CN113106750A - Antibacterial polylactic acid material and preparation method thereof - Google Patents
Antibacterial polylactic acid material and preparation method thereof Download PDFInfo
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- CN113106750A CN113106750A CN202110256619.9A CN202110256619A CN113106750A CN 113106750 A CN113106750 A CN 113106750A CN 202110256619 A CN202110256619 A CN 202110256619A CN 113106750 A CN113106750 A CN 113106750A
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- polylactic acid
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- trimethylsilylpropyl
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 65
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 37
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- LQQFSMCMZMSDQQ-UHFFFAOYSA-M dimethyl-octadecyl-(3-trimethylsilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](C)(C)C LQQFSMCMZMSDQQ-UHFFFAOYSA-M 0.000 claims description 6
- -1 silicon quaternary ammonium salt Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- ZLOWLHDZZWYUQY-UHFFFAOYSA-M CCCCCCCCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] Chemical compound CCCCCCCCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] ZLOWLHDZZWYUQY-UHFFFAOYSA-M 0.000 claims description 3
- BPFXWLPIMRCIJX-UHFFFAOYSA-M CCCCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] Chemical compound CCCCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] BPFXWLPIMRCIJX-UHFFFAOYSA-M 0.000 claims description 3
- LGUBXGUKYFNJQK-UHFFFAOYSA-M CCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] Chemical compound CCCCCC[N+](C)(C)CCC[Si](C)(C)C.[Cl-] LGUBXGUKYFNJQK-UHFFFAOYSA-M 0.000 claims description 3
- SZLNWDJOUHBIRP-UHFFFAOYSA-M C[N+](C)(CCC[Si](C)(C)C)CC1=CC=CC=C1.[Cl-] Chemical compound C[N+](C)(CCC[Si](C)(C)C)CC1=CC=CC=C1.[Cl-] SZLNWDJOUHBIRP-UHFFFAOYSA-M 0.000 claims description 3
- GVMSPQSHPILRIP-UHFFFAOYSA-M hexadecyl-dimethyl-(3-trimethylsilylpropyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCC[Si](C)(C)C GVMSPQSHPILRIP-UHFFFAOYSA-M 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBSLOTWYZHCBTL-UHFFFAOYSA-M trimethyl(3-trimethylsilylpropyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC[Si](C)(C)C CBSLOTWYZHCBTL-UHFFFAOYSA-M 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
- D06M13/507—Organic silicon compounds without carbon-silicon bond
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract
The invention provides an antibacterial polylactic acid material and a preparation method thereof. The preparation method comprises the following steps: soaking a polylactic acid material with a carboxyl functional group and/or a hydroxyl functional group on the surface in an antibacterial solution; draining the wetted polylactic acid material; placing the drained polylactic acid material at the temperature of 100-150 ℃ for heat preservation for 30-150 min; after the heat preservation is finished, cleaning and drying the polylactic acid material; the antibacterial liquid comprises a coupling agent and organosilicon quaternary ammonium salt. The preparation method of the antibacterial polylactic acid material does not need to pretreat the material, has soft texture, can directly utilize a chemical grafting method to obtain the antibacterial active ingredient by coupling and grafting the coupling agent and the active groups on the surface of the material, and has excellent and stable antibacterial performance.
Description
Technical Field
The invention relates to the technical field of material antibacterial modification, and particularly relates to an antibacterial polylactic acid material and a preparation method thereof.
Background
The preparation method of the existing antibacterial material mainly comprises the following steps: blending, physical modification, chemical grafting method and the like. But the blending and physical modification methods cannot ensure the falling of the antibacterial substances, and the antibacterial effect and safety cannot be ensured.
The prior art discloses a preparation method of an antibacterial glass fiber filtering membrane, which comprises the steps of pretreating the glass fiber filtering membrane and then carrying out heat treatment to prepare the quaternary ammonium salt antibacterial glass fiber filtering membrane. The prior art also discloses an antibacterial polylactic acid fiber and a preparation method thereof, wherein the quaternary ammonium salt polylactic acid antibacterial fiber is synthesized by firstly adopting degradation activation on the polylactic acid fiber.
However, these methods either require pretreatment of the material substrate, and have complicated processes, or have high processing difficulty and inconvenient application. Resulting in high cost and difficult access to the actual application field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an antibacterial material which is soft without pretreatment, can be obtained by directly coupling and grafting an antibacterial active ingredient and an active group on the surface of the material by a coupling agent by a chemical grafting method, and has excellent and stable antibacterial performance, and a preparation method thereof.
The preparation method of the antibacterial polylactic acid material is characterized by comprising the following steps:
soaking a polylactic acid material with a carboxyl functional group and/or a hydroxyl functional group on the surface in an antibacterial solution;
draining the wetted polylactic acid material;
placing the drained polylactic acid material at the temperature of 100-150 ℃ for heat preservation for 30-150 min;
after the heat preservation is finished, cleaning and drying the polylactic acid material;
the antibacterial liquid comprises a coupling agent and organic silicon quaternary ammonium salt.
In some embodiments of the present invention, the antibacterial liquid comprises the following components in parts by mass: 80-95% of solvent, 5-15% of pure water, 1-10% of coupling agent and 0.5-3% of organosilicon quaternary ammonium salt.
In some embodiments of the invention, the method further comprises: and uniformly mixing the solvent and the pure water, then sequentially and slowly adding the coupling agent and the organic silicon quaternary ammonium salt, and uniformly stirring for 4-6 hours at the temperature of 15-40 ℃ to obtain the antibacterial liquid.
In some embodiments of the present invention, the solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, tert-amyl alcohol, DMF, DMAc, DMSO, and acetone.
In some embodiments of the present invention, the coupling agent is one or more of methyl orthosilicate, ethyl orthosilicate, KH550, KH560, KH 570.
In some embodiments of the present invention, the silicone quaternary ammonium salt is one or more of (trimethylsilylpropyl) octadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) dodecyl dimethyl ammonium chloride, (trimethylsilylpropyl) benzyl dimethyl ammonium chloride, (trimethylsilylpropyl) octyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexyl dimethyl ammonium chloride, and (trimethylsilylpropyl) trimethyl ammonium chloride.
In some embodiments of the present invention, the soaking time of the polylactic acid material in the antibacterial solution is 1-5 min.
In some embodiments of the present invention, the time for draining the wetted polylactic acid material is 1-30 min.
The antibacterial polylactic acid material provided by the invention is prepared by the method.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a flow chart of the preparation of an antibacterial solution according to an embodiment of the present invention.
Detailed Description
The following detailed description of the present invention, taken in conjunction with the accompanying drawings and examples, is provided to enable the invention and its various aspects and advantages to be better understood. However, the specific embodiments and examples described below are for illustrative purposes only and are not limiting of the invention.
It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
As shown in fig. 1, the preparation method of the antibacterial material provided by the invention comprises the following steps:
s101: and soaking the polylactic acid material with the surface provided with the carboxyl functional group and/or the hydroxyl functional group in the antibacterial liquid.
Among them, the polylactic acid material having a carboxyl functional group and/or a hydroxyl functional group on the surface thereof according to the present invention may be a fibrous product, a nonwoven fabric product or a film product.
The antibacterial liquid comprises a coupling agent and organosilicon quaternary ammonium salt.
Wherein the coupling agent can be silane coupling agent, such as one or more of methyl orthosilicate, ethyl orthosilicate, KH550, KH560 and KH 570. A preferred coupling agent is ethyl orthosilicate.
The organosilicon quaternary ammonium salt can be one or more of (trimethylsilylpropyl) octadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) dodecyl dimethyl ammonium chloride, (trimethylsilylpropyl) benzyl dimethyl ammonium chloride, (trimethylsilylpropyl) octyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexyl dimethyl ammonium chloride and (trimethylsilylpropyl) trimethyl ammonium chloride. Preferred silicone quaternary ammonium salts are: (trimethylsilylpropyl) octadecyldimethylammonium chloride.
The antibacterial liquid of the present invention may further include a solvent and pure water.
The solvent of the invention can be one or more of methanol, ethanol, propanol, isopropanol, butanol, tertiary amyl alcohol, DMF (N, N-dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethyl sulfoxide) and acetone. The preferred solvent is ethanol.
Optionally, the antibacterial liquid comprises the following components in percentage by mass: 80-95% of solvent, 5-15% of pure water, 1-10% of coupling agent and 0.5-3% of organosilicon quaternary ammonium salt.
Optionally, the material is soaked in the antibacterial solution for 1-5min to completely wet the material.
Optionally, the method may further comprise the step of preparing an antibacterial solution:
uniformly mixing a solvent and pure water, then sequentially and slowly adding a coupling agent and the organic silicon quaternary ammonium salt, and uniformly stirring for 4-6 hours at the temperature of 15-40 ℃ to obtain the antibacterial liquid.
S102: draining the wetted polylactic acid material.
The draining is to remove the excess antibacterial solution on the surface of the material so as to facilitate the subsequent graft polymerization reaction.
Optionally, the draining time is 1-30 min.
While draining, the solvent impregnated into the material is volatilized, thereby facilitating the graft polymerization reaction.
S103: and (3) placing the drained polylactic acid material at the temperature of 100-150 ℃ for heat preservation for 30-150 min.
The step is carried out by graft polymerization reaction, so that the organosilicon quaternary ammonium salt is coupled and grafted with carboxyl and/or hydroxyl on the surface of the material through a coupling agent, and the material is modified to have antibacterial performance.
This step can be carried out in a thermostated oven.
S104: and cleaning and drying the polylactic acid material after the heat preservation is finished.
The washing is preferably carried out with water at normal temperature to 50 ℃. The drying temperature is preferably 50-100 ℃.
In order to simplify the chemical grafting method of the antibacterial material, the invention selects a specific material, takes a functional group material which is beneficial to grafting as an antibacterial modified object, and chemically grafts quaternary ammonium salt on the material, thereby preparing the quaternary ammonium salt antibacterial material. The antibacterial material prepared by the invention not only has excellent antibacterial performance, but also has excellent antibacterial performance after being washed by water and used for a long time.
In addition, the antibacterial liquid is soaked into the material in a soaking mode, the mode is easy to operate, the shape of the material is not limited, and the method is very suitable for industrialization.
The present invention will be described below with reference to specific examples. The values of the process conditions taken in the following examples are exemplary and ranges of values are provided as indicated in the foregoing summary, and reference may be made to conventional techniques for process parameters not specifically noted. The detection methods used in the following examples are all conventional in the industry. Unless otherwise indicated, the reagents and instruments used in the technical scheme provided by the invention can be purchased from conventional channels or markets.
Examples
Ethanol and pure water are uniformly mixed, and then tetraethoxysilane and (trimethylsilyl propyl) octadecyl dimethyl ammonium chloride are sequentially and slowly added to form a mixed solution. Stirring at 30 deg.C for 4 hr to obtain antibacterial liquid. Wherein the dosage ratio of ethanol, pure water, ethyl orthosilicate and (trimethylsilyl propyl) octadecyl dimethyl ammonium chloride is 85.5:9.5:3.75: 1.25.
And soaking the polylactic acid non-woven fabric material in the antibacterial solution for 2 min.
After soaking, the polylactic acid non-woven fabric material is taken out, drained and placed for another 10min to volatilize the excessive ethanol.
Then the polylactic acid non-woven fabric material is placed into a blast constant temperature oven for graft polymerization reaction, the reaction temperature is 105 ℃, and the time is 60 min.
After the heat preservation is finished, cleaning for 3 times by adopting water with the temperature of 50 ℃, and drying at the temperature of 50 ℃ to obtain the product.
Comparative example
In the comparative example, the polylactic acid non-woven fabric material is soaked in absolute ethyl alcohol for 30min, then is washed by water at 50 ℃ for 3 times, and is dried at 50 ℃.
The materials of the above examples and comparative examples were subjected to antibacterial property test using the standard method of "Standard test method for measuring antibacterial Activity of antibacterial agent under dynamic contact conditions" of ASTM E2149-13 a. The antibacterial rate of bacteria can be calculated according to the formula: the bacteria antibacterial ratio (1-number of bacteria after shaking/number of bacteria before shaking) × 100%, and the results are shown in table 1 below.
The samples of the materials of the examples and comparative examples were tested for surface Zeta potential using a solid surface Zeta potentiometer (SurPASS type 3) from Aodian Atoba, with KCl as the measuring medium and pH 7, and the test results are shown in Table 2 below.
TABLE 1 antibacterial Properties of the Material samples of the examples and comparative examples
As can be seen from table 1, the antibacterial material prepared in the present application has excellent antibacterial properties against gram-negative bacteria (e.coli) and gram-positive bacteria (s.aureus).
TABLE 2 Zeta potential (mV) on the surface of samples of materials of examples and comparative examples
The Zeta potential on the surface of the solid can reflect the surface charge and the charge intensity of the material, and is an effective means for representing the antibacterial capability of the surface of the material. As can be seen from Table 2, the Zeta potential values of the examples were 31.73mV and the Zeta potential values of the comparative examples were-47.99 mV, respectively, indicating that the quaternary ammonium salt antimicrobial active ingredient had been successfully grafted onto the surface of the material.
To verify the stability of the grafting of the antibacterial active principle, the examples were subjected to a pure water rinse (the comparative examples and examples were used as filters, water was rinsed through the filter) of 60T/m2The Zeta values were tested after drying and the Zeta potential values of the examples were reduced to 24.90mV but were still at higher Zeta potential value levels, which is comparable to Table 1, which was washed with pure water at 60T/m2The later examples still have excellent antibacterial ability, and the results are consistent, which shows that the material prepared by the invention has stable antibacterial performance.
It should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (9)
1. A preparation method of an antibacterial polylactic acid material is characterized by comprising the following steps:
soaking a polylactic acid material with a carboxyl functional group and/or a hydroxyl functional group on the surface in an antibacterial solution;
draining the wetted polylactic acid material;
placing the drained polylactic acid material at the temperature of 100-150 ℃ for heat preservation for 30-150 min;
after the heat preservation is finished, cleaning and drying the polylactic acid material;
the antibacterial liquid comprises a coupling agent and organic silicon quaternary ammonium salt.
2. The method according to claim 1, wherein the antibacterial liquid comprises the following components in parts by mass: 80-95% of solvent, 5-15% of pure water, 1-10% of coupling agent and 0.5-3% of organosilicon quaternary ammonium salt.
3. The method of manufacturing according to claim 2, further comprising:
and uniformly mixing the solvent and the pure water, then sequentially and slowly adding the coupling agent and the organic silicon quaternary ammonium salt, and uniformly stirring for 4-6 hours at the temperature of 15-40 ℃ to obtain the antibacterial liquid.
4. The preparation method according to claim 2, wherein the solvent is one or more selected from methanol, ethanol, propanol, isopropanol, butanol, t-amyl alcohol, DMF, DMAc, DMSO and acetone.
5. The preparation method according to claim 1, wherein the coupling agent is one or more of methyl orthosilicate, ethyl orthosilicate, KH550, KH560 and KH 570.
6. The preparation method according to claim 1, wherein the organosilicon quaternary ammonium salt is one or more of (trimethylsilylpropyl) octadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexadecyl dimethyl ammonium chloride, (trimethylsilylpropyl) dodecyl dimethyl ammonium chloride, (trimethylsilylpropyl) benzyl dimethyl ammonium chloride, (trimethylsilylpropyl) octyl dimethyl ammonium chloride, (trimethylsilylpropyl) hexyl dimethyl ammonium chloride, and trimethylsilylpropyl) trimethyl ammonium chloride.
7. The method according to claim 1, wherein the polylactic acid material is soaked in the antibacterial solution for 1-5 min.
8. The method of claim 2, wherein the time for draining the wetted polylactic acid material is 1-30 min.
9. An antibacterial polylactic acid material prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210819429.8A CN115012214A (en) | 2021-03-09 | 2021-03-09 | Antibacterial material obtained by direct chemical grafting and grafting method thereof |
| CN202110256619.9A CN113106750A (en) | 2021-03-09 | 2021-03-09 | Antibacterial polylactic acid material and preparation method thereof |
| PCT/CN2021/141574 WO2022188513A1 (en) | 2021-03-09 | 2021-12-27 | Antimicrobial polylactic acid material and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110256619.9A CN113106750A (en) | 2021-03-09 | 2021-03-09 | Antibacterial polylactic acid material and preparation method thereof |
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| CN202210819429.8A Division CN115012214A (en) | 2021-03-09 | 2021-03-09 | Antibacterial material obtained by direct chemical grafting and grafting method thereof |
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| CN202110256619.9A Pending CN113106750A (en) | 2021-03-09 | 2021-03-09 | Antibacterial polylactic acid material and preparation method thereof |
| CN202210819429.8A Pending CN115012214A (en) | 2021-03-09 | 2021-03-09 | Antibacterial material obtained by direct chemical grafting and grafting method thereof |
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| CN202210819429.8A Pending CN115012214A (en) | 2021-03-09 | 2021-03-09 | Antibacterial material obtained by direct chemical grafting and grafting method thereof |
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| WO (1) | WO2022188513A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248891A (en) * | 2020-02-11 | 2021-08-13 | 吉林金源北方科技发展有限公司 | Composite antibacterial material based on carbon dioxide copolymer and preparation method thereof |
| CN114395151A (en) * | 2022-01-25 | 2022-04-26 | 方益萍 | Preparation method of antibacterial degradable film and antibacterial degradable film |
| WO2022188513A1 (en) * | 2021-03-09 | 2022-09-15 | 深圳安吉尔饮水产业集团有限公司 | Antimicrobial polylactic acid material and preparation method therefor |
| CN117618624A (en) * | 2023-11-15 | 2024-03-01 | 扬州景怡医疗科技有限公司 | Medical polymer bandage convenient for biodegradation and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| CN115012214A (en) | 2022-09-06 |
| WO2022188513A1 (en) | 2022-09-15 |
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Application publication date: 20210713 |