CN104592459A - Nuclear shell type long-acting antibacterial emulsion and preparation method thereof - Google Patents
Nuclear shell type long-acting antibacterial emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nuclear shell type long-acting antibacterial emulsion. The nuclear shell type long-acting antibacterial emulsion comprises the following raw material components: water, n-butyl acrylate, isobutyl acrylate, isooctyl acrylate, styrene, methyl methacrylate, vinyl acetate, guanidinium oligomer macromonomers, an emulsifying agent, an initiating agent, a cross-linking agent and sodium bicarbonate. The preparation method comprises the following steps: preparing each raw material component; adding water, the emulsifying agent and isooctyl acrylate into a reactor, stirring, heating to 60-70 DEG C, adding the initiating agent to initiate reaction, and after the emulsion becomes blue, maintaining for 60-120 minutes, so as to obtain a nuclear layer emulsion; maintaining the temperature at 70-80 DEG C, adding n-butyl acrylate, heating to 81-85 DEG C, maintaining the temperature, cooling, and discharging, so as to obtain the nuclear shell type long-acting antibacterial emulsion. According to the preparation method, guanidinium and guazatine oligomers are taken as antibacterial functional groups, and guanidyl serves as a main antimicrobial group, has an obvious antibacterial effect and is very safe to human bodies. The preparation method for the nuclear shell type long-acting antibacterial emulsion is simple, rapid, environmentally friendly and suitable for industrial production, and the operation is easy.
Description
Technical field
The present invention relates to a kind of emulsion containing guanidinesalt and preparation method thereof, particularly hud typed long acting antibiotic emulsion of one and preparation method thereof.
Background technology
Coating and paint are Furniture manufacturing in daily life, fit up requisite material at home, common coating and emulsion used in painting, and its oily emulsion waterproof, resistance to soiling are good, but not environmentally; The water-based emulsion feature of environmental protection is good, but water-proof anti-aging is poor, and most importantly neither possesses antibacterial effect.Given this situation, reaching multiple action by introducing specific function group, giving emulsion antibacterial effect, having again environmental protection, water resistance simultaneously as introduced guanidinesalt.
Antiseptic-germicide, according to the difference of its material, can be divided into inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and polymer antibacterial agent etc.Inorganic antiseptic has metal ion type and the large class of oxide compound two, and metal ion type is as Ag+, Zn
2+, Cu
2+deng, oxide type is as nano-ZnO, nano-TiO
2deng.Organic antibacterial agent contains organic acid, benzimidazole, phenols, isothiazolinone etc.Natural antibacterial agent has chitosan, natural extract etc.Polymer antibacterial agent be research organic antibacterial agent and there is anti-microbial property the Antibacterial Mechanism of natural polymer after, people have carried out molecular designing according to the Antibacterial Mechanism of organic antibacterial agent and natural polymer antiseptic-germicide, and the feature of organic antibacterial agent and natural polymer antiseptic-germicide is combined the polymer having synthesized and had anti-microbial property.Because synthesis polymer antibacterial agent can overcome the shortcomings such as the poor heat resistance of natural antibacterial agent, directly the novel antibacterial material with different mechanical properties and biological property can be obtained by synthesis again.
At present, the preparation of antimicrobial emulsion mainly adds specific organic molecule or inorganic salt antiseptic-germicide in traditional emulsion, and to carry out simple physical blended, therebetween the main form with weak bonding or physical adsorption connects, make small molecules antiseptic-germicide very easily move to substrate surface and run off, cause anti-microbial property decline and to environment.
Polymeric guanidine (comprising single guanidine and Guanoctine) has one of bioactive polymkeric substance, guanidine derivative is the widely used environment sterilant such as food factory, pharmaceutical factory, hospital, and also application is had in makeup, textiles, it has the anti-microbial property of high-efficiency broad spectrum, can suppress, kill the microorganism comprising bacterium, mould, virus etc., simultaneously nontoxic to human-body safety.
Polymkeric substance containing guanidine structure is a class effectively antibacterial, antiviral agent, has excellent antimicrobial properties and the security to human body.But so far, the molecular weight of guanidine salt polymer is all smaller, when joining other goods as antiseptic-germicide, easily run off and pollute other goods, and antibacterial effect is not lasting.Therefore, need a kind of antiseptic-germicide at present badly not easily to run off and pollute and the antimicrobial emulsion of durable antibacterial effect.
The information being disclosed in this background technology part is only intended to increase the understanding to general background of the present invention, and should not be regarded as admitting or imply in any form that this information structure has been prior art that persons skilled in the art are known.
Summary of the invention
The object of the present invention is to provide a kind of hud typed long acting antibiotic emulsion and preparation method thereof, thus overcome other goods of pollution, the unabiding shortcoming of antibacterial effect that cause because antiseptic-germicide runs off.
Another object of the present invention is to provide a kind of simple and direct, easy to operate, environmental protection, is applicable to the preparation method of industrial long acting antibiotic emulsion.
For achieving the above object, technical scheme provided by the invention is as follows:
A kind of hud typed long acting antibiotic emulsion, according to ratio of quality and the number of copies, comprise following component raw material: 60 ~ 80 parts, water, n-butyl acrylate 0 ~ 8 part, isobutyl acrylate 0 ~ 10 part, Isooctyl acrylate monomer 0 ~ 15 part, vinylbenzene 0 ~ 8 part, methyl methacrylate 0 ~ 8 part, vinyl acetate 0 ~ 8 part, guanidinesalt oligopolymer polymeric monomer 2 ~ 10 parts, emulsifying agent 0.5 ~ 4 part, initiator 0.2 ~ 2 part, linking agent 0.2 ~ 2 part, sodium bicarbonate 0.1 ~ 0.3 part.
Wherein, described guanidinesalt oligopolymer polymeric monomer prepares gained by following steps method: take that guanidinesalt oligopolymer is soluble in water is made into the guanidine solution that massfraction is 20 ~ 40%; Then rare gas element is passed into; guanidine solution is mixed with the ratio of mol ratio 1:1 ~ 1:1.2 with glycidyl methacrylate (GMA); add in reactor; stirring reaction 12 ~ 24h under room temperature and protection of inert gas condition; until after oil phase completely dissolve, gained is the guanidinesalt oligopolymer polymeric monomer of carbon-carbon double bonds.
Wherein, described guanidinesalt oligopolymer is poly (hexamethylene) hydrochloride or hexamethylene, and molecular weight is 500 ~ 1000.
Wherein, described emulsifying agent is at least one in palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, polysorbate60.
Wherein, described initiator is the one in 2,2'-azo diisobutyl amidine dihydrochloride, azo two isobutyl imidazoline hydrochloride, Potassium Persulphate, ammonium persulphate.
Wherein, described linking agent is at least one in ethylene glycol dimethacrylate, dicumyl peroxide, Vinylstyrene, N,N methylene bis acrylamide.
A preparation method for hud typed long acting antibiotic emulsion, comprises following operation steps:
(1) required each component raw material is taken by portion rate;
(2) stratum nucleare letex polymerization: add 60 ~ 80 parts of water in reactor, emulsifying agent 0.5 ~ 4 part, Isooctyl acrylate monomer 0 ~ 15 part, vinylbenzene 0 ~ 8 part, methyl methacrylate 0 ~ 8 part, vinyl acetate 0 ~ 8 part, linking agent 0.2 ~ 2 part, sodium bicarbonate 0.1 ~ 0.3 part, after stirring 20 ~ 60min, be warming up to 60 ~ 70 DEG C, add 0.05 ~ 0.5 part of initiator initiation reaction, after emulsion blueing, insulation 60 ~ 120min, obtains stratum nucleare emulsion;
(3) shell emulsion synthesize: on the basis of stratum nucleare letex polymerization, temperature is remained 70 ~ 80 DEG C, drip n-butyl acrylate 0 ~ 8 part, isobutyl acrylate 0 ~ 10, guanidinesalt oligopolymer polymeric monomer 2 ~ 10 parts and 0.15 ~ 1.5 part of initiator, time for adding is 60 ~ 120min, after dropwising, temperature is risen to 81 ~ 85 DEG C, insulation 60 ~ 120min, cooling, discharging, obtain milky white liquid and be product.
The present invention mainly utilizes a kind of antibacterial guanidinesalt oligopolymer polymeric monomer, by semi-continuous seed emulsion polymerization legal system for hud typed long acting antibiotic emulsion.
A kind of antibacterial guanidinesalt oligopolymer polymeric monomer is as follows:
Wherein: R=poly (hexamethylene) hydrochloride or hexamethylene, molecular weight is 500 ~ 1000.
Compared with prior art, the present invention has following beneficial effect:
1) a kind of antibacterial guanidinesalt oligopolymer polymeric monomer is mainly utilized, by emulsion polymerization way and the monomer copolymerization such as acrylate, vinylbenzene, antibacterial group is fixed on emulsion macromolecular chain, prepare long acting antibiotic emulsion, as benzene emulsion etc., overcome the shortcoming that Physical adds antiseptic-germicide, the present invention prepares gained emulsion and not easily cleans and dissolve, and has long acting antibiotic effect; Meanwhile, also there is mildew resistance, water tolerance, resistance to soiling, solvent resistance, comparatively low film formation temperature and stability in storage etc.
2) component of hud typed guanidinesalt benzene emulsion of the present invention and structure-controllable, can according to application needs, the component of polymkeric substance and structure are regulated and controled, to obtain the emulsion of applicable different applications needs by the monomeric species and consumption that change latex particle stratum nucleare and shell.
3) simple, the environmental protection of hud typed guanidinesalt benzene emulsion preparation technology of the present invention, is applicable to suitability for industrialized production.
The present invention adopts guanidinesalt, Guanoctine oligopolymer as antibacterial group, analyze from molecular structure, guanidine radicals is main antimicrobial group, guanidinesalt emulsion has higher effective groups density, utilize the positive polarity of functional group to attract effective microbe with electronegative cytolemma, within the very short time, make it lose activity, then make cytolemma break gradually, tenuigenin flows out lethal, thus fool proof to human body; Further this guanidinesalt benzene emulsion is killed with restraining effect remarkable to harmful microbes such as comprising Gram-negative bacteria (taking intestinal bacteria as representative), gram-positive microorganism (taking streptococcus aureus as representative), mould.
Accompanying drawing explanation
Fig. 1 to be legend be emulsion particle transmission electron microscope (TEM) figure of 0.5 μm.
Embodiment
Below the specific embodiment of the present invention is described in detail, but is to be understood that protection scope of the present invention not by the restriction of embodiment.GMA methacrylic acid glycidyl ester in the following example, reactor is four mouthfuls of round-bottomed flasks, has thermometer, dropping funnel, prolong and speed-adjustable stir device (thermometer, dropping funnel, prolong and speed-adjustable stir device place sequence requirement without position).
Embodiment 1
The preparation of poly (hexamethylene) hydrochloride polymeric monomer (GPHMG):
Take molecular weight be 500 poly (hexamethylene) hydrochloride 40g be dissolved in 60g deionized water and be made into the guanidine solution that massfraction is 40%; Logical nitrogen, is slowly added dropwise to 11.3g GMA in this guanidine solution, continues stirring at room temperature reaction 24h under nitrogen protection, until oil phase completely dissolve, namely obtains.
Embodiment 2
The preparation of poly (hexamethylene) hydrochloride polymeric monomer (GPHMG):
Take molecular weight be 700 poly (hexamethylene) hydrochloride 30g be dissolved in 70g distilled water water and be made into the guanidine solution that massfraction is 30%; Logical argon gas, is slowly added dropwise to 6.7g GMA in this guanidine solution, continues stirring at room temperature reaction 18h under argon shield, until oil phase completely dissolve, namely obtains.
Embodiment 3
The preparation of hexamethylene polymeric monomer (GPHMB):
Take molecular weight be 800 hexamethylene 25g be dissolved in 75g purified water and be made into the guanidine solution that massfraction is 25%; Helium injection gas, is slowly added dropwise to 5.1g GMA in this guanidine solution, continues stirring at room temperature reaction 16h under helium protection, until oil phase completely dissolve, namely obtains.
Embodiment 4
The preparation of hexamethylene polymeric monomer (GPHMB):
Take molecular weight be 1000 hexamethylene 20g be dissolved in 80g deionized water and be made into the guanidine solution that massfraction is 20%; Logical nitrogen, is slowly added dropwise to 3.4g GMA in this guanidine solution, continues stirring at room temperature reaction 12h under nitrogen protection, until oil phase completely dissolve, namely obtains.
Embodiment 5
In units of g, take required each component raw material: 80g deionized water, 8g vinylbenzene, 4g vinyl acetate, 6g n-butyl acrylate, the poly (hexamethylene) hydrochloride polymeric monomer obtained by 2g embodiment 1,0.5g emulsifying agent cetyl trimethylammonium bromide, initiator 2, the 2'-azo diisobutyl amidine dihydrochloride of 0.15g, the linking agent ethylene glycol dimethacrylate of 0.2g, the sodium bicarbonate of 0.1g.
(1) stratum nucleare letex polymerization: add 80g deionized water toward the reactor being furnished with thermometer, dropping funnel, prolong and speed-adjustable stir device, 0.5g emulsifying agent cetyl trimethylammonium bromide, 8g vinylbenzene, 4g vinyl acetate, 0.2g linking agent ethylene glycol dimethacrylate, 0.1g sodium bicarbonate, after stirring 20min, be warming up to 65 DEG C, add the initiation reaction of 0.05g initiator 2,2'-azo diisobutyl amidine dihydrochloride, after emulsion blueing, insulation 80min, obtains stratum nucleare emulsion;
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 70 DEG C, then 6g n-butyl acrylate is dripped, 2g poly (hexamethylene) hydrochloride polymeric monomer and 0.15g initiator 2, 2'-azo diisobutyl amidine dihydrochloride, time for adding is 60min, after dropwising, temperature is risen to 81 DEG C, insulation 120min, cooling, discharging, obtain the milky white liquid that solid content is 19.8%, be poly-(vinylbenzene-co-vinyl acetate/poly (hexamethylene) hydrochloride-co-n-butyl acrylate) (St-co-VAC/GPHMG-co-n-BMA) emulsion.
Embodiment 6
In units of g, take required each component raw material: the sodium bicarbonate of the initiator azo two isobutyl imidazoline hydrochloride of 74g distilled water, 8g methyl methacrylate, 6g vinylbenzene, 6g isobutyl acrylate, hexamethylene polymeric monomer, 1.5g emulsifying agent palmityl trimethyl ammonium chloride and 0.5g emulsifier tween 60 obtained by 6g embodiment 3,0.4g, 0.6g linking agent ethylene glycol dimethacrylate and 0.2g linking agent dicumyl peroxide, 0.2g.
(1) stratum nucleare letex polymerization: add 74g distilled water toward the reactor being furnished with thermometer, dropping funnel, prolong and speed-adjustable stir device, 1.5g emulsifying agent palmityl trimethyl ammonium chloride and 0.5g emulsifier tween 60,8g methyl methacrylate, 6g vinylbenzene, 0.6g linking agent ethylene glycol dimethacrylate and 0.2g linking agent dicumyl peroxide, 0.2g sodium bicarbonate, after stirring 30min, be warming up to 60 DEG C, add the initiation reaction of 0.4g initiator azo two isobutyl imidazoline hydrochloride, after emulsion blueing, insulation 120min, obtains stratum nucleare emulsion.
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 75 DEG C, then 6g isobutyl acrylate is dripped, 6g hexamethylene polymeric monomer and 0.6g initiator azo two isobutyl imidazoline hydrochloride, time for adding is 100min, after dropwising, temperature is risen to 83 DEG C, insulation 100min, cooling, discharging, obtain the milky white liquid that solid content is 25.7%, be poly-(methyl methacrylate-co-vinylbenzene/hexamethylene-co-isobutyl acrylate) (MMA-co-St/GPHMB-co-i-BMA) emulsion.
Embodiment 7
In units of g, take required each component raw material: the sodium bicarbonate of the initiator potassium persulfate of 69g purified water, 8g vinyl acetate, 7g Isooctyl acrylate monomer, 8g n-butyl acrylate, poly (hexamethylene) hydrochloride polymeric monomer, 2g emulsifying agent octadecyl trimethyl ammonium chloride and 1g emulsifier tween 60 obtained by 8g embodiment 2,0.6g, 1.2g cross-linker divinylbenzene, 0.25g.
(1) stratum nucleare letex polymerization: add 69g purified water toward the reactor being furnished with thermometer, dropping funnel, prolong and speed-adjustable stir device, 2g emulsifying agent octadecyl trimethyl ammonium chloride and 1g emulsifier tween 60,8g vinyl acetate, 7g Isooctyl acrylate monomer, 1.2g cross-linker divinylbenzene, 0.25g sodium bicarbonate, after stirring 40min, be warming up to 70 DEG C, add the initiation reaction of 0.6g initiator potassium persulfate, after emulsion blueing, insulation 60min, obtains stratum nucleare emulsion.
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 80 DEG C, drip 8g n-butyl acrylate, 8g poly (hexamethylene) hydrochloride polymeric monomer and 0.6g initiator potassium persulfate, time for adding is 80min, after dropwising, temperature is risen to 85 DEG C, insulation 60min, cooling, discharging, obtain the milky white liquid that solid content is 30.6%, be poly-(vinyl acetate-co-Isooctyl acrylate monomer/poly (hexamethylene) hydrochloride-co-n-butyl acrylate) (VAC-co-EHA/GPHMG-co-n-BMA) emulsion.
Embodiment 8
In units of g, take required each component raw material: 60g deionized water, 5g methyl methacrylate, 15g Isooctyl acrylate monomer, 10g isobutyl acrylate, hexamethylene polymeric monomer obtained by 10g embodiment 4, 2g emulsifying agent cetyl trimethylammonium bromide, 0.5g emulsifying agent palmityl trimethyl ammonium chloride, 0.5g emulsifying agent octadecyl trimethyl ammonium chloride and 1g emulsifier tween 60, 0.5g initiator ammonium persulfate, 1.5g initiator azo two isobutyl imidazoline hydrochloride, 0.5g linking agent ethylene glycol dimethacrylate, 0.2g linking agent dicumyl peroxide, 0.3g cross-linker divinylbenzene, 1g linking agent N, N-methylene-bisacrylamide, the sodium bicarbonate of 0.3g.
(1) stratum nucleare letex polymerization: toward being furnished with thermometer, dropping funnel, the reactor of prolong and speed-adjustable stir device adds 60g deionized water, 0.5g emulsifying agent palmityl trimethyl ammonium chloride, 0.5g emulsifying agent octadecyl trimethyl ammonium chloride and 1g emulsifier tween 60, 5g methyl methacrylate, 15g Isooctyl acrylate monomer, 0.5g linking agent ethylene glycol dimethacrylate, 0.2g linking agent dicumyl peroxide, 0.3g cross-linker divinylbenzene, 1g linking agent N, N-methylene-bisacrylamide, 0.3g sodium bicarbonate, after stirring 60min, be warming up to 63 DEG C, add the initiation reaction of 0.5g initiator ammonium persulfate, after emulsion blueing, insulation 100min, obtain stratum nucleare emulsion.
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 72 DEG C, drip 10g isobutyl acrylate, 10g hexamethylene polymeric monomer and 12g initiator ammonium persulfate solution (including 1.2g ammonium persulphate), time for adding is 120min, after dropwising, temperature is risen to 82 DEG C, insulation 80min, cooling, discharging, obtain the milky white liquid that solid content is 40.3%, be poly-(methyl methacrylate-co-Isooctyl acrylate monomer/hexamethylene-co-isobutyl acrylate) (MMA-co-EHA/GPHMB-co-i-BMA) emulsion.
Embodiment 9
In units of g, take required each component raw material: 75g deionized water, 5g vinyl acetate, 6g vinylbenzene, 8g n-butyl acrylate, the poly (hexamethylene) hydrochloride polymeric monomer obtained by 6g embodiment 2,1g emulsifying agent cetyl trimethylammonium bromide, 0.5g emulsifier tween 60,0.1g initiator potassium persulfate, 0.3g initiator 2,2'-azo diisobutyl amidine dihydrochloride, the sodium bicarbonate of 0.5g linking agent N,N methylene bis acrylamide, 0.3g linking agent peroxidation diisopropyl, 0.15g.
(1) stratum nucleare letex polymerization: add 75g deionized water toward the reactor being furnished with thermometer, dropping funnel, prolong and speed-adjustable stir device, 1g emulsifying agent cetyl trimethylammonium bromide, 0.5g emulsifier tween 60,5g vinyl acetate, 6g vinylbenzene, 0.5g linking agent N, the sodium bicarbonate of N-methylene-bisacrylamide, 0.3g linking agent peroxidation diisopropyl, 0.15g, after stirring 30min, be warming up to 65 DEG C, add the initiation reaction of 0.1g initiator potassium persulfate, after emulsion blueing, insulation 80min, obtains stratum nucleare emulsion.
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 75 DEG C, drip 8g n-butyl acrylate, poly (hexamethylene) hydrochloride polymeric monomer obtained by 6g embodiment 2 and 0.3g initiator 2, 2'-azo diisobutyl amidine dihydrochloride, time for adding is 60min, after dropwising, temperature is risen to 83 DEG C, insulation 80min, cooling, discharging, obtain the milky white liquid that solid content is 24.9%, be poly-(vinyl acetate-co-vinylbenzene/poly (hexamethylene) hydrochloride-co-n-butyl acrylate) (VAC-co-St/GPHMG-co-BMA) emulsion.
Embodiment 10
In units of g, take required each component raw material: 65g deionized water, 8g Isooctyl acrylate monomer, 8g vinylbenzene, 10g isobutyl acrylate, hexamethylene polymeric monomer obtained by 9g embodiment 3, 1g emulsifying agent cetyl trimethylammonium bromide, 0.8g emulsifying agent octadecyl ammonium chloride, 1.2g emulsifier tween 60, 0.3g initiator ammonium persulfate, 1g initiator 2, 2'-azo diisobutyl amidine dihydrochloride, 1g linking agent ethylene glycol dimethacrylate, 0.3g cross-linker divinylbenzene, 0.5g linking agent N, N-methylene-bisacrylamide, the sodium bicarbonate of 0.25g.
(1) stratum nucleare letex polymerization: toward being furnished with thermometer, dropping funnel, the reactor of prolong and speed-adjustable stir device adds 65g deionized water, 1g emulsifying agent cetyl trimethylammonium bromide, 0.8g emulsifying agent octadecyl ammonium chloride, 1.2g emulsifier tween 60, 8g Isooctyl acrylate monomer, 8g vinylbenzene, 1g linking agent ethylene glycol dimethacrylate, 0.3g cross-linker divinylbenzene, 0.5g linking agent N, N-methylene-bisacrylamide, the sodium bicarbonate of 0.25g, after stirring 45min, be warming up to 62 DEG C, add the initiation reaction of 0.3g initiator ammonium persulfate, after emulsion blueing, insulation 100min, obtain stratum nucleare emulsion.
(2) shell emulsion synthesize: in (1), the stratum nucleare emulsion of gained keeps temperature to be 77 DEG C, drip 10g isobutyl acrylate, hexamethylene polymeric monomer obtained by 9g embodiment 3 and 1g initiator 2, 2'-azo diisobutyl amidine dihydrochloride, time for adding is 100min, after dropwising, temperature is risen to 85 DEG C, insulation 60min, cooling, discharging, obtain the milky white liquid that solid content is 35.7%, be poly-(Isooctyl acrylate monomer-co-vinylbenzene/hexamethylene-co-isobutyl acrylate) (EHA-co-St/GPHMB-co-i-BMA) emulsion.
Hud typed long acting antibiotic emulsion property testing method prepared by the present invention:
1) emulsion appearance: the physical condition such as color, state, homogeneity of visual observations sample;
2) solids content (i.e. solid content) measures: on watch-glass, take 1g emulsion, put into 120 DEG C of baking oven 1h, and calculate after weighing, calculation formula is as follows:
Weight × 100% of the front resin of the weight/baking of resin after solids content (%)=baking;
3) test of viscosity: be coated with 4 viscometers (Shanghai Ping Xuan scientific instrument company limited) by NDJ-5 type, measures temperature 25 DEG C;
4) emulsion particle diameter and emulsion Zeta potential measure: with the Nano-ZS light scattering tool (Britain) of Malvern, with 0.1mM KCl solution, emulsion is diluted to the KCl solution of 1mg/mL, then at room temperature measures;
5) film-forming properties: a small amount of emulsion is poured on watch-glass, whether seasoning film forming under room temperature, observe the transparency, the slipperiness of film whether evenly, continuously, with or without shrinkage cavity, film and be clamminess;
6) Glass Transition Temperature of Latex Tg measures: measure with differential scanning calorimeter (DSC), by emulsion at room temperature film forming, produces on DSC-7 type differential thermal analyzer carry out dsc analysis, heat-up rate 10 DEG C/min, sweep limit-10 DEG C ~ 90 DEG C in the U.S.;
7) emulsion particle form: samples of latex deionized water dilutes, dip-coating, on copper mesh, is carried out observing and taking a picture with Japanese HITACH company JEM-1000 type transmission electron microscope instrument (TEM) after drying;
8) emulsion anti-microbial activity test: according to regulation test in " antibiotic paint " HG/T3950-2007.
Emulsion film prepared by the present invention and conventional benzene emulsion film carry out anti-microbial property test, and test bacteria is intestinal bacteria and staphylococcus aureus.First anti-microbial property detection is carried out to 2 kinds of films, after having tested, 24h is carried out to emulsion film and repeatedly carries out anti-microbial property test again after sonic oscillation surface cleaning.
The excellent property of hud typed long acting antibiotic emulsion prepared by above-described embodiment 5 ~ 10, specifically see such as following table 1:
The hud typed long acting antibiotic emulsion property that table 1 four embodiments are obtained
By finding out in table 1 that the latex particle median size of emulsion prepared by embodiment 5 ~ 8 is less, be conducive to emulsion long-term stability and deposit, emulsion has obvious positive polarity, film performance is good, and the second-order transition temperature of latex particle is low, easier film forming.
Hud typed long acting antibiotic emulsion anti-microbial property prepared by embodiment 5 ~ 10 and the contrast of conventional benzene emulsion, see such as following table 2:
The antibacterial styrene-acrylate emulsion film that table 2 four embodiments are obtained and conventional benzene emulsion film anti-microbial activity
Above-mentioned table 2 analytical results:
1) product is by the sign such as transmission electron microscope (TEM) (see accompanying drawing 1) and particle diameter test, can find out that the latex particle of obtained emulsion presents spherical nucleocapsid structure, meet product requirement;
2) antibacterial detected result shows, emulsion shows good, long-acting anti-microbial property to intestinal bacteria and staphylococcus aureus.
The aforementioned description to concrete exemplary of the present invention is to illustrate and the object of illustration.These descriptions not want the present invention to be defined as disclosed precise forms, and obviously, according to above-mentioned instruction, can much change and change.The object selected exemplary embodiment and describe is to explain certain principles of the present invention and practical application thereof, thus those skilled in the art can be realized and utilize various different exemplary of the present invention and various different selection and change.Scope of the present invention is intended to limited by claims and equivalents thereof.
Claims (7)
1. a hud typed long acting antibiotic emulsion, it is characterized in that, following component raw material is comprised: 60 ~ 80 parts, water according to ratio of quality and the number of copies, n-butyl acrylate 0 ~ 8 part, isobutyl acrylate 0 ~ 10 part, Isooctyl acrylate monomer 0 ~ 15 part, vinylbenzene 0 ~ 8 part, methyl methacrylate 0 ~ 8 part, vinyl acetate 0 ~ 8 part, guanidinesalt oligopolymer polymeric monomer 2 ~ 10 parts, emulsifying agent 0.5 ~ 4 part, initiator 0.2 ~ 2 part, linking agent 0.2 ~ 2 part, sodium bicarbonate 0.1 ~ 0.3 part.
2. hud typed long acting antibiotic emulsion according to claim 1, is characterized in that, described guanidinesalt oligopolymer polymeric monomer prepares gained by following steps method: take guanidinesalt oligopolymer and be made into the guanidine solution that massfraction is 20 ~ 40%; Pass into rare gas element, mixed by guanidine solution, then add reactor with glycidyl methacrylate with the ratio of mol ratio 1:1 ~ 1:1.2, under room temperature and protection of inert gas condition, react 12 ~ 24h, gained is guanidinesalt oligopolymer polymeric monomer.
3. hud typed long acting antibiotic emulsion according to claim 1, it is characterized in that: described guanidinesalt oligopolymer is poly (hexamethylene) hydrochloride or hexamethylene, molecular weight is 500 ~ 1000.
4. hud typed long acting antibiotic emulsion according to claim 1, is characterized in that: described emulsifying agent is at least one in palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, polysorbate60.
5. hud typed long acting antibiotic emulsion according to claim 1, is characterized in that: described initiator is 2, the one in 2 '-azo diisobutyl amidine dihydrochloride, azo two isobutyl imidazoline hydrochloride, Potassium Persulphate, ammonium persulphate.
6. hud typed long acting antibiotic emulsion according to claim 1, is characterized in that: described linking agent is at least one in ethylene glycol dimethacrylate, dicumyl peroxide, Vinylstyrene, N,N methylene bis acrylamide.
7. a preparation method for hud typed long acting antibiotic emulsion as claimed in claim 1, is characterized in that, comprise following operation steps:
(1) required each component raw material is taken by portion rate;
(2) stratum nucleare letex polymerization: add 60 ~ 80 parts of water in reactor, emulsifying agent 0.5 ~ 4 part, Isooctyl acrylate monomer 0 ~ 15 part, vinylbenzene 0 ~ 8 part, methyl methacrylate 0 ~ 8 part, vinyl acetate 0 ~ 8 part, linking agent 0.2 ~ 2 part, sodium bicarbonate 0.1 ~ 0.3 part, after stirring 20 ~ 60min, be warming up to 60 ~ 70 DEG C, add 0.05 ~ 0.5 part of initiator, after emulsion blueing, insulation 60 ~ 120min, obtains stratum nucleare emulsion;
(3) shell emulsion synthesize: on the basis of stratum nucleare letex polymerization, temperature is remained 70 ~ 80 DEG C, drip n-butyl acrylate 0 ~ 8 part, isobutyl acrylate 0 ~ 10, guanidinesalt oligopolymer polymeric monomer 2 ~ 10 parts and 0.15 ~ 1.5 part of initiator, time for adding is 60 ~ 120min, after dropwising, temperature is risen to 81 ~ 85 DEG C, insulation 60 ~ 120min, cooling, discharging, obtain milky white liquid and be product.
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| CN201510030777.7A CN104592459B (en) | 2015-01-21 | 2015-01-21 | A kind of hud typed long acting antibiotic emulsion and preparation method thereof |
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| CN105462416A (en) * | 2015-12-18 | 2016-04-06 | 三棵树涂料股份有限公司 | Anti-doodling healthy indoor coating water-based latex paint and preparation method thereof |
| CN105462415A (en) * | 2015-12-18 | 2016-04-06 | 三棵树涂料股份有限公司 | Antibacterial water-based emulsion for architectural coating and preparation method thereof |
| CN105505080A (en) * | 2015-12-18 | 2016-04-20 | 三棵树涂料股份有限公司 | Sterilization and mould prevention water-based emulsion paint and preparation method thereof |
| US20170096565A1 (en) * | 2015-10-02 | 2017-04-06 | Gebr. Brasseler Gmbh & Co. Kg | Process for producing an antibacterial coating composition for implants |
| CN106749851A (en) * | 2016-11-29 | 2017-05-31 | 中山市巴德富化工科技有限公司 | A kind of aqueous woodware paint water-and acrylate emulsion and preparation method thereof |
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| CN111154370A (en) * | 2020-01-15 | 2020-05-15 | 华东理工大学 | Antibacterial acrylate coating and preparation method and application thereof |
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| US10669435B2 (en) * | 2015-10-02 | 2020-06-02 | Gebr. Brasseler Gmbh & Co. Kg | Process for producing an antibacterial coating composition for implants |
| US20170096565A1 (en) * | 2015-10-02 | 2017-04-06 | Gebr. Brasseler Gmbh & Co. Kg | Process for producing an antibacterial coating composition for implants |
| CN105462415A (en) * | 2015-12-18 | 2016-04-06 | 三棵树涂料股份有限公司 | Antibacterial water-based emulsion for architectural coating and preparation method thereof |
| CN105505080A (en) * | 2015-12-18 | 2016-04-20 | 三棵树涂料股份有限公司 | Sterilization and mould prevention water-based emulsion paint and preparation method thereof |
| CN105462416A (en) * | 2015-12-18 | 2016-04-06 | 三棵树涂料股份有限公司 | Anti-doodling healthy indoor coating water-based latex paint and preparation method thereof |
| CN106749851A (en) * | 2016-11-29 | 2017-05-31 | 中山市巴德富化工科技有限公司 | A kind of aqueous woodware paint water-and acrylate emulsion and preparation method thereof |
| CN106749851B (en) * | 2016-11-29 | 2018-12-07 | 中山市巴德富化工科技有限公司 | A kind of aqueous woodware paint water-and acrylate lotion and preparation method thereof |
| CN107383283A (en) * | 2017-08-23 | 2017-11-24 | 广州科迩博新材料科技有限公司 | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application |
| CN108004835A (en) * | 2017-12-17 | 2018-05-08 | 李巧珍 | A kind of preparation method of the antibacterial release liners of high temperature resistant |
| CN110951014A (en) * | 2018-09-26 | 2020-04-03 | 合肥杰事杰新材料股份有限公司 | Antibacterial polymethacrylate material and preparation method thereof |
| CN111154370A (en) * | 2020-01-15 | 2020-05-15 | 华东理工大学 | Antibacterial acrylate coating and preparation method and application thereof |
| CN111187549A (en) * | 2020-02-23 | 2020-05-22 | 湖南辰砾新材料有限公司 | Antiviral flame-retardant weather-resistant coating |
| CN113462251A (en) * | 2021-08-06 | 2021-10-01 | 海南赛诺实业有限公司 | Antibacterial coating, preparation method thereof and antibacterial coating film |
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