CN117777692A - Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head - Google Patents
Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head Download PDFInfo
- Publication number
- CN117777692A CN117777692A CN202410202530.8A CN202410202530A CN117777692A CN 117777692 A CN117777692 A CN 117777692A CN 202410202530 A CN202410202530 A CN 202410202530A CN 117777692 A CN117777692 A CN 117777692A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- antibacterial
- degradable polymer
- polymer material
- based degradable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 67
- 229920006237 degradable polymer Polymers 0.000 title claims abstract description 48
- 239000002861 polymer material Substances 0.000 title claims abstract description 48
- 239000000839 emulsion Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 212
- 239000004626 polylactic acid Substances 0.000 claims abstract description 212
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 74
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 74
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 123
- 238000006243 chemical reaction Methods 0.000 claims description 93
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 56
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 42
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 40
- 239000004593 Epoxy Substances 0.000 claims description 30
- OWEGWHBOCFMBLP-UHFFFAOYSA-N 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3-dimethylbutan-2-one Chemical compound C1=CN=CN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 OWEGWHBOCFMBLP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 16
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 50
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 241001391944 Commicarpus scandens Species 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 description 45
- 238000001914 filtration Methods 0.000 description 45
- 238000001291 vacuum drying Methods 0.000 description 28
- 238000002390 rotary evaporation Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 amino hydrogen Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011155 wood-plastic composite Substances 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of plastic materials, in particular to an antibacterial PLA-based degradable polymer material, a preparation method and application thereof in an emulsion pump head. The antibacterial PLA-based degradable polymer material takes polylactic acid as a matrix material and has good biodegradability; the toughening material is introduced into the polylactic acid material, so that the problem that the polylactic acid material is easy to break due to brittle fracture when being impacted by external force caused by high brittleness can be effectively solved; the toughening material comprises organic toughening material nitrile rubber and inorganic toughening material nano silicon dioxide, and the toughening material is connected to polylactic acid molecules through stable chemical bonds, so that the toughening effect is good; the antibacterial agent is added into the polylactic acid material, so that the antibacterial performance of the polylactic acid material can be effectively improved. The antibacterial PLA-based degradable polymer material prepared by the invention can be used for preparing emulsion pump joints, has good antibacterial property, and can prevent the washing and protecting articles at the emulsion pump joints from being polluted when being exposed to the air environment.
Description
Technical Field
The invention relates to the technical field of plastic materials, in particular to an antibacterial PLA-based degradable polymer material, a preparation method and application thereof in an emulsion pump head.
Background
Plastic materials are increasingly used in production and life, such as shampoo, bath lotion, skin care lotion, emulsion-like washing products such as emulsion are packaged by plastic or glass, and the emulsion is pumped out by pressing a plastic pump head when the plastic washing products are used. While bringing convenience to our lives, a large amount of waste plastic materials also cause serious white pollution. For environmental protection purposes, there is an increasing demand for plastics with regard to their degradability properties. PLA (polylactic acid) is a polyester polymer obtained by polymerizing lactic acid as a main raw material, is a novel biodegradable material, can be completely degraded by microorganisms in the nature after being used, and finally generates carbon dioxide and water without polluting the environment. However, polylactic acid is a brittle material, which has low elongation at break and impact strength, and is easily broken by external force. In addition, the cleaning supplies at the pump head are contaminated by exposure to the air environment.
Chinese patent CN106147173B discloses a high-toughness polylactic acid wood-plastic composite material, wherein modified plant fiber and nano calcium carbonate are added into polylactic acid to improve toughness of polylactic acid, the modified plant fiber, the nano calcium carbonate and the polylactic acid are melt blended, dispersion uniformity of the nano calcium carbonate in the polylactic acid is poor, and binding force between the modified plant fiber and the polylactic acid is poor. Chinese patent CN111793337B discloses an antibacterial polylactic acid master batch, which uses nano copper oxide and nano cuprous oxide to modify polylactic acid, so as to increase antibacterial property of polylactic acid, but the nano copper oxide and nano cuprous oxide are dispersed in the polylactic acid in a fusion manner, so that the dispersion uniformity of the nano copper oxide and nano cuprous oxide in the polylactic acid is poor, the compatibility with the polylactic acid is poor, and the antibacterial effect is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an antibacterial PLA-based degradable polymer material, a preparation method and application thereof in an emulsion pump head, which are used for solving the problems that the polylactic acid degradable material in the prior art is poor in toughness and antibacterial performance is to be improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring until the polylactic acid is dissolved, adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, reacting, purifying after the reaction is finished, and drying to obtain nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into ethanol water solution, adding gamma-glycidol ether oxygen propyl trimethoxy silane after ultrasonic treatment, reacting, purifying after the reaction is finished, and drying to obtain epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring until the nitrile rubber modified polylactic acid is dissolved, adding epoxy modified nano silicon dioxide and triethylamine, reacting, purifying and drying after the reaction is finished to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring and dissolving, adding nano silicon dioxide modified polylactic acid, reacting, purifying and drying after the reaction is finished to obtain modified polylactic acid;
and step four, mixing, melting, extruding, cooling and granulating the polylactic acid and the modified polylactic acid to obtain the antibacterial PLA-based degradable polymer material.
Preferably, in the first step, the mass ratio of polylactic acid, acetone, amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine is 140: (600-800): (25-35): (0.5-1).
Preferably, in the first step, the reaction condition is that the reaction is carried out at a temperature of 30-40 ℃ for 3-5h.
Preferably, the purification comprises rotary evaporation, washing.
Preferably, in the second step, the mass ratio of the nano silicon dioxide to the ethanol aqueous solution to the gamma-glycidyl ether oxypropyl trimethoxysilane is 60: (300-350): (65-75), the reaction condition is that the reaction is carried out for 6-8h at the temperature of 50-70 ℃.
Preferably, the aqueous ethanol solution is a 95wt% aqueous ethanol solution.
Preferably, the purification comprises filtration, washing.
Preferably, in the second step, the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is (165-175): (600-700): (6-7): (1-2) under the condition of reacting for 2-4h at 70-90 ℃.
Preferably, the purification comprises rotary evaporation, washing.
Preferably, in the third step, the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone, toluene and nano silicon dioxide modified polylactic acid is (5-10): (600-800): (170-180).
Preferably, in the third step, the reaction condition is that the reaction is carried out at a temperature of 40-60 ℃ for 4-6 hours.
Preferably, the purification comprises filtration, washing.
Preferably, in the fourth step, the mass ratio of the polylactic acid to the modified polylactic acid is 100: (70-95).
Preferably, in the fourth step, the melting temperature is 185-195 ℃.
The invention also discloses an antibacterial PLA-based degradable polymer material prepared by the preparation method of the antibacterial PLA-based degradable polymer material.
Preferably, an antibacterial PLA-based degradable polymeric material as described above is used in an emulsion pump head.
Compared with the prior art, the invention has the following beneficial effects: the degradable polymer material disclosed by the invention takes polylactic acid as a matrix material, has good biodegradability, can be decomposed into water and carbon dioxide under the action of soil, water or microorganisms in nature, has no pollution to air and soil, and is environment-friendly; meanwhile, the toughening material is introduced into the polylactic acid material, so that the problem that the polylactic acid material is easy to break due to brittle fracture when being impacted by external force caused by high brittleness can be effectively solved; the toughening material comprises organic toughening material nitrile rubber and inorganic toughening material nano silicon dioxide, wherein the nitrile rubber reacts with carboxyl at the end position of polylactic acid through amino at the end position to generate an amide bond, so that the organic toughening material is stably connected with the polylactic acid matrix material, and the nitrile rubber modified polylactic acid is obtained; the nano silicon dioxide is reacted with gamma-glycidyl ether oxypropyl trimethoxy silane, an epoxy group is introduced to obtain epoxy modified nano silicon dioxide, and then the epoxy group is subjected to a ring opening reaction with active amino hydrogen N-H on an amide bond in the nitrile rubber modified polylactic acid to realize stable connection of the inorganic toughening material and the polylactic acid matrix material; the introduction of the organic toughening material and the inorganic toughening material can effectively improve the toughness of the polylactic acid material; in the invention, the antibacterial performance of the polylactic acid material is improved by adding the antibacterial agent 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone; when epoxy modified nano silicon dioxide reacts with nitrile rubber modified polylactic acid, secondary amine on an amide bond is converted into tertiary amine, the tertiary amine can react with chlorine element on a bactericide 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone molecule to form quaternary ammonium salt, and the quaternary ammonium salt has excellent antibacterial performance and can further improve the antibacterial performance of a polylactic acid material.
Drawings
FIG. 1 is a flow chart of a preparation process of the modified polylactic acid;
FIG. 2 is a plot of tensile property test results of the prepared antibacterial PLA-based degradable polymer materials of examples 1-6 and comparative examples 1-2 of the invention;
FIG. 3 is a plot of the impact performance test results for the antimicrobial PLA-based degradable polymer materials made in examples 1-6 and comparative examples 1-2 of this invention;
FIG. 4 is a line graph showing the results of antibacterial property tests of the antibacterial PLA-based degradable polymer materials of examples 1-6 and comparative examples 1-2 of the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:600:25:0.5, reacting for 5 hours at 30 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:300:65, reacting for 8 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 165:600:6:1, reacting for 4 hours at 70 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 5:600:170, reacting for 6 hours at 40 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:70, melting at 185 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Example 2
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:800:35:1, reacting for 3 hours at the temperature of 40 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at the temperature of 80 ℃ for 10 hours to obtain nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:350:75, reacting for 6 hours at 70 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 175:700:7:2, reacting for 2 hours at 90 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 10:800:180, reacting for 4 hours at 60 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:95, melting at 195 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Example 3
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:640:27:0.6, reacting for 4 hours at 35 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:310:67, reacting for 7 hours at 60 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at 60 ℃ and a stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 167:620:6.2:1.2, reacting for 3 hours at 80 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 6:640:172, reacting for 5 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:75, melting at 190 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Example 4
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:680:29:0.7, reacting for 4 hours at 35 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:320:69, reacting for 7 hours at 60 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 169:640:6.4:1.4, reacting for 3 hours at 80 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 6:680:174, reacting for 5 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:80, melting at 190 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Example 5
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:720:31:0.8, reacting for 4 hours at 35 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:330:71, reacting for 7 hours at 60 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 171:660:6.6:1.6, reacting for 3 hours at 80 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 6:720:176, reacting for 5 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:85, melting at 190 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Example 6
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:760:33:0.9, reacting for 4 hours at 35 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:340:73, reacting for 7 hours at 60 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 173:680:6.8:1.8, reacting for 3 hours at 80 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring at a stirring speed of 300r/min until the mixture is dissolved, and adding nano silicon dioxide modified polylactic acid, wherein the mass ratio of the 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone to toluene is 6:760:178, reacting for 5 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, drying in a vacuum drying oven at 80 ℃ for 10 hours, and drying to obtain modified polylactic acid;
fourthly, the polylactic acid and the modified polylactic acid are mixed according to the mass ratio of 100:90, melting at 190 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Comparative example 1
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:600:25:0.5, reacting for 5 hours at 30 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into 95wt% ethanol water solution, carrying out ultrasonic treatment for 30min at the frequency of 50Hz, and then adding gamma-glycidoxypropyl trimethoxysilane, wherein the mass ratio of the nano silicon dioxide to the 95wt% ethanol water solution to the gamma-glycidoxypropyl trimethoxysilane is 60:300:65, reacting for 8 hours at 50 ℃, filtering after the reaction is finished, washing with ethanol for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the epoxy modified nano silicon dioxide;
adding nitrile rubber modified polylactic acid into toluene, stirring at the temperature of 60 ℃ and the stirring speed of 300r/min until the nitrile rubber modified polylactic acid is dissolved, and adding epoxy modified nano silicon dioxide and triethylamine, wherein the mass ratio of the nitrile rubber modified polylactic acid to the toluene to the epoxy modified nano silicon dioxide to the triethylamine is 165:600:6:1, reacting for 4 hours at 70 ℃, after the reaction is finished, removing toluene by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain nano silicon dioxide modified polylactic acid;
step three, polylactic acid, nano silicon dioxide modified polylactic acid and 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone are mixed according to the mass ratio of 100:68:2, mixing, melting at 185 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
Comparative example 2
A method for preparing an antibacterial PLA-based degradable polymer material, comprising the following steps:
adding polylactic acid into acetone, stirring at 50 ℃ and a stirring speed of 300r/min until the polylactic acid is dissolved, cooling to room temperature, and adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, wherein the mass ratio of the polylactic acid to the acetone to the amino-terminated liquid nitrile rubber to the 4-dimethylaminopyridine is 140:600:25:0.5, reacting for 5 hours at 30 ℃, after the reaction is finished, removing acetone by rotary evaporation to obtain a reaction crude product, adding ethanol with the mass 10 times of that of the reaction crude product into the reaction crude product, washing, filtering, repeating the washing and filtering operations for three times, and drying in a vacuum drying oven at 80 ℃ for 10 hours to obtain the nitrile rubber modified polylactic acid;
step two, polylactic acid, nitrile rubber modified polylactic acid, nano silicon dioxide, 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone are mixed according to the mass ratio of 100:65.5:1.5:2, mixing, melting at 185 ℃, extruding, cooling and granulating to obtain the antibacterial PLA-based degradable polymer material.
In the above examples and comparative examples: polylactic acid is purchased from Shanghai fly-Mich plasticizing Co., ltd., manufacturer: thailand dall, cat No.: LX175; the amino-terminated liquid nitrile rubber is purchased from Jingjiang, high chemical industry Co., ltd., model: TL55; the nano silicon dioxide is hydroxylation nano silicon dioxide, which is purchased from Beijing Keyou nanotechnology Co., ltd, and has average particle diameter: 200nm.
Test examples
Performance tests were performed on the antibacterial PLA-based degradable polymer materials prepared in examples 1 to 6 and comparative examples 1 to 2:
(1) Mechanical property test: the tensile properties were tested by the method in reference standard GB/T528-2009 and the impact properties were tested by the method in reference standard GB/T1843-2008, the test results are shown in Table 1:
as can be seen from Table 1, the antibacterial PLA-based degradable polymer material prepared by the invention has high elongation at break and high notched Izod impact strength and good toughness. The introduction of the toughening materials of the nitrile rubber and the nano silicon dioxide can effectively improve the flexibility of the polylactic acid, and the nano silicon dioxide and the nitrile rubber are connected with the polylactic acid matrix material through stable chemical bonds, so that the dispersion uniformity of the toughening materials in the matrix material and the compatibility between the toughening materials and the matrix material can be effectively improved, and the toughness of the polylactic acid can be further improved. Compared with the example 1, in the comparative example 1, the antibacterial agent 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone does not react with nano silicon dioxide modified polylactic acid to form quaternary ammonium salt, the toughening effect on the polylactic acid is not affected, and the mechanical property of the prepared antibacterial PLA-based degradable polymer material is equivalent to that of the example 1; in comparative example 2, the nano silica was not connected to the polylactic acid molecule through a chemical bond, the dispersion uniformity in the polylactic acid and the compatibility with the polylactic acid were reduced, and the mechanical properties of the prepared antibacterial PLA-based degradable polymer material were reduced.
(2) Antibacterial performance test: the antibacterial properties of the antibacterial PLA-based degradable polymer materials prepared in examples 1 to 6 and comparative examples 1 to 2, respectively, were tested with reference to the method in standard GB/T31402-2015, and the test results are shown in table 2:
as can be seen from Table 2, the antibacterial PLA-based degradable polymer material prepared by the invention has good antibacterial property. According to the invention, the antibacterial agent 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone is added, so that the antibacterial performance of the polylactic acid material can be effectively improved; the antibacterial agent 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone reacts with tertiary amine in the epoxy modified nano silicon dioxide to form quaternary ammonium salt, and the quaternary ammonium salt has excellent antibacterial performance and can further improve the antibacterial performance of the polylactic acid material. In comparison with example 1, in both comparative example 1 and comparative example 2, no quaternary ammonium salt was formed, and antibacterial efficacy was provided only by the antibacterial agent 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone, and antibacterial properties were reduced.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for preparing an antibacterial PLA-based degradable polymer material, comprising the steps of:
adding polylactic acid into acetone, stirring until the polylactic acid is dissolved, adding amino-terminated liquid nitrile rubber and 4-dimethylaminopyridine, reacting, purifying after the reaction is finished, and drying to obtain nitrile rubber modified polylactic acid;
step two, adding nano silicon dioxide into ethanol water solution, adding gamma-glycidol ether oxygen propyl trimethoxy silane after ultrasonic treatment, reacting, purifying after the reaction is finished, and drying to obtain epoxy modified nano silicon dioxide; adding nitrile rubber modified polylactic acid into toluene, stirring until the nitrile rubber modified polylactic acid is dissolved, adding epoxy modified nano silicon dioxide and triethylamine, reacting, purifying and drying after the reaction is finished to obtain nano silicon dioxide modified polylactic acid;
step three, adding 1- (4-chlorophenoxy) -1- (1H-imidazole-1-yl) -3, 3-dimethyl-2-butanone into toluene, stirring and dissolving, adding nano silicon dioxide modified polylactic acid, reacting, purifying and drying after the reaction is finished to obtain modified polylactic acid;
and step four, mixing, melting, extruding, cooling and granulating the polylactic acid and the modified polylactic acid to obtain the antibacterial PLA-based degradable polymer material.
2. The method for preparing an antibacterial PLA-based degradable polymer material according to claim 1, wherein in the first step, the mass ratio of polylactic acid, acetone, amino-terminated liquid nitrile rubber, 4-dimethylaminopyridine is 140: (800-1000): (25-35): (0.5-1).
3. The method for preparing an antibacterial PLA-based degradable polymer material according to claim 1, wherein in the first step, the reaction condition is that the reaction is performed at a temperature of 20-40 ℃ for 3-5 hours.
4. The method for preparing the antibacterial PLA-based degradable polymer material according to claim 1, wherein in the second step, the mass ratio of nano silica to ethanol aqueous solution to γ -glycidoxypropyl trimethoxysilane is 60: (300-350): (65-75), the reaction condition is that the reaction is carried out for 6-8h at the temperature of 50-70 ℃.
5. The method for preparing the antibacterial PLA-based degradable polymer material according to claim 1, wherein in the second step, the mass ratio of the nitrile rubber modified polylactic acid, toluene, epoxy modified nano silica and triethylamine is (165-175): (600-700): (6-7): (1-2) under the condition of reacting for 2-4h at 70-90 ℃.
6. The method for preparing the antibacterial PLA-based degradable polymer material according to claim 1, wherein in the third step, the mass ratio of 1- (4-chlorophenoxy) -1- (1H-imidazol-1-yl) -3, 3-dimethyl-2-butanone, toluene, nano silica modified polylactic acid is (5-10): (600-800): (170-180).
7. The method for preparing an antibacterial PLA-based degradable polymer material according to claim 1, wherein in the third step, the reaction condition is that the reaction is performed at a temperature of 40-60 ℃ for 4-6 hours.
8. The method for preparing an antibacterial PLA-based degradable polymer material according to claim 1, wherein in the fourth step, the mass ratio of polylactic acid to modified polylactic acid is 100: (70-95) and the melting temperature is 185-195 ℃.
9. An antibacterial PLA-based degradable polymer material prepared by the preparation method of the antibacterial PLA-based degradable polymer material according to any one of claims 1 to 8.
10. Use of an antibacterial PLA-based degradable polymeric material according to claim 9 in an emulsion pump head.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410202530.8A CN117777692B (en) | 2024-02-23 | 2024-02-23 | Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410202530.8A CN117777692B (en) | 2024-02-23 | 2024-02-23 | Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117777692A true CN117777692A (en) | 2024-03-29 |
| CN117777692B CN117777692B (en) | 2024-05-07 |
Family
ID=90381971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410202530.8A Active CN117777692B (en) | 2024-02-23 | 2024-02-23 | Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777692B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063947A (en) * | 2024-04-24 | 2024-05-24 | 汕头市国塑新材料有限公司 | Wear-resistant impact-resistant polylactic acid material added with lead alloy and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831156A (en) * | 2010-05-07 | 2010-09-15 | 四川大学 | Toughened halogen-free flame-retardant polylactic acid blending material |
| CN107459793A (en) * | 2017-08-28 | 2017-12-12 | 华南理工大学 | Strong and unyielding balanced ultra-tough PLA based nano composite material and preparation method thereof |
| CN108659491A (en) * | 2018-06-07 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of lactic acid composite material of activeness and quietness and preparation method thereof |
| CN112375357A (en) * | 2020-12-04 | 2021-02-19 | 温州市隆昌塑料有限公司 | Degradable modified polylactic acid composition and application thereof |
| CN112409772A (en) * | 2020-11-19 | 2021-02-26 | 中山市嘉宝日用制品有限公司 | anti-UV high-transmittance antibacterial PC material and preparation method thereof |
| CN113373536A (en) * | 2021-06-29 | 2021-09-10 | 南陵县麒霆新材料科技有限公司 | Functionalized modified silicon dioxide flame-retardant modified polylactic acid composite fiber and preparation method thereof |
| CN114907677A (en) * | 2021-10-11 | 2022-08-16 | 中国科学院兰州化学物理研究所 | Scratch-resistant polylactic acid material with balanced rigidity and toughness and preparation method thereof |
| CN114957941A (en) * | 2022-04-25 | 2022-08-30 | 青岛科技大学 | Functional material for toughening polylactic acid by modified carboxyl nitrile rubber and preparation method thereof |
-
2024
- 2024-02-23 CN CN202410202530.8A patent/CN117777692B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831156A (en) * | 2010-05-07 | 2010-09-15 | 四川大学 | Toughened halogen-free flame-retardant polylactic acid blending material |
| CN107459793A (en) * | 2017-08-28 | 2017-12-12 | 华南理工大学 | Strong and unyielding balanced ultra-tough PLA based nano composite material and preparation method thereof |
| CN108659491A (en) * | 2018-06-07 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of lactic acid composite material of activeness and quietness and preparation method thereof |
| CN112409772A (en) * | 2020-11-19 | 2021-02-26 | 中山市嘉宝日用制品有限公司 | anti-UV high-transmittance antibacterial PC material and preparation method thereof |
| CN112375357A (en) * | 2020-12-04 | 2021-02-19 | 温州市隆昌塑料有限公司 | Degradable modified polylactic acid composition and application thereof |
| CN113373536A (en) * | 2021-06-29 | 2021-09-10 | 南陵县麒霆新材料科技有限公司 | Functionalized modified silicon dioxide flame-retardant modified polylactic acid composite fiber and preparation method thereof |
| CN114907677A (en) * | 2021-10-11 | 2022-08-16 | 中国科学院兰州化学物理研究所 | Scratch-resistant polylactic acid material with balanced rigidity and toughness and preparation method thereof |
| CN114957941A (en) * | 2022-04-25 | 2022-08-30 | 青岛科技大学 | Functional material for toughening polylactic acid by modified carboxyl nitrile rubber and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 刘雨桐: "刚韧均衡的PLA/NR/SiO2 TPV的制备及其结构和性能的研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), 15 January 2020 (2020-01-15), pages 020 - 601 * |
| 卢亚汝 等: "端氨基丁腈橡胶与纳米SiO2 粒子增韧环氧树脂性能", 工程塑料应用, vol. 46, no. 5, 10 May 2018 (2018-05-10), pages 1 - 5 * |
| 王利平 等: "界面增容剂对丁腈橡胶增韧聚乳酸体系性能的影响", 高分子学报, no. 7, 20 July 2014 (2014-07-20), pages 914 - 921 * |
| 陈俊雄 等: "橡胶对聚乳酸增韧改性的研究进展", 塑料科技, no. 11, 25 November 2023 (2023-11-25), pages 111 - 115 * |
| 黄嘉荣: "聚乳酸/橡胶/无机粒子热塑性硫化胶的制备及其结构与性能研究", 中国博士学位论文全文数据库 (工程科技Ⅰ辑), 15 January 2023 (2023-01-15), pages 016 - 157 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063947A (en) * | 2024-04-24 | 2024-05-24 | 汕头市国塑新材料有限公司 | Wear-resistant impact-resistant polylactic acid material added with lead alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117777692B (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117777692B (en) | Antibacterial PLA-based degradable polymer material, preparation method and application thereof in emulsion pump head | |
| CN107620211B (en) | Fine cellulose fiber composite | |
| TW201920295A (en) | Micro cellulose fiber complex | |
| CN110467804B (en) | Bio-based nylon composite PLA material and preparation method thereof | |
| CN103113740B (en) | Nylon-66 modified elastomer and preparation method thereof | |
| CN107082949B (en) | High-performance polypropylene plastic packaging barrel and preparation method thereof | |
| JP2014136745A (en) | Polyamide resin molded product | |
| CN106750271A (en) | The preparation method of nano silicon reinforced nylon 6 composite | |
| CN102492268A (en) | Alkali resistance glass fiber reinforced thermoplasticity polyester composite material and preparation method thereof | |
| CN106008931A (en) | PBS/basic magnesium sulfate whisker composite and preparation method | |
| CN104592512A (en) | Carbon dioxide based polyurea and preparation method and application thereof | |
| CN113845766A (en) | Preparation method of polyoxyethylene water-soluble film | |
| CN103073887B (en) | Modified elastomer of nylon 1212 and preparation method thereof | |
| CN111438835A (en) | Composite environment-friendly plastic particle and preparation method thereof | |
| CN114479237A (en) | High-density polyethylene composite material and preparation method thereof | |
| CN117587546A (en) | Biodegradable composite brush wire material and preparation method and application thereof | |
| CN114230991B (en) | Preparation method of modified epoxidized vegetable oil toughened polylactic acid material | |
| CN108396402B (en) | High-toughness polyester staple fiber and preparation method thereof | |
| CN105694344A (en) | Plastic alloy for washing machine cover plate and preparation method of plastic alloy | |
| CN107903477A (en) | A kind of degradable polyethylene plastic bag of environmental protection | |
| CN111499951B (en) | Antibacterial toughened polyethylene plastic pipe and preparation method thereof | |
| CN103923446B (en) | A kind of degradable biological matter poly(lactic acid) magnetic card material | |
| CN116589731B (en) | Degradable multilayer composite bubble film and preparation method thereof | |
| CN117328162A (en) | Preparation method of polylactic acid/polycaprolactone antibacterial blend fiber | |
| CN114990731B (en) | PLA/PBAT composite flame-retardant antibacterial degradable short fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |