CN104448115A - Air-permeable and water-absorbent acrylate foam material with silver and zinc anti-bacteria particles, as well as preparation method and application of anti-bacteria air-permeable water-absorbent acrylate foam material - Google Patents
Air-permeable and water-absorbent acrylate foam material with silver and zinc anti-bacteria particles, as well as preparation method and application of anti-bacteria air-permeable water-absorbent acrylate foam material Download PDFInfo
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Abstract
The invention discloses an air-permeable and water-absorbent acrylate foam material with silver and zinc anti-bacteria particles, as well as a preparation method and application of the air-permeable and water-absorbent acrylate foam material. The size of foam cells of the prepared foam material is tiny, the average deionized water absorption rate, the average brine absorption rate, the average artificial urine absorption rate and the average artificial blood absorption rate are all larger than 18g/g, the water retention rate in an hour is more than 85%, and the acrylate foam material is suitable for dispersing and storing fluids containing water; additionally, due to addition of the silver and zinc anti-bacteria particles, the manufactured foam material has good anti-bacteria performance, and the anti-bacterial rate of escherichia coli and staphylococcus aureus are both more than 95%; due to addition of light calcium carbonate, the air penetration amount is larger than 1.5*10-2cm3/(m2*Pa*d), which shows good air permeability. Therefore, the block-shaped soft water-absorbent material is especially suitable for the field of toilet articles.
Description
Technical field
The invention belongs to water-absorbing material field, be specifically related to antibacterial ventilative water suction acrylate foam materials of a kind of silver-colored zinc and its preparation method and application.
Background technology
Present sanitary product, the water-absorbing material of the inside mainly has granular synthetic resins, water suction, inhales urine or can form gel after sucking blood, easily agglomerating, causes more difficultly being fixed on a position, makes us very uncomfortable in actual use procedure.Therefore develop block flexible absorbent material to have great significance.
Common blood is made up of hemocyte, blood plasma etc.The diameter of hemocyte is about 8 μm, and the diameter of acrylic molecules is much smaller than the diameter of hemocyte.Therefore hemocyte not easily absorb by gelatinous super absorbent resin, the surface of super absorbent resin can only be rested on, the compositions such as the blood plasma in the just blood of absorption.So exploitation multi-hole type polymkeric substance, to expand specific surface area, improve perviousness, the aspects such as the absorption rate of accelerating liquid and specific absorption have important technical economic benefit and social benefit.
Applicant have studied a kind of acrylate foam materials 201410147721.5 with suitable aperture, and it has high water-intake rate and preferably water retention property, may be used for making sanitary product.But sanitary product is by after the humoral pollutions such as urine, easy breed bacteria, easily causes the problems such as allergic; In addition, because ventilation property is not enough, the problem of skin pruritus is easily caused too.
In view of this, study a kind of water suction acrylate foam materials with bacteriostasis property and excellent air permeability and can promote the using value of this foam materials at sanitary product further.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of preparation method of antibacterial ventilative water suction acrylate foam materials is provided; Acrylate foam materials prepared by the present invention is except having higher water-intake rate and preferably water retention property, simultaneously owing to the addition of the antibacterial ventilative particulate of the silver-colored zinc with bacteriostatic action, there is outstanding bacteriostasis property, and there is preferably ventilation property, the using value of this foam materials at sanitary product can be promoted.
Another object of the present invention is to provide the antibacterial ventilative water suction acrylate foam materials prepared by preparation method of the present invention.
Another object of the present invention is to provide the application of described antibacterial ventilative water suction acrylate foam materials in sanitary product.
Above-mentioned purpose of the present invention is achieved by following technical solution:
The preparation method of the antibacterial ventilative water suction acrylate foam materials of silver zinc, comprises the steps:
S1. prepare oil-based system: percentage take 50% ~ 85% monofunctional acrylate class monomer, 2% ~ 40% linking agent, 5% ~ 10% the antibacterial ventilative particulate of silver-colored zinc, 5% ~ 8% emulsifier for mixing mixing;
S2. aqueous phase system is prepared: preparation massfraction is the aqueous electrolyte liquid of 0.01 ~ 3%;
S3. at 60 ~ 80 DEG C, aqueous phase system is divided and add in oil-based system for 2 ~ 4 times, and when oil-based system adds aqueous phase first, in system, add the light calcium carbonate relative to oil-based system weight 1 ~ 3%; Stir, the mass ratio of final aqueous phase and oil phase is 10 ~ 50:1;
S4. in the mixed system of step S3, add water soluble starter and carry out emulsion polymerization;
S5. isothermal curing at step S4 gained polymerisate being placed in 80 ~ 100 DEG C, wash, dehydrate and obtain product;
Described monofunctional acrylate class monomer is the mixture of simple function alkyl acrylate and simple function alkyl methacrylate; Wherein, the mass ratio of described simple function alkyl acrylate and simple function alkyl methacrylate is 7:1 ~ 10:1;
Described linking agent is one or more in multifunctional alkyl acrylate or multifunctional alkyl methacrylate.
The antibacterial particulate of silver zinc has been used in the product that the preparation of other field has bacteria resistance function.And contriver finds, for acrylate foam material, the interpolation of the antibacterial particulate of silver-colored zinc can be formed with impact to foaming process abscess.Therefore need to regulate the addition etc. of monomer ratio, antibacterial particulate, just likely obtain and there is higher water-intake rate and preferably water retention property, and there is the acrylate foam material of bacteriostatic action.Contriver finds, if the addition of the antibacterial ventilative particulate of silver-colored zinc is less than 5% in system, then cannot reach obvious fungistatic effect, simultaneously, if the addition of the antibacterial ventilative particulate of silver-colored zinc is greater than 10%, then the abscess-size of product can be caused to diminish, water suction and water retention property decline.Meanwhile, controlling the blending ratio of acrylate monomer, also contributing to the abscess-size to maintaining antibacterial foam material, make it be unlikely to because adding of the antibacterial ventilative particulate of silver-colored zinc causes water suction and water retention property to decline.
Adding of light calcium carbonate, also can there is impact to foaming effect, if but the addition of light calcium carbonate is very few, then can not reach the object improving permeability.Through contriver's research, under relative to oil phase weight 1 ~ 3% ratio, add light calcium carbonate, the object significantly improving permeability can be reached.
Preferably, the mass ratio of described simple function alkyl acrylate and simple function alkyl methacrylate is 8:1.
S3., in, the ratio of aqueous phase and oil phase, can affect the size in foaming aperture equally; Preferably, the mass ratio of described aqueous phase and oil phase is 20 ~ 40:1.
Add the water absorbing properties that ionogen can improve foam material, and the snappiness of material is better, not easily splits.
Ionogen of the present invention is this area conventional soluble ionogen, and object is that the salt ionic concentration of raising system reduces oil-soluble monomer, the comonomer solubleness in aqueous phase, and preferably, described ionogen is one or more in metal ion compound.
Preferably, the positively charged ion of described metal ion compound is potassium ion, sodium ion, calcium ion, magnesium ion, aluminum ion, zine ion or iron ion, and negatively charged ion is chlorion, nitrate ion, borate ion, phosphate anion or carbanion; The ionic compound of above-mentioned positively charged ion and negatively charged ion combination is water insoluble or be slightly soluble in except water.
Preferably, described metal ion compound is calcium chloride, nitrocalcite, aluminum chloride, aluminum nitrate, magnesium chloride, magnesium nitrate, potassiumphosphate, sodium phosphate, potassium borate, Sodium Tetraborate, salt of wormwood or sodium carbonate.Above-mentioned ionogen comprises strong base-weak acid salt or strong acid soft base salt, and these salt have certain pH value shock-absorbing capacity, is more conducive to carrying out smoothly of letex polymerization.In addition, those skilled in the art can get rid of according to general knowledge the situation that many kinds of metal ions compound combination uses generation precipitation.
Preferably, described metal ion compound is calcium chloride, nitrocalcite or aluminum chloride.
Preferably, the massfraction of described aqueous electrolyte liquid is 0.5% ~ 1%.
The antibacterial particulate of described silver-colored zinc is commercially available antibacterial particulate, and it can be the inorganic fungistat of negative Ag-bearing and zinc, as products such as An Dimei-AM1, or organic fungistat of negative Ag-bearing and zinc.Consider that organic carrier contained by organic fungistat may bring unexpected impact to foaming, preferably select the inorganic fungistat of negative Ag-bearing and zinc.
Described light calcium carbonate can be any one or a few in particulate calcium carbonate, micro mist calcium carbonate, fine calcium carbonate, calcium carbonate superfine powder or super fine calcium carbonate, and their classification is according to its original median size.Preferably, described light calcium carbonate be, micro mist calcium carbonate or fine calcium carbonate.These two kinds have better dispersion effect in system of the present invention.
The effect that the present invention adds emulsifying agent is on the one hand make monomer form emulsion in water, for letex polymerization provides condition, on the other hand, be then in order to make the antibacterial particulate of silver-colored zinc, light calcium carbonate is more uniformly dispersed in system.Preferably, described emulsifying agent is poly yamanashi esters emulsifying agent or polyglycerol 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 polyglycerol fatty acid ester class emulsifying agent is Polyglycerine stearic acid emulsifying agent.More preferably, described polyglycerol fatty acid ester class emulsifying agent is Polyglycerine-3 pairs of isostearates.
Adopt mentioned emulsifier all can reach good dispersion effect, and contriver finds, when adopting Polyglycerine-3 pairs of isostearates as emulsifying agent, to the dissemination that silver-colored zinc particulate, light calcium carbonate especially can play, when selecting Polyglycerine-3 pairs of isostearates 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 Isooctyl methacrylate, isodecyl methacrylate, octadecyl methacrylate or lauryl methacrylate(LMA).
Further preferably, described monofunctional acrylate class monomer is the mixture of Isooctyl acrylate monomer and Isooctyl methacrylate.
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 dimethacrylate.
The consumption of the initiator that the present invention uses can be selected according to this area conventional emulsion polymerization, is generally 0.1% ~ 20% of monomer weight.
The kind of described initiator also can be selected according to the kind of this area polymerization single polymerization monomer, and as persulfate initiator, preferably, described initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
The present invention is after determining aqueous phase and the final ratio of oil phase, aqueous phase divides 2 ~ 4 times to add in oil phase, emulsion become sticky thick before add aqueous phase once again, object is that the mode adopting the multistage to add can under identical mixing residence time, the emulsion of obtained high aqueous phase and oil phase weight ratio, can also make the abscess-size of product evenly, unanimously simultaneously.Preferably, aqueous phase is divided into 2/3 and 1/3 two portions, first oil phase is mixed with 2/3 aqueous phase, emulsion become sticky thick before add 1/3 remaining aqueous phase again and mix.In order to make light calcium carbonate mix better, select when oil-based system adds aqueous phase first, light calcium carbonate adds in aqueous phase with oil phase simultaneously.
Be cured as reacted polymerisate emulsion to pour in mould described in step S5 and put into constant temperature oven and solidify, controlling the object of isothermal curing under 80 ~ 100 DEG C of conditions is allowing acrylate quick-setting guarantee simultaneously water not seethe with excitement, avoiding producing pore not of uniform size at material surface.
Wash object described in step S5 to be to remove the remaining equal impurity of initial water, described in dehydrate and also carry out in constant temperature oven or vacuum drying oven, dehydrating temperature is 80 ~ 100 DEG C.
According to the antibacterial ventilative water suction acrylate foam materials that above-mentioned preparation method obtains.
The present invention is by specific formula, and the antibacterial ventilative water suction acrylate foam materials adopting specific preparation method to obtain has certain toughness, and abscess-size is small, and have good water suction, inhale urine, performance of sucking blood, the specific absorption of material is high; Simultaneously owing to the addition of antibacterial particulate, there is the performance of antibacterial taste removal, and there is good ventilation property, have great application prospect in hygiene article sector.Concrete preparation technology's flow process can shown in reference drawing 1.
The range of cell sizes that acrylate foam materials of the present invention has is 10 μm to 30 μm, so be applicable to dispersion and store aqueous fluid.In addition, the diameter due to human body hemocyte is about 8 μm, and the diameter of existing acrylic molecules is much smaller than the diameter of hemocyte, and thus acrylate foam materials of the present invention is particularly suitable for Material Field of sucking blood.
Compared with prior art, the present invention has following beneficial effect:
The invention discloses a kind of preparation method of antibacterial water suction acrylate foam materials, by adding the antibacterial particulate of silver-colored zinc in oil phase, then compound experiment is carried out, the abscess-size of the foam materials prepared is small, it on average sucks ionized water rate, average absorption salt ratio, the on average artificial urine rate of suction, on average suction artificial blood rate are all greater than 18g/g, the water retention of 1 hour, all more than 85%, is suitable for dispersion and stores aqueous fluid; In addition, the present invention adds due to the antibacterial particulate of silver-colored zinc, makes described foam materials have excellent bacteriostasis property, all can reach more than 95% to the bacteriostasis rate of intestinal bacteria and staphylococcus aureus.; Also be added with light calcium carbonate in system of the present invention simultaneously, substantially improve the permeability of product.Therefore block flexible absorbent material of the present invention is specially adapted to hygiene article sector.
Accompanying drawing explanation
Fig. 1 is antibacterial water suction acrylate foam materials preparation technology flow process reference drawing.
Embodiment
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 the conventional reagent in this area and method.In embodiment, the antibacterial particulate of silver-colored zinc used is commercially available An Dimei-AM1 antiseptic-germicide.Light calcium carbonate used is fine calcium carbonate.
The antibacterial effect that the method recorded in GB15979-2002 detects foam materials is pressed in the present invention.
In the present invention, gas-premeable test adopts GB1038-2000 plastics film and thin slice gas-premeable test method.
embodiment 1
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 2
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7g, Isooctyl methacrylate 1g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 7:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 3
S1. oil-based system is prepared, take Isooctyl acrylate monomer 12g, Isooctyl methacrylate 1.5g, Ethylene glycol dimethacrylate 0.4g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 0.8g, tween-80 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 4
S1. oil-based system is prepared, take Isooctyl acrylate monomer 9.6g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 80 DEG C of baking ovens 1 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 5
S1. oil-based system is prepared, take Isooctyl acrylate monomer 9.6g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 8g, then add water to 800g and make it dissolve, now, the massfraction of electrolytic solution is 1%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 530g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 270g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 50:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 90 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 6
S1. oil-based system is prepared, take Isooctyl acrylate monomer 9.6g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 0.16g, then add water to 160g and make it dissolve, now, the massfraction of electrolytic solution is 0.1%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 106g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 54g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 10:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 90 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 7
S1. oil-based system is prepared, take Isooctyl acrylate monomer 9.6g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial particulate of silver-colored zinc of 1.6g, Tween-40 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
embodiment 8
S1. oil-based system is prepared, take Isooctyl acrylate monomer 9.6g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 2.2g, hexanediol diacrylate 0.8g, the antibacterial particulate of silver-colored zinc of 1.6g, Polyglycerine-3 couples of isostearate 0.8g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 8:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
comparative example 1
S1. oil-based system is prepared, take Isooctyl acrylate monomer 6.8g, Isooctyl methacrylate 1.2g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 5.7:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
comparative example 2
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.4g, Isooctyl methacrylate 0.6g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, Isooctyl acrylate monomer and Isooctyl methacrylate be about 12.3:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
comparative example 3
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, that Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.192g, then add water to 960g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 640g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 320g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 60:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
comparative example 4
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 2.4g, tween-80 1.2g, oil phase is stirred stand-by, wherein, that Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
comparative example 5
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.72g, the antibacterial particulate of silver-colored zinc of 0.48g, tween-80 1.2g, oil phase is stirred stand-by, wherein, that Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 0.32g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
Comparative example 6
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred is added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam materials.
Comparative example 7
S1. oil-based system is prepared, take Isooctyl acrylate monomer 7.2g, Isooctyl methacrylate 0.8g, Ethylene glycol dimethacrylate 4.8g, hexanediol diacrylate 0.4g, the antibacterial particulate of silver-colored zinc of 1.6g, tween-80 1.2g, oil phase is stirred stand-by, wherein, the mass ratio of Isooctyl acrylate monomer and Isooctyl methacrylate is 9:1.
S2. prepare aqueous phase system, take calcium chloride 0.096g, then add water to 480g and make it dissolve, now, the massfraction of electrolytic solution is 0.02%, stand-by; Preparation initiator phase, takes ammonium persulphate 1.71g, adds water to 10g and make it dissolve, stand-by.
S3. obtained aqueous phase 320g is proceeded in the there-necked flask of 1000ml, start to stir, be warming up to 75 DEG C, stirring velocity is more than 800 turns, then the oil phase stirred and 1.6g light calcium carbonate are added in there-necked flask, etc. emulsion become sticky thick before, then drip 160g aqueous phase in flask, make the mass ratio of aqueous phase and oil phase be 30:1;
S4. drip initiator in the mixed system of S3, carry out emulsion polymerization, reacted mixed solution is poured in tetrafluoroethylene square plate, cover lid, puts into 97 DEG C of baking ovens 0.5 hour, after forming and hardening, take out extruding and washing, then take inside baking oven and dry; Form block acrylate foam 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, ventilation property are as shown in table 2:
Table 2
As can be seen from the comparative example 1 ~ 3 of table 1, the ratio of the blending ratio in monomer, aqueous phase and oil phase, has impact to the aperture of foam materials of the present invention, thus affects its water-intake rate, salt absorbing rate, urine absorbing rate, rate of sucking blood and water retention property.As can be seen from table 1 comparative example 4, when the add-on of silver-colored zinc particulate is excessive, the water absorbing properties of foam materials can be had a strong impact on.As can be seen from the comparative example 5 of table 2, silver-colored zinc antibacterial particulate addition is too low, then do not have fungistatic effect; Although and comparative example 1 ~ 4 all demonstrates stronger biocidal property, its water absorbing properties is limited, be difficult to be applied in sanitary product.As can be seen from comparative example 6, add after light calcium carbonate, the permeability of acrylate foam be improved significantly.As can be seen from comparative example 7, when the add-on of light calcium carbonate is too high, although permeability increases, water absorbing properties suffers obvious destruction.Adopt the foam materials for preparing of technical solutions according to the invention, there is higher water-intake rate and preferably water retention property, demonstrate bacteriostasis property, the requirement of GB15979 hygienic standard can be met.
Claims (10)
1. the preparation method of the antibacterial ventilative water suction acrylate foam materials of silver zinc, is characterized in that, comprise the steps:
S1. prepare oil-based system: percentage take 50% ~ 85% monofunctional acrylate class monomer, 2% ~ 40% linking agent, 5% ~ 10% the antibacterial particulate of silver-colored zinc, 5% ~ 8% emulsifier for mixing mixing;
S2. aqueous phase system is prepared: preparation massfraction is the aqueous electrolyte liquid of 0.01 ~ 3%;
S3. at 60 ~ 80 DEG C, aqueous phase system is divided and add in oil-based system for 2 ~ 4 times, and when oil-based system adds aqueous phase first, in system, add the light calcium carbonate relative to oil-based system weight 1 ~ 3%; Stir, the mass ratio of final aqueous phase and oil phase is 10 ~ 50:1;
S4. in the mixed system of step S3, add water soluble starter and carry out emulsion polymerization;
S5. isothermal curing at step S4 gained polymerisate being placed in 80 ~ 100 DEG C, wash, dehydrate and obtain product;
Described monofunctional acrylate class monomer is the mixture of simple function alkyl acrylate and simple function alkyl methacrylate; Wherein, the mass ratio of described simple function alkyl acrylate and simple function alkyl methacrylate is 7:1 ~ 10:1;
Described linking agent is one or more in multifunctional alkyl acrylate or multifunctional alkyl methacrylate.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described simple function alkyl acrylate and simple function alkyl methacrylate is 8:1.
3. preparation method according to claim 1 and 2, is characterized in that, the massfraction of described aqueous electrolyte liquid is 0.5% ~ 1%.
4. preparation method according to claim 1, is characterized in that, the antibacterial particulate of described silver-colored zinc is the inorganic fungistat of negative Ag-bearing and zinc.
5. preparation method according to claim 1, it is characterized in that, described emulsifying agent is poly yamanashi esters emulsifying agent or polyglycerol fatty acid ester class emulsifying agent.
6. preparation method according to claim 1 or 2, it is characterized in that, described ionogen is one or more in metal ion compound, the positively charged ion of described metal ion compound is potassium ion, sodium ion, calcium ion, magnesium ion, aluminum ion, zine ion or iron ion, and negatively charged ion is chlorion, nitrate ion, borate ion, phosphate anion or carbanion.
7. preparation method according to claim 1 or 2, it is characterized in that, described simple function alkyl acrylate is Isooctyl acrylate monomer, isodecyl acrylate, octadecyl acrylate or lauryl acrylate, and described simple function alkyl methacrylate is Isooctyl methacrylate, isodecyl methacrylate, octadecyl methacrylate or lauryl methacrylate(LMA);
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 dimethacrylate.
8. preparation method according to claim 1 or 2, is characterized in that, described water soluble starter is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
9. claim 1 to the 8 antibacterial ventilative water suction acrylate foam materials of silver-colored zinc that described in claim, preparation method prepares arbitrarily.
10. the application in sanitary product prepared by the antibacterial ventilative water suction acrylate foam materials of silver-colored zinc described in claim 9.
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| US6245697B1 (en) * | 1998-11-12 | 2001-06-12 | The Procter & Gamble Company | Flexible mat for absorbing liquids comprising polymeric foam materials |
| US6362244B1 (en) * | 1999-02-22 | 2002-03-26 | The Procter & Gamble Company | Method for degassification of high internal phase emulsion components |
| CN1498242A (en) * | 2000-10-10 | 2004-05-19 | Preparation of foam materials from high internal phase amulsion | |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6245697B1 (en) * | 1998-11-12 | 2001-06-12 | The Procter & Gamble Company | Flexible mat for absorbing liquids comprising polymeric foam materials |
| US6362244B1 (en) * | 1999-02-22 | 2002-03-26 | The Procter & Gamble Company | Method for degassification of high internal phase emulsion components |
| CN1498242A (en) * | 2000-10-10 | 2004-05-19 | Preparation of foam materials from high internal phase amulsion | |
| 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 |
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