CN114479369A - Antibacterial PBT (polybutylene terephthalate) composite material and preparation method thereof - Google Patents
Antibacterial PBT (polybutylene terephthalate) composite material and preparation method thereof Download PDFInfo
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- CN114479369A CN114479369A CN202011163202.XA CN202011163202A CN114479369A CN 114479369 A CN114479369 A CN 114479369A CN 202011163202 A CN202011163202 A CN 202011163202A CN 114479369 A CN114479369 A CN 114479369A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001707 polybutylene terephthalate Polymers 0.000 title description 66
- -1 polybutylene terephthalate Polymers 0.000 title description 5
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 79
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 15
- 230000010355 oscillation Effects 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229910002549 Fe–Cu Inorganic materials 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 10
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000002985 plastic film Substances 0.000 claims description 7
- 229920006255 plastic film Polymers 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 84
- 239000000203 mixture Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 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 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000004599 antimicrobial Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 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 4
- 241000894006 Bacteria Species 0.000 description 4
- 239000002158 endotoxin Substances 0.000 description 4
- 229920006008 lipopolysaccharide Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
Abstract
The invention discloses an antibacterial PBT composite material and a preparation method thereof, wherein the antibacterial PBT composite material is prepared from 80-100 parts of PBT, 10-16 parts of modified basalt fiber, 2-4 parts of antibacterial agent and 0.1-0.5 part of antioxidant in parts by weight, wherein the modified basalt fiber is subjected to argon plasma reaction and then reacts with La (NO)3)3·6H2And O is modified after reaction. The antibacterial PBT composite material has excellent mechanical property and antibacterial property.
Description
Technical Field
The invention belongs to the technical field of modification 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 the PBT has the advantages of good fatigue resistance, good heat resistance, excellent dimensional stability and the like, but in a certain specific material application field, the requirements on the mechanical property and the antibacterial property of the PBT are high, and the common PBT composite material cannot meet the requirements.
Disclosure of Invention
In view of the above, the present invention needs to provide an antibacterial PBT composite material, which has excellent mechanical properties and antibacterial properties by adding modified basalt fibers and an antibacterial agent, so as to solve the above problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an antibacterial PBT composite material which is prepared from 80-100 parts of PBT, 10-16 parts of modified basalt fiber, 2-4 parts of an antibacterial agent and 0.1-0.5 part of an antioxidant in parts by weight, wherein the preparation of the modified basalt fiber comprises the following steps:
the basalt fiber is placed in an ethanol solution for ultrasonic oscillation and then dried, and it can be understood that the purpose of the ultrasonic oscillation of the basalt fiber and the ethanol solution is to enable the basalt fiber to be better dispersed and provide excellent conditions for subsequent reaction, so that the time of the ultrasonic oscillation is not particularly limited and can be adjusted according to needs, and preferably, in some specific embodiments of the invention, the time of the ultrasonic oscillation is 6-8 h;
reacting the blow-dried basalt fiber with argon plasma for 2-4h to obtain a first product, reacting the basalt fiber with the argon plasma, and utilizing the argon plasma to impact the surface of the basalt fiber with high energy, so that an oxygen-containing polar group is introduced into a molecular structure of the basalt fiber, thereby enhancing the interface bonding force of the basalt fiber and PBT, and improving the compatibility of the basalt fiber and PBT; (ii) a
Mixing the first product with deionized water and La (NO)3)3·6H2Performing ultrasonic oscillation reaction on O and concentrated nitric acid for 4-6h to obtain a second product, and performing reaction on basalt fiber and argon plasma, and then using rare earth solution La3+The surface of the basalt fiber is modified, so that the interface bonding force between the basalt fiber and the PBT is further improved, and the dispersion of the basalt fiber in the PBT matrix is improved;
after the second product is washed with water until the pH becomes neutral, and dried, the modified basalt fiber is obtained, it is understood that the washing and drying are all conventional operations in the art, and are not particularly limited, and preferably, in some specific embodiments of the present invention, the specific steps are as follows: and (3) washing the second product to be neutral by using deionized water, and placing the washed product at 60-80 ℃ for vacuum drying for 4-8 h. .
According to the invention, after the basalt fiber reacts with the argon plasma, the high-energy impact is carried out on the surface of the basalt fiber, and the high-energy impact is carried out on the surface of the basalt fiber modified PBT, so that an oxygen-containing polar group is introduced into the PBT molecular structure, the interface binding force is further enhanced, the compatibility of the basalt fiber and the PBT is favorably improved, and the mechanical property of the antibacterial PBT composite material can be improved; then passing through rare earth solution La3+The surface of the basalt fiber is modified, so that the interface binding force between the basalt fiber and the PBT matrix is further improved, the affinity between the basalt fiber and the PBT matrix is improved, the dispersibility of the basalt fiber is improved, and the mechanical property of the antibacterial PBT composite material is good through double treatment.
Further, in the present invention, the ratio of the basalt fiber to the ethanol solution is not particularly limited, and preferably, the mass ratio of the basalt fiber to the ethanol solution is (30-40): (160-200).
Preferably, the first product, deionized water, La (NO)3)3·6H2The mass ratio of O to concentrated nitric acid is (20-30): (200-240): (8-12): (10-16).
Furthermore, the antibacterial agent is Fe-Cu/MgO, has good antibacterial performance, and can remarkably improve the antibacterial performance of the PBT composite material.
Further, the preparation of the antibacterial agent comprises the following steps:
adding magnesium nitrate hexahydrate and ammonium carbonate into deionized water, and stirring at normal temperature for reacting for 10-16h to form a first solution;
filtering and washing the first solution, covering the first solution with a plastic film, aging the first solution for 6 to 8 hours at the temperature of between 30 and 50 ℃, drying the first solution for 20 to 24 hours at the temperature of between 80 and 100 ℃, and finally calcining the first solution for 10 to 16 hours at the temperature of between 200 and 240 ℃ to obtain mesoporous MgO;
mixing the mesoporous MgO, potassium pyrophosphate, sodium dodecyl benzene sulfonate and deionized water, and adjusting the pH value to be neutral to obtain a second solution;
mixing iron phosphate, copper phosphate, ammonia water and deionized water to obtain a third solution;
and mixing the second solution, the third solution and glucose, stirring for reaction for 3-5h, separating, washing and drying to obtain the antibacterial agent Fe-Cu/MgO.
As the defects and oxygen vacancies on the surface of the MgO nano-particles can initiate cell peroxidation and generation of active oxygen, bacteria are killed, and meanwhile, the antibacterial effect can be further improved by combining the metal Fe and Cu.
Preferably, in the first solution, the mass ratio of the magnesium nitrate hexahydrate, the deionized water and the ammonium carbonate is (60-80): (120-160): (50-70).
Preferably, in the second solution, the mass ratio of the mesoporous MgO, potassium pyrophosphate, sodium dodecyl benzene sulfonate and deionized water is (30-40): (0.1-0.3): (0.2-0.4): (160-200).
Preferably, in the third solution, the mass ratio of the iron phosphate, the copper phosphate, the ammonia water and the deionized water is (30-40): (20-30): (16-20): (120-160).
Preferably, the mass ratio of the second solution to the third solution to the glucose is (30-40): (20-30): (1-3).
Further, the antioxidant described in the present invention is not particularly limited, and at least one of tris (2, 4-di-t-butyl) phenyl phosphite (abbreviated as Irganox168), pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (abbreviated as Irganox1010), 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-t-butyl-4-hydroxybenzyl) benzene (abbreviated as Irganox1330) may be selected as an antioxidant conventionally used in the art.
The invention also provides a preparation method of the antibacterial PBT composite material, which comprises the following steps:
fully mixing PBT, modified basalt fiber, an antibacterial agent and an antioxidant according to a ratio to obtain a uniform mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt blending and extrusion granulation to obtain the antibacterial PBT composite material.
Fully mixing the PBT, the modified basalt fiber, the antibacterial agent and the antioxidant according to a ratio to obtain a uniform mixed material, wherein the full mixing (including rotating speed, time and the like) is not particularly limited, and the PBT, the modified basalt fiber, the antibacterial agent and the antioxidant are mixed by adopting conventional machinery in the field as long as the purpose of uniform mixing can be realized, and the rotating speed and the time can be adjusted according to needs;
and adding the mixed material into a double-screw extruder, and carrying out melt blending and extrusion granulation to obtain the antibacterial PBT composite material.
The processing temperature of the twin-screw extruder can also be adjusted according to the selection of the matrix resin and the auxiliary agent, and is not particularly limited, and in some specific embodiments of the invention, the twin-screw extruder comprises six temperature zones arranged in sequence: the first zone temperature is 200-220 ℃, the second zone temperature is 240-260 ℃, the third zone temperature is 240-260 ℃, the fourth zone temperature is 240-260 ℃, the fifth zone temperature is 240-260 ℃, the sixth zone temperature is 240-260 ℃, the head temperature is 240-260 ℃, and the screw rotation speed is 200-280 r/min.
Compared with the prior art, the invention has the following beneficial effects:
the antibacterial PBT composite material is added with modified basalt fibers, the modified basalt fibers are firstly treated by argon plasma, and then rare earth solution La is used3+The modified basalt fiber is modified, so that the prepared modified basalt fiber has good dispersibility and good compatibility with PBT, and the mechanical property of the PBT modified by the modified basalt fiber is better mainly due to the following reasons: firstly, argon plasma impacts the surface of the basalt fiber modified PBT in a high energy manner, so that oxygen-containing polar groups are introduced into a PBT molecular structure, the interface bonding force is enhanced, and the compatibility of the basalt fiber and the PBT is favorably improved; ② passing through rare earth solution La3+After treatment, the interface bonding force between the basalt fiber and the PBT matrix is further improved, and the front is improvedThe affinity between the wuyan fibers and the PBT matrix is favorable for improving the dispersion of the basalt fibers in the PBT matrix, and then the mechanical property of the PBT composite material is improved.
In addition, lipopolysaccharide is the main component of cell wall outer membrane of gram-negative bacteria, and sufficient Ca2+Can maintain lipopolysaccharide stability if Ca is added2+The lipopolysaccharide is removed, and the inner layer of naked cells are destroyed. And rare earth La3+Due to the presence of Ca2+Ca with very similar coordination characteristics and ionic radius capable of replacing binding sites2+Thus, the lipopolysaccharide is disintegrated, and the intracellular layer substances of the bacteria are exposed, so that the bacteria can be damaged.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, 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.
It is to be noted that "parts" described in the following examples and comparative examples mean parts by weight unless otherwise specified. The raw materials used in the following examples are specifically:
PBT (model 2002U), Japan treaty; ethanol solution, Shandong Baiyao chemical Co., Ltd; la (NO)3)3·6H2O, new materials, shandong desheng ltd; deionized water, chemical ltd, denna hai rui bao; concentrated nitric acid, Nanjing Shengqing and chemical industry; chitosan powder, Shandong Haidebei Biotech limited; mg (NO)3)2·6H2O, new materials, shandong desheng ltd; ammonium carbonate, Shandonghao Shunhua chemical Co., Ltd; potassium pyrophosphate, harmony between Hangzhou provincesChemical Co., Ltd; sodium dodecyl benzene sulfonate, chemical ltd, denamantan; iron phosphate, shanghai maireil chemical technologies, ltd; copper phosphate, Xin chemical products, Inc., Namingxi Henan; ammonia solution, corridor house peng color fine chemical ltd; glucose, sieravia biotechnology limited; basalt fiber (fiber length 8-12 μm), Jiangsu Kodafu New materials science and technology Co., Ltd; antioxidants (type Irganox168, Irganox1010, Irganox1330), Swiss soda.
Example 1
The preparation method of the antibacterial PBT composite material in the implementation comprises the following steps:
providing modified basalt fibers: placing 300g of basalt fiber in 1.6kg of ethanol, performing ultrasonic oscillation for 6h, and drying; putting the blow-dried basalt fiber into a plasma chamber, and introducing argon plasma for reaction for 2 hours to obtain a first product; 200g of the first product were taken together with 2.0kg of deionized water and 80g of La (NO)3)3·6H2And mixing O and 100g of concentrated nitric acid, ultrasonically oscillating for 4h, washing by using deionized water until the pH value is neutral, and vacuum drying for 4h at 60 ℃ to obtain the modified basalt fiber.
Providing an antimicrobial agent: 600g of magnesium nitrate hexahydrate (Mg (NO) was weighed3)2·6H2O), 1.2kg of deionized water and 500g of ammonium carbonate are put into a reaction vessel and stirred to react for 10 hours at normal temperature to form a first solution; filtering the first solution, washing, putting the first solution into a reaction vessel, covering the first solution with a plastic film, aging the first solution for 6 hours at the temperature of 30 ℃, taking the first solution out, putting the first solution into a high-temperature drying oven at the temperature of 80 ℃ for drying for 20 hours, and then roasting the dried first solution in a muffle furnace at the temperature of 200 ℃ for 10 hours to obtain mesoporous MgO; weighing 300g of mesoporous MgO, 1g of potassium pyrophosphate, 2g of sodium dodecyl benzene sulfonate and 1.6kg of deionized water, mixing, and adjusting the pH value of the solution to be neutral to form a first solution; weighing 300g of iron phosphate, 200g of copper phosphate, 160g of ammonia water solution and 1.2kg of deionized water, and mixing to form a second solution; and (3) stirring 300g of the first solution, 200g of the second solution and 10g of glucose at normal temperature to react for 3 hours, filtering, washing, drying at 50 ℃ for 10 hours, and grinding to obtain the Fe-Cu/MgO antibacterial agent.
Preparing an antibacterial PBT composite material: fully mixing 80 parts of PBT, 10 parts of modified basalt fiber, 2 parts of Fe-Cu/MgO antibacterial agent and 0.1 part of Irganox1010 to obtain a uniform mixture; and adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the antibacterial PBT composite material, wherein the processing parameters of the double-screw extruder are that the first-zone temperature is 200 ℃, the second-zone temperature is 240 ℃, the third-zone temperature is 240 ℃, the fourth-zone temperature is 240 ℃, the fifth-zone temperature is 240 ℃, the sixth-zone temperature is 240 ℃, the head temperature is 240 ℃, and the screw rotation speed is 200 r/min.
Example 2
The preparation method of the antibacterial PBT composite material in the implementation comprises the following steps:
providing modified basalt fibers: placing 400g of basalt fibers in 2.0kg of ethanol, performing ultrasonic oscillation for 8 hours, and drying; putting the blow-dried basalt fiber into a plasma chamber, and introducing argon plasma for reaction for 4 hours to obtain a first product; 300g of the first product and 2.4kg of deionized water, 120g of La (NO) were taken3)3·6H2And mixing O and 160g of concentrated nitric acid, ultrasonically oscillating for 6 hours, washing with deionized water until the pH value is neutral, and drying in vacuum at 80 ℃ for 8 hours to obtain the modified basalt fiber.
Providing an antimicrobial agent: 800g of magnesium nitrate hexahydrate (Mg (NO) are weighed3)2·6H2O), 1.6kg of deionized water and 700g of ammonium carbonate are put into a reaction vessel and stirred to react for 16 hours at normal temperature to form a first solution; filtering the first solution, washing, putting the first solution into a reaction vessel, covering the first solution with a plastic film, aging the first solution for 8 hours at 50 ℃, taking the first solution out, putting the first solution into a high-temperature drying oven at 100 ℃ for drying for 24 hours, and then roasting the dried first solution in a muffle furnace at 240 ℃ for 16 hours to obtain mesoporous MgO; weighing 400g of mesoporous MgO, 3g of potassium pyrophosphate, 4g of sodium dodecyl benzene sulfonate and 2.0kg of deionized water, mixing, and adjusting the pH value of the solution to be neutral to form a first solution; weighing 400g of iron phosphate, 300g of copper phosphate, 200g of ammonia water solution and 1.6kg of deionized water, and mixing to form a second solution; and stirring 400g of the first solution, 300g of the second solution and 30g of glucose at normal temperature to react for 5 hours, filtering, washing, drying at 70 ℃ for 12 hours, and grinding to obtain the Fe-Cu/MgO antibacterial agent.
Preparing an antibacterial PBT composite material: fully mixing 100 parts of PBT, 16 parts of modified basalt fiber, 4 parts of antibacterial agent, 0.1 part of Irganox168 and 0.4 part of Irganox1010 to obtain a uniform mixture; and adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the antibacterial PBT composite material, wherein the processing parameters of the double-screw extruder are 220 ℃ in the first zone, 260 ℃ in the second zone, 260 ℃ in the third zone, 260 ℃ in the fourth zone, 260 ℃ in the fifth zone, 260 ℃ in the sixth zone, 260 ℃ in the head temperature and 280r/min in the screw rotation speed.
Example 3
The preparation method of the antibacterial PBT composite material in the implementation comprises the following steps:
providing modified basalt fibers: placing 350g of basalt fibers in 1.8kg of ethanol, performing ultrasonic oscillation for 7h, and drying; putting the blow-dried basalt fiber into a plasma chamber, and introducing argon plasma for reaction for 3 hours to obtain a first product; 250g of the first product and 2.2kg of deionized water, 100g of La (NO) were taken3)3·6H2And mixing O and 130g of concentrated nitric acid, ultrasonically oscillating for 5h, washing by using deionized water until the pH value is neutral, and vacuum-drying at 70 ℃ for 6h to obtain the modified basalt fiber.
Providing an antimicrobial agent: 700g of magnesium nitrate hexahydrate (Mg (NO) was weighed3)2·6H2O), 1.4kg of deionized water and 600g of ammonium carbonate are put into a reaction vessel and stirred for reaction for 13 hours at normal temperature to form a first solution; filtering the first solution, washing, putting the first solution into a reaction vessel, covering the first solution with a plastic film, aging for 7 hours at 40 ℃, taking out the first solution, drying the first solution in a high-temperature drying oven at 90 ℃ for 22 hours, and then roasting in a muffle furnace at 220 ℃ for 13 hours to obtain mesoporous MgO; weighing 350g of mesoporous MgO, 2g of potassium pyrophosphate, 3g of sodium dodecyl benzene sulfonate and 1.8kg of deionized water, mixing, and adjusting the pH value of the solution to be neutral to form a first solution; weighing 350g of iron phosphate, 250g of copper phosphate, 200g of ammonia water solution and 1.6kg of deionized water, and mixing to form a second solution; and (3) stirring 350g of the first solution, 250g of the second solution and 20g of glucose at normal temperature to react for 4 hours, filtering, washing, drying at 60 ℃ for 11 hours, and grinding to obtain the Fe-Cu/MgO antibacterial agent.
Preparing an antibacterial PBT composite material: fully mixing 90 parts of PBT, 13 parts of modified basalt fiber, 3 parts of antibacterial agent, 0.2 part of Irganox1010 and 0.1 part of Irganox1330 to obtain a uniform mixture; and adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the antibacterial PBT composite material, wherein the processing parameters of the double-screw extruder are 210 ℃ in the first zone, 250 ℃ in the second zone, 250 ℃ in the third zone, 250 ℃ in the fourth zone, 250 ℃ in the fifth zone, 250 ℃ in the sixth zone, 250 ℃ in the head temperature and 240r/min in the screw rotation speed.
Example 4
The preparation method of the antibacterial PBT composite material in the implementation comprises the following steps:
providing modified basalt fibers: placing 360g of basalt fiber in 1.9kg of ethanol, performing ultrasonic oscillation for 8 hours, and drying; putting the blow-dried basalt fiber into a plasma chamber, and introducing argon plasma for reaction for 3 hours to obtain a first product; 280g of the first product and 2.1kg of deionized water, 110g of La (NO) were taken3)3·6H2And mixing O and 150g of concentrated nitric acid, ultrasonically oscillating for 6 hours, washing by using deionized water until the pH value is neutral, and vacuum-drying for 5 hours at 65 ℃ to obtain the modified basalt fiber.
Providing an antimicrobial agent: 650g of magnesium nitrate hexahydrate (Mg (NO) was weighed3)2·6H2O), 1.5kg of deionized water and 650g of ammonium carbonate are put into a reaction vessel and stirred to react for 13 hours at normal temperature to form a first solution; filtering the first solution, washing, putting the first solution into a reaction vessel, covering the first solution with a plastic film, aging for 7 hours at 45 ℃, taking out the first solution, putting the first solution into a high-temperature drying oven at 95 ℃ for drying for 21 hours, and then roasting in a muffle furnace at 210 ℃ for 12 hours to obtain mesoporous MgO; weighing 360g of mesoporous MgO, 1g of potassium pyrophosphate, 3g of sodium dodecyl benzene sulfonate and 1.9kg of deionized water, mixing, and adjusting the pH value of the solution to be neutral to form a first solution; weighing 380g of iron phosphate, 270g of copper phosphate, 190g of ammonia water solution and 1.5kg of deionized water, and mixing to form a second solution; taking 380g of the first solution, 270g of the second solution and 10g of glucose, stirring and reacting at normal temperature for 5h, then carrying out suction filtration, washing, drying at 55 ℃ for 10h, and grinding to obtain the Fe-Cu/MgO antibacterial agent.
Preparing an antibacterial PBT composite material: fully mixing 85 parts of PBT, 15 parts of modified basalt fiber, 4 parts of antibacterial agent, 0.1 part of Irganox1010 and 0.2 part of Irganox1330 to obtain a uniform mixture; and adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the antibacterial PBT composite material, wherein the processing parameters of the double-screw extruder are the first-zone temperature of 205 ℃, the second-zone temperature of 245 ℃, the third-zone temperature of 245 ℃, the fourth-zone temperature of 245 ℃, the fifth-zone temperature of 245 ℃, the sixth-zone temperature of 245 ℃, the head temperature of 245 ℃ and the screw rotation speed of 205 r/min.
Example 5
The preparation method of the antibacterial PBT composite material in the implementation comprises the following steps:
providing modified basalt fibers: putting 390g of basalt fiber in 1.7kg of ethanol, performing ultrasonic oscillation for 7h, and drying; putting the blow-dried basalt fiber into a plasma chamber, and introducing argon plasma for reaction for 4 hours to obtain a first product; 290g of the first product, 2.1kg of deionized water, 110g of La (NO) were taken3)3·6H2And mixing O and 130g of concentrated nitric acid, ultrasonically oscillating for 5h, washing by using deionized water until the pH value is neutral, and vacuum drying at 75 ℃ for 5h to obtain the modified basalt fiber.
Providing an antimicrobial agent: 750g of magnesium nitrate hexahydrate (Mg (NO) is weighed3)2·6H2O), 1.5kg of deionized water and 680g of ammonium carbonate are put into a reaction vessel and stirred to react for 15 hours at normal temperature to form a first solution; filtering the first solution, washing, putting into a reaction vessel, covering with a plastic film, aging for 6h at 35 ℃, taking out, drying in a 100 ℃ high-temperature drying oven for 24h, and roasting in a 230 ℃ muffle furnace for 16h to obtain mesoporous MgO; weighing 310g of mesoporous MgO, 2g of potassium pyrophosphate, 2g of sodium dodecyl benzene sulfonate and 1.9kg of deionized water, mixing, and adjusting the pH value of the solution to be neutral to form a first solution; weighing 370g of iron phosphate, 270g of copper phosphate, 190g of ammonia water solution and 1.5kg of deionized water, and mixing to form a second solution; and (3) taking 370g of the first solution, 290g of the second solution and 20g of glucose, stirring and reacting for 5 hours at normal temperature, carrying out suction filtration, washing, drying at 60 ℃ for 12 hours, and grinding to obtain the Fe-Cu/MgO antibacterial agent.
Preparing an antibacterial PBT composite material: fully mixing 85 parts of PBT, 14 parts of modified basalt fiber, 3 parts of antibacterial agent, 0.1 part of Irganox1010 and 0.1 part of Irganox168 to obtain a uniform mixture; and adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the antibacterial PBT composite material, wherein the processing parameters of the double-screw extruder are that the first-zone temperature is 215 ℃, the second-zone temperature is 255 ℃, the third-zone temperature is 255 ℃, the fourth-zone temperature is 255 ℃, the fifth-zone temperature is 255 ℃ and the sixth-zone temperature is 255 ℃, the head temperature is 255 ℃ and the screw rotation speed is 255 r/min.
Comparative example 1
The basalt fiber of the present invention is not reacted with the argon plasma as in example 1, and the other steps are the same as in example 1.
Comparative example 2
In contrast to example 1, the basalt fiber of the present invention has not been subjected to La (NO)3)3·6H2The rest of the modification was the same as in example 1.
Comparative example 3
In the present invention, the same procedures as in example 1 were repeated except that "10 parts of modified basalt fiber and 2 parts of antimicrobial agent" were replaced with "10 parts of modified basalt fiber and 2 parts of chitosan fine powder" in comparison with example 1.
Test example
The antibacterial PBT composite material prepared in the examples and the all proportions is injected into a sample strip for relevant performance test, and the result is shown in Table 1:
TABLE 1 antibacterial PBT composite Material Performance test results
Note: in Table 1, the tensile specimens used were of the type (170.0. + -. 5.0) mmX (13.0. + -. 0.5) mmX (3.2. + -. 0.2) mm and a tensile rate of 50 mm/min;
the cantilever beam notch impact strength sample bars used are of the type: (125.0 + -5.0) mmX (13.0 + -0.5) mmX (3.2 + -0.2) mm, and the notch is machined to have a notch depth (2.6 + -0.2) mm.
As can be seen from the test results in table 1: compared with the comparative examples 1 and 2, the antibacterial PBT composite material disclosed by the invention has better physical properties in the examples 1-5, which shows that the double treatment mode of the basalt fiber adopted by the invention has a synergistic effect and the physical properties are more excellent.
In addition, the antibacterial properties of the antibacterial PBT composite material of examples 1 to 5 are better than those of comparative example 3, which shows that the antibacterial agent of the present invention is superior to the commercially available antibacterial agent.
From the above, it can be seen that the antibacterial property and physical property of the present invention are very beneficial, and have great significance and progress.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The antibacterial PBT composite material is characterized by being prepared from 80-100 parts of PBT, 10-16 parts of modified basalt fiber, 2-4 parts of antibacterial agent and 0.1-0.5 part of antioxidant in parts by weight, wherein the preparation of the modified basalt fiber comprises the following steps:
placing basalt fibers in an ethanol solution, performing ultrasonic oscillation, and drying;
reacting the blow-dried basalt fiber with argon plasma for 2-4h to obtain a first product;
mixing the first product with deionized water and La (NO)3)3·6H2Performing ultrasonic oscillation reaction on the O and the concentrated nitric acid for 4-6 hours to obtain a second product;
and washing the second product with water until the pH value is neutral, and drying to obtain the modified basalt fiber.
2. The antibacterial PBT composite material of claim 1, wherein the mass ratio of the basalt fiber to the ethanol solution is (30-40): (160-200).
3. The antimicrobial PBT composite of claim 1, wherein the first product, deionized water, La (NO)3)3·6H2The mass ratio of O to concentrated nitric acid is (20-30): (200-240): (8-12): (10-16).
4. The antibacterial PBT composite material of claim 1, wherein the antibacterial agent is Fe-Cu/MgO.
5. The antibacterial PBT composite material of claim 4, wherein the preparation of the antibacterial agent comprises the steps of:
adding magnesium nitrate hexahydrate and ammonium carbonate into deionized water, and stirring at normal temperature for reacting for 10-16h to form a first solution;
filtering and washing the first solution, covering the first solution with a plastic film, aging the first solution for 6 to 8 hours at the temperature of between 30 and 50 ℃, drying the first solution for 20 to 24 hours at the temperature of between 80 and 100 ℃, and finally calcining the first solution for 10 to 16 hours at the temperature of between 200 and 240 ℃ to obtain mesoporous MgO;
mixing the mesoporous MgO, potassium pyrophosphate, sodium dodecyl benzene sulfonate and deionized water, and adjusting the pH value to be neutral to obtain a second solution;
mixing iron phosphate, copper phosphate, ammonia water and deionized water to obtain a third solution;
and mixing the second solution, the third solution and glucose, stirring for reaction for 3-5h, separating, washing and drying to obtain the antibacterial agent Fe-Cu/MgO.
6. The antibacterial PBT composite material of claim 4, wherein in the first solution, the mass ratio of the magnesium nitrate hexahydrate, the deionized water, and the ammonium carbonate is (60-80): (120-160): (50-70).
7. The antibacterial PBT composite material of claim 4, wherein in the second solution, the mass ratio of the mesoporous MgO to the potassium pyrophosphate to the sodium dodecyl benzene sulfonate to the deionized water is (30-40): (0.1-0.3): (0.2-0.4): (160-200).
8. The antibacterial PBT composite material according to claim 4, wherein in the third solution, the mass ratio of the iron phosphate to the copper phosphate to the ammonia water to the deionized water is (30-40): (20-30): (16-20): (120-160).
9. The antibacterial PBT composite material of claim 4, wherein the mass ratio of the second solution to the third solution to the glucose is (30-40): (20-30): (1-3).
10. The process for the preparation of the antibacterial PBT composite of any one of claims 1 to 9, comprising the steps of:
fully mixing PBT, modified basalt fiber, an antibacterial agent and an antioxidant according to a ratio to obtain a uniform mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt blending and extrusion granulation to obtain the antibacterial PBT composite material.
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