reaction for 6-18 hours, adding ethyl acetate after the reaction, drying an upper solution for dewatering after extraction and separation, and removing an ethyl acetate solvent by rotary evaporation to obtain an N, N-dimethylamino chloropropane intermediate;
(2) Dissolving the N, N-dimethylamino azidopropane intermediate and p-dibromobenzyl into acetonitrile solvent, heating to 75-90 ℃ for reaction for 24-48h, performing rotary evaporation on the acetonitrile solvent after the reaction, washing a crude product with diethyl ether, and performing recrystallization and purification in ethanol to obtain the bisazidophenyl bisquaternary ammonium salt compound.
8. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 7, wherein: the mass fraction of the sodium carbonate aqueous solution in (1) is 2-5%.
9. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 7, wherein: the mass of the sodium azide is 40-55% of that of the N, N-dimethylamino chloropropane hydrochloride.
10. The method for preparing ABS plastic containing quaternary ammonium salt polymer antibacterial agent according to claim 7, wherein: the mass of the N, N-dimethylamino azidopropane intermediate is 90-140% of that of the dibromobenzyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5629347A (en) * | 1991-07-05 | 1997-05-13 | Merck Sharp & Dohme Ltd. | Aromatic compounds, pharmaceutical compositions containing them and their use in therapy |
| CN103408746A (en) * | 2013-07-23 | 2013-11-27 | 西北工业大学 | Preparation method of methoxy polyethylene glycol with end groups containing bisazide |
| CN106220569A (en) * | 2016-08-05 | 2016-12-14 | 大连理工大学 | A kind of quaternary halogen amine antibacterial precursor, preparation and the application process immobilized for inactive surfaces |
| CN112538228A (en) * | 2020-12-04 | 2021-03-23 | 安徽强茗塑业科技有限公司 | Antibacterial ABS plastic and preparation method thereof |
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| US20210017180A1 (en) * | 2018-03-30 | 2021-01-21 | Centre National De La Recherche Scientifique | Pyclen-based macrocyclic ligands, chelates thereof and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5629347A (en) * | 1991-07-05 | 1997-05-13 | Merck Sharp & Dohme Ltd. | Aromatic compounds, pharmaceutical compositions containing them and their use in therapy |
| CN103408746A (en) * | 2013-07-23 | 2013-11-27 | 西北工业大学 | Preparation method of methoxy polyethylene glycol with end groups containing bisazide |
| CN106220569A (en) * | 2016-08-05 | 2016-12-14 | 大连理工大学 | A kind of quaternary halogen amine antibacterial precursor, preparation and the application process immobilized for inactive surfaces |
| CN112538228A (en) * | 2020-12-04 | 2021-03-23 | 安徽强茗塑业科技有限公司 | Antibacterial ABS plastic and preparation method thereof |
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