CN102899168A - Double-layer coated essence microcapsule and preparation method thereof - Google Patents
Double-layer coated essence microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a double-layer coated essence microcapsule and a preparation method thereof. The essence microcapsule takes an oil soluble liquid essence as a capsule core, a gelatin modified amino resin composite material as a first-layer capsule wall and an acrylate polymer as a second-layer capsule wall, wherein a grafting transition area is formed by graft copolymerization of gelatin and acrylate between the first-layer capsule wall and the second-layer capsule wall. The preparation method comprises a step of prepolymer compounding, emulsification dispersion, microcapsule continuous double-layer coating and post-treatment. Compared with a single-layer coated microcaposule, the essence microcapsule has the advantages that the slow release performance, the heat resistance performance and the capsule wall material mechanical property are greatly improved, and the essence microcapsule can be used for most of microencapsulated essence products processed by heat extrusion molding of high molecular materials.
Description
Technical field
The present invention relates to a kind of essence microcapsule and preparation method thereof.
Background technology
Microcapsulary has been applied to the fields such as industry, agricultural, medical treatment, such as pressure-sensitive carbon paper, and the sustained-release and controlled release of micro encapsulation red phosphorus combustion inhibitor, medicine or essence etc.According to different application scenarios, microcapsule wall material can be protected the capsule-core material, makes its impact of avoiding external environment, or slows down the release rate of volatile material.
Essence has the smell of pleasant, can eliminate peculiar smell, improve people's quality of life, be widely used in the daily life, but essence generally is the high volatile volatile material, exist that boiling point is low, volatility is high, fragrance remaining time is short and have the characteristics such as chemical reactivity, so that the preservation of essence and add the important topic that stability in the product becomes everybody common concern to.The essence microcapsule of making capsule-core preparation of essence can address the above problem, and essence is behind micro encapsulation, because the volatilization loss that the sealing function of cyst wall can establishment essence improves the stability of essence and prolongs fragrance remaining time.But the wall material of existing essence microcapsule can not satisfy the processing request of macromolecular material thermoforming at fragrance remaining time, wall material mechanical strength, thermotolerance Shortcomings.
Summary of the invention
The invention provides a kind of double-coated essence microcapsule and preparation method thereof, be intended to improve sustained release performance, raising wall material mechanical strength and the resistance toheat of essence microcapsule, satisfy the processing request of macromolecular material thermoforming.
To achieve these goals, the invention provides following technical scheme:
A kind of double-coated essence microcapsule is characterized in that: described essence microcapsule has capsule-core and double-coated cyst wall; Described capsule-core is oil soluble liquid essence, the second layer cyst wall that the first layer cyst wall that described double-coated cyst wall is made of gelatin modified aminoresin matrix material and acrylic ester polymer consist of forms, and forms the grafting zone of transition by gelatin and acrylic ester grafted copolymerization between described the first layer cyst wall and the second layer cyst wall.
Further, described gelatin modified aminoresin matrix material the first layer cyst wall is by the aminoresin monomer, and formaldehydes material and gelatin make by prepolymerization reaction and polycondensation; The quality of described aminoresin monomer is the 20-70% of essence quality, and the quality of formaldehydes material is the 15-120% of aminoresin monomer mass, and the quality of gelatin is the 3-16% of aminoresin monomer mass; Described acrylic ester polymer second layer cyst wall is formed by the acrylate monomer copolymerization, and the quality of described acrylate monomer is the 20%-40% of essence quality.
Preferably, described aminoresin monomer is selected from trimeric cyanamide, urea, one or more in the phenyl guanamine; Described formaldehydes material is selected from formaldehyde or Paraformaldehyde 96; Described acrylic ester polymer is by vinyl cyanide, ethyl propenoate, butyl acrylate, methacrylic acid, methyl acrylate, one or more copolymerizations of methyl methacrylate.
Further, described acrylic ester polymer is by the acrylate monomer copolymerization, and acrylate monomer comprises vinyl cyanide and acrylate, and wherein the quality of vinyl cyanide is the 15%-30% of acrylate quality.
The gelatin modified aminoresin consumption of the first layer wall material has larger impact to the physicals of micro encapsulation essence, and when consumption was less than normal, cyst wall was partially thin, high temperature resistant and poor mechanical property; When consumption was bigger than normal, cyst wall was partially thick, and particle diameter is bigger than normal, and the relative mass of essence descends too much.In the starting monomer of second layer wall material/polymer, anti-solvent and the air-tightness of vinyl cyanide are good, and its consumption has larger impact to the release performance of micro encapsulation essence, when the vinyl cyanide consumption is less than normal, the resistance to air loss of cyst wall is not enough, the easy seepage of capsule-core essence during high temperature process; When consumption was bigger than normal, the resistance to air loss of cyst wall made the slow release speed of essence excessively slow, and the quality optimization of vinyl cyanide is that the 15%-30% of acrylate quality is the best.Capsule material use quantity of the present invention accounts for the 45-60% of microcapsule essence product.
The particle diameter of described essence microcapsule is 1-10 μ m.
A kind of preparation method of double-coated essence microcapsule is characterized in that: comprise that prepolymer is synthetic, emulsion dispersion, the continuous double-coated of microcapsule and post-processing step:
Described prepolymer is synthetic to be gelatin, aminoresin monomer and formaldehydes material to be added water stir, in the mixed solution consumption of water be the essence quality 15-20 doubly, with lye pH adjustment value 7.0-11, then be heated to 60-90 ℃, rear insulation reaction 20-60 minute of reaction solution clarification obtains gelatin modified aminoresin prepolymer;
Described emulsion dispersion is that the oil soluble liquid essence mixture that will be dissolved with acrylate monomer, initiator, linking agent joins in the aqueous dispersant, at room temperature carries out homogenizing emulsifying, obtains the essence emulsion;
The continuous double-coated of described microcapsule is that described essence emulsion and gelatin modified aminoresin prepolymer are mixed, then adding acid conditioning agent adjust pH is 2-6,15-60 ℃ of lower reaction 1-5 hour, polycondensation occurs on essence drop surface in the aminoresin prepolymer, generate the first layer cyst wall, then be warming up to 50-90 ℃ and continue reaction 1-5 hour, the acrylate monomer of dissolving issues in the effect of initiator and gives birth to free-radical polymerized and partially grafted with gelatin in the essence drop, generate second layer cyst wall, reaction is cooled to room temperature after finishing, and is neutralized to pH value 6.5-9.0 with alkali lye;
Described post-processing step is essence suspension filtered, washing, the separation and dry that will carry out after double coating is processed, obtains the Powdered double-coated micro encapsulation essence product of good fluidity.
Gelatin plays two kinds of effects simultaneously in preparation essence capsule process: at first, under the alkaline condition, amino in the gelatin molecule and the addition reaction of formaldehydes material generation methylolation, the methylol that generates forms ehter bond with aminoresin prepolymer generation dehydration condensation under acidity and heating condition, obtain gelatin modified aminoresin, improved the mechanical properties such as toughness of aminoresin; Secondly, the more structural α of gelatin molecule-H atom site can be used as active grafting site, participate in the free radicals copolymerization reaction of acrylate monomer, form the grafting zone of transition that the molecular chain grafting is twined at two layers of cyst wall interlayer, improved compactness, toughness and the resistance toheat of capsule material, thereby its hot-work stability is improved.
Dispersion agent in preparation method's emulsion dispersion step of described essence microcapsule is at least a in gelatin, gum arabic, starch, Walocel MT 20.000PV, Natvosol, carboxymethyl cellulose, polyvinyl alcohol, the sodium polyacrylate; Dispersion agent plays emulsion stabilization in the essence emulsion dispersion stage, and it is little to add behind the described dispersion agent in the emulsion essence size droplet diameter, the Microcapsules Size narrowly distributing that makes, and the essence clad ratio is high, can make the Powdered micro encapsulation essence product of good fluidity.
Described initiator is selected from one or more in Diisopropyl azodicarboxylate, di-cyclohexylperoxy dicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the lauroyl peroxide;
Described linking agent is at least a in Viscoat 295, triallyl isocyanurate, Ethylene glycol dimethacrylate, the methacrylic acid butanediol ester, contains the two key active groups more than two or two in the cross-linker molecules;
The consumption of described dispersion agent is the 1%-20% of essence quality, and the consumption of water is 15-20 times of essence quality.The consumption of linking agent is the 1%-10% of acrylate monomer; Initiator amount is the 0.1%-2% of acrylate monomer.Essence emulsion dispersion of the present invention carries out at aqueous phase, and the consumption of water has certain impact to operation.When the water yield was on the low side, easily at reactor surface knot wall, when the water yield was on the high side, production efficiency was low for product.Consider operation and production efficiency factor, the consumption of water is 15-20 times of essence quality, and preferred 16-19 doubly.
Preferably, described initiator is Diisopropyl azodicarboxylate; Described linking agent is Viscoat 295 or triallyl isocyanurate; Described dispersion agent is gum arabic or carboxymethyl cellulose.
Alkali lye in the synthetic and double encapsulation steps of microcapsule of preparation method's prepolymer of described essence microcapsule is at least a in sodium hydroxide solution, potassium hydroxide solution, aqua calcis, sodium carbonate solution, the sodium hydrogen carbonate solution; The acid conditioning agent is at least a in hydrochloric acid, acetic acid, ammonium chloride, the primary ammonium phosphate in the double encapsulation steps of described microcapsule;
Preferably, described alkali lye is sodium hydroxide solution or sodium bicarbonate; Described acid conditioning agent is acetic acid or hydrochloric acid.
Beneficial effect of the present invention is as follows:
1, compares with the essence microcapsule of prior art, the sustained release performance of essence microcapsule of the present invention, resistance toheat, capsule material mechanical property have obtained greatly improving, can tolerate high temperature and shearing force that macromolecular material produces in the hot extrusion course of processing, can be used for the micro encapsulation essence product of most of macromolecular material hot extrusion processing.The heat decomposition temperature of essence microcapsule of the present invention and softening temperature all can reach more than 200 ℃, the mechanical property such as resistance toheat and toughness is excellent, can satisfy macromolecular material hot-work to the requirement of essence resistance toheat and screw rod injection moulding, through on probation, micro encapsulation essence is at 220 ℃ of not broken capsules, and fragrance remaining time is more than 1 year.
2, the product application that makes of the present invention still maintains fragrance in EVA foaming plate (addition 1.5%) after 1 year.
3, product of the present invention is the powdery product of good fluidity, and size distribution is at 1-10 μ m, easier in macromolecular material Uniform Dispersion.
Embodiment:
A kind of double-coated essence microcapsule of the present invention, described essence microcapsule has capsule-core and double-coated softgel shell; Capsule-core is 12g Flower of Arabian Jasmine enriching essence (upper Hailin handkerchief spices company limited), the inner casing that the shell that the double-coated cyst wall is made of gelatin modified aminoresin matrix material and acrylic ester polymer consist of forms, and forms the grafting zone of transition by gelatin and acrylic ester grafted copolymerization between described inner casing and the shell.
Embodiment 1
The preparation method of a kind of double-coated essence microcapsule of the present invention comprises that prepolymer is synthetic, emulsion dispersion, the double coating of microcapsule and post-processing step:
1, prepolymer is synthetic: experiment equipment is thermometer, agitator, the there-necked flask with reflux condensing tube, beaker.
With 0.36g gelatin, 3.6g trimeric cyanamide, 37% formaldehyde 4.0g and 25g water join respectively in the 250ml there-necked flask, with sodium hydroxide solution adjust pH 8.0, then be heated to 65 ℃, rear insulation reaction 20-60 minute of reaction solution clarification, make gelatin modified resin pre-polymer solution, it is for subsequent use to be down to room temperature.
2, emulsion dispersion: in the 500ml beaker, add the 180g water that is dissolved with the 0.2g gum arabic, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), add 12.0g Flower of Arabian Jasmine enriching essence (upper Hailin handkerchief spices company limited), 0.5g vinyl cyanide, 2.6g the mixture of methyl methacrylate, 0.05g Diisopropyl azodicarboxylate, 0.2g Viscoat 295, at room temperature emulsion dispersion is 40 minutes, makes water-dispersion essence emulsion, and is for subsequent use.
3, microcapsule coated: above-mentioned water-dispersion essence emulsion joined thermometer is housed, in the 500ml there-necked flask of agitator and reflux condensing tube, add gelatin modified resin pre-polymer solution, at 50 ℃ of lower hydrochloric acid that add, regulate pH value to 3.5, reacted 3 hours, gelatin modified resin prepolymer is in essence drop surface aggregate film forming, obtain the capsule that the first layer coats, then be warming up to 70 ℃ and continue reaction 3 hours, acrylate monomer in the essence drop is under the radical initiator effect, copolyreaction occurs and being separated, with the gelatin grafting of shell, makes gelatin modified melamine resin/acrylate double-coated microcapsule essence simultaneously; Be cooled to room temperature after reaction finishes, with sodium hydrogen carbonate solution adjust pH 7.0, filter, washing, 40-60 ℃ of drying 24 hours makes the micro-yellow powder shape micro encapsulation essence product of good fluidity, and Microcapsules Size is 1-10 μ m.
Following 2-6 embodiment difference from Example 1 is the difference of cyst wall composition and content, and the dispersion agent, initiator and the linking agent that add in each step of preparation essence microcapsule are different, and the processing parameter in the preparation process is different:
Embodiment 2
Embodiment 3
Embodiment 4
Embodiment 5
Embodiment 6
Comparative example 1:
1, prepolymer is synthetic: the formalin and the 100.0g water that add 10.6g trimeric cyanamide, 14.0g mass concentration 37% in the 250ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, sodium hydroxide solution adjust pH 8.5 with mass concentration 10%, be warmed up to 80 ℃, the transparent rear insulation reaction of reaction solution 0.5 hour, aminoresin prepolymer solution, it is for subsequent use to be down to room temperature.
2, emulsion dispersion: in the 500ml beaker, add successively the aqueous solution that 200.0g is dissolved with the 0.5g carboxymethyl cellulose, open homogeneous emulsifying machine (model ESR, Shanghai Sample Model Factory), add 12.0g Flower of Arabian Jasmine enriching essence (upper Hailin handkerchief spices company limited), emulsion dispersion is 40 minutes under the room temperature, make water-dispersion essence emulsion, for subsequent use.
3, microcapsule coated: above-mentioned water-dispersion essence emulsion is joined in the 500ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, add above-mentioned aminoresin prepolymer solution, 50 ℃ of lower acetic acid that add, regulate the pH value to 3.5-4.5, reacted 3 hours, and then be warming up to 70 ℃ and continue reaction 3 hours; Be cooled to room temperature after reaction finishes, with the sodium hydroxide solution adjust pH 6.5-7.5 of mass concentration 5%, filter, washing, 50-80 ℃ of drying 24 hours makes white powder micro encapsulation essence product.
The micro encapsulation essence of embodiment 1-6 and comparative example 1 is got respectively the 1g sample put into test tube, measure resistance toheat with the 220OC silicone oil bath; Get respectively the 50g sample, whether ball mill grinding 5 minutes breaks with the microscopic examination microcapsule, judges the mechanical property of wall material; Get respectively the 10g sample, put into weighing bottle, place 55 ℃ of baking ovens, every day weigh once, the mass loss rate contrast sustained release performance by essence, result such as following table.
As can be seen from the table, under identical capsule material use quantity, the individual layer that embodiment 1-6 has the double-layer sustained release successful of acrylate endothecium structure to be better than comparative example 1 coats.
Claims (10)
1. double-coated essence microcapsule, it is characterized in that: described essence microcapsule has capsule-core and double-coated cyst wall; Described capsule-core is oil soluble liquid essence, the second layer cyst wall that the first layer cyst wall that described double-coated cyst wall is made of gelatin modified aminoresin matrix material and acrylic ester polymer consist of forms, between described the first layer cyst wall and the second layer cyst wall by gelatin and acrylic ester grafted formation zone of transition.
2. a kind of double-coated essence microcapsule according to claim 1, it is characterized in that: described gelatin modified aminoresin matrix material cyst wall is by the aminoresin monomer, and formaldehydes material and gelatin make by prepolymerization reaction and polycondensation; The quality of described aminoresin monomer is the 20-70% of essence quality, and wherein the quality of formaldehydes material is the 15-120% of aminoresin monomer mass, and the quality of gelatin is the 3-16% of aminoresin monomer mass; Described acrylic ester polymer cyst wall is by the acrylate monomer copolymerization, and the quality of described acrylate monomer is the 20%-40% of essence quality.
3. a kind of double-coated essence microcapsule according to claim 2 is characterized in that:
Described aminoresin monomer is selected from trimeric cyanamide, urea, one or more in the phenyl guanamine;
Described formaldehydes material is selected from formaldehyde or Paraformaldehyde 96;
Described acrylic ester polymer is by vinyl cyanide, ethyl propenoate, butyl acrylate, methacrylic acid, methyl acrylate, one or more copolymerizations of methyl methacrylate.
4. a kind of double-coated essence microcapsule according to claim 3, it is characterized in that: described acrylic ester polymer is by the acrylate monomer copolymerization, acrylate monomer comprises vinyl cyanide and acrylate, and wherein the quality of vinyl cyanide is the 15%-30% of acrylate quality.
5. a kind of double-coated essence microcapsule according to claim 1, it is characterized in that: the particle diameter of described essence microcapsule is 1-10 μ m.
6. the preparation method of a kind of double-coated essence microcapsule claimed in claim 1 is characterized in that: comprise that prepolymer is synthetic, emulsion dispersion, the double coating of microcapsule and post-processing step:
Described prepolymer is synthetic to be gelatin, aminoresin monomer and formaldehydes material to be added water stir, and with lye pH adjustment value 7.0-11, then is heated to 60-90 ℃, and rear insulation reaction 20-60 minute of reaction solution clarification obtains gelatin modified aminoresin prepolymer;
Described emulsion dispersion is that the oil soluble liquid essence that will be dissolved with acrylate monomer, initiator, linking agent joins in the aqueous dispersant, at room temperature carries out homogenizing emulsifying, obtains the essence emulsion;
The continuous double-coated of described microcapsule is that described essence emulsion and gelatin modified aminoresin prepolymer are mixed, then adding acid conditioning agent adjust pH is 2-6,15-60 ℃ of lower reaction 1-5 hour, polycondensation occurs on essence drop surface in the aminoresin prepolymer, generate the first layer cyst wall, then be warming up to 50-90 ℃ and continue reaction 1-5 hour, the acrylate monomer of dissolving issues in the effect of initiator and gives birth to free-radical polymerized and partially grafted with gelatin in the essence drop, generate second layer cyst wall, reaction is cooled to room temperature after finishing, and is neutralized to pH value 6.5-9.0 with alkali lye;
Described post-processing step is essence suspension filtered, washing, the separation and dry that will carry out after double coating is processed, obtains the Powdered double-coated micro encapsulation essence product of good fluidity.
7. the preparation method of a kind of double-coated essence microcapsule according to claim 6, it is characterized in that: the dispersion agent in preparation method's emulsion dispersion step of described essence microcapsule is one or more in gelatin, gum arabic, starch, Walocel MT 20.000PV, Natvosol, carboxymethyl cellulose, polyvinyl alcohol, the sodium polyacrylate;
Described initiator is selected from one or more in Diisopropyl azodicarboxylate, di-cyclohexylperoxy dicarbonate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the lauroyl peroxide;
Described linking agent is one or more in Viscoat 295, triallyl isocyanurate, Ethylene glycol dimethacrylate, the methacrylic acid butanediol ester;
The consumption of described dispersion agent is the 1%-20% of essence quality, and the consumption of water is 15-20 times of essence quality.The consumption of linking agent is the 1%-10% of acrylate monomer; Initiator amount is the 0.1%-2% of acrylate monomer.
8. the preparation method of a kind of double-coated essence microcapsule according to claim 7, it is characterized in that: described initiator is Diisopropyl azodicarboxylate; Described linking agent is Viscoat 295 or triallyl isocyanurate; Described dispersion agent is gum arabic or carboxymethyl cellulose.
9. the preparation method of a kind of double-coated essence microcapsule according to claim 6 is characterized in that: the alkali lye in preparation method's pre-polymerization of described essence microcapsule and the double encapsulation steps of microcapsule is at least a in sodium hydroxide solution, potassium hydroxide solution, aqua calcis, sodium carbonate solution, the sodium hydrogen carbonate solution; The acid conditioning agent is at least a in hydrochloric acid, acetic acid, ammonium chloride, the primary ammonium phosphate in the double encapsulation steps of described microcapsule.
10. the preparation method of a kind of double-coated essence microcapsule according to claim 9, it is characterized in that: described alkali lye is sodium hydroxide solution or sodium bicarbonate; Described acid conditioning agent is acetic acid or hydrochloric acid.
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Effective date of registration: 20190823 Address after: 410329 No. 175 Kangping Road, Liuyang Economic and Technological Development Zone, Changsha City, Hunan Province Co-patentee after: Hefei University of Technology Patentee after: Hunan Fangtaida Technology Co., Ltd. Address before: 410329 Hunan Yixiang Technology Co., Ltd. Kangping Road, Liuyang Industrial Park, Changsha City, Hunan Province Co-patentee before: Hefei University of Technology Patentee before: Hunan Yixiang Technology Co., Ltd. |