CN117165042A - Antibacterial PBT composite material and preparation method thereof - Google Patents
Antibacterial PBT composite material and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 240000000491 Corchorus aestuans Species 0.000 claims abstract description 42
- 235000011777 Corchorus aestuans Nutrition 0.000 claims abstract description 42
- 235000010862 Corchorus capsularis Nutrition 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000011343 solid material Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 23
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 235000011147 magnesium chloride Nutrition 0.000 claims description 11
- 229910021538 borax Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 10
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical group [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 10
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 2
- 210000004666 bacterial spore Anatomy 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 38
- 238000007873 sieving Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000002791 soaking Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- -1 Polybutylene terephthalate Polymers 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- JXLYSJRDGCGARV-WWYNWVTFSA-N Vinblastine Natural products O=C(O[C@H]1[C@](O)(C(=O)OC)[C@@H]2N(C)c3c(cc(c(OC)c3)[C@]3(C(=O)OC)c4[nH]c5c(c4CCN4C[C@](O)(CC)C[C@H](C3)C4)cccc5)[C@@]32[C@H]2[C@@]1(CC)C=CCN2CC3)C JXLYSJRDGCGARV-WWYNWVTFSA-N 0.000 description 1
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- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 150000003432 sterols Chemical class 0.000 description 1
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- JXLYSJRDGCGARV-XQKSVPLYSA-N vincaleukoblastine Chemical compound C([C@@H](C[C@]1(C(=O)OC)C=2C(=CC3=C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C)C=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 JXLYSJRDGCGARV-XQKSVPLYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an antibacterial PBT composite material and a preparation method thereof, wherein the antibacterial PBT composite material comprises the following components: 80-100 parts of PBT, 10-16 parts of modified jute fiber, 2-4 parts of antibacterial agent and 0.1-0.5 part of antioxidant; the modified jute fiber is obtained by immersing jute fiber in alkali liquor, and then washing to neutrality; the antibacterial agent is Mg 2+ ‑ZrO 2 AgO-Ag type antibacterial agent in which Ag is effective for separating ZrO 2 The photo-generated electron hole pair in the material generates OH with extremely strong oxidation capability, so that bacterial spores are deactivated, and the antibacterial capability of the material is improved. The antibacterial agent can produce synergistic effect with modified jute fiber, and can improve antibacterial ability of composite materialAnd the mechanical property of the material is improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antibacterial PBT composite material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is a widely used high molecular polyester resin, and has the advantages of good fatigue resistance, good heat resistance, good dimensional stability and the like, but has high requirements on physical properties and antibacterial properties of PBT in specific application fields, so that the PBT composite material is limited to be applied in specific fields.
At present, the use of the conventional antibacterial agent has limited improvement on the antibacterial property of the PBT, and in addition, the use of part of the antibacterial agent improves the antibacterial property of the PBT, but reduces the physical property of the PBT, so that the problem that the physical property and the antibacterial property of the PBT are difficult to balance is caused.
Disclosure of Invention
Aiming at the defects, the invention innovatively synthesizes a novel high-performance antibacterial PBT composite material, which has good physical property and antibacterial property, solves the technical problems of limited physical property and antibacterial capability of the PBT in the prior art
In order to achieve the above purpose, the technical scheme of the invention is as follows:
an antibacterial PBT composite material comprises the following components:
wherein:
the modified jute fiber is obtained by immersing jute fiber in alkali liquor at room temperature, and then washing to neutrality; further, the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 10-12 μm in NaOH solution with the mass fraction of 4% for 1h, taking out, repeatedly washing with dilute hydrochloric acid solution with the mass fraction of 5% to neutrality, and placing into a blast drying oven to dry at 80 ℃ to constant weight to obtain modified jute fiber; the jute fiber contains a large amount of lignin, so that the fiber is coarse and hard and has poor compatibility with polymers, and the lignin in the jute fiber can be removed by soaking the jute fiber in NaOH solution, so that the compatibility between the jute fiber and PBT is improved.
The antioxidant is at least one of antioxidant 168, antioxidant 1010 and antioxidant 1330.
The preparation method of the antibacterial agent comprises the following steps:
(1) Weighing zirconium nitrate pentahydrate and magnesium dichloride (MgCl) 2 ) Adding the solution and the solvent into a reaction vessel, and reacting for 8-12h at 100-160 ℃ to obtain a mixed material A; the mass ratio of the zirconium nitrate pentahydrate to the magnesium dichloride solution to the solvent is (30-40): (40-50): (180-240); preferably, the solvent is acetone, ethanol or isopropanol;
(2) Filtering the mixed material A to remove the solvent, sequentially washing, calcining, grinding, sieving with 100 mesh sieve to obtain zirconium dioxide loaded with magnesium ions, and marking as Mg 2+ -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the calcination temperature is 600-680 ℃ and the calcination time is 10-16h;
(3) Weighing Mg 2+ -ZrO 2 Adding ammonia water solution, silver chloride (AgCl) and a reducing agent into a reaction vessel, and reacting for 10-16h at normal temperature to obtain a mixed material B; preferably, the solvent is an acetone solution; the reducing agent is sodium borate (NaBH) 4 ) The method comprises the steps of carrying out a first treatment on the surface of the The Mg is 2+ -ZrO 2 Aqueous ammonia, silver chloride (AgCl), sodium borate (NaBH) 4 ) The mass ratio of (3) is (30-50): (160-200): (40-60): (0.2-0.6); the mass fraction of the ammonia water solution is 25%.
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 6-8 hours in a vacuum drying oven at 50-70 ℃, grinding the solid material, and sieving the solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent.
The preparation method of the antibacterial PBT composite material provided by the invention comprises the following steps:
(1) Weighing 80-100 parts of PBT, 10-16 parts of modified jute fiber, 2-4 parts of antibacterial agent and 0.1-0.5 part of antioxidant, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain the PBT composite material. Wherein: the double-screw extruder comprises six temperature areas which are sequentially arranged, and the temperatures of the temperature areas are as follows: the temperature of the first area is 200-220 ℃, the temperature of the second area is 240-260 ℃, the temperature of the third area is 240-260 ℃, the temperature of the fourth area is 240-260 ℃, the temperature of the fifth area is 240-260 ℃, and the temperature of the sixth area is 240-260 ℃; the temperature of the head of the double-screw extruder is 240-260 ℃, and the rotating speed of the screw is 200-280 r/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) This patent synthesizes a novel Mg 2+ -ZrO 2/ The antibacterial mechanism of the AgO-Ag antibacterial agent mainly comprises: due to Ag adhering to ZrO 2 The ZrO may be added to the surface of the material 2 The generated photo-generated electrons are transferred to the Ag simple substance, photo-generated electron hole pairs and ZrO can be effectively separated 2 The valence band cavity in the material can react with-OH in water molecules to generate OH with extremely strong oxidizing ability, so that bacterial spores are deactivated, and the antibacterial ability of the material is improved.
(2) The jute fiber contains a large amount of jute sterol substances and derivatives thereof, is an effective natural antibacterial substance, can block the metabolism and physiological activities of microorganisms such as mould and the like, destroy the structure of thalli, has antibacterial effect, can cooperate with the antibacterial agent of the patent, and can improve the mechanical property of the material while improving the antibacterial capability.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to specific embodiments that are now described. Unless otherwise defined as such, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The raw materials used in the following examples are as follows:
zirconium nitrate pentahydrate, shanghai, chemical Co., ltd; acetone solution, jinan Yongrui chemical Co., ltd; magnesium dichloride solution, shanghai super Smart chemical Co., ltd; silver chloride, hubei Xinrun chemical Co., ltd; sodium borate, henan Hongzhi chemical Co., ltd; PBT (model 1100-211M), taiwan vinblastine engineering plastics (Jiangsu Co., ltd.); antioxidants (model Irganox168, irganox1010, irganox 1330), ciba, switzerland, inc.; sodium hydroxide, analytically pure, tianjin city continental chemical reagent plant; hydrochloric acid, analytically pure, mainland chemical reagent plant in the Tianjin city; jute fiber, qingdao Jin Lingwo International trade company, inc.
In addition, the preparation processes in the following examples are conventional means in the art unless specifically described, and therefore, will not be described in detail; the parts in the following embodiments refer to parts by weight.
Preparation example 1
(1) 300g of zirconium nitrate pentahydrate, 400g of magnesium dichloride solution and 1.8kg of acetone solution are weighed and added into a reaction vessel to react for 8 hours at 100 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing the obtained material, calcining in a muffle furnace at 600 ℃ for 10 hours, grinding and sieving with a 100-mesh sieve to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 ；
(3) Weigh 300gMg 2+ -ZrO 2 1.6kg of an aqueous ammonia solution with a mass fraction of 25%, 400g of silver chloride (AgCl), 2g of sodium borate (NaBH) 4 ) Adding the mixture into a reaction vessel, and reacting for 10 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 6 hours in a vacuum drying oven at 50 ℃, grinding the solid material, and sieving the solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent N1.
Application example 1
(1) Weighing 80 parts of PBT, 10 parts of modified jute fiber, 2 parts of antibacterial agent N1 and 0.1 part of antioxidant 1010, mixing and uniformly stirring to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 10 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is denoted as P1. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the machine head is 240 ℃, and the rotating speed of the screw is 200r/min.
Preparation example 2
(1) 400g of zirconium nitrate pentahydrate, 500g of magnesium dichloride solution and 2.4kg of acetone solution are weighed and added into a reaction vessel to react for 12 hours at 160 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing the obtained material, calcining in a muffle furnace at 680 ℃ for 16 hours, grinding and sieving with a 100-mesh sieve to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 ；
(3) 500g of Mg is weighed 2+ -ZrO 2 2.0kg of an aqueous ammonia solution with a mass fraction of 25%, 600g of silver chloride (AgCl), 6g of sodium borate (NaBH) 4 ) Adding the mixture into a reaction vessel, and reacting for 16 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 8 hours in a vacuum drying oven at 70 ℃, grinding the solid material, and sieving the solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent N2.
Application example 2
(1) Weighing 100 parts of PBT, 16 parts of modified jute fiber, 4 parts of antibacterial agent N2, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.2 part of antioxidant 1330, mixing and uniformly stirring to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 12 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as P2. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 220 ℃, the temperature of the second area is 260 ℃, the temperature of the third area is 260 ℃, the temperature of the fourth area is 260 ℃, the temperature of the fifth area is 260 ℃, the temperature of the sixth area is 260 ℃, the temperature of the machine head is 260 ℃, and the rotating speed of the screw is 280r/min.
Preparation example 3
(1) 350g of zirconium nitrate pentahydrate, 450g of magnesium dichloride solution and 2.1kg of acetone solution are weighed and added into a reaction vessel for reaction for 10 hours at 130 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing the obtained material, calcining in a muffle furnace at 640 ℃ for 13 hours, grinding and sieving with a 100-mesh sieve to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 ；
(3) 400g of Mg are weighed 2+ -ZrO 2 1.8kg of an aqueous ammonia solution with a mass fraction of 25%, 500g of silver chloride (AgCl), 4g of sodium borate (NaBH) 4 ) Adding the mixture into a reaction vessel, and reacting for 13 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 7 hours in a vacuum drying oven at 60 ℃, grinding the solid material, and sieving the solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent N3.
Application example 3
(1) Weighing 90 parts of PBT, 13 parts of modified jute fiber, 3 parts of antibacterial agent N3, 0.1 part of antioxidant 168 and 0.2 part of antioxidant 1010, mixing and uniformly stirring to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 11 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as P3. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 210 ℃, the temperature of the second area is 250 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the machine head is 250 ℃, and the rotating speed of the screw is 240r/min.
Preparation example 4
(1) 380g of zirconium nitrate pentahydrate, 460g of magnesium dichloride solution and 1.9kg of acetone solution are weighed and added into a reaction vessel for reaction for 11 hours at 140 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing the obtained material, calcining in a muffle furnace at 645 ℃ for 15 hours, grinding and sieving with a 100-mesh sieve to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 ；
(3) Weigh 420g Mg 2+ -ZrO 2 1.9kg of an aqueous ammonia solution with a mass fraction of 25%, 480g of silver chloride (AgCl), 5g of sodium borate (NaBH) 4 ) Adding the mixture into a reaction vessel, and reacting for 12 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 8 hours in a 55 ℃ vacuum drying oven, grinding the solid material, and sieving the solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent N4.
Application example 4
(1) Weighing 85 parts of PBT, 15 parts of modified jute fiber, 4 parts of antibacterial agent N4, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 1330, mixing and uniformly stirring to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 11 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as P4. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 205 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 230r/min.
Preparation example 5
(1) 380g of zirconium nitrate pentahydrate, 420g of magnesium dichloride solution and 2.2kg of acetone solution are weighed and added into a reaction vessel for reaction for 9 hours at 145 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing the obtained material, calcining in a muffle furnace at 645 ℃ for 15 hours, grinding and sieving with a 100-mesh sieve to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 ；
(3) 380g of Mg is weighed 2+ -ZrO 2 1.9kg of an aqueous ammonia solution with a mass fraction of 25%, 480g of silver chloride (AgCl), 5g of sodium borate (NaBH) 4 ) Adding the mixture into a reaction vessel, and reacting for 11 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing the solid material, drying the solid material for 7 hours in a 55 ℃ vacuum drying oven, grinding the solid material, and sieving the ground solid material with a 100-mesh sieve to obtain Mg 2+ -ZrO 2 An AgO-Ag type antibacterial agent N5.
Application example 5
(1) Weighing 95 parts of PBT, 11 parts of modified jute fiber, 2 parts of antibacterial agent N5, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168, mixing and stirring uniformly to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 10 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as P5.
Wherein the temperature and the screw rotating speed of each zone of the double-screw extruder are respectively as follows: the temperature of the first area is 205 ℃, the temperature of the second area is 255 ℃, the temperature of the third area is 255 ℃, the temperature of the fourth area is 255 ℃, the temperature of the fifth area is 255 ℃, the temperature of the sixth area is 255 ℃, the temperature of the machine head is 255 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 1 was used
(1) Weighing 95 parts of PBT, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168, mixing and stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as D1. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 205 ℃, the temperature of the second area is 255 ℃, the temperature of the third area is 255 ℃, the temperature of the fourth area is 255 ℃, the temperature of the fifth area is 255 ℃, the temperature of the sixth area is 255 ℃, the temperature of the machine head is 255 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 2 was used
(1) Weighing 95 parts of PBT, 2 parts of an antibacterial agent N5, 0.1 part of an antioxidant 1010 and 0.1 part of an antioxidant 168, mixing and stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as D2.
Comparative example 3 was used
(1) Weighing 95 parts of PBT, 11 parts of modified jute fiber, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168, mixing and stirring uniformly to obtain a mixture; the preparation method of the modified jute fiber comprises the following steps: soaking jute fiber with the monofilament diameter of 11 mu m in NaOH solution with the mass fraction of 4%, taking out the fiber from the solution after 1h, repeatedly washing the fiber with dilute hydrochloric acid solution with the mass fraction of 5% to be neutral, and then putting the fiber into a blast drying oven to be dried at 80 ℃ to constant weight;
(2) Extruding and granulating the mixture obtained in the step (1) from an extruder to obtain the PBT composite material, which is marked as D3. Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 205 ℃, the temperature of the second area is 255 ℃, the temperature of the third area is 255 ℃, the temperature of the fourth area is 255 ℃, the temperature of the fifth area is 255 ℃, the temperature of the sixth area is 255 ℃, the temperature of the machine head is 255 ℃, and the rotating speed of the screw is 245r/min.
The antibacterial ratio test of the PBT composite materials obtained in the above application examples 1 to 5 and comparative examples 1 to 3 was conducted in accordance with JIS Z2801, using test pieces of (50 mm.+ -. 2 mm) × (6 mm.+ -. 0.1 mm) specification, and after 24 hours of inoculation time.
Tensile strength testing was performed in accordance with standard ASTM D638 using a tensile bar model of (170.0±5.0) mm (13.0±0.5) mm (3.2±0.2) mm, and a tensile rate of 50mm/min;
the notched Izod impact strength was measured according to standard ASTM D256, using the notched Izod impact strength bars model: (125.0+ -5.0) mm (13.0+ -0.5) mm (3.2+ -0.2) mm, notch machined, notch depth (2.6+ -0.2) mm.
The performance data are shown in table 1 below:
table 1 results of Performance test of PBT composite Material prepared in each application example and comparative example
As can be seen from the table, the P1-P5 has better physical property and antibacterial property than the P1, the P2 and the P3, which indicates that the PBT composite material prepared by the method provided by the invention has excellent comprehensive property and can expand the application field of the PBT composite material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. An antibacterial PBT composite material, which is characterized in that: the composition comprises the following components:
the modified jute fiber is obtained by immersing jute fiber in alkali liquor, and then washing to neutrality;
the preparation method of the antibacterial agent comprises the following steps:
(1) Weighing zirconium nitrate pentahydrate, magnesium dichloride solution and solvent, adding into a reaction vessel, and reacting for 8-12h at 100-160 ℃ to obtain a mixed material A;
(2) Filtering the mixed material A to remove the solvent, sequentially washing and calcining the obtained material, and grinding to obtain zirconium dioxide loaded with magnesium ions, which is marked as Mg 2+ -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The calcining temperature is 600-680 ℃ and the calcining time is 10-16h;
(3) Weighing Mg 2+ -ZrO 2 Adding ammonia water solution, silver chloride and a reducing agent into a reaction vessel, and reacting for 10-16 hours at normal temperature to obtain a mixed material B;
(4) Filtering the mixed material B to obtain a solid material, sequentially washing, drying and grinding the solid material to obtain Mg 2 + -ZrO 2 An AgO-Ag type antibacterial agent.
2. The antibacterial PBT composite material of claim 1, wherein: in the step (1), the mass ratio of the zirconium nitrate pentahydrate, the magnesium dichloride solution and the solvent is (30-40): (40-50): (180-240); the solvent is acetone, ethanol or isopropanol.
3. The antibacterial PBT composite material of claim 1, wherein: in the step (3), the reducing agent is sodium borate; the Mg is 2+ -ZrO 2 The mass ratio of the ammonia water solution, the silver chloride and the sodium borate is (30-50): (160-200): (40-60): (0.2-0.6); the mass fraction of the ammonia water solution is 25%.
4. The antibacterial PBT composite material of claim 1, wherein: in the step (4), the drying is performed in a vacuum drying oven; the drying temperature is 50-70 ℃ and the drying time is 6-8h.
5. The antibacterial PBT composite material of claim 1, wherein: the preparation method of the modified jute fiber comprises the following steps: and (3) putting the jute fibers into NaOH solution for dipping treatment, taking out, washing to be neutral, and drying to obtain the modified jute fibers.
6. The antibacterial PBT composite material of claim 5, wherein: the monofilament diameter of the jute fiber is 10-12 mu m.
7. The antibacterial PBT composite material of claim 5, wherein: the mass fraction of the NaOH solution is 4%; the time of the dipping treatment was 1h.
8. The antibacterial PBT composite material of claim 1, wherein: the antioxidant is at least one of antioxidant 168, antioxidant 1010 and antioxidant 1330.
9. The method of preparing an antibacterial PBT composite material according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
(1) Weighing 80-100 parts of PBT, 10-16 parts of modified jute fiber, 2-4 parts of antibacterial agent and 0.1-0.5 part of antioxidant, and uniformly mixing to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain the PBT composite material.
10. The method for preparing the antibacterial PBT composite material according to claim 9, wherein: the double-screw extruder comprises six temperature areas which are sequentially arranged, and the temperatures of the temperature areas are as follows: the temperature of the first area is 200-220 ℃, the temperature of the second area is 240-260 ℃, the temperature of the third area is 240-260 ℃, the temperature of the fourth area is 240-260 ℃, the temperature of the fifth area is 240-260 ℃, and the temperature of the sixth area is 240-260 ℃; the temperature of the head of the double-screw extruder is 240-260 ℃, and the rotating speed of the screw is 200-280 r/min.
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