CN104403047B - Silver zinc antibacterial hydrophilic acrylic ester foamed materials and its preparation method and application - Google Patents
Silver zinc antibacterial hydrophilic acrylic ester foamed materials and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of silver zinc antibacterial hydrophilic acrylic ester foamed materials and its preparation method and application, the abscess-size of the foamed materials prepared is small, its averagely suck ionized water rate, average absorption salt ratio, average inhale artificial urine rate, average artificial blood rate of inhaling is all higher than 18g/g, the water retention of 1 hour, all more than 85%, is suitable for dispersion and stores aqueous fluid；It addition, due to the fact that the addition of the silver antibacterial microgranule of zinc, make described foamed materials have good bacteriostasis property, the bacteriostasis rate of escherichia coli and staphylococcus aureus all can be reached more than 95%.Therefore the block flexible absorbent material of the present invention is particularly well-suited to hygiene article sector.
Description
Technical field
The invention belongs to absorbent material field, be specifically related to a kind of silver zinc antibacterial hydrophilic acrylic ester foamed materials and its preparation method and application.
Background technology
Present hygienic article, the absorbent material of the inside mainly has granular synthetic resin, absorbs water, inhales urine or can form gel after sucking blood, the most agglomerating, causes more difficult being fixed on a position, actually used during make us very uncomfortable.Therefore the flexible absorbent material developing bulk has great significance.
Common blood is made up of hemocyte, blood plasma etc..A diameter of about 8 m of hemocyte, and the diameter of acrylic molecules is much smaller than the diameter of hemocyte.The compositions such as therefore hemocyte is difficult to be absorbed by gelatinous super absorbent resin, can only rest on the surface of super absorbent resin, the blood plasma in the simply blood of absorption.So exploitation porous type polymer, to expand specific surface area, improve the aspects such as permeability, the infiltration rate of accelerating liquid and absorbance and there is important technical economic benefit and social benefit.
Applicant has studied a kind of acrylate foamed materials 201410147721.5 with suitable aperture, and it has high water absorption rate and preferably water retention property, may be used for making hygienic article.But hygienic article is by after the humoral pollutions such as urine, easy breed bacteria, causes the problems such as skin allergy.
In view of this, study a kind of hydrophilic acrylic ester foamed materials with bacteriostasis property and can promote this foamed materials using value at hygienic article further.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, it is provided that the preparation method of a kind of antibacterial hydrophilic acrylic ester foamed materials；Acrylate foamed materials prepared by the present invention, except having higher water absorption rate and preferably water retention property, simultaneously because with the addition of the antibacterial microgranule of silver-colored zinc with bacteriostasis, has outstanding bacteriostasis property, promotes this foamed materials using value at hygienic article.
It is a further object to provide the antibacterial hydrophilic acrylic ester foamed materials prepared by preparation method of the present invention.
It is a further object to provide the application in hygienic article of the described antibacterial hydrophilic acrylic ester foamed materials.
The above-mentioned purpose of the present invention is achieved by following technical solution:
The preparation method of silver zinc antibacterial hydrophilic acrylic ester foamed materials, comprises the steps:
S1. oil-based system is prepared: percentage weighs 50%～85% monofunctional acrylate class monomer, 2%～40% cross-linking agent, 5%～the antibacterial microgranule of silver-colored zinc of 10%, 5%～8% emulsifier for mixing mixing；
S2. aqueous phase system is prepared: preparation mass fraction is the electrolyte aqueous solution of 0.01～3%；
S3. dividing aqueous phase system 2～4 times at 60～80 DEG C to add in oil-based system, stir, final aqueous phase is 10～50:1 with the mass ratio of oil phase；
S4. in the mixed system of step S3, add water soluble starter carry out emulsion polymerization；
S5. step S4 gained polymerizate is placed in isothermal curing, washing, dehydrate at 80～100 DEG C and i.e. obtains product；
Described monofunctional acrylate class monomer is simple function alkyl acrylate and the mixture of simple function alkyl methacrylate；Wherein, described simple function alkyl acrylate is 7:1～10:1 with the mass ratio of simple function alkyl methacrylate；
Described cross-linking agent is one or more in multifunctional alkyl acrylate or multifunctional alkyl methacrylate.
The silver antibacterial microgranule of zinc has been applied in the preparation of other field and has the product of bacteria resistance function.And inventor finds, for acrylate expanded material, the interpolation of the silver antibacterial microgranule of zinc can be formed with impact to foaming process abscess.It is thus desirable to the addition etc. of monomer ratio, antibacterial microgranule is adjusted, its is possible to obtain there is higher water absorption rate and preferably water retention property, and there is the acrylate expanded material of bacteriostasis.Inventor finds, if the addition of the silver antibacterial microgranule of zinc is less than 5% in system, is then unable to reach obvious fungistatic effect, meanwhile, if the addition of the silver antibacterial microgranule of zinc is more than 10%, then the abscess-size of product can be caused to diminish, and water suction and water retention property decline.Meanwhile, the mixed proportion of acrylate monomer is controlled, it helps to the abscess-size maintaining antibacterial expanded material so that it is be unlikely to because the addition of the silver antibacterial microgranule of zinc causes water suction and water retention property to decline.
Preferably, described simple function alkyl acrylate is 8:1 with the mass ratio of simple function alkyl methacrylate.
S3. in, aqueous phase and the ratio of oil phase, the size in foaming aperture can be affected equally；Preferably, described aqueous phase is 20 ~ 40:1 with the mass ratio of oil phase.
Add electrolyte and can improve the water absorbing properties of expanded material, and the pliability of material is more preferable, is difficult to split.
Electrolyte of the present invention is this area conventional soluble electrolyte, it is therefore an objective to the salt ionic concentration improving system reduces oil-soluble monomer, the comonomer dissolubility in aqueous phase, it is preferable that described electrolyte is one or more in metal ion compound.
Preferably, the cation of described metal ion compound is potassium ion, sodium ion, calcium ion, magnesium ion, aluminium ion, zinc ion or iron ion, and anion is chloride ion, nitrate ion, borate ion, phosphate anion or carbanion；The ionic compound of above-mentioned cation and anion combination is water insoluble or except being slightly soluble in water.
Preferably, described metal ion compound is calcium chloride, calcium nitrate, aluminum chloride, aluminum nitrate, magnesium chloride, magnesium nitrate, potassium phosphate, sodium phosphate, potassium borate, sodium borate, potassium carbonate or sodium carbonate.Above-mentioned electrolyte comprises strong base-weak acid salt or strong acid soft base salt, and these salt have certain pH value shock-absorbing capacity, is more beneficial for being smoothed out of emulsion polymerization.Additionally, those skilled in the art can get rid of many kinds of metal ions compound according to general knowledge is applied in combination the situation of generation precipitation.
Preferably, described metal ion compound is calcium chloride, calcium nitrate or aluminum chloride.
Preferably, the mass fraction of described electrolyte aqueous solution is 0.5%～1%.
The described silver antibacterial microgranule of zinc is commercially available antibacterial microgranule, and it can be to be loaded with silver and the inorganic antibacterial of zinc, such as products such as An Dimei-AM1, or is loaded with organic antibacterial of silver and zinc.Foaming may be brought unexpected impact in view of organic carrier contained by organic antibacterial, preferably select the inorganic antibacterial being loaded with silver and zinc.
On the one hand the present invention adds the effect of emulsifying agent is to make monomer form emulsion in water, is polymerized offer condition for emulsion, on the other hand, is then to make the silver antibacterial microgranule of zinc spread more evenly across in system.Preferably, described emulsifying agent is poly yamanashi esters emulsifying agent or polyglyceryl fatty acid ester class emulsifying agent.
Preferably, described poly yamanashi esters emulsifying agent is preferably tween 20, Tween-40, Tween-60 or tween 80.
Preferably, described polyglyceryl fatty acid ester class emulsifying agent is polyglycereol stearic acid emulsifying agent.It is highly preferred that described polyglyceryl fatty acid ester class emulsifying agent is-3 pairs of isostearates of polyglycereol.
Use mentioned emulsifier all can reach preferable dispersion effect, and inventor finds, when using-3 pairs of isostearates of polyglycereol as emulsifying agent, the peptizaiton that silver zinc microgranule especially can be played, when selecting-3 pairs of isostearates of polyglycereol as emulsifying agent, unexpectedly, the bacteriostasis property of product is further enhanced.
Preferably, described simple function alkyl acrylate is Isooctyl acrylate monomer, isodecyl acrylate, octadecyl acrylate or lauryl acrylate, and described simple function alkyl methacrylate is 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, octadecyl methacrylate or lauryl methacrylate.
It is further preferred that the mixture that described monofunctional acrylate class monomer is Isooctyl acrylate monomer and 2-Propenoic acid, 2-methyl-, isooctyl ester.
Described multifunctional alkyl acrylate is hexanediol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate or tripropylene glycol diacrylate, and described multifunctional alkyl methacrylate is Ethylene glycol dimethacrylate, TEGDMA, dipropylene or tripropylene glycol dimethylacrylate.
The consumption of the initiator that the present invention uses can select according to this area conventional emulsion polymerization, usually the 0.1%～20% of monomer weight.
The kind of described initiator also can select, such as persulfate initiator, it is preferable that described initiator is Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate according to the kind of this area polymerization monomer.
The present invention is after determining aqueous phase and the final ratio of oil phase, aqueous phase divides in 2～4 addition oil phases, aqueous phase once on adding before emulsion becomes viscous, purpose is that the mode using the multistage to add can be under identical mixing residence time, prepare high aqueous phase and the emulsion of oil phase weight ratio, simultaneously it is also possible that the abscess-size of product is uniform, consistent.Preferably, aqueous phase is divided into 2/3 and 1/3 two parts, first by oil phase and 2/3 aqueous phase mix homogeneously, before emulsion becomes viscous, adds remaining 1/3 aqueous phase mix homogeneously.
It is cured as described in step S5 pouring reacted polymerizate emulsion into mould being put in constant temperature oven and solidifies, controlling the purpose of isothermal curing under the conditions of 80～100 DEG C is to ensure that water does not seethes with excitement while acrylate fast setting allowing, it is to avoid produce pore not of uniform size at material surface.
Washing purpose described in step S5 to be to remove the remaining equal impurity of initial water, described dehydrate is also carried out in constant temperature oven or vacuum drying oven, and dehydrate temperature is 80～100 DEG C.
The antibacterial hydrophilic acrylic ester foamed materials obtained according to above-mentioned preparation method.
The present invention passes through specific formula, and the antibacterial hydrophilic acrylic ester foamed materials using specific preparation method to prepare has certain toughness, and abscess-size is small, has preferably water suction, inhales urine, performance of sucking blood, and the absorbance of material is high；Simultaneously because with the addition of antibacterial microgranule, there is the performance of antibacterial taste removal, have great application prospect in hygiene article sector.Concrete preparation technology flow process is referred to shown in Fig. 1.
The range of cell sizes that the acrylate foamed materials of the present invention has is 10 m to 30 m, so being suitable for dispersion and storing aqueous fluid.Additionally, due to a diameter of about 8 m of human body hemocyte, the diameter of existing acrylic molecules is much smaller than the diameter of hemocyte, thus the acrylate foamed materials of the present invention is particularly suitable for Material Field of sucking blood.
Compared with prior art, there is advantages that
The invention discloses the preparation method of a kind of antibacterial hydrophilic acrylic ester foamed materials, by adding the silver antibacterial microgranule of zinc in oil phase, then compound experiment is carried out, the abscess-size of the foamed materials prepared is small, its averagely suck ionized water rate, average absorption salt ratio, average inhale artificial urine rate, average artificial blood rate of inhaling is all higher than 18g/g, the water retention of 1 hour, all more than 85%, is suitable for dispersion and stores aqueous fluid；It addition, due to the fact that the addition of the silver antibacterial microgranule of zinc, described foamed materials is made to have the bacteriostasis property of excellence, to the bacteriostasis rate of escherichia coli and staphylococcus aureus all up to more than 95%.Therefore the block flexible absorbent material of the present invention is particularly well-suited to hygiene article sector.
Accompanying drawing explanation
Fig. 1 is that antibacterial hydrophilic acrylic ester foamed materials preparation technology flow process is with reference to figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, involved in embodiment reagent, method are reagent commonly used in the art and method.In embodiment, the silver antibacterial microgranule of zinc used is commercially available An Dimei-AM1 antibacterial.
In the present invention as described in GB15979 2002 method detection foamed materials antibacterial effect.
Embodiment
1
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7.2g, 2-Propenoic acid, 2-methyl-, isooctyl ester 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 9:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
2
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 7:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
3
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 12g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.5g, Ethylene glycol dimethacrylate 0.4g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 0.8g, tween 80 0.8g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
4
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 9.6g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 0.8g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
5
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 9.6g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 0.8g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 8g, add water and make it dissolve to 800g, now, the mass fraction of electrolyte is 1%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 530g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 270g aqueous phase in flask, making aqueous phase is 50:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 90 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
6
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 9.6g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 0.8g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.16g, add water and make it dissolve to 160g, now, the mass fraction of electrolyte is 0.1%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 106g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 54g aqueous phase in flask, making aqueous phase is 10:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 90 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
7
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 9.6g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial microgranule of silver-colored zinc of 1.6g, Tween-40 0.8g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Embodiment
8
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 9.6g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial microgranule of silver-colored zinc of 1.6g ,-3 couples of isostearate 0.8g of polyglycereol, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 8:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Comparative example
1
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 6.8g, 2-Propenoic acid, 2-methyl-, isooctyl ester 1.2g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer is 5.7:1 with the mass ratio of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Comparative example
2
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7.4g, 2-Propenoic acid, 2-methyl-, isooctyl ester 0.6g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer and the about 12.3:1 of 2-Propenoic acid, 2-methyl-, isooctyl ester.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Comparative example
3
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7.2g, 2-Propenoic acid, 2-methyl-, isooctyl ester 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 1.6g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer and 2-Propenoic acid, 2-methyl-, isooctyl ester for 9:1.
S2. preparing aqueous phase system, weigh calcium chloride 0.192g, add water and make it dissolve to 960g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 640g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 320g aqueous phase in flask, making aqueous phase is 60:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Comparative example
4
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7.2g, 2-Propenoic acid, 2-methyl-, isooctyl ester 0.8g, Ethylene glycol dimethacrylate 4g, hexanediol diacrylate 0.4g, the antibacterial microgranule of silver-colored zinc of 2.4g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer and 2-Propenoic acid, 2-methyl-, isooctyl ester for 9:1.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
Comparative example
5
S1. oil-based system is prepared, weigh Isooctyl acrylate monomer 7.2g, 2-Propenoic acid, 2-methyl-, isooctyl ester 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.72g, the antibacterial microgranule of silver-colored zinc of 0.48g, tween 80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer and 2-Propenoic acid, 2-methyl-, isooctyl ester for 9:1.
S2. preparing aqueous phase system, weigh calcium chloride 0.096g, add water and make it dissolve to 480g, now, the mass fraction of electrolyte is 0.02%, stand-by；Preparation initiator phase, weighs Ammonium persulfate. 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. prepared aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start stirring, it is warming up to 75 DEG C, mixing speed is more than 800 turns, then the oil phase stirred is added in there-necked flask, before becoming viscous etc. emulsion, then dripping 160g aqueous phase in flask, making aqueous phase is 30:1 with the mass ratio of oil phase；
S4. dropping initiator is in the mixed system of S3, carries out emulsion polymerization, reacted mixed liquor is poured in politef square plate, close the lid, put in 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take drying inside baking oven；Form block acrylate foamed materials.
The soaking effect of product prepared by each embodiment and comparative example is as shown in table 1:
Table 1
。
The fungistatic effect of product prepared by each embodiment and comparative example is as shown in table 2:
Table 2
。
From the comparative example 1 ~ 3 of table 1 it can be seen that mixed proportion monomer, aqueous phase and the ratio of oil phase, the aperture of foamed materials of the present invention is had an impact, thus affects its water absorption rate, salt absorbing rate, urine absorbing rate, rate of sucking blood and water retention property.From table 1 comparative example 4 it can be seen that when the addition of silver zinc microgranule is excessive, the water absorbing properties of foamed materials can be had a strong impact on.From the comparative example 5 of table 2 it can be seen that silver zinc antibacterial microgranule addition is too low, the most not there is fungistatic effect；Although and comparative example 1 ~ 4 all demonstrates stronger biocidal property, but its water absorbing properties is limited, it is difficult to be applied in hygienic article.Use the foamed materials for preparing of technical solutions according to the invention, there is higher water absorption rate and preferably water retention property, demonstrate bacteriostasis property, the requirement of GB15979 sanitary standard can be met.
Claims (9)
1. the preparation method of silver zinc antibacterial hydrophilic acrylic ester foamed materials, it is characterised in that comprise the steps:
S1. prepare oil-based system: percentage weigh 50%～85% monofunctional acrylate class monomer,
The antibacterial microgranule of silver-colored zinc of 2%～40% cross-linking agent, 5%～10%, 5%～8% emulsifier for mixing mixing；
S2. aqueous phase system is prepared: preparation mass fraction is the electrolyte aqueous solution of 0.01～3%；
S3. divide aqueous phase system 2～4 times at 60～80 DEG C to add in oil-based system, stir, final aqueous phase
It is 20～40:1 with the mass ratio of oil phase；
S4. in the mixed system of step S3, add water soluble starter carry out emulsion polymerization；
S5. step S4 gained polymerizate is placed at 80～100 DEG C isothermal curing, washing, dehydrate and get final product
Product；
Described monofunctional acrylate class monomer is simple function alkyl acrylate and simple function methacrylate
The mixture of ester；Wherein, described simple function alkyl acrylate and the quality of simple function alkyl methacrylate
Ratio is 8:1；
Described cross-linking agent is one or more in multifunctional alkyl acrylate or multifunctional alkyl methacrylate.
Preparation method the most according to claim 1, it is characterised in that the quality of described electrolyte aqueous solution is divided
Number is 0.5%～1%.
Preparation method the most according to claim 1, it is characterised in that the described silver antibacterial microgranule of zinc is for being loaded with
Silver and the inorganic antibacterial of zinc.
Preparation method the most according to claim 1, it is characterised in that described emulsifying agent is poly yamanashi esters emulsifying
Agent or polyglyceryl fatty acid ester class emulsifying agent.
Preparation method the most according to claim 1, it is characterised in that described electrolyte is metal ion compound
In one or more, the cation of described metal ion compound is potassium ion, sodium ion, calcium ion, magnesium
Ion, aluminium ion, zinc ion or iron ion, anion be chloride ion, nitrate ion, borate ion,
Phosphate anion or carbanion.
Preparation method the most according to claim 1, it is characterised in that described simple function alkyl acrylate is third
The different monooctyl ester of olefin(e) acid, isodecyl acrylate, octadecyl acrylate or lauryl acrylate, described simple function first
Base alkyl acrylate is 2-Propenoic acid, 2-methyl-, isooctyl ester, isodecyl methacrylate, methacrylic acid octadecyl
Ester or lauryl methacrylate；
Described multifunctional alkyl acrylate is hexanediol diacrylate, triethylene glycol diacrylate, dipropylene glycol
Diacrylate or tripropylene glycol diacrylate, described multifunctional alkyl methacrylate is dimethyl allene
Acid glycol ester, TEGDMA, dipropylene or tripropylene glycol two
Methacrylate.
Preparation method the most according to claim 1, it is characterised in that described water soluble starter be Ammonium persulfate.,
Sodium peroxydisulfate or potassium peroxydisulfate.
8. the antibacterial hydrophilic acrylic of silver-colored zinc that preparation method described in claim 1 to 7 arbitrarily claim prepares
Ester foamed materials.
9. silver zinc antibacterial hydrophilic acrylic ester foamed materials application in preparing hygienic article described in claim 8.
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| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
| CN101812153A (en) * | 2010-04-21 | 2010-08-25 | 浙江顺虎德邦涂料有限公司 | Waterborne antibacterial styrene-acrylate emulsion and preparation method thereof |
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| DE10022406A1 (en) * | 2000-05-09 | 2001-11-15 | Creavis Tech & Innovation Gmbh | New antimicrobial copolymers used for disinfection of water or production of microbicidal coatings, obtained by copolymerisation of amino-functional acrylate or acrylamide with non-functionalised monomers |
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| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
| CN101812153A (en) * | 2010-04-21 | 2010-08-25 | 浙江顺虎德邦涂料有限公司 | Waterborne antibacterial styrene-acrylate emulsion and preparation method thereof |
| CN103936918A (en) * | 2014-04-14 | 2014-07-23 | 广东联塑科技实业有限公司 | Water-absorbing acrylate foam material and preparation method and application thereof |
| CN104164204A (en) * | 2014-08-07 | 2014-11-26 | 深圳市顾康力化工有限公司 | Mildew-proof anti-bacterial white latex and preparation method thereof |
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