CN1970633A - Polymer/ montorillonite clay- soy bean lecithin-sulfadiazine silver nano antibacterial composite material and its preparation method - Google Patents

Polymer/ montorillonite clay- soy bean lecithin-sulfadiazine silver nano antibacterial composite material and its preparation method Download PDF

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Publication number
CN1970633A
CN1970633A CN 200610097422 CN200610097422A CN1970633A CN 1970633 A CN1970633 A CN 1970633A CN 200610097422 CN200610097422 CN 200610097422 CN 200610097422 A CN200610097422 A CN 200610097422A CN 1970633 A CN1970633 A CN 1970633A
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sulfadiazine silver
polymer
lecithin
soybean lecithin
soy bean
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CN100480330C (en
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周宁琳
刘颖
孟娜
沈健
李利
魏少华
章峻
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Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention discloses a nanometer antibiotic composite material of polymer/montmorillonite-soya bean lecithin-silvadene, which comprises the following parts: 100g polymer, 0.1-10g montmorillonite-soya bean lecithin-silvadene composition, 0-400g dispersing dielectric, 0-10g crosslinking agent and 0-1g accelerant, wherein the polymer is composed of raw rubber of silicon rubber, polyurethane or two copolymer or polyolefin material; the raw rubber of silicon rubber is selected from indoor-temperature silicon rubber, high-temperature silicon rubber, addition-typed silicon rubber; the polyolefin material can be PE, PVC, PP. The invention improves stretching strength by 370%, which increases fracture extending rate by 480%.

Description

Polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material and preparation method thereof
Technical field
The invention provides a kind of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material and preparation method thereof, specially refer to functional type intercalator soybean lecithin-Sulphadiazine Sodium silver composite and with the class montmorillonite filled one base polymer/montorillonite clay-soy bean lecithin-sulfadiazine silver nano Antibacterial Composite Material and Preparation Method that forms in the polymeric matrix of this class functional type intercalator modification.
Background technology
The bio-medical tube material has extensive market prospects and juice.Statistical information shows that the world's various bio-medical tube material annual sales amount has reached 3,000,000,000 dollars.The bio-medical tube material must have corresponding biological function, thermomechanical property, biocompatibility and security.Along with society and expanding economy, people's standard of living improves constantly, and is clinical in the constantly higher requirement of proposition of tube material, needs conduit industry to constantly bring forth new ideas to satisfy clinical needs.The having of base material that can be used as the bio-medical conduit: polyvinyl chloride (PVC), polyethylene (PE), urethane (PU), silicone elastomer (SR), biological hydrogel material and their matrix material.Mainly concentrate at present and use various antibiotic coatings and silver-plated conduit-, but the former is short the anti-infective time, the clinical effectiveness instability promptly at catheter surface deposition one deck silver alloys for the Research on antibacterial of tube material; Latter's complex manufacturing, cost is higher.These all influence applying of they, so itself have antibiotic or bacteriostatic action and the conduit that can keep somewhere for a long time causes people's interest.
Composite nano polymer/clay material is one of effective means of preparation high performance composite because of the performance that shows many excellences has caused people's great interest, is an emerging research field that has development potentiality.Generally below 100nm, the organic polymer/clay nanocomposites of preparation is meant that inorganic disperse phase yardstick has the matrix material of one dimension less than 100nm at least to the thickness of clay layer.When clay is dispersed in the polymeric matrix with one lamella, matrix material just may have many new performances, and can improve its original performance.Because specific surface that nano-dispersed is mutually big and strong interfacial interaction show nano composite material and are different from general macroscopical performance of composites.In addition, also have property or function that each independent component does not possess, thereby provide new opportunity for designing and preparing high-performance multifunctional novel material.
Natural soybean lecithin is a kind of natural amphoterics, chemical name is a phosphatide phthalein choline, lecithin molecules is (polar group) and hydrophobic fat acidic group (non-polar group) such as possess hydrophilic property phosphoric acid fat phenolic group choline or cholamine simultaneously, can form oil-in-water emulsion, have emulsification property, moisture-keeping function, can improve some medicines in gi tract or the effect when skin absorbs, can obtain to eliminate in higher Plasma Concentration and the body slower, bioavailability is significantly improved.Application aspect pharmaceutical carrier is very extensive, can be used as the emulsifying agent of solubilizing agent, emulsifying agent, vein fat injection liquid.Sulfadiazine Silver (SilverSulphadiazine) is a national essential drugs, chemical name: N-2-pyrimidyl-4-aminobenzene sulfonamide silver salt, have the converging action of the anti-microbial effect and the silver salt of Sulphadiazine Sodium, this medicine has powerful restraining effect to fungies such as enterobacteriaceae lactobacteriaceae, Pseudomonas aeruginosa, streptococcus aureus, enterococcus spp, candidiasis.
Summary of the invention
In order to overcome the problem that exists in the prior art, the invention provides one base polymer/montorillonite clay-soy bean lecithin-sulfadiazine silver nano antimicrobial composite material, the present invention also will provide the preparation method of this anti-biotic material.
The present invention will insert the sheet interlayer of stratiform polynite as a kind of novel function intercalator with soybean lecithin-Sulphadiazine Sodium silver composite; Form functional antibiosis intercalator-montmorillonite-based nano intermediate, pass through the further intercalation of polymkeric substance again, make disperse phase peel off lamella, evenly be filled in the polymeric matrix, obtain polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material into the nano level polynite.This kind preparation method, not only can improve the germ resistance of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, but also can improve the mechanical property of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano matrix material and the sustained release performance of Sulfadiazine Silver medicine, can prepare high performance polymer/montorillonite clay-soy bean lecithin-sulfadiazine silver nano antimicrobial composite material.
In order to finish the foregoing invention task, the invention provides a kind of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, its feed composition and weight part content are as follows:
Polymkeric substance 100
Montorillonite clay-soy bean lecithin-sulfadiazine silver mixture 0.1~10
Dispersion medium 0~400
Linking agent 0~10
Promotor 0~1.
The present invention can reach by following requirement:
The polymkeric substance that the present invention was suitable for is that raw-silastic continuously (room temperature silicon rubber, high temperature silicon rubber, addition-type silicon rubber), urethane or the multipolymer of the two are formed; Described polymkeric substance can also be polyolefine material (PE, PVC, PP).
The functional intercalator that the present invention was suitable for is soybean lecithin-Sulphadiazine Sodium silver composite.
The polynite that the present invention was suitable for is the inorganics that a class has laminate structure, and loading capacity (being called for short CEC) can reach (70~120) mmol/100g polynite.
The used dispersion medium of the present invention is alcohols, N,N-dimethylacetamide, toluene, dimethylbenzene, hexanaphthene, methyl-sulphoxide etc. or their mixture; This class dispersion medium can make montmorillonite particle be uniformly dispersed and carry out cation exchange reaction; And when the solution method intercalation, the montorillonite clay-soy bean lecithin-sulfadiazine silver mixture is dispersed in the polymeric matrix.
The used linking agent of the present invention can be the organoalkoxysilane of alkyl silane, multiple functional radical of multiple functional radical or superoxide or Pt or need not, as tetraethoxy, coupling agent, dicumyl peroxide (DCP), 2,4,2 ', 4 '-tetrachloro benzoyl peroxide (DCBP), 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (DMDBH) or Pt or need not.
The used promotor of the present invention can be dibutyl tin laurate, stannous octoate or need not.
More optimize and in more detail: polymer-montmorillonoid-soybean lecithin of the present invention-sulfadiazine silver nano antibacterial composite material is the material for preparing in accordance with the following methods:
Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added down in the polynite colloid aqueous solution that dispersion treatment is crossed at 20~90 ℃, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, washing; Vacuum-drying, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered in the dispersion medium under 20~60 ℃, add polymkeric substance, ultra-sonic dispersion 0.5min~10min, add linking agent, promotor, be coated on the mould, place at least for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour;
Or with above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized again, add 0~3 part of moulding of linking agent, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
The method for preparing this polymkeric substance/clay nano composite material, its raw material are formed:
Polymkeric substance 100
Montorillonite clay-soy bean lecithin-sulfadiazine silver mixture 0.1~10
Dispersion medium 0~400
Linking agent 0~10
Promotor 0~1.
Preparation method's operation steps is as follows:
Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added down in the polynite colloid aqueous solution that dispersion treatment is crossed at 20~90 ℃, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, washing; Vacuum-drying, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered in the dispersion medium under 20~60 ℃, add polymkeric substance, ultra-sonic dispersion 0.5min~10min, add linking agent, promotor, be coated on the mould, place at least for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour;
Or with above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized again, add 0~3 part of moulding of linking agent, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
More optimize and in more detail, above-mentioned preparation method's concrete steps are:
With 0.1~10 part of polynite, be dissolved in 2~500mL aqueous solution high-speed stirring dispersion treatment 20min~2 hours; Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added under 20~90 ℃ in the polynite colloidal solution that dispersion treatment is crossed for 0.1~20 part, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing.
0.1~10 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered under 20~60 ℃ in 0~400 part of dispersion medium, add 100 parts of polymkeric substance, ultra-sonic dispersion 0.5min~10min, make its thorough mixing, add 0~10 part of linking agent, 0~1 part of promotor is coated on the mould, places at least for 20~60 ℃ and promptly gets polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour.
Or with 0.1~10 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and 100 parts of polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized (linking agent 0~3) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
The technology that the present invention produces polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material also can adopt in-situ inserted polymeric method except that solution intercalation method or fusion intercalation polymeric method.
In preparation intercalation type nano composite material process, the selection of intercalator and use are crucial.The present invention utilizes the modification of functional type intercalator the class montmorillonite filled one base polymer/montorillonite clay-soy bean lecithin-sulfadiazine silver nano composite antibacterial material that forms in the polymeric matrix.There is no with soybean lecithin-Sulphadiazine Sodium silver composite the report of the class montmorillonite filled polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano composite antibacterial material that forms in the polymeric matrix that is the intercalator modification through document and patent retrieval.
The invention has the beneficial effects as follows:
The present invention selects for use polynite to do matrix, is based on the process technology performance that polynite has a series of excellences: as good swelling swelling property, dispersion suspension, cationic exchange, adsorptivity, thermostability etc.; Through the polynite of purifying is nontoxic, non-stimulated, anti-oxidant mucous membrane there is provide protection in addition, the characteristic of its laminate structure and heterogeneity charge distribution and have certain fixing, restraining effect simultaneously antibacterials also to be had synergism to virus, germ.
The present invention inserts functional intercalator soybean lecithin-Sulphadiazine Sodium silver composite between cheating engaging layer by cationic exchange, form functional antibiosis montorillonite clay-soy bean lecithin-sulfadiazine silver nano intermediate, be beneficial to the macromolecular chain insertion of polymkeric substance and the formation of exfoliated nano-antibacterial composite material.
The present invention can make the montmorillonite layer that has soybean lecithin-Sulphadiazine Sodium silver composite be evenly distributed in the polymeric matrix with nano structured unit, when soybean lecithin-when the Sulphadiazine Sodium silver composite spreads in polymeric matrix, montmorillonite layer can make soybean lecithin-Sulphadiazine Sodium silver composite spread by straight line, force soybean lecithin-Sulphadiazine Sodium silver composite to take a devious route, the evolving path is increased, so the Sulfadiazine Silver release rate slows down, sustained release performance is good, thereby obviously prolong the anti-microbial property of material; When material surface antiseptic-germicide concentration reduced, antiseptic-germicide can constantly move to the surface mutually certainly by polymeric matrix, thereby realized the continuous dynamic embellishment to dynamic interface; In addition, soybean lecithin can be used as solubilizing agent, emulsifying agent aspect pharmaceutical carrier, enhancement is played in the release of Sulfadiazine Silver pharmaceutical properties.
The present invention has solved the difficulty of nano lamellar particulate in polymeric matrix well and has disperseed, easily reunites and the inconsistent problem in interface, the self-assembly of nano lamellar particulate is arranged and has been produced collaborative enhancing, toughening effect, so can prepare high performance polymer/montorillonite clay-soy bean lecithin-sulfadiazine silver nano antimicrobial composite material.This matrix material also can improve the mechanical property of polymeric matrix simultaneously because its nanostructure can be improved the anti-microbial property of polymkeric substance better.The tensile strength of the mechanical property of the comparable polymer body of mechanical property of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material can improve 370% at least, and elongation at break can improve 480% at least.
The present invention produces the technology of polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, both can adopt in-situ inserted polymerization process, and also can adopt solution intercalation or fusion intercalation polymeric method, its synthetic method is simple, preparation cycle is short, is easy to industrialization.
The material of the present invention preparation can be extensively antibiotic with antibiotic device (as the medical antibacterial conduit etc.), in discharge opeing, perfusion, dispensing, aspects such as auxiliary importing medical apparatus such as blood sampling and food product pack, storing also have application widely.
Description of drawings
Fig. 1 is the XRD figure of polynite, polynite/soybean lecithin-Sulfadiazine Silver;
Fig. 2 is the XRD figure of polymer-montmorillonoid-soybean lecithin-Sulphadiazine Sodium silver composite material;
The antibacterial ring lab diagram of Fig. 3 polymer-montmorillonoid-soybean lecithin-Sulphadiazine Sodium silver composite material
Embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but these there is not any restriction to scope of the present invention.
Embodiment 1
With 0.1 part of polynite, be dissolved in the 20mL aqueous solution, high-speed stirring dispersion treatment 20min, functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 0.3 part, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
0.1 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered under 20~60 ℃ in 100 parts of toluene, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 0.5min, make its thorough mixing, add 1 part of tetraethoxy, 0.1 part of dibutyl tin laurate, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 2
With 10 parts of polynites, be dissolved in the 500mL ethanolic soln, high-speed stirring dispersion treatment 2h, with 20 parts of functional antibiosis intercalator soybean lecithins-Sulphadiazine Sodium silver composite, add in the polynite colloidal solution that dispersion treatment is crossed down at 20~90 ℃, react 0.5h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
10 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes are scattered under 20~60 ℃ in 200 parts of ethanol, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 10min, make its thorough mixing, add 10 parts of tetraethoxys, 1 part of dibutyl tin laurate, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 3
With 2 parts of polynites, be dissolved in the 10mL aqueous solution, high-speed stirring dispersion treatment 0.5h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 1 part, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
3 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes are scattered under 20~60 ℃ in 100 parts of dimethylbenzene, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 2min, make its thorough mixing, add 2 parts of tetraethoxys, 2 parts of dibutyl tin laurates, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 4
With 8 parts of polynites, be dissolved in the 300mL aqueous solution, high-speed stirring dispersion treatment 1.5h, functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 10 parts, react 2h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
10 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes are scattered under 20~60 ℃ in 200 parts of normal hexanes, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 3min, make its thorough mixing, add 4 parts of tetraethoxys, 1 part of dibutyl tin laurate, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 5
With 5 parts of polynites, be dissolved in the 250mL aqueous solution, high-speed stirring dispersion treatment 0.6h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 8 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered in 100 parts of N for 0.5 part under 20~60 ℃, in the N-N,N-DIMETHYLACETAMIDE, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 4min, make its thorough mixing, add 6 parts of anilinomethyl trimethoxy silanes, 1 part of dibutyl tin laurate, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 24 hours, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 6
With 7 parts of polynites, be dissolved in the 450mL aqueous solution, high-speed stirring dispersion treatment 0.8h, functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 10 parts, react 1.5h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
7 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes are scattered under 20~60 ℃ in 300 parts of hexanaphthenes, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 5min, make its thorough mixing, add 8 parts of anilinomethyl triethoxysilanes, 1 part of stannous octoate, be coated on the mould, at least place for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 24 hours, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 7
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
5 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes are scattered under 20~60 ℃ in the mixture of 100 parts of hexanaphthenes and methyl-sulphoxide, add in 100 parts of room temperature vulcanized silicone rubbers, ultra-sonic dispersion 6min, make its thorough mixing, add 10 parts 5 parts of tetraethoxys, 0.5 part of stannous octoate is coated on the mould, places at least for 20~60 ℃ and promptly gets polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 24 hours.
Embodiment 8,
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 0.1 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and 100 parts of polyethylene thorough mixing, again with twin screw extruder with the melt extrusion sulfidization molding, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material all has good antibacterial effect to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicans etc.
Embodiment 9 is substantially with embodiment 8, and just polyethylene changes polyvinyl chloride into.
Embodiment 10 is substantially with embodiment 8, and just polyethylene changes polypropylene into.
Embodiment 11 is substantially with embodiment 8, and just polyethylene changes urethane into.
Embodiment 12
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1.5h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 6 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes and 100 parts of high temperature silicon rubber thorough mixing, with twin screw extruder melt extrusion is vulcanized (1 part of crosslink agent DCP) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect, and this matrix material is to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicanss etc. all have good antibacterial effect.
Embodiment 13
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1.5h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 8 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes and 100 parts of high temperature silicon rubber thorough mixing, with twin screw extruder melt extrusion is vulcanized (1.2 parts of linking agent DCBP) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material all has good antibacterial effect to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicans etc.
Embodiment 14
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 2h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 10 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes and 100 parts of high temperature silicon rubber thorough mixing, with twin screw extruder melt extrusion is vulcanized (linking agent DMDBH1.5 part) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material all has good antibacterial effect to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicans etc.
Embodiment 15
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1.5h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 10 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes and 100 parts of high temperature silicon rubber thorough mixing, with twin screw extruder melt extrusion is vulcanized (linking agent DMDBH3 part) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material all has good antibacterial effect to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicans etc.
Embodiment 16 is substantially with embodiment 22, and just silicon rubber changes silicon rubber-polyurethane copolymer into
Embodiment 17
With 9 parts of polynites, be dissolved in the 400mL aqueous solution, high-speed stirring dispersion treatment 1.5h adds functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite in the polynite colloidal solution that dispersion treatment is crossed under 20~90 ℃ for 9 parts, react 1h down at 20~90 ℃, obtain flocks; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
With 10 parts of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complexes and 100 parts of addition-type silicon rubber thorough mixing, with twin screw extruder melt extrusion is vulcanized (0.3 part of linking agent Pt) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, this matrix material all has good antibacterial effect to intestinal bacteria, streptococcus aureus, Pseudomonas aeruginosa, Candida albicans etc.
The foregoing description limits the present invention never in any form, and all employings are equal to the technical scheme that form obtained of replacement or equivalent transformation, all drop within protection scope of the present invention.

Claims (6)

1, polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material, its feed composition and weight part content are as follows:
Polymkeric substance 100
Montorillonite clay-soy bean lecithin-sulfadiazine silver mixture 0.1~10
Dispersion medium 0~400
Linking agent 0~10
Promotor 0~1.
2, polymer-montmorillonoid-soybean lecithin according to claim 1-sulfadiazine silver nano antibacterial composite material is characterized in that: described polymkeric substance is that raw-silastic continuously, urethane or the multipolymer of the two are formed; Or polyolefine material;
Described raw-silastic continuously is selected from: room temperature silicon rubber, high temperature silicon rubber, addition-type silicon rubber;
Described polyolefine material is selected from: PE, PVC, PP;
The structure of described soybean lecithin is as follows:
R wherein 1, R 2Be the fatty acid hydrocarbon chain;
Described Sulfadiazine Silver structure is as follows:
Figure A2006100974220002C2
Described linking agent is the organoalkoxysilane of alkyl silane, multiple functional radical of multiple functional radical or superoxide or Pt or need not; Be selected from respectively: tetraethoxy, coupling agent, DCP, DCBP, DMDBH or Pt;
Described promotor is dibutyl tin laurate, stannous octoate or need not.
3, polymer-montmorillonoid-soybean lecithin according to claim 1 and 2-sulfadiazine silver nano antibacterial composite material is characterized in that: described polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material is the material for preparing in accordance with the following methods:
Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added down in the polynite colloid aqueous solution that dispersion treatment is crossed at 20~90 ℃, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, washing; Vacuum-drying, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered in the dispersion medium under 20~60 ℃, add polymkeric substance, ultra-sonic dispersion 0.5min~10min, add linking agent, promotor, be coated on the mould, place at least for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour;
Or with above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized again, add 0~3 part of moulding of linking agent, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
4, polymer-montmorillonoid-soybean lecithin according to claim 3-sulfadiazine silver nano antibacterial composite material is characterized in that, described preparation method's concrete steps are:
With 0.1~10 part of polynite, be dissolved in 2~500mL aqueous solution high-speed stirring dispersion treatment 20min~2 hours; Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added under 20~90 ℃ in the polynite colloidal solution that dispersion treatment is crossed for 0.1~20 part, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Under 20~60 ℃, be scattered in 0~400 dispersion medium above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex for 0.1~10 part, add 100 parts of polymkeric substance, ultra-sonic dispersion 0.5min~10min, make its thorough mixing, add 0~10 part of linking agent, 0~1 part of promotor is coated on the mould, places at least for 20~60 ℃ and promptly gets polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour.
Or with 0.1~10 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and 100 parts of polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized (linking agent 0~3) moulding again, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
5, the preparation method of the described polymer-montmorillonoid-soybean lecithin of a kind of claim 1-sulfadiazine silver nano antibacterial composite material, its parts by weight of raw materials form is:
Polymkeric substance 100
Montorillonite clay-soy bean lecithin-sulfadiazine silver mixture 0.1~10
Dispersion medium 0~400
Linking agent 0~10
Promotor 0~1.
Preparation method's operation steps is as follows:
Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added down in the polynite colloid aqueous solution that dispersion treatment is crossed at 20~90 ℃, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, washing; Vacuum-drying, the solid of gained is the anti-mattress mixture of functional montorillonite clay-soy bean lecithin-sulfadiazine silver after pulverizing;
Above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex is scattered in the dispersion medium under 20~60 ℃, add polymkeric substance, ultra-sonic dispersion 0.5min~10min, add linking agent, promotor, be coated on the mould, place at least for 20~60 ℃ and promptly got polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour;
Or with above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized again, add 0~3 part of moulding of linking agent, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
6, according to the preparation method of the described polymer-montmorillonoid-soybean lecithin of claim 5-anti-mattress matrix material of sulfadiazine silver nano, it is characterized in that concrete steps are:
With 0.1~10 part of polynite, be dissolved in 2~500mL aqueous solution high-speed stirring dispersion treatment 20min~2 hours; Functional antibiosis intercalator soybean lecithin-Sulphadiazine Sodium silver composite is added under 20~90 ℃ in the polynite colloidal solution that dispersion treatment is crossed for 0.1~20 part, react 0.5h~5h down, obtain flocks at 20~90 ℃; With this sedimentation and filtration, use distilled water wash; 60 ℃ of following vacuum-drying 24h, the solid of gained is functional montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex after pulverizing;
Under 20~60 ℃, be scattered in 0~400 dispersion medium above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex for 0.1~10 part, add 100 parts of polymkeric substance, ultra-sonic dispersion 0.5min~10min, make its thorough mixing, add 0~10 part of linking agent, 0~1 part of promotor is coated on the mould, places at least for 20~60 ℃ and promptly gets polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material in 0.2~24 hour;
Or with 0.1~10 part of above-mentioned functions montorillonite clay-soy bean lecithin-sulfadiazine silver antibiotic complex and 100 parts of polymkeric substance thorough mixing, with twin screw extruder melt extrusion is vulcanized again, add 0~3 part of moulding of linking agent, promptly get polymer-montmorillonoid-soybean lecithin-sulfadiazine silver nano antibacterial composite material.
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US9433580B2 (en) 2011-07-21 2016-09-06 Sun Pharmaceutical Industries Limited Topical pharmaceutical composition comprising nanonized silver sulfadiazine
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Publication number Priority date Publication date Assignee Title
CN102234392A (en) * 2010-04-22 2011-11-09 中国石油化工股份有限公司 Antibacterial biaxially oriented polypropylene film and preparation method thereof
CN102234392B (en) * 2010-04-22 2013-02-27 中国石油化工股份有限公司 Antibacterial biaxially oriented polypropylene film and preparation method thereof
WO2012017349A3 (en) * 2010-08-02 2012-08-02 Ranbaxy Laboratories Limited Topical pharmaceutical composition comprising nanonized silver sulfadiazine and chlorhexidine gluconate
US9572777B2 (en) 2010-08-02 2017-02-21 Sun Pharmaceutical Industries Limited Topical pharmaceutical composition comprising nanonized silver sulfadiazine
US9433580B2 (en) 2011-07-21 2016-09-06 Sun Pharmaceutical Industries Limited Topical pharmaceutical composition comprising nanonized silver sulfadiazine
CN103131108A (en) * 2011-12-05 2013-06-05 黄俊哲 Antibiosis composite materials, preparing method of antibiosis composite materials and antibiosis liquid
CN103131108B (en) * 2011-12-05 2015-12-02 黄俊哲 The preparation method of antimicrobial composite material, antimicrobial composite material, and antimicrobial fluid
CN105462261A (en) * 2015-12-22 2016-04-06 合肥仲农生物科技有限公司 Anti-infection nano composite material
CN108929543A (en) * 2018-08-27 2018-12-04 南京师范大学 Silicon rubber/carrying nano silver ester/modified montmorillonite nano antimicrobial composite material and preparation method thereof

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