CN101298511A - Antibiotic polymer composite material, and preparation and use thereof - Google Patents
Antibiotic polymer composite material, and preparation and use thereof Download PDFInfo
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- CN101298511A CN101298511A CNA2007101196832A CN200710119683A CN101298511A CN 101298511 A CN101298511 A CN 101298511A CN A2007101196832 A CNA2007101196832 A CN A2007101196832A CN 200710119683 A CN200710119683 A CN 200710119683A CN 101298511 A CN101298511 A CN 101298511A
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Abstract
The invention pertains to an anti-bacterial polymer composite material, which relates to a polyester/clay composite material and polyolefin composite material. Intercalation treatment is carried out to nano-silver particles and montmorillonite by carrying out esterification and polycondensation reaction to phthalic acid monomer and ethylene glycol or butanediol monomer, or ester exchange and polycondensation reaction to the phthalic acid monomer and the ethylene glycol or the butanediol monomer as well as a melting method, and the anti-bacterial polyester composite materials with uniformly dispersed nano-silver particles are prepared. The invention can be widely applied to building materials and civil products, especially to the children articles field. For anti-bacterial polyolefin composite materials, the invention can be used for manufacturing consumer electronic products such as cell phone housing and computer operation keyboards; and also is suitable for manufacturing home appliance products such as the housing materials of washing machines and refrigerators.
Description
Technical field
The present invention relates to a kind of polymer composites, particularly a kind of thermoplastic polyalcohol/clay soil matrix material.
Background technology
Composite nano polymer/clay material is the most potential class nano composite material in current numerous inorganic nano particle modified matrix materials.
00105494.5 disclose a kind of preparation of polyolefins method that contains nano imvite.Wherein the direct graft process of Cai Yonging be with monomer in advance intercalation in the mineral filler of laminate structure, aggregate into polymer then; Another kind of directly intercalation compounding be under the polymer melt state directly intercalation in montmorillonite layered silicate.Two kinds of above-mentioned graft process all must carry out pre-intercalation processing to polynite in advance, promptly utilize cation exchange reaction between montmorillonite layered silicate layer that the positively charged ion of organic molecule is inserted between montmorillonite layered silicate layer, and the increase interlamellar spacing, improve clay to polyolefinic affinity.Above-mentioned polyolefine is polyethylene or polypropylene.
97104194.6 and 97104055.9 disclose the method for utilizing the monomer intercalation polymerization to prepare polybutylene terephthalate/clay nanocomposites and polyethylene terephthalate/clay nanocomposites respectively.This matrix material has improved the mechanical property of product, is used widely in the engineering plastics field.
To extrude through clay and polymeric amide melt blending on twin screw extruder of intercalation processing 97112237.7 disclose, and clay be combined and with polyamide substrate, thereby be prepared into the high-performance nano matrix material with the nanoscale homodisperse.
Above-mentioned monomer intercalation polymerization or polymer melt graft process all need pre-intercalation processing is carried out in polynite, promptly utilize cation exchange reaction between montmorillonite layered silicate layer that the positively charged ion of organic molecule is inserted between montmorillonite layered silicate layer, and the increase interlamellar spacing, improve the affinity of clay to polymkeric substance.
200510011772.6 disclose the Pdyester/carbon nano tube nano composite material, it is that carbon nanotube, polyester raw material are dispersed in the polyester solvent, form stable Pdyester/carbon nano tube solution or dispersion liquid, obtain Pdyester/carbon nano tube nanofiber or film composite material by electrostatic spinning.
Based on the polyester material physical strength and the modulus height of intercalation, thermotolerance, flame retardant resistance and dimensional stability are good, and chemical stability and weathering resistance are good, have good workability simultaneously again.But above-mentioned nano composite material does not possess anti-microbial property.
98124542.0 disclose metallic compounds such as a kind of use Silver Nitrate, zinc oxide, zinc nitrate, by specific support zeolite appendix, make antiseptic-germicide, directly be added on polyvinyl chloride, in the polymer supports such as polyethylene, make antibiotic plastic.
01129106.0 disclose special material for nano polypropylene tubing material, by with Co-polypropylene, nanoclay organises, dispersion agent, each component of nano silver ion antibiotic agent, thorough mixing under solid state, then under molten state fully after the melting blend, the screw rod extruding pelletization.
The above-mentioned patent that contains antiseptic-germicide is in polymer support, adopts blending method to add metallic compounds such as antibacterial components Silver Nitrate, and it is even inadequately that blend components disperses in carrier, influences antibacterial effect.
USG 7052765 discloses the trevira that contains nano-Ag particles, and nano-Ag particles wherein is to prepare through method of reducing by the presoma Silver Nitrate.Though have certain anti-microbial effect, its homogeneity has much room for improvement.
Goal of the invention
Antibiotic polymer composite material of the present invention, polymkeric substance and clay compound intercalation principle have been utilized, overcome in the prior art when preparing antibiotic plastic or polypropylene dedicated material by blend method, exist metallic compound or nano-silver ionic to disperse shortcoming even inadequately even that be separated, provide a kind of the nanometer silver particulate is carried out intercalation by intercalator and clay, then, when terephthalic acid or dimethyl terephthalate (DMT) and the polymerization of ethylene glycol monomer or polyester under melting condition with intercalation form altogether, make nanometer silver particulate and clay, be dispersed in the polymeric matrix at random, thus the antibacterial polyester matrix material of formation intercalation composite structure.
Another object of the present invention is to adopt polyolefine and nanometer silver particulate and clay to prepare anti-bacterial polyolefin composite materials.
Summary of the invention
Antibiotic polymer composite material of the present invention comprises antibacterial polyester and anti-bacterial polyolefin composite materials.
Above-mentioned antibacterial polyester matrix material summary of the invention is as follows:
One. the present invention adopts direct esterification method or ester-interchange method to prepare the antibacterial polyester matrix material
1. direct esterification method: comprise following component and content by weight:
Dicarboxylic acid monomer 70-75
Dibasic alcohol monomer 25-30
Clay 0.5-10
Intercalator 0.001-5
Catalyzer 0.001-5
Dispersion medium water 1-1200
Protonating agent 0.001-10
Additive 0.005-1
Nanometer silver particulate 0.005-0.1 is preferably 0.01-0.1
Above-mentioned dicarboxylic acid monomer is terephthalic acid (PTA); Above-mentioned dibasic alcohol monomer is ethylene glycol or butyleneglycol;
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, cationic exchange total volume (CEC) 80-200meq/100g.
Above-mentioned intercalator is long chain alkyl ammonium salt, diethanolamine, 6-aminocaprolc acid, ten diamino acid;
Above-mentioned long chain alkyl ammonium salt is preferably palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride;
Above-mentioned catalyzer is antimony acetate, antimonous oxide or tetrabutyl titanate;
Above-mentioned protonating agent is phosphoric acid or hydrochloric acid;
Above-mentioned additive is hexanediamine, stablizer, lubricant or nucleator;
Above-mentioned nanometer silver diameter of particle is 1-100nm.
2. ester-interchange method: comprise following component and content by weight:
Dibasic acid dimethyl ester monomer 70-75
Dibasic alcohol monomer 25-30
Clay 0.5-10
Catalyzer 0.001-5
Dispersion medium water 1-1200
Intercalator 0.001-5
Protonating agent 0.001-10
Additive 0.005-1
Nanometer silver particulate 0.005-0.1 is preferably 0.01-0.1
Above-mentioned dibasic acid dimethyl ester monomer is dimethyl terephthalate (DMT) (DMT); Above-mentioned dibasic alcohol monomer is ethylene glycol or butyleneglycol;
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, cationic exchange total volume (CEC) 80-200meq/100g;
Above-mentioned catalyzer is antimony acetate, antimonous oxide or tetrabutyl titanate;
Above-mentioned protonating agent is phosphoric acid or hydrochloric acid.
Above-mentioned intercalator is long chain alkyl ammonium salt, diethanolamine, 6-aminocaprolc acid, ten diamino acid; Above-mentioned long chain alkyl ammonium salt is preferably palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride;
Above-mentioned additive is hexanediamine, stablizer, lubricant or nucleator;
Above-mentioned nanometer silver diameter of particle is 1-100nm.
Two. the present invention adopts melting intercalation method to prepare the antibacterial polyester matrix material, comprises following component and content by weight:
Polyester 85-98
Intercalation mixture 2-15
Auxiliary agent 0-1
Above-mentioned intercalation mixture comprises following component and content by weight:
Clay 2-15
Intercalator 0.001-5
Nanometer silver particulate 0.005-0.1 is preferably 0.01-0.1
Above-mentioned polyester is polyethylene terephthalate or polybutylene terephthalate;
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, cationic exchange total volume (CEC) 80-200meq/100g;
Above-mentioned intercalator is long chain alkyl ammonium salt, diethanolamine, 6-aminocaprolc acid, ten diamino acid;
Above-mentioned long chain alkyl ammonium salt is preferably palmityl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride; Above-mentioned auxiliary agent is hexanediamine, stablizer, lubricant or nucleator; The particle diameter of above-mentioned nanometer silver particulate is 1-100nm.
The preparation method of antibacterial polyester matrix material of the present invention is divided into:
One. the monomer intercalation method:
1. diprotic acid and dibasic alcohol monomer intercalation method, by weight, the concrete operations step is as follows:
(1) is that the calcium base of 80meq-100meq/100g or the base montmorillonite 0.5-10 part of receiving are stirred in dispersion medium water 1-1000 part with the ion-exchange total volume, forms suspension; (2) protonating agent phosphoric acid 0.001-10 part and intercalator diethanolamine 0.001-5 part are added water dissolution, nanometer silver particulate 0.005-0.1 part, be preferably 0.01-0.1 part, be added to and carry out intercalation processing in the above-mentioned montmorillonite suspension liquid; (3) with dicarboxylic acid monomer 70-75 part, dibasic alcohol monomer 25-30 part and catalyzer 0.001-5 part join in the suspension of above-mentioned intercalation processing, extract water out, after the drying, carried out esterification 8-10 hour at 220-250 ℃, add additive 0.005-1 part, be evacuated to below the 80Pa, prepare polyester macromolecule by polycondensation at 265-280 ℃.
Above-mentioned diprotic acid is a terephthalic acid;
Above-mentioned dibasic alcohol is ethylene glycol or butyleneglycol;
Above-mentioned catalyzer is antimony acetate or antimonous oxide.
Above-mentioned additive is hexanediamine, stablizer, lubricant or nucleator.
2. dibasic acid dimethyl ester and dibasic alcohol monomer intercalation method, by weight, the concrete operations step is as follows:
(1) is that the calcium base of 80meq-100meq/100g or the base montmorillonite 0.5-10 part of receiving are stirred in dispersion medium water 1-1000 part with the ion-exchange total volume, forms suspension; (2) protonating agent phosphoric acid 0.001-10 and intercalator ethylene glycol amine 0.001-5 are added water dissolution, nanometer silver particulate 0.005-0.1, be preferably 0.01-0.1, be added to and carry out intercalation processing in the above-mentioned montmorillonite suspension liquid; (3) with dibasic acid dimethyl ester monomer 70-75, dibasic alcohol monomer 25-30, catalyzer 0.001-5 joins in the suspension of above-mentioned intercalation processing, extract water out, after the drying, carried out transesterification reaction 8-10 hour, add additive 0.005-1 part at 220-250 ℃, be evacuated to and be warming up to below the 80Pa, 265-280 ℃ made in polymerization 1-3 hour.
Above-mentioned dibasic acid dimethyl ester is a dimethyl terephthalate (DMT);
Above-mentioned dibasic alcohol is ethylene glycol or butyleneglycol;
Above-mentioned catalyzer is a tetrabutyl titanate;
Above-mentioned additive is hexanediamine, stablizer, lubricant or nucleator.
Two. the melt intercalation compounding is to carry out in the following order:
Polyester antimicrobial composite material of the present invention, by weight, concrete preparation method is as follows:
1, is the calcium base of 80meq-100meq/100g with the ion-exchange total volume or receives base montmorillonite 2-15 part in the presence of the water dispersion medium of 10-500 part that to form slurry standby through stirring;
2, with diethanolamine intercalator 0.001-5 part and nanometer silver particulate 0.005-0.1 part in water dispersion medium 5-100 part after mixing, inject above-mentioned slurry, at 60-80 ℃, carry out common intercalation processing, after filtration, drying obtains the homodisperse blend; 3, with vibrin 85-98 part, be warming up to 265-270 ℃ and make the resin fusion, stir and to add the above-mentioned dispersion blend of 2-15 part down, obtained the polyester antimicrobial composite material in insulated and stirred 0.5-2 hour.
Above-mentioned polyester is polyethylene terephthalate or polybutylene terephthalate.
Polyester antimicrobial composite material of the present invention is easy to machine-shaping, can extensively make plastics, is suitable as building materials and civilian goods, particularly articles for children.
The present invention can adopt polyolefine (polyethylene or polypropylene) and nanometer silver particulate and clay to prepare anti-bacterial polyolefin composite materials.Antibacterial polyethylene or polypropylene nano plastics are used to prepare the sheating material of consumption electronic products such as phone housing, computation keyboard and household appliances such as washing machine, refrigerator.
The invention effect
Silver itself can not sterilization under metallic state, so the fungistatic effect of plain metal silver is extremely faint, and argent is processed into nanometer silver, active extremely strong nanometer silver particulate shows extraordinary antibacterial ability, can kill pathogenic microorganisms such as common bacterium, fungi, mycoplasma, chlamydozoan under the concentration of ppm (ppm).Antibiotic polymer composite material of the present invention has the antibiotic and sterilizing effect because of containing the nanometer silver particulate of intercalation, experiment showed, that the sterilization rate to bacteriums such as intestinal bacteria reaches more than 95%.And having broad-spectrum antimicrobial, render a service lasting, characteristics such as chance water sterilizing power is stronger, safety and environmental protection, is the ideal anti-biotic material, can be widely used in numerous industries.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 80meq/100g or the base montmorillonite clay 5g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.01g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, get intercalation solution through stirring 0.5 hour, terephthalic acid 500g, ethylene glycol 250g, antimony acetate 0.3g joins in the above-mentioned intercalation solution, extracts water out, after the drying, carried out esterification 8 hours at 220 ℃, add additive hexanediamine 0.05g, be evacuated to below the 80Pa, made in 2 hours 265 ℃ of polycondensations.
Embodiment 2: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 100meq/100g or the base montmorillonite clay 5g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.01g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, get intercalation solution through stirring 0.5 hour, terephthalic acid 500g, ethylene glycol 250g, antimony acetate 0.3g joins in the above-mentioned intercalation solution, extracts water out, after the drying, carried out esterification 8 hours at 220 ℃, add additive hexanediamine 0.05g, be evacuated to below the 80Pa, made in 2 hours 270 ℃ of polycondensations.
Embodiment 3: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 130meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.06g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, get intercalation solution through stirring 0.5 hour, terephthalic acid 500g, ethylene glycol 250g, antimony acetate 0.3g joins in the above-mentioned intercalation solution, extracts water out, after the drying, carried out esterification 8 hours at 250 ℃, add additive hexanediamine 0.05g, be evacuated to below the 80Pa, made in 2 hours 280 ℃ of polycondensations.
Embodiment 4: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 80meq/100g or the base montmorillonite clay 5g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.01g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, get intercalation solution through stirring 0.5 hour, dimethyl terephthalate (DMT) 500g, ethylene glycol 250g, tetrabutyl titanate 0.3g joins in the above-mentioned intercalation solution, extracts water out, after the drying, carried out transesterification reaction 8 hours at 220 ℃, add additive hexanediamine 0.05g, be evacuated to below the 80Pa, made in 2 hours 265 ℃ of polycondensations.
Embodiment 5: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 100meq/100g or the base montmorillonite clay 5g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.01g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, get intercalation solution through stirring 0.5 hour, dimethyl terephthalate (DMT) 500g, ethylene glycol 250g, tetrabutyl titanate.0.3g join in the above-mentioned intercalation solution, extract water out, after the drying, carried out transesterification reaction 8 hours at 220 ℃, add tetrabutyl titanate 0.3g and additive hexanediamine 0.05g and be evacuated to below the 80Pa, made in 2 hours 270 ℃ of polycondensations.
Embodiment 6: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 130meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.06g, phosphoric acid 0.06g and diethanolamine 0.03g, add water 15g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, got intercalation solution in 0.5 hour through stirring, with dimethyl terephthalate (DMT) 500g, ethylene glycol 250g, tetrabutyl titanate 0.3g, join in the above-mentioned intercalation solution, extract water out, after the drying, carried out transesterification reaction 8 hours at 250 ℃, add tetrabutyl titanate 0.3g and additive hexanediamine 0.05g, be evacuated to below the 80Pa, at 280 ℃, polycondensation made in 2 hours.
Embodiment 7: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 80meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.01g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, and it is joined in the above-mentioned slurry, get intercalation solution in 0.5 hour through stirring, and cooling is filtered, washing, and drying, it is standby that pulverizing makes the intercalation thing; With the 98g polyethylene terephthalate, be put in the there-necked flask, in oil bath, be warming up to 265 ℃ and make the resin fusion.Stir the back and add the above-mentioned blend of 2g, and insulated and stirred obtained polyester composite in 2 hours.
Embodiment 8: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 100meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With nanometer silver particulate 0.06g, phosphoric acid 0.06g and diethanolamine 0.03g add water 15g after 60 ℃ of stirrings, and it is joined in the above-mentioned slurry, get intercalation solution in 0.5 hour through stirring, through cooling, filter, and washing, drying, it is standby that pulverizing makes the intercalation thing; With the 98g polyethylene terephthalate, be put in the there-necked flask, in oil bath, be warming up to 270 ℃ and make the resin fusion.Stir the back and add the above-mentioned blend of 2g, and insulated and stirred obtained polyester composite in 2 hours.
Embodiment 9: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 80meq-100meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With palmityl trimethyl ammonium chloride 34g, with nanometer silver particulate 0.06g, add water 100g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, through stirring 1 hour, cooling is filtered, washing, drying is pulverized standby; With melt flow rate (MFR) is the Co-polypropylene 85g of 0.20g/10min, Ployethylene Wax 0.3g, and above-mentioned blend 2g mixes under solid-state state, at 190 ℃ of fusions, extruding pelletization.
Embodiment 10: with the ion-exchange total volume is that high-speed stirring obtained slurry after the calcium base of 80meq-100meq/100g or the base montmorillonite clay 8g that receives added water 100g and wait to be uniformly dispersed; With palmityl trimethyl ammonium chloride 34g, with nanometer silver particulate 0.06g, add water 100g after 60 ℃ of stirrings, it is joined in the above-mentioned slurry, through stirring 1 hour, cooling is filtered, washing, drying is pulverized standby; With melt flow rate (MFR) is the polyethylene 85g of 0.20g/10min, Ployethylene Wax 0.3g, and above-mentioned blend 2g mixes under solid-state state, at 180 ℃ of fusions, extruding pelletization.
Claims (12)
1. antibiotic polymer composite material is characterized in that described antibacterial polyester matrix material comprises following component and content by weight:
Dicarboxylic acid monomer 70-75
Dibasic alcohol monomer 25-30
Clay 0.5-10
Intercalator 0.001-5
Catalyzer 0.001-5
Dispersion medium water 1-1200
Protonating agent phosphoric acid 0.001-10
Additive 0.005-1
Nanometer silver particulate 0.005-0.1
Above-mentioned dicarboxylic acid monomer is terephthalic acid (PTA); Above-mentioned dibasic alcohol monomer is ethylene glycol or butyleneglycol;
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, cationic exchange total volume (CEC) 80-200meq/100g;
Above-mentioned intercalator is a diethanolamine;
Above-mentioned catalyzer is antimony acetate, antimonous oxide;
Above-mentioned additive is a hexanediamine;
Above-mentioned nanometer silver diameter of particle is 1-100nm.
2. antibiotic polymer composite material is characterized in that described polyester composite comprises following component and content by weight:
Dibasic acid dimethyl ester monomer 70-75
Dibasic alcohol monomer 25-30
Clay 0.5-10
Catalyzer 0.001-5
Dispersion medium water 1-1200
Intercalator 0.001-5
Protonating agent phosphoric acid 0.001-10
Additive 0.005-1
Nanometer silver particulate 0.005-0.1
Above-mentioned dibasic acid dimethyl ester monomer is dimethyl terephthalate (DMT) (DMT); Above-mentioned dibasic alcohol monomer is ethylene glycol or butyleneglycol;
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, cationic exchange total volume (CEC) 80-200meq/100g;
Above-mentioned catalyzer is a tetrabutyl titanate;
Above-mentioned intercalator is a diethanolamine;
Above-mentioned additive is a hexanediamine;
Above-mentioned nanometer silver diameter of particle is 1-100nm.
3. antibiotic polymer composite material is characterized in that described antibacterial polyester matrix material comprises following component and content by weight:
Polyester 85-98
Intercalation mixture 2-15
Auxiliary agent 0-1
Above-mentioned intercalation mixture comprises following component and content by weight:
Clay 2-15
Intercalator 0.001-5
Nanometer silver particulate 0.005-0.1
Above-mentioned clay is Na-polynite, H-polynite, Ca-polynite, Li-polynite, and cationic exchange total volume (CEC) is 80-200meq/100g;
Above-mentioned polyester is polyethylene terephthalate or polybutylene terephthalate;
Above-mentioned intercalator is a diethanolamine;
The particle diameter of above-mentioned nanometer silver particulate is 1-100nm;
Above-mentioned auxiliary agent is hexanediamine or lubricant.
4. according to claim 1,2 or 3 described a kind of antibiotic polymer composite materials, it is characterized in that described nanometer silver particulate is 0.01-0.1.
5. the preparation method of a kind of antibiotic polymer composite material according to claim 1, it is characterized in that: (1) is that the calcium base of 80meq-100meq/100g or the base montmorillonite 0.5-10 part of receiving are stirred in dispersion medium water 1-1000 part with the ion-exchange total volume, forms suspension; (2) protonating agent phosphoric acid 0.001-10 and intercalator ethylene glycol amine 0.001-5 are added water dissolution, nanometer silver particulate 0.005-0.1, be added to and carry out intercalation processing in the above-mentioned montmorillonite suspension liquid; (3) with terephthalic acid monomers 70-75, ethylene glycol or butyleneglycol monomer 25-30 and catalyst acetic acid antimony 0.001-5 join in the suspension of above-mentioned intercalation processing, extract water out, after the drying, carried out esterification 8-10 hour at 220-250 ℃, add additive hexanediamine 0.005-1, be evacuated to below the 80Pa, prepare polyester macromolecule by polycondensation at 250-280 ℃.
6. the preparation method of a kind of antibiotic polymer composite material according to claim 2, it is characterized in that (1) is that the calcium base of 80meq-100meq/100g or the base montmorillonite 0.5-10 part of receiving are stirred with the ion-exchange total volume in dispersion medium water 1-1000 part, form suspension; (2) protonating agent phosphoric acid 0.001-10 and intercalator ethylene glycol amine 0.001-5 are added water dissolution, nanometer silver particulate 0.005-0.1, be added to and carry out intercalation processing in the above-mentioned montmorillonite suspension liquid; (3) with dimethyl terephthalate (DMT) monomer 70-75, ethylene glycol or butyleneglycol monomer 25-30, catalyzer metatitanic acid four butyl ester 0.001-5 join in the suspension of above-mentioned intercalation processing, after the drying, carried out transesterification reaction 8-10 hour at 220-250 ℃, add additive hexanediamine 0.005-1 part, be evacuated to and be warming up to below the 80Pa, 265-280 ℃ made in polymerization 1-3 hour.
7. the preparation method of a kind of antibiotic polymer composite material according to claim 3, to it is characterized in that the ion-exchange total volume be the calcium base of 80meq-100meq/100g or receive base montmorillonite 2-15 part in the presence of the water dispersion medium of 10-500 part, forms slurry through stirring; With ethylene glycol amine intercalator 0.001-5 part and nanometer silver particulate 0.005-0.1 part in water dispersion medium 5-100 part after mixing, inject above-mentioned slurry, at 60-80 ℃, carry out common intercalation processing, after filtration, drying obtains the homodisperse blend; With vibrin 85-98 part, be warming up to 265-270 ℃ and make the resin fusion, stir and to add the above-mentioned dispersion blend of 2-15 part down, obtained the polyester antimicrobial composite material in insulated and stirred 0.5-2 hour.
8. according to the preparation method of claim 5,6 or 7 described a kind of antibiotic polymer composite materials, it is characterized in that described nanometer silver fraction of particle is 0.01-0.1.
9. the purposes of a kind of antibiotic polymer composite material according to claim 1 is characterized in that described antibacterial polyester matrix material is as building materials and civilian goods.
10. the purposes of a kind of antibiotic polymer composite material according to claim 9 is characterized in that the articles for children in the civilian goods.
11. the purposes of a kind of antibiotic polymer composite material according to claim 9 is characterized in that being used as consumption electronic products such as phone housing, computation keyboard.
12. the purposes of a kind of antibiotic polymer composite material according to claim 9 is characterized in that being used for the sheating material of household appliances such as washing machine, refrigerator.
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| CN101696287B (en) * | 2009-11-03 | 2011-06-29 | 侯占营 | Antibacterial composite sports protective gear material and preparation method thereof |
| CN101768253B (en) * | 2008-12-29 | 2012-08-29 | 合肥杰事杰新材料股份有限公司 | Polyester foam composite material with high melt strength and preparation method thereof |
| CN102711852A (en) * | 2010-01-15 | 2012-10-03 | 伊西康公司 | Antimicrobial polymer compositions and the use thereof |
| CN103131108A (en) * | 2011-12-05 | 2013-06-05 | 黄俊哲 | Antibiosis composite materials, preparing method of antibiosis composite materials and antibiosis liquid |
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| CN104497530A (en) * | 2014-12-15 | 2015-04-08 | 倪荣琴 | Composite material for computer keyboards |
| CN107540063A (en) * | 2016-06-29 | 2018-01-05 | 瑞钛晶科技有限公司 | Antibacterial monomer structure and its manufacture method |
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