CN103263877B - A kind of preparation method of microcapsules of Silica-coated essential oil - Google Patents
A kind of preparation method of microcapsules of Silica-coated essential oil Download PDFInfo
- Publication number
- CN103263877B CN103263877B CN201310186523.5A CN201310186523A CN103263877B CN 103263877 B CN103263877 B CN 103263877B CN 201310186523 A CN201310186523 A CN 201310186523A CN 103263877 B CN103263877 B CN 103263877B
- Authority
- CN
- China
- Prior art keywords
- silica
- essential oil
- microcapsules
- preparation
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a kind of preparation method of microcapsules of Silica-coated essential oil, comprising: essential oil, silica precursor and assistant for emulsifying agent are mixed, obtain oil phase mixed liquor; In the aqueous dispersions of silica, add acid for adjusting pH to 4.5 ~ 5.7, then mix with oil phase mixed liquor, obtain fine crankshaft liquid through ultrasonic disperse; By fine crankshaft liquid at 10 DEG C ~ 60 DEG C capping 1h ~ 6h, obtain the colloid emulsion of the microcapsules of Silica-coated essential oil.Liquid essential oil is wrapped in the hard shell of silica by preparation method of the present invention, preparation process is quick and convenient, cleanliness without any pollution, the microcapsule granule size of Silica-coated essential oil is little, structural strength is high, good dispersion in aqueous phase, microcapsules to wrap up the release performance adjustable extent of essential oil large.Preparation method of the present invention is suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to the preparation field of microcapsules in field of fine chemical, be specifically related to a kind of preparation method of microcapsules of Silica-coated essential oil.
Background technology
Essential oil has skin nourishment, pacifies agitation, improving water flood, stimulate circulation, strengthen the effects such as function immunity, when essential oil is used for the Aroma finishing of the grade textiles such as silk, can give the fabrics such as underwear, pillow cover, nightwear, necktie to calm the nerves, calmness, the health-care efficacy such as hypnosis, even physiotherapy.
But due to the oily matter that most essential oil is all liquid at normal temperatures, and high volatility, oxidizable in atmosphere.Thus directly use natural essential oil to have many problems, the essential oil mobility as liquid state is difficult to too by force processing and uses; Liquid essential oil property compatible with water is poor, although under the emulsification of a large amount of emulsifying agent, Absorbable organic halogens is scattered in aqueous phase, and inconvenience is attached to the target matrix such as fabric further, and the essential oil droplets specific area after emulsification enlarges markedly, more volatile and oxidation deterioration.
By the material such as organic polymer, inorganic particle parcel essential oil droplets, make essential oil microcapsules, then can improve the problems referred to above.The many merits such as with inorganic silicon dioxide be wherein that microcapsules prepared by wall material have capsule size and wall equipment structure controllability is strong, essential oil rate of release adjustable range is large, good biocompatibility, pollution are little.Such as publication number is the preparation method that the Chinese invention patent application of CN101259399A discloses a kind of method for preparing inorganic nano microcapsule by one-step, comprise: emulsifying agent, pH adjusting agent are dissolved in the water, obtaining pH value is the emulsifying agent of 3 ~ 13 and the mixed solution of pH adjusting agent; Monomer, small molecule hydrocarbon template compound and co-stabilizer are mixed, joins in mixed solution, with ultrasonic wave dispersion, obtain stable miniemulsion; Miniemulsion temperature is adjusted to 30 DEG C ~ 80 DEG C, reacts after 3 hours ~ 5 days, obtain that inorganic compound is shell, small molecule hydrocarbon is the inorganic nano microcapsule of core.Above-mentioned product take small molecule hydrocarbon as core, is single shell material with the nanometer silicon dioxide particle that the condensation of silica precursor TEOS mono-one-step hydrolysis generates, and the sandwich construction of shell can ensure microcapsules inner material and extraneous controlled exchange.But by all SiO in the inorganic microcapsules product that above-mentioned one-step method is obtained
2shell is produced by TEOS hydrolytic condensation completely.Therefore, there is the shortcomings such as preparation time length, severe reaction conditions, structural strength are good not in the method.
In the physics composite algorithm preparation of microcapsules, mainly use physisorption and content fast, is controllably wrapped in coating material.Wherein, pik woods Emulsification effect (Pickering Emulsification effect) is a kind of typical effect mechanism comparatively commonly used.This effect refer to granule have all the time automatic absorbing to large particle surface thus effectively reduce whole system total surface can trend.Although application Pickering Emulsification effect prepares microcapsules have the advantages such as speed is fast, stable system, but it is still a kind of physics compound action with Dynamic Adsorption balance characteristics in essence, granule and adsorbed between large scale material and lack enough mutual cementations, therefore, pik woods Emulsification effect is comparatively subject to the change of external environment and lost efficacy.
Summary of the invention
The invention provides a kind of preparation method of microcapsules of Silica-coated essential oil, liquid essential oil is wrapped in the hard shell of silica, preparation process is quick and convenient, the microcapsule granule size of Silica-coated essential oil is little, structural strength is high, good dispersion in aqueous phase, microcapsules to wrap up the release performance adjustable extent of essential oil large.
A preparation method for the microcapsules of Silica-coated essential oil, comprises the following steps:
(1) essential oil, silica precursor and assistant for emulsifying agent are mixed, obtain oil phase mixed liquor;
(2) in the aqueous dispersions of silica, add acid for adjusting pH to 4.5 ~ 5.7, then mix with the oil phase mixed liquor of step (1), obtain fine crankshaft liquid through ultrasonic disperse;
(3) by the fine crankshaft liquid in step (2) at 10 DEG C ~ 60 DEG C capping 1h ~ 6h, obtain the colloid emulsion of the microcapsules of Silica-coated essential oil.
The colloid emulsion of the microcapsules of Silica-coated essential oil can obtain the microcapsules of Silica-coated essential oil after breakdown of emulsion, suction filtration, drying.
The present invention in conjunction with Pickering physical absorption and original position Interface debond technology, rapid build inorganic hard shell, thus realize liquid towards essential oil small size microencapsulation parcel.The microcapsules of the Silica-coated essential oil obtained are inorganic hard shell with inorganic silicon dioxide, take essential oil as core.Specifically with essential oil sub-micro drop for core template, the silica granule being first adsorbed in essential oil droplets surface with Pickering effect is the skeleton particle of inorganic shell, then with the SiO that oil-water interfaces place silica precursor hydrolysis-condensation reaction produces
2material is the binding agent between above-mentioned skeleton particle.The SiO that in the aqueous dispersions of final silica, silica dioxide granule and silica precursor hydrolysis-condensation reaction produce
2form the continuous inorganic shell with better compactness extent and structural strength, thus finally realize the effective parcel to essential oil droplets.
In step (1), described essential oil can select existing essential oil on market as required, is preferably sandalwood essential oil, olive essential oil, Rosemary Oil, Rosa Damascana or cinnamon essential oil.Above-mentioned essential oil odor type is stable, effect is obvious, lipophile is strong and be widely used, and is modal commercialization plants essential oil.
These essential oils can with silica precursor with arbitrarily than miscible, thus easily form the homogeneous mixture of essential oil and silica precursor, under the homeo-osmosis effect of assistant for emulsifying agent, be dispersed in uniformly and stably in the aqueous phase system containing silica dioxide granule with sub-micro drops after ultrasonic disperse, thus form fine crankshaft liquid.
Silica precursor is used for the SiO produced at oil-water interfaces place hydrolysis-condensation reaction
2as the intergranular binding agent of framework silica, thus form compactness extent and the good solid-state hard shell of silica of structural strength, as preferably, described silica precursor is ethyl orthosilicate (hereinafter referred to as TEOS), and ethyl orthosilicate can produce SiO at oil-water interfaces place hydrolysis-condensation reaction
2, be conducive to obtaining compactness extent and the better silicon oxide hard shell of structural strength.
Described assistant for emulsifying agent plays the effect of homeo-osmosis, and as preferably, described assistant for emulsifying agent is hexadecane, and further preferably, described assistant for emulsifying agent is isohexadecane (being called for short HD).
As preferably, described silica precursor and the mass ratio of essential oil are 3 ~ 60:100, appropriate silica precursor can at oil-water interfaces generation hydrolysis, the a large amount of silica dioxide granules of Pickering physical absorption in oil-water interfaces place can be tied by these newly-generated silica species, and this is conducive to the silicon oxide hard shell forming high compactness extent and high structural strength fast.
It is a small amount of that the use amount of described assistant for emulsifying agent can select those skilled in the art to know, and as preferably, described assistant for emulsifying agent and the mass ratio of essential oil are 2.5 ~ 10:100, are conducive to forming fine crankshaft liquid.
In step (2), need drip acid to regulate pH to 4.5 ~ 5.7 of the aqueous dispersions (i.e. aqueous phase system) of silica, this is to regulate the static behaviour of silica particles and intergranular active force.Because the equipotential points of nanometer silicon dioxide particle is at about pH=2.5, when system pH=4.5 ~ 5.7, silica particles is by with appropriate negative electrical charge (now particle surface Zeta potential is about-42 ~-27mv).The fainter electrostatic repulsion provided by these appropriate negative electrical charges can ensure that silica dioxide granule has good dispersion stabilization in aqueous phase, is unlikely to again to have a strong impact on the dense packing of droplet interfaces place silica sol granule after fine crankshaft process simultaneously.If aqueous pH values is lower than this scope, be in stronger sour environment, then not only silica particles Ztea current potential is low, electrostatic repulsion is weak, easily large-scale aggregating is there is between particle, and can Essential Oil Chemistry composition in destruction system before microcapsules complete, affect the odor type of microcapsules.If aqueous pH values is higher than this scope, system is in neutrality, then silica particles is electrically strong, and mutual repulsion force is large.Namely be enablely adsorbed in sub-micro essential oil droplets surface, also can produce a large amount of spaces between silica dioxide granule, this had both been unfavorable for improving effective parcel to essential oil, was also unfavorable for the structural strength improving microcapsules.Described acid can adopt pure acid or aqueous acid, regulates pH for convenience, as preferably, selects aqueous acetic acid.This weak acid is few to ambient influnence, and is easily removed by mode of heating.Under ultrasonic disperse (i.e. hyperacoustic high force dispersion) effect; produce a large amount of submicron order essential oil droplets and a large amount of oil-water interfaces; utilize the Pickering Emulsification effect between bulky grain and granule simultaneously; low electronegative silica dioxide granule is adsorbed onto efficiently and stably the large drop surface of oil phase (for reducing the interface energy of whole system; silica dioxide granule can be adsorbed onto between oil-water interfaces automatic uniform), form stable Pickering emulsion.
With the aqueous dispersions of acid for adjusting pH to 4.5 ~ 5.7 silica as aqueous phase, inherently containing a certain amount of water in the aqueous dispersions of silica, after the aqueous dispersions of silica mixes with the oil phase mixed liquor of step (1), can supplement as required and add a certain amount of water.The constant that the use total amount of water can adopt those skilled in the art to know, water content and supplement and add water content sum in the aqueous dispersions that the use total amount of water is silica, as preferably, in step (2), the total amount of water and the mass ratio of essential oil are 300 ~ 1800:100.
As preferably, in the aqueous dispersions of described silica, the particle diameter of silica dioxide granule is 5 ~ 30nm, power due to silica dioxide granule absorption is the Pickering Emulsification effect between large drop and granule, therefore the silica dioxide granule particle diameter used must meet certain size, just efficiently can be adsorbed onto the oil phase drop surface that ultrasonic homogenation becomes fast, reach the effect of stable emulsion, realize the preliminary adjustment to shell thickness simultaneously.Adsorption between excessive silica sol granule (>30nm) and drop is more weak, easily causes silica sol granule dissociating in continuous aqueous phase; And too small silica dioxide granule (<5nm), then cannot ensure the good structural strength of capsule shell and compactness.Further preferably, in the aqueous dispersions of described silica, the particle diameter of silica dioxide granule is 5 ~ 15nm, the silica dioxide granule of above-mentioned size efficiently can be adsorbed onto the oil phase drop surface of ultrasonic homogenation one-tenth fast, reach the effect of stable emulsion, and after capping, form the silicon oxide hard shell that structural strength is good and compactness is good.
As preferably, in the aqueous dispersions of described silica, the mass ratio of silica dioxide granule and essential oil is 10 ~ 100:100, and silica dioxide granule consumption directly affects Pickering emulsion intercalation method.As very few in silica dioxide granule amount, oil phase drop size is large and adsorption is insufficient, then not easily form stable Pickering emulsion system.And under crossing the silica dioxide granule of volume, aqueous phase free silicon dioxide particle increases, granular absorption efficiency reduces.Meanwhile, wall material thickens, and the bonding of silica binder to silica dioxide granule that silica precursor hydrolytic condensation produces is insufficient, can cause the reduction of effect microcapsule wall structural strength.
As preferably, the condition of described ultrasonic disperse: ultrasonic power 40W ~ 200W, ultrasonic 3s ~ 7s, the ultrasonic generation amount of heat of interval 3s ~ 7s(, and then system temperature can be caused to raise fast, in ultrasonic procedure, it is have more chance outwards to dispel the heat for ease of system that interval stops ultrasonic, such as to water-bath release heat), effective ultrasonic time is 300s ~ 700s.Namely at ultrasonic power 40W ~ 200W first ultrasonic 3s ~ 7s, then interval 3s ~ 7s, more ultrasonic 3s ~ 7s, then interval 3s ~ 7s, replace successively, batch (-type) is ultrasonic, and ultrasonic temporal summation is effective ultrasonic time, is 300s ~ 700s.To be homogenized intensity by regulation system, effectively can control the particle diameter of essential oil microcapsules.Under normal circumstances, ultrasonic power is higher, ultrasonic time is longer, and the made particle size of mini-emulsion polymerization is less.Experiment finds under above-mentioned ultrasonic disperse condition, the microcapsules average grain diameter of made Silica-coated essential oil is generally at 180nm ~ 410nm, domain size distribution index Span value (Span=(D90-D10)/D50, particle size corresponding when the mass accumulation that wherein D90, D10 and D50 represent the side little by particle diameter is respectively equivalent to 90%, 10% and 50% of gross weight)≤1.Domain size distribution in this case time, the capsule size of Silica-coated essential oil is more homogeneous, system is more stable.Further preferably, the condition of described ultrasonic disperse: ultrasonic power 40W ~ 200W, ultrasonic 5s, interval 5s, effective ultrasonic time is 500s.
Described ultrasonic disperse preferably carries out in ice-water bath, and ultrasonic generation amount of heat, is conducive to water-bath release heat.
As preferably, in the fine crankshaft liquid after ultrasonic disperse, add emulsifying agent, the stability of fine crankshaft liquid can be improved.Further preferably, described emulsifying agent is softex kw (hereinafter referred to as CTAB), softex kw (CTAB) is a kind of cationic surfactant, has certain emulsification, can improve the stability of emulsification system.The more important thing is this cationic surface active agent positively charged being present in oil-water interfaces place, good electrostatic adsorption is had with the silica dioxide granule of negatively charged in system, thus the dense packing of oil-water interfaces silica dioxide granule is conducive to, fine crankshaft liquid after adding emulsifying agent carries out capping, also be conducive to silica precursor hydrolysis and generate the enrichment of silica dioxide granule at oil-water interfaces and the bonding to silica dioxide granule, thus be conducive to forming the silicon oxide hard shell that structural strength is good and compactness is good.
It is a small amount of that the use amount of described emulsifying agent can select those skilled in the art to know, and as preferably, described emulsifying agent and the mass ratio of essential oil are 0.75 ~ 3:100, and the emulsifying agent of above-mentioned use amount just can improve the stability of emulsification system well.
In step (3), as preferably, fine crankshaft liquid is at 30 DEG C ~ 50 DEG C capping 2h ~ 4h, and along with the rising of system temperature, silica precursor hydrolysis can sharply be accelerated.Thus too high reaction temperature is unfavorable for the bonding of newly-generated silica to silica dioxide granule in the aqueous dispersions of silica.In addition, under higher temperature, essential oil volatilization strengthens, also more perishable, the guarantee of unfavorable aromatic micro-capsule quality.But reaction temperature is too low, hydrolysis reaction can be comparatively slow, unfavorable production.Take into account reaction efficiency and essential oil quality, the temperature of described capping is 30 DEG C ~ 50 DEG C.Experiment finds, under the reaction condition of nitrogen protection deoxygenation, react after 2h ~ 4h hour, silica precursor conversion ratio is basic more than 90%.And reaction rate is moderate, course of reaction is stablized, end product essential oil pure in smell.
In step (3), as preferably, described capping is 200 ~ 300rmin in stir speed (S.S.)
-1under carry out, because the hydrolysis of silica precursor is relatively slow, and reacting environment is at oil-water interfaces.Therefore, extraneous disturbance is moderate, and excessive disturbance can make oil-water interfaces unstable, affects the absorption of nano silicon, causes Pickering emulsion unstable.In addition, excessive disturbance also can affect the morphosis of microcapsules, the perfect degree of the sphericity of microcapsules and parcel essential oil is deteriorated, and disturbs silica precursor to generate SiO
2to the cementation of silica dioxide granule.If but disturbance undermixing, the aqueous phase insufficient flow on oil phase drop surface, easily causes microcapsules in system to suspend not enough, and then affects the stability of reaction system.
From characterization data, the effect of embodiment 5 and embodiment 10 is best, essential oil coating efficiency is high, release performance is good, therefore, and can be preferred further, first preferred technical scheme, in step (1), described silica precursor and the mass ratio of essential oil are 25:100, and described assistant for emulsifying agent and the mass ratio of essential oil are 5:100.In step (2), in the aqueous dispersions of described silica, the mass ratio of silica dioxide granule and essential oil is 50:100, and described emulsifying agent and the mass ratio of essential oil are 1.5:100.Wherein, in the mass ratio of silica precursor and essential oil and the aqueous dispersions of silica, the mass ratio of silica dioxide granule and essential oil is important influence factor, the microcapsules of made Silica-coated essential oil, essential oil coating efficiency is high, particle size is little, structure is strong, good dispersion, and the sustained release performance of the microcapsules of Silica-coated essential oil is good.
In the present invention, described stirring, ultrasonic disperse etc. are the typical unit operation in chemical process, object be make mixing of materials evenly, be uniformly dispersed, and make sample segment produce the oiliness droplet with specific modality structure, existing conventional equipment can be adopted to realize.
Compared with prior art, the present invention has following beneficial effect:
One, the preparation method of the microcapsules of inventive silica parcel essential oil, in conjunction with Pickering physical absorption and original position interfacial polymerization two kinds of microcapsule preparation methods, wherein Pickering physical absorption silica forms the skeleton of shell, and the silica that original position interfacial polymerization generates is as the binding agent between above-mentioned skeleton particle.Thus can rapidly high volatility, perishable liquid essential oil be coated in the silica wall material of porous hard, and then realize " small size is powdered curing " of liquid towards essential oil.Above-mentioned preparation process is quick and convenient, cleanliness without any pollution, and the particle size of the microcapsules of made Silica-coated essential oil is little, structure strong, good dispersion, and the release performance adjustable extent of the microcapsules of Silica-coated essential oil is large.
Two, the present invention is by controlling the content of silica dioxide granule, particle diameter and silica precursor consumption, controls the wall material thickness size on wall material and wall material crosslinking compactness extent and strengthens.This not only effectively can improve the external stressed opposing of microcapsules, prevents caving in and molten problem of essential oil microcapsules, ensures that microcapsules have good nucleocapsid structure.And what is more important, the adjustability of wall material thickness, compactness extent is large, can give the volatilization release adjustability that microcapsules are wider.
Three, the product that preparation method of the present invention is made is the polymolecularity latex having blue light, essential oil microcapsules structural strength is wherein high, in water and polar organic matter dispersiveness all better, a large amount of harsh chemical environments such as strong acid and strong base can be tolerated.Uniform and stable white powder can be obtained through simple breakdown of emulsion, suction filtration, drying under normal temperature, the fields such as weaving, building, furniture can be applied to as additive and filler easily.
Four, preparation method of the present invention is raw materials used is easy to get, technique is simple, the controllability of microencapsulated forms structure is good, do not relate to organic solvent, the problems such as the solvent-free pollution of process, can avoid existing silica precursor (TEOS) one-step method to generate in shell method the problems such as shell rise time length, uneven thickness, release poor controllability.Preparation method of the present invention is suitable for industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the microcapsules of Silica-coated essential oil prepared by embodiment 5;
Fig. 2 is transmission electron microscope (TEM) photo of the microcapsules of Silica-coated essential oil prepared by embodiment 1;
Fig. 3 is ESEM (SEM) photo of colloid emulsion through breakdown of emulsion, suction filtration, dry gained white powder of the microcapsules of Silica-coated essential oil prepared by embodiment 5.
Detailed description of the invention
Embodiment 1 ~ 15
(1) essential oil, silica precursor TEOS and 0.5g assistant for emulsifying agent (isohexadecane, HD) are mixed, obtain oil phase mixed liquor;
(2) in the aqueous dispersions of silica, add aqueous acetic acid regulate pH to 4.5 ~ 5.7, embodiment 1 regulates pH to 4.5, embodiment 11 regulates pH to 5.7, other embodiments all regulate pH to 5, mix with the oil phase mixed liquor of step (1) again, add appropriate water, mixed total amount is made to be adjusted to 100g, then ice-water bath is put into, through ultrasonic disperse (ultrasonic 5s, interval 5s, effective ultrasonic time is 500s) obtain fine crankshaft liquid, in the fine crankshaft liquid after ultrasonic disperse, add 0.15g emulsifying agent softex kw (CTAB);
(3) be 200 ~ 300rmin by adding the fine crankshaft liquid after emulsifying agent in stir speed (S.S.)
-1under, at 10 DEG C ~ 60 DEG C capping 1h ~ 6h, obtain the colloid emulsion of the microcapsules of the Silica-coated essential oil of polymolecularity.
The colloid emulsion obtaining the microcapsules of the Silica-coated essential oil of polymolecularity is the polymolecularity latex having blue light, can obtain uniform and stable white powder through simple breakdown of emulsion, suction filtration, drying.
Other Parameter Conditions of embodiment 1 ~ 13 are as shown in table 1.
Table 1
The characterizing method related in embodiment 1 ~ 15 illustrates:
Measured the granularity of microcapsule granule by laser particle analyzer (LB-550 of Japanese Holiba company), obtain its average size and domain size distribution index Span value.
The morphosis of microcapsule granule in hanging drop sample is observed by transmission electron microscope (Japanese JEOL company JSM-1200EX T20).
The morphosis of essential oil microcapsules powder is observed by cold field emission ESEM (FE-SEM) transmission electron microscope (German Zeiss company ULTRA55).
The content being wrapped essential oil is analyzed in microcapsules by thermogravimetic analysis (TGA) (the Pyris1 type thermogravimetric analyzer of PE company of the U.S.).Concrete test process is: by the colloid emulsion of the microcapsules of Silica-coated essential oil through simple breakdown of emulsion, suction filtration, dry and can obtain white powder, be rapidly heated to 180 DEG C, and measure its weight-loss curve under this constant temperature.Etc. recording wherein weightless part after constant weight---the proportion of essential oil in microscapsule powder, is designated as X%.
Be calculated as follows the parcel efficiency of essential oil in essential oil microcapsules:
Percentage weightless when X:TGA curve reaches constant weight
M
ludox: add silica sol granule quality in 100 grams of systems
In upper two formulas, M
tEOS: add TEOS quality in 100 grams of systems
M
essential oil: add essential oil quality in 100 grams of systems
In addition, with the time in microcapsules needed for essential oil volatilization half for index, the release performance of essential oil in microcapsules is evaluated.
Transmission electron microscope (TEM) photo of the colloid emulsion of the microcapsules of Silica-coated essential oil prepared by embodiment 5, as shown in Figure 1, can obviously see the microcapsules presenting hollow structure, the size of microcapsules between 270 ~ 410nm, the hard shell that surface is made up of silica.
Transmission electron microscope (TEM) photo of the colloid emulsion of the microcapsules of Silica-coated essential oil prepared by embodiment 1, as shown in Figure 2, can find the microcapsules of the solid of a greater number or little liquid core, this is that oil phase ratio is low to be caused because embodiment 1 essential oil content is low.
The colloid emulsion of the microcapsules of Silica-coated essential oil prepared by embodiment 5 is through ESEM (SEM) photo of breakdown of emulsion, suction filtration, dry gained white powder, as shown in Figure 3, the hollow microcapsule broken in a large number can be seen clearly, illustrate that oil phase is coated on microcapsules inside preferably.Meanwhile, Fig. 3 effect microcapsule wall that breaks shows the compactness of shell and the feature of " hard " well.
Embodiment 1 ~ 15 measured result is as shown in table 2.
Table 2
Measured result and the composition graphs stave of table 2 are levied known, the microcapsules of Silica-coated essential oil prepared by embodiment 1 ~ 15, can well liquid essential oil be wrapped in the hard shell of silica, the microcapsule granule size of Silica-coated essential oil is little, structural strength is high, good dispersion in aqueous phase, microcapsules to wrap up the release performance adjustable extent of essential oil large.Wherein, the microcapsules of Silica-coated essential oil prepared by embodiment 5 and embodiment 10, levy from the measured result of table 2 and composition graphs stave, its tactical rule, microcapsules homogeneity is good, and dispersed in aqueous phase, essential oil coating efficiency is high, release performance is good, and embodiment 5 and embodiment 10 are optimum embodiment.
Claims (6)
1. a preparation method for the microcapsules of Silica-coated essential oil, is characterized in that, comprises the following steps:
(1) essential oil, silica precursor and assistant for emulsifying agent are mixed, obtain oil phase mixed liquor;
Described silica precursor and the mass ratio of essential oil are 3 ~ 60:100;
Described essential oil is sandalwood essential oil, olive essential oil, Rosemary Oil, Rosa Damascana or cinnamon essential oil;
Described silica precursor is ethyl orthosilicate;
Described assistant for emulsifying agent is hexadecane;
(2) in the aqueous dispersions of silica, add acid for adjusting pH to 4.5 ~ 5.7, then mix with the oil phase mixed liquor of step (1), obtain fine crankshaft liquid through ultrasonic disperse, in the fine crankshaft liquid after ultrasonic disperse, add emulsifying agent;
In the aqueous dispersions of described silica, the mass ratio of silica dioxide granule and essential oil is 10 ~ 100:100;
Described emulsifying agent is softex kw;
(3) by the fine crankshaft liquid in step (2) at 10 DEG C ~ 60 DEG C capping 1h ~ 6h, obtain the colloid emulsion of the microcapsules of Silica-coated essential oil.
2. the preparation method of the microcapsules of Silica-coated essential oil according to claim 1, is characterized in that, in step (2), in the aqueous dispersions of described silica, the particle diameter of silica dioxide granule is 5 ~ 30nm.
3. the preparation method of the microcapsules of Silica-coated essential oil according to claim 1, is characterized in that, in step (1), described silica precursor and the mass ratio of essential oil are 25:100;
In step (2), in the aqueous dispersions of described silica, the mass ratio of silica dioxide granule and essential oil is 50:100.
4. the preparation method of the microcapsules of Silica-coated essential oil according to claim 1, is characterized in that, in step (2), the condition of described ultrasonic disperse: ultrasonic power 40W ~ 200W, ultrasonic 3s ~ 7s, interval 3s ~ 7s, effective ultrasonic time is 300s ~ 700s.
5. the preparation method of the microcapsules of Silica-coated essential oil according to claim 1, is characterized in that, in step (3), fine crankshaft liquid is at 30 DEG C ~ 50 DEG C capping 2h ~ 4h.
6. the preparation method of the microcapsules of Silica-coated essential oil according to claim 1, is characterized in that, in step (3), described capping is 200 ~ 300rmin in stir speed (S.S.)
-1under carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310186523.5A CN103263877B (en) | 2013-05-17 | 2013-05-17 | A kind of preparation method of microcapsules of Silica-coated essential oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310186523.5A CN103263877B (en) | 2013-05-17 | 2013-05-17 | A kind of preparation method of microcapsules of Silica-coated essential oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103263877A CN103263877A (en) | 2013-08-28 |
| CN103263877B true CN103263877B (en) | 2015-09-30 |
Family
ID=49007563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310186523.5A Active CN103263877B (en) | 2013-05-17 | 2013-05-17 | A kind of preparation method of microcapsules of Silica-coated essential oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103263877B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073346A (en) * | 2013-03-27 | 2014-10-01 | 丽华（广州）香精有限公司 | Nanometer level microcapsule sweet orange essence and preparing method thereof |
| CN103554347B (en) * | 2013-10-18 | 2016-03-02 | 江南大学 | A kind of preparation method of after-finishing of textile products oxide compound/essential oil/emulsion particle composite particles |
| CN104198343A (en) * | 2014-09-12 | 2014-12-10 | 浙江浙能催化剂技术有限公司 | Detection method for particle size distribution of titanium dioxide |
| CN106148005B (en) * | 2016-07-01 | 2018-12-28 | 西南大学 | A kind of embedding food flavor walks quickly and keeps away microcapsules of red flour beetle and preparation method thereof |
| CN106567257A (en) * | 2016-11-07 | 2017-04-19 | 陕西科技大学 | Slow fragrance type and super-hydrophobic cotton fabric and preparation method thereof |
| CN108175718A (en) * | 2017-12-19 | 2018-06-19 | 彭枭雄 | A kind of sun-proof camellia of heat-resistance antibacterial with long-term sustained release effect receives microcapsules and preparation method thereof |
| CN108993332B (en) * | 2018-07-27 | 2021-07-13 | 云南中烟工业有限责任公司 | Preparation method of heat-resistant essence microcapsule |
| CN109137482A (en) * | 2018-08-02 | 2019-01-04 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of air-permeable cool type finishing agent |
| CN109287628A (en) * | 2018-09-18 | 2019-02-01 | 广西大学 | A kind of preparation process of nano silica antibacterial microcapsule |
| WO2021129968A1 (en) * | 2019-12-25 | 2021-07-01 | Unilever Ip Holdings B.V. | Microcapsules and cosmetic compositions comprising the same |
| WO2021132729A1 (en) * | 2019-12-27 | 2021-07-01 | 花王株式会社 | Method for preparing microcapsule |
| CN111421624A (en) * | 2020-04-22 | 2020-07-17 | 东北林业大学 | Slow-release aromatic veneer and manufacturing method thereof |
| CN112090378A (en) * | 2020-07-29 | 2020-12-18 | 淮阴工学院 | Preparation method of photo-thermal conversion enhanced microcapsule phase change material |
| CN113441095B (en) * | 2021-04-30 | 2022-06-21 | 江西农业大学 | Preparation method of silicon dioxide-essential oil microcapsule |
| CN113480744B (en) * | 2021-06-04 | 2022-08-05 | 上海应用技术大学 | Multifunctional Pickering emulsion and preparation method thereof |
| CN113499309A (en) * | 2021-06-04 | 2021-10-15 | 上海应用技术大学 | Pickering emulsion with dual functionality and stability and preparation method thereof |
| CN114711411A (en) * | 2022-03-31 | 2022-07-08 | 重庆小丸生物科技股份有限公司 | Self-dispersed oil microcapsule in water and preparation method thereof |
| CN116037067A (en) * | 2022-12-26 | 2023-05-02 | 核工业北京化工冶金研究院 | Water-soluble ionic liquid microcapsule and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259399A (en) * | 2007-12-18 | 2008-09-10 | 浙江大学 | Method for preparing inorganic nano microcapsule by one-step method |
| CN102030990A (en) * | 2009-09-28 | 2011-04-27 | 复旦大学 | Silicone oil microcapsule with slow-release characteristics and preparation method thereof |
| CN102732379A (en) * | 2012-04-23 | 2012-10-17 | 上海应用技术学院 | Temperature-sensitive capsules of silica-loaded essential oil, and preparation method thereof |
| CN102885785A (en) * | 2012-09-26 | 2013-01-23 | 复旦大学附属金山医院 | Adriamycin-containing nanometer medicament microspheres and preparation method thereof |
-
2013
- 2013-05-17 CN CN201310186523.5A patent/CN103263877B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259399A (en) * | 2007-12-18 | 2008-09-10 | 浙江大学 | Method for preparing inorganic nano microcapsule by one-step method |
| CN102030990A (en) * | 2009-09-28 | 2011-04-27 | 复旦大学 | Silicone oil microcapsule with slow-release characteristics and preparation method thereof |
| CN102732379A (en) * | 2012-04-23 | 2012-10-17 | 上海应用技术学院 | Temperature-sensitive capsules of silica-loaded essential oil, and preparation method thereof |
| CN102885785A (en) * | 2012-09-26 | 2013-01-23 | 复旦大学附属金山医院 | Adriamycin-containing nanometer medicament microspheres and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103263877A (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103263877B (en) | A kind of preparation method of microcapsules of Silica-coated essential oil | |
| CN105238361B (en) | A kind of multi-functional microencapsulated phase change material based on silver/silicon dioxide bilayer wall material and preparation method thereof | |
| CN102059083B (en) | Method for preparing phase-transformation microcapsule with wall material inlaid with nano alumina | |
| Wang et al. | Synthesis of silica-coated ZnO nanocomposite: the resonance structure of polyvinyl pyrrolidone (PVP) as a coupling agent | |
| Wu et al. | Preparation of Mannitol@ Silica core–shell capsules via an interfacial polymerization process from water-in-oil emulsion | |
| CN106367031A (en) | High thermal conductivity composite phase change microcapsule and preparation method thereof | |
| CN106711415B (en) | A kind of porous silicon composite cathode material and preparation method thereof | |
| CN106811832B (en) | A kind of pearl-decorated curtain shape BiFeO3The preparation method and products obtained therefrom of micro nanometer fiber | |
| CN109837080B (en) | A kind of viscosity reduction system and preparation method thereof for microwave heavy crude producing | |
| CN103496724B (en) | The preparation method of a kind of nano alumina sol and gel | |
| CN103818906A (en) | Carbon resistance superfine nano wolfram carbide material as well as preparation method and application thereof | |
| CN108774499A (en) | A kind of graphene-silica compound wall materials phase transformation Nano capsule and preparation method | |
| CN106637453A (en) | A preparing process of a chitosan/polyvinyl alcohol composite nanometer electrically-conductive fiber | |
| CN106497063A (en) | A kind of kill the antibacterial silicone rubber insulation material of algae and preparation method | |
| CN103406078A (en) | Preparation method of magnetic iron sesquioxide particle coated with silicon dioxide and provided with oval-shaped nuclear shell type structure | |
| KR101585319B1 (en) | Microcapsules comprising phase change material enclosed by conductive polymers and method for preparing the same | |
| CN109468122A (en) | One kind " core-shell structure copolymer " type mesoporous silicon oxide/organic phase change material composite Nano capsule and preparation method thereof | |
| CN108862356A (en) | A kind of method that loaded Catalyst By Water-in-oil Microemulsion prepares nanometer barium sulfate grains | |
| CN102181126B (en) | Low surface energy polymer microcapsules and preparation method thereof | |
| CN108545754A (en) | A kind of preparation method of nanometer titanium dioxide silicon ball | |
| Fan et al. | Preparation and phase change performance of Na2HPO4· 12H2O@ poly (lactic acid) capsules for thermal energy storage | |
| CN106753722A (en) | A kind of giant electro-rheological liquid and preparation method thereof | |
| Mao et al. | In situ polymerization of uniform poly (urea–formaldehyde) microcapsules containing paraffins under the high-speed agitation without emulsifier | |
| CN114181563B (en) | High-magnification self-temperature-control graphene powder, self-temperature-control ink and graphene self-temperature-control heating coating | |
| CN104046020B (en) | A kind of preparation method of high dispersive anisotropy electromagnetism function and service film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |