CN104592459B - A kind of hud typed long acting antibiotic emulsion and preparation method thereof - Google Patents
A kind of hud typed long acting antibiotic emulsion and preparation method thereof Download PDFInfo
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- CN104592459B CN104592459B CN201510030777.7A CN201510030777A CN104592459B CN 104592459 B CN104592459 B CN 104592459B CN 201510030777 A CN201510030777 A CN 201510030777A CN 104592459 B CN104592459 B CN 104592459B
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Abstract
A kind of hud typed long acting antibiotic emulsion, component raw material is water, n-butyl acrylate, isobutyl acrylate, Isooctyl acrylate monomer, styrene, methyl methacrylate, vinylacetate, guanidinesalt oligomer polymeric monomer, emulsifying agent, initiator, crosslinking agent, sodium acid carbonate.Its preparation methods steps are：Take each component raw material；Added water in toward reactor, emulsifying agent, Isooctyl acrylate monomer etc. are warming up to after stirring after 60~70 DEG C, plus initiator initiation reaction, emulsion blueing, be incubated 60~120min, produce stratum nucleare emulsion；Temperature is remained into 70~80 DEG C, plus n-butyl acrylate etc., temperature rises to 81~85 DEG C, and insulation cools down, discharged, produces product.The present invention is using guanidinesalt, Guanoctine oligomer as antibacterial functions group, and guanidine radicals is main antimicrobial group, and antibacterial effect is substantially, fool proof to human body.The present invention is a kind of simple and direct, easy to operate, and environmental protection is adapted to the preparation method of industrial long acting antibiotic emulsion.
Description
Technical field
The present invention relates to a kind of emulsion containing guanidinesalt and preparation method thereof, more particularly to a kind of hud typed long acting antibiotic emulsion
And preparation method thereof.
Background technology
Coating and paint are Furniture manufacturings in daily life, fit up essential material, common coating and oil at home
Emulsion used in paint, 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
Property it is poor, and most importantly neither possess the effect of antibacterial.Given this situation, is reached by introducing specific function group
Multiple action, such as introduces guanidinesalt and assigns emulsion antibacterial effect, while having environmental protection, water resistance again.
Antiseptic can be divided into inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and macromolecule according to the difference of its material
Antiseptic etc..Inorganic antiseptic has metal ion type and the major class of oxide two, metal ion type such as Ag+, Zn2+、Cu2+Deng oxidation
Thing type such as nano-ZnO, nano-TiO2Deng.Organic antibacterial agent contains organic acid, benzimidazole, phenols, OIT etc..My god
Right antiseptic has chitosan, natural extract etc..Polymer antibacterial agent is research organic antibacterial agent and the day with anti-microbial property
After right high molecular Antibacterial Mechanism, people have carried out molecule according to the Antibacterial Mechanism of organic antibacterial agent and natural polymer antiseptic
Design, combines the characteristics of by organic antibacterial agent and natural polymer antiseptic and has synthesized the macromolecule with anti-microbial property.
Because the shortcomings of synthesis polymer antibacterial agent can overcome the poor heat resistance of natural antibacterial agent, directly it can be obtained again by synthesis
Novel antibacterial material with different mechanical properties and biological property.
At present, the preparation of antimicrobial emulsion mainly adds specific organic molecule in traditional emulsion or inorganic salts are anti-
Microbial inoculum carries out simple physical blending, main therebetween to be connected in the form of weak bonding or physical absorption, makes small molecule antibacterial
Agent easily moves to substrate surface and is lost in, and causes anti-microbial property to decline and polluted to environment.
Polymeric guanidine (including single guanidine and Guanoctine) is one of polymer with bioactivity, and guanidine derivative is food
The widely used environment bactericide such as product factory, pharmaceutical factory, hospital, and also have application in cosmetics, textile, it has efficiently wide
The anti-microbial property of spectrum, can suppress, microorganism including bacterium, mould, virus etc. be killed, while nothing safe to the human body
Poison.
Polymer containing guanidine structure is the effective antibacterial of a class, antivirotic, with excellent antimicrobial properties and
To the security of human body.But, so far, the molecular weight of guanidine salt polymer is all smaller, and other are added to as antiseptic
During product, easily it is lost in and pollutes other products, and antibacterial effect is not lasting.Therefore, a kind of antiseptic is needed badly at present
Not easily run off pollute and durable antibacterial effect antimicrobial emulsion.
The information for being disclosed in the background section is merely intended to understanding of the increase to the general background of the present invention, without answering
When the prior art for being considered as recognizing or implying the information structure in any form well known to persons skilled in the art.
The content of the invention
It is an object of the invention to provide a kind of hud typed long acting antibiotic emulsion and preparation method thereof, so as to overcome because of antibacterial
Agent be lost in and cause the other products of pollution, the unabiding shortcoming of antibacterial effect.
A kind of simple and direct, easy to operate, the environmental protection another object of the present invention is to provide, is adapted to industrial long acting antibiotic breast
The preparation method of liquid.
To achieve the above object, the technical scheme that the present invention is provided is as follows：
A kind of hud typed long acting antibiotic emulsion, according to quality parts ratio, includes following components raw material：60~80 parts of water, third
0~8 part of olefin(e) acid N-butyl, 0~10 part of isobutyl acrylate, 0~15 part of Isooctyl acrylate monomer, 0~8 part of styrene, methyl-prop
0~8 part of e pioic acid methyl ester, 0~8 part of vinylacetate, 2~10 parts of guanidinesalt oligomer polymeric monomer, 0.5~4 part of emulsifying agent, initiator
0.2~2 part, 0.2~2 part of crosslinking agent, 0.1~0.3 part of sodium acid carbonate.
Wherein, described guanidinesalt oligomer polymeric monomer prepares gained by following steps method：Guanidinesalt oligomer is weighed to be dissolved in
The guanidine solution that mass fraction is 20~40% is made into water；Inert gas is then passed to, by guanidine solution and Glycidyl methacrylate
Glyceride (GMA) is with mol ratio 1:1~1:1.2 ratio mixing, is added in reactor, in room temperature and inert gas shielding bar
12~24h of stirring reaction under part, after oil phase is wholly absent, gained is the guanidinesalt oligomer polymeric monomer of carbon-carbon double bonds.
Wherein, described guanidinesalt oligomer is poly (hexamethylene) hydrochloride or hexamethylene, molecule
Measure as 500~1000.
Wherein, described emulsifying agent is hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, octadecyl
At least one of trimethyl ammonium chloride, polysorbate60.
Wherein, described initiator is 2,2'- azo diisobutyl amidines dihydrochloride, the isobutyl imidazoline hydrochloric acid of azo two
One kind in salt, potassium peroxydisulfate, ammonium persulfate.
Wherein, described crosslinking agent be ethylene glycol dimethacrylate, cumyl peroxide, divinylbenzene, N,
At least one of N- methylene-bisacrylamides.
A kind of preparation method of hud typed long acting antibiotic emulsion, includes following operating procedure：
(1) required each component raw material is weighed by portion rate；
(2) stratum nucleare emulsion polymerization：60~80 parts of water, 0.5~4 part of emulsifying agent, Isooctyl acrylate monomer 0 are added in toward reactor
~15 parts, 0~8 part of styrene, 0~8 part of methyl methacrylate, 0~8 part of vinylacetate, 0.2~2 part of crosslinking agent, carbonic acid
After 0.1~0.3 part of hydrogen sodium, 20~60min of stirring, 60~70 DEG C are warming up to, 0.05~0.5 part of initiator initiation reaction is added,
After emulsion blueing, 60~120min is incubated, stratum nucleare emulsion is produced；
(3) shell emulsion is synthesized：On the basis of stratum nucleare emulsion polymerization, temperature is remained 70~80 DEG C, propylene is added dropwise
Sour 0~8 part of N-butyl, isobutyl acrylate 0~10,2~10 parts and 0.15~1.5 part initiator of guanidinesalt oligomer polymeric monomer,
Time for adding is 60~120min, after completion of dropping, and temperature is risen into 81~85 DEG C, is incubated 60~120min, cooling, discharging,
Obtain milky white liquid as product.
The present invention mainly utilizes a kind of antibacterial guanidinesalt oligomer polymeric monomer, and core is prepared by semi-continuous seed emulsion polymerization method
Shell mould long acting antibiotic emulsion.
A kind of antibacterial guanidinesalt oligomer polymeric monomer is as follows：
Wherein：R=poly (hexamethylene) hydrochlorides or hexamethylene, molecular weight are 500~1000.
Compared with prior art, the present invention has the advantages that：
1) a kind of antibacterial guanidinesalt oligomer polymeric monomer is mainly utilized, passes through emulsion polymerization way and acrylate, styrene
Deng monomer copolymerization, antibacterial group is fixed on emulsion macromolecular chain, long acting antibiotic emulsion is prepared, such as styrene-acrylic emulsion overcomes
Physical adds the shortcoming of antiseptic, and the present invention prepares gained emulsion and is difficult to clean and dissolves, with long acting antibiotic effect；Together
When, also with mildew resistance, water resistance, resistance to soiling, solvent resistance, compared with low film formation temperature and storage stability etc..
2) component and structure-controllable of hud typed guanidinesalt styrene-acrylic emulsion of the invention, can be according to needs be applied, by changing
The monomeric species and consumption of latex particle stratum nucleare and shell regulate and control to the component and structure of polymer, are adapted to difference to obtain
The emulsion that applications need.
3) hud typed guanidinesalt styrene-acrylic emulsion preparation technology of the invention is simple and environmentally-friendly, is adapted to industrialized production.
The present invention, as antibacterial functions group, is analyzed, guanidine radicals is main using guanidinesalt, Guanoctine oligomer from molecular structure
Antimicrobial group, guanidinesalt emulsion have higher effective groups density, using the electropositive of functional group attracted effectively it is micro-
Biology carries electronegative cell membrane, makes it lose activity within the very short time, then cell membrane is gradually ruptured, cell
Mass flow goes out lethal thus fool proof to human body；The further guanidinesalt styrene-acrylic emulsion to including Gram-negative bacteria (with large intestine
Bacillus is to represent), gram-positive bacteria (using staphylococcus aureus as representative), the harmful microbe such as mould kill and suppress
Effect is notable.
Brief description of the drawings
Fig. 1 is emulsion particle transmission electron microscope (TEM) figure that legend is 0.5 μm.
Embodiment
The embodiment to the present invention is described in detail below, it is to be understood that protection scope of the present invention is not
Limited by embodiment.GMA methacrylic acids ethylene oxidic ester in the following example, reactor is that four mouthfuls of round bottoms burn
Bottle, have thermometer, dropping funel, condenser pipe and speed-adjustable stir device (thermometer, dropping funel, condenser pipe and speed-adjustable stir device without
Place sequence requirement in position).
Embodiment 1
The preparation of poly (hexamethylene) hydrochloride polymeric monomer (GPHMG)：
Weigh the poly (hexamethylene) hydrochloride 40g that molecular weight is 500 and be dissolved in and be made into mass fraction in 60g deionized waters and be
40% guanidine solution；Logical nitrogen, 11.3g GMA are slowly added dropwise in the guanidine solution, and continuation is stirred at room temperature under nitrogen protection
24h is reacted, until oil phase is wholly absent, that is, is made.
Embodiment 2
The preparation of poly (hexamethylene) hydrochloride polymeric monomer (GPHMG)：
Weigh the poly (hexamethylene) hydrochloride 30g that molecular weight is 700 and be dissolved in and be made into mass fraction in 70g distilled water water and be
30% guanidine solution；Logical argon gas, 6.7g GMA are slowly added dropwise in the guanidine solution, continue to be stirred at room temperature instead under argon gas protection
18h is answered, until oil phase is wholly absent, that is, is made.
Embodiment 3
The preparation of hexamethylene polymeric monomer (GPHMB)：
Weigh the hexamethylene 25g that molecular weight is 800 and be dissolved in and be made into mass fraction in 75g purified waters and be
25% guanidine solution；Helium injection gas, 5.1g GMA are slowly added dropwise in the guanidine solution, continue to be stirred at room temperature instead under helium protection
16h is answered, until oil phase is wholly absent, that is, is made.
Embodiment 4
The preparation of hexamethylene polymeric monomer (GPHMB)：
Weigh the hexamethylene 20g that molecular weight is 1000 and be dissolved in 80g deionized waters and be made into quality point
Number is 20% guanidine solution；Logical nitrogen, 3.4g GMA are slowly added dropwise in the guanidine solution, are continued room temperature under nitrogen protection and are stirred
Reaction 12h is mixed, until oil phase is wholly absent, that is, is made.
Embodiment 5
In units of g, each component raw material needed for weighing：80g deionized waters, 8g styrene, 4g vinylacetates, 6g propylene
Poly (hexamethylene) hydrochloride polymeric monomer, 0.5g emulsifying agent cetyl trimethyl bromines obtained by sour N-butyl, 2g embodiments 1
Change ammonium, 0.15g initiator 2,2'- azo diisobutyl amidines dihydrochloride, 0.2g crosslinking agent ethyleneglycol dimethacrylate
The sodium acid carbonate of ester, 0.1g.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
80g deionized waters, 0.5g emulsifying agents cetyl trimethylammonium bromide, 8g styrene, 4g vinylacetates, 0.2g crosslinking agent second
After diol dimethacrylate, 0.1g sodium acid carbonates, stirring 20min, 65 DEG C are warming up to, 0.05g initiators 2 are added, 2'- is even
After nitrogen diisobutyl amidine dihydrochloride initiation reaction, emulsion blueing, 80min is incubated, stratum nucleare emulsion is produced；
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 70 DEG C in, and 6g acrylic acid then is being added dropwise just
Butyl ester, 2g poly (hexamethylene) hydrochlorides polymeric monomer and 0.15g initiators 2,2'- azo diisobutyl amidine dihydrochlorides are added dropwise
After time is 60min, completion of dropping, temperature is risen to 81 DEG C, 120min is incubated, cooling, discharging, it is 19.8% to obtain solid content
Milky white liquid, as poly- (styrene-co- vinylacetates/poly (hexamethylene) hydrochloride-co- n-butyl acrylates)
(St-co-VAC/GPHMG-co-n-BMA) emulsion.
Embodiment 6
In units of g, each component raw material needed for weighing：74g distilled water, 8g methyl methacrylates, 6g styrene, 6g third
Hexamethylene polymeric monomer, 1.5g emulsifying agent cetyl front threes obtained by olefin(e) acid isobutyl ester, 6g embodiments 3
Ammonium chloride and 0.5g emulsifier tweens 60, the 0.4g isobutyl imidazoline hydrochloride of initiator azo two, 0.6g crosslinking agents second two
Alcohol dimethylacrylate and 0.2g crosslinking agents cumyl peroxide, 0.2g sodium acid carbonate.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
74g distilled water, 1.5g emulsifying agents hexadecyltrimethylammonium chloride and 0.5g emulsifier tweens 60,8g methyl methacrylates,
6g styrene, 0.6g crosslinking agents ethylene glycol dimethacrylate and 0.2g crosslinking agents cumyl peroxide, 0.2g bicarbonates
After sodium, stirring 30min, 60 DEG C are warming up to, the isobutyl imidazoline hydrochloride initiation reaction of 0.4g initiators azo two is added, emulsion is general
Lan Hou, is incubated 120min, produces stratum nucleare emulsion.
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 75 DEG C in, 6g acrylic acid is then added dropwise different
Butyl ester, 6g hexamethylenes polymeric monomer and the isobutyl imidazoline hydrochloride of 0.6g initiators azo two, time for adding
For 100min, after completion of dropping, temperature is risen to 83 DEG C, 100min is incubated, cooling, discharging, it is 25.7% to obtain solid content
Milky white liquid, as poly- (methyl methacrylate-co- styrene/hexamethylene-co- i-butyls
Ester) (MMA-co-St/GPHMB-co-i-BMA) emulsion.
Embodiment 7
In units of g, each component raw material needed for weighing：69g purified waters, 8g vinylacetates, 7g Isooctyl acrylate monomers, 8g
Poly (hexamethylene) hydrochloride polymeric monomer, 2g emulsifying agent octadecyl trimethyls obtained by n-butyl acrylate, 8g embodiments 2
Ammonium chloride and 1g emulsifier tweens 60,0.6g initiator potassium persulfate, 1.2g cross-linker divinylbenzenes, 0.25g carbonic acid
Hydrogen sodium.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
69g purified waters, 2g emulsifying agents OTAC and 1g emulsifier tweens 60,8g vinylacetates, 7g acrylic acid
After different monooctyl ester, 1.2g cross-linker divinylbenzenes, 0.25g sodium acid carbonates, stirring 40min, 70 DEG C are warming up to, 0.6g is added and triggers
After agent potassium peroxydisulfate initiation reaction, emulsion blueing, 60min is incubated, stratum nucleare emulsion is produced.
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 80 DEG C in, and 8g n-butyl acrylates are added dropwise,
8g poly (hexamethylene) hydrochlorides polymeric monomer and 0.6g initiator potassium persulfates, will after time for adding is 80min, completion of dropping
Temperature rises to 85 DEG C, is incubated 60min, cooling, discharging obtain the milky white liquid that solid content is 30.6%, as poly- (acetic acid second
Alkene ester-co- Isooctyl acrylate monomers/poly (hexamethylene) hydrochloride-co- n-butyl acrylates) (VAC-co-EHA/GPHMG-co-
N-BMA) emulsion.
Embodiment 8
In units of g, each component raw material needed for weighing：60g deionized waters, 5g methyl methacrylates, 15g acrylic acid are different
Monooctyl ester, 10g isobutyl acrylates, the hexamethylene polymeric monomer obtained by 10g embodiments 4,2g emulsifying agents ten
Six alkyl trimethyl ammonium bromides, 0.5g emulsifying agents hexadecyltrimethylammonium chloride, 0.5g emulsifying agent octadecyl trimethyl chlorine
Change ammonium and 1g emulsifier tweens 60,0.5g initiator ammonium persulfates, the isobutyl imidazoline hydrochloride of 1.5g initiators azo two, 0.5g
Crosslinking agent ethylene glycol dimethacrylate, 0.2g crosslinking agents cumyl peroxide, 0.3g cross-linker divinylbenzenes, 1g are handed over
Join agent N, N- methylene-bisacrylamide, 0.3g sodium acid carbonate.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
60g deionized waters, 0.5g emulsifying agents hexadecyltrimethylammonium chloride, 0.5g emulsifying agents OTAC and 1g
Emulsifier tween 60,5g methyl methacrylates, 15g Isooctyl acrylate monomers, 0.5g crosslinking agents ethylene glycol dimethacrylate,
0.2g crosslinking agents cumyl peroxide, 0.3g cross-linker divinylbenzenes, 1g crosslinking agents N,N methylene bis acrylamide,
After 0.3g sodium acid carbonates, stirring 60min, 63 DEG C are warming up to, 0.5g initiator ammonium persulfate initiation reactions, emulsion blueing is added
Afterwards, 100min is incubated, stratum nucleare emulsion is produced.
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 72 DEG C in, and 10g i-butyls are added dropwise
Ester, 10g hexamethylenes polymeric monomer and 12g initiator ammonium persulfate solutions (including 1.2g ammonium persulfates), drop
It is after 120min, completion of dropping, temperature to be risen to 82 DEG C, 80min is incubated between added-time, cools down, discharges, obtaining solid content is
40.3% milky white liquid, as poly- (methyl methacrylate-co- Isooctyl acrylate monomers/cosmocil stearate acid
Salt-co- isobutyl acrylates) (MMA-co-EHA/GPHMB-co-i-BMA) emulsion.
Embodiment 9
In units of g, each component raw material needed for weighing：75g deionized waters, 5g vinylacetates, 6g styrene, 8g propylene
Poly (hexamethylene) hydrochloride polymeric monomer, 1g emulsifying agent cetyl trimethyl brominations obtained by sour N-butyl, 6g embodiments 2
Ammonium, 0.5g emulsifier tweens 60,0.1g initiator potassium persulfates, 0.3g initiators 2,2'- azo diisobutyl amidine dihydrochlorides,
0.5g crosslinking agents N,N methylene bis acrylamide, 0.3g crosslinking agent peroxidating diisopropyl, 0.15g sodium acid carbonate.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
75g deionized waters, 1g emulsifying agents cetyl trimethylammonium bromide, 0.5g emulsifier tweens 60,5g vinylacetates, 6g benzene second
Alkene, 0.5g crosslinking agents N, N- methylene-bisacrylamide, 0.3g crosslinking agent peroxidating diisopropyl, 0.15g sodium acid carbonate, stirring
After 30min, 65 DEG C are warming up to, is added after 0.1g initiator potassium persulfate initiation reactions, emulsion blueing, 80min is incubated, produces core
Layer emulsion.
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 75 DEG C in, dropwise addition 8g n-butyl acrylates,
Poly (hexamethylene) hydrochloride polymeric monomer and 0.3g initiator 2,2'- azo diisobutyl amidine disalts obtained by 6g embodiments 2
Hydrochlorate, after time for adding is 60min, completion of dropping, 83 DEG C are risen to by temperature, are incubated 80min, cooling, discharging obtain solid content
For 24.9% milky white liquid, as poly- (vinylacetate-co- styrene/poly (hexamethylene) hydrochloride-co- acrylic acid
N-butyl) (VAC-co-St/GPHMG-co-BMA) emulsion.
Embodiment 10
In units of g, each component raw material needed for weighing：65g deionized waters, 8g Isooctyl acrylate monomers, 8g styrene, 10g
Hexamethylene polymeric monomer, 1g emulsifying agent cetyl front threes obtained by isobutyl acrylate, 9g embodiments 3
Base ammonium bromide, 0.8g emulsifying agents octadecyl ammonium chloride, 1.2g emulsifier tweens 60,0.3g initiator ammonium persulfates, 1g trigger
Agent 2,2'- azo diisobutyl amidine dihydrochlorides, 1g crosslinking agents ethylene glycol dimethacrylate, 0.3g crosslinking agent divinyl
Benzene, 0.5g crosslinking agents N,N methylene bis acrylamide, 0.25g sodium acid carbonate.
(1) stratum nucleare emulsion polymerization：Added toward the reactor equipped with thermometer, dropping funel, condenser pipe and speed-adjustable stir device
65g deionized waters, 1g emulsifying agents cetyl trimethylammonium bromide, 0.8g emulsifying agents octadecyl ammonium chloride, 1.2g emulsifying agents
Polysorbate60,8g Isooctyl acrylate monomers, 8g styrene, 1g crosslinking agents ethylene glycol dimethacrylate, 0.3g crosslinking agent divinyls
After base benzene, 0.5g crosslinking agents N, N- methylene-bisacrylamide, 0.25g sodium acid carbonate, stirring 45min, 62 DEG C are warming up to, plus
Enter after 0.3g initiator ammonium persulfate initiation reactions, emulsion blueing, be incubated 100min, produce stratum nucleare emulsion.
(2) shell emulsion is synthesized：(1) the stratum nucleare emulsion keeping temperature of gained is 77 DEG C in, and 10g i-butyls are added dropwise
Hexamethylene polymeric monomer and 1g initiator 2,2'- azo diisobutyls amidine two obtained by ester, 9g embodiments 3
Hydrochloride, after time for adding is 100min, completion of dropping, 85 DEG C are risen to by temperature, are incubated 60min, cooling, discharging, consolidate
Content is 35.7% milky white liquid, as poly- (Isooctyl acrylate monomer-co- styrene/hexamethylene-
Co- isobutyl acrylates) (EHA-co-St/GPHMB-co-i-BMA) emulsion.
Hud typed long acting antibiotic emulsion property method of testing prepared by the present invention：
1) emulsion appearance：The physical states such as color, state, the uniformity of visual observations sample；
2) solids content (i.e. solid content) is determined：1g emulsions are weighed on surface plate, 1h in 120 DEG C of baking ovens is put into, weighed
After calculate, calculation formula is as follows：
After solids content (%)=baking before weight/baking of resin resin weight × 100%；
3) test of viscosity：4 viscosimeters (Shanghai Ping Xuan scientific instrument Co., Ltd) are applied with NDJ-5 types, temperature 25 is determined
℃；
4) emulsion particle diameter and emulsion Zeta potential are determined：With the Nano-ZS light scattering tools (Britain) of Malvern, use
Emulsion is diluted to 1mg/mL KCl solution by 0.1mM KCl solution, is then measured at room temperature；
5) film forming：A small amount of emulsion is poured on surface plate, film forming is spontaneously dried at room temperature, whether observation film uniform,
Continuously, shrinkage cavity, the transparency of film, slickness and whether tacky are whether there is；
6) Glass Transition Temperature of Latex Tg is determined：Determined with differential scanning calorimeter (DSC), by emulsion film forming at room temperature,
Dsc analysis, 10 DEG C/min of programming rate, -10 DEG C of scanning range~90 DEG C are carried out on U.S.'s production DSC-7 type differential thermal analyzers；
7) emulsion particle form：Samples of latex is diluted with deionized water, and dip-coating uses Japan HITACH on copper mesh after drying
Company JEM-1000 type transmission electron microscope instrument (TEM) is observed and taken a picture；
8) emulsion antibacterial activity is tested：According to《Antibiotic paint》Test is provided in HG/T3950-2007.
Emulsion film prepared by the present invention carries out anti-microbial property test with conventional styrene-acrylic emulsion film, and test bacteria is large intestine
Bacillus and Staphylococcus aureus.Anti-microbial property detection is carried out to 2 kinds of films first, after the completion of test, 24h is carried out to emulsion film
Anti-microbial property test is carried out again after sonic oscillation surface clean repeatedly.
The function admirable of hud typed long acting antibiotic emulsion prepared by above-described embodiment 5~10, referring specifically to such as table 1 below：
Hud typed long acting antibiotic emulsion property made from 1 four embodiments of table
It can be seen that the latex particle average grain diameter of emulsion prepared by embodiment 5~8 is smaller in table 1, be conducive to emulsion long
Phase stable storage, emulsion has obvious electropositive, film performance good, and the glass transition temperature of latex particle is low, is easier to film forming.
The contrast of hud typed long acting antibiotic emulsion anti-microbial property prepared by embodiment 5~10 and conventional styrene-acrylic emulsion, referring to
Such as table 2 below：
Antibacterial styrene-acrylate emulsion film made from 2 four embodiments of table and conventional styrene-acrylic emulsion film antibacterial activity
The above-mentioned analysis result of table 2：
1) product is characterized by transmission electron microscope (TEM) (see accompanying drawing 1) and particle diameter test etc., it can be seen that obtained
Spherical nucleocapsid structure is presented in the latex particle of emulsion, meets product requirement；
2) antibacterial testing result shows, emulsion shows good, long-acting resist to Escherichia coli and Staphylococcus aureus
Bacterium performance.
It is foregoing to the present invention specific illustrative embodiment description be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should
With so that those skilled in the art can realize and using the present invention a variety of exemplaries and
A variety of selections and change.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (5)
1. a kind of hud typed long acting antibiotic emulsion, it is characterised in that include following components raw material according to quality parts ratio：Water 60 ~
80 parts, 0~8 part of n-butyl acrylate, 0~10 part of isobutyl acrylate, 0~15 part of Isooctyl acrylate monomer, 0~8 part of styrene,
0~8 part of methyl methacrylate, 0~8 part of vinylacetate, 2~10 parts of guanidinesalt oligomer polymeric monomer, 0.5~4 part of emulsifying agent,
0.2~2 part of initiator, 0.2~2 part of crosslinking agent, 0.1~0.3 part of sodium acid carbonate；Wherein, described guanidinesalt oligomer polymeric monomer
Gained is prepared by following steps method：Weigh guanidinesalt oligomer and be made into the guanidine solution that mass fraction is 20 ~ 40%；It is passed through indifferent gas
Body, according to the guanidinesalt oligomer that contains in guanidine solution and GMA into mol ratio 1:1~1:1.2 ratio,
Guanidine solution and GMA are mixed, reactor is then added, in room temperature and inert gas shielding condition
12 ~ 24h of lower reaction, gained is guanidinesalt oligomer polymeric monomer；
The preparation method of described hud typed long acting antibiotic emulsion, it is characterised in that include following operating procedure：
（1）Required each component raw material is weighed by portion rate；
（2）Stratum nucleare emulsion polymerization：60 ~ 80 parts of water, 0.5 ~ 4 part of emulsifying agent, Isooctyl acrylate monomer 0~15 are added in toward reactor
Part, 0~8 part of styrene, 0~8 part of methyl methacrylate, 0~8 part of vinylacetate, 0.2 ~ 2 part of crosslinking agent, sodium acid carbonate
0.1 ~ 0.3 part, stir after 20 ~ 60min, be warming up to 60~70 DEG C, add after 0.05 ~ 0.5 part of initiator, emulsion blueing, insulation
60~120min, produces stratum nucleare emulsion；Wherein, the stratum nucleare emulsion monomer is not 0；
（3）Shell emulsion is synthesized：On the basis of stratum nucleare emulsion polymerization, temperature is remained 70~80 DEG C, acrylic acid is being added dropwise just
0~8 part of butyl ester, isobutyl acrylate 0~10,2~10 parts and 0.15 ~ 1.5 part initiator of guanidinesalt oligomer polymeric monomer, during dropwise addition
Between be 80~120min, after completion of dropping, temperature is risen to 81~85 DEG C, 60~120min is incubated, cooling, discharging obtain breast
White liquid is product.
2. hud typed long acting antibiotic emulsion according to claim 1, it is characterised in that：Described guanidinesalt oligomer is poly- six
Methylene guanidine hydrochloride or hexamethylene, molecular weight are 500 ~ 1000.
3. hud typed long acting antibiotic emulsion according to claim 1, it is characterised in that：Described emulsifying agent is cetyl
At least one of trimethyl ammonium chloride, cetyl trimethylammonium bromide, OTAC, polysorbate60.
4. hud typed long acting antibiotic emulsion according to claim 1, it is characterised in that：Described initiator is 2,2'- even
One kind in nitrogen diisobutyl amidine dihydrochloride, the isobutyl imidazoline hydrochloride of azo two, potassium peroxydisulfate, ammonium persulfate.
5. hud typed long acting antibiotic emulsion according to claim 1, it is characterised in that：Described crosslinking agent is ethylene glycol two
At least one of methacrylate, divinylbenzene, N,N methylene bis acrylamide.
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| DE102015219139B4 (en) * | 2015-10-02 | 2017-09-28 | Gebr. Brasseler Gmbh & Co. Kg | Process for the preparation of 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 |
| CN105462416B (en) * | 2015-12-18 | 2018-12-11 | 三棵树涂料股份有限公司 | Anti-graffiti indoor coating aqueous latex paint of health 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 |
| CN111154370B (en) * | 2020-01-15 | 2021-06-08 | 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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| CN101024749A (en) * | 2006-02-17 | 2007-08-29 | 西北师范大学 | Water high-molecular anti-bacteria coating and preparing method thereof |
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